CN102107930B - Underground water nitrogen-fixation remediation filtering material and preparation method thereof - Google Patents
Underground water nitrogen-fixation remediation filtering material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 238000005341 cation exchange Methods 0.000 claims abstract description 12
- 150000001767 cationic compounds Chemical group 0.000 claims abstract description 12
- 229910001412 inorganic anion Inorganic materials 0.000 claims abstract description 12
- 229910001411 inorganic cation Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005349 anion exchange Methods 0.000 claims abstract description 10
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- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 7
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 7
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
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- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005096 rolling process Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 6
- 238000002156 mixing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003673 groundwater Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000010534 mechanism of action Effects 0.000 description 3
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- 206010020852 Hypertonia Diseases 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 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 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 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
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- -1 haydite Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses an underground water nitrogen-fixation remediation filtering material and a preparation method thereof, belonging to the field of underground water remediation. The filtering material is prepared from the following components in percentage by weight: 10-50% of plastic binding mineral, 1-10% of permeable substrate and 40-80% of inorganic cation exchange substrate or inorganic anion exchange substrate. The preparation method comprises the following steps: preparing raw materials according to the percentage by weight, and pulverizing the plastic binding mineral and the inorganic cation exchange substrate or inorganic anion exchange substrate to 200 meshes for later use; pulverizing the permeable substrate to 50 meshes for later use; thoroughly mixing the pulverized raw materials, granulating, and rolling to obtain balls; and calcining the obtained ball-shaped filtering material. The remediation filtering material can be combined with other biological curing materials, and has the technical advantages of low water resistance coefficient, almost no short stream or circle stream, and the like.
Description
Technical field
What the present invention relates to is a kind of filtrate of repairing for the underground water original position and preparation method thereof, says more specifically a kind of underground water nitrogen-fixation remediation filtering material and preparation method thereof.
Background technology
The principal mode of inorganic nitrogen is ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in the underground water.The former is positively charged ion, and both are negatively charged ion afterwards, quantitatively take ammonia nitrogen as main.It is biologic treating technique and materialization treatment technology that the underground water inorganic nitrogen pollutes the removal technical point.So-called original position reparation utilizes biological treatment or materialization treatment technology method exactly, need not underground water is extracted out, reaches the purpose of removing groundwater pollutant in original position.
Since the seventies in last century, the multiple based technique for in-situ remediation such as aeration and underground water aeration in permeable reactive barrier, the well has appearred in Organic Contamination of Groundwater control and reparation.The earliest original position is repaired Documentary Records [the Raymond R.L. that appears at 1975, Jamison V.M. and Hudson J.O. 1975, Final Report on Beneficial of Bacterial Activity in Groundwater Containing Petroleum Products, Committee on Environmental Affairs, American Petroleum Institute, Washington, D.C.] processing of gasoline being revealed, by injecting air and nutritive ingredient the oleaginousness of underground water is reduced, and obtained thus patent [Raymond, U.S. Patent 4588506].Formed comparatively complete technology in the original position reparation eighties in unsaturated soil underground water reparation field subsequently.After entering the nineties, along with the breakthrough of day by day serious and every technology of groundwater pollution, the biology in situ recovery technique begins to increase gradually on using.
What the underground water based technique for in-situ remediation generally used at present is biologic treating technique, and research contents comprises microbial population screening, nutrition and electron donor (oxygen and organic carbon) conveying etc., seldom sees the research about filtrate.PRB(Permeable Reactive Barrier, permeable reactive barrier) technology also belongs to one of underground water in-situ treatment, filling material commonly used comprises Zero-valent Iron, gac and zeolite etc., and its mechanism of action is respectively provides electron acceptor(EA), absorption and ion-exchange.The used every kind of filling material of PRB generally is independent use in certain concrete reparation well, has no to mix the precedent of using.Problem in practice is that composition and the mechanism of action are single, and use range is limited.
Also use gac and zeolite in the filtrate involved in the present invention.Gac is a kind of as the perviousness base-material, and its content is no more than 10%.Zeolite (clinoptilolite and mordenite) is as main cationic exchange base-material, and content is at 40-80%.Be its over-all properties (prescription that the spheroidal particle water resistance is little, the nitrogen of variform can be taken into account removal, filtrate can suitably be adjusted according to groundwater quality) by the synthetic filtrate of the raw mineral materials of multiple performance than the advantage of one matter filler.
