CN110964711B - Acid-resistant microbial capsule embedding liquid, microbial capsule, and preparation methods and applications thereof - Google Patents
Acid-resistant microbial capsule embedding liquid, microbial capsule, and preparation methods and applications thereof Download PDFInfo
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- CN110964711B CN110964711B CN201811142305.0A CN201811142305A CN110964711B CN 110964711 B CN110964711 B CN 110964711B CN 201811142305 A CN201811142305 A CN 201811142305A CN 110964711 B CN110964711 B CN 110964711B
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- 239000002775 capsule Substances 0.000 title claims abstract description 85
- 230000000813 microbial effect Effects 0.000 title claims abstract description 72
- 239000007788 liquid Substances 0.000 title claims abstract description 47
- 239000002253 acid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 244000005700 microbiome Species 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- 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 abstract description 13
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 13
- 239000000661 sodium alginate Substances 0.000 claims abstract description 13
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 12
- 239000012498 ultrapure water Substances 0.000 claims abstract description 12
- UKVHQGHRJIEIML-UHFFFAOYSA-L calcium boric acid dichloride Chemical class [Cl-].[Cl-].[Ca+2].OB(O)O UKVHQGHRJIEIML-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 239000008188 pellet Substances 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000000945 filler Substances 0.000 claims description 28
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 21
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000012856 packing Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000002912 waste gas Substances 0.000 claims description 7
- 230000001580 bacterial effect Effects 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000000034 method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses an acid-resistant microbial capsule embedding liquid, a microbial capsule and a preparation method and application thereof, wherein the preparation method of the microbial capsule comprises the following steps: step 1, polyvinyl alcohol and sodium alginate are added into ultrapure water, and heated until the polyvinyl alcohol and the sodium alginate are completely dissolved to obtain a mixed solution; step 2, adding activated carbon powder and a pH buffering agent into the mixed solution, and cooling to 30-40 ℃, wherein the mass of the activated carbon powder is 0.9-1.3% of the mass of the mixed solution, and the mass of the pH buffering agent is 1.5-2.5% of the mass of the mixed solution; and step 3, adding the cooled mixed solution into an equal volume of microbial liquid, and uniformly mixing to obtain the embedding liquid. And (3) dripping the microorganism capsule embedding liquid into a saturated boric acid-calcium chloride solution, placing the obtained pellets in the saturated boric acid-calcium chloride solution for crosslinking reaction for 20-30 hours at the temperature of 3-5 ℃, and taking out and cleaning the obtained microorganism capsule. The acid-resistant microbial capsules of the present invention can withstand lower pH.
Description
Technical Field
The invention relates to the technical field of atmospheric treatment, in particular to an acid-resistant microbial capsule embedding liquid, a microbial capsule, a preparation method and application thereof.
Background
The immobilized microorganism technology is developed from immobilized enzyme technology, and the technology adopts a physical and chemical method to immobilize free microorganisms in a limited space, so that the activity of the microorganisms can be maintained and the microorganisms can be recycled. Compared with the common biotechnology, the immobilized microorganism technology has been widely applied and researched in the environmental field, especially in the water treatment field, and more attention has been paid to the immobilized microorganism technology in the waste gas treatment field in the last twenty years because of the advantages of small enzyme activity loss, high microorganism density, less microorganism loss, high reaction speed, strong poisoning resistance, stronger environmental adaptation capability, small occupation of treatment equipment and the like.
Agriculture and animal husbandry, industrial production, and municipal waste disposal utilities can emit significant amounts of malodorous contaminants. The malodor pollutant is used as an important air pollutant and mainly comprises hydrocarbon, oxygen-containing organic matters, sulfur-containing organic matters, nitrogen-containing organic matters, halogen, derivatives thereof and the like, and because the malodor pollutant has the unique pollution characteristics, the malodor pollutant not only can affect the psychology and the sense of living and working people nearby the malodor pollution source and reduce the working efficiency and the quality of life, but also seriously damages the respiratory system, the digestive system and the nervous system, so that the malodor pollutant in the atmosphere is required to be effectively removed by adopting proper technical means. The biological method for treating malodorous gas has the advantages of economy, no secondary pollution and the like, and is widely applied all the time. Common equipment for biological treatment process includes biological filtering tower, biological dripping filtering tower and biological washing tower.
