CN101337156B - A method for purifying and treating low-concentration formaldehyde waste gas - Google Patents
A method for purifying and treating low-concentration formaldehyde waste gas Download PDFInfo
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- CN101337156B CN101337156B CN2008100588003A CN200810058800A CN101337156B CN 101337156 B CN101337156 B CN 101337156B CN 2008100588003 A CN2008100588003 A CN 2008100588003A CN 200810058800 A CN200810058800 A CN 200810058800A CN 101337156 B CN101337156 B CN 101337156B
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 270
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002912 waste gas Substances 0.000 title claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 238000000746 purification Methods 0.000 claims abstract description 27
- 239000007791 liquid phase Substances 0.000 claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000011734 sodium Substances 0.000 claims description 34
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 18
- 229920002866 paraformaldehyde Polymers 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 10
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 244000005700 microbiome Species 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000007792 gaseous phase Substances 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 241000233866 Fungi Species 0.000 claims description 2
- 230000001580 bacterial effect Effects 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 9
- 230000002708 enhancing effect Effects 0.000 abstract 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000011138 biotechnological process Methods 0.000 description 2
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 2
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000000813 microbial effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- ZCCYIBRFOWNOCF-UHFFFAOYSA-N 1-[3,4-bis(hydroxymethyl)-2,5-dioxoimidazolidin-4-yl]-1,3-bis(hydroxymethyl)urea formaldehyde Chemical compound C=O.OCN1C(NC(C1(CO)N(C(=O)NCO)CO)=O)=O ZCCYIBRFOWNOCF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 229920003051 synthetic elastomer Polymers 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Treating Waste Gases (AREA)
Abstract
The invention relates to a method for purifying the low-concentrating formaldehyde waste gas. In the method, a biomembrane reactor is adopted to subject the gas phase of the formaldehyde waste gas to the biochemical degradation purification, and subject formaldehyde dissolving into a circulation liquid to the chemical absorption reaction purification. The chemical absorption reaction purification is carried out by adding sodium sulfite with the molar concentration of 0.01 to 0.1 M into the biomembrane reactor circulation liquid, and subjecting formaldehyde into the liquid phase to the chemical absorption purification. By adopting the method, the gas phase biochemical degradation purification and the liquid phase chemical absorption purification can be simultaneously carried out in the biomembrane reactor; the purification efficiency of the reactor to the formaldehyde waste gas is higher than 90%; and the unit volume load of the reactor is higher than 20 mg/L*h and is improved by more than 80% compared with that of the reactor without sodium sulfite added into the reaction circulation liquid. The method can prevent secondary pollution and reduce the device cost and the operation cost while enhancing the effect of the biomembrane reactor for purifying the formaldehyde waste gas.
Description
One, technical field
The present invention relates to a kind of purifying treatment method of low concentration formaldehyde waste gas.The formaldehyde that promptly adopts the biodegradation of formaldehyde exhaust-gas gas phase to purify, be dissolved in liquid phase adopts the purification formaldehyde exhaust-gas method of chemisorbing purifying reaction combination.Belong to the waste gas purification technical field.
Two, background technology
It is one of environmental issue that is subjected at present people's extensive concern that formaldehyde exhaust-gas pollutes, and in the world wide, it is the most serious a kind of that formaldehyde is that volatile organism pollutes.Formaldehyde is 142mg/kg to people's lethal dose.National Institute and health tissues have announced that formaldehyde may have carcinogenesis to the people.Formaldehyde has the intense stimulus smell and than high toxicity, and is volatile, has water-soluble.The formaldehyde Diazolidinyl Urea easily causes dermatitis, 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 0.08; The ministry of Health of China standard, formaldehyde maximum permissible concentration 3mg/m in the workshop air
3
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 absorption, absorption, burning and utilize method, but recycling is not worth but also the low concentration formaldehyde waste gas (concentration＜200mg/m of serious harm health and atmospheric environment for not only having
3) purified treatment at home and abroad all be one of difficult problem of environmental protection aspect.Although methods such as the existing at present both at home and abroad absorption absorption reaction method of purification, biological clarification, photocatalytic oxidation, ozone oxidation method, formaldehyde scavenger, but these methods mostly because have secondary pollution, treatment effect instability, factor such as purification efficiency is low, service life is short, processing cost height and can not applying on a large scale, so the purified treatment of low concentration formaldehyde waste gas just becomes one of hot subject in the domestic and international in recent years air contaminant treatment technical research field and difficult problem.
