CN103496827A - Acidic carboxymethylcellulose condensate treatment method - Google Patents
Acidic carboxymethylcellulose condensate treatment method Download PDFInfo
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- CN103496827A CN103496827A CN201310476012.7A CN201310476012A CN103496827A CN 103496827 A CN103496827 A CN 103496827A CN 201310476012 A CN201310476012 A CN 201310476012A CN 103496827 A CN103496827 A CN 103496827A
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Abstract
The invention discloses an acidic carboxymethylcellulose condensate treatment method. The acidic CMC condensate firstly enters an adjusting sedimentation tank to adjust the water amount and water quality, and then enters a neutralizing tank. A Na2CO3 solution is added into the neutralizing tank to allow the pH value of waste water to be stabilized between 6.5 to 7.5. The waste water is purified through a UBF reactor in an anaerobic manner and flows into a BAF reactor, and is purified through an aerobic biofilm to discharge or reuse. The UBF reactor is filled with polyurethane-based porous rotating spherical filler and the BAF reactor is filled with clinoptilolites and bio-ceramics as fillers, and the UBF reactor and the BAF reactor respectively culture and acclimate anaerobic biofilms and aerobic biofilms, metabolic effects, filtration effects and multi-stage biological predator effects of heterotrophic bacteria on the biofilms are utilized, and biological purification of the CMC condensate is realized.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind for the treatment of process of acid carboxymethyl cellulose phlegma.
Background technology
Carboxymethyl cellulose (Carboxyl Methyl Cellulose is called for short CMC), have another name called Xylo-Mucine, is a kind of, material that have ether structure that produce by the chemical reaction modification by the natural macromolecular material Mierocrystalline cellulose, and the title of " industrial monosodium glutamate " is arranged.Be widely used in the industries such as food, medicine, toothpaste, weaving, market sales volume is large, profitable.Yet, exquisite linters, Mono Chloro Acetic Acid, ethanol etc. are take at present domestic extensive employing, and as the technique ubiquity of raw material production Xylo-Mucine the problem that raw material consumption is large and utilization ratio is low, (particularly the chloroacetic utilization ratio of etherifying agent is very low, only have and 50～60% utilized), the complete raw material of unreacted also enters in factory effluent; Therefore, the Xylo-Mucine factory effluent of generation had both contained the organism such as hydroxyethanoic acid sodium, Mono Chloro Acetic Acid, ethanol, sodium ethylate, contained again the polymer organism such as Mierocrystalline cellulose, Xylo-Mucine, COD
crup to 20000～25000mg/L, the biological nutrition elements such as nonnitrogenous (N), phosphorus (P).
Because having to reclaim, the carboxymethyl cellulose that still contains 15-20% in the process waste liquor as production food grade carboxymethyl cellulose (do not contain the carboxymethyl cellulose level do not reclaimed in technical grade CMC waste liquid lower, be less than 5%, recovery value is less), by after its distillation, the major ingredient of gained residual residue is carboxymethyl cellulose, can be used as cement additire.At present, this carboxymethyl cellulose cement additire market value is about 12000 yuan/tons of left and right, profit is higher, demand is large, more domestic CMC manufacturing enterprises start to utilize distil process, and food grade carboxymethyl cellulose waste liquid is carried out to the multiple-effect evaporation processing, and the gained distillation residue are cement additire product-carboxymethyl cellulose, steam heat recovery, phlegma effluxes as factory effluent.This phlegma mainly contains the volatile organic matters such as oxyacetic acid, Mono Chloro Acetic Acid, ethanol, and water temperature is 30-40 ℃, and COD is about 2000-4000mg/L, pH=2.5-3.0.