The traditional biological filtration tower and the biological trickling filtration tower are often made of natural materials, and problems such as filler replacement required in the actual operation process, reduced acidification performance of the reactor, biomembrane blocking of gaps caused by excessive gas load, drying of a filler layer caused by low humidity and the like can occur in the filler degradation process. Particularly in the aspect of treating halogen-containing VOCs and sulfides, a large amount of acidic degradation products can be generated in a short time, so that the pH value in the tower and in percolate is low, and the growth metabolism of microorganisms and the removal efficiency of VOCs or sulfides are affected. The use of continuous spraying and frequent replacement of the spray liquid has been proposed by the scholars to remove acidic products and maintain the pH environment in the column, but this can increase the water content in the column which is detrimental to mass transfer and creates more economic costs.
Disclosure of Invention
Aiming at the technical defects in the prior art, the invention provides an acid-resistant microbial capsule embedding liquid, a microbial capsule, a preparation method and application thereof, wherein the microbial capsule embedding liquid can keep stable form and size under the condition of low pH for a long time, and has a protective effect on microorganisms used for degrading waste gas in a filler, so that the microbial capsule embedding liquid can keep high removal efficiency on acid-producing waste gas under long-term operation.
The technical scheme adopted for realizing the purpose of the invention is as follows:
an acid-resistant microbial capsule embedding liquid is prepared according to the following steps:
step 1, polyvinyl alcohol and sodium alginate are added into ultrapure water, and heated until the polyvinyl alcohol and the sodium alginate are completely dissolved to obtain a mixed solution, wherein the mass of the polyvinyl alcohol is 3-5% of the mass of the ultrapure water, and the mass of the sodium alginate is 5-7% of the mass of the ultrapure water;
step 2, adding activated carbon powder and a pH buffering agent into the mixed solution, and cooling to 30-40 ℃, wherein the mass of the activated carbon powder is 0.9-1.3% of the mass of the mixed solution, and the mass of the pH buffering agent is 1.5-2.5% of the mass of the mixed solution;
and step 3, adding the cooled mixed solution into an equal volume of microbial liquid, and uniformly mixing to obtain the embedding liquid.
In the above technical solution, the pH buffer is sodium bicarbonate or sodium phosphate.
In the technical scheme, the microbial liquid is activated sludge, and MLSS is 10000-30000mg/L.
In another aspect of the present invention, a method for preparing an acid-resistant microbial encapsulation liquid, comprising the steps of:
step 1, polyvinyl alcohol and sodium alginate are added into ultrapure water, and heated until the polyvinyl alcohol and the sodium alginate are completely dissolved to obtain a mixed solution, wherein the mass of the polyvinyl alcohol is 3-5% of the mass of the ultrapure water, and the mass of the sodium alginate is 5-7% of the mass of the ultrapure water;
step 2, adding activated carbon powder and a pH buffering agent into the mixed solution, and cooling to 30-40 ℃, wherein the mass of the activated carbon powder is 0.9-1.3% of the mass of the mixed solution, and the mass of the pH buffering agent is 1.5-2.5% of the mass of the mixed solution;
and step 3, adding the cooled mixed solution into an equal volume of microbial liquid, and uniformly mixing to obtain the embedding liquid.
In another aspect of the invention, the invention also comprises an acid-resistant microbial capsule, the diameter of the microbial capsule is 3.0-3.3mm (the capsule with the particle size range can maintain good mass transfer performance and ensure good mechanical performance), and the mass ratio of bacterial liquid is 40%, and the microbial liquid is prepared according to the following steps: and (3) dripping the microorganism capsule embedding liquid into a saturated boric acid-calcium chloride solution, placing the obtained pellets in the saturated boric acid-calcium chloride solution for crosslinking reaction for 20-30 hours at the temperature of 3-6 ℃, and taking out and cleaning the obtained microorganism capsule.
In the technical proposal, after soaking for 7 to 30 days under the condition of pH 3, the swelling degree of the acid-resistant microorganism capsule is 5 to 10 percent,
in the technical scheme, the microorganism capsule embedding liquid is dripped into the saturated boric acid-calcium chloride solution, preferably 35cm, from a height of 30-40cm at a constant speed through a microsyringe pump, the obtained pellets are placed in the environment of 3-5 ℃ and subjected to a crosslinking reaction for 24 hours, preferably 4 ℃.
In another aspect of the invention, the use of said acid resistant microbial capsules as a packing in a biofilter tower for treating acid waste gases is also included.
