CN102815833A - Membrane-process treatment and reusing technique for oxalic production wastewater containing nitric acid - Google Patents
Membrane-process treatment and reusing technique for oxalic production wastewater containing nitric acid Download PDFInfo
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- CN102815833A CN102815833A CN2012103164381A CN201210316438A CN102815833A CN 102815833 A CN102815833 A CN 102815833A CN 2012103164381 A CN2012103164381 A CN 2012103164381A CN 201210316438 A CN201210316438 A CN 201210316438A CN 102815833 A CN102815833 A CN 102815833A
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Abstract
A membrane-process treatment and reusing technique for oxalic production wastewater containing nitric acid belongs to the technical field of environmental protection and comprehensive utilization of resources. The combined membrane-process treatment and reusing technique includes processes of pre-treatment, primary continuous roll-type reverse osmosis, high-pressure flat reverse osmosis, supper-high-pressure flat reverse osmosis, evaporation crystallization, secondary reverse osmosis and the like. Oxalic acid production wastewater containing nitric acid can be completely treated to meet the standard and reused after being treated by the combined technology, zero emission of oxalic acid production wastewater containing nitric acid is achieved, and nitrate in wastewater can be recycled. The membrane-process treatment and reusing technique has the advantages that the combined technology is used, technology is flexible, occupied space is small, investment is economized, efficiency is high, operation cost is low, effect is stable and reliable, and the like.
Description
Technical field
The invention belongs to environment protection and comprehensive utilization of resources technical field, particularly provide a kind of embrane method that contains the hexanodioic acid factory effluent of nitric acid to handle reuse technology.
Background technology
Hexanodioic acid is commonly called as adipic acid, is a kind of very important industrial chemicals.In the waste water of hexanodioic acid production process discharging; The nitric acid and the various low-molecular-weight organic acid (like hexanodioic acid, pentanedioic acid, Succinic Acid, propanedioic acid, oxalic acid, propionic acid, acetate, formic acid etc.) that contain higher concentration; In addition; Also contain trace heavy metals ion etc., belong to the high concentrated organic wastewater of high nitrogenous, high COD.Its C/N ratio (COD:TN) can be lower than 3 ~ 5:1 usually, adopts very difficulty of conventional bioremediation, needs to adopt other effective means more economically, and the major part of removing nitric acid in the waste water (nitrate ion) can be carried out conventional biological treatment.
China is the country of a serious water shortage, per capita Freshwater resources be merely world average level 1/4, rank 110 in the world, be one of whole world country that water resources is the poorest per capita.China is the water resources critical shortage not only, and water pollutes and remains serious, and the brainstrust warning: " China will can not find drinkable water resources after 20 years ", water resources critical shortage have seriously restricted Chinese economic development.Therefore it is vital developing new waste water treatment, recovery and utilization.
Membrane separation technique is progressively to grow up the middle and later periods in 20th century.Over nearly 30 years, various membrane filtrations such as micro-filtration, ultrafiltration, nanofiltration, r-o-, electrodialysis have all obtained fast development, in electronics, chemical industry, environmental protection, food, pharmacy and drink every field such as pure water and all obtained using widely.Along with updating of mould material, the continuous progress of stripping technique, the antifouling property of various films is greatly improved, the applied more and more aspect environmental protection and WWT.
Summary of the invention
The object of the present invention is to provide a kind of embrane method that contains the hexanodioic acid factory effluent of nitric acid to handle reuse technology; Adopt multistage reverse osmosis membrane separation system that the hexanodioic acid factory effluent that contains nitric acid is carried out concentration; Dense water is through evaporative crystallization; Reclaim nitrate salt wherein, permeate water is passed through multistage reverse-osmosis treated again, directly carries out reuse.The present invention substitutes traditional biological process of wastewater treatment with membrane process craft, have take up an area of few, reduced investment, advantage such as efficient is high, and working cost is low, and effect stability is reliable.