At present, have no the research report that relevant acid CMC phlegma is processed.The treatment process of CMC factory effluent had to following three kinds abroad: the ultraviolet chlorination process of (1) U.S.; (2) the hydrogen peroxide chemical oxidization method of Japan; (3) exchange resin method of Germany.Domestic have the commonplace booth of Pan, Yang Jun etc. to adopt UASB, MBR, micro-electrolysis-UASB-bio-contact oxidation combination process to CMC production liquid waste disposal research report, has no the practical engineering application report.Wherein: (1) " environmental science " volume o. 11th 3324-3328 page November the 30th in 2009 has reported that the commonplace booth of Pan etc. utilizes UASB to carry out reactor start-up with inoculation granule sludge and digested sludge mixed soil under mesophilic condition, when flooding velocity is 0.047L/h, influent COD 4000mg/L, volumetric loading 6.86kg/(m
3d), the time, its COD clearance can reach more than 80%; (2) " environmental engineering " October the 30th in 2012, volume the 5th phase 39-41 page was reported the employing MBBR such as Yang Jun
tM+ biochemical reaction+MBR combination process is processed high salt, high density CMC waste water, makes effluent COD concentration reach the adapter standard of industrial park sewage work; (3) " Journal of Chemical Industry and Engineering " May the 61st in 2010, volume the 5th phase 1275-1281 page was reported the micro-electrolysis of employing such as the commonplace booth of Pan-UASB-bio-contact oxidation combination process processing high density CMC waste water, when influent COD is 20000mg/L, micro-electrolysis clearance is 35%, dilution is processed by UASB and two-stage contact oxidation method, the COD clearance is 80%, and its final outflow water COD concentration is less than 100mg/L.
The water quality difference that acid CMC phlegma of the present invention and CMC produce waste liquid is larger, the former only contains the volatile organic matters such as oxyacetic acid, Mono Chloro Acetic Acid, ethanol, and the latter had both been contained the larger molecular organicses such as Mierocrystalline cellulose, carboxymethyl cellulose, contain again the inorganic salt such as the small organic molecules such as hydroxyethanoic acid sodium, Mono Chloro Acetic Acid, ethanol, sodium ethylate and sodium-chlor.Therefore, process how efficiently, cheaply acid CMC phlegma and become the technical problem that industry is badly in need of solution.
Anaerobic upflow UBF(Upflow Blanket Filter) be a kind of anaerobic biological reactor be composited in conjunction with the advantage of up-flow anaerobic sludge blanket (UASB) and anaerobic biofilter (AF), that this reactor adapted is processed is few containing suspended substance, COD concentration is high, COD:N:P nutrition is than low waste water, has the characteristics such as processing efficiency is high, energy consumption is little, working cost is low.In addition, also can produce a large amount of capable of recovering energy sources---biogas in treating processes.BAF BAF(Biological AeratedFilter) be a kind of aerobe reactor in conjunction with the reaction of aerobic bacterium living beings and filling adsorption physical action, have that volumetric loading is high, hydraulic detention time is short, effluent quality is good, floor space is little, initial cost is few, energy consumption and an advantage such as running cost is low.
The present invention, according to the water quality characteristics of acid CMC phlegma, proposes a kind for the treatment of process of the UBF-BAF of employing technique, utilizes the biological metabolism of heterotrophic bacterium on the anaerobic-aerobic microbial film to be used for decomposing organism wherein, reaches the purpose that reduces COD in waste water.At present, the domestic existing reports such as UBF-BAF art breading coking chemical waste water, high ammonia nitrogen pharmacy waste water that utilize.As, " Chinese water supply and drainage " November the 23rd in 2007, volume the 21st phase 93-97 page reported that Zhu Shunni etc. utilizes UBF-BAF art breading coking chemical waste water, COD, NH
3the clearance of-N, TN, TOC and volatile phenol is respectively 81.5%, 96.4%, 56.9%, 81.8% and 99.9%.And for example " environmental chemistry " 2011 06 month the 30th volume the 6th phase 1168-1174 page has reported that Zhang Wenyi (being the inventor) etc. utilizes the high ammonia nitrogen pharmacy waste water of UBF-BAF art breading, COD and NH
3-N clearance is all higher than 80%.
Summary of the invention
Main purpose of the present invention is: the method that proposes the acid CMC phlegma of a kind of UBF-BAF of employing art breading.
