CN1973968B - Combined gas and liquid phase biotechnological process for purifying waste formaldehyde gas - Google Patents

Combined gas and liquid phase biotechnological process for purifying waste formaldehyde gas Download PDF

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CN1973968B
CN1973968B CN2006100488330A CN200610048833A CN1973968B CN 1973968 B CN1973968 B CN 1973968B CN 2006100488330 A CN2006100488330 A CN 2006100488330A CN 200610048833 A CN200610048833 A CN 200610048833A CN 1973968 B CN1973968 B CN 1973968B
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formaldehyde
gas
liquid phase
biomembrane
tower
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CN1973968A (en
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孙珮石
黄若华
郑顺生
邓辅唐
王洁
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Yixing Environmental Protection Research Institute, Nanjing University
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Yunnan University YNU
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Abstract

The present invention is combined gas and liquid phase biotechnological process for purifying waste gas containing formaldehyde. One biomembrane packed tower for treating formaldehyde in gas phase and one active sludge treating unit for treating formaldehyde in liquid phase are combined, so that the waste gas containing formaldehyde entering the combined purifying system is double degrading purified to reach excellent purifying effect. The present invention has high efficiency of eliminating low concentrate formaldehyde from waste gas, complete elimination of formaldehyde, simple operation, low treating cost, no secondary pollution and other advantages.

Description

A kind of combined gas and liquid phase biotechnological process for purifying of formaldehyde exhaust-gas
Technical field: the present invention relates to a kind of employing gas phase and liquid phase biological clarification, handle the exhaust gas purifying method of formaldehyde, particularly handle low concentration formaldehyde waste gas (concentration<100mg/m 3) combined gas and liquid phase biotechnological process for purifying.Belong to environmental technology field.
Technical background: it is one of environmental issue that is subjected at present people's extensive concern that formaldehyde exhaust-gas pollutes.Formaldehyde exhaust-gas is mainly from production processes such as timber processing, textile of chemical fibre, plastics, organic synthesis, synthetic rubber, paints, and what the daily impression of people was maximum is that the formaldehyde gas that timber processing, TPR plywood and wood furniture are distributed pollutes.For the purified treatment high-concentration formaldehyde exhaust-gas, processings such as at present existing ripe chemical absorbing, absorption and utilize method, but recycling is not worth but also the low concentration formaldehyde waste gas (concentration<100mg/m of serious harm health and atmospheric environment for not only having 3), although purification methods such as at present existing both at home and abroad photocatalytic oxidation, adsorption cleaning method, ozone oxidation method, the cold plasma method of purification, formaldehyde catching agent, but these methods are mostly owing to treatment effect instability, processing cost height, have factor such as secondary pollution and can not apply on a large scale, so the purified treatment of low concentration formaldehyde waste gas just becomes in recent years one of hot subject in the air contaminant treatment technical research field both at home and abroad and difficult problem.
Formaldehyde (HCHO) has the intense stimulus smell and than high toxicity, and is volatile, also has bigger water-soluble simultaneously.Formaldehyde is very strong to the toxicity of people and warm-blooded animal, is 142mg/kg to people's lethal dose.The formaldehyde Diazolidinyl Urea easily causes dermatitis, and under a cloud the people is had carcinogenesis.If the mankind survive in by the formaldehyde contaminated environment for a long time, then can cause giddy, anaemia and the nervous system disease.Certain density formaldehyde can directly react with protein, DNA, the RNA in the microbial body, causes microbial death or suppresses its biologically active.In recent years, the formaldehyde exhaust-gas pollution problem has been subjected to people's generally attention, and has carried out some pollution control work, and country has also issued a series of relevant rule and standard.For example, " discharge standard of air pollutants " (GB16297-1996) stipulated, the highest permission concentration of emission of formaldehyde is 25mg/m in the industrial waste gas 3" sanitary standard of formaldehyde in indoor air " (GB/T16127-1995) regulation formaldehyde maximum permissible concentration is 0.08mg/m 3
The biological waste gas purification technology is as an exhaust-gas treatment new technology, with its economy, effectively, pollutant handles thoroughly, is suitable for handling characteristics such as low-concentration industrial waste gas, more and more be subjected to people's extensive attention, therefore it progressively develops into the hot research field, a forward position of industrial waste gas purifying in the world in recent years.The research and the application practice of this technical method show, its solve almost recycle be worth, the purified treatment difficulty is big and expense is high, aspect the purified treatment difficult problem of the low-concentration industrial waste gas that simultaneously harm of health and ecological environment be can not be ignored again (all being one of difficult problem of environmental protection aspect), have special effect at home and abroad.Closely during the last ten years, domestic some biological method purification low concentration VOC (volatile organic matter), H of having carried out of China 2S, SO 2, NOx waste gas etc. research and application work, and obtained some researchs and commercial Application achievements.
