CN107265582A - A kind of compound shellfish modification biological dephosphorization material and its preparation method and application - Google Patents
A kind of compound shellfish modification biological dephosphorization material and its preparation method and application Download PDFInfo
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- CN107265582A CN107265582A CN201710320290.1A CN201710320290A CN107265582A CN 107265582 A CN107265582 A CN 107265582A CN 201710320290 A CN201710320290 A CN 201710320290A CN 107265582 A CN107265582 A CN 107265582A
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- Prior art keywords
- shellfish
- modification biological
- dephosphorization material
- biological dephosphorization
- compound
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F2101/105—Phosphorus compounds
Abstract
The invention discloses a kind of compound shellfish modification biological dephosphorization material and its preparation method and application, this method uses a certain proportion of Trachyostracous mussel shell, oyster shell and scallop shell for raw material, by carrying out the pre-heat treatment, calcination processing and isothermal holding to the raw material after crushing, powdered compound shellfish modification biological dephosphorization material is made, and the dephosphorization material is applied to waste water dephosphorization.The preparation technology of the present invention is simple, the recycling of waste resource is realized, with certain society, economy and environmental benefit.The modification biological dephosphorization material of preparation, its clearance to water systems'phosphorus has reached more than 90%, with good dephosphorization water purification ability.By changing dosing method, after modification biological dephosphorization material is wrapped up with sustained release bag in input water body, phosphor-removing effect can be obviously improved and held time.
Description
Technical field
The invention belongs to material for water treatment technical field, and in particular to a kind of compound shellfish modification biological dephosphorization material and its
Preparation method and application.
Background technology
Water pollution problems has seriously constrained Chinese society further development and the raising of living standards of the people.With work
Industry, urbanization speed are accelerated, and the world is faced with shortage of water resources, with serious pollution challenge, in China, especially samll cities and towns
The body eutrophication that the fast-developing, expansion of urban population and agricultural pollution etc. are caused, is that China's water resource is topmost
Problem.Eutrophication causes blue-green alga bloom to take place frequently, it is a series of tight to threaten reference water head site safety, industrial or agricultural water can not meet etc.
High problem.
The main cause of body eutrophication be rich nutritive material input into water ecosystem it is a large amount of it is accumulative caused by, its
In, phosphorus is the essential element for producing body eutrophication.Control at present, removal P elements are mainly used at biodegradable, chemistry
The methods such as reason, physical absorption.
Physisorphtion is will to cause the P elements of the strong state of eutrophication in water body using the porous material of surface porosity
Absorption is on its surface so as to disengage it from water body.This method dephosphorization efficiency is not high, delivers after a large amount of adsorbent powders, and mud increases
It is many, reclaim difficult, secondary pollution is more serious；Method of chemical treatment is to enter polluted-water using adding chemical reagent, by with
Free state P elements generation chemical reaction disengages it from water body in water body,.This method needs to deliver substantial amounts of chemical reagent, into
This height, the sludge that reagent enters water body formation can cause the secondary pollution of water body；Biological degradation method is to utilize animal, plant, micro-
Biology etc. is removed to the phosphorus being enriched with water body, this method clean environment firendly, does not cause other to pollute, but takes time and effort running
Time interval is longer.
Because more or less all there is different degrees of defect in above-mentioned phosphorus removing method, therefore, find it is more environmentally friendly, efficient,
The problem of cheap modification biological dephosphorization material is still one very important.
The content of the invention
For the above mentioned problem of prior art, it is an object of the invention to provide a kind of efficient, high adsorption capacity, effect are bright
Aobvious, instant effect and the low compound shellfish modification biological dephosphorization material of cost and its preparation method and application.
In order to solve the above problems, the technical scheme that the present invention is provided includes the following aspects.
The first aspect of the present invention provides a kind of preparation method of compound shellfish modification biological dephosphorization material, the dephosphorization
The mass percent of each component is in the composition of raw materials of material：Trachyostracous mussel shell 30%, oyster shell 45%, scallop shell 25%；
The preparation method comprises the following steps：
(1) the biological shell of shellfish is weighed by composition of raw materials, is ground into a diameter of 50~150mm particle；
(2) preheated 1~3 hour at a temperature of the biological shell of shellfish after crushing being placed in into 350~500 DEG C, then heat to 700
~850 DEG C are calcined 0.5~2 hour；
(3) 200~300 DEG C are cooled the temperature to, 1~3 hour is incubated, the compound shellfish modification biological dephosphorization material is made
Material.
