CN104761045B - A kind of modified natural zeolite filler preparation method for biologic packing material column - Google Patents

A kind of modified natural zeolite filler preparation method for biologic packing material column Download PDF

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Publication number
CN104761045B
CN104761045B CN201510124406.5A CN201510124406A CN104761045B CN 104761045 B CN104761045 B CN 104761045B CN 201510124406 A CN201510124406 A CN 201510124406A CN 104761045 B CN104761045 B CN 104761045B
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zeolite
natural zeolite
packing material
metal ion
biologic packing
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CN104761045A (en
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谭文渊
袁东
付大友
周良芹
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Sichuan University of Science and Engineering
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Sichuan University of Science and Engineering
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The invention discloses a kind of modified natural zeolite filler preparation method for biologic packing material column, preparation method includes (1) and natural zeolite is crushed 1~3mm of sieving, is cleaned with tap water, is dried for standby in 120 DEG C;(2) by pretreated zeolite, 1mol.L is used‑1Salt acid soak for 24 hours, take out clean, drying, it is spare;(3) in addition metal ion A and the B mixed solution that step (2) is obtained to zeolite, 30 DEG C of isothermal vibrations 24 hours, take out on the oscillator, clean, and drying obtains modified natural zeolite in 550 DEG C of calcination 2h.The modified natural zeolite filler LAS exchange capacities of the present invention are up to 1mg.g‑1,30mg.L‑1LAS removal rates are up to more than 85%.It can be found by contrast experiment, zeolite filler prepared by this method, the metal ion of the exclusive degrading microorganism growths of LAS can be promoted due to introducing, therefore the filler degradation efficiency is high, stable water outlet.