In the technical proposal, the height of the biological filtration tower is 50cm, the inner diameter is 8cm, the wall thickness is 0.5cm, the stacking height of the used microorganism capsule embedding liquid is 22cm, and the filling volume of the used microorganism capsule is 1.110m 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, the chlorobenzene is treated for 1-100 days in a starting period under the condition that the particle size of the ceramsite is about 3-5mm, the efficiency of removing the chlorobenzene by the microbial capsules is stabilized to be more than 70%, and the diameter of the microbial capsules is 90-98% of the diameter of the first day after the chlorobenzene is treated for 100 days.
In the technical proposal, the height of the biological filtration tower is 50cm, the inner diameter is 8cm, the wall thickness is 0.5cm, the stacking height of the used microorganism capsule embedding liquid is 22cm, and the filling volume of the used microorganism capsule is 1.110m 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, hydrogen sulfide is removed for 1-100 days in a starting period under the condition that the particle size of the ceramsite is about 3-5mm, the removal efficiency is 80-85%, and the diameter of the microbial capsule is 90-97% of the diameter of the microbial capsule in the first day after the hydrogen sulfide is treated for 100 days.
In the technical proposal, the microorganism capsule embedding liquid is piled up in the tower height of the biological filtration tower of 50cm, the inner diameter of 8cm and the wall thickness of 0.5cmThe height was 22cm and the filler volume of the microbial capsules used was 1.110m 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, the removal efficiency is 80-85% after the removal of ethanethiol for 1-100 days in a starting period under the condition that the particle size of the ceramsite is about 3-5mm, and the diameter of the microbial capsule is 90-98% of the diameter of the microbial capsule in the first day after the hydrogen sulfide is treated for 100 days.
Compared with the prior art, the invention has the beneficial effects that:
1. the acid-resistant microbial capsules can bear lower pH, the swelling degree of the acid-resistant microbial capsules is 5-10% after being soaked for 7 days under the condition that the pH is 3, and the swelling degree of the acid-resistant microbial capsules is basically the same as that of the acid-resistant microbial capsules after being soaked for 30 days and the acid-resistant microbial capsules are not damaged after being soaked for 7 days.
2. The acid-resistant microbial capsule can reduce the influence of pH change or toxicity in the external environment on the activity of microorganisms, can play a role in buffering and protecting due to the limited diffusion of a carrier under the condition that the system environment suddenly becomes severe, and has better tolerance to low pH by adding sodium bicarbonate into the capsule as a buffering agent.
3. The acid-resistant microbial capsule disclosed by the invention has high microbial density, and the mass ratio of the bacterial liquid is up to 40%. The same biomass occupies small volume, the higher the microorganism concentration in the reactor is, the treatment load is correspondingly improved, the shorter the required reaction time is, the volume and the occupied area of the treatment device are reduced, and the miniaturization of the waste gas treatment equipment is facilitated. When the filler is applied to a biological filter tower, the filler is easy to operate and maintain, the spraying time and the replacement period are shortened, and the investment cost and the operation cost are reduced.
4. The preparation method of the acid-resistant microbial capsule uses the microsyringe pump to push the embedding liquid, is simple and convenient to operate, and the prepared microbial capsule is controllable and uniform in size, and enables the microbial capsule to be basically stabilized at 3-3.3mm, and the capsule occupation ratio in the diameter range is more than 98%.
5. The acid-resistant microbial capsule has the advantages of good mechanical strength, uniform pore canal size and stable material due to the addition of the activated carbon, and can be suitable for long-term operation conditions.
Drawings
FIG. 1 is a diagram of an immobilized microorganism packing material when not placed in a biofilter column;
FIG. 2 is a graphical representation of the immobilized microorganism packing material after 100 days of operation in a biological filtration column.
Detailed Description
The invention is described in further detail below with reference to the drawings and the specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The invention will now be further described with the exception of chlorobenzene removal from the biofiltration column by way of example of the acid resistant microbial capsule packing, and this embodiment is intended to further illustrate the preparation and use of the acid resistant microbial capsule packing, but embodiments of the invention are not limited thereto.
