CN102249506A - Treatment method of PTA (purified terephthalic acid) chemical wastewater excess sludge - Google Patents
Treatment method of PTA (purified terephthalic acid) chemical wastewater excess sludge Download PDFInfo
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- CN102249506A CN102249506A CN 201010178273 CN201010178273A CN102249506A CN 102249506 A CN102249506 A CN 102249506A CN 201010178273 CN201010178273 CN 201010178273 CN 201010178273 A CN201010178273 A CN 201010178273A CN 102249506 A CN102249506 A CN 102249506A
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Abstract
Aiming at the accumulation of a large number of chemical wastewater excess sludge, high treatment difficulty of partial treatment methods and other disadvantages, the invention discloses a treatment method of PTA (purified terephthalic acid) chemical wastewater excess sludge. The treatment method comprises the following steps of regulating the pH value of unconcentrated PTA chemical wastewater excess sludge (the water content of which is 99.4-99.6%) from a secondary settling tank of a petrochemical plant, adding 0.5- 5.0g of nitrate to per liter of the sludge, then standing, introducing a composite air floatation agent from the bottom of an air flotation column for further carrying out air-flotation concentration on the sludge, and thus effectively separating the sludge and water. The treatment method disclosed by the invention has the advantages of short residence time, high treatment efficiency and small occupation area; by the adoption of the treatment method, the treatment cost is reduced, the water quality of effluent is improved and the subsequent treatment burden of the sludge is reduced.
Description
Technical field
The present invention relates to a kind of concentration method of PTA wastewater from chemical industry excess sludge; Relate in particular to the method for a kind of air supporting treatment PTA and other wastewater from chemical industry excess sludge.
Background field
Pure terephthalic acid (PTA) is a kind of important chemical material, is widely used for various synthon, washs fiber, many aspects such as production of softening agent and coating.Give off the COD load in its production process up to 5-15kg/m
3Principal pollutant in the PTA sewage are terephthalic acid, acetic acid and phenylformic acid etc., and this water COD concentration is higher.
Domestic now industrialized PTA waste disposal plant has many covers, mainly comprises with the China Petrochemical Industry being the anaerobic-aerobic treatment process of representative and being the two ends aerobic treatment process of representative with the PetroChina Company Limited..Certain petro-chemical corporation's PTA Waste Water Treatment after processing is put in makeup, the surplus sludge volume of generation about 25 * 10
4T/a, the pH value is 7.5-9.0, and water ratio is 99.6%, and sludge concentration is lower.PTA wastewater from chemical industry excess sludge concentration basin (flat flow) gravity settling stopped after 8-12 hour, still can't flocculating settling.Reason has: the first, and the excess sludge through second pond is got rid of still has higher COD concentration, the DO wretched insufficiency in the system, low DO concentration is to cause a chemical engineering sewage processing sludge bulking; The second, the petrochemical wastewater complicated component, the organic concentration height changes greatly, and some of them can make cytotoxic death to material such as the heavy metal Pb and the organochlorine of the toxic effect of microorganism, and this also is one of reason of mud come-up; In addition, when water inlet contains oil quantity when too high, grease can agglomeration on the zoogloea surface, make the bacterium hypoxia death, cause proportion to reduce and float.Because effectively muddy water layering causes second pond water outlet band mud to a large amount of excess sludges is accumulated in the system, not only influence draining water quality but also increase the biochemical treatment cost and the activity of reduction system biochemical sludge.
Sludge concentration method commonly used can be divided three classes: gravity concentrates, centrifugal concentrate and air supporting concentrates.
(1), gravity concentrates: utilizing the natural subsidence separate mode of action of gravity, do not need external energy, is the most energy-conservation a kind of sludge concentration method.It is a kind of settlement separate technology that gravity concentrates, and it is by form the purpose that the high concentration sludge layer reaches thickened sludge in precipitation, is the main body of present sludge concentration method.It is independently to finish in the gravity concentration basin that independent gravity concentrates, and technology is simply effective, but the residence time may produce stink when longer, and be not to be applicable to all mud; If when being applied to the biological phosphate-eliminating excess sludge and concentrating, a large amount of releases of phosphorus can occur, its supernatant liquor need adopt chemical method to carry out dephosphorization and handle.It is sludge concentration method commonly used at present, but floor space is big, mud concentrated effect to the settling property difference is bad, mud come-up and corruption etc. take place easily, relatively be suitable for the big mud of density, heavy as before mud, chemical sludge and microbial film mud etc., it is not good density to be approached 1 light mud concentrated effect.
