CN110423617A - Frass and its residue are for the application in heavy metal-passivated - Google Patents
Frass and its residue are for the application in heavy metal-passivated Download PDFInfo
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- CN110423617A CN110423617A CN201910697247.6A CN201910697247A CN110423617A CN 110423617 A CN110423617 A CN 110423617A CN 201910697247 A CN201910697247 A CN 201910697247A CN 110423617 A CN110423617 A CN 110423617A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to frass indissolvable components for the application in heavy metal-passivated.Wherein, the frass is the excrement that at least one of Scarabaeoidea (Scarabaeoidea) insect generates, and the heavy metal includes at least one of Pb, Cu and Cd.
Description
Technical field
The present invention relates to frass for the application in heavy metal-passivated, especially from the frass residue wherein extracted with
Application in heavy metal-passivated.
Background technique
Heavy metal pollution problem is one of the problem that the world today is faced.Soil is the important composition portion of natural environment
Point, heavy-metal contaminated soil simultaneously can pollute water environment and atmospheric environment, can be in atmospheric thermodynamics, water body circle and biological chain
It is constantly shifted and is enriched with, for example, being enriched in agricultural product, influence agricultural output and safety, and by food chain to dynamic
The life and health of object and the mankind cause damages.The strategy of heavy metal reparation at present is broadly divided into two types, and one kind is removing, and one
Kind is solidification.Removal refers to through certain technological means, and heavy metal is separated from soil, achievees the purpose that rehabilitating soil.
Solidification is then that heavy metal is limited in a certain region, and to reduce the harmfulness of pollution, which needs special material.Whether it goes
Except strategy, or solidification strategy, it is big to there is cost in the mode of operation of existing rehabilitating soil, the problems such as is not easy to promote.
Summary of the invention
The excrement that one of present invention provides the generation of at least one of Scarabaeoidea (Scarabaeoidea) insect is being used for
Application in heavy metal-passivated.
In a specific embodiment, the heavy metal includes at least one of Pb, Cu and Cd.
In a specific embodiment, the insect is selected from cetoniidae (Cetoniidae), rhinoceros Scarabaeidae
(Dynastidae), Passalidae (Passalidae), quasi- Lucanidae (Sinodendridae), Lucanidae (Lucanidae), excrement
Scarabaeidae (Geotrupidae), Trogidae (Trogidae), Aphodiidae (Aphodiidae), spot Scarabaeidae
(Trichiidae), at least one of fat Scarabaeidae (Valgidae), Scarabaeidae (Scarabaeidae) insect.
In a specific embodiment, the insect is selected from protaetia brevitarsis (Protaetia
BrevitarsisLewis), Allomyrina dichotoma (Allomyrina dichtoma), in dung beetle (Catharsius molossus)
At least one.
In a specific embodiment, the excrement is at least one of Scarabaeoidea (Scarabaeoidea) insect
Larva and/or adult generate excrement.
In a specific embodiment, the excrement is at least one of Scarabaeoidea (Scarabaeoidea) insect
Larva generate excrement.
The two of the present invention provide a kind of frass residue for the application in heavy metal-passivated, and the frass residue is the
One of one frass residue, the second frass residue and third frass residue, the heavy metal are as any in one of present invention
The heavy metal in application described in one；
Wherein, the preparation method of the frass residue includes the following steps:
1) in terms of by water content in 3% dry excrement below, excrement is mixed with solvent with the mass ratio of 1:1 to 1:10
Afterwards, adjusting pH value is 8 to 12, and temperature is 30 DEG C to 100 DEG C, handles 20 minutes to 60 minutes, obtains treatment fluid；Wherein, described
Excrement is at least one of the Scarabaeoidea (Scarabaeoidea) in the application as described in any one of one of present invention elder brother
The excrement that worm generates；
2) pH for adjusting the treatment fluid is 6 to 8, is settled 0 to 48 hour at 1 DEG C to 50 DEG C, heavy by what is settled down
Object and thick supernatant separation drop, to obtain the sediment, the sediment is the first frass residue；
3) the thick supernatant is separated by solid-liquid separation, to obtain the second frass residue for solid component.