(1) Adding polyvinyl alcohol (4%) and sodium alginate (6%) into 1000ml of ultrapure water, and heating the mixture to 95-100 ℃ in a water bath in a heat-collecting constant-temperature heating magnetic stirrer until the mixture is completely dissolved;
(2) Adding 1% of active carbon powder and 2% of sodium bicarbonate into the mixed solution heated in the water bath in the step (2), uniformly mixing, and cooling to 30 ℃;
(3) Adding 1000ml of activated sludge (MLSS is 20000 mg/L) with equal volume into the cooled mixed solution, and uniformly mixing to obtain embedding solution;
(4) Filling the embedding liquid obtained in the step (3) into 50ml of needle tubes, then placing the needle tubes on a micro sample injection pump (ALC-IP 900 type), regulating the sample injection speed of the micro sample injection pump to 25ml/min, slowly and uniformly dripping the embedding liquid from a position of 30cm into saturated boric acid (3.8 percent) -calcium chloride solution (2 percent) placed on a constant-temperature magnetic stirrer at the moment to form microbial capsules of about 3mm, wherein the method is an automatic process, can be used for mass production of the microbial capsules, and has quite uniform size of the produced capsules, the whole process is stable and rapid, and the produced microbial capsules are still placed in the saturated boric acid-calcium chloride solution and are subjected to cross-linking reaction for 24 hours in a refrigerator of 4 ℃;
(5) Taking out the microbial capsules which are obtained in the step (4) and are completely crosslinked, and repeatedly flushing the microbial capsules with ultrapure water;
(6) And (5) placing the microbial capsules obtained in the step (5) into a biological filter tower made of organic glass material to serve as a filler. The height of the biological filtration tower is 50cm, the inner diameter is 8cm, the wall thickness is 0.5cm, the stacking height of the immobilized bead filler is 22cm, and the volume of the immobilized bead filler is about 1.110m 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, and the particle size of the ceramsite is about 3-5mm. The concentration of the chlorobenzene is 200-600mg/m 3 The air flow rate of the blast is 0.075m 3 The residence time of chlorobenzene is about 53s, the spray liquid is inorganic salt nutrient solution, and the spray liquid is sprayed for 10min every 24h;
(7) After a starting period of about ten days, the efficiency of removing chlorobenzene of the biological filter tower is stabilized to be more than 70%, and the starting speed and the removing efficiency are superior to those of the biological filter tower filled with the traditional filler. After about 100 days, the removal efficiency remained above 70%, and the acid-resistant microbial capsules were not broken, but the morphology size was slightly reduced, but the removal efficiency of the p-chlorobenzene was not affected.
When the content of polyvinyl alcohol in the capsule is high, the needle is easy to be blocked due to the high viscosity, and the balling is difficult. After the addition of 4% of polyvinyl alcohol, 6% of sodium alginate is added, the interior of the microbial capsule has a good porous structure, a large number of holes are inlaid in the microbial capsule, and the holes are larger, so that mass transfer is facilitated.
The active carbon can be added into the embedding agent to increase a plurality of micropores in the immobilized particles, so that a plurality of substrates and products are contacted, mass transfer between microorganisms and the substrates is enhanced, and metabolites produced by the microorganisms are easily discharged from the interiors of the particles. Thus, it was determined that the optimal mass fraction of activated carbon for the improved immobilization method was 1%.
When the concentration of the bacterial liquid is increased and the ratio of the mud water quantity is increased, the microorganisms which are metabolized in the grid of the microbial capsule are increased, and meanwhile, the contact between the microorganisms and the waste gas is increased, so that the degradation efficiency is improved. If the concentration of the bacterial liquid is too large, the mechanical strength of the microbial capsule filler is reduced, so that the optimal bacterial liquid concentration is determined to be 20mg/L.
Adding a certain amount of CaCl into saturated boric acid 2 Not only weakens the hydrogen bond function in the gel molecular chain and reduces the viscosity, but also makes the preparation process easier, the mass transfer property and the mechanical strength are better, and the CaCl is added 2 The optimum concentration of (2%).
Example 2
The resulting microbial capsules were placed in a biofilter of organic glass material as a packing in the same manner as in example 1. The height of the biological filtration tower is 50cm, the inner diameter is 8cm, the wall thickness is 0.5cm, the stacking height of the immobilized bead filler is 22cm, and the volume of the immobilized bead filler is about 1.110m 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, and the particle size of the ceramsite is about 3-5mm. The concentration of the hydrogen sulfide is 100-500mg/m 3 The air flow rate of the air blown in was 0.1m 3 And/h, the residence time of the hydrogen sulfide is about 39s, the spray liquid is inorganic salt nutrient solution, and the spray liquid is sprayed for 10min every 24h;
after a starting period of about ten days, the efficiency of the biological filter tower for removing hydrogen sulfide is stabilized to be more than 85%, and the starting speed and the removing efficiency are superior to those of the biological filter tower filled with the traditional filler. After about 100 days, the removal efficiency remained above 80%, and the acid-resistant microbial capsules were not broken, but the morphology size was slightly reduced, but the removal efficiency of hydrogen sulfide was not affected.
