CN110404511A - A kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium - Google Patents
A kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium Download PDFInfo
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- CN110404511A CN110404511A CN201910381657.XA CN201910381657A CN110404511A CN 110404511 A CN110404511 A CN 110404511A CN 201910381657 A CN201910381657 A CN 201910381657A CN 110404511 A CN110404511 A CN 110404511A
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- earthworm
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- 241000361919 Metaphire sieboldi Species 0.000 title claims abstract description 62
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 49
- 239000002250 absorbent Substances 0.000 title claims abstract description 36
- 230000002745 absorbent Effects 0.000 title claims abstract description 36
- 239000002893 slag Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052791 calcium Inorganic materials 0.000 title claims description 18
- 239000011575 calcium Substances 0.000 title claims description 18
- 210000003608 fece Anatomy 0.000 claims abstract description 21
- 238000000855 fermentation Methods 0.000 claims abstract description 18
- 230000004151 fermentation Effects 0.000 claims abstract description 17
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000006174 pH buffer Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
- 239000011449 brick Substances 0.000 claims description 5
- 230000000813 microbial effect Effects 0.000 claims description 5
- 239000002985 plastic film Substances 0.000 claims description 5
- 229920006255 plastic film Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 241000186046 Actinomyces Species 0.000 claims description 3
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 3
- 241000235342 Saccharomycetes Species 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 3
- 239000002361 compost Substances 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 230000017448 oviposition Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007605 air drying Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 9
- 244000144977 poultry Species 0.000 description 9
- 244000144972 livestock Species 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000010871 livestock manure Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 235000013365 dairy product Nutrition 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000009368 vermiculture Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 241001233061 earthworms Species 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K67/00—Rearing or breeding animals, not otherwise provided for; New or modified breeds of animals
- A01K67/033—Rearing or breeding invertebrates; New breeds of invertebrates
- A01K67/0332—Earthworms
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/10—Animal feeding-stuffs obtained by microbiological or biochemical processes
- A23K10/12—Animal feeding-stuffs obtained by microbiological or biochemical processes by fermentation of natural products, e.g. of vegetable material, animal waste material or biomass
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/20—Animal feeding-stuffs from material of animal origin
- A23K10/26—Animal feeding-stuffs from material of animal origin from waste material, e.g. feathers, bones or skin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The present invention provides a kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nano calcium oxide, belongs to biomass resource and recycles and environmental protection technical field.The adsorbent is the earthworm excrement for raising earthworm generation after pre fermentation by excrement slag, cow dung and n-CaO, and is obtained by air-drying, being sieved.The present invention has many advantages, such as that raw material is easy to get, is low in cost, is easy to operate, is environmentally protective, has suction-operated to heavy metal, can be with scale centralized production and processing.
Description
Technical field
It is recycled the invention belongs to biomass resource and environmental protection technical field, and in particular to one kind is based on excrement slag earthworm
The heavy metal absorbent preparation method of excrement and nanometer calcium.
Background technique
It is continued to develop with industrialization and urbanization, is originated from sewage irrigation, agriculture chemical, metallurgical industry, garbage waste material
Deng heavy metal cause its accumulation in water body and soil by all means.Heavy metal pollution problem is urgently to be resolved.
China is livestock and poultry cultivation big country, and feces of livestock and poultry resource is especially abundant, and in growth trend year by year, it was reported that nearly 20
Nian Lai, the various scale feces of livestock and poultry output of fresh ranges in China are 16.29 hundred million~32.64 hundred million t.Currently, scale raising livestock and poultry
Based on excrement is mainly produced with organic commercial fertilizer, however, being originated from the organic commercial fertilizer of scale raising animal manure production on the market
There is no welcome in the imagination, and then cause it very limited to the consumption power of animal manure and its heap fertile resource.Therefore, it is necessary to expand poultry
Other processing modes of poultry manure and resource utilization approach, therefore, while the present invention is using animal manure production organic fertilizer, research is new
Type heavy metal absorbent, the two is organically combined, and realizes utmostly economic benefit and environmental benefit.
