CN117985848A - Method for preparing particle carrier by utilizing steel slag and electrolytic manganese slag and application - Google Patents
Method for preparing particle carrier by utilizing steel slag and electrolytic manganese slag and application Download PDFInfo
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- CN117985848A CN117985848A CN202311760012.XA CN202311760012A CN117985848A CN 117985848 A CN117985848 A CN 117985848A CN 202311760012 A CN202311760012 A CN 202311760012A CN 117985848 A CN117985848 A CN 117985848A
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- 239000002893 slag Substances 0.000 title claims abstract description 80
- 239000011572 manganese Substances 0.000 title claims abstract description 49
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 48
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 40
- 239000010959 steel Substances 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 title claims abstract description 37
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 20
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000012876 carrier material Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000008188 pellet Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000012798 spherical particle Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000007605 air drying Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000003599 detergent Substances 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000010865 sewage Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005273 aeration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- 229920005372 Plexiglas® Polymers 0.000 claims 1
- 239000004926 polymethyl methacrylate Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 244000005700 microbiome Species 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- 239000002699 waste material Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241001453382 Nitrosomonadales Species 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 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 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- -1 nitrate (NO 3 -) ions Chemical class 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention is applicable to the technical field of anaerobic ammonia oxidation denitrification, and provides a method for preparing a particle carrier by utilizing steel slag and electrolytic manganese slag, which comprises the following steps: cleaning the massive steel slag and electrolytic manganese slag with a detergent, drying, mixing according to a certain proportion, grinding into powder by using a ball mill, and sieving to obtain powder A; weighing 5-10 g of powder A, adding a proper amount of oxalic acid for soaking and standing for a period of time; then making into pellets, and placing into a blast drying oven for air drying for 2 hours to obtain spherical particles; and placing the particles in a tube furnace or a muffle furnace, and obtaining the particle carrier material through preheating, sintering and cooling processes. The application of the spherical particle carrier material prepared by the method in denitrification in an anaerobic ammonia oxidation system is also provided. The particle carrier prepared by the invention fully utilizes the synergistic effect of Fe and Mn, improves the utilization performance of microorganisms, and strengthens the high-efficiency low-carbon denitrification effect of an Anamox process.
Description
Technical Field
The invention belongs to the technical field of anaerobic ammonia oxidation denitrification, and particularly relates to a method for preparing a particle carrier by utilizing steel slag and electrolytic manganese slag and application thereof.
Background
Water pollution due to excessive nutrient input is a serious problem worldwide. Nitrogen (N) compounds, such as those that produce ammonium (NH 4 +) and nitrate (NO 3 -) ions, are the most common water contaminants. Considering that the nitrification process adopted by sewage treatment plants (WWTPs) can effectively remove NH 4 +-N,NO3 - -N, which is the main N form in the tail water of sewage treatment plants, generally contains a higher Total N (TN) concentration. An elevated concentration of NO 3 - -N can damage the water ecosystem and pose a risk to aquatic organisms and human health. Therefore, the tail water of the sewage treatment plant needs to be further treated.
Anaerobic ammonia oxidation (Anammox) technology refers to a process in which microorganisms convert ammonia to nitrogen gas under anaerobic or anoxic environments with nitrite as an electron acceptor, as shown in the following formula (1). Compared with the traditional denitrification technology, the method has the advantages of short reaction process, low oxygen demand, low operation cost, no need of organic carbon source, low emission of greenhouse gases, low sludge yield and the like. If the method can be popularized and applied to municipal sewage with larger nitrogen pollution discharge volume, the method has important significance for the overall energy conservation and consumption reduction of the water treatment industry and the improvement of urban water environment. How to strengthen the growth metabolism of Anamox bacteria, improve denitrification efficiency and ensure long-term stable operation of the process is a research hotspot of the current Anamox process.
NH4 ++1.32NO2 -+0.066HCO3 -+0.13H+→1.02N2+0.26NO3 -+0.066CH2O0.5N0.15+2.03H2(1)
Metal-enhanced Anammox is an economical and practical measure that optimizes Anammox bacterial growth metabolism, enhances the abiotic denitrification reaction, and increases the denitrification efficiency of the system. Wherein manganese oxide is used as the oxidizing agent, changing or creating a new oxidation pathway during the nitrogen cycle. By using manganese oxide as the oxidant for NH 4 +, the thermodynamically favourable reaction of nitration can be carried out in an anaerobic reaction. In the anaerobic nitrification process, manganese can act as an electron acceptor to produce NO 3 -, which is then reduced to N 2 (as shown in formulas (2) - (3)) by either biologically mediated denitrification or chemical denitrification. However, in engineering popularization, the long-term cost of continuous dosing of chemical agents is high, and the source of manganese needs to be further optimized. Thus, there is a need to develop lower cost alternatives.
