CN104971699B - A kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing and preparation method thereof, using and methods for using them - Google Patents
A kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing and preparation method thereof, using and methods for using them Download PDFInfo
- Publication number
- CN104971699B CN104971699B CN201510445656.9A CN201510445656A CN104971699B CN 104971699 B CN104971699 B CN 104971699B CN 201510445656 A CN201510445656 A CN 201510445656A CN 104971699 B CN104971699 B CN 104971699B
- Authority
- CN
- China
- Prior art keywords
- organic matter
- complexing agent
- zeolite
- modified
- modified zeolite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000008139 complexing agent Substances 0.000 title claims abstract description 59
- 239000005416 organic matter Substances 0.000 title claims abstract description 58
- 239000010865 sewage Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010457 zeolite Substances 0.000 claims abstract description 64
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 44
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 17
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 28
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 22
- 239000011574 phosphorus Substances 0.000 abstract description 22
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000701 coagulant Substances 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 14
- 238000004065 wastewater treatment Methods 0.000 abstract description 9
- 239000000356 contaminant Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 102000002322 Egg Proteins Human genes 0.000 description 4
- 108010000912 Egg Proteins Proteins 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 210000003278 egg shell Anatomy 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 anion nitrogen class Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000011026 diafiltration Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GMTYREVWZXJPLF-AFHUBHILSA-N butorphanol D-tartrate Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O.N1([C@@H]2CC3=CC=C(C=C3[C@@]3([C@]2(CCCC3)O)CC1)O)CC1CCC1 GMTYREVWZXJPLF-AFHUBHILSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002975 chemoattractant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Modified zeolite organic matter complexing agent the invention discloses a kind of sewage synchronous denitrification dephosphorizing and preparation method thereof, using and methods for using them, belong to field of waste water treatment.Present invention cetyl trimethylammonium bromide and lanthanum chloride mixed solution are modified as modified solution to zeolite, then modified zeolite is combined in varing proportions with PAFC (PAFC) and is configured to modified zeolite organic matter complexing agent, the modified zeolite organic matter complexing agent is applied in sewage treatment plant's biochemical tail water, NH_3-N treating effect is preferable, nitrate nitrogen and total phosphorus treatment effect have very big lifting, the present invention has preparation simple, settling property is better than conventional coagulant, high treating effect, it is widely used, the advantage of nitrate nitrogen and ammonia nitrogen can simultaneously be removed, in Practical Project operation, reagent dosage can flexibly be changed and reach preferable treatment effect, the nitrogen that can synchronously go in water removal, phosphor contaminant, especially to the nitrogen of low concentration in biochemical tail water, phosphorus has good clean-up effect.
Description
Technical field
The invention belongs to field of waste water treatment, more specifically to a kind of modified zeolite of sewage synchronous denitrification dephosphorizing
Organic matter complexing agent and preparation method thereof, using and methods for using them.
Background technology
In the last few years, as China's rapid economic development and urbanization process are accelerated, the discharge capacity of municipal sewage is increasingly
Many, largely the biochemical tail water without advanced treating is entered in river and lake, and nitrogen P elements are largely gathered in making environment water, very
Extremely nitrogen P elements are exceeded in some surface water.Nitrogen phosphorus is exceeded to be to cause the key factor of body eutrophication.Needed for biology
The nutriments such as nitrogen, phosphorus largely enter water body, cause algae and other planktonic organisms to breed rapidly, and water body dissolved oxygen amount declines, fish
Class and other biological mortalities.The aquatile of mortality deposits to lakebed, is decomposed by the microorganisms, and consumes substantial amounts of dissolving
Oxygen, drastically reduces Dissolved Oxygen in Water content, and water quality deterioration, so that having influence on the existence of fish, has greatly accelerated the richness of water body
Nutrient laden process.Therefore water body denitrification dephosphorization has become a problem demanding prompt solution.
The technology commonly used in domestic sewage denitrifying-dephosphorizing advanced treating has：Coagulant sedimentation, sand filtration method, charcoal absorption
Method, ion-exchange, UF membrane etc..The technologies such as charcoal absorption, ion exchange and UF membrane are because its construction cost is high, equipment
Complicated, operating cost is high etc., and reason restricts its large-scale application, and coagulating sedimentation is ripe because of its efficiency high, processing method
Stabilization, power consumption are low, simple operation and other advantages, increasingly get more and more people's extensive concerning in actual applications.
