CN104150613A - Permeable reactive filler for removing nitrate organisms from underground water, system and filling method thereof - Google Patents
Permeable reactive filler for removing nitrate organisms from underground water, system and filling method thereof Download PDFInfo
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- CN104150613A CN104150613A CN201410441671.1A CN201410441671A CN104150613A CN 104150613 A CN104150613 A CN 104150613A CN 201410441671 A CN201410441671 A CN 201410441671A CN 104150613 A CN104150613 A CN 104150613A
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- buffering
- permeable reactive
- nutritive element
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000000945 filler Substances 0.000 title claims abstract description 44
- 229910002651 NO3 Inorganic materials 0.000 title abstract description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 128
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- 241000894006 Bacteria Species 0.000 claims abstract description 34
- 230000004888 barrier function Effects 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000006004 Quartz sand Substances 0.000 claims abstract description 9
- 230000000050 nutritive effect Effects 0.000 claims description 49
- 230000003139 buffering effect Effects 0.000 claims description 41
- 238000012856 packing Methods 0.000 claims description 29
- 239000003673 groundwater Substances 0.000 claims description 19
- 229960000892 attapulgite Drugs 0.000 claims description 18
- 229910052625 palygorskite Inorganic materials 0.000 claims description 18
- 239000011257 shell material Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000011398 Portland cement Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002054 inoculum Substances 0.000 claims description 7
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 244000215068 Acacia senegal Species 0.000 claims description 4
- 229920000084 Gum arabic Polymers 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 239000000205 acacia gum Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000011081 inoculation Methods 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- YKXCWZVUWWQSAV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O YKXCWZVUWWQSAV-BTVCFUMJSA-N 0.000 claims description 3
- 229920002907 Guar gum Polymers 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 239000012792 core layer Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000000665 guar gum Substances 0.000 claims description 3
- 235000010417 guar gum Nutrition 0.000 claims description 3
- 229960002154 guar gum Drugs 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 244000005700 microbiome Species 0.000 abstract description 4
- 239000006174 pH buffer Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 235000015097 nutrients Nutrition 0.000 abstract 2
- 238000005067 remediation Methods 0.000 abstract 2
- 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 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011824 nuclear material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003895 groundwater pollution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
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- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a permeable reactive filler for removing nitrate organisms from underground water, a system and a filling method thereof, and belongs to the field of underground water pollution remediation. The filler for the permeable reactive barrier system is formed by the mixture of biological slow release carbon source materials, pH buffer nutrient element materials and bacteria enrichment water treatment fillers, the process inlet and outlet areas of the permeable reactive barrier system are filled with water treatment filters, a process reaction area is filled with the mixture of quartz sand or basalt and fillers, and the bacteria enrichment water treatment fillers inoculated with acclimatized native denitrifying bacteria. According to the invention, slow release carbon source materials, slow release pH nutrient element materials and water treatment fillers can be flexibly added, and the shortcomings that the carbon source materials are inoculated with hang membrane materials and native microorganisms in the remediation area are insufficient are avoided. The water treatment filters in the water outlet area are capable of preventing secondary pollution.
Description
Technical field
The invention belongs to groundwater pollution and repair field, more particularly, relate to a kind of permeable reactive barrier packing material, system and fill method thereof for groundwater azotate biological eliminating.
Background technology
Underground water recovery technique is a hot issue of present environmental area research.A large amount of research has been carried out to the reparation of groundwater pollution in countries in the world especially American-European countries, extracting processing out is to apply the most general technology, the method can be limited in zone of pollution out well upstream effectively, but there are many defects as a kind of long-term Groundwater Treatment Methods in it, as further diffusion that can only limit pollution, can not repair on the spot at scene, and processing costs costliness, also may cause the waste of groundwater resource simultaneously, destroy local original ecotope, problem is repaired in the pollution that can not fundamentally solve underground water.
