CN103523909A - Process method and reactor for recycling elemental sulfur from organic waste water containing sulfate - Google Patents
Process method and reactor for recycling elemental sulfur from organic waste water containing sulfate Download PDFInfo
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- CN103523909A CN103523909A CN201310531279.1A CN201310531279A CN103523909A CN 103523909 A CN103523909 A CN 103523909A CN 201310531279 A CN201310531279 A CN 201310531279A CN 103523909 A CN103523909 A CN 103523909A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
The invention provides a process method and reactor for recycling elemental sulfur from organic waste water containing sulfate. An aeration system of the reactor is optimized, elemental sulfur is generated in the biological desulphurization process, the elemental sulfur is separated from waste water by adopting the air stripping technology, S-porous corrugated plate packing is used for capturing the elemental sulfur, the elemental sulfur is recycled, and the problems that elemental sulfur is difficult to be separated from outlet water and the recovery rate is low in the current biological desulphurization technology of organic waste water containing high-concentration sulfate are solved. The reactor comprises a water inlet pipe, a water outlet pipe, an aeration head, a reactor barrel body, a three-phase separator, an absorption packing chamber, a dissolved oxygen online monitoring meter, a temperature control meter, and the like. The reactor is simple, easy to operate, low in operating cost, high in elemental sulfur recovery rate, and high in purity.
Description
Technical field
The present invention relates to a kind of processing method and reactor thereof that reclaims elemental sulfur from high-concentration sulfuric acid salt organic waste water.
Background technology
Along with developing rapidly of the industry such as electric power, chemical fibre production, refining of petroleum, food fermentation, light industry, pharmacy, Organic Wastewater Containing Sulfate is a large amount of to be produced and discharge, and environment has been caused to severe contamination.The processing of Organic Wastewater Containing Sulfate has been the difficult problem that faces of water treatment field and the focus of concern, for the processing of containing sulfate waste water, is mainly first to utilize biological reducing effect to be translated into sulfide or H
2s, and then generate elemental sulfur through biological oxidation process, thus reach the object of removal.
Although biological desulfurizing technology has been widely recognized, this technology is still applied less in trade effluent actual treatment at present.Because the sulfide, the especially H that utilize sulphate reducing bacteria anaerobic biological treatment waste water to produce
2s, can suppress even to poison anaerobic bacteria flora directly or indirectly, causes anaerobic reactor treatment effect low, even causes the collapse of whole biochemical treatment system.Recovery and the purifying of the elemental sulfur that secondly, this type of biological desulfurizing technology produces are unsolved serious problems.
For the elemental sulfur producing in wastewater treatment process, existing technique is to adopt all kinds of precipitation technologys realize the separated of elemental sulfur and reclaim, but in actual treatment system, the separating effect of elemental sulfur is also bad, and purity is lower.
The feature that under utilization limit oxygen or micro-aerobic condition, sulphate reducing bacteria and sulfur-oxidizing bacteria can coexist, set up rational ecological regulation and control policy control elemental sulfur as end product, associating stripping technology, thereby realize and when sulfate reduction-oxidation operation technique unit synchronously carries out, realize the coupling of elemental sulfur generation-extraction-removal process, for processing and the resource utilization of Organic Wastewater Containing Sulfate provides new approach.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of method that reclaims elemental sulfur from sulfate-containing organic wastewater, the method mild condition, the elemental sulfur rate of recovery is high, be convenient to suitability for industrialized production widely, further reduce costs, reduce the secondary pollution to environment;
Another object of the present invention is to provide a kind of reactor that reclaims elemental sulfur from sulfate-containing organic wastewater, and it has easy to operate easy to control, and process economy is good and reclaim the high advantage of elemental sulfur purity.
The present invention is achieved like this, a kind of method that reclaims elemental sulfur from sulfate-containing organic wastewater of the present invention, high concentration sulfate wastewater is carried out after biological desulphurization processing, adopt stripping technology to make the elemental sulfur that biological desulphurization process produces realize separated with waste water, utilize S-porous ripple plate filler to catch elemental sulfur, reclaim elemental sulfur.