Wherein it should be pointed out that in step 2), the sedimentation time be 0 when, also mean that do not settle and directly to place
Reason liquid is separated by solid-liquid separation, therefore at this point, is actually to eliminate the separation of sediment and thick supernatant and direct in step 2)
It enters step in 3), therefore, the thick supernatant in step 3) is equal to the processing after being adjusted to pH 6 to 8 at this time
Liquid is intended merely to statement conveniently, is no longer distinguish herein.In addition, readily comprehensible, sediment and thick supernatant in step 2)
The separation of liquid may simply be container where pumping out thick supernatant and sediment stayed to the process in the container.
Excrement used in the step 1), can be for by dry excrement, or the excrement of undried processing
Just.That is, the dry excrement is not required, to dry in terms of excrement, merely to accurately stating each component as far as possible
Between dosage relation.In addition, it is dry can be dry be also possible to not higher than in frass residue preparation process temperature (such as
80 DEG C) under dry.In addition, the excrement can carry out pulverization process before mixing with solvent, it can also be after being mixed with solvent
Carry out pulverization process.The excrement can be used ball crusher and/or pulverizer etc. and crush or pulverize frass.Its with it is molten
After agent (such as water) mixing, ultrasonic wave can also be used further to homogenize.
According to inventor to the frass residue obtained under the conditions of different disposal temperature, pH and the extraction efficiency of frass extract
It was found that, under alkaline condition, using higher Temperature Treatment frass, the extraction of higher frass extract can be obtained
Yield, to greatest extent separate frass residue with frass extract.I.e. actually lower than 30 DEG C at a temperature of, can also
To obtain the separation of certain a certain amount of frass residue and frass extract.But in order to obtain higher separation yield, preferably
Use higher treatment temperature.
Therefore, in a specific embodiment, in the step 1), temperature can be 30 DEG C, 35 DEG C, 40 DEG C, 45
DEG C, 35 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C.
In a specific embodiment, in the step 1), the processing time can be 20 minutes, 21 minutes, 22 points
Clock, 23 minutes, 24 minutes, 25 minutes, 26 minutes, 27 minutes, 28 minutes, 29 minutes, 30 minutes, 31 minutes, 32 minutes, 33 points
Clock, 34 minutes, 35 minutes, 36 minutes, 37 minutes, 38 minutes, 39 minutes, 40 minutes, 41 minutes, 42 minutes, 43 minutes, 44 points
Clock, 45 minutes, 46 minutes, 47 minutes, 48 minutes, 49 minutes, 50 minutes, 51 minutes, 52 minutes, 53 minutes, 54 minutes, 55 points
Clock, 56 minutes, 57 minutes, 58 minutes, 59 minutes or 60 minutes.
Treatment temperature and influence of the processing time to yield have certain correlation, can handle at a higher temperature compared with
Few time obtains relatively high yield.
In a specific embodiment, in the step 1), by water content in 3% dry excrement below in terms of, will
After excrement is mixed with water with the mass ratio of 1:3 to 1:6, adjusting pH value is 9 to 11, and temperature is 50 DEG C to 100 DEG C, is handled 30 minutes
To 40 minutes, the treatment fluid is obtained.
In a specific embodiment, in the step 1), by water content in 3% dry excrement below in terms of, will
After excrement is mixed with water with the mass ratio of 1:3 to 1:6, adjusting pH value is 9 to 11, and temperature is 60 DEG C to 90 DEG C, is handled 30 minutes
To 40 minutes, the treatment fluid is obtained.
In a specific embodiment, in the step 1), by water content in 3% dry excrement below in terms of, will
After excrement is mixed with water with the mass ratio of 1:3 to 1:6, adjusting pH value is 9 to 11, and temperature is 70 DEG C to 90 DEG C, is handled 30 minutes
To 40 minutes, the treatment fluid is obtained.
In a specific embodiment, in the step 1), the solvent is polar solvent.
In a specific embodiment, in the step 1), the solvent is water.
In a specific embodiment, in the step 2), the pH for adjusting the treatment fluid is 7.0 to 7.5,15
DEG C to settling 2 hours to 24 hours at 40 DEG C, by the sediment to settle down and the thick supernatant separation, to obtain
The sediment, the sediment are the first frass residue.