Zeolite has larger specific surface area, there are many hole ducts inside particle, and pore volume reaches zeolite this body
Long-pending more than 50% so that it has very strong absorption property.The suction-operated of zeolite is dispersion force and electrostatic force collective effect
Result, the K in zeolite+、Na+、Ca2+、Mg2+Strong local positive electric field is formed Deng metal ion, can not only attract polarity point
The negative pole center of son, can also make some nonpolar molecules polarize, so zeolite is to polar molecule and easy pole by electrostatic induction
Chemoattractant molecule has preferential selection suction-operated.Due to the hole diameter (0.6-1.5nm) and channel diameter (0.3- of zeolite
1.0nm) it is more than NH4 +Ionic diameter (0.29nm), so zeolite can preferably adsorb the NH in waste water4 +.Natural zeolite
Exploitation is limited by zeolite content and beneficiation method, and in recent years, many scholars are devoted to the research of artificial zeolite's synthesis, and handle
Its Successful utilization is in wastewater treatment.But artificial zeolite still has many restrictions in sewage denitrification and dephosphorization, to artificial zeolite
It is modified, the performance for making it possess denitrogenation dephosphorizing, as people's research direction.
Through retrieval, China applies for a patent the A of Publication No. CN 102380343, and the applying date is in August, 2011 patent of 31 days
Application documents disclose a kind of micro-polluted water synchronous denitrification dephosphorizing modifying artificial zeolite and preparation method thereof, invention rare earth unit
Plain (billows or cerium) and flyash are modified to zeolite, after zeolite is modified, can synchronously remove the nitrogen and phosphorus pollution in sewage
Thing, the particularly ammonia nitrogen to low concentration and total nitrogen-phosphorus wastewater have good clean-up effect, but do not refer to and nitrate nitrogen is gone
Except effect.The A of Chinese patent application Publication No. CN 103539217, the applying date is the patent application text on November 06th, 2013
Part discloses the Zeolite modifying method of a kind of synchronous removal sewage cationic and anion nitrogen class and anion phosphor contaminant,
The method is used as improved chemical immersion natural zeolite powder by cetyl trimethylammonium bromide (HDTMA-Br), is placed in constant temperature and shakes
Vibration 24h in device (25 DEG C, 200r/min) is swung, is dried naturally and is obtained modified zeolite, the modified zeolite of the invention can go
Water removal cationic and anion nitrogen class and anion phosphor contaminant, but modified zeolite is to the removal effect of nitrate nitrogen
Typically, total phosphorus removal effect is not good, while also not referring to the removal effect to NITROGEN IN LOW CONCENTRATION phosphor contaminant.Chinese patent application
The A of Publication No. CN 103288164, the applying date is that the patent application document on June 25 in 2013 is disclosed and uses modified zeolite
Combine the method to sewage synchronous denitrification dephosphorizing with modified eggshell, modifying process is as follows：By MgSO4Solution mixes with zeolite, often
5mL MgSO are added in gram zeolite4Solution, lasting stirring, filters, and with distilled water diafiltration 1-5 times, be finally putting into baking after 24h
Case, 100 mesh sieves are crossed after being dried at 100 DEG C；By FeCl3Solution or AlCl3Solution mixes with discarded egg-shell meal, every gram of egg-shell meal
Middle addition 5mL FeCl3Solution or AlCl3Solution, lasting stirring, filters, and with distilled water diafiltration 1-5 times, be finally putting into after 24h
Baking oven, 100 mesh sieves are crossed after being dried at 100 DEG C；Denitrogenation dephosphorizing process is as follows：By the modified zeolite for obtaining respectively with modified eggshell
By 1:1 mixing, in the pending water sample of addition.Comprehensive institute is above-mentioned, ammonia nitrogen effect in existing natural zeolite and artificial zeolite removal water body
Fruit is fine, but not fully up to expectations to the removal effect of total phosphorus and nitrate nitrogen.Also seldom referred to modified zeolite in document simultaneously
Mix with PAFC, be applied in sewerage advanced treatment process.
The content of the invention
1. the problem to be solved
Have that dosage is big, operating cost is high for existing sewage-treating agent, to ammonia nitrogen and nitrate nitrogen treatment effect not
It is good, the problems such as treatment effect is unstable, the present invention provides a kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing
And preparation method thereof, using and methods for using them, the present invention mixes the cetyl trimethylammonium bromide and lanthanum chloride of various concentrations
Solution immersion artificial zeolite is closed, is combined in varing proportions with PAFC (PAFC) by modified zeolite, be made and change
Property zeolite organic matter complexing agent, can apply to the nitrogen and phosphorus pollution thing synchronously gone in biochemical sewage tail water processing procedure in water removal, this
It is outer also to can apply to the very low advanced treatment of wastewater of concentration of nitrogen and phosphorus, good purification.