Permeable reactive barrier (PRB) is at present in the emerging method for original position removal underground water and soil pollution components of many developed countries such as America and Europe.The advantage such as PRB technology has can in-situ treatment multiple pollutant, treatment effect is good, installation is convenient, running cost is low, the selection of active material is the whether good key of subsurface infiltration wall repairing effect.At present, PRB technology is removed pollutent mechanism and is comprised biological and abiotic two kinds, biological process has become groundwater azotate original position and has repaired one of most economical effective means, and research is widely used, wherein heterotrophic denitrification method has effective for removing nitrate, the advantages such as operation and maintenance cost is low, but in practice, also exist some problems, in underground reservoir, organic carbon source and denitrifying bacteria are all less, denitrification is fainter, need to supplement enough carbon sources and be conducive to trace element, basicity and the microbe carrier that denitrifying bacteria is grown.Chinese Patent Application No. 201210265071.5 discloses permeable reactive barrier packing material of removing in nitrate and preparation method thereof, packing material in this patent is pretreated iron powder, gac and coarse sand, in this packing material, do not add pH buffer reagent and nutritive element, original inhabitants' denitrifying bacteria disappearance nutritive element causes denitrification faint, water treatment poor effect, China Patent No. 201210022650.7 discloses biological permeable reactive barrier filled with medium and preparation method that original position is repaired underground water, the carrier of this filled with medium using polyvinyl alcohol as embedded immobilization dominant degradation bacteria, linking agent using phosphoric acid salt as polyvinyl alcohol gel, additive using turfy soil as phosphorylation polyvinyl alcohol, the dominant degradation bacteria embedding of target contaminant is fixed therein, avoid the loss of dominant degradation bacteria, improve its impact resistance, but the permeable reactive barrier in this patent is not considered the rising (microorganism alienation reduction or carbon source self release) of water outlet ammonia nitrogen and colourity, although nitrate concentration reduces, but ammonia nitrogen and colourity further raise on the contrary, cause secondary pollution.
At present, in permeable reactive barrier fill process, mainly there are the following problems, and (1) cannot adjust the addition of pH buffer reagent and nutritive element according to actual needs flexibly; (2) carbon source material is microbial inoculant and biofilm material simultaneously, and the blocked up meeting of operation long period artifact film causes material surface to stop up, and affects pollutant removal; (3) between PRB fill process district material, porosity is large, and steadiness is poor, causes preferential flow, affects removal effect; (4) rising (microorganism alienation reduction or carbon source self release) of ammonia nitrogen and colourity is not considered in the water outlet of PRB fill process, cause secondary pollution etc., therefore a kind of water treatment of urgent need research and development is effective, environmental protection and economy can long playing permeable reactive barrier fill process.
Summary of the invention
1. the problem that will solve
For the denitrifying bacteria carbon source deficiency existing in existing permeable reactive barrier fill process, denitrification is faint, there is preferential flow and secondary pollution problems, the invention provides a kind of permeable reactive barrier packing material for groundwater azotate biological eliminating, system and fill method thereof, can add flexibly biological slow-released carbon source material, pH buffering nutritive element material and water treatment filler, can also carry out the process combination of 3 kinds of material different ratioss, having avoided carbon source material is also the drawback of inoculation membrane formation material and restoring area indigenous microorganism deficiency, outlet area water treatment filter material can adsorb ammonia nitrogen and macromole colour developing organism, prevent secondary pollution.
2. technical scheme
In order to address the above problem, the technical solution adopted in the present invention is as follows:
A kind of permeable reactive barrier packing material for groundwater azotate biological eliminating, mix and form by biological slow-released carbon source material, pH buffering nutritive element material and enriching floras water treatment filler, the mass percent of each component is respectively: biological slow-released carbon source material 75～85%, pH buffering nutritive element material 5～15%, enriching floras water treatment filler 5～15%, described biological slow-released carbon source material is the material that carbon iron microbattery slowly-releasing carbon source filler preparation method given in Nanjing University's national inventing patent application 201310727268.0 prepares.
Preferably, described pH buffering nutritive element material is made up of kernel and shell, and the composition of kernel and mass percent are:
The composition of shell and mass percent are:
Ordinary Portland cement 25～30%
Attapulgite 55～65%
Diatomite 5～15%
Described nutritive element is CuSO
45H
2o, CaCl
22H
2o, FeSO
47H
2o, ZnSO47H
2o, MnCl
24H
2o, (NH
4) 6Mo
7o
244H
2two or more arbitrary combination in O; Described tackiness agent is a kind of or two kinds of mixing arbitrarily in sodium alginate, gum arabic, guar gum.
