CN106365281B - A kind of water body dephosphorized dose of preparation method and water body dephosphorized method - Google Patents
A kind of water body dephosphorized dose of preparation method and water body dephosphorized method Download PDFInfo
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- CN106365281B CN106365281B CN201610925717.6A CN201610925717A CN106365281B CN 106365281 B CN106365281 B CN 106365281B CN 201610925717 A CN201610925717 A CN 201610925717A CN 106365281 B CN106365281 B CN 106365281B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004567 concrete Substances 0.000 claims abstract description 62
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 6
- 230000000694 effects Effects 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 51
- 229910052698 phosphorus Inorganic materials 0.000 description 49
- 239000011574 phosphorus Substances 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002351 wastewater Substances 0.000 description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000012851 eutrophication Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- -1 phosphate anion Chemical class 0.000 description 4
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000009533 lab test Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000007836 KH2PO4 Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011464 hollow brick Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a kind of water body dephosphorized dose of preparation method and water body dephosphorized method, low-temperature activation handles 10 ~ 30min at 200 ~ 300 DEG C after being first crushed discarded concrete when preparation, by low-temperature activation, treated that concrete block crushes as discarded concrete powder again, and using 100 ~ 325 meshes to discarded concrete dressing sieve point, it collects screenings and obtains gelling matrix, after gelling matrix is mixed with surfactant, ball milling is carried out using ball mill and is activated 2 ~ 10min, is made described water body dephosphorized dose.The water body dephosphorized method is to add water body dephosphorized dose made from the method in staying water, removes the P elements in water body.Using dephosphorization agent of the present invention carry out it is water body dephosphorized have the advantages that dephosphorization reaction speed is fast, the dephosphorization time is short, dephosphorization efficiency is high, phosphor-removing effect is stable, dephosphorizing rate is up to 99% or more.
Description
Technical field
The invention belongs to discarded concrete technical field of resource utilization, and in particular to a kind of water body dephosphorized dose of preparation method
And water body dephosphorized method.
Background technique
According to State Statistics Bureau " China Statistical Yearbook 2004-2013 " data, China's building waste yield is from 2003
2.97 hundred million tons, it is increased rapidly to 11.31 hundred million tons in 2012.With the quickening of China's infrastructure and Urbanization Construction, city
Transformation and the rapid development of building industry, some old buildings, structures, urban infrastructure the length of service expire and tear open
It removes, more and more building wastes will be generated.Xi'an University of Architecture and Technology is in " construction refuse resource Study on Industry Development "
Prediction: reaching 60% calculating by urbanization rate, arrives the year two thousand twenty or so, and urban building waste yield is up to 2,600,000,000 tons, and the year two thousand thirty will
Reach 7,300,000,000 tons.And most building wastes are to transport countryside to by unit in charge of construction to carry out air storage or landfill, cause dregs
Receiving factory load it is increasing, can with stacking area is fewer and fewer, the higher and higher a series of problems of accumulation cost, therefore build
Rubbish has become a big public hazards in city, this has not only buried huge security risk, brings great environmental risk, also makes
At the resource of extreme, land wastage.Data shows that quantitatively discarded concrete is important component in building waste,
Account for about the 34% of building waste total amount, and China's discarded concrete resource utilization rate is less than 5%, only resource utilization portion
Point also discarded concrete in being crushed, be classified, clean to recycle sandstone aggregate therein and be used to prepare again in turn by multi-focus
In terms of raw aggregate concrete；And main component in discarded concrete, be also during concrete production resources and energy consumption it is maximum,
Carrying capacity of environment is most heavy, the highest discarded gelled matrix of economic cost does not obtain enough attention but and effective recycling benefit
With.
