CN104743680B - A kind of preparation method of modified pearl rock biologic packing material - Google Patents

A kind of preparation method of modified pearl rock biologic packing material Download PDF

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CN104743680B
CN104743680B CN201510155211.7A CN201510155211A CN104743680B CN 104743680 B CN104743680 B CN 104743680B CN 201510155211 A CN201510155211 A CN 201510155211A CN 104743680 B CN104743680 B CN 104743680B
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pearl rock
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CN104743680A (en
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李文新
狄君绿
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Li Jianzhen
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Jinhua Zhichan Wuyuan Information Technology Co Ltd
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Abstract

The invention discloses the preparation method of a kind of modified pearl rock biologic packing material, comprise the steps: 1, configure modification liquid；2, the preparation of modified pearl rock；3, the preparation of Ti/Zn ZSM 5；4, filling carrier is prepared；5, by mixed bacteria liquid uniform application on the filling carrier surface that step 4 obtains, repaste and smear the sodium alginate soln that mass percent is 0.5%, by clean water after placing about 24 hours, be dried 20 hours at 40 DEG C, obtain modification biological filler.The modification biological filler utilizing this method to obtain has more preferable biofilm, can decompose long chain alkane and polycyclic aromatic hydrocarbon by active adsorption, does not interferes with the normal growth of microorganism.