Stripping technology of the present invention is blasted pressurized air or hypoxic air in waste water by stripping blower fan, load volume is 10-100mL/min, reactor bottom is aided with stirring, make the dissolved oxygen concentration in water reach 0.2-1.5mg/L, by contacting and diffusion of liquid film and gas, making volatile elemental sulfur enter triphase separator carries out by bottom, dry load chamber, entering dry load chamber after separation, by entering S-porous ripple plate packing layer after even gas distribution, throttling action by S-porous ripple plate packing layer is held back gaseous elemental sulphur with solid form, thereby reach the object that reclaims elemental sulfur, stripping technology of the present invention separated elemental sulfur from biological desulphurization water outlet, simple to operation, separating effect is obvious, has avoided the shortcoming of traditional precipitator method inferior separating effect.
Dry load of the present invention chamber is comprised of condensing chamber, and it is 20-25 ℃ that condensing chamber is controlled temperature, and condensing chamber is inner with S-porous ripple plate filler.Adopt S-porous ripple plate filler that elemental sulfur is caught and reclaimed, not only the rate of recovery is high, also can avoid the shortcoming that traditional precipitator method impurity is many simultaneously.Biological desulphurization of the present invention for to utilize the synergy of sulphate reducing bacteria and sulfur-oxidizing bacteria to carry out wastewater treatment in same reactor, and vitriol is reduced to sulfide as electron acceptor(EA) by sulphate reducing bacteria and (comprises H
2s, S
2-and HS
-), sulfur-oxidizing bacteria is oxidized to elemental sulfur by sulfides from wastewater.The present invention, before high-concentration sulfuric acid salt organic waste water carries out biological desulphurization processing, by processed waste water partial reflux, mixes with the former water of waste water.By adding organic waste water or industrial organic products, regulate TOC content in waste water, add the content that sodium sulfate regulates vitriol, make SO in waste water
4 2-content is 2-5g/L, and TOC content is 2-5g/L.
A kind of method that reclaims elemental sulfur from sulfate-containing organic wastewater of the present invention specifically comprises the following steps:
(1) sludge acclimatization: the active sludge of getting municipal wastewater treatment plant, with the organic waste water of containing sulfate, under micro-aerobic environment, tame, through the separation and purification of bacterial classification, obtain the active sludge that is rich in oxytolerant SRB (sulphate reducing bacteria) and SOB (sulfur-oxidizing bacteria) of mixed culture;
(2) generation of elemental sulfur: the active sludge of having tamed is joined to elemental sulfur and reclaim in reactor, pass into pending waste water, regulate temperature, pH, DO, TOC, SO
4 2-, aeration rate, hydraulic detention time, control elemental sulfur as end product;
(3) elemental sulfur stripping recovery: aeration stirring in biochemical reaction process, by elemental sulfur stripping and with other gases, together get rid of, elemental sulfur is trapped within on S-porous ripple plate filler through S-porous ripple plate throttling action, and periodic replacement S-corrugated plate packing, reclaims elemental sulfur.
A kind of reactor that reclaims elemental sulfur from sulfate-containing organic wastewater of the present invention includes reactor shell, intake pump, reflux pump, scrubbing bottle, triphase separator, dry load chamber, aeration head; The gas skirt of described triphase separator is trumpet type, is not less than 45 ℃ with horizontal sextant angle, and diameter is greater than reactor shell diameter, upper end straight tube and inlet pipe form sleeve pipe, annular space is not less than 1mm, hydraucone lower end and wall gap 5mm, and triphase separator left side wall is provided with water outlet; Described reactor shell is flat, and because reaction is micro-aerobic aeration, when aeration intensity can not meet stirring, bottom is aided with magnetic agitation, and the external use electric heating of reactor cylinder chuck is controlled temperature by thermocouple; Described aeration head is spherical, evenly perforate downwards, aperture 2mm; Described dry load chamber is comprised of condensing chamber, and condensing chamber is inner with S-corrugated plate packing; Described reactor also comprises temperature controller and dissolved oxygen on-line monitoring instrument, and temperature controller and dissolved oxygen on-line monitoring instrument are installed in the top of triphase separator, controls respectively temperature and the dissolved oxygen of sulfate-containing organic wastewater.
Advantage of the present invention is: (1) the inventive method is by aeration and mixing control dissolved oxygen concentration, and has set up rational ecological regulation and control strategy, the main end product of successfully processing elemental sulfur as sulfate-containing organic wastewater; (2) aeration mode in the inventive method, when playing oxygenation, stirring, also has stripping effect to elemental sulfur, and the method rate of recovery of holding back elemental sulfur recovery by S-corrugated plate packing is high, and the elemental sulfur purity of recovery is high and simple to operation; (3) the reactor collection wastewater treatment in the present invention and elemental sulfur stripping are recovered in one, and technical process is simple, control easily, are applicable to large-scale industrial production, meet environmental protection requirements of the times.