Although domestic and foreign scholars have carried out the trial of some resource utilizations to gelled matrix in discarded concrete, mostly
Building materials field is concentrated on, and added value is relatively low, therefore resource utilization interest is not high.For example, prior art table
It is bright in building materials field, using gelled matrix exploitation cement concrete mixing material in discarded concrete or as auxiliary material
Hollow brick is produced, and grinding calcining cement etc. all has certain technical problem in the process again, this is mainly due to discarded
Behavior of Hardened Cement Paste porosity is big, mark thick water requirement is high, activity index is low, with the building material product workability of its preparation and mechanical property compared with
Difference.Simultaneously because the gelled matrix separated from discarded concrete contains a certain amount of inertia silica, this is also raw to cement
The burning zone of feed powder mill and clinker is next difficult, increases f-CaO content in clinker, and clinker quality decline, increased production cost.Together
When there is certain limit to mix when gelled matrix prepares related construction materials in using discarded concrete due to the above reasons,
Amount, utilization rate are relatively low.To sum up, in discarded concrete gelled matrix be poorly suitable for recycling make as the field of building materials
With.
Phosphorus is one important element of the ecosphere, and various phosphorus-containing compound is in mankind's industrial and agricultural production and daily life
In play important role, but this also makes a large amount of phosphorus-containing wastewaters be discharged into natural water simultaneously, and it is to draw that phosphorus is enriched in water body
The major reason for playing Water Eutrophication seriously threatens aquatic ecosystem balance, causes great environmental problem.It needs to refer to
Out, phosphorus is a kind of non-renewable resources, if phosphorus is unidirectional, general in the flowing of nature without the mankind's positive intervention
Titanium pigment is transformed by land indissoluble phosphorus under various materializations effect, and eventually enters into ocean by means of land water flow.According to estimating
The rock phosphate in powder for capableing of economical and effective exploitation on the meter earth will will exhaust in 50~100 years.It is constantly withered in order to cope with phosphor resource
The situation exhausted, the international meeting recycled three times about phosphorus held from foreign countries can be seen that current international research hotspot
It is how preferably to improve the utilization efficiency of phosphorus, and then to alleviate phosphorus ore from containing phosphor resource is removed and recycled in phosphorus water and produce
Resource is increasingly deficient constantly to be increased with phosphorus content in water body and leads to this contradiction of eutrophication.
In recent years, with the continuous development of technology and innovation, some new dephosphorization and phosphorus recovery technology, for example, it is electrolysis, anti-
Infiltration, ion exchange etc. have obtained stable development.But since traditional chemical precipitation, crystallization, absorption method etc. can achieve quite
High removal and the rate of recovery, and technical maturity is stable, easily realizes that automatic control, at low cost, easy to handle high-density phosphorus is useless
The advantages that water, is at home and abroad still used as preferable dephosphorization and phosphorus recovering means.However in this course, research and use compared with
More precipitating reagent, crystal seed or adsorbents is mainly Ca (OH)2、CaO、CaCl2, lime stone, tobermorite, hydrous alumino silicates etc.
Compound, above-mentioned dephosphorization material carry out artificial synthesized after generally requiring exploitation natural crystal through complicated technology, this process is not only
It is likely to result in the destruction of ecological environment, can also consume a large amount of energy and resource, there is certain shortcomings.
Summary of the invention
In view of the above shortcomings of the prior art, it sinks the technical problem to be solved by the present invention is being used for existing dephosphorization
Shallow lake agent, crystal seed or adsorbent need artificial synthesized through complicated technology after exploitated ore more, destroy ecological environment, can consume a large amount of energy
Source and resource, and gelled matrix does not obtain the technical issues of good recovery utilizes in discarded concrete in the prior art, and mention
For it is a kind of using the gelled matrix isolated in discarded concrete be primary raw material water body dephosphorized dose of preparation method.
It is another object of the present invention to provide a kind of water body dephosphorized methods.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme: a kind of water body dephosphorized dose of preparation method,
Include the following steps:
1) discarded concrete is broken for recycled concrete aggregate of the partial size less than 25 mm, by the recycled concrete aggregate in
Low-temperature activation is handled 10 ~ 30 minutes at 200 ~ 300 DEG C；
2) pulverization process is carried out to step 1) low-temperature activation treated recycled concrete aggregate and obtains discarded concrete powder, adopted
The discarded concrete powder is sieved with 100 ~ 325 meshes, screenings is collected and obtains hardening gel matrix；
3) it carries out hardening gel matrix and surfactant that step 2 obtains to be mixed to get mixed raw material, using ball milling
Machine carries out ball milling to the mixed raw material and is activated 2 ~ 10 min, is made described water body dephosphorized dose.