2. technical scheme
In order to solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of preparation method of the modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing, its step is：
(1) modified solution is prepared：Prepare cetyl trimethylammonium bromide solution and matter that mass concentration is 5~40g/L
Amount fraction is 0.3~0.8% rare earth element solution；
(2) Zeolite modifying：Cetyl trimethylammonium bromide solution and rare earth element solution in step (1) is pressed into volume
Than 1:(1~2) mix, be subsequently adding zeolite, mass concentration of the zeolite in mixed solution is 0.03~0.05g/mL, in vibration
Zeolite is washed till neutrality by 20~24h of constant temperature oscillation in case, vibration after terminating, and modified zeolite is obtained after drying；
(3) modified zeolite organic matter complexing agent is prepared：The modified zeolite and PAFC that will be obtained in step (2)
In mass ratio (0.5~1):1 ratio mixing, obtains modified zeolite organic matter complexing agent.
Preferably, the rare earth element solution in the step (1) is lanthanum chloride solution.
Preferably, the zeolite in the step (2) is artificial zeolite, and fineness is 60~80 mesh.
Preferably, vibration case operating temperature is 20~25 DEG C in the step (2), and hunting speed is 100r/min；Drying
Temperature is 55 DEG C, and drying time is 2~4h.
Preferably, vibration case operating temperature is 25 DEG C in the step (2).
A kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing, is prepared into using above-mentioned preparation method
Arrive.
A kind of modified zeolite organic matter complexing agent of above-mentioned sewage synchronous denitrification dephosphorizing is in the treatment of biochemical sewage tail water
Application.
A kind of modified zeolite organic matter complexing agent of above-mentioned sewage synchronous denitrification dephosphorizing is in the treatment of biochemical sewage tail water
Application process, its step is：
A modified zeolite organic matter complexing agent that () prepares the above method is added in biochemical sewage tail water, stirring
Stood after uniform.
Preferably, the whipping process in step (a) is：30~40s is quickly first stirred with the speed of 200~400r/min,
Then 25~40min is stirred with the speed of 25~40r/min；Time of repose is 30~60min.
The coagulant to sewage synchronous denitrification dephosphorizing in the present invention is a kind of modified zeolite organic matter complexing agent, by 16
Alkyl trimethyl ammonium bromide (HDTMA-Br) is modified to zeolite, is then obtained with PAFC reaction, has coagulation concurrently
And adsorption function, after being added to water body, zeolite is core, and PAFC (PAFC) forms flco, zeolite adsorption water body nitrogen phosphorus
Pollutant is settled, and flco has settlement action, can also remove part nitrogen phosphorus, and coagulant in this process to suspension in water
Easily sedimentation.Nitrate nitrogen removal more difficult than ammonia nitrogen in sewage, is primarily due to adsorption effect of the conventional adsorbent to nitrate nitrogen
Difference, and the modified zeolite organic matter complexing agent in the present invention has good adsorption capacity to nitrate nitrogen, it is mainly modified
Zeolite is to nitrate nitrogen high adsorption capacity, and its adsorption capacity to the nitrate nitrogen in sewage when being used together with PAFC
It been significantly enhanced.Although PAFC is that one kind applies more extensive coagulant, but its in advanced treatment of wastewater
There are problems that dosage is big, operating cost is high, to ammonia nitrogen and nitrate nitrogen treatment effect not, simply add PAFC
It being difficult to solve the problems, such as denitrogenation dephosphorizing in biochemical tail water, and combining with theoretical analysis of the present invention and substantial amounts of experimental study, will pass through
The modified zeolite of specific condition is used cooperatively with PAFC, achieves extraordinary synchronous denitrification dephosphorizing effect, in addition
It is found surprisingly that in experimentation, when adding modified zeolite organic matter complexing agent treatment sewage, rationally controls mixing speed (first
30~40s is quickly stirred with the speed of 200~400r/min, 25~40min is then stirred with the speed of 25~40r/min), can
To obtain the effect got twice the result with half the effort, it is that wastewater treatment efficiency is greatly enhanced, and has saved modified zeolite organic matter complexing agent to use
Amount.
