CN106365281A - Preparation method of water phosphate removing agent and water phosphate removing method - Google Patents
Preparation method of water phosphate removing agent and water phosphate removing method Download PDFInfo
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- CN106365281A CN106365281A CN201610925717.6A CN201610925717A CN106365281A CN 106365281 A CN106365281 A CN 106365281A CN 201610925717 A CN201610925717 A CN 201610925717A CN 106365281 A CN106365281 A CN 106365281A
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- water body
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- dephosphorized
- body dephosphorized
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 17
- 239000010452 phosphate Substances 0.000 title abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract 14
- 239000004567 concrete Substances 0.000 claims abstract description 58
- 239000002699 waste material Substances 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 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
- 239000002245 particle Substances 0.000 claims description 5
- 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
- 230000035484 reaction time Effects 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 52
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 50
- 239000011574 phosphorus Substances 0.000 abstract description 50
- 230000000694 effects Effects 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000001994 activation Methods 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 229940026189 antimony potassium tartrate Drugs 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 4
- 230000007613 environmental effect Effects 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
- 239000000047 product Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009533 lab test Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 238000001354 calcination 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
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 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
- 210000000476 body water Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000012141 concentrate Substances 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 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
- 239000008239 natural water Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 239000003643 water by type Substances 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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a preparation method of a water phosphate removing agent and a water phosphate removing method. The preparation method comprises the steps that waste concrete is crushed and then subjected to low-temperature activation treatment for 10 min to 30 min at the temperature of 200 DEG C to 300 DEG C; concrete blocks obtained after low-temperature activation treatment are crushed into waste concrete powder, the waste concrete powder is screened with a 100-325-mesh screen, and an undersize product is collected to obtain a gelling substrate; after the gelling substrate and a surfactant are mixed, ball-milling activating treatment is conducted for 2 min to 10 min through a ball mill, and then the water phosphate removing agent is prepared. The water phosphate removing method comprises the steps that the water phosphate removing agent prepared through the method is put into water to be treated, and then phosphorus in the water is removed. When water phosphate removing is conducted by adopting the phosphate removing agent prepared through the method, the advantages of being high in phosphate removing reaction speed, short in phosphate removing time, high in phosphate removing efficiency and stable in phosphate removing effect are achieved, and the phosphate removing rate can reach 99% or above.
Description
Technical field
The invention belongs to discarded concrete technical field of resource utilization is and in particular to a kind of water body dephosphorized dose of preparation method
And water body dephosphorized method.
Background technology
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 of 2012.With the quickening of China's infrastructure and Urbanization Construction, city
Transformation and the developing rapidly of building industry, the length of service of some old buildings, structures, urban infrastructure expires and tears open
Remove, increasing building waste will be produced.Xi'an University of Architecture and Technology is in " construction refuse resource Study on Industry Development "
Prediction: reach 60% calculating by urbanization rate, to about the year two thousand twenty, urban building waste yield is up to 2,600,000,000 tons, the year two thousand thirty will
Reach 7,300,000,000 tons.And overwhelming majority building waste is to transport countryside to by unit in charge of construction to carry out air storage or landfill, cause dregs
By Na Chang load increasing, available stack that area is fewer and feweri, pile up the higher and higher series of problems of cost, therefore build
Rubbish has become big public hazards in city, and this has not only buried huge potential safety hazard, brings great environmental risk, also makes
Resource, the land wastage of extreme are become.Data shows, quantitatively, discarded concrete is important component part in building waste,
Account for the 34% of building waste total amount, and China's discarded concrete resource utilization rate is less than 5%, only recycling portion
Point also multi-focus are in carrying out crushing by discarded concrete, be classified, clean to reclaim sandstone aggregate therein and then for preparing again
Raw aggregate concrete aspect；And main component in discarded concrete, be also during concrete production resources and energy consumption maximum,
Carrying capacity of environment is the heaviest, Financial cost highest is discarded gelled matrix and but do not obtained enough attention and effective resource profit
With.