(2), centrifugal concentrating: force of gravity thickening efficiency height, the time spent is short, but is applicable to mixing sludge, and working cost is higher.Centrifugal concentrated ratio juris is to utilize solid, liquid proportion in the mud different and different centrifugal force that have concentrates.Non-stop run, HRT only is 3min, the mud extraction solid content can reach more than 4%.
(3), air supporting concentrates
A air supporting method: commonly used have dissolved air flotation, an induction flotation method.It is particularly remarkable to approach water, hydrophobic mud effect for concentrated density; The air flotation pool residence time is shorter, and volume is less.In recent years, Cui Zhi extensively wait studied municipal effluent excess sludge air supporting concentrate in the kind of collecting agent and consumption, be used with PAM and the influence of factor such as pH, wherein collecting agent SESN consumption is 37.5mg/L, and during air supporting 5min, the water ratio of mud reduces to 96.8% from average 99.44%; The consumption of collecting agent SEAN is 18.75mg/L, and air supporting 5min can make moisture percentage in sewage sludge reduce to 96.4% from 99.4%, and volume is 1/5 before concentrating; And best results when the ZFS12 consumption is 75mg/L in a series of fatty-acid collectors.。But this method has only carried out subtracting appearance to mud, does not have the obvious degradation effect for a large amount of poisonous and hazardous organism that exists in the wastewater from chemical industry excess sludge, have secondary pollution, and the operate continuously energy consumption is big.
B biogas float glass process: the Dizinsk.s of Czech in 1992 and the Dalhammarg of Sweden etc. has proposed a kind of new residual active sludge concentration method---biogas float glass process thickened sludge technology, promptly utilize the denitrifying capacity of mud itself, by adding nitrocalcite, the gas that utilizes the sludge denitrification effect to produce floats mud and then reaches spissated purpose.The gas of biogas float glass process thickened sludge is produced by the denitrification of mud own, in case surpassing its saturation solubility in solution, gas volume promptly discharges with the form of microbubble, be wrapped in the mud flco, form ideal gas enclosure wadding grain, only there is microbubble to stick on the mud granule, need not to add the adhesion notes energy that flocculation agent is strengthened mud and bubble on the mud top layer.And utilize in the mud solution, sludge absorption and the organism of sludge hydrolytic as denitrifying carbon source, after the sludge treatment down clear liquid COD obviously reduce.But independent utilization and operation excessive cycle, and the reducing sludge volume effect is on the low side.Major influence factors that there are some researches show organism gas float is: nitrate concentration, and temperature, sludge concentration, mud source, the influence of nitrate concentration is mainly considered in the processing of the PTA wastewater from chemical industry excess sludge of handling for the present invention.
Other research of mud is handled in C air supporting: in January, 2006, disclosed patent CN1724421A used high-efficiency oil sludge separating agent and relevant air flotation technology, most of sandstone, earth in the oily sludge are separated, realized the utilization of the pollution-free resource utilization of oily sludge.In October, 2006 disclosed patent CN1843980A and in September, 2007 disclosed patent CN101037286A and in May, 2008 disclosed CN101186421A all used air supporting and handled oily sludge, all assisted biology, ozone to also have the ultrasonic air supporting of strengthening respectively, finally can both reach refiltered oil, and can reach mud-water separation, shorten the treatment time, improve treatment effect, reach innoxious.Above patent has all related to the air supporting method and has handled mud, but all with respect to oily sludge, to density than water little or with there is no to subtract preferably and hold and degradation effect of the approaching wastewater from chemical industry excess sludge of water.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of wastewater from chemical industry of PTA efficiently excess sludge treatment process for the treatment process that solves existing PTA wastewater from chemical industry excess sludge has problems such as processing efficiency is low, the cycle is long.Promote the wastewater from chemical industry excess sludge to subtract and hold and the waste water degraded, reduce the harm of environment.