A kind of absorption absorption reaction type formaldehyde eliminating agent is disclosed in the document of CN 1513579A.This remover is made up of absorption absorbent and reactant sodium sulfite, ammonium salt or sodium sulfite, hydroxylamine hydrochloride, and the absorption absorbent is active carbon, aluminium oxide, diatomite, polyamide, water etc., is divided into two kinds of forms of solid and liquid.It eliminates mechanism: at first utilize the absorption absorbent that formaldehyde absorption is absorbed, the formaldehyde that is adsorbed absorption rapidly with remover in reactant react, generate bronsted lowry acids and bases bronsted lowry and corresponding product, acid-base neutralization generation salt and water.Its reaction mechanism equation is as follows:
HCHO+Na
2SO
3+H
2O＝HCH(OH)SO
3Na+NaOH
6HCHO+4NH
+ 4(ammonium salt)=+ 3H
++ 6H
2O
HCHO+NH
2OH.HCL＝RCH＝NOH+H
2O+HCL
OH
-+H
+＝H
2O
The result shows: solid type remover and formaldehyde 1-18 time of contact days, and the elimination factor 64-76% of formaldehyde, liquid-type remover PARA FORMALDEHYDE PRILLS(91,95) elimination factor is all more than 90%.Formaldehyde and reaction reaction in this method generate bronsted lowry acids and bases bronsted lowry and corresponding product, and acid-base neutralization generates salt and water, but corresponding product HCH (OH) SO
3Na, (CH
2)
6N
4H
+, whether RCH=NOH but exists, bring secondary pollution and security to remain to be investigated.
A kind of combined gas and liquid phase biotechnological process for purifying of formaldehyde exhaust-gas is disclosed in the document of CN 1973968A.This method is a kind of combined gas and liquid phase biotechnological process for purifying of formaldehyde exhaust-gas, 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, respectively by the biological cleaning of a biomembrane filled tower enforcement to formaldehyde in the gas phase, implement biological treatment by one or more circulating fluid biological treatment devices (by the operation of activated sludge process aeration processing mode) to 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.The result shows, when operating under different formaldehyde entrance concentration conditions, the clean-up effect that the combined biological cleaning technique device of the gas-liquid system PARA FORMALDEHYDE PRILLS(91,95) waste gas of 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; When operating under the gas with various flow condition, the clean-up effect that the combined biological cleaning technique device of the gas-liquid system PARA FORMALDEHYDE PRILLS(91,95) waste gas of 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.This invention is at the water-based that is soluble in of formaldehyde, take the dual bioanalysis combination purification of gas, liquid method to improve the biological method purification effect of formaldehyde, this method just increases the microorganism concn in the circulation fluid on the basis of biomembrane filled tower purification formaldehyde exhaust-gas method, and when increasing operating cost, cost of equipment is also increasing.
Three, summary of the invention
The object of the invention provides a kind of purifying treatment method to low concentration formaldehyde waste gas.This method is that a kind of biofilm reactor that utilizes carries out the formaldehyde exhaust-gas gas phase biochemical degradation purification, is dissolved in the formaldehyde exhaust-gas purification method that the formaldehyde in the circulation fluid water carries out chemical absorbing reaction purification.This method can make biofilm reactor PARA FORMALDEHYDE PRILLS(91,95) exhaust purification efficiency reach more than 90%, the unit volume load B＞20mg/L.h of biofilm reactor.The present invention overcomes the weakness of above-mentioned existing purification techniques, in enhanced biological membrane reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas purification effect, does not bring secondary pollution, reduces cost of equipment and operating cost.