Cardinal principle of the present invention is: at first utilize Na
2cO
3in solution and acid CMC phlegma, make the pH value stabilization of waste water between 6.5-7.5, drip the agricultural composite fertilizer solution of mass ratio 10%, the nutrition required with heterotrophic microorganism metabolism on assurance anaerobic and aerobic microbial film is than COD:N:P=(100-200): 5:1 simultaneously.Then with the zeolite of filling in the polyurethane-base porous rotary spherical filler of filling in the UBF reactor and BAF reactor, biological ceramic particle is bio-carrier, cultivate, domestication anaerobic and aerobic microbial film, utilizing the UBF reactor is small organic molecule and methane by the biological action of heterotrophic bacterium on microbial film by the organic substance decomposing in waste water, carbonic acid gas, water etc., zeolite in recycling BAF reactor, the aerobic biologic membrane of biological ceramic particle and apposition growth thereof is treatment media, give full play to the biological metabolism effect, biological multistage predation in the physical adsorption effect of physical filtering effect and filler and reactor, realize that pollutent further removes.
Technical scheme of the present invention comprises the following steps:
1) acid CMC phlegma enters the adjusting settling tank, carries out the water yield, water quality regulation.
2) gravity flow of the CMC phlegma in above-mentioned adjusting settling tank enters neutralization tank, adds massfraction and be 15% industrial Na
2cO
3alkaline solution neutralizes acid CMC phlegma, utilizes pH on-line control system monitoring waste water ph and alkali lye dosage, makes waste water ph in neutralization tank be stabilized between 6.5-7.5.
3) waste water step 2) injects the UBF reactor bottom by corrosion-resistant chemical pump, waste water biological membrane anaerobic effect on carrier and purifying in reactor, and the biogas that anaerobism produces is collected by the biogas cabinet.
4) water outlet of step 3) enters the BAF reactor bottom, enter water collecting basin to top after the physical cleanings such as the aerobic decomposition of microbial film on the built-in filler of BAF reactor and Filtration Adsorption after qualified discharge or reuse.
5), during the BAF reactor back flushing of step 4), by the bottom of backwashing pump injecting reactor, the impurity such as the microbial film that back flushing comes off, mud are back to the adjusting settling tank with the back flushing draining.
6) excess sludge of the precipitating sludge of above-mentioned adjusting settling tank and UBF reactor is disposed to respectively sludge thickener, utilize plate-and-frame filter press to carry out filter-press dehydration to sludge thickener mud, mud cake outward transport after dehydration, the sludge press filtration liquid readjustment joint settling tank of concentration basin supernatant liquor and plate-and-frame filter press.
The nutritive substances such as the present invention N used, P are commercial agricultural composite fertilizer, and its main nutrient elements content is: N15%, P15%, K15%.Its dosing method is: commercial agricultural composite fertilizer is mixed with to the solution of mass ratio 10%, is placed in container, by the valve controlling flow amount, utilize action of gravity that the solution of preparation is added drop-wise in neutralization tank 2.
The present invention adopts the monitoring of pH on-line control system to regulate pH value and the alkali lye dosage of settling tank, neutralization tank.This system is comprised of 2 road pH electrode, 1 programmable logic controller PLC and 1 corrosion-resistant volume pump, but Real-Time Monitoring is regulated the waste water ph in settling tank, neutralization tank, and can regulate in real time the flow of corrosion-resistant volume pump, thereby control the dosage of alkaline solution, make the waste water ph in neutralization tank be stabilized between 6.5-7.5; The alkaline solution added is the industrial Na that massfraction is 15%
2cO
3solution.
The present invention's pH electrode used is GLOBAL industrial ph (model: GB-YP100TY), programmable logic controller used is Siemens PLC C(model: S7-200), corrosion-resistant volume pump used is frequency conversion METERING DIAPHRAGM PUMPS (model: GB650), biogas cabinet used is flexible two film gas storage holders.
The electric submersible agitator is installed at the bottom of the pond of neutralization tank of the present invention, and mixing speed is 40-65r/min.