The present invention prepares the outstanding modified biological material of efficient dephosphorization drop using the above method, make use of the compound shellfish to be modified
The high-effective cationic polarity of biological phosphate-eliminating material, efficient absorption ability and the characteristic reacted is combined with P elements, can
Reach good phosphor-removing effect.
Due to Trachyostracous mussel shell, oyster shell and scallop shell, its main component is CaCO3, the CaCO after high-temperature calcination3Decompose
For CaO and CO2, and different calcining heats and calcination time can influence the CaO and CaCO in final material3Content.CaO
Into after water body, further hydrolysis generates calcium hydroxide and discharges OH-, the OH-Reacted with the phosphate anion in water body, from
And cause the P elements in water body with hydroxyapatite CaHPO4-2H2O form is fixed, and reaches dephosphorization purifying water body
Effect.
It is preferred that, the biological shell of shellfish described in step (2) is preheated 2 hours at a temperature of 450 DEG C, then in 750 DEG C
Calcined 1 hour under temperature conditionss.
It is preferred that, the temperature of the step (3) is down to 250 DEG C, is incubated 2 hours.
The second aspect of the present invention provides a kind of compound shellfish of the technical scheme preparation using above-mentioned first aspect and changed
Property biological phosphate-eliminating material.
The third aspect of the present invention provides a kind of compound shellfish modification biological dephosphorization material using above-mentioned second aspect
Remove the application of Phosphorus From Wastewater.
It is preferred in one embodiment, added into phosphorus-containing wastewater and shellfish modification biological dephosphorization material is combined described in 3~15g
Material, the reaction time is 30~40min.
Preferred in one embodiment, quality of the compound shellfish modification biological dephosphorization material in phosphorus-containing wastewater is dense
Spend for 0.2~0.4g/L, more preferably 0.35g/L.
In one embodiment, added into waste water and shellfish modification biological dephosphorization material is combined described in 0.1~1.0g/L, place
The reason time is 2~3d.
In one embodiment, the compound shellfish modification biological dephosphorization material is wrapped up with the sustained release bag of 150~250 mesh,
Then the material after parcel is added in phosphorus-containing wastewater.
Preferred in one embodiment, the sustained release bag is made up of non-woven fabrics.
Compared with prior art, the present invention has the advantages that：
1) present invention is using discarded Trachyostracous mussel shell, oyster shell, scallop shell as raw material, and compound material simultaneously forge by its progress high temperature
Modification is burnt, compound shellfish modification biological dephosphorization material is prepared, its technique is simple, realizes the recycling of waste resource, has
There are certain society, economy and environmental benefit.
2) compound shellfish modification biological dephosphorization material prepared by the present invention, it is to the total phosphorus in phosphorus-containing wastewater and black-odor riverway
Clearance takes into account nitrogen removal rate more than 60% more than 90%, with good dephosphorization water purification ability.
3) material dephosphorizing rate maximum of the present invention can reach 200mg/g materials'use rates, by changing dosing method, with sustained release
After bag such as non-woven fabrics wraps up modification biological dephosphorization material in input water body, phosphor-removing effect can be obviously improved and held time.
Brief description of the drawings
Fig. 1 show the surface texture photo of the modification biological dephosphorization material in one embodiment of the invention.