8MnO2+2NH4 ++12H+→8Mn2++2NO3 -+10H2O (2)
5Mn2++2NO3 -+4H2O→5MnO2+N2+8H+ (3)
The electrolytic manganese slag is acid leaching waste slag generated by the reaction of manganese ore and sulfuric acid in the electrolytic manganese production process. Due to the continuous reduction of the grade of manganese ores in recent years, the yield of electrolytic manganese slag is gradually increased every ton of metal manganese, and the newly increased manganese slag in China exceeds tens of millions of tons every year, and contains a large amount of soluble salts such as water-soluble manganese, ammonia nitrogen and the like, so that the application of the electrolytic manganese slag is greatly influenced. The steel slag is solid waste generated in the steelmaking process, 270-300 kg of steel slag is simultaneously generated when 1 ton of steel is produced, the annual discharge amount in China is close to 1000 ten thousand tons, and the application of the steel slag is seriously hindered due to the existence of the high-alkalinity industrial residue. The main chemical composition of the steel slag is CaO, siO 2、Al2O3、MgO、Fe2O3 and the like, the steel slag and the electrolytic manganese slag are mixed and ground, and in the grinding process, the electrolytic manganese slag can have an immobilization containing effect under the CaO and alkaline conditions to contain and fix Mn 2+ ions, as shown in formulas (4) - (5). In addition, the presence of CaO causes an increase in ambient temperature during milling, accelerates the conversion of ammonium salts to the free form and release as ammonia gas, as in formulas (6) - (7), and the presence of Fe also enhances the efficient low carbon denitrification effect of the Anammox process.
MnSO4+H2O+CaO→Mn(OH)2+CaSO4 (4)
Mn(OH)2+CO2+H2O→MnCO3+2H2O (5)
NH 4++OH-→NH3 (free) +H 2 O (6)
NH 3 (free state) +Q (thermal energy) -NH 3 (gaseous state) (7)
Based on the research results, the invention provides a carrier prepared by mixing, grinding and firing steel slag and electrolytic manganese slag according to a certain proportion, which fully utilizes the synergistic effect of Fe and Mn, improves the utilization performance of microorganisms, and strengthens the high-efficiency low-carbon denitrification effect of an Anamox process so as to overcome the defects in the current practical application.
Disclosure of Invention
The invention aims to provide a method for preparing a particle carrier by utilizing steel slag and electrolytic manganese slag and application thereof, wherein the steel slag and the electrolytic manganese slag which are easy to obtain are selected as raw materials, mixed, ground and fired according to a certain proportion to prepare the carrier, the carrier fully utilizes the synergistic effect of Fe and Mn, the utilization performance of microorganisms is improved, and the high-efficiency low-carbon denitrification effect of an Anamox process is enhanced.
The embodiment of the invention is realized in such a way that the method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag comprises the following steps:
Step 1, cleaning massive steel slag and electrolytic manganese slag with a detergent, drying, mixing according to a certain proportion, grinding into powder by using a ball mill, and sieving to obtain powder A;
Step 2, weighing 5-10 g of powder A, adding a proper amount of oxalic acid for soaking, and standing for a period of time; then making into pellets, and placing into a blast drying oven for air drying for 2 hours to obtain spherical particles;
And step 3, placing the particles in a tube furnace or a muffle furnace, and obtaining the particle carrier material through preheating, sintering and cooling processes.
According to a further technical scheme, in the obtained powder A in the step 1, the mass percentage of the powder steel slag is 40% -60%, and the mass percentage of the electrolytic manganese slag is 40% -60%.
In a further technical scheme, in the step 1, the screening mesh number of the screening is 80-200 meshes.
In the further technical scheme, in the step 2, the concentration of the oxalic acid solution is 0.01-0.05 mol/L, and the solid-liquid ratio of the powder A to the oxalic acid solution is 4-5: 1kg/L; the diameter of the prepared small ball is 3 mm-5 mm.
In the step 3, the preheating temperature is 200-400 ℃ and the preheating time is 30-60 min; the sintering temperature is 700-900 ℃ and the sintering time is 10-30 min.
Another object of the embodiment of the invention is to use the spherical particle carrier material prepared by the method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag in denitrification in an anaerobic ammonia oxidation system.