Summary of the invention: order of the present invention is to overcome the shortcoming of above-mentioned prior art, invent in the combined system purifying exhaust air of a biomembrane filled tower of employing and one or more circulating fluid biological treatment devices, then adopt gas phase and liquid phase biological clarification, handle the waste gas purification new technology of formaldehyde, particularly handle low concentration formaldehyde waste gas (concentration<100mg/m 3) the combined biological purification method of gas-liquid of formaldehyde exhaust-gas.
Goal of the invention of the present invention is with waste gas in the environmental protection field, wastewater treatment microorganism fungus kind cohort commonly used is the basis, adopt proprietary waste gas purification special bacteria gas phase screening breeding apparatus [utility model patent simultaneously, patent No. ZL200320104770.8] screen breeding method with technology and conventional bacterial classification liquid phase, obtain under gas phase and liquid phase environment condition, all to have the microorganism fungus kind cohort that biodegradation purifies the formaldehyde performance by screening and cultivation domestication, and, the combination biological purification plant is possessed operate needed biological cleaning performance when moving with this bacterial classification cohort biofilm making biomembrane filled tower and the activated sludge of inoculating in the domestication circulating fluid biological treatment device.
The combined gas and liquid phase biotechnological process for purifying technical scheme of formaldehyde exhaust-gas of the present invention is: the biomembrane filled tower that is about to formaldehyde in the purified treatment gas phase carries out integrated combination with the Wastewater Treated by Activated Sludge Process device of handling formaldehyde in the liquid phase, make that formaldehyde molecule can experience gas phase and the dual biodegradable purified treatment mechanism of liquid phase in the waste gas that enters in the combination purification system, thereby reach the optimum efficiency of PARA FORMALDEHYDE PRILLS(91,95) exhaust gas biological purifying.
When operating this combined system purification formaldehyde exhaust-gas, by the biological cleaning of biomembrane filled tower enforcement to formaldehyde in the gas phase, and need to use the biomembrane on circulated sprinkling liquid wetting inner-tower filling material surface, so that its grow needed nutriment or environment adjusting material to be provided to biomembrane; Simultaneously, implement biological treatment by circulating fluid biological treatment device (by the operation of activated sludge process aeration processing mode) to formaldehyde in the liquid phase.Biomembrane filled tower adopts the gas-liquid counter current mode to operate, allow formaldehyde exhaust-gas at the bottom of tower, enter earlier, in uphill process, contact with wetting biomembrane absorption attached to the solid packing surface, a part of formaldehyde wherein by the microbial bacteria in the biomembrane catch, the biodegradation purification; Another part formaldehyde then can dissolve and enter in the circulated sprinkling liquid that flows from top to bottom, purified gas is discharged from the cat head of biomembrane filled tower, after containing the circulation fluid that dissolves formaldehyde and going out from tower bottom flow, entering the circulating fluid biological treatment device again moves by activated sludge process aeration processing mode, carry out after the biodegradation, purified treatment of formaldehyde in the liquid phase, circulation fluid flows into storage tank and gets to cat head by water circulating pump and sprays downwards on the biofilm packing, recycles.
This technology method is with waste gas in the environmental protection field, wastewater treatment microorganism fungus kind cohort commonly used is the basis, adopt proprietary waste gas purification special bacteria gas phase screening breeding apparatus and technology and conventional bacterial classification liquid phase screening breeding method simultaneously, obtain under gas phase and liquid phase environment condition, all to have the microorganism fungus kind cohort that biodegradation purifies the formaldehyde performance by screening and cultivation domestication, and, the combination biological purification plant is possessed operate needed biological cleaning performance when moving with this bacterial classification cohort biofilm making biomembrane filled tower and the activated sludge of inoculating in the domestication circulating fluid biological treatment device.