The present invention is compared with prior art, it is proposed that a kind of modified zeolite organic matter to have coagulation and adsorption function concurrently
Complexing agent is the treatment method for waste water of core.It is compared to patent (A of CN 102380343) and patent (CN 103288164
A), novel coagulant has absorption and coagulation function concurrently in the present invention, reasonably controls mixing speed (first with 200~400r/min
The quick 30~40s of stirring of speed, 25~40min is then stirred with the speed of 25~40r/min) can play adsorption function
To maximum, there is good removal effect to nitrate nitrogen in sewage.Patent (A of CN 103539217) is compared to, it is new in the present invention
Phosphor contaminant and coagulant precipitation suspension effect are superimposed to adsorb in water for type coagulant, and the removal efficiency to total phosphorus is carried significantly
Height, can almost reach the effect for removing completely, and the removal effect to nitrate nitrogen and total phosphorus in sewage disposal is shown
Write and improve.The present invention is not the simple combination of prior art, and the present invention is greatly improved on the basis of conventional absorbtion, multiple
Using modified zeolite adsorption and sedimentation in mixture, PAFC enhanced coagulation centered on modified zeolite, and in coagulant precipitation
During adsorb after zeolite can enhanced flocculation effect, and be found surprisingly that during absorption and coagulation to more difficult removal in the past
Nitrate nitrogen have preferable removal effect.It is low dense that complexing agent in the present invention is also applied in above-mentioned patent not refer to
Degree nitrogen phosphorus field of wastewater, and in practical engineering application, PAFC has removal effect well to suspension in sewage
Really, its extensive use in field of sewage especially advanced treatment of wastewater field has been widened significantly.
3. beneficial effect
Compared to prior art, beneficial effects of the present invention are：
(1) preparation method of the invention is simple, it is easy to operate, and zeolite need to only mix with modified solution, vibrate at normal temperatures
20~24 hours, without HTHP, modified solution consumption was less, with low cost, modified zeolite and PAFC
(PAFC) mixed with certain proportion, directly add mixing in water, operating process is simple；
(2) the modified zeolite organic matter complexing agent that the present invention is prepared is a kind of new coagulant, is added to water body
Afterwards, PAFC (PAFC) forms flco, and zeolite is core, adsorbed water body nitrogen and phosphorus pollutantses sedimentation, because flco is to zeolite
The net effect of catching, increase flco relative density so that coagulant formed flco be easy to sedimentation, be conducive in Practical Project
Shorten hydraulic detention time, reduce coagulative precipitation tank floor space；
(3) the preparation side of the modified zeolite organic matter complexing agent of a kind of sewage synchronous denitrification dephosphorizing provided in the present invention
Method, after zeolite vibrates 20~24h in modified solution, the modified solution for being attached to zeolite surface is rinsed to neutrality by clear water,
Modified product leaching rate is low, does not result in secondary pollution；
(4) the modified zeolite organic matter complexing agent function admirable for preparing of the present invention, in can synchronously removing sewage
Nitrogen and phosphorus pollutantses, solve single medicament (zeolite or PAFC) and add, and removal target contaminant is single, and removal effect is not good etc. asks
Topic, substantially increases NITROGEN IN LOW CONCENTRATION phosphor contaminant clearance；
(5) the modified zeolite organic matter complexing agent that the present invention is prepared, can be according to treatment in Practical Project operation
Effect flexibly changes reagent dosage, to reach good economic benefit and social benefit.
Brief description of the drawings
Fig. 1 is modified zeolite organic matter complexing agent of the invention to ammonia nitrogen removal design sketch；
Fig. 2 is modified zeolite organic matter complexing agent of the invention to total phosphorus removal effect figure；
Fig. 3 is modified zeolite organic matter complexing agent of the invention to nitrate nitrogen removal effect figure.
Specific embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
Raw material：Artificial zeolite is purchased from Nanjing Chemistry Reagent Co., Ltd., and lot number is 11060120497, artificial zeolite grain
It is 60~80 mesh to spend, white particle, a kind of hydrated sodium aluminosilicate salt of the mixed melting such as potter's clay, silica sand, sodium carbonate, insoluble
Yu Shui.Commercially available cetyl trimethylammonium bromide white powder and PAFC (PAFC).
The preparation process of modified zeolite organic matter complexing agent (novel coagulant)：
(1) by cetyl trimethylammonium bromide be configured to mass concentration respectively 5g/L, 10g/L, 20g/L, 30g/L,
40g/L solution；
(2) lanthanum chloride is configured to the earth solution that mass concentration is 0.5%；
(3) artificial zeolite of 60~80 mesh is dried into 4h in 100 DEG C；
(4) 5 conical flasks are taken, it is 5g/L, 10g/L, 20g/L, 30g/L, 40g/L to add concentration in conical flask respectively
Cetyl trimethylammonium bromide solution 100mL is then dilute to the lanthanum chloride for adding mass concentration to be 0.5% in each conical flask
Native solution 150mL, two kinds of solution are mixed, and weigh with scale 5 parts of 10g artificial zeolites, is separately added into mixed solution.At 25 DEG C
Under the conditions of, with the speed constant temperature oscillation 24h of 100r/min in constant temperature oscillation case, the artificial zeolite that will soak modified solution is used
Pure water is washed till neutrality.Then 4h is dried in 55 DEG C, is obtained by modified artificial zeolite.