Fig. 2 show the phosphor-removing effect of the modification biological dephosphorization material and traditional dephosphorization material in one embodiment of the invention
Comparison diagram, wherein, a) show the phosphor-removing effect figure of traditional dephosphorization material；B) it show the modification biological dephosphorization material of the present invention
The phosphor-removing effect figure of material.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained on the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
What the total phosphorus (TP) in the embodiment of the present invention was write according to State Environmental Protection Administration《Water and effluent monitoring analysis side
Method (fourth edition)》Middle regulation " molybdenum-antimony anti-spectrophotometric method " is measured；
Total nitrogen (TN) is write according to foundation State Environmental Protection Administration《Water and effluent monitoring analysis method (fourth edition)》
Middle regulation " peroxide potassium sulfate-ultraviolet spectrophotometry " is measured；
What the content of chlorophyll was write according to State Environmental Protection Administration《Water and effluent monitoring analysis method (fourth edition)》
Middle regulation " Determination of primary productivity " method is measured.
Embodiment 1
A kind of preparation method of compound shellfish modification biological dephosphorization material is present embodiments provided, this method includes following step
Suddenly：
1) by fresh Trachyostracous mussel, oyster, scallop removes wherein meat tissue, after being cleaned up with clear water, and housing is natural
Air-dry 2~5 days, weeds and other materials for removing surface attachment are standby.
2) by mass percentage be Trachyostracous mussel shell 30%, oyster shell 45%, scallop shell 25% weigh respectively air-dry after
Shell housing, and it is crushed into a diameter of 50~150mm particle.
2) take the about 250g of the particle after above-mentioned crushing to be put into crucible, Muffle furnace energization temperature is risen to 350 DEG C, temperature is treated
After stable, crucible is put into Muffle furnace and preheated 1 hour, muffle furnace is then risen to 700 DEG C, is calcined 0.5 hour.
3) calcination time is arrived, and muffle furnace is down into 200 DEG C, is incubated 1 hour, is then shut off Muffle furnace power supply, natural
Material in cooling, crucible is preserved in powdered rear taking-up in the case where humidity is not more than 30% dry environment.
Embodiment 2
A kind of preparation method of compound shellfish modification biological dephosphorization material is present embodiments provided, this method includes following step
Suddenly：
1) by fresh Trachyostracous mussel, oyster, scallop removes wherein meat tissue, after being cleaned up with clear water, and housing is natural
Air-dry 2~5 days, weeds and other materials for removing surface attachment are standby.
2) take the about 250g of the particle after above-mentioned crushing to be put into crucible, Muffle furnace energization temperature is risen to 450 DEG C, temperature is treated
After stable, crucible is put into Muffle furnace and preheated 2 hours, muffle furnace is then risen to 750 DEG C, is calcined 1 hour.
3) calcination time is arrived, and muffle furnace is down into 250 DEG C, is incubated 2 hours, is then shut off Muffle furnace power supply, natural
Material in cooling, crucible is preserved in powdered rear taking-up in the case where humidity is not more than 30% dry environment.
The surface texture photo of the compound shellfish modification biological dephosphorization material of the present embodiment refers to Fig. 1.
Embodiment 3
A kind of preparation method of compound shellfish modification biological dephosphorization material is present embodiments provided, this method includes following step
Suddenly：
1) by fresh Trachyostracous mussel, oyster, scallop removes wherein meat tissue, after being cleaned up with clear water, and housing is natural
Air-dry 2~5 days, weeds and other materials for removing surface attachment are standby.
2) take the about 250g of the particle after above-mentioned crushing to be put into crucible, Muffle furnace energization temperature is risen to 500 DEG C, temperature is treated
After stable, crucible is put into Muffle furnace and preheated 3 hours, muffle furnace is then risen to 800 DEG C, is calcined 2 hours.
3) calcination time is arrived, and muffle furnace is down into 300 DEG C, is incubated 3 hours, is then shut off Muffle furnace power supply, natural
Material in cooling, crucible is preserved in powdered rear taking-up in the case where humidity is not more than 30% dry environment.
Embodiment 4
The embodiment of the present invention 2 is combined shellfish modification biological dephosphorization material performance measurement：
Configure the simulation phosphorus-containing wastewater (KH that initial phosphorus concentration is 100mg/L2PO4The aqueous solution) 100mL；Contain to above-mentioned simulation
The compound shellfish modification biological dephosphorization material of 20g embodiments 2 is added in phosphorus waste water；Reacted under 25 DEG C of temperature conditionss, reaction
Cleaning is taken to determine phosphorus concentration after end after static 10min, measurement result is shown in Fig. 2 b) shown in.Wherein, Fig. 2 a) gives
Traditional dephosphorization material gravel, the measurement result of volcanic rock and zeolite under above-mentioned similarity condition.