It in a specific embodiment, further include described in crushing in the step 1) or before the step 1)
The step of excrement.
In a specific embodiment, heavy using sedimentation centrifuge, inclined plate settler and inclined tube in the step 3)
It drops at least one of device and realizes separation of solid and liquid, to obtain the second frass residue.
In a specific embodiment, the method also includes the steps 4) after the step 3): by described first
Frass residue and the second frass residue consolidation, obtain the third frass residue.
In a specific embodiment, the method also includes steps 5): by the first frass residue, described second
Frass residue or the third frass residue are dry.So can reduce volume, and facilitate storage and transport etc..
In a specific embodiment, the processing of the step 1) and the step 2) can not in same container into
Row, such as in step 1), can be carried out in the reactor for being conducive to its treatment conditions；And in step 2), it can be by step
It is rapid 1) in treatment fluid move on in the containers such as settling tank and carry out.
Beneficial effects of the present invention:
By using technology of the invention can directly to byproduct --- the frass generated in chafer breeding process, or
Person frass is further extracted after byproduct --- residue is used, realize by suction-operated come in effective fixing soil
Heavy metal purpose, this method not only has the advantages that at low cost, and will not generate any side effect.In addition, by supporting
This material of heavy metal will further be adsorbed, be passivated from soil by growing chafer and can also realizing that existing agricultural wastes are converted
It is removed in earth, can remove the heavy metal in soil, can reach the purpose of complete rehabilitating soil.
Term used is the term of this field usual definition in the present invention.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the exemplary only explanation of the embodiment of the present invention,
No matter these embodiments do not constitute a limitation of the invention under any circumstance.
Corn etc. is collected to do the crushing of object stalk or collect the edible fungi residues such as mushroom or collect the herbivores excrement such as cattle and sheep
Just protaetia brevitarsis larva is fed as raw material.
Leaching of Heavy Metals quantity measuring method: referring to " solid waste Leaching leaching method hac buffer method " (HJ/
T 300-2007): according to the moisture content of pedotheque, appropriate pedotheque is weighed, and according to liquid-solid ratio 20: 1 (L/kg), to soil
Appropriate digestion agent is added in earth sample, vibrates, centrifugation takes supernatant to cross 0.45 μm of filter membrane removal particulate matter, inhaled with NITRATE BY FLAME ATOMIC
It receives (flame atomic absorption spectrophotometer, Hitachi Z-2000) measurement and leaches content of beary metal.Three repetitions are set, and data are made even
Mean value.
Embodiment 1
The preparation of frass residue
(1) collect protaetia brevitarsis larva frass and in 80 DEG C of drying dryings, make its water content in 3wt% hereinafter, powder
It is broken, cross 20 meshes.
(2) it is put into the sieving frass and water that mass ratio is 1:4 in the reactor, adjusting pH value with NaOH is 11, in temperature
Processing 40 minutes under 90 DEG C or so, and be stirred, dissolve grub excrement.
(3) reaction mass in step (2) is put into liquid storage tank, is down to environment temperature (25 DEG C), using phosphoric acid by soda acid
Degree modulation is neutral, pH 7.0；Above-mentioned neutral mixture pump is entered sedimentation centrifuge to be separated by solid-liquid separation, the isolated insoluble system of solutions
Point.
(4) indissolvable component is dried 2 hours in 100 DEG C, obtains frass residue 1#.The yield of frass residue is with dry powder g/ worm
Excrement g is calculated as 75%.
Embodiment 2
The preparation of frass residue --- investigate influence of the usage ratio of frass and water to yield
The quality such as table 1 of drying frass and water in step (2).Other are the same as embodiment 1.The yield of frass residue is with dry
Powder g/ frass g meter.
Table 1
Embodiment 3
The preparation of frass residue --- pH value, temperature and the processing time in step (2) treatment process are investigated to yield
It influences
PH value, temperature and processing time such as table 2 in step (2).Other are the same as embodiment 1.The yield of frass residue is with dry
Powder g/ frass g meter.