Further technical scheme, the application includes the following steps:
Setting two anaerobic SBR reactors, which are a control group and an experimental group respectively; the reactor of the control group is provided with a stirring device, a temperature control device and a water inlet peristaltic pump, the temperature is set, the water discharge ratio is controlled, the water inlet mode adopts disposable water inlet, and SBR is carried out according to the operation modes of disposable water inlet, stirring, water discharge and idling during the reaction; the sewage water stays for a certain time hydraulically, so that the starting time of each stage is designed and arranged and controlled by a time control switch; the experimental group is to add a certain mass of particulate carrier material to the reactor, the rest steps being the same as the control group.
According to a further technical scheme, the reactor is made of organic glass, and the effective volume is 3L; the reactor is also covered with tinfoil, and an aeration device which is used for meeting the requirement of the nitrification and denitrification and has adjustable air inflow is arranged in the reactor, and the air inflow is 0.2-0.8L/min.
According to a further technical scheme, the set temperature is 35+/-1 ℃; the drainage ratio is 30% -80%; the stirring speed is 50-120 r/min; the hydraulic retention time of the sewage is 11.5h.
According to a further technical scheme, the concentration of the particle carrier material added into the reactor by the experimental group is 1g/L.
The method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag and the application thereof provided by the embodiment of the invention have the following beneficial effects:
1) The electrolytic manganese slag and the steel slag are used as carriers, so that waste is changed into valuable, the thought of treating waste by waste is utilized, the negative influence of waste on the environment is reduced, multiple positive effects of resource recovery, denitrification efficiency improvement, economic benefit and the like are brought, and the sustainable waste management mode has important environmental and economic significance;
2) The prepared particle carrier not only can influence the anaerobic ammonia oxidation activity in the anaerobic ammonia oxidation process, thereby influencing the nitrogen removal efficiency and the starting to different degrees, but also can obviously change the abundance of a microbial community by changing the concentration of the particle carrier, thereby influencing the overall performance of the reaction process;
3) The manganese oxide in the prepared spherical composite carrier is used as an oxidant, a new oxidation path is changed or created in the nitrogen circulation process, and the manganese oxide is added into an anaerobic ammonia oxidation system in cooperation with the iron oxide, so that the manganese oxide is beneficial to maintaining an anaerobic environment suitable for the growth of Anamox bacteria, the nitrate yield can be reduced, and the nitrogen removal rate is further improved.
Drawings
FIG. 1 is a designed anaerobic SBR reactor;
FIG. 2 is an XRD pattern for the preparation of a particulate support;
FIG. 3 is a graph showing the effect of the particle carrier applied to anaerobic ammonium oxidation denitrification of sludge.
In the figure: 1-overflow port, 2-water inlet, 3-sampling port I, 4-sampling port II, 5-sampling port III, 6-sampling port IV, 7-sampling port V, 8-water bath inlet, 9-water bath outlet, 10-water inlet tank, 11-water inlet pump, 12-constant temperature water bath, 13-water bath layer, 14-stirrer, 15-water outlet pump, 16-water outlet tank, 17-aeration disc, 18-air flowmeter, 19-air pump.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
Example 1
The method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag provided by one embodiment of the invention comprises the following steps:
Step 1, cleaning massive steel slag and electrolytic manganese slag with a detergent, drying, mixing according to a certain proportion, grinding into powder by using a ball mill, and sieving to obtain powder A;
step 2, weighing 5g of powder A, adding a proper amount of oxalic acid for soaking, and standing for a period of time; then making into pellets, and placing into a blast drying oven for air drying for 2 hours to obtain spherical particles;
And step 3, placing the particles in a tube furnace or a muffle furnace, and obtaining the particle carrier material through preheating, sintering and cooling processes.
In the step 1, the mass percentages of the powder steel slag and the electrolytic manganese slag in the obtained powder A are 40% and 60%, respectively, and the dry heavy components in the mixed sample meet the following formula:
In step1, the number of the sieved sieve is 80 mesh.
In the step 2, the concentration of the oxalic acid solution is 0.01 mol/L, and the solid-liquid ratio of the powder A to the oxalic acid solution is 4:1kg/L.
In step 2, the diameter of the pellets obtained was 3mm.
In the step 3, the preheating temperature is 200 ℃, and the preheating time is 30min; the sintering temperature is 700 ℃ and the sintering time is 10min.
Example 2
The method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag provided by one embodiment of the invention comprises the following steps:
Step 1, cleaning massive steel slag and electrolytic manganese slag with a detergent, drying, mixing according to a certain proportion, grinding into powder by using a ball mill, and sieving to obtain powder A;
step 2, weighing 10g of powder A, adding a proper amount of oxalic acid for soaking, and standing for a period of time; then making into pellets, and placing into a blast drying oven for air drying for 2 hours to obtain spherical particles;
And step 3, placing the particles in a tube furnace or a muffle furnace, and obtaining the particle carrier material through preheating, sintering and cooling processes.