Technical scheme of the present invention is the mode that rhythmic reaction is handled, and reaches the purpose that promotes that PTA wastewater from chemical industry excess sludge concentrates and promotes subsequent disposal.
Technical scheme of the present invention is as follows:
A kind of treatment process of wastewater from chemical industry excess sludge of terephthalic acid, Fig. 1 is seen in its technical process, concrete steps are as follows:
A, terephthalic acid wastewater from chemical industry residue mud is regulated the pH value to 6.5-7.5, in air-flotation column, leave standstill mud generation denitrification, the wherein partial organic substances degraded of spissated while of mud after adding nitrate;
B, mud do not continue the come-up after, treat that steady air current is in the tensimeter range after, in terephthalic acid wastewater from chemical industry excess sludge, add deployed compound gas floatation agent, the promoting the circulation of qi of going forward side by side is floating, mud leaves standstill after obtaining further concentrating, and manifests mud last, and clear water is in clear layering down;
C, upper strata mud is separated with the lower floor clear water.
Above-mentioned treatment process, described nitrate can be iron nitrate or ammonium nitrate, and add-on is 0.5g/L～5.0g/L.
Above-mentioned treatment process, described compound gas floatation agent can be polyacrylamide (number-average molecular weight is 8,000,000-1,500 ten thousand) or polymerize aluminum chloride and organic acid is composite forms, and described organic acid can be lauric acid, tetradecanoic acid, palmitinic acid or stearic acid.
Above-mentioned treatment process, the polyacrylamide of described compound gas floatation agent or the add-on of polymerize aluminum chloride are that every liter of excess sludge adds 15mg-75mg, and the organic acid add-on is that every liter of excess sludge adds 0.5g/L～5.0g/L.
This art breading result can reduce the water ratio of excess sludge, improves effluent characteristics; Promote to subtract to hold and shorten the sludge treatment cycle, be beneficial to follow-up anaerobic digestion of excess sludge and dehydration, alleviate the subsequent disposal load; Save processing cost, reduce the pressure of environment protection aspect.
Table 1 has shown under several representative processes conditions, medicament and the dosage, treatment PTA chemical industry excess sludge of the present invention water ratio and COD decreasing ratio (concrete with reference to implementing 1-5) later.
Table 1
| Embodiment | Water ratio drop-out value (%) | COD drop-out value (%) |
| 1 | 1.62 | 33.6 |
| 2 | 2.05 | 41.8 |
| 3 | 1.56 | 45.2 |
| 4 | 2.29 | 35.5 |
| 5 | 1.85 | 32.3 |
Beneficial effect
1, the present invention utilizes easily the expand characteristic of the difficult flocculating settling of come-up of wastewater from chemical industry excess sludge, adds nitrate in sludge thickener, and mud generation biological denitrification produces bubble and further floats; In conjunction with the microbubble step pressure air supporting again that mechanical means produces, improve the concentrated effect of PTA wastewater from chemical industry excess sludge greatly, make the water ratio of mud be reduced to 97.3% by 99.6% time, sludge volume reduces greatly.The present invention is specially adapted to density and approaches water, the complicated wastewater from chemical industry excess sludge of the come-up that easily expands.
2, the present invention concentrates air-float technology than mud commonly used, more promoted organic decomposition in sludge degradation and the waste water in the time of reducing sludge volume, the following clear liquid water quality of handling improves, COD is reduced to 302.9mg/L by under the 552.7mg/L, reduce the load of processing links such as mud subsequent anaerobic digestion and dehydration, reduced the expense of subsequent processing device and medicament.
3, the present invention handles excess sludge employing biological air supporting earlier and forces air floating method again, and is obvious than independent biogas float glass process mud concentrated effect, and mud concentrates cycle shortening, processing efficiency height.
4, organism gas float of the present invention and mechanical forced air supporting are carried out in same reactor, reduce mud concentration technology treatment facility.
5, the present invention is simple to operate, and is easy to implement.
Description of drawings
Fig. 1 is the synoptic diagram of the flow process of the inventive method, wherein: 1 air-flotation column; 2 sand core funnels; The 3 gas floatation agents groove that feeds intake; 4 under meters; 5 three-way valves; 6 surge tanks; 7 tensimeters; 8 air compressor.