The filtrate of at present filter tank, waterworks use is generally the [Xia Qiongqiong such as gac, hard coal, haydite, quartz sand, the biological reinforced filtration treatment usefulness of tap water and factor of influence research commentary [J] thereof, Hohai University's journal, 2006], the filtrate that use in the industrial sewage filter tank also comprises [the Miu Wei such as iron sand, manganese sand, the synthetic filtrate of flyash, the synthetic filtrate of clay, Compound Punch rod filtrate is removed ammonia nitrogen and organic test research, Forest Engineering, 2009].But the use of these filtrates is under the condition of relatively high, the abundant keeping of earth's surface engineering, Pollutant levels, filtrate back flushing or replacing.And groundwater environment is that low temperature, nitrogen pollutant concentration are low, oxygen supply is not enough for carbon, replaceable filtrate hardly.Obviously the environment for use of underground water original position nitrogen immobilization reparation is harsher, and is also higher to the requirement of filtrate.
Summary of the invention
1, invents the technical problem that will solve
Shortage for existing underground water nitrogen immobilization repair materials and in-situ remediation method, the invention provides a kind of underground water nitrogen-fixation remediation filtering material and preparation method thereof, polluted by nitrogen is effectively removed in the processing that the filtrate for preparing by the present invention can pollute for the inorganic nitrogen of underground water.
2, technical scheme
Inventive principle:
The adsorptive power of natural mineral and processing modified product thereof and ion-exchange capacity can satisfy the groundwater recovery technique is detained carrying capacity to nitrogen pollutant demand, also have simultaneously price low, free of contamination environmental friendliness advantage.Thereby used in a large number in the present invention.Among the present invention various raw materials are divided into (with) ion-exchange base-material, plasticity bonding mineral and hypertonicity base-material three major types.The cationic exchange base-material is for the manufacture of there being the cationic filtrate that is detained carrying capacity to ammonia nitrogen, the anionresin base-material is for the manufacture of nitrite nitrogen and nitrate nitrogen are had the anionic filtrate that is detained carrying capacity.Plasticity bonding mineral mainly play the effect of plasticity balling-up granulation.The hypertonicity base-material makes the inside and outside absorption room UNICOM of ball-type filtrate, increases the delay carrying capacity to nitrogen pollutant of filtrate.Its mechanism of action is that the lower concentration inorganic nitrogen is cured in filtrate by ion exchange, be carried in sustainable ammonia nitrogen or nitric nitrogen and the gasification of engulfing the enrichment that is cured in filtrate of denitrifier in the filtrate, the oxygen release agent that adds in the auxiliary shaft and carbon source can be kept the lasting survival of denitrifier.
Technical scheme of the present invention is as follows:
A kind of underground water nitrogen-fixation remediation filtering material, one of them consists of to exchange base-material by plasticity bonding mineral, perviousness base-material and inorganic cation exchange base-material or inorganic anion, and wherein the weight content of each component is: plasticity bonding mineral 10～50%, perviousness base-material 1～10%, inorganic cation exchange base-material or inorganic anion exchange base-material 40～80%.
Inorganic cation exchange base-material wherein is natural mineral clinoptilolite, mordenite, vermiculite or pillared montmorillonite.Inorganic anion exchange base-material wherein is hydrotalcite.Plasticity bonding mineral are repeatly stone, kaolin or montmorillonite of slope.
Described perviousness base-material is diatomite, pearlstone or gac.
A kind of preparation method of underground water nitrogen-fixation remediation filtering material the steps include:
(1) content is by weight: plasticity bonding mineral 10～50%, perviousness base-material 1～10%, inorganic cation exchange base-material or inorganic anion exchange base-material 40～80% are prepared raw materials, and plasticity is bondd, and all to be crushed to 200 orders for subsequent use for mineral and inorganic cation exchange base-material or inorganic anion exchange base-material raw material;
(2) perviousness base-material raw material pulverizing to 50 order is for subsequent use;
(3) the various raw materials after step (1) and (2) pulverizing are allocated in proportion, fully mixed, in tablets press, add water and be rolled into ball-type, until the expection particle diameter;
(4) the ball-type filtrate that step (3) is obtained obtains underground water nitrogen-fixation remediation filtering material 500～800 ℃ of calcinings 1～4 hour.