In the step 1, the mass percentages of the powder steel slag and the electrolytic manganese slag in the obtained powder A are respectively 60% and 40%, and the dry heavy components in the mixed sample meet the following formula:
in step 1, the number of the sieved sieve is 200 mesh.
In the step 2, the concentration of the oxalic acid solution is 0.05 mol/L, and the solid-liquid ratio of the powder A to the oxalic acid solution is 5:1kg/L.
In step 2, the diameter of the pellets obtained was 5mm.
In the step 3, the preheating temperature is 400 ℃ and the preheating time is 60min; the sintering temperature is 900 ℃ and the sintering time is 30min.
Example 3
The method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag provided by one embodiment of the invention comprises the following steps:
Step 1, cleaning massive steel slag and electrolytic manganese slag with a detergent, drying, mixing according to a certain proportion, grinding into powder by using a ball mill, and sieving to obtain powder A;
step 2, weighing 7.5g of powder A, adding a proper amount of oxalic acid for soaking, and standing for a period of time; then making into pellets, and placing into a blast drying oven for air drying for 2 hours to obtain spherical particles;
And step 3, placing the particles in a tube furnace or a muffle furnace, and obtaining the particle carrier material through preheating, sintering and cooling processes.
In the step 1, the mass percentages of the powder steel slag and the electrolytic manganese slag in the obtained powder A are respectively 50% and 50%, and the dry heavy components in the mixed sample meet the following formula:
in step 1, the number of the sieved sieve is 140 mesh.
In the step 2, the concentration of the oxalic acid solution is 0.03 mol/L, and the solid-liquid ratio of the powder A to the oxalic acid solution is 4.5:1kg/L.
In step 2, the diameter of the pellets obtained was 4mm.
In the step 3, the preheating temperature is 300 ℃ and the preheating time is 45min; the sintering temperature is 800 ℃ and the sintering time is 20min.
As shown in fig. 1-3, an embodiment of the present invention also provides the use of spherical particulate support materials prepared by a method for preparing particulate supports from steel slag and electrolytic manganese slag in an anaerobic ammonia oxidation system for denitrification, comprising the steps of:
Setting two anaerobic SBR reactors, which are a control group and an experimental group respectively; the reactor of the control group is provided with a stirring device, a temperature control device and a water inlet peristaltic pump, a certain temperature is set, a certain water discharge ratio is controlled, the water inlet mode adopts disposable water inlet, and SBR is carried out according to the operation modes of disposable water inlet, stirring, water discharge and idling during the reaction; the sewage water stays for a certain time hydraulically, so that the starting time of each stage is designed and arranged and controlled by a time control switch; the experimental group is to add a certain mass of particulate carrier material to the reactor, the rest steps being the same as the control group. As shown in figure 3, the ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the wastewater are obviously reduced after the prepared particle carrier is added.
Wherein, the reactor is made of organic glass, the effective volume is 3L, in order to avoid the inhibition effect of illumination on denitrification effect of anaerobic ammonia oxidizing bacteria, the outside of the reactor is covered with tinfoil, which can play roles of heat preservation and light prevention; in order to ensure the anaerobic ammoxidation reaction, an aeration device is arranged in the reactor, the air inflow is regulated to be 0.2-0.8L/min, preferably 0.5L/min, and a small amount of oxygen for partial nitration reaction is satisfied.
The stirring speed is 50-120 r/min, preferably 80r/min; setting a certain temperature to be 35+/-1 ℃; the drainage ratio is 30% -80%, preferably 50%; the hydraulic retention time of the sewage is 11.5 hours; the experimental group is to add a certain mass of particle carrier material into the reactor, and the concentration of the particle carrier material with a certain mass is 1g/L.
It should be noted that, the anaerobic SBR reactor may be in the manner shown in fig. 1, or may be in other forms, and when the manner shown in fig. 1 is adopted, a water bath layer 13 is provided on the side wall of the reactor, and a stirrer 14 for stirring the materials in the reactor is provided; the water in the water inlet tank 10 is conveyed to the water inlet 2 of the reactor by adopting the water inlet pump 11; a constant-temperature water bath 12 is arranged and connected with a water bath inlet 8 and a water bath outlet 9 of the reactor; an aeration disc 17 is arranged at the bottom of the reactor; the reactor is provided with a sampling port I3, a sampling port II 4, a sampling port III 5, a sampling port IV 6 and a sampling port V7 from top to bottom respectively; the water outlet of the reactor is also connected with a water outlet tank 16 through a water outlet pump 15; the top of the reactor is also provided with an overflow port 1; the bottom of the reactor was also connected to an air pump 19 and equipped with an air flow meter 18 for monitoring.