Currently, livestock and poultry dung recovery is utilized less with heavy metal prevention and treatment combination correlative study.Patent application (Shen
Number it please 201210001405.8) provide a kind of method for producing earthworm excrement active carbon using wormcast.The earthworm excrement is to use feces of livestock and poultry
It raises peaceful No. two earthworms to obtain, and then it is pyrolyzed to obtain earthworm excrement active carbon, and there is good adsorption effect.But it was prepared
Journey needs high-temperature process, and preparation cost is expensive, does not have economic feasibility.Patent application (application 201811016682.X) provides
A kind of adsorbent for heavy-metal contaminated soil reparation mainly passes through absorption-Co-bioremediation method.But exist
The disadvantages of adsorbent material degradation causes heavy metal to discharge again, and plant absorption enriching heavy metal is slow.Excrement slag earthworm of the present invention
Excrement and the heavy metal absorbent of nanometer calcium can improve livestock and poultry dung recovery utilization very well, and effectively prevent heavy metal-polluted
Dye.
Summary of the invention
In view of the problems of the existing technology, it is an object of the invention to design to provide one kind based on excrement slag earthworm excrement and nanometer
The technical solution of the heavy metal absorbent preparation method of calcium.
A kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium, it is characterised in that including with
Lower step:
(1) the excrement slag of collection is mixed with cow dung according to mass ratio 1-5:5-9, addition 0.5%-10% nano calcium oxide stirring is equal
It is even, then 100g/t microbe leaven is added in said mixture, then water content is adjusted to 55-75%, pH with distilled water
Buffer adjusts pH value to 6.0-8.0, and makes mixture C/N value to 20-35:1；
(2) mixture for obtaining step (1) is handled using nature pre fermentation, and surface was covered with plastic film, every 15 days left sides
Right turning 1 time, and 2L/t microbial fermentation agent solution is added, it keeps water content in 55-75%, obtains within pre- the compost time 30-45 days
Bait must be tried, when examination bait color is dark brown, free from extraneous odour, quality is soft, and not viscous, as fermentation is completed；
(3) the examination bait for being obtained regulating step (2) with pH buffer to pH value is 6.0-8.0, obtains bait；
(4) earthworm bed is made in the obtained bait heap of step (3), and launches " No. 2 peaceful " earthworm kind to earthworm bed, control bait in earthworm bed
Moisture in 60-75%, pH value 6.0-8.0, temperature is 18-22 DEG C, every 4-9 weeks collections wormcast and to the addition of earthworm bed it is fresh
Bait；
The dispensing earthworm kind is inoculated with oviposition kind earthworm according to density 25-32g/kg；
In the collection earthworm excrement and the fresh bait step of addition, collecting earthworm excrement and adding the mass ratio of bait is 1:1-1:5；
(5) 10-100 mesh is crossed after the earthworm excrement that step (4) are collected being air-dried in the cool, rolled obtains heavy metal adsorption
Agent.
A kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium, it is characterised in that described micro-
Bio-fermentation agent includes bacillus, actinomyces, saccharomycete or other beneficial bacteriums, and living bacteria count is hundred million cfu/ml of 5-10.
A kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium, it is characterised in that the pH
Buffer is the mixture of one or more of acetic acid, vinegar, citric acid, clarification limewash arbitrary proportion.
A kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium, it is characterised in that the earthworm
Bed is semi-underground type, digs 0.3-0.5m downwards on ground, and the pond of 15-30cm high is built by laying on ground, and for surrounding with brick, here is native
Layer, in earthworm bed bait bank up with a thickness of 15-35cm, length 30-120m, width 1-3m.
Application of the heavy metal absorbent based on excrement slag earthworm excrement and nanometer calcium in heavy metal adsorption is fixed.
The application, it is characterised in that the heavy metal absorbent is in pH 3~6,2~10:1 of solid-to-liquid ratio and 15-55 DEG C
When can Pb, Cd effectively in steady removal solution.
The invention has the following advantages:
(1) present invention is bait progress earthworm breeding using excrement slag cow dung and n-CaO, can combine environmental sanitation animal husbandry in one's power
Night soil-treatment is had environmentally protective, low in cost, simple operation and other advantages, can also be focused on scale.