Hole, filled with polyurethane foam Quito rotary spherical filler in UBF reactor of the present invention, its format diameter is Ф 80mm, specific surface area 600-800m
2/ m
3, porosity is greater than 99%, proportion 1.03.
In BAF reactor of the present invention, filler is zeolite and biological ceramic particle, respectively accounts for half of filler total height, and the zeolite filling is in the bottom of BAF reactor, and the haydite filling is in top.The present invention's haydite specification used, parameter are: particle diameter 4-5mm, tap density 0.63-0.82g/cm
3, apparent density 1.45-1.61g/cm
3, density 2.10-2.44g/cm
3, specific surface area 1.22-1.43cm
2/ g, hydrochloric acid soluble rate 1.49-1.96%, wear rate<1.5%.The present invention's zeolite used is clinoptilolite, and its specification, parameter are: particle diameter 4～6mm, porosity is 52.47%, wear rate<1.0%, apparent density 2.00-2.60g/cm
3, specific surface area 5.0-8.4cm
2/ g.Before use, first clinoptilolite is immersed in to 5h in the dilute hydrochloric acid solution of 0.01mol/L, then cleans to neutral with the NaCl solution of 0.8mol/L.
In UBF of the present invention, BAF reactor, microbial film cultivation acclimation method is: UBF anaerobe film is carried out in the synchronous series connection of employing sanitary sewage and the BAF aerobic biologic membrane is cultivated, tamed hydraulic load 0.18-0.20m
3/ (m
2h), temperature 30-40 ℃, cultivate domestication time 15-20d.For promoting the formation of anaerobism, aerobic biologic membrane, add natural pond, the pig farm slag that water ratio is 99% in water inlet.
The backwashing period of BAF reactor of the present invention is 5-7d, adopts air-water associating back flushing, and method is: first by roots blower aeration 10min, aeration intensity is 50-65m
3/ (m
2h), restart backwash pump, the water inlet flow velocity is 15-20m
3/ (m
2h), combined water and air backwash 10min, after closing roots blower, then water is turned one's coat and is rinsed 10min.
The present invention UBF-BAF used processes acid CMC phlegma processing parameter: reactor temperature 30-40 ℃, pH6.5-7.5, hydraulic load 0.10-0.20m
3/ (m
2h), gas-water ratio is 3:1.Press 1m
3the CMC phlegma add the agricultural composite fertilizer of 10-15g, take and guarantee that on the anaerobic and aerobic microbial film, the required nutrition ratio of heterotrophic microorganism metabolism is COD:N:P=(100-200): 5:1.
The accompanying drawing explanation
Accompanying drawing: UBF-BAF processes acid CMC phlegma process flow diagram
In figure: 1-adjusting settling tank; 2-neutralization tank; 3-corrosion-resistant chemical pump; 4-UBF reactor; 5-BAF reactor; 6-corrosion-resistant volume pump (frequency conversion METERING DIAPHRAGM PUMPS); 7-pH on-line control system (PLC, pH electrode); 8-biogas cabinet (flexible two film gas storage holders); 9-roots blower; 10-water collecting basin; 11-backwashing pump; 12-sludge thickener; 13-plate-and-frame filter press.