Circulating fluid has evaporation loss and the consumption that includes component in the circulated sprinkling process, needs regularly add in the circulation fluid storage tank supplementing water, carbon phosphorus nutrition composition.
The combined gas and liquid phase biotechnological process for purifying of formaldehyde exhaust-gas of the present invention can carry out integrated combination with the Wastewater Treated by Activated Sludge Process device of formaldehyde in the biomembrane filled tower of formaldehyde in the purified treatment gas phase and a plurality of processing liquid phase, to reach the maximum biochemical degradation removal effect to formaldehyde in the waste gas.
When operating this combined system purification formaldehyde exhaust-gas, by the biological cleaning of biomembrane filled tower enforcement to formaldehyde in the gas phase, and need to use the biomembrane on circulated sprinkling liquid wetting inner-tower filling material surface, so that its grow needed nutriment or environment adjusting material to be provided to biomembrane; Simultaneously, implement biological treatment by circulating fluid biological treatment device (by the operation of activated sludge process aeration processing mode) to formaldehyde in the liquid phase.The integrated combination technique that the present invention promptly carries out a biological disposal upon mutually by this gas-liquid reaches the purpose of formaldehyde in the biological cleaning waste gas.
The technology of the present invention principle: because of formaldehyde gas is that (its solubility in water is 4.0 * 105mg/L) to organic gas soluble in water, purify in the process of formaldehyde gas at applying biological film packed tower, it is water-soluble and be present in the circulation fluid to understand some formaldehyde gas (about inlet amount 1/4~1/3), therefore with regard to the treating apparatus that needs to increase circulated sprinkling liquid the formaldehyde in the liquid phase is handled, to reach biological cleaning purpose (rather than formaldehyde is transferred to liquid phase from gas phase) truly to formaldehyde in the waste gas.Based on this situation, the present invention attempts adopting biomembrane filled tower to purify formaldehyde in the gas phase, add the circulating fluid biological treatment device simultaneously and handle the method for formaldehyde in the liquid phase, the combined biological cleaning new technology of the gas-liquid of exploratory development formaldehyde exhaust-gas, on the basis of summing up successful experimental studies results, formed new technology of the present invention.
In the operation, the waste gas (in case of necessity do cooling grade preliminary treatment) that contains formaldehyde is sent into biomembrane filled tower [utility model patent, patent No. ZL97211331.2] by blower fan and is carried out purified treatment.Biomembrane filled tower adopts the gas-liquid counter current mode to operate.Formaldehyde exhaust-gas enters at the bottom of tower, in uphill process, contact with wetting biomembrane absorption attached to the solid packing surface, a formaldehyde part wherein by the microbial bacteria in the biomembrane catch, the biodegradation purification; Another part then can dissolve and enter in the circulated sprinkling liquid that flows from top to bottom.Purified gas is discharged from the cat head of biomembrane filled tower.After the circulation fluid that contains the formaldehyde of dissolving goes out from tower bottom flow, enter biodegradation, purified treatment that circulating fluid biological treatment device (by the operation of activated sludge process aeration processing mode) carries out formaldehyde in the liquid phase.Afterwards, circulation fluid flows into storage tank and gets to cat head by water circulating pump and sprays downwards on the biofilm packing, recycles.When needing, several circulating fluid biological treatment devices of can connecting after a biomembrane filled tower are to reach the maximum biochemical degradation removal effect to formaldehyde in the waste gas.Because circulating fluid has evaporation loss and includes the consumption of component in the circulated sprinkling process, therefore to regularly in the circulation fluid storage tank, add supplementing water, the carbon phosphorus nutrition becomes to grade.
Technical spirit of the present invention promptly is that the biomembrane filled tower of formaldehyde in the purified treatment gas phase and the Wastewater Treated by Activated Sludge Process device of handling formaldehyde in the liquid phase are carried out integrated combination, make that formaldehyde molecule can experience gas phase and the dual biodegradable purified treatment mechanism of liquid phase in the waste gas that enters in the combination purification system, to reach the optimum efficiency of PARA FORMALDEHYDE PRILLS(91,95) exhaust gas biological purifying.