Description

A kind of preparation method of modified pearl rock biologic packing material
Technical field
The present invention relates to the preparation method of a kind of modified pearl rock biologic packing material, belong to field of environment protection.
Background technology
Along with quickly increasing and industrialized propelling of the size of population, the pollution level of water body is day by day serious, and occurs Organic difficult decomposed substance and tradition ammonia nitrogen, the novel pollution type of the compound pollution of COD, traditional wastewater processing method is to this type of The treatment effect of sewage is the best.Utilizing microorganism to process polluted-water is a research of current water treatment field Focus direction, be also a kind of green high-efficient, the process means of non-secondary pollution.Wherein biomembrance process is in filling surface biofilm By the micropopulation on biomembrane, the pollutant in sewage are degraded.
The biologic packing material used at present the most in various degree there is defect.Present immobilized microorganism material is universal Existence and stability is poor, the feature of microorganism colonization poor performance, mechanical property difference.Due to drainage flow and the fluctuation of water quality, The microorganism added is easy to run off, or is preyed on by protozoacide, it is difficult to keep stablizing lasting removal effect.Fixed fill out Specific surface area is little, biofilm biomass is few for material, and smooth surface, and biomembrane is easy to fall off.The microbial method removal to difficult decomposing organic matter Poor effect.
Summary of the invention
The problem existed for above-mentioned prior art, the present invention provides the preparation side of a kind of modified pearl rock biologic packing material Method, the method comprises the steps:
(1), preparation modification liquid (in parts by weight):
N hydroxymethyl acrylamide 40-60
3-chloro-2-hydroxypropyl trimethylammonium amine hydrochlorate 15-30
Triethanolamine 60-90
Polyvinyl alcohol 12-18
Acrylic acid methyl ester. 6-8
MgCl2 10-15
Water 100-150；
(2), the preparation of modified pearl rock: taking the modification liquid of 500g part step (1), then adding 150g granularity is 500 mesh Perlite, continuously stirred 30 minutes, after perlite scatter, be warming up to 80 DEG C, stir 1-3h at such a temperature, filter To solid matter be washed with deionized 3 times after be dried, dried pressed powder is placed in Muffle furnace in air atmosphere 400 DEG C of roastings 3 hours, obtain modified pearl rock；
(3), the preparation of Ti/Zn-ZSM-5: take Titanium Nitrate and zinc nitrate is dissolved in the deionized water of 250ml, wherein nitric acid The gross weight of titanium and zinc nitrate is 1.625g, standby after stirring and dissolving；ZSM-5 is dispersed in ammonia spirit, keeps at 100 DEG C 5 hours, it is dried after filtration, dried powder 15g is added in the solution of above-mentioned Titanium Nitrate and zinc nitrate, be then warming up to 80 DEG C, Constant temperature stirs 20 hours, filters and dry solids, obtains the modified ZSM-5 of Ti and Zn；
(4), take Ti/Zn-ZSM-5 and modified pearl rock that mass ratio is 3:1, add in agitator, then add appropriate Ludox and distilled water, pull an oar, filter after be dried, after 450 DEG C of roasting 0.5h, broken sieve, take the granule conduct of 50-100 mesh Filling carrier；
(5), by mixed bacteria liquid uniform application on the filling carrier surface that step (4) obtains, repaste and smear mass percent It is the sodium alginate soln of 0.5%, by clean water after placing about 2-4 hour, is dried 20 hours at 40 DEG C, obtain modified raw Thing filler.
In step (5), the preparation method of mixed bacteria liquid is as follows:
Culture medium is utilized to filter out Paracoccus denitrificans, Bacillus licheniformis, sticky red rhodotorula and wax from water body or mud Shape bacillus cereus；
Paracoccus denitrificans, Bacillus licheniformis, sticky red rhodotorula and Bacillus cercus are respectively connected to Carnis Bovis seu Bubali cream albumen Peptone fluid medium, after 36 DEG C are cultivated 24h, centrifugal 10min under the rotating speed of 5000rpm, by raw for the solid sediment obtained Resuspended 3 times of reason saline, obtains four kinds of bacteria suspensions；
By the bacteria suspension of Paracoccus denitrificans, the bacteria suspension of Bacillus licheniformis, the bacteria suspension of sticky red rhodotorula and wax-like bud The bacteria suspension of spore bacillus is mixed to get microorganism species by the volume ratio of 1: 1: 1: 2, accesses in culture medium and obtains connecing bacterium amount 8% Plastc ring；
Plastc ring by the Paracoccus denitrificans obtained, Bacillus licheniformis, sticky red rhodotorula and Bacillus cercus Putting in container, the pH value being diluted to mixed liquor with deionized water is neutrality, adds polyvinyl alcohol and forms mixed bacteria liquid.
Preparation modification liquid (in parts by weight) in step (1):
N hydroxymethyl acrylamide 50
3-chloro-2-hydroxypropyl trimethylammonium amine hydrochlorate 20
Triethanolamine 75
Polyvinyl alcohol 16
Acrylic acid methyl ester. 7
MgCl2 12.5
Water 125.
It is an advantage of the current invention that:
(1) N hydroxymethyl acrylamide in modification liquid, triethanolamine, polyvinyl alcohol, acrylic acid methyl ester., MgCl2Occur Cooperative effect, the perlite of the present invention liquid that is modified is modified, improves the degree of roughness on surface, further increases filler Specific surface area and the bond area of microorganism so that it is there is excellent microorganism colonization performance；
(2) the modified perlite carrier of the liquid that is modified has the absorption of higher long chain alkane and polycyclic aromatic hydrocarbon yield and divides Solution ability；
(3) modified perlite filler carrier mechanical property is obviously improved；
(4) present invention use perlite simple as low raw-material cost, rich reserves, and production technology, with micro- Biological compound tense, does not interferes with the normal growth of microorganism, substantially without microorganism brings murder by poisoning reaction, avoids simultaneously yet Water body is caused secondary pollution.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
First preparing mixed bacteria liquid, concrete grammar is as follows:
Culture medium is utilized to filter out Paracoccus denitrificans, Bacillus licheniformis, sticky red rhodotorula and wax from water body or mud Shape bacillus cereus；
Paracoccus denitrificans, Bacillus licheniformis, sticky red rhodotorula and Bacillus cercus are respectively connected to Carnis Bovis seu Bubali cream albumen Peptone fluid medium, after 36 DEG C are cultivated 24h, centrifugal 10min under the rotating speed of 5000rpm, by raw for the solid sediment obtained Resuspended 3 times of reason saline, obtains four kinds of bacteria suspensions；