As shown in Figure 2 the compound shellfish modification biological dephosphorization material of the present embodiment be placed in P elements enrichment waste water in 30~
After 40min, sampling and testing is to water body tp removal rate more than 90%.
Embodiment 5
The compound shellfish modification biological dephosphorization material for taking 3~15g embodiments 2 to prepare, 20L water is added into above-mentioned material,
And stir so that material therein is uniformly dispersed, then static placement obtains compound shellfish modification biological dephosphorization material solution；
Configuration simulation high-concentration phosphorus-containing wastewater (20g/L KH2PO4The aqueous solution)；
Above-mentioned high-concentration phosphorus-containing wastewater is added into modification biological dephosphorization material solution several times, each addition is
5mL.It is stirred after adding every time, the remaining P elements that question response takes supernatant to determine in liquid after in half an hour are dense
Degree, if not up to saturation state, continuously adds phosphorus-containing wastewater, determines residual concentration.
Experimental result shows that 3~15g of the invention is combined shellfish modification biological dephosphorization material maximum processing access times dimension
Hold at 7~12 times, remove maximum P elements quality and be between 596~722mg.The compound shellfish modification biological dephosphorization of the present invention
Material dephosphorizing rate maximum can reach 200mg/g materials'use rates.
Mass concentration of the compound shellfish modification biological dephosphorization material in phosphorus-containing wastewater of the present invention be preferably 0.2~
0.4g/L, more preferably 0.35g/L.When dosage is 0.4g/L, continue that water ecosystem state can be made in 2~3 days
Change, now occur ecological process change by removing P elements by initial eutrophy muddy water state, be changed into clear water
State.
Embodiment 6
Take 3~15g embodiments 2 prepare compound shellfish modification biological dephosphorization material, and by material with 150~250 mesh without
The sustained release bag that spinning cloth is made is wrapped up, it is ensured that parcel is tight；20L water is added into the above-mentioned material wrapped, makes water complete
Non-woven fabrics is flooded, it is then static to place；
Configuration simulation high-concentration phosphorus-containing wastewater (20g/L KH2PO4The aqueous solution)；
Above-mentioned high-concentration phosphorus-containing wastewater is added into the water body containing modification biological dephosphorization material several times, added every time
Measure as 5mL.It is stirred after adding every time, question response takes supernatant to determine the remaining P elements in liquid after in half an hour
Concentration, if not up to saturation state, continuously adds phosphorus-containing wastewater, determines residual concentration.
Experimental result is shown, is placed in after using non-woven fabrics, modification biological dephosphorization material is wrapped up in water body, to total phosphorus (TP)
Removal situation is changed, and the 3~15g maximum access times of modification biological dephosphorization material are brought up to 8~12 times, and maximum dephosphorization
Measure as 687~743mg, phosphor-removing effect can be lifted and hold time by changing dosing method.
In eutrophication water add non-woven wraps compound shellfish modification biological dephosphorization material after, total phosphorus (TP) with
Increase and reduce, according to the different of quality of materials and difference are added, total tp removal rate takes into account total nitrogen (TN) more than 90%
Clearance more than 60%.The pH of simulation high-concentration phosphorus-containing wastewater is raised, and pH value changes between being in 8.8~12.5.
The every 1 gram content clearance to eutrophication water chlorophyll of material of the present invention is in 1~10 μ g/L, in blue-green algae, water
Magnificent early stage is acted on using inhibited and reduction is broken out to it.
Compared with prior art, the present invention has the advantages that：
1) present invention is carried out at high-temperature calcination modification using discarded Trachyostracous mussel shell, oyster shell, scallop shell as raw material
Reason, prepares compound shellfish modification biological dephosphorization material, and its technique is simple, the recycling of waste resource is realized, with certain
Society, economy and environmental benefit.
2) compound shellfish modification biological dephosphorization material prepared by the present invention, it is to the total phosphorus in phosphorus-containing wastewater and black-odor riverway
Clearance takes into account nitrogen removal rate more than 60% more than 90%, with good dephosphorization water purification ability.