The present invention is achieved through the following technical solutions:
1, biofilm reactor biofilm: the haydite that diameter is housed is 8-10mm in the biofilm reactor is as filler, with concentration＜200mg/m
3Formaldehyde exhaust-gas by the reactor spirit feeding reactor that enters the mouth mutually, waste gas from bottom to top by packing layer with lead to the reactor head liquid inlet by head tank and spray strain liquid counter current contacting on the reactor filler from top to bottom, formaldehyde exhaust-gas by the reactor filler layer is got rid of by the reactor top gaseous phase outlet, the wetting whole packing layer of strain liquid, and bacterial classification is sticked on the filler, strain liquid liquid outlet at the bottom of the reactor is discharged and is entered Lower tank, connect by liquid circulation pump between head tank and the Lower tank, make strain liquid in reactor, keep the liquid phase continued operation.It is formulated that strain liquid promptly adopts the activated sludge of city domestic sewage treatment plant to be that microorganism fungus kind adds water, the strain liquid total amount reaches and can make strain liquid as getting final product on the ceramics filling of liquid phase continuous phase circulated sprinkling in biofilm reactor, and strain liquid is also referred to as circulation fluid.In biofilm reactor, formaldehyde exhaust-gas contacts with circulation fluid (strain liquid) continuous flow upstream, the reactor operating temperature is a normal temperature, circulation fluid pH is controlled to be alkalescence, reactor moves continuously, when making the purification efficiency of reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas be tending towards a stationary value, then biofilm is finished, about 15-30 of biofilm time days.
2, the formaldehyde exhaust-gas biochemical degradation purifies: the formaldehyde exhaust-gas entrance concentration is＜200mg/m
3, enter biofilm reactor by reactor bottom gas phase inlet, in formaldehyde exhaust-gas uphill process from bottom to top, contact and by biochemical degradation, degraded purifies back generation carbon dioxide (CO with biomembrane in the reactor
2) and water (H
2O), CO
2Gas is discharged from the reactor top gaseous phase outlet.Make contain N salt, P salt and the pH of its growth, wetting needs enter circulation fluid for alkaline strain liquid for keeping biomembranous growth, need providing, operating condition is operated with biofilm.Circulation fluid is by every premium on currency phosphoric acid sodium dihydrogen (NaH
2PO
4) 4.4g, sodium nitrate (NaNO
3) the 26.8g preparation, the amount of circulation fluid is can make circulation fluid as getting final product on the biomembrane of liquid phase continuous phase circulated sprinkling in biofilm reactor.
3, chemisorbing purifying: because formaldehyde exhaust-gas is that (its solubility in water is 4.0 * 10 to organic gas soluble in water
5Mg/L), purify in the process of formaldehyde exhaust-gas at the applying biological membrane reactor, the formaldehyde exhaust-gas that has an inlet amount 1/4～1/3 is water-soluble and be present in the circulation fluid, this part is not entered Lower tank by the formaldehyde that the biomembrane biochemistry degraded purifies with circulation fluid, adds in the Lower tank circulation fluid and presses circulation fluid and Na
2SO
3Volume ratio is 25: 1, and molar concentration is that the sodium sulfite of 0.01-0.1 carries out the chemisorbing purifying reaction to this part formaldehyde, and reaction promptly generates formaldehyde-sodium bisulfite (HCH (OH) SO
3Na) and NaOH (NaOH), purifying reaction by liquid phase chemical further is cleaned formaldehyde exhaust-gas.
4, the chemisorbing purifying product is handled: contain formaldehyde-sodium bisulfite (HCH (OH) SO
3Na) and the circulation fluid of NaOH (NaOH) knock head tank by circulating pump down through Lower tank, enter biofilm reactor by head tank by the reactor head liquid inlet, formaldehyde-sodium bisulfite (HCH (OH) SO
3Na) be a kind of biodegradable material, NaOH (NaOH) is the alkaline matter that is fit to growth of microorganism environment needs, then formaldehyde-sodium bisulfite (HCH (OH) SO
3N gets back to biofilm reactor and is generated CO by the biomembrane biochemistry degraded
2, H
2O and NaOH, CO
2Discharged by reactor head, NaOH stays in the reactor as the growth of microorganism environmental key-element, has finally strengthened the clean-up effect of biofilm reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas, eliminates secondary pollution simultaneously.