Embodiment
Certain PTA of petro-chemical corporation wastewater from chemical industry excess sludge (tawny), water ratio 99.6%, the pH value is 7.5～8.5.The concrete steps of utilizing present method to handle: PTA wastewater from chemical industry excess sludge is poured in the air-flotation column 1, and regulating the pH value is 6.5, adds iron nitrate 1.0g/L, leaves standstill 1h, mud, water sepn occur; Add the composite floating chemical that polyacrylamide (number-average molecular weight 8,000,000) 15mg/L and lauric acid (grinding to form microgranular) 1.5g/L are deployed into from the gas floatation agent groove 3 that feeds intake, core 2 upper surfaces by air-flotation column bed load core funnel import, open air compressor 8 steady air currents in tensimeter 7 ranges, air is behind surge tank 6 buffer memorys, by three-way valve 5 and under meter 4, regulating under meter 4 makes air flow remain on 0.15L/min (air-flotation column d=4cm, V
0=540mL adds sludge volume V=200mL), last gas is dispersed into microbubble air supporting PTA wastewater from chemical industry excess sludge by sand core funnel 2, and air supporting 2min leaves standstill 1min.Occur on the mud clear layering under water and do not continue come-up.Whole process water ratio has descended 1.62%, and water outlet COD has descended 33.6%.
Other condition changes operational condition with embodiment 1: regulating the pH value is 7, adds iron nitrate 2.0g/L, leaves standstill 1h, mud, water sepn occur; Feed the composite floating chemical that polyacrylamide 30mg/L (number-average molecular weight 1,000 ten thousand) and tetradecanoic acid (grinding to form microgranular) 0.5g/L are deployed into; Air supporting 2min leaves standstill 1min in air flow 0.15L/min air supporting reactor.Occur on the mud clear layering under water and do not continue come-up.Water ratio has descended 2.05% in the whole process, and water outlet COD has descended 41.8%.
Other condition changes operational condition with embodiment 1: regulating the pH value is 7, adds iron nitrate 5g/L and leaves standstill 1h, mud, water sepn occur; Feed the composite floating chemical that polymerize aluminum chloride 50mg/L and palmitinic acid (grinding to form microgranular) 2g/L are deployed into; Air supporting 2min leaves standstill 1min in air flow 0.15L/min air supporting reactor.Occur on the mud clear layering under water and do not continue come-up.Whole process water ratio has descended 1.56%, and water outlet COD has descended 45.2%.
Other condition changes operational condition with embodiment 1: regulating the pH value is 7.5, adds ammonium nitrate 3.0g/L and leaves standstill 1h, mud, water sepn occur; The composite floating chemical that polyacrylamide 75mg/L (number-average molecular weight 1,500 ten thousand) and stearic acid (grinding to form microgranular) 5g/L are deployed into; Air supporting 2min leaves standstill 1min in air flow 0.15L/min air supporting reactor.Occur on the mud clear layering under water and do not continue come-up.Whole process water ratio has descended 2.29%, and water outlet COD has descended 35.5%.
Other condition changes operational condition with embodiment 1: regulating the pH value is 7, adds ammonium nitrate 0.5g/L and leaves standstill 1h, mud, water sepn occur; Feed the composite floating chemical that polymerize aluminum chloride 75mg/L and lauric acid (grinding to form microgranular) 2g/L are deployed into; Air supporting 2min leaves standstill 1min in air flow 0.15L/min air supporting reactor.Occur on the mud clear layering under water and do not continue come-up.Whole process water ratio descends 1.85%, and water outlet COD has descended 32.3%.
Claims (4)
1. the treatment process of the wastewater from chemical industry excess sludge of a terephthalic acid is characterized in that being made up of the following step:
A, terephthalic acid wastewater from chemical industry residue mud is regulated the pH value to 6.5-7.5, in air-flotation column (1), leave standstill mud generation denitrification, the wherein partial organic substances degraded of spissated while of mud after adding nitrate;
After B, mud do not continue come-up, add deployed compound gas floatation agent from the gas floatation agent groove (3) that feeds intake, upper surface by air-flotation column bottom sand core funnel (2) imports, open air compressor (8) steady air current ground and in tensimeter (7) range, air admission surge tank (6), behind the buffer memory, by three-way valve (5) and under meter (4), last gas is dispersed into microbubble air supporting terephthalic acid wastewater from chemical industry excess sludge by the core of sand core funnel (2), mud leaves standstill after obtaining further concentrating, manifest mud last, clear water is in clear layering down;
C, upper strata mud is separated with the lower floor clear water.