A kind of water body dephosphorized method will be used and be added in staying water with right for water body dephosphorized dose made from the method
P elements in staying water are removed；Wherein, the mass volume ratio of described water body dephosphorized dose and staying water is 0.3
~ 10 g:1000 mL.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention isolates gelled matrix from discarded concrete and prepares water body dephosphorized dose for priming reaction, this hair
It is bright first to carry out low-temperature activation processing with Muffle furnace after discarded concrete coarse crushing, to reduce hardening gelling matrix in discarded concrete
With the binding force of aggregate, then by electromagnetic oscillation and isolated hardening gel is sieved, it will hardening gel and surface-active
Agent carries out mechanical ball mill activation processing together, is made water body dephosphorized dose.By above-mentioned " broken-low-temperature activation-electromagnetism separation-
Mechanical grading " is able to the calcareous cement hydrated product C-S-H gel that energy consumption is big in discarded concrete, economic value is high
Separation, and add surfactant and increase the specific surface area of separating obtained C-S-H gel and the dissolution of calcium after carrying out ball milling
Ability, so that prepared dephosphorization agent has comparatively ideal dephosphorization ability.
2, the present invention is prepared water body dephosphorized dose using gelled matrix in discarded concrete and be applied to containing phosphorus in phosphorus water
The removal of element, main dephosphorization mechanism are following two points:
1) water body dephosphorized dose of main component prepared by be containing the hydrolysis product of cement C-S-H gel in discarded concrete,
There is outstanding molten calcium ability after the processing of above-mentioned physical chemistry means, the calcium ion of dissolution is in conjunction with the phosphate anion in water
Form calcium phosphate compound；Laggard mistake is separated by filtration and removes.
2) water body dephosphorized dose of sheet prepared by is as the biggish porous structure material of surface area, the calcium ion and hydrogen-oxygen of release
Radical ion to reach certain basicity (8 or more pH value) containing phosphorus water, while the concentration of calcium being made to reach saturation；Therefore its can adsorb it is molten
Phosphate anion in liquid simultaneously forms the advantageous microenvironment that can make calcium phosphate crystal, precipitation, growth in the local surfaces of dephosphorization agent,
So that phosphate radical is wrapped in dephosphorization agent surface, separates and remove from water body by filtering.
Using dephosphorization agent produced by the present invention is fast with dephosphorization reaction speed, the dephosphorization time is short, dephosphorization efficiency is high, dephosphorization effect
The stable advantage of fruit, dephosphorizing rate is up to 99% or more.Moreover, it is carried out using water body dephosphorized dose of the present invention except phosphorus reaction, reaction
Temperature range is wide and can carry out at room temperature, less to the limitation of reaction condition, it is easier to be operated, and save energy
Source.
3, the present invention also creatively carries out hydro-thermal reaction to hardening gelling matrix, discards after being handled by hydro-thermal reaction mixed
Calcium oxide and silica in solidifying soil further react, and thereby reduce subsequent water body dephosphorized using dephosphorization agent obtained progress
The amount of dissolution of the calcium constituent in water body in the process rises the water outlet of the water body after dephosphorization pH less, reduces water after dephosphorization
The dosage of acid during body pH readjustment, and keep the pH value of dephosphorization reaction environment more stable, it ensure that dephosphorization efficiency.
4, water body dephosphorized dose of raw materials of the invention are mainly gelled matrix in discarded concrete, do not need to carry out complicated
Balanced ingredient again, preparation process is simple, requires appointed condition low, it is easy to accomplish industrialized production.
5, dephosphorization agent prepared by the method for the present invention is environmental-friendly, and the dirt of two secondary environments is not present in the process for water body dephosphorized
Dye problem meets the policy guidance of the development of national green economy, circular economy.