Description

A kind of modified natural zeolite filler preparation method for biologic packing material column
Technical field
The present invention relates to biologic packing material column technology field more particularly to a kind of modified natural zeolites for biologic packing material column Filler preparation method.
Background technology
Environmental protection is the common issue that the 21 century mankind are faced, and global Journal of Sex Research, development environment material are in the ascendant. Mainly there are environment mineral material and synthesis high molecular material currently used as biological column or bio-filter stuffing.Synthesize macromolecule material Material, have many advantages, such as service life it is long, it is non-degradable, customize special construction, reference area is big, bioactivity is high, as polyvinyl chloride, Polypropylene, Propylene polymerization material etc., but higher price, waste and old filler easily cause secondary pollution;Environment mineral material is at water Reason has high treating effect, easily obtains, of low cost and do not easily cause the advantages such as secondary pollution, while environment mineral material is also It can recycle, but be influenced by self structure property, bioactivity is less than filling material of polymers.Zeolite is as a kind of heavy The environment mineral material wanted has the special natures such as cation exchange property, selective absorption performance, molecular sieve effect, is locating Reason field of sewage has more Demonstration Application.Zeolite is modified, is combined with biotechnology, plays modified zeolite particularity Matter acts synergistically with biological treatment, to achieve the purpose that improve treatment effect.
Invention content
The present invention provides a kind of modified natural zeolite filler preparation methods for biologic packing material column.
The present invention adopts the following technical scheme that:
The present invention's is as follows for the modified natural zeolite filler preparation method of biologic packing material column:
(1) natural zeolite is crushed into 1~3mm of sieving, is cleaned with tap water, is dried for standby in 120 DEG C;
(2) by pretreated zeolite, 1mol.L is used-1Salt acid soak for 24 hours, take out clean, drying, it is spare;
(3) step (2) is obtained adding in metal ion A and B mixed solution in zeolite, on the oscillator 30 DEG C of constant temperature shakes It swings 24 hours, takes out, clean, drying obtains modified natural zeolite in 550 DEG C of calcination 2h.
In step (3), the specific name of the metal ion A and metal ion B are Mn2+And Na+
In step (3), the weight ratio of two kinds of ions is 1 in metal ion A and B mixed solution:1, Mn in mixed solution2+With Na+Concentration be all 0.5g/L;
In step (3), the w/v of zeolite and metal ion A and B mixed solution is 5:100g/mL;
The preparation side of biologic packing material column obtained from modified natural zeolite filler filling prepared by the method for the present invention Method is as follows:
Modified zeolite and natural zeolite are respectively charged into two Organic glass columns, filling is highly 30cm, organic glass A diameter of 2cm of column, the loading density of zeolite is all 1.04gcm-3, using the cycle physics fixation of BAC, culture solution point Not under the promotion of pump, flow 0.5mL (ming)-1, pass through zeolite packed column, iterative cycles 12h so that in culture solution Microorganism is fixed on filler.
The positive effect of the present invention is as follows:
The modified natural zeolite filler preparation method for biologic packing material column of the present invention has method simple, and operation is simple Easily, it is low for equipment requirements, it is environmentally safe the advantages that, and using the present invention method prepare modified natural zeolite filler The ability of biologic packing material column load microorganism is strong obtained from filling, and bioactivity is high, excellent wastewater treatment effect and water outlet water Matter is stablized.
The present invention modified natural zeolite filler preparation method that LAS biologic packing materials column is handled suitable for waste water.LAS is exchanged Capacity is up to 1mg/g, 30mg.L-1LAS removal rates are up to more than 85%.It can be found by contrast experiment, boiling prepared by this method Hardcore can promote the metal ion of the exclusive degrading microorganism growths of LAS due to introducing, therefore the filler degradation efficiency is high, goes out Water is stablized.
Description of the drawings
Fig. 1 is the picture of natural zeolite.
This picture is natural clinoptilolite particle picture.
Fig. 2 is the XRD diffraction patterns of natural zeolite.
This picture is the XRD diffraction patterns of natural zeolite, as seen from the figure, former natural zeolite diffraction maximum mostly miscellaneous, explanation With the presence of more impurity in natural zeolite surface or gap.
Fig. 3 is the SEM pictures of natural zeolite.
This picture is the SEM pictures of natural zeolite, and there are more fine particles on natural zeolite surface as seen from the figure.
Fig. 4 is the SEM pictures of zeolite after HCl treatment.
This picture is the SEM pictures of zeolite after HCl treatment, and the particle of zeolite surface significantly reduces as seen from the figure.
Fig. 5 is the XRD diffraction patterns of zeolite after HCl treatment.
This picture is the XRD diffraction patterns of zeolite after HCl treatment, and diffraction maximum significantly reduces as seen from the figure, this is due to sky The reason of gap and surface impurity are removed.
Fig. 6 is the SEM pictures of modified zeolite.
This picture is Mn2+And Na+The SEM pictures of modification zeolite, as seen from the figure, in zeolite surface, there are Mn2+ And Na+Fine particle.
Fig. 7 is microorganism fixing device schematic diagram.
This picture is microorganism fixing device figure.
Fig. 8 is the schematic diagram of filled column dissolved oxygen depletion.
This picture is the schematic diagram of filled column dissolved oxygen depletion, and the bioactivity of modified zeolite is higher than day as seen from the figure Right zeolite.
Fig. 9 is water treatment facilities figure.
This picture is water treatment facilities figure.
Figure 10 is bioactivation zeolite filler column processing LAS waste water situation maps.
This picture is bioactivation zeolite filler column processing LAS waste water situation maps, as seen from the figure the place of modified zeolite It manages effect and is higher than natural zeolite.
Specific embodiment
The following examples are that the present invention is described in further detail.
Embodiment 1
The present invention's is as follows for the modified natural zeolite filler preparation method of biologic packing material column:
(1) natural zeolite is crushed into 1~3mm of sieving, is cleaned with tap water, is dried for standby in 120 DEG C;
(2) by pretreated zeolite, 1mol.L is used-1Salt acid soak for 24 hours, take out clean, drying, it is spare;
(3) step (2) is obtained adding in metal ion A and B mixed solution in zeolite, on the oscillator 30 DEG C of constant temperature shakes It swings 24 hours, takes out, clean, drying obtains modified natural zeolite in 550 DEG C of calcination 2h.
In step (3), the specific name of the metal ion A and metal ion B are Mn2+And Na+
In step (3), the weight ratio of two kinds of ions is 1 in metal ion A and B mixed solution:1, Mn in mixed solution2+With Na+Concentration be all 0.5g/L;
In step (3), the w/v of zeolite and metal ion A and B mixed solution is 5g:100mL;
The preparation side of biologic packing material column obtained from modified natural zeolite filler filling prepared by the method for the present invention Method is as follows:
Modified zeolite and natural zeolite are respectively charged into two Organic glass columns, filling is highly 30cm, organic glass A diameter of 2cm of column, the loading density of zeolite is all 1.04gcm-3, using the cycle physics fixation of BAC, culture solution point Not under the promotion of pump, flow 0.5mL (ming)-1, pass through zeolite packed column, iterative cycles 12h so that in culture solution Microorganism is fixed on filler.Cyclic microorganism fixing device is shown in Fig. 7.
Biomembrane zeolite filler column handles LAS waste water situations
With the 30mgL of preparation-1LAS solution is handled.Natural zeolite and modified zeolite filled column are each led into, is located The specific load of column is managed at 0.44mL (ming)-1-0.56mL·(min·g)-1.Before processing is to LAS liquid phases in waste water Chromatography is detected the content of LAS after its content and processing.And the waste water come out in processing every 1h detection single treatments, and It deals with out LAS content curves in waste water, observation curvilinear motion can grasp degradation situation of the microorganism to LAS in real time. It is compared by passing in and out column LAS contents situation to waste water, analyzes the effect of modified zeolite and biofilm mode to the processing of zeolite. Water treatment facilities is shown in Fig. 9.
The result shows that:The ability of zeolite loading microorganisms after modification is stronger, and bioactivity is higher, high treating effect and And stable effluent quality.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace And modification, the scope of the present invention is defined by the appended.