Although Chinese scholars have carried out the trial of some recyclings to gelled matrix in discarded concrete, mostly
Concentrate on building materials field, and added value is relatively low, therefore recycling interest is not high.For example, prior art table
Bright in building materials field, the gelled matrix exploitation cement concrete mixing material or as auxiliary material by the use of in discarded concrete
Produce hollow brick, and all there is certain technical problem during grinding calcining cement etc. again, this is mainly due to discarded
Behavior of Hardened Cement Paste porosity is big, the thick water requirement of mark is high, activity index is low, building material product workability that is being prepared with it and mechanical property relatively
Difference.Simultaneously because detached gelled matrix contains a certain amount of inertia silicon dioxide from discarded concrete, this mud life of also feeding water
The calcining of feed powder mill and grog brings difficulty, so that f-cao content in grog is increased, clinker quality declines, and production cost improves.With
When for above-mentioned reasons, in using discarded concrete, gelled matrix has certain limit to mix when preparing related construction materials
Amount, utilization rate is relatively low.To sum up, in discarded concrete gelled matrix be poorly suitable for reclaim make as building material field
With.
Phosphorus is one important element of 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 enter natural water simultaneously, and it is to draw that phosphorus is enriched with water body
Play the major reason of Water Eutrophication, it seriously threatens aquatic ecosystem to balance, and causes great environmental problem.Need to refer to
Go out, phosphorus is a kind of non-renewable resources, if the no positive intervention of the mankind, phosphorus is unidirectional in the flowing of nature, will
Under various materializations effect, titanium pigment is transformed into by land indissoluble phosphorus, and eventually enters into ocean by means of land current.According to estimating
The rock phosphate in powder being capable of economical and effective exploitation on the meter earth will will exhaust in 50～100 years.Constantly withered in order to tackle phosphor resource
The situation exhausting, the international meeting reclaimed with regard to phosphorus from three times abroad holding can be seen that international study hotspot at present
It is how preferably from containing phosphorus water to remove and reclaims phosphor resource, to improve the utilization ratio of phosphorus, and then alleviate phosphorus ore product
Resource is increasingly deficient constantly to be increased and leads to this contradiction of eutrophication with phosphorus content in water body.
In recent years, the continuous development with technology and innovation, some new dephosphorization and phosphorus recovery technology, for example, be electrolysed, instead
Infiltration, ion exchange etc. have obtained stable development.But because traditional chemical precipitation, crystallization, absorption method etc. can reach quite
High removal and the response rate, and technical maturity is stable, easily realization automatically controls, low cost, disposable high-density phosphorus give up
The advantages of water, at home and abroad still it is used as preferable dephosphorization and phosphorus recovering meanses.But in this course, study and using relatively
Many precipitant, crystal seed or adsorbent are mainly ca (oh)2、cao、cacl2, limestone, tobermorite, hydrous alumino silicates etc.
Compound, above-mentioned dephosphorization material carries out synthetic through complicated technology after generally requiring to exploit natural crystal, and this process is not only
It is likely to result in the destruction of ecological environment, also can consume the substantial amounts of energy and resource, there is certain weak point.
Content of the invention
For deficiencies of the prior art, the technical problem to be solved in the present invention is: for existing dephosphorization with sinking
Needing shallow lake agent, crystal seed or adsorbent, through complicated technology synthetic after exploitated ore, to destroy ecological environment, a large amount of energy can be consumed more
In discarded concrete in source and resource, and prior art, gelled matrix does not obtain the technical problem of good recovery utilization, and carries
For a kind of be water body dephosphorized dose of primary raw material of preparation method using the gelled matrix isolated in discarded concrete.
Further object is that providing a kind of water body dephosphorized method.
In order to solve above-mentioned technical problem, the present invention adopts the following technical scheme that a kind of water body dephosphorized dose of preparation method,
Comprise the steps:
1) discarded concrete is broken for the waste concrete block that particle diameter is less than 25 mm, by described waste concrete block in 200 ~
At 300 DEG C, low-temperature activation is processed 10 ~ 30 minutes；
2) pulverization process is carried out to the waste concrete block after the process of step 1) low-temperature activation and obtain discarded concrete powder, adopt
100 ~ 325 mesh sieves sieve to described discarded concrete powder, collect siftage and obtain hardening gel matrix；
3) by step 2) the hardening gel matrix that obtains carries out being mixed to get mixed material, using ball mill pair with surfactant
Described mixed material carries out ball milling activation processing 2 ~ 10 min, is obtained described water body dephosphorized dose.
A kind of water body dephosphorized method, water body dephosphorized dose that adopts methods described to be obtained is added in staying water with right
P elements in staying water are removed；Wherein, the described water body dephosphorized dose of mass volume ratio with staying water is 0.3
~ 10 g:1000 ml.