Preferably, described pH adjusting agent is two or more arbitrary combination in citric acid, acetic acid, glucose sodium saccharate, Sodium Pyrosulfite, Sodium phosphate dibasic, sodium hydroxide.
Preferably, described enriching floras water treatment filler is the arbitrary combination of one or any two kinds in porous spherical filler, biological ceramic particle, Pall ring and cascade ring, and its particle diameter is 4～5mm, and on filler, inoculation has denitrifying bacteria.
Preferably, described denitrifying bacteria is the indigenous denitrifying bacteria that needs restoring area through separating-purifying.
The preparation method of above-mentioned pH buffering nutritive element material, its preparation process is as follows:
(1) diatomite and quartz sand powder are broken to 40～60 orders;
(2) by nutritive element, pH adjusting agent, attapulgite and tackiness agent powdery raw material according to above-mentioned ratio blending and mixing, progressively drop in tablets press, after starting tablets press, repeatedly spray water on a small quantity, make powder raw material roll into particulate state, obtain the slowly-releasing kernel taking pH buffering nutritive element as core layer;
(3) by the slowly-releasing kernel natural air drying 1～3 day obtaining in step (2) or with baking oven 30～35 DEG C of oven dry, until the granule strength of slowly-releasing kernel reaches 30～45N/, obtain the kernel of pH buffering nutritive element material;
(4) shell material ordinary Portland cement, attapulgite and diatomite are fully mixed in above-mentioned ratio;
(5) kernel of pH buffering nutritive element material step (3) being obtained is inserted in tablets press, add mixed shell material in step (4), interpolation waterside, limit rolling granulation simultaneously, kernel outside surface at pH buffering nutritive element material forms shell, the thickness of controlling shell is 1～1.5mm, obtains pH buffering nutritive element material;
(6) the pH buffering nutritive element material obtaining in step (5) is positioned over to air-dry 3～7 days of shady and cool place.
For a permeable reactive barrier system for groundwater azotate biological eliminating, described permeable reactive barrier system is divided into 3 regions by water (flow) direction, is followed successively by technique inhalant region, technological reaction district and Process for Effluent district.
The fill method of above-mentioned a kind of permeable reactive barrier system for groundwater azotate biological eliminating, water treatment filter material is filled to by technique inhalant region and Process for Effluent district, and above-mentioned packing material and quartz sand or basalt by volume 5:5 successively evenly mix and are filled in technological reaction district to 7:3.
Preferably, described water treatment filter material is a kind of or two kinds of arbitrary combination in amargosite, Fuller's earth, natural zeolite filtrate, sepiolite, volcanics filtrate, ANTHRACITE FILTER MEDIA, coke filtrate, and its particle diameter is 4～5mm.
Preferably, on technological reaction district packing material enriching floras water treatment filler, inoculate denitrifying bacteria, in technological reaction district water, denitrifying bacteria inoculum density is 10
5～10
8individual/ml.
3. beneficial effect
Than prior art, beneficial effect of the present invention is:
(1) the permeable reactive barrier system in the present invention can be simultaneously for the biological nitrate processing of original position or dystopy, can add flexibly slow-release carbon source material, pH buffering nutritive element material and water treatment filler, 4 kinds of different kind of material of water treatment filter material according to different periods and effluent quality simultaneously, be easy to control, avoided in the past carbon source material, pH adjusting agent and nutritive element in material to mix the pattern being fixed in a kind of material;
(2) slow-release carbon source material in the present invention is made by agricultural wastes, has reached the object of the treatment of wastes with processes of wastes against one another;
(3) quartz sand or basalt are filled by the technological reaction district in the present invention, avoid reaction zone material part because preferential flow and steadiness that porosity causes are greatly poor;
(4) water treatment filler in the present invention, as biofilm carrier, reacts blocked up the resulting in blockage of microbial film that in wall, carbon source material covers before having avoided, and is more conducive to microbial inoculant, growth and enrichment;
(5) technique in the present invention plays absorption ammonia nitrogen and macromole colour developing organism into and out of pool water treatment filter material, has reduced effluent color dilution and turbidity, prevents the effect such as underground water bidirectional flow and packed bed filtrate Float upward function.