6, the present invention provides new approaches and methods to hardening gel resource utilization in discarded concrete, improves
The utility value of discarded concrete, the water body dephosphorized dose produced by the present invention improvement that can carry out phosphorus-containing wastewater are China river, lake
The improvement containing phosphorus water such as pool, industrial and life contaminated water provide it is a kind of it is from a wealth of sources, cheap and easy to get, low energy consumption, environmentally protective
New material, be a kind of technical method of " waste recycling " that can be widely used, lake, river administered with dephosphorization agent of the present invention
Caused by during the eutrophication of the unhurried current natural water such as bay and mankind's industrial and agricultural production and daily life
Phosphorus-containing wastewater can achieve the purpose for effectively avoiding the aquatic ecosystem crisis caused by water eutrophication from occurring, tool
There is applications well prospect.
Detailed description of the invention
Fig. 1 is influence of the water body dephosphorized dose of different dosages to water body dephosphorized effect made from embodiment 1；
Fig. 2 is influence of the stirring rate to water body dephosphorized effect；
Fig. 3 is influence of the dephosphorization reaction time to water body dephosphorized effect；
Fig. 4 is influence of the dephosphorization reaction temperature to phosphor-removing effect.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.The implementation case is being with the technology of the present invention
Under the premise of implemented, now provide detailed embodiment and specific operating process illustrate the present invention it is creative, but
Protection scope of the present invention embodiment not limited to the following.
Embodiment 1:
A kind of water body dephosphorized dose of preparation method, includes the following steps:
1) discarded concrete is broken for recycled concrete aggregate of the granularity less than 25 mm with jaw crusher, it will be described useless
Concrete block low-temperature activation at 300 DEG C is abandoned to handle 20 minutes；
2) pulverization process is carried out using electromagnetic oscillation pulverizer to step 1) low-temperature activation treated recycled concrete aggregate
10 seconds, obtain discarded concrete powder, be followed successively by 0.075 using screen size from top to bottom, 0.05,0.3,0.6,1.18,2.36,
4.75, the standard sandstone bushing screen of 9.5mm carries out mechanical grading to the discarded concrete powder, to remove in discarded concrete powder
Coarse particles of aggregates object collects screenings and obtains hardening gel matrix；
3) the hardening gel matrix that step 2 obtains is fitted into vacuum ball grinder together with surfactant triethanolamine
After being mixed, ball milling is carried out using planetary ball mill and is activated 5 min, is made described water body dephosphorized dose；Wherein, the glue
The mass ratio of solidifying matrix and surfactant is 1000:3.
A kind of water body dephosphorized method adds water body dephosphorized dose made from the present embodiment in staying water to treat place
P elements in reason water body are removed, specifically to water body dephosphorized dose of dosage during dephosphorization, stirring rate, stirring dephosphorization
Time and reaction temperature do following research:
1, dephosphorization agent dosage made from the present embodiment during dephosphorization is investigated:
1) KH is used2PO4The phosphorus-containing wastewater simulated solution that initial phosphorus concentration is 20mg/L (in terms of P mass concentration) is configured, a system is taken
The beaker for arranging 250mL, is successively separately added into the phosphorus-containing wastewater simulated solution 100mL of above-mentioned preparation, and place the beaker magnetic agitation
On device.
2) it using 20 mg as initial concentration, and using 20 mg as mass gradient, is stated upwards in turn equipped with phosphorus-containing wastewater simulated solution
Beaker in dephosphorization agent made from different quality the present embodiment is added, control group is not added.At room temperature, with 100 r/min
Stirring intensity under handle 60 min.
3) it removes after beaker stands a moment and filter, successively takes in each beaker filtered fluid in colorimetric cylinder with micropipettor
In, add distilled water to dilute, the mix reagent of sulfuric acid, potassium antimony tartrate, ammonium molybdate and ascorbic acid composition is added, is stood after shaking up
10min.Make blank reference with distilled water, measure filtered fluid absorbance at wavelength 880nm with visible spectrophotometer, with assessment
The phosphor-removing effect of different amounts dephosphorization agent, experimental result are as shown in Figure 1.
As can be seen from Figure 1 with the increase of prepared dephosphorization dosage, it is discharged the decline of phosphorus concentration straight line, when dosage reaches
0.3 g Shi Shuizhong phosphorus concentration is reduced to 2mg/L hereinafter, having reached national relevant emission standards from 20mg/L；It is further added by dephosphorization
The dosage phosphorus concentration of agent is held essentially constant.Under same experimental conditions, experimental result (lines a1, a2, a3 in Fig. 1) has three times
Preferable repeatability, it is seen that the present embodiment is separated and prepare water body dephosphorized dose of C-S-H gel have it is comparatively ideal water body dephosphorized
And phosphorus recovering effect, and dephosphorization process is stablized, the optimum amount of dephosphorization agent is 0.05 ~ 1g.