(5) the above-mentioned artificial zeolite modified through various concentrations is pressed 1 with PAFC (PAFC) respectively:1 mode
Mixing, obtains the modified zeolite organic matter complexing agent (being designated as modified 1 to modified 5 successively respectively) of 5 types.
Embodiment 2
Prepare the simulation sewage containing ammonia nitrogen 8mg/L, nitrate nitrogen 14mg/L and phosphorus 1.5mg/L, to simulation sewage in add
The modified zeolite organic matter complexing agent (modified 1) prepared in embodiment 1, dosage of PAC is 200mg/L.It is first fast with mixer
Speed is sufficiently stirred for (300r/min) 30 seconds, then low rate mixing (30r/min) 25 minutes, and supernatant is taken after standing 30min.Supernatant
Liquid determines ammonia nitrogen concentration with Berthelot spectrophotometry, and nitrate is determined with thymol spectrophotometry method, uses molybdic acid
Salt light splitting Photometric Determination of Phosphorus concentration.Remaining type modified zeolite organic matter complexing agent (modified 2 prepared i.e. in embodiment 1 to
It is modified 5) also according to supernatant after method as above measure respective handling.When then individually determining only zeolite, to mould
Intend the removal effect of sewage.
As can be seen that the modified zeolite organic matter complexing agent of the preparation of embodiment 1 is to ammonia nitrogen removal effect from accompanying drawing 1~3
More stable, clearance can be stablized between 65-70%, the removal to total phosphorus, with modified zeolite organic matter complexing agent
The increase of the surfactant of modified zeolite, the removal efficiency of modified zeolite organic matter complexing agent is in reduction, but clearance is basic
On can stablize more than 90%.Modified zeolite organic matter complexing agent is larger to the clearance fluctuation ratio of nitrate nitrogen, and clearance exists
Fluctuated between 30-80%.
Embodiment 3
Certain sewage treatment plant's bio-chemical effluent is taken, its water quality index is：Ammonia nitrogen concentration is 7.56mg/L, and total phosphorus concentration is
1.12mg/L, nitrate is 10.32mg/L.
Modified 1 is prepared by the method for embodiment 1 (to be prepared when i.e. cetyl trimethylammonium bromide mass concentration is 5g/L
Modified zeolite organic matter complexing agent), weigh modified zeolite organic matter complexing agent that 200mg prepares in the beaker of 2L,
The water outlet of the 1L sewage treatment plants is added, first (300r/min) is quickly sufficiently stirred for 30 seconds with mixer, then low rate mixing
(30r/min) 25 minutes, supernatant measure is taken after standing 1h.Ammonia nitrogen removal frank can reach 70.21%, and total tp removal rate can be with
92.35% is reached, nitrate nitrogen clearance can reach 52.64%, and effluent quality reaches《Urban wastewater treatment firm pollutant emission
Standard》(GB18918-2002) one-level A standards.
Embodiment 4
Sewage treatment plant's bio-chemical effluent is taken, its water quality index is：Ammonia nitrogen concentration is 8.30mg/L, and total phosphorus concentration is
1.25mg/L, nitrate is 9.86mg/L.
Modified 3 are prepared by the method for embodiment 1 (to be prepared into when i.e. cetyl trimethylammonium bromide mass concentration is 20g/L
The modified zeolite organic matter complexing agent for arriving), modified zeolite organic matter complexing agent that 200mg prepares is weighed in the beaker of 2L
In, the water outlet of the 1L sewage treatment plants is added, first quickly it is sufficiently stirred for (300r/min) 30 seconds with mixer, then low rate mixing
(30r/min) 25 minutes, supernatant measure is taken after standing 1h.Ammonia nitrogen removal frank can reach 55.21%, and total tp removal rate can be with
95.25% is reached, nitrate nitrogen clearance can reach 40.64%, and effluent quality reaches《Urban wastewater treatment firm pollutant emission
Standard》(GB18918-2002) one-level A standards.
Embodiment 5
A certain sewage treatment plant's bio-chemical effluent is taken, its water quality index is：Ammonia nitrogen concentration is 8.78mg/L, and total phosphorus concentration is
1.03mg/L, nitrate is 8.92mg/L.
Modified 5 are prepared by the method for embodiment 1 (to be prepared into when i.e. cetyl trimethylammonium bromide mass concentration is 20g/L
The modified zeolite organic matter complexing agent for arriving), modified zeolite organic matter complexing agent that 200mg prepares is weighed in the beaker of 2L
In, the water outlet of the 1L sewage treatment plants is added, first quickly it is sufficiently stirred for (300r/min) 30 seconds with mixer, then low rate mixing
(30r/min) 25 minutes, supernatant measure is taken after standing 1h.Ammonia nitrogen removal frank can reach 52.31%, and total tp removal rate can be with
95.04% is reached, nitrate nitrogen clearance can reach 38.64%, and effluent quality reaches《Urban wastewater treatment firm pollutant emission
Standard》(GB18918-2002) one-level A standards.