Claims (4)

1. a kind of modified natural zeolite filler preparation method for biologic packing material column, it is characterised in that:The method it is specific Step is as follows:
(1) natural zeolite is crushed into 1~3mm of sieving, is cleaned with tap water, is dried for standby in 120 DEG C;
(2) by pretreated zeolite, 1mol.L is used-1Salt acid soak for 24 hours, take out clean, drying, it is spare;
(3) step (2) is obtained adding in metal ion A and B mixed solution in zeolite, on the oscillator 30 DEG C of isothermal vibrations 24 Hour, it takes out, cleans, drying obtains modified natural zeolite in 550 DEG C of calcination 2h;
In step (3), the specific name of the metal ion A and metal ion B are Mn2+And Na+
In step (3), the weight ratio of two kinds of ions is 1 in metal ion A and B mixed solution:1, Mn in mixed solution2+And Na+ Concentration all be 0.5g/L.
2. it to be used for the modified natural zeolite filler preparation method of biologic packing material column as described in claim 1, it is characterised in that:Step Suddenly in (3), the w/v 5 of zeolite and metal ion A and B mixed solution:100g/mL.
3. obtained from a kind of modified natural zeolite filler filling prepared using such as claim 1-2 any one of them method Biologic packing material column.
4. biologic packing material column as claimed in claim 3, it is characterised in that:The preparation method of the biologic packing material column is as follows:It will Modified zeolite and natural zeolite are respectively charged into two Organic glass columns, filling height for 30cm, Organic glass column it is a diameter of 2cm, the loading density of zeolite is all 1.04gcm-3, using the cycle physics fixation of BAC, culture solution carrying in pump respectively Under rising, flow 0.5mL (ming)-1, pass through zeolite packed column, iterative cycles 12h so that the microorganism in culture solution is fixed On filler.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1551659A1 (en) * 1986-10-28 1990-03-23 Производственное объединение "Грузгорнохимпром" Method of removing arsenic compounds from waste water
RU2184722C1 (en) * 2001-11-08 2002-07-10 КОРЧАК Владимир Николаевич Method of oxidation of benzene to phenol
CN101544412A (en) * 2009-05-11 2009-09-30 浙江皇冠科技有限公司 Aquaculture water purifying agent and preparation method thereof
CN101696066A (en) * 2009-10-29 2010-04-21 同济大学 Method for removing organic pollutants from water by drinking water enhanced treatment
CN102755913A (en) * 2012-06-28 2012-10-31 燕山大学 Method for improving ammonium exchange capacity of natural zeolite ammonium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1551659A1 (en) * 1986-10-28 1990-03-23 Производственное объединение "Грузгорнохимпром" Method of removing arsenic compounds from waste water
RU2184722C1 (en) * 2001-11-08 2002-07-10 КОРЧАК Владимир Николаевич Method of oxidation of benzene to phenol
CN101544412A (en) * 2009-05-11 2009-09-30 浙江皇冠科技有限公司 Aquaculture water purifying agent and preparation method thereof
CN101696066A (en) * 2009-10-29 2010-04-21 同济大学 Method for removing organic pollutants from water by drinking water enhanced treatment
CN102755913A (en) * 2012-06-28 2012-10-31 燕山大学 Method for improving ammonium exchange capacity of natural zeolite ammonium

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