Brief description of the drawings
Fig. 1 is PRB fill process schematic diagram;
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
A kind of permeable reactive barrier packing material for groundwater azotate biological eliminating, mix and form by biological slow-released carbon source material, pH buffering nutritive element material and enriching floras water treatment filler, the mass percent of each component is respectively: biological slow-released carbon source material 75%, pH buffering nutritive element material 15%, enriching floras water treatment filler 10%, wherein, biological slow-released carbon source material prepares according to the embodiment 1 in the given carbon iron microbattery slowly-releasing carbon source filler preparation method of Nanjing University's national inventing patent application 201310727268.0; Inner nuclear material composition and the mass percent of pH buffering nutritive element material are: CuSO
45H
2o 15%, CaCl
22H
2o 10%, citric acid 25%, attapulgite 40%, sodium alginate 10%, sheating material composition and mass percent are: ordinary Portland cement 25%, attapulgite 60%, diatomite 15%; Enriching floras water treatment filler is porous spherical filler, particle diameter 4～5mm, inoculate indigenous denitrifying bacteria above, the inoculation of denitrifying bacteria and domestication process are: enriching floras water treatment filler and denitrifying bacteria liquid (the indigenous denitrifying bacteria of restoring area is through separating-purifying) are mixed, water inlet nitrate concentration is 20～25mg/L, water inlet pH value is 7.0, add maize straw (being crushed to fibrous), denitrifying bacteria is tamed 3 weeks to the enriching floras filler that obtains having tamed and bacterium liquid.
The preparation process of pH buffering nutritive element material is as follows:
(1) diatomite and quartz sand powder are broken to 40～60 orders;
(2) by CuSO
45H
2o, CaCl
22H
2o, pH adjusting agent, attapulgite and tackiness agent powdery raw material are according to above-mentioned ratio blending and mixing, progressively drop in tablets press, after startup tablets press, repeatedly spray water on a small quantity (powder material can progressively ball up), roll into particulate state, nuclear raw material while repeatedly add water on a small quantity in dropping into subsequently, particle surface is formed thick, so that the interior nuclear raw material of follow-up interpolation is easily adsorbed on the particle surface of moulding, observe the granulating situation of granulation disc, if also have the not powder raw material of bonding, continue to add water, so that powder raw material all bonding gets on, particle diameter to 0.3～0.5mm, obtain the slowly-releasing kernel taking pH buffering nutritive element as core layer,
(3), by the slowly-releasing kernel natural air drying obtaining in step (2) 2 days, until the granule strength of slowly-releasing kernel reaches 30～45N/, obtain the kernel of pH buffering nutritive element material;
(4) shell material ordinary Portland cement, attapulgite and diatomite are fully mixed in above-mentioned ratio;
(5) kernel of pH buffering nutritive element material step (3) being obtained is inserted in tablets press, add mixed shell material in step (4), interpolation waterside, limit rolling granulation simultaneously (granulation process is the same), kernel outside surface at pH buffering nutritive element material forms shell, the thickness of controlling shell is 1～1.5mm, obtains pH buffering nutritive element material;
(6) the pH buffering nutritive element material obtaining in step (5) is positioned over to air-dry 3～7 days of shady and cool place.
PRB fill process schematic diagram as shown in Figure 1, technological reaction section length is 35cm (along water (flow) direction), wide is 5cm (Transverse to the flow direction), react into, exhalant region length is 5cm (along water (flow) direction), width is 5cm (Transverse to the flow direction), wherein, by react into, amargosite is all filled in exhalant region, by above-mentioned biological slow-released carbon source material, the packing material that pH buffering nutritive element material and enriching floras water treatment filler mix composition and quartz sand by volume 7:3 successively evenly mix and are filled in technological reaction district, in technological reaction district water, denitrifying bacteria inoculum density is 10
5individual/mL.
Adopt above-mentioned permeable reactive barrier system packing material and fill process to process the nitrate in underground water, water inlet is the water body of azotate pollution, the concentration of nitrate nitrogen is 25～40mg/L, after moving 3 months, the degradation rate of nitrate nitrogen can reach 61.12%～66.45%, and the dissolved oxygen concentration in former water is reduced to 0.02～0.28mg/L left and right by 0.5～1.0mg/L; Regulating pH value is 7.0～7.8 (pH while only adding carbon source material is 9.70～10.02).