2, stirring rate during dephosphorization is investigated:
7 250mL beakers are taken, pipetting prepared concentration respectively is that 20mg/L simulates 100 mL of phosphorus-containing wastewater in beaker
In, and beaker is placed on magnetic stirring apparatus, 0.50 g dephosphorization agent is successively added into 7 beakers, at 25 DEG C of room temperature, uses
Magnetic stirring apparatus is respectively with 60r/min, 80r/min, 100r/min, 120r/min, 140r/min, 160r/min, 180r/min
Speed conditions under react 60min, after to treated, water is diluted, and sulfuric acid, potassium antimony tartrate, ammonium molybdate is added
With the mix reagent of ascorbic acid composition, 10min is stood after shaking up, using distilled water as blank control, uses visible spectrophotometer
Filtrate absorbance is measured at wavelength 880nm, to assess the phosphor-removing effect of dephosphorization agent under different stirring intensities, experimental result is as schemed
Shown in 2.
As shown in Figure 2, under other factors certain condition, with the increase of stirring intensity, phosphorus concentration is of a straight line type in water outlet
Decline, when speed of agitator reaches 140r/min, phosphorus concentration is preferably minimized in water outlet, continues growing stirring intensity water outlet phosphorus concentration
Fuctuation within a narrow range no longer changes substantially, and parallel laboratory test (lines a1, a2, a3 in Fig. 2) has preferable repeatability three times, shows
Best stirring intensity is 140r/min.
3, the influence of dephosphorization time:
7 250mL beakers are taken, pipetting prepared concentration respectively is that 20mg/L simulates phosphorus-containing wastewater 100mL in beaker,
And beaker is placed on magnetic stirring apparatus, 0.50 g dephosphorization agent is successively added into 7 beakers, in magnetic stirring apparatus revolving speed
Under the conditions of 140 25 DEG C of r/min room temperatures, to the phosphorus-containing wastewater dephosphorization time in 7 beakers be respectively set to 5min, 15min,
30min, 45min, 60min, 75min, 90min are carried out except phosphorus reaction.After to treated, water is diluted, and be added simultaneously
The mix reagent of sulfuric acid, potassium antimony tartrate, ammonium molybdate and ascorbic acid composition is added, stands 10min after shaking up, is with distilled water
Blank control measures filtrate absorbance with visible spectrophotometer, to assess under differential responses time conditions at wavelength 880nm
The phosphor-removing effect of dephosphorization agent, experimental result are as shown in Figure 3.
Fig. 3 shows that under other factors permanence condition, parallel laboratory test (lines a1, a2, a3 in Fig. 3) all shows three times
In preceding 15min, with the progress of reaction, phosphorus concentration rapidly drops to 2mg/L hereinafter, having reached national emission standard in water outlet,
Continue to extend the reaction time, be discharged phosphorus concentration fuctuation within a narrow range, substantially no longer change, reacts phosphorus-containing wastewater simulated solution after 30 min
Concentration falls to 0.03mg/L, and dephosphorization efficiency reaches 99% or more.
4, the influence of dephosphorization temperature
7 250mL beakers are taken, pipetting prepared concentration respectively is that 20 mg/L simulate phosphorus-containing wastewater 100mL in beaker
In, and beaker is placed on magnetic stirring apparatus, 0.50g dephosphorization agent is successively added into 7 beakers, magnetic stirring apparatus is set
Revolving speed 140r/min reacts 15min under the conditions of 15 DEG C, 30 DEG C, 45 DEG C, 60 DEG C, 75 DEG C, 90 DEG C, 105 DEG C respectively, after
To treated, water is diluted, and the mix reagent of sulfuric acid, potassium antimony tartrate, ammonium molybdate and ascorbic acid composition is added, and is shaken
10min is stood after even, and filtrate absorbance is measured at wavelength 880nm with visible spectrophotometer using distilled water as blank control,
To assess the phosphor-removing effect of dephosphorization agent under the conditions of differential responses temperature, experimental result is as shown in Figure 4.