Embodiment 6
The preparation process of modified zeolite organic matter complexing agent (novel coagulant)：
(1) cetyl trimethylammonium bromide is configured to mass concentration for 10g/L solution；
(2) lanthanum chloride is configured to the earth solution that mass concentration is 0.3%；
(3) artificial zeolite of 60~80 mesh is dried into 4h in 100 DEG C；
(4) it is the cetyl trimethylammonium bromide solution 100mL of 10g/L concentration to be added in conical flask, then to cone
The lanthanum chloride earth solution 200mL that mass concentration is 0.3% is added in shape bottle, two kinds of solution are mixed, weigh with scale 10g people
Zeolite is made, in addition mixed solution.Under the conditions of 20 DEG C, with the speed constant temperature oscillation 24h of 100r/min in constant temperature oscillation case,
The artificial zeolite pure water that modified solution will be soaked is washed till neutrality.Then 2h is dried in 55 DEG C, is obtained by modified
Artificial zeolite.
(5) above-mentioned modified artificial zeolite and PAFC (PAFC) are pressed 0.5:1 mode mixes, and is modified
Zeolite organic matter complexing agent (is designated as modified 6).
Certain sewage treatment plant's bio-chemical effluent is taken, its water quality index is：Ammonia nitrogen concentration is 8.50mg/L, and total phosphorus concentration is
1.32mg/L, nitrate is 8.79mg/L.
Modified zeolite organic matter complexing agent (modified the 6 of i.e. above-mentioned preparation) that 200mg prepares is weighed in the beaker of 2L
In, the water outlet of the 1L sewage treatment plants is added, first quickly it is sufficiently stirred for (200r/min) 40 seconds with mixer, then low rate mixing
(40r/min) 30 minutes, supernatant measure is taken after standing 50min.Ammonia nitrogen removal frank can reach 49.75%, total tp removal rate
92.56% can be reached, nitrate nitrogen clearance can reach 37.68%, and effluent quality reaches《Urban wastewater treatment firm pollutant
Discharge standard》(GB18918-2002) one-level A standards.
Embodiment 7
The preparation process of modified zeolite organic matter complexing agent (novel coagulant)：
(1) cetyl trimethylammonium bromide is configured to mass concentration for 30g/L solution；
(2) lanthanum chloride is configured to the earth solution that mass concentration is 0.8%；
(3) artificial zeolite of 60~80 mesh is dried into 4h in 100 DEG C；
(4) it is the cetyl trimethylammonium bromide solution 100mL of 30g/L concentration to be added in conical flask, then to cone
The lanthanum chloride earth solution 100mL that mass concentration is 0.8% is added in shape bottle, two kinds of solution are mixed, weigh with scale 10g people
Zeolite is made, in addition mixed solution.Under the conditions of 23 DEG C, with the speed constant temperature oscillation 24h of 100r/min in constant temperature oscillation case,
The artificial zeolite pure water that modified solution will be soaked is washed till neutrality.Then 3h is dried in 55 DEG C, is obtained by modified
Artificial zeolite.
(5) above-mentioned modified artificial zeolite and PAFC (PAFC) are pressed 0.8:1 mode mixes, and is modified
Zeolite organic matter complexing agent (is designated as modified 7).
Certain sewage treatment plant's bio-chemical effluent is taken, its water quality index is：Ammonia nitrogen concentration is 8.23mg/L, and total phosphorus concentration is
1.07mg/L, nitrate is 7.69mg/L.
Modified zeolite organic matter complexing agent (modified the 7 of i.e. above-mentioned preparation) that 200mg prepares is weighed in the beaker of 2L
In, the water outlet of the 1L sewage treatment plants is added, first quickly it is sufficiently stirred for (400r/min) 35 seconds with mixer, then low rate mixing
(25r/min) 40 minutes, supernatant measure is taken after standing 1h.Ammonia nitrogen removal frank can reach 51.35%, and total tp removal rate can be with
91.87% is reached, nitrate nitrogen clearance can reach 38.22%, and effluent quality reaches《Urban wastewater treatment firm pollutant emission
Standard》(GB18918-2002) one-level A standards.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. the preparation method of the modified zeolite organic matter complexing agent of a kind of sewage synchronous denitrification dephosphorizing, its step is：
(1) modified solution is prepared：Prepare cetyl trimethylammonium bromide solution and quality point that mass concentration is 5~40g/L
Number is 0.3~0.8% lanthanum chloride solution；
(2) Zeolite modifying：By the cetyl trimethylammonium bromide solution and rare earth element solution in step (1) by volume 1:
(1~2) mix, be subsequently adding zeolite, mass concentration of the zeolite in mixed solution is 0.03~0.05g/mL, in case is vibrated
Zeolite is washed till neutrality by 20~24h of constant temperature oscillation, vibration after terminating, and modified zeolite is obtained after drying；
(3) modified zeolite organic matter complexing agent is prepared：The modified zeolite that will be obtained in step (2) is with PAFC by matter
Amount is than (0.5~1):1 ratio mixing, obtains modified zeolite organic matter complexing agent.