The combined biological purification method of the gas-liquid of formaldehyde exhaust-gas of the present invention is a kind of advantage and characteristic of optimizing integrated gas phase and liquid phase biological clarification, and the novel process technology with formaldehyde in the purifying exhaust air of integrated combination novel concept has and low concentration formaldehyde biological cleaning efficient height, formaldehyde biochemical degradation in the waste gas is removed advantages such as more complete, simple to operation, device good operation stability, processing cost are low, formaldehydeless secondary pollution.
Description of drawings: below in conjunction with embodiment technical process of the present invention is elaborated, but protection domain is not limited to embodiment.
Fig. 1 is the combined system technical process schematic diagram of a biomembrane filled tower of the present invention and a circulating fluid biological treatment device.
Among the figure: 1-preprocessor (using in case of necessity); The 2-air-introduced machine; The 3-biomembrane filled tower; 4-circulation fluid biological treatment device (activated sludge process contains aerator); 5-circulation fluid storage tank and pump.
Fig. 2 relatively [operates tolerance Q=0.2m for formaldehyde entrance concentration before and after the circulation fluid treating apparatus is installed to the influence of purification efficiency 3/ h, liquid measure L=20L/h] empirical curve.
Fig. 3 compares [operation tolerance Q=0.2m for formaldehyde entrance concentration before and after the circulation fluid treating apparatus is installed to biochemical removal amount influence 3/ h, liquid measure L=20L/h] empirical curve.
[formaldehyde is gone into the dense C=10~25mg/m of implication to Fig. 4 for gas flow before and after the installation circulation fluid treating apparatus compares the influence of purification efficiency 3, liquid measure L=20L/h] empirical curve.
Fig. 5 installs gas flow before and after the circulation fluid treating apparatus, and relatively [formaldehyde is gone into the dense C=10~25mg/m of implication to the influence of biochemical removal amount 3, liquid measure L=20L/h] in empirical curve.
The specific embodiment: embodiment 1: adopt the combined biological cleaning technology of gas-liquid of the present invention PARA FORMALDEHYDE PRILLS(91,95) waste gas to carry out the purified treatment contrast experiment.The experimental provision flow process as shown in Figure 1, wherein biomembrane filled tower is that tower diameter is the small-sized glass biomembrane filled tower of 100mm, the spherical haydite of class that to divide two sections filling diameters in the packed tower be 2.5cm, packing volume 3.18L * 2.Biomembrane filled tower is by making through the purifying formaldehyde bacterial classification cohort biofilm of screening and culturing acquisition in advance.Increase the circulating fluid biological treatment device of installing and make by the glass tube of diameter 95mm, long 1200mm, the built-in activated sludge liquid 3.5L that contains the purifying formaldehyde flora, sending into the aeration gas flow by little blower fan is 0.01m 3/ h.Microorganism fungus kind cohort in the system is mainly by pseudomonas putida P.putida, pseudomonas pseudoalcaligenes P.pseudoalcaligens, Pseudomonas aeruginosa P.aeruginosa, formations such as fusiform bacillus B.fusiformis.
Experimental implementation is carried out under normal temperature and pressure conditions, and biomembrane filled tower operating gas flow is 0.2m 3/ h, concentration of formaldehyde is 5~90mg/m in the waste gas 3The circulated sprinkling flow quantity is 20L/h.Gas phase, liquid phase formaldehyde sample all adopt the acetylacetone,2,4-pentanedione AAS to carry out check and analysis and measure.In the experiment respectively by in the biomembrane filled tower waste gas cleaning system, increase installing and two kinds of methods operations of circulating fluid biological treatment device be not installed, twice independently experimental result such as Fig. 2, shown in Figure 3.
Experimental result shows, when operating under different formaldehyde entrance concentration conditions, the clean-up effect that the present invention increases the combined biological cleaning technique device of the gas-liquid system PARA FORMALDEHYDE PRILLS(91,95) waste gas that the circulation fluid biological treatment device is installed obviously is better than not installing the clean-up effect of the simple biomembrane filled tower cleaning system of circulation fluid biological treatment device.