Membrane method treating process provided by the invention may further comprise the steps:
(1) pre-treatment: the hexanodioic acid waste water that contains nitric acid is regulated PH to 6.0～8.0 with sodium hydroxide; According to water quality situation process more medium filter+Hollow Fiber Ultrafiltration system; Perhaps disc-type strainer+Hollow Fiber Ultrafiltration system; Perhaps wire gauzee filter+methods such as ceramic membrane system are carried out pre-filtering, make to filter back WPI (SDI) less than 3, and waste water gets into raw water box after the pre-treatment;
(2) the type continuously rolled r-o-of one-level: through the pressurization of one-level service pump,, get into the type continuously rolled reverse osmosis system of one-level through pretreated waste water, under 1～4MPa, carry out 3～10 times of continuous concentration through security personnel's strainer.The dense water of first-stage reverse osmosis collects the dense water tank of one-level respectively with product water and one-level is produced water tank; One-level is produced water such as up to standardly can be carried out reuse or discharging, and is up to standard as not, need proceed the processing of (6) step;
(3) high pressure flat plate reverse osmosis: the dense water of first-stage reverse osmosis through security personnel's strainer, gets into the dull and stereotyped reverse osmosis system of high pressure through the dull and stereotyped reverse osmosis system service pump pressurization of high pressure, under 4～12MPa, carries out 2～4 times and concentrates. The dull and stereotyped reverse osmosis produced water of high pressure is back to raw water box or one-level is produced water tank continuation processing, and dense water is collected the dull and stereotyped dense water tank of high pressure; The dull and stereotyped concentrated stream amount of high pressure is directly carried out (5) step as satisfying the evaporative crystallization traffic requirement, continues to concentrate otherwise carry out (4) step;
(4) ultra-high voltage flat plate reverse osmosis: the dull and stereotyped dense water of high pressure through security personnel's strainer, gets into ultra-high voltage flat plate reverse osmosis system through the service pump pressurization of ultra-high voltage flat plate reverse osmosis system, under 8～16MPa, carries out 2～3 times and concentrates; Ultra-high voltage flat plate reverse osmosis product water is back to raw water box to be continued to handle, after dense water concentrates 12～120 times to raw wastewater, and the devaporation crystallization;
(5) evaporative crystallization: evaporative crystallization can adopt economic benefits and social benefits or multiple-effect evaporation crystallization, perhaps MVR evaporative crystallization.Crystalline solid collecting packing, water of condensation are collected one-level product water tank and are proceeded to handle;
(6) two-pass reverse osmosis: one-level is produced water (containing the evaporative crystallization water of condensation) through the pressurization of two-pass reverse osmosis service pump, through security personnel's strainer, gets into the two-pass reverse osmosis system, under 1～3MPa, carries out 4～10 times and concentrates; The two-pass reverse osmosis concentrate recirculation is proceeded to handle to raw water box, produces water and collects secondary product water tank; Secondary produces water can reach reuse standard usually.
Handle through this combination process, the hexanodioic acid factory effluent that contains nitric acid can be handled reuse up to standard fully, and realization contains the zero release of the hexanodioic acid factory effluent of nitric acid, and can reclaim the nitrate salt in the waste water.
Description of drawings
Fig. 1 handles recovering process flow figure for a kind of embrane method that contains the hexanodioic acid factory effluent of nitric acid.
Embodiment
Below in conjunction with embodiment the present invention is done further explanation.
Embodiment:
7.5 ten thousand tons of certain adipic acid plant scales, year 7500 hours running times, normal wastewater flow 55 m
3/ h, maximum wastewater flow 75 m
3/ h, 25 ℃ of water temperatures, PH 1～3, COD 7500 ppm, waste water composition (wt%): hexanodioic acid 0.03, nitric acid 0.99, other organic acid 0.54, metals ion trace.
(1), pre-treatment: acid-bearing wastewater 55 m
3/ h adds 30% sodium hydroxide solution 1960 m continuously
3/ h, PH is adjusted to 7.0 with waste water, passes through the hollow fiber ultrafiltration membrane system then, ultrafiltration water outlet TDS 20.9g/L, SDI 2.5, and the ultrafiltration water outlet gets into the ultrafiltration water tank;
(2), one-level rolling r-o-: 8+4 two-stage structure, film model SW30XLE-400i, membrane area 37.2 ㎡, salt rejection 99.7%.Advance film pressure 42Bar, advance film flow 86.2 m
3/ h, concentrated stream amount 23.1 m
3/ h produces discharge 63.1 m
3/ h produces water TDS 520 mg/L.