Technical scheme purification process equation:
HCHO+ biomembrane → CO
2+ H
2O
HCHO+Na
2SO
3+H
2O＝HCH(OH)SO
3Na+NaOH
HCH (OH) SO
3Na+ biomembrane → CO
2+ H
2O+NaOH
5, sample analysis: the gas phase sample is collected, is gathered by air sampler.Gas phase, liquid phase sample acetylacetone,2,4-pentanedione colorimetric method, 721 automatic digital display spectrophotometers are analyzed, test, and the test wavelength is 420mm.The computing formula B=(C1-C2) of the unit volume load B of biofilm reactor * Q/V-(C3-C4) * L/V.Be unit interval, the unit volume microorganism removal effect total to the gas, liquid pollutant, the unit volume load B of biofilm reactor is a quantitative target of weighing microbiological treatment purifying contaminated thing.Wherein: C1-exhaust gas entrance concentration mg/m
3C2-waste gas outlet concentration mg/m
3Q-exhaust gas flow m
3/ h; V-biofilm packing volume m
3C3-nutrition circulation fluid liquid outlet concentration mg/m
3C4-nutrition circulation fluid liquid inlet concentration mg/m
3L-nutrition circulation fluid fluid flow L/h.
Compare advantage and good effect that the present invention has with known technology
1, to realize the thorough purification of biofilm reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas, just must carry out purified treatment the formaldehyde that is dissolved in liquid phase.The present invention adds molar concentration in the biofilm reactor circulation fluid be that the sodium sulfite of 0.01-0.1M carries out chemisorbing purifying to the formaldehyde that enters liquid phase, finishing in biofilm reactor simultaneously, PARA FORMALDEHYDE PRILLS(91,95) waste gas carries out gas phase biodegradation purification, the operation of liquid phase chemical absorption cleaning, the purification efficiency of reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas is reached more than 90%, unit volume load＞the 20mg/L.h of reactor, the unit volume load that does not add the reactor of sodium sulfite in reactor cycles liquid has improved more than 80%.
2, the reaction of formaldehyde and sodium sulfite generates formaldehyde-sodium bisulfite (HCH (OH) SO in the circulation fluid
3Na) and NaOH (NaOH), formaldehyde-sodium bisulfite (HCH (OH) SO
3Na) be a kind of biodegradable material, NaOH (NaOH) is the alkaline matter that is fit to growth of microorganism environment needs, and circulation fluid returns in the reactor and circulates, and makes formaldehyde-sodium bisulfite (HCH (OH) SO
3N is generated CO by the biomembrane biochemistry degraded
2And H
2O, NaOH (NaOH) are as the growth of microorganism environmental key-element, and the clean-up effect of final enhanced biological membrane reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas solves the indeterminable secondary pollution problem of single chemical absorption method simultaneously.Four, description of drawings: Fig. 1 is a process chart; Fig. 2 is the unit volume load graph of a relation of formaldehyde exhaust-gas inlet concentration and biofilm reactor.
Five, the specific embodiment
The present invention implements in biofilm reactor.Contrast adds Na in circulation fluid
2SO
3Do not add Na
2SO
3The variation of the unit volume load of biofilm reactor PARA FORMALDEHYDE PRILLS(91,95).
Embodiment 1: biofilm reactor is the device that the glass tube of internal diameter φ 95mm is made, and diameter is housed in the reactor is about the haydite of 8-10mm as filler.The height overall of packing layer is 1m, is divided into two-layerly, middle is separated by filter screen, and reactor is in a gas access of bottom design and an outlet that is connected Lower tank liquid, at a gas vent of top design and an inlet that is connected head tank liquid.With concentration is 123.84-156.21mg/m
3Formaldehyde exhaust-gas is contacted with circulation fluid is reverse by the reactor spirit feeding reactor that enters the mouth mutually, and the formaldehyde exhaust-gas flow-control is at 0.1-0.4m
3/ h, circulating fluid volume is 30-40L, presses circulation fluid and Na in circulation fluid
2SO
3Volume ratio is 25: 1 adding 0.01MNa
2SO
3, circulating fluid flow rate is 13L/h, and operating temperature is 20-28 ℃, and pH is controlled between the 7.0-8.5; The result shows: circulation fluid adds 0.01M Na
2SO
3After, the unit volume load that can make the biofilm reactor PARA FORMALDEHYDE PRILLS(91,95) that the present invention adopts is by not adding 0.01M Na
2SO
3The time 4.88mg/L, h bring up to 25.3mg/L, h, the unit volume load improves 80.7%.