(2) present invention is handled using Natural compost pre fermentation, is then translated into rich in organic matter and is received using earthworm
The multiple polymers of rice calcium oxide (n-CaO), can play absorption or chelation to heavy metal.
Detailed description of the invention
Fig. 1 is the adsorption isothermal curve figure of adsorbent of the present invention；Wherein CV-5%n-CaO is excrement slag, cow dung and 5%n-
The adsorbent that CaO is obtained after vermiculture, CV-10%n-CaO are that excrement slag, cow dung and 10%n-CaO are obtained after vermiculture
The adsorbent obtained, Qe are adsorbance, and Ce is adsorption equilibrium concentration.
Fig. 2 is adsorbent adsorbance of the present invention and temperature relation figure, and Qe is adsorbance.
Fig. 3 is adsorbent adsorbance of the present invention and initial pH relational graph.
Fig. 4 is adsorbent adsorbance of the present invention and initial solid-to-liquid ratio relational graph.
Specific embodiment
Further illustrate the present invention with reference to embodiments.
Embodiment 1: the preparation of heavy metal absorbent
(1) the excrement slag of collection is mixed with cow dung according to mass ratio 3:7, it is equal then adds 5% nano calcium oxide (n-CaO) stirring
It is even, 100g/t microbe leaven is added in said mixture, adjusts water content with distilled water and pH buffer and pH distinguishes
To 65% and 6.5, and make mixture C/N value to 25:1；
Wherein, excrement slag comes from Hangzhou Jianggan District environmental sanitation institute, and cow dung comes from the evergreen dairy cow farm in Hangzhou, in interior after collection
Room temperature is distinguished nature and is placed 15 days or so, and n-CaO calcium is purchased from Wuhan Li Sijie Science and Technology Ltd., and microbe leaven is purchased from river
Biotech company is visitd in southern Europe, and microbe leaven includes bacillus, actinomyces, saccharomycete or other beneficial bacteriums, effectively
Viable count is hundred million cfu/ml of 5-10；
(2) mixture for obtaining step (1) is handled using pre fermentation, and surface is covered with plastic film, turned over every 15 days or so
Heap 1 time, and 2L/t microbial fermentation inoculum solution is added, keep water content 65%, pretreated fermentation obtains examination bait after 35 days；
(3) step (2) is obtained into examination bait pH with pH buffer and is adjusted to 7.0, obtain bait；
(4) bait that step (3) obtains (is dug into 0.4m on ground, 25cm high is built by laying on ground using the cultivation of semi-underground pool downwards
Pond, surrounding is with brick, and here is soil layer, and it is 20cm, a length of 30m, width 2m that bait, which banks up thickness), and launch to earthworm bed close
30g/kg " No. 2 peaceful " earthworm kind is spent, the moisture content for controlling angleworm bait in earthworm bed is 65%, pH value 7.0, and temperature is
20 DEG C, and supplement 1.5 times bait primary every 30 days collection earthworm excrement；
(5) it is sieved with 100 mesh sieve after the earthworm excrement that step (4) are collected being air-dried in the cool, rolled and obtains heavy metal absorbent.
Embodiment 2: the preparation of heavy metal absorbent
(1) the excrement slag of collection is mixed with cow dung according to mass ratio 5:9, then adds 10% nano calcium oxide (n-CaO) stirring
Uniformly, 100g/t microbe leaven is added in said mixture, adjusts water content and pH points with distilled water and pH buffer
Not to 55% and 7.0, and make mixture C/N value to 20:1；
Wherein, excrement slag comes from Hangzhou Jianggan District environmental sanitation institute, and cow dung comes from the evergreen dairy cow farm in Hangzhou, in interior after collection
Room temperature is distinguished nature and is placed 15 days or so, and n-CaO calcium is purchased from Wuhan Li Sijie Science and Technology Ltd., and microbe leaven is purchased from river
Visit biotech company in southern Europe；
(2) mixture for obtaining step (1) is handled using pre fermentation, and surface is covered with plastic film, turned over every 15 days or so
Heap 1 time, and 2L/t microbial fermentation agent solution is added, keep water content 75%, pretreated fermentation obtains examination bait after 42 days；
(3) step (2) is obtained into examination bait pH with pH buffer and is adjusted to 8.0, obtain bait；
(4) bait that step (3) obtains (is dug into 0.4m on ground, 25cm high is built by laying on ground using the cultivation of semi-underground pool downwards
Pond, surrounding is with brick, and here is soil layer, and it is 35cm, a length of 50m, width 1m that bait, which banks up thickness), and launch to earthworm bed close
25g/kg " No. 2 peaceful " earthworm kind is spent, the moisture content for controlling angleworm bait in earthworm bed is 70%, pH value 8.0, and temperature is
22 DEG C, and supplement 1 times bait primary every 42 days collection earthworm excrement；
(5) it is sieved with 100 mesh sieve after the earthworm excrement that step (4) are collected being air-dried in the cool, rolled and obtains heavy metal absorbent.