Accompanying drawing explanation
Fig. 1 is a kind of structural representation that reclaims the reactor of elemental sulfur from sulfate-containing organic wastewater of the present invention.
Aeration opening 2, sleeve pipe 3, air outlet 4, dry load chamber 5, condensation-water drain 6, scrubbing bottle 7, dissolved oxygen on-line monitoring instrument 8, temperature controller 9, water of condensation import 10, water outlet 11, triphase separator 12, gas skirt 13, thief hole 14, reflux pump 15, circulating water channel 16, aeration opening 17, reactor shell 18, intake pump 19, former water storage tank 20, water-in in the drawings, 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details;
Embodiment one: as shown in Figure 1, a kind of reactor that reclaims elemental sulfur from sulfate-containing organic wastewater described in present embodiment, it includes reactor shell (17), intake pump (18), reflux pump (14), scrubbing bottle (6), triphase separator (11), dry load chamber (4), aeration head (16); The gas skirt (12) of described triphase separator (11) is trumpet type, be not less than 45 ℃ with horizontal sextant angle, diameter is greater than reactor shell (17) diameter, upper end straight tube and inlet pipe (1) form sleeve pipe (2), annular space is not less than 1mm, hydraucone lower end and wall gap 5mm, triphase separator (11) left side wall is provided with water outlet; Described reactor shell (17) is flat, and because reaction is micro-aerobic aeration, when aeration intensity can not meet stirring, bottom is aided with magnetic agitation, and the outer electric heating chuck that uses of reactor shell (17), controls temperature by thermocouple; Described aeration head (16) is spherical, evenly perforate downwards, aperture 2mm; Described dry load chamber (4) is comprised of condensing chamber, and condensing temperature is 20-25 ℃; Described reactor also comprises temperature controller (8) and dissolved oxygen on-line monitoring instrument (7), and temperature controller (8) and dissolved oxygen on-line monitoring instrument (7) are installed in the top of triphase separator (11), controls respectively temperature and the dissolved oxygen of sulfate-containing organic wastewater; During use, the suction port of intake pump (18) is communicated with the inlet flume (19) that is loaded with former water, and the suction port of reflux pump (14) is communicated with the circulating water channel (15) that is loaded with recirculated water.
Embodiment two: as shown in Figure 1, dry load chamber (4) also comprises water of condensation import (9) and condensation-water drain (5) described in present embodiment, condensing chamber is inner with S-porous ripple plate filler.By said apparatus, a kind of method that reclaims elemental sulfur from sulfate-containing organic wastewater, it specifically comprises the following steps:
(1) sludge acclimatization: the active sludge of getting municipal wastewater treatment plant, with the organic waste water of containing sulfate, under micro-aerobic environment, tame, through the separation and purification of bacterial classification, obtain the active sludge that is rich in oxytolerant SRB (sulphate reducing bacteria) and SOB (sulfur-oxidizing bacteria) of mixed culture;
(2) generation of elemental sulfur: the active sludge of having tamed is joined to elemental sulfur and reclaim in reactor, pass into pending waste water, control temperature, pH, DO, TOC, SO
4 2-, aeration rate, hydraulic detention time, make elemental sulfur as end product;
(3) elemental sulfur stripping recovery: aeration stirring in biological process, by elemental sulfur stripping and with other gases, together get rid of, elemental sulfur is trapped within on S-porous ripple plate filler through S-porous ripple plate throttling action, and periodic replacement S-porous ripple plate filler, reclaims elemental sulfur.
It is below a kind of preferred embodiment that reclaims the technique of elemental sulfur from sulfate-containing organic wastewater of the present invention;
Embodiment 1
Take waste water in pharmaceutical plants as water inlet, and its leading indicator is respectively: pH:8.0-8.5; TOC:2000-2500mg/L; SO
4 2-: 3000-4000 mg/L, wastewater temperature is adjusted to 25-28 ℃, and it is 20 ℃ that temperature is controlled in dry load chamber.Hydraulic detention time 20 hours, reflux ratio 5:1, aeration rate 35mL/min, bottom is aided with stirring, and dissolved oxygen concentration is 0.45mg/L.By this art breading.SO in waste water
4 2-clearance is that 90%, TOC clearance is 95%, and the elemental sulfur rate of recovery is 67%, and elemental sulfur purity is greater than 98.5%.