Embodiment 2: the reactor implementation and operation is with embodiment 1.The formaldehyde entrance concentration is 123.84-156.21mg/m3, presses circulation fluid and Na in the circulation fluid
2SO
3Volume ratio is 25: 1 adding 0.05M Na
2SO
3, the result shows: circulation fluid adds 0.05M Na
2SO
3After, the unit volume load that can make the biofilm reactor PARA FORMALDEHYDE PRILLS(91,95) that the present invention adopts is by not adding 0.05M Na
2SO
3The time 3.87mg/L, h bring up to 21.31mg/L, h, the unit volume load improves 81.8%.
Embodiment 3: the reactor implementation and operation is with embodiment 1.The formaldehyde entrance concentration is 123.84-156.21mg/m3, presses circulation fluid and Na in the circulation fluid
2SO
3Volume ratio is 25: 1 adding 0.1M Na
2SO
3, the result shows: circulation fluid adds 0.1M Na
2SO
3After, the unit volume load that can make the biofilm reactor PARA FORMALDEHYDE PRILLS(91,95) that the present invention adopts is by not adding 0.1M Na
2SO
3The time 3.98mg/L, h bring up to 23.59mg/L, h, the unit volume load improves 83.1%.
In biofilm reactor, control operation condition gas flow 0.1-0.4m3/h, fluid flow 13L/h, formaldehyde gas entrance concentration 113.38-157.24mg/m
3, gas phase sampling 0.5L/min, sampling time 5min presses circulation fluid and Na in circulation fluid
2SO
3Volume ratio is that 25: 1 ratio adds 0.01,0.05 respectively, 0.1MNa
2SO
3, add Na in the investigation circulation fluid
2SO
3Do not add Na
2SO
3Biofilm reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas unit volume load changes.The result as shown in Figure 2.
As seen from Figure 2: the formaldehyde entrance concentration is 123.84-156.21mg/m
3, circulation fluid adds 0.01M, 0.05M and 0.1M Na
2SO
3After, the unit volume load is by not adding Na
2SO
3The time 4.88mg/L, h, 3.87mg/L, h, 3.98mg/L, h bring up to 25.3mg/L, h, 21.31mg/L, h and 23.59mg/L, h, the unit volume load improves 80.7%, 81.8% and 83.1%.
Claims (4)
1. the purifying treatment method of a low concentration formaldehyde waste gas, it is characterized in that: this method realizes by following steps:
1), biofilm reactor biofilm: the haydite that diameter is housed is 8-10mm in the biofilm reactor is as filler, with concentration＜200mg/m
3Formaldehyde exhaust-gas by the reactor spirit feeding reactor that enters the mouth mutually, waste gas from bottom to top by packing layer with lead to the reactor head liquid inlet by head tank and spray strain liquid counter current contacting on the reactor filler from top to bottom, formaldehyde exhaust-gas by the reactor filler layer is got rid of by the reactor top gaseous phase outlet, the wetting whole packing layer of strain liquid, and bacterial classification is sticked on the filler, strain liquid liquid outlet at the bottom of the reactor is discharged and is entered Lower tank, it is formulated that strain liquid promptly adopts the activated sludge of city domestic sewage treatment plant to be that microorganism fungus kind adds water, the strain liquid total amount reaches and can make strain liquid as getting final product on the ceramics filling of liquid phase continuous phase circulated sprinkling in biofilm reactor, in biofilm reactor, formaldehyde exhaust-gas is that the strain liquid continuous flow upstream contacts with circulation fluid, the reactor operating temperature is a normal temperature, circulation fluid pH is controlled to be alkalescence, reactor moves continuously, when making the purification efficiency of reactor PARA FORMALDEHYDE PRILLS(91,95) waste gas be tending towards a stationary value, then biofilm is finished, 15-30 days biofilm time;
2), the formaldehyde exhaust-gas biochemical degradation purifies: the formaldehyde exhaust-gas entrance concentration that needs to purify is＜200mg/m