Embodiment
Acid CMC phlegma treatment process of the present invention, first adopt UBF reactor anaerobism, recycling BAF aerobic treatment, and its process flow sheet as shown in Figure 1.After acid CMC phlegma enters and regulates settling tank 1 homogeneous, precipitation, gravity flow enters neutralization tank 2, and Xiang Chizhong adds the industrial Na that massfraction is 15%
2cO
3the solution alkaline solution, make waste water ph in neutralization tank be stabilized between 6.5-7.5, drips the agricultural composite fertilizer solution of mass ratio 10% simultaneously.Waste water after electric submersible agitator at the bottom of the neutralization tank pond stirs is injected the bottom of UBF reactor 4 by corrosion-resistant chemical pump 3, waste water flows into BAF reactor 5 after the biological membrane anaerobic on carrier in reactor purifies to top, the collecting methane that anaerobism produces is to biogas cabinet 8.PH on-line control system 7 the real time measure are regulated pH value in settling tank and neutralization tank, and control in real time the flow of corrosion-resistant volume pump 6, thereby control the dosage of alkaline solution.Waste water after the UBF reactor for treatment flows into the BAF reactor bottom, roots blower 9 carries out aeration aerating from bottom to the BAF packing layer, discharge to top after biological metabolism, physical filtering and the biological adsorption etc. of attached biological film on packing layer purify, flow into the rear qualified discharge of water collecting basin 10 or reuse.Simultaneously, the water in water collecting basin 10 also doubles as the back flushing feedwater of BAF reactor.During the back flushing of BAF reactor, extracted the bottom that clear water injects BAF reactor 5 by backwashing pump 11 from water collecting basin 10, the impurity such as the microbial film that back flushing comes off, mud flow to and regulate settling tank 1 with the back flushing draining.Regulate the precipitating sludge of settling tank 1 and the excess sludge of UBF reactor 4 and be disposed to respectively sludge thickener 12, utilize the mud of 13 pairs of sludge thickeners 12 of plate-and-frame filter press to carry out filter-press dehydration, mud cake outward transport after dehydration, the sludge press filtration liquid of concentration basin supernatant liquor and plate-and-frame filter press 13 flows into regulates settling tank 1.
The backwashing period of BAF reactor is 5-7d, adopts air-water associating back flushing, and method is: first by roots blower 5 aeration 10min, aeration intensity is 50-65m
3/ (m
2h), restart backwash pump 11, the water inlet flow velocity is 15-20m
3/ (m
2h), combined water and air backwash 10min, after closing roots blower 5, water is turned one's coat and is rinsed 10min.
Adopt sanitary sewage between the biofilms domestication incubation period, and regulate in settling tank and add natural pond, the pig farm slag 10kg/d that water ratio is 99%, incubation time 15-20d, hydraulic load 0.18-0.20m in water inlet
3/ (m
2h); Normal operation period, reactor temperature is controlled at 30-40 ℃; Press 1m
3the CMC phlegma add the agricultural composite fertilizer of 10-15g, take and guarantee that on the anaerobic and aerobic microbial film, the required nutrition ratio of heterotrophic microorganism metabolism is COD:N:P=(100-200): 5:1.
The adjusting settling tank, the neutralization tank volume that adopt in test are 1.5m
3, UBF and BAF reactor are cylindrical, wherein: UBF reactor virtual height H
1=2800mm, inner diameter d
1=260mm, packed height h
1=2400mm, bottom connects water inlet pipe, and top connects biogas cabinet and rising pipe; BAF reactor virtual height is H
2=2500mm, inner diameter d
2=260mm, packed height h
2=2200mm.As temperature 30-40 ℃, pH6.5-7.5, hydraulic load 0.10-0.20m
3/ (m
2h), the BAF gas-water ratio is while being 3:1, the UBF reactor can reach 84.90-86.53% to the COD clearance in waste water, the biogas generation can reach 1.73-2.80m
3/ kgCOD, BAF can reach 80.53-87.18% to the COD clearance in waste water, and the total clearance of COD reaches 96.94-98.25%, and final outflow water COD is lower than the primary standard limit value (COD≤100mg/L) in " integrated wastewater discharge standard (GB8978-1996) ".5 embodiment that table 1 is the acid CMC phlegma of UBF-BAF art breading.
Table 1 adopts the acid CMC phlegma of UBF-BAF art breading effect embodiment
Claims (4)
1. the treatment process of an acid carboxymethyl cellulose phlegma is characterized in that adopting following steps:
1) acid CMC phlegma enters the adjusting settling tank, carries out the water yield, water quality regulation.
2) gravity flow of the CMC phlegma in above-mentioned adjusting settling tank enters neutralization tank, adds massfraction and be 15% industrial Na
2cO
3alkaline solution neutralizes acid CMC phlegma, utilizes pH on-line control system monitoring waste water ph and alkali lye dosage, makes waste water ph in neutralization tank be stabilized between 6.5-7.5.