Compared to existing technology, the invention has the following beneficial effects:
1st, the present invention isolates gelled matrix from discarded concrete and prepares water body dephosphorized dose for priming reaction, and the present invention is first
Low-temperature activation process will be carried out with Muffle furnace, to reduce hardening gelling matrix and bone in discarded concrete after discarded concrete coarse crushing
The adhesion of material, then the gel that hardens is obtained by electromagnetic oscillation and screening separation, will harden gel and surfactant one
Rise and carry out mechanical ball milling activation processing, be obtained water body dephosphorized dose.Through above-mentioned " broken low-temperature activation electromagnetic separation machinery
Screening " makes the calcareous cement hydrated product c-s-h gel that energy resource consumption in discarded concrete is big, economic worth is high be divided
From, and add surfactant and after carrying out ball milling, increase the specific surface area of separating obtained c-s-h gel and the dissolution energy of calcium
Power is so that prepared dephosphorization agent has comparatively ideal dephosphorization ability.
2nd, 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, its main dephosphorization mechanism is at following 2 points:
1) prepared by, water body dephosphorized dose of main component is containing the hydrolysis product of cement c-s-h gel in discarded concrete, through upper
State after physical chemistry means are processed and there is outstanding molten calcium ability, the calcium ion of dissolution is combined to form with the phosphate anion in water
Calcium phosphate compound；Laggard cross filtration separation and remove.
2) prepared by, water body dephosphorized dose of basis is as the larger porous structure material of surface area, the calcium ion of its release and hydrogen-oxygen
Radical ion makes to reach certain basicity (ph value more than 8) containing phosphorus water, makes the concentration of calcium reach saturation simultaneously；Therefore its can adsorb molten
Phosphate anion in the liquid local surfaces in dephosphorization agent form and can make calcium phosphate crystal, precipitations, the favourable microenvironment growing,
So that phosphate radical is wrapped in dephosphorization agent surface, remove by filtering to separate from water body.
Have using the dephosphorization agent that the present invention is obtained that dephosphorization response speed is fast, the dephosphorization time is short, dephosphorization efficiency is high, dephosphorization effect
Really stable advantage, dephosphorizing rate is up to more than 99%.Moreover, carry out, except phosphorus reaction, reacting using water body dephosphorized dose of the present invention
Temperature range width and can carrying out at room temperature, less to the restriction of reaction condition it is easier to operate, and save energy
Source.
3rd, the present invention also creatively carries out hydro-thermal reaction to hardening gelling matrix, discarded mixed after being processed by hydro-thermal reaction
Calcium oxide in solidifying soil and silicon dioxide react further, so reduce subsequently carried out using prepared dephosphorization agent water body dephosphorized
During stripping quantity in water body for the calcium constituent, so that the water body water outlet ph after dephosphorization is increased less, decrease water after dephosphorization
The consumption of acid during body ph readjustment, and make the ph value of dephosphorization reaction environment more stably it is ensured that dephosphorization efficiency.
4th, water body dephosphorized dose of raw materials of the present invention be mainly discarded concrete in gelled matrix it is not necessary to carry out complexity
Equilibrium dispensing again, preparation process is simple, to appointed condition require low, it is easy to accomplish industrialized production.
5th, the dephosphorization agent environmental friendliness prepared by the inventive method, dirty for there are not two secondary environments during water body dephosphorized
Dye problem, meets the policy guidance of the development of national green economy, recycling economy.
6th, the present invention provides new approaches and methods to hardening gel recycling in discarded concrete, improves
The value of discarded concrete, be obtained water body dephosphorized dose of the present invention can carry out the improvement of phosphorus-containing wastewater, is China river, lake
The improvement that pool, industrial and life contaminated water etc. contain phosphorus water provides a kind of wide material sources, cheap and easy to get, energy consumption is low, environmental protection
New material, be a kind of can widely used " waste recycling " technical method, with dephosphorization agent of the present invention administer lake, river
Produced with during the eutrophication of the natural waters that flow slowly such as bay and mankind's industrial and agricultural production and daily life
Phosphorus-containing wastewater, can reach and be prevented effectively from the purpose occurring by the aquatic ecosystem crisis that body eutrophication is caused, tool
There is applications well prospect.