Embodiment 2
With embodiment 1, difference is: pH buffering nutritive element material 10%, and enriching floras water treatment filler is porous ball-shaped filling material, mass percent is 15%; Biological slow-released carbon source material prepares according to the embodiment 2 in the given carbon iron microbattery slowly-releasing carbon source filler preparation method of Nanjing University's national inventing patent application 201310727268.0; Inner nuclear material composition and the mass percent of pH buffering nutritive element material are: FeSO
47H
2o 15%, ZnSO
47H
2o 15%, acetic acid 30%, attapulgite 30%, gum arabic 10%, sheating material composition and mass percent are: ordinary Portland cement 28%, attapulgite 60%, diatomite 12%; In denitrifying bacteria domestication process, water inlet nitrate concentration is 25～30mg/L; Reaction is all filled to Fuller's earth into and out of pool, packing material is filled in technological reaction district for 6:4 successively evenly mixes by volume with quartz sand; In technological reaction district water, denitrifying bacteria inoculum density is 10
8individual/mL.Technological reaction section length is 50cm (along water (flow) direction), and wide is 13cm (Transverse to the flow direction), and reaction is 8cm (along water (flow) direction) into and out of pool filtrate length, and width is 13cm (Transverse to the flow direction).
Adopt above-mentioned permeable reactive barrier system packing material and fill process to process the nitrate in underground water, water inlet is the water body of azotate pollution, the concentration of nitrate nitrogen is 40～60mg/L, after moving 3 months, the degradation rate of nitrate nitrogen can reach 63.26%～75.42%, and the dissolved oxygen concentration in former water is reduced to 0.02～0.28mg/L left and right by 0.5～1.0mg/L; Regulating pH value is 7.0～7.8 (pH while only adding carbon source material is 9.70～10.02).
Embodiment 3
With embodiment 1, difference is, biological slow-released carbon source material 80%, and pH buffering nutritive element material 5%, enriching floras water treatment filler is Pall ring, mass percent is 15%; Biological slow-released carbon source material prepares according to the embodiment 3 in the given carbon iron microbattery slowly-releasing carbon source filler preparation method of Nanjing University's national inventing patent application 201310727268.0; Inner nuclear material composition and the mass percent of pH buffering nutritive element material are: MnCl
24H
2o 20%, ZnSO47H
2o 15%, Sunmorl N 60S 30%, attapulgite 30%, guar gum 5%, sheating material composition and mass percent are: ordinary Portland cement 30%, attapulgite 65%, diatomite 5%; In denitrifying bacteria domestication process, water inlet nitrate concentration is 30～40mg/L; To react the equal filled natural zeolite filler into and out of pool, packing material will be filled in technological reaction district for 5:5 successively evenly mixes by volume with basalt; In technological reaction district water, denitrifying bacteria inoculum density is 10
7individual/mL.Technological reaction section length is 70cm (along water (flow) direction), and wide is 17cm (Transverse to the flow direction), and reaction is 8cm (along water (flow) direction) into and out of pool filtrate length, and width is 17cm (Transverse to the flow direction).
Adopt above-mentioned permeable reactive barrier system packing material and fill process to process the nitrate in underground water, water inlet is the water body of azotate pollution, the concentration of nitrate nitrogen is 60～80mg/L, after moving 3 months, the degradation rate of nitrate nitrogen can reach 70.18%～79.67%, and the dissolved oxygen concentration in former water is reduced to 0.02～0.28mg/L left and right by 0.5～1.0mg/L; Regulating pH value is 7.0～7.8 (pH while only adding carbon source material is 9.70～10.02).
Embodiment 4
With embodiment 1, difference is, biological slow-released carbon source material 85%, and pH buffering nutritive element material 10%, enriching floras water treatment filler is cascade ring, mass percent is 5%; Biological slow-released carbon source material prepares according to the embodiment 4 in the given carbon iron microbattery slowly-releasing carbon source filler preparation method of Nanjing University's national inventing patent application 201310727268.0; Inner nuclear material composition and the mass percent of pH buffering nutritive element material are: MnCl
24H
2o 13%, ZnSO47H
2o 14%, SODIUM PHOSPHATE, MONOBASIC 25%, attapulgite 38%, sodium alginate 10%, sheating material composition and mass percent are: ordinary Portland cement 30%, attapulgite 55%, diatomite 15%; In denitrifying bacteria domestication process, water inlet nitrate concentration is 40～55mg/L; Reaction is all filled to hard coal into and out of pool, packing material is filled in technological reaction district for 5:5 successively evenly mixes by volume with basalt; Technological reaction section length is 100cm (along water (flow) direction), wide is 25cm (Transverse to the flow direction), reaction is 15cm (along water (flow) direction) into and out of pool filtrate length, and width is 25cm (Transverse to the flow direction).