3) waste water step 2) injects the UBF reactor bottom by corrosion-resistant chemical pump, waste water biological membrane anaerobic effect on carrier and purifying in reactor, and the biogas that anaerobism produces is collected by the biogas cabinet.
4) water outlet of step 3) enters the BAF reactor bottom, enter water collecting basin to top after the physical cleanings such as the aerobic decomposition of microbial film on the built-in filler of BAF reactor and Filtration Adsorption after qualified discharge or reuse.
5), during the BAF reactor back flushing of step 4), by the bottom of backwashing pump injecting reactor, the impurity such as the microbial film that back flushing comes off, mud are back to the adjusting settling tank with the back flushing draining.
6) excess sludge of the precipitating sludge of above-mentioned adjusting settling tank and UBF reactor is disposed to respectively sludge thickener, utilize plate-and-frame filter press to carry out filter-press dehydration to sludge thickener mud, mud cake outward transport after dehydration, the sludge press filtration liquid readjustment joint settling tank of concentration basin supernatant liquor and plate-and-frame filter press.
2. the treatment process of a kind of acid carboxymethyl cellulose phlegma according to claim 1, is characterized in that: adopt the synchronous series connection of sanitary sewage to carry out UBF anaerobe film and the cultivation of BAF aerobic biologic membrane, tame hydraulic load 0.18-0.20m
3/ (m
2h), temperature 30-40 ℃, cultivate domestication time 15-20d.For promoting the formation of anaerobism, aerobic biologic membrane, add natural pond, the pig farm slag that water ratio is 99% in water inlet.
3. the treatment process of a kind of acid carboxymethyl cellulose phlegma according to claim 1 is characterized in that: hole, filled with polyurethane foam Quito rotary spherical filler in the UBF reactor of described step 3), its format diameter is Ф 80mm, specific surface area 600-800m
2/ m
3, porosity is greater than 99%, proportion 1.03.
4. the treatment process of a kind of acid carboxymethyl cellulose phlegma according to claim 1, it is characterized in that: the nutritive substances such as the nitrogen added (N), phosphorus (P) are commercial agricultural composite fertilizer, and its main nutrient elements content is: N15%, P15%, K15%.Press 1m
3the CMC phlegma add the agricultural composite fertilizer of 10-15g, to guarantee that on UBF, BAF microbial film, condition is compared in the required nutrition of heterotrophic microorganism metabolism.
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Cited By (1)
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|---|---|---|---|---|
| CN111115979A (en) * | 2020-01-19 | 2020-05-08 | 江苏省环科院环境科技有限责任公司 | Evaporation concentration treatment device and method for high-concentration waste liquid |
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| WO2008132296A2 (en) * | 2007-03-02 | 2008-11-06 | Degremont | Method and equipment for processing waste water containing sulphides and ammonium |
| CN103193360A (en) * | 2012-01-09 | 2013-07-10 | 济南大学 | Nitrogen and phosphorus removal integrated biological aerated filter water purification system and water purification method thereof |
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2013
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Patent Citations (2)
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|---|---|---|---|---|
| WO2008132296A2 (en) * | 2007-03-02 | 2008-11-06 | Degremont | Method and equipment for processing waste water containing sulphides and ammonium |
| CN103193360A (en) * | 2012-01-09 | 2013-07-10 | 济南大学 | Nitrogen and phosphorus removal integrated biological aerated filter water purification system and water purification method thereof |
Non-Patent Citations (1)
| Title |
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| 温丽丽等: "UBF-BAF固定化微生物系统处理中老龄垃圾渗滤液的研究", 《应用基础与工程科学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115979A (en) * | 2020-01-19 | 2020-05-08 | 江苏省环科院环境科技有限责任公司 | Evaporation concentration treatment device and method for high-concentration waste liquid |
| CN111115979B (en) * | 2020-01-19 | 2024-03-29 | 江苏省环境工程技术有限公司 | Evaporation concentration treatment device and method for high-concentration waste liquid |
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