Table 2
Embodiment 4
The preparation of frass residue --- investigate influence of step (2) the different alkali to yield
Alkali type such as table 3 in step (2).Other are the same as embodiment 1.Frass insoluble component yield is in terms of dry powder g/ frass g.
Table 3
Embodiment 5
The preparation of frass residue --- pH value, temperature and the sedimentation time in step (3) treatment process are investigated to yield
It influences
PH value, temperature and sedimentation time such as table 4 in step (3) are centrifuged after sedimentation.Other are the same as embodiment 1.Worm
The yield of excrement residue is in terms of dry powder g/ frass g.
Table 4
Embodiment 6
Frass residue active constituent is to Pb2+Passivation ability
To containing Pb2+Respectively according to the ratio of 0.2wt%, 0.40wt%, 0.80wt% and 1.60wt% in contaminated soil
Insoluble component is prepared in addition embodiment 1 to 5 to example respectively --- frass residue；Keeping water content after mixing is field
Under conditions of water-holding capacity 60% when passivation reaction 5d, Pb in soil is measured2+Leaching concentration.Not add the soil of any excrement
As blank control.It the results are shown in Table 5.
5 Pb of table2+Leaching concentration (mg/L)
According to table 5 it is found that the frass residue of protaetia brevitarsis larva is to Pb2+With passivation ability, i.e. frass residue can
Reduce Pb2+Leaching concentration, and with the increase of frass sludge concentration, passivation ability increases；Different frass residue samples exist
There was no significant difference in the identical processing time.
Embodiment 7
Frass residue active constituent is to Cu2+Passivation ability
To containing Cu2+Respectively according to the ratio of 0.2wt%, 0.40wt%, 0.80wt% and 1.60wt% in contaminated soil
Insoluble component is prepared in addition embodiment 1 to 5 to example respectively --- frass residue；Keeping water content after mixing is field
Under conditions of water-holding capacity 60% when passivation reaction 5d, Cu in soil is measured2+Leaching concentration.Not add the soil of any excrement
As blank control.It the results are shown in Table 6.
6 Cu of table2+Leaching concentration (mg/L)
According to table 6 it is found that the frass residue of protaetia brevitarsis larva is to Cu2+With passivation ability, i.e. frass residue can
Reduce Cu2+Leaching concentration, and with the increase of frass sludge concentration, passivation ability increases；Different frass residue samples exist
There was no significant difference in the identical processing time.
Embodiment 8
Frass residue active constituent is to Cd2+Passivation ability
To containing Cd2+Respectively according to the ratio of 0.2wt%, 0.40wt%, 0.80wt% and 1.60wt% in contaminated soil
Insoluble component is prepared in addition embodiment 1 to 5 to example respectively --- frass residue；Keeping water content after mixing is field
Under conditions of water-holding capacity 60% when passivation reaction 5d, Cd in soil is measured2+Leaching concentration.Not add the soil of any excrement
As blank control.It the results are shown in Table 7.
7 Cd of table2+Leaching concentration (mg/L)
According to table 7 it is found that the frass residue of protaetia brevitarsis larva is to Cd2+With passivation ability, i.e. frass residue can
Reduce Cd2+Leaching concentration, and with the increase of frass sludge concentration, passivation ability increases；Different frass residue samples exist
There was no significant difference in the identical processing time.
Claims (10)
1. the excrement that at least one of Scarabaeoidea (Scarabaeoidea) insect generates is for answering in heavy metal-passivated
With.
2. application according to claim 1, which is characterized in that the heavy metal includes at least one in Pb, Cu and Cd
Kind.
3. application according to claim 1 or 2, which is characterized in that the insect is selected from cetoniidae
(Cetoniidae), rhinoceros Scarabaeidae (Dynastidae), Passalidae (Passalidae), quasi- Lucanidae (Sinodendridae),
Lucanidae (Lucanidae), dorbeetle section (Geotrupidae), Trogidae (Trogidae), Aphodiidae
(Aphodiidae), spot Scarabaeidae (Trichiidae), fat Scarabaeidae (Valgidae), in Scarabaeidae (Scarabaeidae)
At least one insect.