Embodiment 3: the preparation of heavy metal absorbent
(1) the excrement slag of collection is mixed with cow dung according to mass ratio 1:5, then adds 0.5% nano calcium oxide (n-CaO) stirring
Uniformly, 100g/t microbe leaven is added in said mixture, adjusts water content and pH points with distilled water and pH buffer
Not to 60% and 8.0, and make mixture C/N value to 35:1；
Wherein, excrement slag comes from Hangzhou Jianggan District environmental sanitation institute, and cow dung comes from the evergreen dairy cow farm in Hangzhou, in interior after collection
Room temperature is distinguished nature and is placed 15 days or so, and n-CaO calcium is purchased from Wuhan Li Sijie Science and Technology Ltd., and microbe leaven is purchased from river
Visit biotech company in southern Europe；
(2) mixture for obtaining step (1) is handled using pre fermentation, and surface is covered with plastic film, turned over every 15 days or so
Heap 1 time, and 2L/t microbial fermentation agent solution is added, keep water content 55%, pretreated fermentation obtains examination bait after 30 days；
(3) step (2) is obtained into examination bait pH with pH buffer and is adjusted to 7.5, obtain bait；
(4) bait that step (3) obtains (is dug into 0.4m on ground, 25cm high is built by laying on ground using the cultivation of semi-underground pool downwards
Pond, surrounding is with brick, and here is soil layer, and it is 15cm, a length of 100m, width 3m that bait, which banks up thickness), and launch to earthworm bed close
32g/kg " No. 2 peaceful " earthworm kind is spent, the moisture content for controlling angleworm bait in earthworm bed is 60%, pH value 6.0, and temperature is
18 DEG C, and supplement 2 times bait primary every 45 days collection earthworm excrement；
(5) it is sieved with 100 mesh sieve after the earthworm excrement that step (4) are collected being air-dried in the cool, rolled and obtains heavy metal absorbent.
Embodiment 5: Absorbency Test
(1) raw material and reagent heavy metal absorbent are prepared by embodiment 1, and are air-dried, pulverize, sieved with 100 mesh sieve in shady place
Afterwards for testing, main physical and chemical is shown in Table 1:
The main physical and chemical of 1 heavy metal absorbent of table
| Ingredient | Content |
| C | 11.9% |
| N | 1.0% |
| H | 1.3% |
| 0 | 8.1% |
| pH | 7.04 |
| Conductivity (EC) | 1074μs/cm |
| Ash content | 65.4% |
| Cation exchange capacity (CEC) | 538.6cmol/Kg |
| Specific surface area m2/g | 5.2 |
| Aperture nm | 104.5 |
| Voidage cm3/kg | 27.27 |
Background solution (0.01mol/LNaNO3Solution) it prepares: weigh 1.7gNaNO3Solid dissolves constant volume into the volumetric flask of 2L,
With distilled water constant volume to graduation mark.
10g/L Cd2+Mother liquor: 27.44g Cd (NO is weighed3)2·4H2O solid dissolves constant volume into the volumetric flask of 1L,
With background solution constant volume to graduation mark.
10g/L Pb2+Mother liquor: 15.985g Pb (NO is weighed3)2Solid dissolves in the volumetric flask of constant volume 1L, uses background
Solution constant volume is to graduation mark.