As seen from Figure 4, in studied temperature range (15 DEG C~105 DEG C), parallel laboratory test (lines in Fig. 4 three times
A1, a2, a3) all show to be discharged phosphorus concentration as the variation of temperature is wavy, fluctuation is smaller, and reaction temperature is to water outlet phosphorus concentration
Influence is smaller, this also indicates that prepared dephosphorization agent has good adaptation in water body dephosphorized and phosphorus removal process in practical application
Property, dephosphorization process can carry out at normal temperature.
Embodiment 2
A kind of water body dephosphorized dose of preparation method, includes the following steps:
1) discarded concrete is broken for recycled concrete aggregate of the granularity less than 25 mm with jaw crusher, it will be described useless
Concrete block low-temperature activation at 250 DEG C is abandoned to handle 25 minutes；
2) pulverization process is carried out using electromagnetic oscillation pulverizer to step 1) low-temperature activation treated recycled concrete aggregate
10 seconds, discarded concrete powder is obtained, mechanical grading is carried out to the discarded concrete powder using 170 mesh sandstone sieves, it is useless to remove
The coarse particles of aggregates object in concrete powder is abandoned, screenings is collected and obtains hardening gel matrix；
3) the hardening gel matrix that step 2 obtains is packed into vacuum ball grinder together with surfactant triisopropanolamine
In mixed after, using planetary ball mill carry out ball milling be activated 7 min, be made described water body dephosphorized dose；The gelling
The mass ratio of matrix and surfactant is 1000:4.
Dephosphorization agent made from 0.50 g the present embodiment is put into 100 mL KH2PO4The initial phosphorus concentration of configuration is 20mg/L
In (in terms of P mass concentration) phosphorus-containing wastewater simulated solution, 15min is stirred to react with the stirring rate of 140r/min at normal temperature, it is right
P elements are removed in water body, are detected to P elements in water after processing, and dephosphorization efficiency is 99.89% as the result is shown.
Embodiment 3
A kind of water body dephosphorized dose of preparation method, includes the following steps:
1) discarded concrete is broken for recycled concrete aggregate of the granularity less than 25 mm with jaw crusher, it will be described useless
Concrete block low-temperature activation at 220 DEG C is abandoned to handle 30 minutes；
2) pulverization process is carried out using electromagnetic oscillation pulverizer to step 1) low-temperature activation treated recycled concrete aggregate
10 seconds, obtain discarded concrete powder, be followed successively by 0.075 using screen size from top to bottom, 0.05,0.3,0.6,1.18,2.36,
4.75, the standard sandstone bushing screen of 9.5mm carries out mechanical grading to the discarded concrete powder, to remove in discarded concrete powder
Coarse particles of aggregates object collects screenings and obtains hardening gel matrix；
3) the hardening gel matrix that step 2 obtains is placed in hydrothermal reaction kettle, hydro-thermal is carried out under 180 DEG C, 1.0MPa
120min is handled, gelling matrix is obtained；
4) the gelling matrix that step 3) obtains (is fitted into vacuum ball grinder together and is mixed with surfactant ethylene glycol
After conjunction, ball milling is carried out using planetary ball mill and is activated 10 min, is made described water body dephosphorized dose；The gelling matrix and table
The mass ratio of face activating agent is 1000:5.
Dephosphorization agent made from 0.5 g the present embodiment is put into 100 mL KH2PO4The initial phosphorus concentration of configuration is 20mg/L
In (in terms of P mass concentration) phosphorus-containing wastewater simulated solution, 15min is stirred to react with the stirring rate of 140r/min at normal temperature, it is right
P elements are removed in water body, are detected to P elements in water after processing, and dephosphorization efficiency is 99.50% as the result is shown.