3Enter biofilm reactor by reactor bottom gas phase inlet, in formaldehyde exhaust-gas uphill process from bottom to top, contact and by biochemical degradation with biomembrane in the reactor, degraded purifies back generation carbon dioxide and the aqueous vapor body is discharged from the reactor top gaseous phase outlet, for keeping biomembranous growth, need provide and make its growth, wetting needs contain N salt, P salt and pH enter circulation fluid for the strain liquid of alkalescence, form new circulation fluid, operating condition is operated with biofilm, above-mentioned N salt is sodium nitrate, addition is for containing sodium nitrate 26.8g preparation by every premium on currency, P salt is sodium dihydrogen phosphate, addition is for preparing by every premium on currency phosphoric acid sodium dihydrogen 4.4g, and the amount of new circulation fluid is can make circulation fluid as getting final product on the biomembrane of liquid phase continuous phase circulated sprinkling in biofilm reactor;
3), chemisorbing purifying: the formaldehyde that is purified by the biomembrane biochemistry degraded does not enter Lower tank with circulation fluid, adds in the Lower tank circulation fluid and presses circulation fluid and Na
2SO
3Volume ratio is 25: 1, and molar concentration is that the sodium sulfite of 0.01-0.1M carries out the chemisorbing purifying reaction to this part formaldehyde, and reaction promptly generates formaldehyde-sodium bisulfite and NaOH;
4), the chemisorbing purifying product is handled: the circulation fluid that contains formaldehyde-sodium bisulfite and NaOH is got to head tank by circulating pump through Lower tank, enter biofilm reactor by head tank by the reactor head liquid inlet, formaldehyde-sodium bisulfite is got back to biofilm reactor and is generated CO by the biomembrane biochemistry degraded
2, H
2O and NaOH, CO
2Discharge by reactor head.
2. the purifying treatment method of low concentration formaldehyde waste gas according to claim 1, it is characterized in that: biofilm reactor is that the glass tube of internal diameter φ 95mm is made, the haydite that diameter is housed is 8-10mm in the reactor is as filler, the height overall of packing layer is 1m, be divided into two-layer, middle by the filter screen separation, be 123.84-156.21mg/m with concentration
3Formaldehyde exhaust-gas is contacted with circulation fluid is reverse by the reactor spirit feeding reactor that enters the mouth mutually, and the formaldehyde exhaust-gas flow-control is at 0.1-0.4m
3/ h, the circulation fluid total amount is 30-40L, presses circulation fluid and Na in circulation fluid
2SO
3Volume ratio is 25: 1 adding 0.01M Na
2SO
3, circulating fluid flow rate is 13L/h, and operating temperature is 20-28 ℃, and pH is controlled between the 7.0-8.5.
3. the purifying treatment method of low concentration formaldehyde waste gas according to claim 1, it is characterized in that: the formaldehyde entrance concentration is 123.84-156.21mg/m
3, press circulation fluid and Na in the circulation fluid
2SO
3Volume ratio is 25: 1 adding 0.05M Na
2SO
3
4. the purifying treatment method of low concentration formaldehyde waste gas according to claim 1, it is characterized in that: the formaldehyde entrance concentration is 123.84-156.21mg/m
3, press circulation fluid and Na in the circulation fluid
2SO
3Volume ratio is 25: 1 adding 0.1M Na
2SO
3
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| CN103785478B (en) * | 2014-01-11 | 2016-01-06 | 清华大学 | A kind of device and technique preparing Formaldehyde decomposition felt |
| CN105032166A (en) * | 2015-06-10 | 2015-11-11 | 常州大学 | Integrated formaldehyde waste gas treatment device |
| CN105169447A (en) * | 2015-10-09 | 2015-12-23 | 北京师范大学 | Method for removing formaldehyde in wood fiber powder |
| CN105854523B (en) * | 2016-05-20 | 2024-09-27 | 池州市金能供热有限公司 | Harmful gas treatment method and device |
| CN106310909B (en) * | 2016-11-09 | 2019-05-14 | 浙江大学宁波理工学院 | A kind of anion formaldehyde eliminating agent and preparation method thereof |
| CN110280102A (en) * | 2019-06-03 | 2019-09-27 | 衢州学院 | A kind of biofilm formaldehyde exhaust-gas biodegrading process |
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