3. beneficial effect
The invention provides a kind of underground water nitrogen-fixation remediation filtering material and preparation method thereof, the present invention repairs filtrate and adopts the multicomponent inorganic raw material composite, solve all commutative absorption of positively charged ion, negatively charged ion, can unite with other biological solidify material (carbon source material, oxygen release material) problem of use.Owing to having adopted even ball-type agglomeration technique, also have simultaneously a water resistance coefficient little, short stream nothing such as streams at the technical superiority hardly.Filtrate of the present invention directly is added in use in the underground water reparation well and uses].
Embodiment
Embodiment 1
The clinoptilolite of proportioning 70% weight ratio; the slope of 25% weight ratio is stone repeatly; the diatomite powder of 5% weight ratio; clinoptilolite and slope repeatly stone flour are broken to 200 orders; fully mix; the limit adds the waterside and rolls and to make the ball-type filtrate of particle diameter 3mm in tablets press, 800 ℃ of temperature lower calcinations 4 hours, makes the ammonia nitrogen absorption filtrate.Its material characteristics is BET=25m2/g, porosity 80%, granule strength 55N/.Use this filtrate to the underground water of initial ammonia nitrogen concentration as 1.0mg/l, experience 1 hour equilibrium adsorption after, feed ratio is the 1:20(filtrate: water), ammonia nitrogen removal frank reaches 12.5%.
Embodiment 2
The mordenite of proportioning 80% weight ratio; the kaolin of 19% weight ratio; the absorbent charcoal powder body of 1% weight ratio; mordenite and kaolin powder are broken to 200 orders; fully mix; the limit adds the ball-type filtrate that particle diameter 3mm is made in the waterside rolling in tablets press, and calcining is 2 hours under 500 ℃ of temperature and protection of reducing atmosphere, makes the ammonia nitrogen absorption filtrate.Its material characteristics is BET 42m2/g, porosity 93%, granule strength 41N/.Use this filtrate to the underground water of ammonia nitrogen starting point concentration as 1.0mg/l, experience 1 hour equilibrium adsorption after, feed ratio is the 1:20(filtrate: water), ammonia nitrogen removal frank reaches 31%.
Embodiment 3
The hydrotalcite of proportioning 80% weight ratio, the montmorillonite of 10% weight ratio, the diatomite of 10% weight ratio fully mixes, and the limit adds the waterside and rolls and to make the ball-type filtrate of particle diameter 3mm in tablets press, 800 ℃ of temperature lower calcinations 1 hour, makes the nitric nitrogen absorbent filter medium.Its material characteristics is BET 76m2/g, porosity 42%, granule strength 61N/.Use this filtrate to the underground water of nitric nitrogen starting point concentration as 1.0mg/l, experience 1 hour equilibrium adsorption after, feed ratio is the 1:20(filtrate: water), the nitric nitrogen clearance reaches 53%.
Embodiment 4
The clinoptilolite of proportioning 40% weight ratio; the slope of 50% weight ratio is stone repeatly; the gac of 10% weight ratio; clinoptilolite and slope repeatly stone flour are broken to 200 orders; fully mix; the limit adds the ball-type filtrate that particle diameter 3mm is made in the waterside rolling in tablets press, and calcining is 1 hour under 600 ℃ of temperature and protection of reducing atmosphere, makes the nitrogen absorbent filter medium.Its material characteristics is BET=95m2/g, porosity 94%, granule strength 25N/.Use this filtrate initial ammonia nitrogen, nitrite and nitrate concentration to be respectively the human configuration underground water of 1.0mg/l, 0.5 mg/l and 0.8 mg/l, after experiencing 1 hour equilibrium adsorption, feed ratio is the 1:20(filtrate: water), ammonia nitrogen removal frank reaches 22.5%, and nitrite and nitrate removal rate reach respectively 31% and 26%.