(2) test procedure isothermal adsorption and temperature influence test: pressing 4gL-1Solid-to-liquid ratio heavy metal absorbent is added dense
Degree is 100~1000mgL-1Cd2+Solution and 200~1200mgL-1Pb2+Solution, with 140r at pH=5,25 DEG C
min-1Oscillation is for 24 hours.Separately weigh by 4gL-1It is 400mgL that concentration, which is added, in heavy metal absorbent by solid-to-liquid ratio-1Cd2+Solution and
800mg·L-1Pb2+Solution, with 140rmin at pH=5,15~55 DEG C of temperature-1Oscillation is for 24 hours.Then in 3800rpm from
Heart 5min crosses 0.22 μm of miillpore filter, with pb in flame atomic absorption spectrophotometer measurement filtrate2+、Cd2+Concentration, meter
It calculates to Pb2+、Cd2+Adsorbance (Qe, mgg-1) and adsorption rate (AR).Each sample is repeated 3 times.
Using Henry (formula (1)), Freundlich (formula (2)) and Langmuir (formula (3)) isotherm adsorption model fitting etc.
Warm adsorption process [19], each equation is as follows:
Qe=A+Kh*Ce(1)；
Qe=Kf*Ce b(2)；
Ce/Qe=Ce/Qm+1/(KL*Qm) (3)；
In formula: CeFor adsorption equilibrium concentration, mgL-1；QeAdsorbance for resistance control agent to Pb and Cd, mgg-1；KfHold for absorption
Amount, mgg-1；B indicates adsorption strength size；QmFor maximal absorptive capacity, mgg-1；KLIndicate resistance control agent to heavy metal ion
Affinity, Lmg-1；A and KhIt is absorption constant.
It influences test: heavy metal absorbent is weighed in 10ml centrifuge tube, by 4gL-1Concentration is added in solid-to-liquid ratio
400mg·L-1Cd2+Solution and 800mgL-1Pb2+Solution, pH are respectively 2.0 ± 0.05,3.0 ± 0.05,4. 0 ± 0.05,
5.0 ± 0.05,6.0 ± 0.05.Then with 140rmin in constant temperature (25 DEG C) oscillator-1For 24 hours, 3800rpm is centrifuged for oscillation
5min crosses 0.22 μm of miillpore filter, with Pb in flame atomic absorption spectrophotometer measurement filtrate2+、Cd2+Concentration, and calculate
Its adsorbance (Qe, mgg-1) and adsorption rate (AR).
Solid-to-liquid ratio influences test: weighing heavy metal absorbent in 10ml centrifuge tube, presses 1~10gL of solid-to-liquid ratio respectively-1
Addition concentration is 400mgL-1Cd2+Solution and 800mgL-1Pb2+Solution, with 140rmin at pH=5,25 DEG C-1Oscillation
For 24 hours, 3800rpm is centrifuged 5min, crosses 0.22 μm of miillpore filter, with Pb in flame atomic absorption spectrophotometer measurement filtrate2+、
Cd2+Concentration, and calculate its adsorbance (Qe, mgg-1) and adsorption rate (AR).
(3) result is with the adsorption isothermal curve of analysis heavy metal absorbent of the present invention as shown in Figure 1, as equilibrium concentration increases
Add, the adsorbance to Pb and Cd is in gradually increase trend.Isothermal adsorption of the heavy metal absorbent to Pb and Cd as shown in Table 2
Meeting outer surface monolayer adsorption shown in Langmuir isothermal adsorption process, fitting coefficient range is respectively 0.8506~
0.9554 and 0.9071~0.9201, compare maximal absorptive capacity Q in Langmuir modelmIt is found that as n-CaO ratio increases,
QmIncrease, and CV-10%n-CaO is to the Q of Pb and CdmMaximum, respectively 318.58mgg-1And 198.11mgg-1。
2. heavy metal absorbent of table is to Pb, Cd isothermal adsorption parameter
The absorption property and temperature relation of adsorbent of the present invention increase, CV-5% as shown in Fig. 2, at 15~55 DEG C with temperature
Maximal absorptive capacity Q of the n- CaO and CV-10%n-CaO to Pb and CdmIt is held essentially constant, respectively 200mgg-1With
100mg·g-1Left and right
The adsorbance of heavy metal absorbent of the present invention and pH variation relation are as shown in figure 3, when pH is 2~6, as pH constantly rises
The maximal absorptive capacity Q of height, CV-5%n-CaO and CV-10%n-CaO to Pb and CdmConstantly increase, until balance, and CV-
Maximal absorptive capacity Q of the 5%n-CaO and CV-10%n-CaO to Pb and CdmIt can achieve balance and stability at 3~6 pH.