Example 3
The resulting microbial capsules were placed in a biofilter of organic glass material as a packing in the same manner as in example 1. The height of the biological filtration tower is 50cm, the inner diameter is 8cm, the wall thickness is 0.5cm, the stacking height of the immobilized bead filler is 22cm, and the volume of the immobilized bead filler is about 1.110m 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, and the particle size of the ceramsite is about 3-5mm. The concentration of the introduced ethanethiol is 100-500mg/m 3 The air flow rate of the blast is 0.075m 3 And/h, the residence time of the ethanethiol is about 53s, the spray liquid is inorganic salt nutrient solution, and the spray liquid is sprayed for 10min every 24h;
after a starting period of about ten days, the efficiency of removing ethanethiol of the biological filter tower is stabilized to be more than 85%, and the starting speed and the removing efficiency are superior to those of the biological filter tower filled with the traditional filler. After about 100 days, the removal efficiency is still maintained at 80% or more, and the acid-resistant microbial capsules are not broken, but the form size is slightly reduced, but the removal efficiency of ethanethiol is not affected.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The acid-resistant microbial capsules are applied to treating acid waste gas as a filler in a biological filtering tower, the diameter of the microbial capsules is 3.0-3.3mm, and the mass ratio of bacterial liquid is 40%, and the microbial capsules are prepared according to the following steps: dropping the microorganism capsule embedding liquid into saturated boric acid-calcium chloride solution, placing the obtained pellets in the saturated boric acid-calcium chloride solution for crosslinking reaction for 20-30 hours at the temperature of 3-6 ℃, taking out the obtained microorganism capsule and cleaning;
the microbial capsule embedding liquid is prepared through the following steps:
step 1, polyvinyl alcohol and sodium alginate are added into ultrapure water, and heated until the polyvinyl alcohol and the sodium alginate are completely dissolved to obtain a mixed solution, wherein the mass of the polyvinyl alcohol is 3-5% of the mass of the ultrapure water, and the mass of the sodium alginate is 5-7% of the mass of the ultrapure water;
step 2, adding activated carbon powder and a pH buffering agent into the mixed solution, and cooling to 30-40 ℃, wherein the mass of the activated carbon powder is 0.9-1.3% of the mass of the mixed solution, and the mass of the pH buffering agent is 1.5-2.5% of the mass of the mixed solution;
step 3, adding the cooled mixed solution into an equal volume of microbial liquid, and uniformly mixing to obtain embedding liquid;
the pH buffer is sodium bicarbonate or sodium phosphate, the microbial liquid is activated sludge, and the MLSS is 10000-30000mg/L;
and (3) uniformly dripping the microorganism capsule embedding liquid into the saturated boric acid-calcium chloride solution from a height of 30-40cm through a microsyringe pump.
2. The use according to claim 1, wherein the acid-resistant microbial capsules have a swelling degree of 5 to 10% after soaking for 7 to 30 days at a pH of 3.
3. The use according to claim 1, wherein the microbial capsules used have a packing height of 22cm and a packing volume of 1.110m at a height of 50cm, an inner diameter of 8cm and a wall thickness of 0.5cm in the biofiltration column 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, the chlorobenzene is treated for 1-100 days in a starting period under the condition that the particle size of the ceramsite is 3-5mm, the efficiency of removing the chlorobenzene by the microbial capsules is stabilized to be more than 70%, and the diameter of the microbial capsules is 90-98% of the diameter of the first day after the chlorobenzene is treated for 100 days.
4. The use according to claim 1, wherein the microorganism capsule embedding liquid is used at a height of 22cm and a packing volume of 1.110m in the biofiltration tower of 50cm, an inner diameter of 8cm and a wall thickness of 0.5cm 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, hydrogen sulfide is removed for 1-100 days in a starting period under the condition that the particle size of the ceramsite is 3-5mm, the removal efficiency is 80-85%, and the diameter of the microbial capsule is 90-97% of the diameter of the microbial capsule in the first day after the hydrogen sulfide is treated for 100 days.
5. The use according to claim 1, wherein the microorganism capsule embedding liquid is used at a height of 22cm and a packing volume of 1.110m in the biofiltration tower of 50cm, an inner diameter of 8cm and a wall thickness of 0.5cm 3 The lower part of the filler adopts 5cm thick ceramsite as a supporting layer, the ethanethiol is removed for 1-100 days in the starting period under the condition that the grain diameter of the ceramsite is 3-5mm, the removal efficiency is 80-85%, and the micro-scale is formed after the ethanethiol is treated for 100 daysThe diameter of the bio-capsules is 90-98% of the first day.
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