The embodiment of the invention provides a method for preparing a particle carrier by utilizing steel slag and electrolytic manganese slag and application thereof, and the method has the main advantages that:
1) The electrolytic manganese slag and the steel slag are used as carriers, so that waste is changed into valuable, the thought of treating waste by waste is utilized, the negative influence of waste on the environment is reduced, multiple positive effects of resource recovery, denitrification efficiency improvement, economic benefit and the like are brought, and the sustainable waste management mode has important environmental and economic significance;
2) The prepared particle carrier not only can influence the anaerobic ammonia oxidation activity in the anaerobic ammonia oxidation process, thereby influencing the nitrogen removal efficiency and the starting to different degrees, but also can obviously change the abundance of a microbial community by changing the concentration of the particle carrier, thereby influencing the overall performance of the reaction process;
3) The manganese oxide in the prepared spherical composite carrier is used as an oxidant, a new oxidation path is changed or created in the nitrogen circulation process, and the manganese oxide is added into an anaerobic ammonia oxidation system in cooperation with the iron oxide, so that the manganese oxide is beneficial to maintaining an anaerobic environment suitable for the growth of Anamox bacteria, the nitrate yield can be reduced, and the nitrogen removal rate is further improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag is characterized by comprising the following steps of:
Step 1, cleaning massive steel slag and electrolytic manganese slag with a detergent, drying, mixing according to a certain proportion, grinding into powder by using a ball mill, and sieving to obtain powder A;
Step 2, weighing 5-10 g of powder A, adding a proper amount of oxalic acid for soaking, and standing for a period of time; then making into pellets, and placing into a blast drying oven for air drying for 2 hours to obtain spherical particles;
And step 3, placing the particles in a tube furnace or a muffle furnace, and obtaining the particle carrier material through preheating, sintering and cooling processes.
2. The method for preparing the particle carrier by utilizing the steel slag and the electrolytic manganese slag according to claim 1, wherein in the step 1, the obtained powder A comprises 40-60% by mass of the powder steel slag and 40-60% by mass of the electrolytic manganese slag.
3. The method for preparing a particulate carrier using steel slag and electrolytic manganese slag as claimed in claim 1 or 2, wherein in step 1, the number of the sieves screened is 80 to 200 mesh.
4. The method for preparing a particle carrier by utilizing steel slag and electrolytic manganese slag according to claim 1, wherein in the step2, the concentration of oxalic acid solution is 0.01-0.05 mol/L, and the solid-liquid ratio of powder A to oxalic acid solution is 4-5: 1kg/L;
the diameter of the prepared small ball is 3 mm-5 mm.
5. The method for preparing a particulate carrier by using steel slag and electrolytic manganese slag as claimed in claim 1, wherein in the step 3, the preheating temperature is 200-400 ℃ and the preheating time is 30-60 min;
The sintering temperature is 700-900 ℃ and the sintering time is 10-30 min.
6. Use of the spherical particulate support material prepared by the method for preparing a particulate support from steel slag and electrolytic manganese slag as claimed in any one of claims 1 to 5 in denitrification in an anaerobic ammonia oxidation system.
7. The use according to claim 6, characterized by the steps of:
setting two anaerobic SBR reactors, which are a control group and an experimental group respectively;
The reactor of the control group is provided with a stirring device, a temperature control device and a water inlet peristaltic pump, the temperature is set, the water discharge ratio is controlled, the water inlet mode adopts disposable water inlet, and SBR is carried out according to the operation modes of disposable water inlet, stirring, water discharge and idling during the reaction;
the sewage water stays for a certain time hydraulically, so that the starting time of each stage is designed and arranged and controlled by a time control switch;
The experimental group is to add a certain mass of particulate carrier material to the reactor, the rest steps being the same as the control group.
8. The use according to claim 7, wherein the reactor is made of plexiglas and has an effective volume of 3L;
The reactor is also covered with tinfoil, and an aeration device which is used for meeting the requirement of the nitrification and denitrification and has adjustable air inflow is arranged in the reactor, and the air inflow is 0.2-0.8L/min.
9. The use according to claim 7, wherein the temperature is set at 35 ℃ ± 1 ℃;
The drainage ratio is 30% -80%;
The stirring speed is 50-120 r/min;
the hydraulic retention time of the sewage is 11.5h.
10. The use according to claim 7, wherein the concentration of particulate carrier material added to the reactor by the experimental group is 1g/L.
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