To sum up, the present invention has dephosphorization reaction speed using water body dephosphorized dose of gelling matrix preparation in discarded concrete
Fastly, the advantage that the dephosphorization time is short, dephosphorization efficiency is high, phosphor-removing effect is stable, dephosphorizing rate is up to 99% or more.Using water body of the present invention
Dephosphorization agent is carried out except phosphorus reaction, and range of reaction temperature is wide and can carry out at room temperature, less to the limitation of reaction condition, is easier to
In being operated, and save the energy.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (7)
1. a kind of water body dephosphorized dose of preparation method, which comprises the steps of:
1) discarded concrete is broken for recycled concrete aggregate of the partial size less than 25 mm, by the recycled concrete aggregate in 200 ~
Low-temperature activation is handled 10 ~ 30 minutes at 300 DEG C；
2) pulverization process is carried out to step 1) low-temperature activation treated recycled concrete aggregate and obtains discarded concrete powder, used
100 ~ 325 meshes sieve the discarded concrete powder, collect screenings and obtain hardening gel matrix；
3) it carries out hardening gel matrix and surfactant that step 2 obtains to be mixed to get mixed raw material, using ball mill pair
The mixed raw material carries out ball milling and is activated 2 ~ 10 min, is made described water body dephosphorized dose；
Surfactant described in step 3) is triethanolamine, triisopropanolamine, ethylene glycol or diethylene glycol；
The mass ratio of the hardening gel matrix and surfactant is 1000:2 ~ 1000:5.
2. water body dephosphorized dose of preparation method according to claim 1, which is characterized in that the hardening gel for obtaining step 2
Matrix is placed in hydrothermal reaction kettle, and 10 ~ 150 min of hydro-thermal reaction is carried out under conditions of 150 ~ 190 DEG C, 0.6 ~ 1.5MPa, is obtained
To gelling matrix；The gelling matrix is mixed with surfactant and carries out ball milling and is activated 2 ~ 10 min, is made described
Water body dephosphorized dose.
3. water body dephosphorized dose of preparation method according to claim 2, which is characterized in that under conditions of 180 DEG C, 1.0MPa
Carry out hydro-thermal reaction 120min.
4. a kind of water body dephosphorized method, which is characterized in that will be using water body dephosphorized made from any the method for claim 1 ~ 3
Agent adds in staying water to be removed to the P elements in staying water；Wherein, described water body dephosphorized dose with to
The mass volume ratio for handling water body is 0.3 ~ 10 g:1000 mL；
Described water body dephosphorized dose is added in staying water, it is stirred to react 15 under the stirring rate of 60 ~ 180 r/min ~
60 min。
5. water body dephosphorized method according to claim 4, which is characterized in that described water body dephosphorized dose with the matter of staying water
Amount volume ratio is 5 g:1000 mL.
6. water body dephosphorized method according to claim 4, which is characterized in that the stirring rate is 140 r/min.
7. water body dephosphorized method according to claim 4, which is characterized in that the time being stirred to react is 15 min.
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| CN107694512B (en) * | 2017-09-22 | 2019-12-13 | 长江师范学院 | Preparation method of heavy metal ion remover |
| CN107522276B (en) * | 2017-09-22 | 2020-04-07 | 长江师范学院 | Preparation method of water defluorinating agent |
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| CN107540041B (en) * | 2017-09-22 | 2020-05-12 | 长江师范学院 | Application of waste concrete in water body defluorination |
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| CN109704446B (en) * | 2019-01-10 | 2022-01-14 | 四川大学 | Method for efficiently removing phosphorus in eutrophic water body |
| CN109574182B (en) * | 2019-01-24 | 2021-06-15 | 长江师范学院 | Preparation method of acid wastewater neutralizer |
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| CN111908654A (en) * | 2020-07-14 | 2020-11-10 | 河北美卡诺生物科技有限公司 | Efficient phosphorus removal agent for removing phosphorus from sewage |
| CN112142177B (en) * | 2020-09-25 | 2023-07-14 | 北京环球中科水务科技股份有限公司 | Inorganic polymer dephosphorizing agent and preparation method and application thereof |
| CN113295630B (en) * | 2021-04-12 | 2023-04-11 | 长江师范学院 | Research for rapidly recycling nitrogen and phosphorus in aquaculture wastewater by using magnetic material |
| CN113926424A (en) * | 2021-10-12 | 2022-01-14 | 北京尚水清源水处理技术有限公司 | Preparation method of phosphorus removal agent |
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