2. treatment process according to claim 1 is characterized in that: described nitrate is iron nitrate or ammonium nitrate, and add-on is 0.5g/L～5.0g/L.
3. treatment process according to claim 1 is characterized in that: described compound gas floatation agent is polyacrylamide or polymerize aluminum chloride and organic acid is composite forms, and described organic acid is lauric acid, tetradecanoic acid, stearic acid or palmitinic acid.
4. treatment process according to claim 3, it is characterized in that: the polyacrylamide of described compound gas floatation agent or the add-on of polymerize aluminum chloride are that every liter of excess sludge adds 15mg-75mg, and the organic acid add-on is that every liter of excess sludge adds 0.5g/L～5.0g/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157651A (en) * | 2013-03-28 | 2013-06-19 | 东南大学 | Resource utilization method of high-water-content pure terephthalic acid (PTA) residue |
| CN103588349A (en) * | 2012-08-17 | 2014-02-19 | 中国石油化工股份有限公司 | Processing method of terephthalic acid waste water |
| CN103663843A (en) * | 2012-09-06 | 2014-03-26 | 中国石油化工股份有限公司 | Treatment method of p-aminodiphenylamine production device wastewater |
| CN104250053A (en) * | 2013-06-27 | 2014-12-31 | 中国石油化工股份有限公司 | Method for treating ammonia-nitrogen containing p-aminodiphenyl amine production wastewater |
| CN105293845A (en) * | 2015-10-26 | 2016-02-03 | 广州立白企业集团有限公司 | Treatment method for sludge reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5638197A (en) * | 1979-09-06 | 1981-04-13 | Hitachi Plant Eng & Constr Co Ltd | Concentrating method for sludge |
| CN1843980A (en) * | 2005-04-06 | 2006-10-11 | 中国科学院成都生物研究所 | Biological air floatation method for oil-containing sludge |
| CN101186421A (en) * | 2007-12-27 | 2008-05-28 | 大庆石油管理局 | Method for treating oil-containing sludge |
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2010
- 2010-05-19 CN CN 201010178273 patent/CN102249506B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638197A (en) * | 1979-09-06 | 1981-04-13 | Hitachi Plant Eng & Constr Co Ltd | Concentrating method for sludge |
| CN1843980A (en) * | 2005-04-06 | 2006-10-11 | 中国科学院成都生物研究所 | Biological air floatation method for oil-containing sludge |
| CN101186421A (en) * | 2007-12-27 | 2008-05-28 | 大庆石油管理局 | Method for treating oil-containing sludge |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588349A (en) * | 2012-08-17 | 2014-02-19 | 中国石油化工股份有限公司 | Processing method of terephthalic acid waste water |
| CN103588349B (en) * | 2012-08-17 | 2015-09-02 | 中国石油化工股份有限公司 | A kind for the treatment of process of terephthalic acid wastewater |
| CN103663843A (en) * | 2012-09-06 | 2014-03-26 | 中国石油化工股份有限公司 | Treatment method of p-aminodiphenylamine production device wastewater |
| CN103157651A (en) * | 2013-03-28 | 2013-06-19 | 东南大学 | Resource utilization method of high-water-content pure terephthalic acid (PTA) residue |
| CN103157651B (en) * | 2013-03-28 | 2015-07-15 | 东南大学 | Resource utilization method of high-water-content pure terephthalic acid (PTA) residue |
| CN104250053A (en) * | 2013-06-27 | 2014-12-31 | 中国石油化工股份有限公司 | Method for treating ammonia-nitrogen containing p-aminodiphenyl amine production wastewater |
| CN104250053B (en) * | 2013-06-27 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of process is containing the method for ammonia nitrogen mutual-amido two polyaniline factory effluent |
| CN105293845A (en) * | 2015-10-26 | 2016-02-03 | 广州立白企业集团有限公司 | Treatment method for sludge reduction |
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