By the bacteria suspension of Paracoccus denitrificans, the bacteria suspension of Bacillus licheniformis, the bacteria suspension of sticky red rhodotorula and wax-like bud The bacteria suspension of spore bacillus is mixed to get microorganism species by the volume ratio of 1: 1: 1: 2, accesses in culture medium and obtains connecing bacterium amount 8% Plastc ring；
Plastc ring by the Paracoccus denitrificans obtained, Bacillus licheniformis, sticky red rhodotorula and Bacillus cercus Putting in container, the pH value being diluted to mixed liquor with deionized water is neutrality, adds polyvinyl alcohol and forms mixed bacteria liquid.
Embodiment 1
(1), preparation modification liquid (in parts by weight):
N hydroxymethyl acrylamide 40
3-chloro-2-hydroxypropyl trimethylammonium amine hydrochlorate 15
Triethanolamine 60
Polyvinyl alcohol 12
Acrylic acid methyl ester. 6
MgCl2 10
Water 100；
(2), the preparation of modified pearl rock: taking the modification liquid of 500g part step (1), then adding 150g granularity is 500 mesh Perlite, continuously stirred 30 minutes, after perlite scatter, be warming up to 80 DEG C, stir 1h at such a temperature, be filtrated to get Solid matter be washed with deionized 3 times after be dried, dried pressed powder is placed in Muffle furnace in air atmosphere 400 DEG C roasting 3 hours, obtains modified pearl rock；
(3), the preparation of Ti/Zn-ZSM-5: take Titanium Nitrate and zinc nitrate is dissolved in the deionized water of 250ml, wherein nitric acid The gross weight of titanium and zinc nitrate is 1.625g, standby after stirring and dissolving；ZSM-5 is dispersed in ammonia spirit, keeps at 100 DEG C 5 hours, it is dried after filtration, dried powder 15g is added in the solution of above-mentioned Titanium Nitrate and zinc nitrate, be then warming up to 80 DEG C, Constant temperature stirs 20 hours, filters and dry solids, obtains the modified ZSM-5 of Ti and Zn；
(4), take Ti/Zn-ZSM-5 and modified pearl rock that mass ratio is 3:1, add in agitator, then add appropriate Ludox and distilled water, pull an oar, filter after be dried, after 450 DEG C of roasting 0.5h, broken sieve, take the granule conduct of 50-100 mesh Filling carrier；
(5), by mixed bacteria liquid uniform application on the filling carrier surface that step (4) obtains, repaste and smear mass percent It is the sodium alginate soln of 0.5%, by clean water after placing about 2 hours, is dried 20 hours at 40 DEG C, obtains modification biological Filler.
The modified interface shear strength of this biologic packing material improves 38%, and microorganism colonization amount improves 30%, how long alkane The clearance of hydrocarbon reaches 98%, and the clearance of polycyclic aromatic hydrocarbon is reached 99%.
Embodiment 2
(1), preparation modification liquid (in parts by weight):
N hydroxymethyl acrylamide 40-60
3-chloro-2-hydroxypropyl trimethylammonium amine hydrochlorate 15-30
Triethanolamine 60-90
Polyvinyl alcohol 12-18
Acrylic acid methyl ester. 6-8
MgCl2 10-15
Water 100-150；
(2), the preparation of modified pearl rock: taking the modification liquid of 500g part step (1), then adding 150g granularity is 500 mesh Perlite, continuously stirred 30 minutes, after perlite scatter, be warming up to 80 DEG C, stir 1-3h at such a temperature, filter To solid matter be washed with deionized 3 times after be dried, dried pressed powder is placed in Muffle furnace in air atmosphere 400 DEG C of roastings 3 hours, obtain modified pearl rock；
(3), the preparation of Ti/Zn-ZSM-5: take Titanium Nitrate and zinc nitrate is dissolved in the deionized water of 250ml, wherein nitric acid The gross weight of titanium and zinc nitrate is 1.625g, standby after stirring and dissolving；ZSM-5 is dispersed in ammonia spirit, keeps at 100 DEG C 5 hours, it is dried after filtration, dried powder 15g is added in the solution of above-mentioned Titanium Nitrate and zinc nitrate, be then warming up to 80 DEG C, Constant temperature stirs 20 hours, filters and dry solids, obtains the modified ZSM-5 of Ti and Zn；
(4), take Ti/Zn-ZSM-5 and modified pearl rock that mass ratio is 3:1, add in agitator, then add appropriate Ludox and distilled water, pull an oar, filter after be dried, after 450 DEG C of roasting 0.5h, broken sieve, take the granule conduct of 50-100 mesh Filling carrier；
(5), by mixed bacteria liquid uniform application on the filling carrier surface that step (4) obtains, repaste and smear mass percent It is the sodium alginate soln of 0.5%, by clean water after placing about 2-4 hour, is dried 20 hours at 40 DEG C, obtain modified raw Thing filler.
This biologic packing material magnesium oxide modified rear interface shear strength improves 51%, and microorganism colonization amount improves 41%, many The clearance of long chain alkane reaches 99%, and the clearance of polycyclic aromatic hydrocarbon is reached 99%.
Embodiment 3
(1), preparation modification liquid (in parts by weight):
N hydroxymethyl acrylamide 60
3-chloro-2-hydroxypropyl trimethylammonium amine hydrochlorate 30
Triethanolamine 90
Polyvinyl alcohol 18
Acrylic acid methyl ester. 8
MgCl2 15
Water 150；
(2), the preparation of modified pearl rock: taking the modification liquid of 500g part step (1), then adding 150g granularity is 500 mesh Perlite, continuously stirred 30 minutes, after perlite scatter, be warming up to 80 DEG C, stir 3h at such a temperature, be filtrated to get Solid matter be washed with deionized 3 times after be dried, dried pressed powder is placed in Muffle furnace in air atmosphere 400 DEG C roasting 3 hours, obtains modified pearl rock；
(3), the preparation of Ti/Zn-ZSM-5: take Titanium Nitrate and zinc nitrate is dissolved in the deionized water of 250ml, wherein nitric acid The gross weight of titanium and zinc nitrate is 1.625g, standby after stirring and dissolving；ZSM-5 is dispersed in ammonia spirit, keeps at 100 DEG C 5 hours, it is dried after filtration, dried powder 15g is added in the solution of above-mentioned Titanium Nitrate and zinc nitrate, be then warming up to 80 DEG C, Constant temperature stirs 20 hours, filters and dry solids, obtains the modified ZSM-5 of Ti and Zn；
(4), take Ti/Zn-ZSM-5 and modified pearl rock that mass ratio is 3:1, add in agitator, then add appropriate Ludox and distilled water, pull an oar, filter after be dried, after 450 DEG C of roasting 0.5h, broken sieve, take the granule conduct of 50-100 mesh Filling carrier；
(5), by mixed bacteria liquid uniform application on the filling carrier surface that step (4) obtains, repaste and smear mass percent It is the sodium alginate soln of 0.5%, by clean water after placing about 4 hours, is dried 20 hours at 40 DEG C, obtains modification biological Filler.
This biologic packing material magnesium oxide modified rear interface shear strength improves 60%, and microorganism colonization amount improves 50%, many The clearance of long chain alkane reaches 99%, and the clearance of polycyclic aromatic hydrocarbon is reached 99.5%.