4. application according to claim 1 or 2, which is characterized in that the insect is selected from protaetia brevitarsis
(Protaetia brevitarsis Lewis), Allomyrina dichotoma (Allomyrina dichtoma), dung beetle (Catharsius
At least one of molossus).
5. application as claimed in any of claims 1 to 4, which is characterized in that the excrement is Scarabaeoidea
At least one of (Scarabaeoidea) excrement that the larva of insect and/or adult generate.
6. application as claimed in any of claims 1 to 5, which is characterized in that the excrement is Scarabaeoidea
At least one of (Scarabaeoidea) excrement that the larva of insect generates.
7. a kind of frass residue is for the application in heavy metal-passivated, the frass residue is the first frass residue, the second worm
One of excrement residue and third frass residue, the heavy metal are in the application as described in any one of claim 1 to 6
The heavy metal；
Wherein, the preparation method of the frass residue includes the following steps:
1) it in terms of by water content in 3% dry excrement below, after excrement is mixed with solvent with the mass ratio of 1:1 to 1:10, adjusts
Saving pH value is 8 to 12, and temperature is 30 DEG C to 100 DEG C, handles 20 to 60 minutes, obtains treatment fluid；Wherein, the excrement is as weighed
Benefit require any one of 1 to 6 described at least one of Scarabaeoidea (Scarabaeoidea) insect in application generate
Excrement；
2) pH for adjusting the treatment fluid is 6 to 8, is settled 0 to 48 hour at 1 DEG C to 50 DEG C, the sediment that will be settled down
With thick supernatant separation, to obtain the sediment, the sediment is the first frass residue；
3) the thick supernatant is separated by solid-liquid separation, to obtain the second frass residue for solid component.
8. below dry 3% with water content the method according to the description of claim 7 is characterized in that in the step 1)
Dry excrement meter, after excrement is mixed with water with the mass ratio of 1:3 to 1:6, adjusting pH value is 9 to 11, and temperature is 50 DEG C to 100
DEG C, it handles 30 minutes to 40 minutes, obtains the treatment fluid；
Preferably, in the step 1), by water content in 3% dry excrement below in terms of, by excrement and water with 1:3 to 1:6
Mass ratio mixing after, adjust pH value be 9 to 11, temperature be 60 DEG C to 90 DEG C, handle 30 minutes to 40 minutes, obtain the place
Manage liquid；
Preferably, in the step 1), by water content in 3% dry excrement below in terms of, by excrement and water with 1:3 to 1:6
Mass ratio mixing after, adjust pH value be 9 to 11, temperature be 70 DEG C to 90 DEG C, handle 30 minutes to 40 minutes, obtain the place
Manage liquid；
Preferably, in the step 1), the solvent is polar solvent；
Preferably, in the step 1), the solvent is water；
In the step 2), the pH for adjusting the treatment fluid is 7.0 to 7.5, is settled at 15 DEG C to 40 DEG C 2 hours to 24 small
When, by the sediment to settle down and the thick supernatant separation, to obtain the sediment, the sediment is institute
State the first frass residue.
9. method according to claim 7 or 8, which is characterized in that in the step 1) or before the step 1),
Further include the steps that crushing the excrement；
Preferably, real using at least one of sedimentation centrifuge, inclined plate settler and inclined tube settler in the step 3)
It is now separated by solid-liquid separation, to obtain the second frass residue；
Preferably, the method also includes the steps 4) after the step 3): by the first frass residue and described second
Frass residue consolidation obtains the third frass residue.
10. the method according to any one of claim 7 to 9, which is characterized in that the method also includes steps 5):
The first frass residue, the second frass residue or the third frass residue is dry.
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| CN201910697247.6A CN110423617B (en) | 2019-07-30 | 2019-07-30 | Application of insect manure and residue thereof in passivation of heavy metals |
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| CN201910697247.6A CN110423617B (en) | 2019-07-30 | 2019-07-30 | Application of insect manure and residue thereof in passivation of heavy metals |
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| CN1223627A (en) * | 1996-06-27 | 1999-07-21 | 奥根诺弗劳尔(控股)有限公司 | Method of preparing base material of liquid fertilizer |
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