Brief description
Fig. 1 is the water body dephosphorized dose of different impact to water body dephosphorized effect for the dosage that embodiment 1 is obtained；
Fig. 2 is the impact to water body dephosphorized effect for the stir speed (S.S.)；
Fig. 3 is the impact to water body dephosphorized effect for the dephosphorization response time；
Fig. 4 is the impact to phosphor-removing effect for the dephosphorization reaction temperature.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.The implementation case with the technology of the present invention is being
Under the premise of implemented, now provide detailed embodiment and specific operating process be creative the present invention to be described, but
Protection scope of the present invention is not limited to below example.
Embodiment 1:
A kind of water body dephosphorized dose of preparation method, comprises the steps:
1) discarded concrete jaw crusher is broken for the waste concrete block that granularity is less than 25 mm, will be described discarded mixed
Solidifying soil block low-temperature activation at 300 DEG C is processed 20 minutes；
2) pulverization process is carried out 10 seconds using electromagnetic oscillation pulverizer to the waste concrete block after the process of step 1) low-temperature activation,
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 described discarded concrete powder, thick in discarded concrete powder to remove
Particles of aggregates thing, collects siftage and obtains hardening gel matrix；
3) by step 2) the hardening gel matrix that obtains loaded in vacuum ball grinder together with surfactant triethanolamine and carries out
After mixing, ball milling activation processing 5 min is carried out using planetary ball mill, be obtained described water body dephosphorized dose；Wherein, described gelling base
Body is 1000:3 with the mass ratio of surfactant.
A kind of water body dephosphorized method, prepared for the present embodiment water body dephosphorized dose is added in staying water to treat place
P elements in reason water body are removed, specifically to water body dephosphorized dose of dosage during dephosphorization, stir speed (S.S.), stirring dephosphorization
Time and reaction temperature are done and are studied as follows:
1st, the dephosphorization agent dosage that the present embodiment during dephosphorization is obtained is investigated:
1) use kh2po4Configure the phosphorus-containing wastewater simulated solution that initial phosphorus concentration is 20mg/l (in terms of p mass concentration), take a series of
The beaker of 250ml, is separately added into the phosphorus-containing wastewater simulated solution 100ml of above-mentioned preparation successively, and beaker is placed in magnetic stirring apparatuss
On.
2) with 20 mg as initial concentration, and with 20 mg as mass gradient, successively to above-mentioned equipped with phosphorus-containing wastewater simulated solution
Beaker in add the dephosphorization agent that different quality the present embodiment is obtained, matched group is not added with.At ambient temperature, with 100 r/min
Stirring intensity under process 60 min.
3), after taking off beaker standing a moment sucking filtration, take in each beaker filtrate successively in color comparison tube with micropipettor
In, plus distilled water diluting, add sulphuric acid, the mix reagent of antimony potassium tartrate, ammonium molybdate and ascorbic acid composition, stand after shaking up
10min.Blank reference is made with distilled water, measures filtrate absorbance at wavelength 880nm with visible spectrophotometer, to assess
The phosphor-removing effect of different amounts dephosphorization agent, experimental result is as shown in Figure 1.
As can be seen from Figure 1 with the increase of prepared dephosphorization dosage, water outlet phosphorus concentration straight line declines, when dosage reaches
In water during 0.3 g, phosphorus concentration is reduced to below 2mg/l from 20mg/l, has reached national relevant emission standards；It is further added by dephosphorization
The dosage phosphorus concentration of agent is held essentially constant.Under same experimental conditions, three times experimental result (lines a1, a2, a3 in Fig. 1) has
Preferably repeatability it is seen that the present embodiment is separated and water body dephosphorized dose of c-s-h gel that prepare have comparatively ideal water body dephosphorized
And phosphorus recovering effect, and dephosphorization process stabilization, the optimum amount of dephosphorization agent is 0.05 ~ 1g.