2. the preparation side of the modified zeolite organic matter complexing agent of a kind of sewage synchronous denitrification dephosphorizing according to claim 1
Method, it is characterised in that：Zeolite in the step (2) is artificial zeolite, and fineness is 60~80 mesh.
3. the preparation side of the modified zeolite organic matter complexing agent of a kind of sewage synchronous denitrification dephosphorizing according to claim 2
Method, it is characterised in that：Vibration case operating temperature is 20~25 DEG C in the step (2), and hunting speed is 100r/min；Drying temperature
It is 55 DEG C to spend, and drying time is 2~4h.
4. the preparation side of the modified zeolite organic matter complexing agent of a kind of sewage synchronous denitrification dephosphorizing according to claim 3
Method, it is characterised in that：Vibration case operating temperature is 25 DEG C in the step (2).
5. the modified zeolite organic matter complexing agent of a kind of sewage synchronous denitrification dephosphorizing, it is characterised in that：Using described in claim 1
Preparation method prepare.
6. a kind of modified zeolite organic matter complexing agent of the sewage synchronous denitrification dephosphorizing described in claim 5 is in biochemical sewage tail water
Application in treatment.
7. a kind of modified zeolite organic matter complexing agent of the sewage synchronous denitrification dephosphorizing described in claim 5 is in biochemical sewage tail water
Application process in treatment, its step is：
A modified zeolite organic matter complexing agent that () prepares claim 1 is added in biochemical sewage tail water, is stirred
After stand.
8. a kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing according to claim 7 is in biochemical sewage
Application process in tail water treatment, it is characterised in that：Whipping process in step (a) is：First with the speed of 200~400r/min
30~40s of quick stirring, then stirs 25~40min with the speed of 25~40r/min；Time of repose is 30~60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510445656.9A CN104971699B (en) | 2015-07-27 | 2015-07-27 | A kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing and preparation method thereof, using and methods for using them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510445656.9A CN104971699B (en) | 2015-07-27 | 2015-07-27 | A kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing and preparation method thereof, using and methods for using them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104971699A CN104971699A (en) | 2015-10-14 |
| CN104971699B true CN104971699B (en) | 2017-06-09 |
Family
ID=54268991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510445656.9A Expired - Fee Related CN104971699B (en) | 2015-07-27 | 2015-07-27 | A kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing and preparation method thereof, using and methods for using them |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104971699B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082411B (en) * | 2016-07-12 | 2019-03-01 | 河南永泽环境科技有限公司 | A kind of preparation method of efficient dephosphorization compounding coagulation agent |
| CN106669598B (en) * | 2016-12-21 | 2020-04-10 | 浙江大学 | Zeolite adsorbent for removing anionic pollutants in water and preparation method thereof |
| CN108079940B (en) * | 2018-01-08 | 2019-06-14 | 哈尔滨工业大学 | It is a kind of for synchronizing the preparation method of the modified zeolite of advanced treating nitrogen phosphorus |
| CN109647348A (en) * | 2019-01-28 | 2019-04-19 | 江西理工大学 | A kind of combined modified montmorillonite adsorbent of denitration and dephosphorization and preparation method thereof |
| CN109847691A (en) * | 2019-03-22 | 2019-06-07 | 中国人民大学 | A kind of lanthanum iron modified zeolite dephosphorization adsorbent and the preparation method and application thereof |
| CN110655124A (en) * | 2019-05-24 | 2020-01-07 | 江苏省环境科学研究院 | Functional composite medicament for advanced wastewater treatment and preparation method thereof |
| CN110683596B (en) * | 2019-10-09 | 2021-01-26 | 中国科学院南京地理与湖泊研究所 | Production method for realizing phosphorus fixation capacity amplification of clay mineral |
| CN111547931B (en) * | 2019-12-05 | 2022-04-19 | 肇庆领誉环保实业有限公司 | Rapid nitrogen and phosphorus removal treatment method for sewage |
| CN111498961A (en) * | 2020-04-07 | 2020-08-07 | 浙江海逸环科院有限公司 | Composite mineral for sewage treatment |
| CN111362468A (en) * | 2020-04-14 | 2020-07-03 | 哈尔滨工业大学 | Ozone, modified zeolite and ultrafiltration membrane composite device and using method thereof |