Adopt above-mentioned permeable reactive barrier system packing material and fill process to process the nitrate in underground water, water inlet is the water body of azotate pollution, the concentration of nitrate nitrogen is 80～100mg/L, after moving 3 months, the degradation rate of nitrate nitrogen can reach 74.55%～82.64%, and the dissolved oxygen concentration in former water is reduced to 0.02～0.28mg/L left and right by 0.5～1.0mg/L; Regulating pH value is 7.0～7.8 (pH while only adding carbon source material is 9.70～10.02).
Embodiment 5
With embodiment 1, difference is: pH buffering nutritive element material 10%, and enriching floras water treatment filler is biological ceramic particle, mass percent is 15%; Biological slow-released carbon source material prepares according to the embodiment 2 in the given carbon iron microbattery slowly-releasing carbon source filler preparation method of Nanjing University's national inventing patent application 201310727268.0; Inner nuclear material composition and the mass percent of pH buffering nutritive element material are: (NH
4)
6mo
7o
244H
2o 33%, Sodium Pyrosulfite 30%, attapulgite 30%, gum arabic 7%, sheating material composition and mass percent are: ordinary Portland cement 30%, attapulgite 55%, diatomite 15%; In denitrifying bacteria domestication process, water inlet nitrate concentration is 40～55mg/L; Reaction is all filled to sepiolite into and out of pool, packing material is filled in technological reaction district for 5:5 successively evenly mixes by volume with basalt; Technological reaction section length is 100cm (along water (flow) direction), wide is 25cm (Transverse to the flow direction), reaction is 15cm (along water (flow) direction) into and out of pool filtrate length, and width is 25cm (Transverse to the flow direction).
Adopt above-mentioned permeable reactive barrier system packing material and fill process to process the nitrate in underground water, water inlet is the water body of azotate pollution, the concentration of nitrate nitrogen is 80～100mg/L, after moving 3 months, the degradation rate of nitrate nitrogen can reach 70.55%～94.08, and the dissolved oxygen concentration in former water is reduced to 0.01～0.22mg/L left and right by 0.5～1.0mg/L; Regulating pH value is 7.0～7.8 (pH while only adding carbon source material is 9.70～10.02).
Enriching floras water treatment filler of the present invention is selected the arbitrary combination of one or any two kinds in porous spherical filler, biological ceramic particle, Pall ring and cascade ring, and its particle diameter is 4～5mm; Principle communicates, as long as can inoculate denitrifying bacteria on filler, their arbitrary combination all can, those of ordinary skill in the art are according to embodiments of the invention and in conjunction with this area general knowledge, also can infer them arbitrary combination all can, so present specification is not repeating.Two or more arbitrary combination in pH adjusting agent optimization citric acid in the present invention, acetic acid, glucose sodium saccharate, Sodium Pyrosulfite, Sodium phosphate dibasic, sodium hydroxide, these several materials do not have negative effect to other materials in packing material, principle communicates, as long as can regulate pH, their arbitrary combination all can, those of ordinary skill in the art are according to embodiments of the invention and in conjunction with this area general knowledge, also can infer them arbitrary combination all can, so present specification is not repeating.
Claims (10)
1. the permeable reactive barrier packing material for groundwater azotate biological eliminating, it is characterized in that: described packing material is by biological slow-released carbon source material, pH buffering nutritive element material and enriching floras water treatment filler mix composition, the mass percent of each component is respectively: biological slow-released carbon source material 75～85%, pH buffering nutritive element material 5～15%, enriching floras water treatment filler 5～15%, described biological slow-released carbon source material is the material that carbon iron microbattery slowly-releasing carbon source filler preparation method given in Nanjing University's national inventing patent application 201310727268.0 prepares.