2nd, stir speed (S.S.) during dephosphorization is investigated:
Take 7 250ml beakers, pipette the concentration preparing respectively for 20mg/l simulation phosphorus-containing wastewater 100 ml in beaker, and
Beaker is placed on magnetic stirring apparatuss, adds 0.50 g dephosphorization agent in 7 beakers successively, at 25 DEG C of room temperature, use magnetic force
Agitator turning with 60r/min, 80r/min, 100r/min, 120r/min, 140r/min, 160r/min, 180r/min respectively
React 60min under the conditions of speed, after terminating, the water after processing is diluted, and add sulphuric acid, antimony potassium tartrate, ammonium molybdate and resist
The mix reagent of bad hematic acid composition, stands 10min after shaking up, with distilled water as blank, with visible spectrophotometer in ripple
Filtrate absorbance, to assess the phosphor-removing effect of dephosphorization agent under different stirring intensities, experimental result such as Fig. 2 institute is measured at long 880nm
Show.
As shown in Figure 2, under other factorses certain condition, with the increase of stirring intensity, the linear type of phosphorus concentration in water outlet
Decline, in the water outlet when speed of agitator reaches 140r/min, phosphorus concentration is preferably minimized, continue to increase stirring intensity water outlet phosphorus concentration
Fuctuation within a narrow range, no longer changes substantially, and three parallel laboratory tests (lines a1, a2, a3 in Fig. 2) have preferable repeatability, show
Optimal stirring intensity is 140r/min.
3rd, the impact of dephosphorization time:
Take 7 250ml beakers, pipette the concentration preparing respectively for 20mg/l simulation phosphorus-containing wastewater 100ml in beaker, and will
Beaker is placed on magnetic stirring apparatuss, adds 0.50 g dephosphorization agent successively, in magnetic stirring apparatuss rotating speed 140 r/ in 7 beakers
Under the conditions of 25 DEG C of min room temperature, the phosphorus-containing wastewater dephosphorization time in 7 beakers is respectively set to 5min, 15min, 30min,
45min, 60min, 75min, 90min are carried out except phosphorus reaction.After end, the water after processing is diluted, and adds and add sulfur
Acid, the mix reagent of antimony potassium tartrate, ammonium molybdate and ascorbic acid composition, stand 10min after shaking up, right for blank with distilled water
According to measuring filtrate absorbance with visible spectrophotometer at wavelength 880nm, to assess dephosphorization agent under differential responses time conditions
Phosphor-removing effect, experimental result is as shown in Figure 3.
Fig. 3 shows under other factorses permanence condition, and three parallel laboratory tests (lines a1, a2, a3 in Fig. 3) all show,
In front 15min, with the carrying out of reaction, in water outlet, phosphorus concentration rapidly drops to below 2mg/l, reaches discharging standards,
Continue to extend the response time, water outlet phosphorus concentration fuctuation within a narrow range, substantially no longer change, phosphorus-containing wastewater simulated solution after reaction 30 min
Lowering of concentration is 0.03mg/l, and dephosphorization efficiency reaches more than 99%.
4th, the impact of dephosphorization temperature
Take 7 250ml beakers, pipetting the concentration preparing respectively is that 20 mg/l simulate phosphorus-containing wastewater 100ml in beaker, and
Beaker is placed on magnetic stirring apparatuss, adds 0.50g dephosphorization agent in 7 beakers successively, magnetic stirring apparatuss rotating speed is set
140r/min, reacts 15min, respectively to place after terminating 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
Water after reason is diluted, and adds sulphuric acid, the mix reagent of antimony potassium tartrate, ammonium molybdate and ascorbic acid composition, after shaking up
Standing 10min, with distilled water as blank, measures filtrate absorbance with visible spectrophotometer, to comment at wavelength 880nm
Estimate the phosphor-removing effect of dephosphorization agent under differential responses temperature conditionss, experimental result is as shown in Figure 4.
As seen from Figure 4, in studied temperature range (15 DEG C～105 DEG C), three parallel laboratory tests (lines in Fig. 4
A1, a2, a3) all show the change undulate with temperature for the water outlet phosphorus concentration, fluctuation is less, and reaction temperature is to water outlet phosphorus concentration
Impact is less, and this also indicates that in practical application that prepared dephosphorization agent has good adaptation in water body dephosphorized and phosphorus removal process
Property, dephosphorization process can be carried out at normal temperatures.