(3), high pressure flat plate reverse osmosis: 26+20 two-stage structure, film model PT80-U209, membrane area 10.0 ㎡, salt rejection 99.0%.Advance film pressure 72Bar, advance film flow 23 m
3/ h, concentrated stream amount 10.5 m
3/ h produces discharge 12.5 m
3/ h produces water TDS 7801 mg/L.
(4), ultra-high voltage flat plate reverse osmosis: 14+10 two-stage structure, film model PT160-U209, membrane area 10.0 ㎡, salt rejection 99.0%.Advance film pressure 148Bar, advance film flow 10.6 m
3/ h, concentrated stream amount 4.5 m
3/ h produces discharge 6.1 m
3/ h produces water TDS 15106 mg/L, dense water TDS 185 g/L.
(5), evaporative crystallization: adopt the double-effect evaporation crystallization, obtain thick SODIUMNITRATE crystal 850 kg/h, water of condensation is got back to the ultrafiltration water tank and is repeated to apply mechanically.
(6), secondary rolling r-o-: 5+2 two-stage structure, film model SW30XLE-400i, membrane area 37.2 ㎡, salt rejection 99.7%.Advance film pressure 22Bar, advance film flow 62.5 m
3/ h, concentrated stream amount 12.5 m
3/ h produces discharge 50.0 m
3/ h produces water TDS 15.6 mg/L.Two-pass reverse osmosis produces water and is back to use production line.
Through above processing, water resources is fully used, and has really realized zero release, and simultaneously, the thick SODIUMNITRATE crystal that obtains can be used as fertilizer and uses.
Claims (1)
1. an embrane method that contains the hexanodioic acid factory effluent of nitric acid is handled reuse technology, and it is characterized in that: the technical parameter of process step and control is following:
(1) pre-treatment: the hexanodioic acid waste water that contains nitric acid is regulated PH to 6.0～8.0 with sodium hydroxide; According to water quality situation process more medium filter+Hollow Fiber Ultrafiltration system; Perhaps disc-type strainer+Hollow Fiber Ultrafiltration system; Perhaps wire gauzee filter+methods such as ceramic membrane system are carried out pre-filtering, make to filter back WPI SDI less than 3, and waste water gets into raw water box after the pre-treatment;
(2) the type continuously rolled r-o-of one-level: through the pressurization of one-level service pump,, get into the type continuously rolled reverse osmosis system of one-level through pretreated waste water, under 1～4MPa, carry out 3～10 times of continuous concentration through security personnel's strainer.The dense water of first-stage reverse osmosis collects the dense water tank of one-level respectively with product water and one-level is produced water tank; One-level produces that water is up to standard promptly to carry out reuse or discharging; Not up to standard, need proceed the processing of (6) step;
(3) high pressure flat plate reverse osmosis: the dense water of first-stage reverse osmosis through security personnel's strainer, gets into the dull and stereotyped reverse osmosis system of high pressure through the dull and stereotyped reverse osmosis system service pump pressurization of high pressure, under 4～12MPa, carries out 2～4 times and concentrates. The dull and stereotyped reverse osmosis produced water of high pressure is back to raw water box or one-level is produced water tank continuation processing, and dense water is collected the dull and stereotyped dense water tank of high pressure; The dull and stereotyped concentrated stream amount of high pressure has satisfied the evaporative crystallization traffic requirement, directly carries out (5) step, continues to concentrate otherwise carry out (4) step;
(4) ultra-high voltage flat plate reverse osmosis: the dull and stereotyped dense water of high pressure through security personnel's strainer, gets into ultra-high voltage flat plate reverse osmosis system through the service pump pressurization of ultra-high voltage flat plate reverse osmosis system, under 8～16MPa, carries out 2～3 times and concentrates; Ultra-high voltage flat plate reverse osmosis product water is back to raw water box to be continued to handle, after dense water concentrates 12～120 times to raw wastewater, and the devaporation crystallization;