3) material dephosphorizing rate maximum of the present invention can reach 200mg/g materials'use rates, by changing dosing method, with sustained release
After bag such as non-woven fabrics wraps up modification biological dephosphorization material in input water body, phosphor-removing effect can be obviously improved and held time.
Described above has fully disclosed the embodiment of the present invention.It is pointed out that being familiar with the field
Scope of any change that technical staff is done to the embodiment of the present invention all without departing from claims of the present invention.
Correspondingly, the scope of claim of the invention is also not limited only to previous embodiment.
Claims (10)
1. a kind of preparation method of compound shellfish modification biological dephosphorization material, it is characterised in that the raw material of the dephosphorization material is matched somebody with somebody
The mass percent of each component is in side：Trachyostracous mussel shell 30%, oyster shell 45%, scallop shell 25%；
The preparation method comprises the following steps：
(1) the biological shell of shellfish is weighed by composition of raw materials, is ground into a diameter of 50~150mm particle；
(2) preheated 1~3 hour at a temperature of the biological shell of shellfish after crushing being placed in into 350~500 DEG C, then heat to 700~
850 DEG C are calcined 0.5~2 hour；
(3) 200~300 DEG C are cooled the temperature to, 1~3 hour is incubated, the compound shellfish modification biological dephosphorization material is made.
2. the preparation method of compound shellfish modification biological dephosphorization material according to claim 1, it is characterised in that step
(2) the biological shell of shellfish described in is preheated 2 hours at a temperature of 450 DEG C, then in calcining 1 hour under 750 DEG C of temperature conditionss.
3. the preparation method of compound shellfish modification biological dephosphorization material according to claim 1, it is characterised in that the step
Suddenly the temperature of (3) is down to 250 DEG C, is incubated 2 hours.
4. a kind of compound shellfish modification biological dephosphorization material, it is characterised in that the material is any using claims 1 to 3
It is prepared by the preparation method described in one.
5. a kind of application of compound shellfish modification biological dephosphorization material, it is characterised in that be combined one kind described in claim 4
Shellfish modification biological dephosphorization material is applied to waste water dephosphorization.
6. a kind of application of compound shellfish modification biological dephosphorization material according to claim 5, it is characterised in that to phosphorous
Added in waste water and shellfish modification biological dephosphorization material is combined described in 3~15g, the reaction time is 30~40min.
7. the application of a kind of compound shellfish modification biological dephosphorization material according to claim 6, it is characterised in that described multiple
It is 0.2~0.4g/L to close mass concentration of the shellfish modification biological dephosphorization material in phosphorus-containing wastewater.
8. the application of a kind of compound shellfish modification biological dephosphorization material according to claim 5, it is characterised in that to waste water
In add shellfish modification biological dephosphorization material be combined described in 0.1~1.0g/L, processing time is 2~3d.
9. the application of a kind of compound shellfish modification biological dephosphorization material according to claim 5, it is characterised in that use 150
The sustained release bag of~250 mesh wraps up the compound shellfish modification biological dephosphorization material, is then added to the material after parcel phosphorous
In waste water.
10. the application of a kind of compound shellfish modification biological dephosphorization material according to claim 9, it is characterised in that described
Sustained release bag is made up of non-woven fabrics.
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| CN107913670A (en) * | 2017-12-15 | 2018-04-17 | 浙江海洋大学 | A kind of water body lock phosphorus agent and preparation method thereof |
| CN108101233A (en) * | 2018-01-11 | 2018-06-01 | 上海汀滢环保科技有限公司 | To be modified mixing ecology filler, compounded mix ball, purification slot device and the preparation process based on shellfish |
| CN111109297A (en) * | 2019-12-31 | 2020-05-08 | 上海海洋大学 | Application of shell powder of mytilus coruscus in bacteriostasis of marine bacteria |
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| CN111109297A (en) * | 2019-12-31 | 2020-05-08 | 上海海洋大学 | Application of shell powder of mytilus coruscus in bacteriostasis of marine bacteria |
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