The absorption property of heavy metal absorbent of the present invention with solid-to-liquid ratio relationship as shown in figure 4, as solid-to-liquid ratio increases, it is right
The maximal absorptive capacity Q of Pb and CdmConstantly decline, the Q of PbmQm higher than Cd, still, CV-5%n-CaO are 4~10 in solid-to-liquid ratio:
Adsorption rate of the 1 and CV-10%n-CaO in 2~10:1 tends towards stability.That is CV-5%n-CaO is 4~10:1 range in solid-to-liquid ratio
Interior, CV-10%n-CaO is that can efficiently remove to Pb, Cd within the scope of 2~10:1 in solid-to-liquid ratio.
Claims (6)
1. a kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium, it is characterised in that the following steps are included:
(1) the excrement slag of collection is mixed with cow dung according to mass ratio 1-5:5-9, addition 0.5%-10% nano calcium oxide stirring is equal
It is even, then 100 g/t microbe leavens are added in said mixture, then water content is adjusted to 55-75%, pH with distilled water
Buffer adjusts pH value to 6.0-8.0, and makes mixture C/N value to 20-35:1；
(2) mixture for obtaining step (1) is handled using nature pre fermentation, and surface was covered with plastic film, every 15 days left sides
Right turning 1 time, and 2 L/t microbial fermentation agent solutions are added, it keeps water content in 55-75%, obtains within pre- the compost time 30-45 days
Bait must be tried, when examination bait color is dark brown, free from extraneous odour, quality is soft, and not viscous, as fermentation is completed；
(3) the examination bait for being obtained regulating step (2) with pH buffer to pH value is 6.0-8.0, obtains bait；
(4) earthworm bed is made in the obtained bait heap of step (3), and launches " No. 2 peaceful " earthworm kind to earthworm bed, control bait in earthworm bed
Moisture in 60-75%, pH value 6.0-8.0, temperature is 18-22 DEG C, every 4-9 weeks collections wormcast and to the addition of earthworm bed it is fresh
Bait；
The dispensing earthworm kind is inoculated with oviposition kind earthworm according to density 25-32g/kg；
In the collection earthworm excrement and the fresh bait step of addition, collecting earthworm excrement and adding the mass ratio of bait is 1:1- 1:5；
(5) 10-100 mesh is crossed after the earthworm excrement that step (4) are collected being air-dried in the cool, rolled obtains heavy metal adsorption
Agent.
2. a kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium as described in claim 1, feature
It is that the microbe leaven includes bacillus, actinomyces, saccharomycete or other beneficial bacteriums, living bacteria count 5-10
Hundred million cfu/ml.
3. a kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium as described in claim 1, feature
It is that the pH buffer is the mixing of one or more of acetic acid, vinegar, citric acid, clarification limewash arbitrary proportion
Object.
4. a kind of heavy metal absorbent preparation method based on excrement slag earthworm excrement and nanometer calcium as described in claim 1, feature
Be that the earthworm bed is semi-underground type, dig 0.3-0.5m downwards on ground, the pond of 15-30cm high is built by laying on ground, surrounding with brick,
Here is soil layer, in earthworm bed bait bank up with a thickness of 15-35cm, length 30-120m, width 1-3m.
5. the heavy metal absorbent based on excrement slag earthworm excrement and nanometer calcium being prepared by claim 1 is solid in heavy metal adsorption
Application in fixed.
6. application as claimed in claim 5, it is characterised in that the heavy metal absorbent in pH 3 ~ 6,2 ~ 10:1 of solid-to-liquid ratio and
It can Pb, Cd effectively in steady removal solution at 15-55 DEG C.
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| CN113105277A (en) * | 2021-03-25 | 2021-07-13 | 杭州师范大学 | Preparation method of functional earthworm cast with Pb and Cd adsorption performance |
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