(5) evaporative crystallization: evaporative crystallization adopts economic benefits and social benefits or multiple-effect evaporation crystallization, perhaps MVR evaporative crystallization; Crystalline solid collecting packing, water of condensation are collected one-level product water tank and are proceeded to handle;
(6) two-pass reverse osmosis: one-level is produced water through the pressurization of two-pass reverse osmosis service pump, through security personnel's strainer, gets into the two-pass reverse osmosis system, under 1～3MPa, carries out 4～10 times and concentrates; The two-pass reverse osmosis concentrate recirculation is proceeded to handle to raw water box, produces water and collects secondary product water tank; Secondary produces water and reaches reuse standard.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693729A (en) * | 2013-12-24 | 2014-04-02 | 中国天辰工程有限公司 | Treatment method for nitric-acid-containing wastewater in adipic acid production technology |
| CN104129882A (en) * | 2014-08-25 | 2014-11-05 | 成都美富特膜科技有限公司 | Novel treatment technology of high-concentration industrial wastewater |
| CN104961635A (en) * | 2015-07-03 | 2015-10-07 | 新疆独山子天利高新技术股份有限公司 | Method and device of wastewater reuse pretreatment in adipic acid refining process |
| CN105152434A (en) * | 2014-05-26 | 2015-12-16 | 中冶东方工程技术有限公司秦皇岛研究设计院 | Method and device for treating pickling waste water from stainless steel cold-rolling |
| CN105293793A (en) * | 2014-05-26 | 2016-02-03 | 中冶东方工程技术有限公司秦皇岛研究设计院 | Treatment device and method for stainless steel cold-rolling pickling waste water |
| CN107601748A (en) * | 2017-11-10 | 2018-01-19 | 浙江威明环境科技有限公司 | A kind of desulfurization wastewater Zero discharging system |
| CN110357336A (en) * | 2019-07-19 | 2019-10-22 | 中冶南方工程技术有限公司 | A kind for the treatment of process and system of the high waste water containing nitrate nitrogen |
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| JP2006095363A (en) * | 2004-09-28 | 2006-04-13 | Kurita Water Ind Ltd | Treatment apparatus of wastewater containing organic nitrogen compound |
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| JP2006095363A (en) * | 2004-09-28 | 2006-04-13 | Kurita Water Ind Ltd | Treatment apparatus of wastewater containing organic nitrogen compound |
| CN101181981A (en) * | 2007-11-14 | 2008-05-21 | 洪泽银珠化工集团有限公司 | Recovery utilizing technique for indirect steam generated by nitrate evaporation |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693729A (en) * | 2013-12-24 | 2014-04-02 | 中国天辰工程有限公司 | Treatment method for nitric-acid-containing wastewater in adipic acid production technology |
| CN103693729B (en) * | 2013-12-24 | 2015-06-24 | 中国天辰工程有限公司 | Treatment method for nitric-acid-containing wastewater in adipic acid production technology |
| CN105152434A (en) * | 2014-05-26 | 2015-12-16 | 中冶东方工程技术有限公司秦皇岛研究设计院 | Method and device for treating pickling waste water from stainless steel cold-rolling |
| CN105293793A (en) * | 2014-05-26 | 2016-02-03 | 中冶东方工程技术有限公司秦皇岛研究设计院 | Treatment device and method for stainless steel cold-rolling pickling waste water |
| CN105293793B (en) * | 2014-05-26 | 2018-09-07 | 中冶沈勘秦皇岛工程设计研究总院有限公司 | The processing unit and method of stainless steel cold-rolling pickling wastewater |
| CN104129882A (en) * | 2014-08-25 | 2014-11-05 | 成都美富特膜科技有限公司 | Novel treatment technology of high-concentration industrial wastewater |
| CN104961635A (en) * | 2015-07-03 | 2015-10-07 | 新疆独山子天利高新技术股份有限公司 | Method and device of wastewater reuse pretreatment in adipic acid refining process |
| CN107601748A (en) * | 2017-11-10 | 2018-01-19 | 浙江威明环境科技有限公司 | A kind of desulfurization wastewater Zero discharging system |
| CN110357336A (en) * | 2019-07-19 | 2019-10-22 | 中冶南方工程技术有限公司 | A kind for the treatment of process and system of the high waste water containing nitrate nitrogen |
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Application publication date: 20121212 |