2. a kind of permeable reactive barrier packing material for groundwater azotate biological eliminating according to claim 1, is characterized in that: described pH buffering nutritive element material is made up of kernel and shell, and the composition of kernel and mass percent are:
The composition of shell and mass percent are:
Ordinary Portland cement 25～30%
Attapulgite 55～65%
Diatomite 5～15%
Described nutritive element is CuSO
45H
2o, CaCl
22H
2o, FeSO
47H
2o, ZnSO47H
2o, MnCl
24H
2o, (NH
4) 6Mo
7o
244H
2two or more arbitrary combination in O; Described tackiness agent is a kind of or two kinds of mixing arbitrarily in sodium alginate, gum arabic, guar gum.
3. a kind of permeable reactive barrier packing material for groundwater azotate biological eliminating according to claim 2, is characterized in that: described pH adjusting agent is two or more arbitrary combination in citric acid, acetic acid, glucose sodium saccharate, Sodium Pyrosulfite, Sodium phosphate dibasic, sodium hydroxide.
4. a kind of permeable reactive barrier packing material for groundwater azotate biological eliminating according to claim 1, it is characterized in that: described enriching floras water treatment filler is the arbitrary combination of one or any two kinds in porous spherical filler, biological ceramic particle, Pall ring and cascade ring, its particle diameter is 4～5mm, and on filler, inoculation has denitrifying bacteria.
5. a kind of permeable reactive barrier packing material for groundwater azotate biological eliminating according to claim 4, is characterized in that: described denitrifying bacteria is the indigenous denitrifying bacteria that needs restoring area through separating-purifying.
6. the preparation method of pH buffering nutritive element material claimed in claim 1, its preparation process is as follows:
(1) diatomite and quartz sand powder are broken to 40～60 orders;
(2) by nutritive element, pH adjusting agent, attapulgite and tackiness agent powdery raw material according to the ratio blending and mixing described in claim 2, progressively drop in tablets press, after starting tablets press, repeatedly spray water on a small quantity, make powder raw material roll into particulate state, obtain the slowly-releasing kernel taking pH buffering nutritive element as core layer;
(3) by the slowly-releasing kernel natural air drying 1～3 day obtaining in step (2) or with baking oven 30～35 DEG C of oven dry, until the granule strength of slowly-releasing kernel reaches 30～45N/, obtain the kernel of pH buffering nutritive element material;
(4) shell material ordinary Portland cement, attapulgite and diatomite are fully mixed in the ratio in claim 2;
(5) kernel of pH buffering nutritive element material step (3) being obtained is inserted in tablets press, add mixed shell material in step (4), interpolation waterside, limit rolling granulation simultaneously, kernel outside surface at pH buffering nutritive element material forms shell, the thickness of controlling shell is 1～1.5mm, obtains pH buffering nutritive element material;
(6) the pH buffering nutritive element material obtaining in step (5) is positioned over to air-dry 3～7 days of shady and cool place.
7. for a permeable reactive barrier system for groundwater azotate biological eliminating, it is characterized in that: described permeable reactive barrier system is divided into 3 regions by water (flow) direction, be followed successively by technique inhalant region, technological reaction district and Process for Effluent district.
8. according to the fill method of a kind of permeable reactive barrier system for groundwater azotate biological eliminating in claim 7, it is characterized in that: water treatment filter material is filled to by technique inhalant region and Process for Effluent district, and the packing material in claim 1 and quartz sand or basalt by volume 5:5 successively evenly mix and are filled in technological reaction district to 7:3.
9. the fill method of a kind of permeable reactive barrier system for groundwater azotate biological eliminating according to claim 8, it is characterized in that: described water treatment filter material is a kind of or two kinds of arbitrary combination in amargosite, Fuller's earth, natural zeolite filtrate, sepiolite, volcanics filtrate, ANTHRACITE FILTER MEDIA, coke filtrate, and its particle diameter is 4～5mm.
10. the fill method of a kind of permeable reactive barrier system for groundwater azotate biological eliminating according to claim 8, it is characterized in that: on technological reaction district packing material enriching floras water treatment filler, inoculate denitrifying bacteria, in technological reaction district water, denitrifying bacteria inoculum density is 10
5～10
8individual/ml.
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