Embodiment 2
Take synthetic wastewater as water inlet, and it forms and mainly comprises glucose, sodium acetate, lactic acid, sodium sulfate, potassium primary phosphate, ammonium chloride, sodium bicarbonate, magnesium chloride, calcium chloride, ferrous sulfate, xitix etc.Its leading indicator is respectively: pH:8.0-8.5; TOC:3000-3500mg/L; SO
4 2-: 3500-4000 mg/L, wastewater temperature is adjusted to 30-35 ℃, and it is 20 ℃ that temperature is controlled in dry load chamber.Hydraulic detention time 20 hours, reflux ratio 5:1, aeration rate 35mL/min, bottom is aided with stirring, and dissolved oxygen concentration is 0.45mg/L.By this art breading.SO in waste water
4 2-clearance is that 95%, TOC clearance is 96%, the elemental sulfur rate of recovery 75%, and elemental sulfur purity is greater than 98.5%.
Embodiment 3
Take synthetic wastewater as water inlet, and it forms and mainly comprises glucose, sodium acetate, lactic acid, sodium sulfate, potassium primary phosphate, ammonium chloride, sodium bicarbonate, magnesium chloride, calcium chloride, ferrous sulfate, xitix etc.Its leading indicator is respectively: pH:7.0-7.5; TOC:3000-3500mg/L; SO
4 2-: 3000-4000 mg/L, wastewater temperature is adjusted to 25-28 ℃, and it is 25 ℃ that temperature is controlled in dry load chamber.Hydraulic detention time 20 hours, reflux ratio 5:1, aeration rate 35mL/min, bottom is aided with stirring, and dissolved oxygen concentration is 0.45mg/L.By this art breading.SO in waste water
4 2-clearance is that 88%, TOC clearance is 90%, the elemental sulfur rate of recovery 69%, and elemental sulfur purity is greater than 98.5%.
Embodiment 4
Take synthetic wastewater as water inlet, and it forms and mainly comprises glucose, sodium acetate, lactic acid, sodium sulfate, potassium primary phosphate, ammonium chloride, sodium bicarbonate, magnesium chloride, calcium chloride, ferrous sulfate, xitix etc.Its leading indicator is respectively: pH:8.0-8.5; TOC:3000-3500mg/L; SO
4 2-: 3000-4000 mg/L, wastewater temperature is adjusted to 25-28 ℃, and it is 20 ℃ that temperature is controlled in dry load chamber.Hydraulic detention time 20 hours, reflux ratio 5:1, aeration rate 35mL/min, bottom is aided with stirring, and dissolved oxygen concentration is 0.45mg/L.By this art breading.SO in waste water
4 2-clearance is that 92%, TOC clearance is 95%, the elemental sulfur rate of recovery 73%, and elemental sulfur purity is greater than 98.5%.
Embodiment 5
Take synthetic wastewater as water inlet, and it forms and mainly comprises glucose, sodium acetate, lactic acid, sodium sulfate, potassium primary phosphate, ammonium chloride, sodium bicarbonate, magnesium chloride, calcium chloride, ferrous sulfate, xitix etc.Its leading indicator is respectively: pH:8.0-8.5; TOC:3000-3500mg/L; SO
4 2-: 3000-4000 mg/L, wastewater temperature is adjusted to 30-35 ℃, and it is 25 ℃ that temperature is controlled in dry load chamber.Hydraulic detention time 20 hours, reflux ratio 5:1, aeration rate 20mL/min, bottom is aided with stirring, and dissolved oxygen concentration is 0.3mg/L.By this art breading.SO in waste water
4 2-clearance is that 92%, TOC clearance is 95%, the elemental sulfur rate of recovery 65%, and elemental sulfur purity is greater than 98.5%.
Claims (10)
1. a processing method that reclaims elemental sulfur from Organic Wastewater Containing Sulfate, it is characterized in that, described side's Process is that Organic Wastewater Containing Sulfate is carried out after biological desulphurization processing, adopt stripping technology to make the elemental sulfur that biological desulphurization process produces realize separated with waste water, utilize S-porous ripple plate filler to catch elemental sulfur, reclaim elemental sulfur.
2. a kind of processing method that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 1, it is characterized in that, described stripping technology is by stripping blower fan, pressurized air or hypoxic air to be blasted in waste water, load volume is 10-100mL/min, reactor bottom is aided with stirring, make the dissolved oxygen concentration in water reach 0.2-1.5mg/L, by contacting and diffusion of liquid film and gas, making volatile elemental sulfur enter triphase separator carries out by bottom, dry load chamber, entering dry load chamber after separation, by entering S-porous ripple plate packing layer after even gas distribution, throttling action by S-porous ripple plate packing layer is held back gaseous elemental sulphur with solid form, thereby reach the object that reclaims elemental sulfur.