Claims (3)

1. the preparation method of a modified pearl rock biologic packing material, it is characterised in that the method comprises the steps:
(1), modification liquid is prepared, in parts by weight:
N hydroxymethyl acrylamide 40-60
3-chloro-2-hydroxypropyl trimethylammonium amine hydrochlorate 15-30
Triethanolamine 60-90
Polyvinyl alcohol 12-18
Acrylic acid methyl ester. 6-8
MgCl2 10-15
Water 100-150；
(2), the preparation of modified pearl rock: take the modification liquid of 500g part step (1), then add the treasure that 150g granularity is 500 mesh Zhu Yan, continuously stirred 30 minutes, after perlite scatter, is warming up to 80 DEG C, stirs 1-3h at such a temperature, be filtrated to get Solid matter is dried after being washed with deionized 3 times, and dried pressed powder is placed in Muffle furnace in air atmosphere 400 DEG C Roasting 3 hours, obtains modified pearl rock；
(3), the preparation of Ti/Zn-ZSM-5: take Titanium Nitrate and zinc nitrate be dissolved in the deionized water of 250ml, wherein Titanium Nitrate and The gross weight of zinc nitrate is 1.625g, standby after stirring and dissolving；Being dispersed in ammonia spirit by ZSM-5, at 100 DEG C, holding 5 is little Time, it is dried after filtration, dried powder 15g is added in the solution of above-mentioned Titanium Nitrate and zinc nitrate, be then warming up to 80 DEG C, constant temperature Stir 20 hours, filter and dry solids, obtain the modified ZSM-5 of Ti and Zn；
(4), take Ti/Zn-ZSM-5 and modified pearl rock that mass ratio is 3:1, add in agitator, then add proper amount of silicon molten Glue and distilled water, pull an oar, filter after be dried, after 450 DEG C of roasting 0.5h, broken sieve, take the granule of 50-100 mesh as filler Carrier；
(5), by mixed bacteria liquid uniform application on the filling carrier surface that step (4) obtains, repaste and smear mass percent and be The sodium alginate soln of 0.5%, by clean water after placing 2-4 hour, is dried 20 hours at 40 DEG C, obtains modification biological and fill out Material.
2. preparation method as claimed in claim 1, it is characterised in that in step (5), the preparation method of mixed bacteria liquid is as follows:
Culture medium is utilized to filter out Paracoccus denitrificans, Bacillus licheniformis and sticky red rhodotorula and wax-like bud from water body or mud Spore bacillus；
Paracoccus denitrificans, Bacillus licheniformis, sticky red rhodotorula and Bacillus cercus are respectively connected to beef extract-peptone liquid Body culture medium, after 36 DEG C are cultivated 24h, centrifugal 10min, the solid sediment physiology salt that will obtain under the rotating speed of 5000rpm Resuspended 3 times of water, obtains four kinds of bacteria suspensions；
By the bacteria suspension of Paracoccus denitrificans, the bacteria suspension of Bacillus licheniformis, the bacteria suspension of sticky red rhodotorula and wax-like spore bar The bacteria suspension of bacterium is mixed to get microorganism species by the volume ratio of 1: 1: 1: 2, accesses in culture medium and is mixed connecing bacterium amount 8% Bacteria suspension；
The plastc ring of the Paracoccus denitrificans obtained, Bacillus licheniformis, sticky red rhodotorula and Bacillus cercus is put into In container, the pH value being diluted to mixed liquor with deionized water is neutrality, adds polyvinyl alcohol and forms mixed bacteria liquid.
3. preparation method as claimed in claim 1, it is characterised in that preparation modification liquid in step (1), in parts by weight:
N hydroxymethyl acrylamide 50
3-chloro-2-hydroxypropyl trimethylammonium amine hydrochlorate 20
Triethanolamine 75
Polyvinyl alcohol 16
Acrylic acid methyl ester. 7
MgCl2 12.5
Water 125.
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