Embodiment 2: adopt the combined biological cleaning technology of gas-liquid of the present invention PARA FORMALDEHYDE PRILLS(91,95) waste gas to carry out the purified treatment contrast experiment.The experimental provision flow process as shown in Figure 1, wherein biomembrane filled tower is that tower diameter is the small-sized glass biomembrane filled tower of 100mm, the spherical haydite of class that to divide two sections filling diameters in the packed tower be 2.5cm, packing volume 3.18L * 2.Biomembrane filled tower is by making through the purifying formaldehyde bacterial classification cohort biofilm of screening and culturing acquisition in advance.Increase the circulating fluid biological treatment device of installing and make by the glass tube of diameter 95mm, long 1200mm, the built-in activated sludge liquid 3.5L that contains the purifying formaldehyde flora, sending into the aeration gas flow by little blower fan is 0.01m 3/ h.Microorganism fungus kind cohort in the system is mainly by pseudomonas putida P.putida, and hormone pseudomonad P.testosterone grabs methyl bacillus M.extorquens, formations such as Pseudomonas fluorescens P.fluorescens.
Experimental implementation is carried out under normal temperature and pressure conditions, and biomembrane filled tower operating gas flow is 0.2~0.6m 3/ h, concentration of formaldehyde is 10~25mg/m in the waste gas 3The circulated sprinkling flow quantity is 20L/h.Gas phase, liquid phase formaldehyde sample all adopt the acetylacetone,2,4-pentanedione AAS to carry out check and analysis and measure.In the experiment respectively by in the biomembrane filled tower waste gas cleaning system, increase installing and two kinds of methods operations of circulating fluid biological treatment device be not installed, twice independently experimental result such as Fig. 4, shown in Figure 5.
Experimental result shows, when operating under different gas flow conditions, the clean-up effect that the present invention increases the combined biological cleaning technique device of the gas-liquid system PARA FORMALDEHYDE PRILLS(91,95) waste gas that the circulation fluid biological treatment device is installed obviously is better than not installing the clean-up effect of the simple biomembrane filled tower cleaning system of circulation fluid biological treatment device.

Claims (2)

1. the combined gas and liquid phase biotechnological process for purifying of a formaldehyde exhaust-gas, it is characterized in that the Wastewater Treated by Activated Sludge Process device that is about to the biomembrane filled tower of formaldehyde in the purified treatment gas phase and handles formaldehyde in the liquid phase carries out integrated combination, make that formaldehyde molecule can experience gas phase and the dual biodegradable purified treatment mechanism of liquid phase in the waste gas that enters in the combination purification system, thereby reach the optimum efficiency of PARA FORMALDEHYDE PRILLS(91,95) exhaust gas biological purifying;
When operating this combination purification system purification formaldehyde exhaust-gas, by the biological cleaning of biomembrane filled tower enforcement to formaldehyde in the gas phase, and need to use the biomembrane on circulated sprinkling liquid wetting inner-tower filling material surface, so that its grow needed nutriment or environment adjusting material to be provided to biomembrane; Simultaneously, by the biological treatment of implementing by the circulating fluid biological treatment device of activated sludge process aeration processing mode operation formaldehyde in the liquid phase;
Biomembrane filled tower adopts the gas-liquid counter current mode to operate, allow formaldehyde exhaust-gas at the bottom of tower, enter earlier, in uphill process, contact with wetting biomembrane absorption attached to the solid packing surface, a part of formaldehyde wherein by the microbial bacteria in the biomembrane catch, the biodegradation purification; Another part formaldehyde then can dissolve and enter in the circulated sprinkling liquid that flows from top to bottom, purified gas is discharged from the cat head of biomembrane filled tower, after containing the circulated sprinkling liquid that dissolves formaldehyde and going out from tower bottom flow, entering the circulating fluid biological treatment device again moves by activated sludge process aeration processing mode, carry out after the biodegradation, purified treatment of formaldehyde in the liquid phase, circulated sprinkling liquid flows into storage tank and gets to cat head by water circulating pump and sprays downwards on the biofilm packing, recycles.
2. the combined gas and liquid phase biotechnological process for purifying of formaldehyde exhaust-gas according to claim 1, it is characterized in that the Wastewater Treated by Activated Sludge Process device of formaldehyde in the biomembrane filled tower of formaldehyde in the purified treatment gas phase and a plurality of processing liquid phase is carried out integrated combination, to reach maximum biochemical degradation removal effect to formaldehyde in the waste gas.
CN2006100488330A 2006-11-21 2006-11-21 Combined gas and liquid phase biotechnological process for purifying waste formaldehyde gas Expired - Fee Related CN1973968B (en)

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CN105841237A (en) * 2016-04-06 2016-08-10 程铁柱 Ecologic air purifier
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