| CN111847616B (en) * | 2020-08-03 | 2022-06-07 | 江西理工大学 | Composite modified montmorillonite for synchronously denitrifying and dephosphorizing and preparation method thereof |
| CN111871384B (en) * | 2020-08-10 | 2021-07-13 | 南京大学 | Modified carbon nano tube and preparation method and application thereof |
| CN112023873A (en) * | 2020-08-25 | 2020-12-04 | 广西桂林新大桂工环境科技中心(有限合伙) | Preparation method of heavy metal scavenging agent for sewage treatment |
| CN113398888B (en) * | 2021-07-13 | 2021-12-31 | 江苏建霖环保科技有限公司 | Composite water purifying agent and preparation method thereof |
| CN115350692A (en) * | 2022-09-19 | 2022-11-18 | 北京林业大学 | Modified geopolymer-zeolite with nitrogen and phosphorus removal functions and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7183235B2 (en) * | 2002-06-21 | 2007-02-27 | Ada Technologies, Inc. | High capacity regenerable sorbent for removing arsenic and other toxic ions from drinking water |
| CN100594975C (en) * | 2007-06-22 | 2010-03-24 | 华东理工大学 | Arsenic-removing adsorbent containing lanthanum mesic-porous molecular sieve and its production |
| CN102380343A (en) * | 2011-08-31 | 2012-03-21 | 环境保护部华南环境科学研究所 | Simultaneous nitrogen and phosphorus removal modified artificial zeolite for micro-polluted water, and preparation method thereof |
| CN103288164B (en) * | 2013-06-25 | 2015-07-01 | 南京信息工程大学 | A method for synchronous nitrogen and phosphorus removal in sewage by combining modified zeolite and modified eggshell |
| CN103539217A (en) * | 2013-11-06 | 2014-01-29 | 四川大学 | Zeolite modification method for synchronously removing cationic and anionic nitrogen and anionic phosphorus pollutants from sewage |
-
2015
- 2015-07-27 CN CN201510445656.9A patent/CN104971699B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104971699A (en) | 2015-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104971699B (en) | A kind of modified zeolite organic matter complexing agent of sewage synchronous denitrification dephosphorizing and preparation method thereof, using and methods for using them | |
| Feng et al. | Performance and mechanism of a biochar-based Ca-La composite for the adsorption of phosphate from water | |
| CN102151546B (en) | Modified zeolite as well as preparation method and application thereof | |
| CN101913675B (en) | Method for removing phosphorus in water by modifying waste egg shell | |
| CN102553533A (en) | Method for preparing composite dephosphorus adsorbent by virtue of activated carbon fiber loaded with metal | |
| CN102491729B (en) | Method for preparing zeolite water-supply sludge ceramsite for pretreating micro-polluted water | |
| CN102718295B (en) | Compound medicament for treating coking wastewater and preparation method thereof | |
| CN103288164B (en) | A method for synchronous nitrogen and phosphorus removal in sewage by combining modified zeolite and modified eggshell | |
| CN101830652B (en) | Method for preparing concrete admixture by utilizing oyster shells and applications | |
| CN103230772A (en) | Pumice-loaded nanometer zero-valent iron adsorption material as well as preparation method and application thereof | |
| CN109928510A (en) | A kind of Schwertmannite preparation method based on ZVI reduction coupling microorganism | |
| CN107758823A (en) | A kind of domestic sewage treating compound and preparation method thereof | |
| CN107649092A (en) | A kind of clay-based build adsorbent and preparation method thereof | |
| CN109879353A (en) | A kind of aquiculture waste water treatment process | |
| CN112624328B (en) | Positive-charge solid slow-release carbon source and preparation method and application thereof | |
| CN102060371B (en) | Composite material for processing sewage | |
| CN106045058B (en) | The method of photocatalysis biological adsorption agent processing landfill leachate | |
| CN105622028B (en) | A kind of compound porous sewage treating material of organic-inorganic and preparation method thereof | |
| CN115646445B (en) | Preparation method of modified biochar for selectively adsorbing nitrate | |
| CN110975837A (en) | Modified oyster shell, preparation method and application thereof | |
| CN103663703B (en) | The Worm biological filter tank filtrate preparation method of dealing with earthworm layer is made of inorganic filtrate | |
| CN106747641B (en) | Method for preparing foam liquid and porous ceramic for foam concrete by using cow dung | |
| CN102145972B (en) | Method for reducing excess sludge of aerobic unit of sewage treatment system by activated sludge process | |
| CN107915271A (en) | A kind of resident living sewage-treating agent | |
| CN108002524B (en) | Modified aeration biological filter composite filler and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170609 |