Claims (2)
1. underground water nitrogen-fixation remediation filtering material, one of them consists of to it is characterized in that exchanging base-material by plasticity bonding mineral, perviousness base-material and inorganic cation exchange base-material or inorganic anion, and wherein the weight content of each component is: plasticity bonding mineral 10～50%, perviousness base-material 1～10%, inorganic cation exchange base-material or inorganic anion exchange base-material 40～80%; Inorganic cation exchange base-material wherein is natural mineral clinoptilolite, mordenite, vermiculite or pillared montmorillonite; Inorganic anion exchange base-material wherein is hydrotalcite; Plasticity bonding mineral wherein are repeatly stone, kaolin or montmorillonite of slope; Perviousness base-material wherein is gac.
2. the preparation method of a underground water nitrogen-fixation remediation filtering material the steps include:
(1) content is by weight: plasticity bonding mineral 10～50%, perviousness base-material 1～10%, inorganic cation exchange base-material or inorganic anion exchange base-material 40～80% are prepared raw materials, and plasticity is bondd, and all to be crushed to 200 orders for subsequent use for mineral and inorganic cation exchange base-material or inorganic anion exchange base-material raw material;
(2) perviousness base-material raw material pulverizing to 50 order is for subsequent use;
(3) the various raw materials after step (1) and (2) pulverizing are allocated in proportion, fully mixed, in tablets press, add water and be rolled into ball-type, until the expection particle diameter;
(4) the ball-type filtrate that step (3) is obtained obtains underground water nitrogen-fixation remediation filtering material 500～800 ℃ of calcinings 1～4 hour.
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| CN102372343B (en) * | 2011-10-09 | 2013-09-11 | 王鲁泉 | Wastewater treatment filling material and preparation method thereof |
| CN102491497B (en) * | 2011-12-16 | 2013-07-31 | 河海大学 | Controlled-release carbon source material for repairing polluted underground water organisms and preparation method thereof |
| CN102491502B (en) * | 2011-12-19 | 2014-02-26 | 南京大学 | Slow oxygen releasing material for repairing underground water and preparation method for slow oxygen releasing material |
| CN102718466B (en) * | 2012-06-14 | 2013-12-11 | 深圳市华水环保科技有限公司 | Multimedia biofilter material and preparation method thereof |
| CN102701552B (en) * | 2012-06-21 | 2014-03-12 | 南京大学 | Covering material for immobilized in-situ remediation of nitrogen in bottom sediment |
| CN106032296B (en) * | 2015-03-13 | 2019-04-09 | 轻工业环境保护研究所 | It is a kind of for repairing the material and preparation method thereof of underground water petroleum hydrocarbon pollution |
| CN104909424A (en) * | 2015-05-25 | 2015-09-16 | 常州大学 | Method for treatment of high concentration ammonia nitrogen in monosodium glutamate wastewater |
| CN105271463A (en) * | 2015-11-20 | 2016-01-27 | 威海广阳环保科技有限公司 | Efficient solid filter material used for sewage treatment and manufacturing method thereof |
| CN106365317A (en) * | 2016-09-26 | 2017-02-01 | 南京格丰环保材料有限公司 | Constructed wetland treatment system for village and town sanitary sewage |
| CN106430819A (en) * | 2016-09-26 | 2017-02-22 | 南京格丰环保材料有限公司 | Total nitrogen removal material, preparation method thereof and micro-power integrated domestic sewage treatment equipment |
| CN110076182A (en) * | 2018-01-26 | 2019-08-02 | 蔡永辉 | A kind of bicyclic synchronous circulating type is electronic-permeable reactive barrier soil remediation equipment |
| CN110078222B (en) * | 2019-04-26 | 2022-05-03 | 福建工程学院 | Preparation and use method of bacterial vector |
| CN112551703A (en) * | 2020-11-20 | 2021-03-26 | 苏州科技大学 | Porous slow-release carbon source filler and preparation method and application thereof |
| CN116040731B (en) * | 2023-01-31 | 2023-11-10 | 广东名桂环保有限公司 | Composite water treatment agent and preparation method thereof |
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