3. a kind of processing method that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 1, it is characterized in that, described Organic Wastewater Containing Sulfate regulates organic content in waste water by adding organic waste water or industrial organic products, add the content that sodium sulfate regulates vitriol, make SO in waste water
4 2-content is 2-5g/L, and TOC content is 2-5g/L.
4. a kind of processing method that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 1, is characterized in that, described processing method comprises following concrete steps:
(1) sludge acclimatization: get the active sludge of municipal wastewater treatment plant, tame under micro-aerobic environment with the organic waste water of containing sulfate, obtain the active sludge that is rich in oxytolerant sulphate reducing bacteria and sulfur-oxidizing bacteria of mixed culture;
(2) generation of elemental sulfur: the active sludge of having tamed is joined to elemental sulfur and reclaim in reactor, pass into pending waste water, control temperature, pH, DO, TOC, SO
4 2-, aeration rate, hydraulic detention time, in same reactor, utilize the synergy of sulphate reducing bacteria and sulfur-oxidizing bacteria to process waste water, vitriol is reduced to sulfide as electron acceptor(EA) by sulphate reducing bacteria, and sulfur-oxidizing bacteria is oxidized to elemental sulfur by sulfides from wastewater;
(3) elemental sulfur stripping recovery: aeration stirring in biochemical reaction process, by elemental sulfur stripping and with other gases, together get rid of, elemental sulfur is trapped within on S-porous ripple plate filler through S-porous ripple plate throttling action, and periodic replacement S-porous ripple plate filler, reclaims elemental sulfur.
5. the processing method reactor used that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 1, it comprises reactor shell (17), intake pump (18), reflux pump (14), scrubbing bottle (6) and triphase separator (11), it is characterized in that, described reactor also comprises aeration head (16), dry load chamber (4); Described triphase separator (11) is positioned at the top of reactor shell (17), and reactor shell (17) upper end sidewall is provided with thief hole (13), and lower end sidewall is provided with water-in (20); Dry load chamber (4) is communicated with escape pipe (3), and after elemental sulfur reclaims, gas passes through scrubbing bottle (6) processing again.
6. the processing method reactor used that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 5, it is characterized in that: the gas skirt (12) of described triphase separator (11) is trumpet type, with horizontal sextant angle >=45 ℃, diameter is greater than the diameter of reactor shell (17), upper end straight tube and inlet pipe (1) form sleeve pipe, annular space >=1mm, hydraucone lower end and wall gap 5mm, triphase separator (11) left side wall is provided with water outlet (10).
7. the processing method reactor used that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 5, it is characterized in that: described reactor shell (17) bottom is for flat, the outer electric heating chuck that uses of reactor shell (17), controls temperature by thermocouple.
8. the processing method reactor used that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 5, is characterized in that, described aeration head (16) is spherical, evenly perforate downwards, aperture 2mm.
9. the processing method reactor used that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 5, it is characterized in that, described dry load chamber (4) is comprised of condensing chamber, it comprises water of condensation import (9) and condensation-water drain (5), controlling condensing temperature is 20 ℃-25 ℃, and condensing chamber is inner with S-porous ripple plate filler.
10. the processing method reactor used that reclaims elemental sulfur from Organic Wastewater Containing Sulfate as claimed in claim 5, it is characterized in that: described reactor also comprises temperature controller (8) and dissolved oxygen on-line monitoring instrument (7), temperature controller (8) and dissolved oxygen on-line monitoring instrument (7) are installed in the top of triphase separator (11), control respectively temperature and the dissolved oxygen of sulfate-containing organic wastewater.
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Cited By (2)
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| CN104911138A (en) * | 2015-06-03 | 2015-09-16 | 浙江大学 | Rapid domesticating and enriching method of alkali-resisting sulfur oxidizing bacteria for biogas biological desulfurization |
| CN110484485A (en) * | 2019-09-05 | 2019-11-22 | 北京本农投资控股有限公司 | A method of the sulfate reducing bacteria of the high resistance to cadmium of separation |
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| CN110484485A (en) * | 2019-09-05 | 2019-11-22 | 北京本农投资控股有限公司 | A method of the sulfate reducing bacteria of the high resistance to cadmium of separation |
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Application publication date: 20140122 |