Embodiment 2
A kind of water body dephosphorized dose of preparation method, comprises the steps:
1) discarded concrete jaw crusher is broken for the waste concrete block that granularity is less than 25 mm, will be described discarded mixed
Solidifying soil block low-temperature activation at 250 DEG C is processed 25 minutes；
2) pulverization process is carried out 10 seconds using electromagnetic oscillation pulverizer to the waste concrete block after the process of step 1) low-temperature activation,
Obtain discarded concrete powder, using 170 mesh sandstone sieves, mechanical grading is carried out to described discarded concrete powder, to remove discarded coagulation
Thick particles of aggregates thing in native powder, collects siftage and obtains hardening gel matrix；
3) by step 2) the hardening gel matrix that obtains loads in vacuum ball grinder together with surfactant triisopropanolamine
After row mixing, ball milling activation processing 7 min is carried out using planetary ball mill, be obtained described water body dephosphorized dose；Described gelling matrix
Mass ratio with surfactant is 1000:4.
The dephosphorization agent that 0.50 g the present embodiment is obtained puts into 100 ml kh2po4The initial phosphorus concentration of configuration is 20mg/l
In (in terms of p mass concentration) phosphorus-containing wastewater simulated solution, at normal temperatures with stir speed (S.S.) stirring reaction 15min of 140r/min, right
In water body, P elements are removed, and P elements in water after processing are detected, result display dephosphorization efficiency is 99.89%.
Embodiment 3
A kind of water body dephosphorized dose of preparation method, comprises the steps:
1) discarded concrete jaw crusher is broken for the waste concrete block that granularity is less than 25 mm, will be described discarded mixed
Solidifying soil block low-temperature activation at 220 DEG C is processed 30 minutes；
2) pulverization process is carried out 10 seconds using electromagnetic oscillation pulverizer to the waste concrete block after the process of step 1) low-temperature activation,
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 described discarded concrete powder, thick in discarded concrete powder to remove
Particles of aggregates thing, collects siftage and obtains hardening gel matrix；
3) by step 2) the hardening gel matrix that obtains is placed in hydrothermal reaction kettle, carries out hydrothermal treatment consists under 180 DEG C, 1.0mpa
120min, obtains the matrix that is gelled；
4) the gelling matrix that step 3) is obtained and surfactant ethylene glycol (together with load in vacuum ball grinder and mixed
Afterwards, ball milling activation processing 10 min is carried out using planetary ball mill, be obtained described water body dephosphorized dose；Described gelling matrix and surface
The mass ratio of activating agent is 1000:5.
The dephosphorization agent that 0.5 g the present embodiment is obtained puts into 100 ml kh2po4The initial phosphorus concentration of configuration is 20mg/l
In (in terms of p mass concentration) phosphorus-containing wastewater simulated solution, at normal temperatures with stir speed (S.S.) stirring reaction 15min of 140r/min, right
In water body, P elements are removed, and P elements in water after processing are detected, result display dephosphorization efficiency is 99.50%.
To sum up, the present invention utilizes water body dephosphorized dose of gelling matrix preparation in discarded concrete, has dephosphorization response speed
Hurry up, the dephosphorization time is short, dephosphorization efficiency is high, phosphor-removing effect is stable advantage, dephosphorizing rate is up to more than 99%.Using water body of the present invention
Dephosphorization agent carries out except phosphorus reaction, range of reaction temperature width and can carrying out at room temperature, and the restriction to reaction condition is less, is more easy to
In being operated, and save the energy.
Finally illustrate, above example only in order to technical scheme to be described and unrestricted, although with reference to relatively
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent, the objective without deviating from technical solution of the present invention and scope, and it all should be covered at this
In the middle of the right of invention.
Claims (10)
1. a kind of water body dephosphorized dose of preparation method is it is characterised in that comprise the steps:
1) discarded concrete is broken for the waste concrete block that particle diameter is less than 25 mm, by described waste concrete block in 200 ~
At 300 DEG C, low-temperature activation is processed 10 ~ 30 minutes；
2) pulverization process is carried out to the waste concrete block after the process of step 1) low-temperature activation and obtain discarded concrete powder, adopt
100 ~ 325 mesh sieves sieve to described discarded concrete powder, collect siftage and obtain hardening gel matrix；
3) by step 2) the hardening gel matrix that obtains carries out being mixed to get mixed material, using ball mill pair with surfactant
Described mixed material carries out ball milling activation processing 2 ~ 10 min, is obtained described water body dephosphorized dose.
2. according to claim 1 water body dephosphorized dose of preparation method it is characterised in that surfactant described in step 3)
For triethanolamine, triisopropanolamine, ethylene glycol or diethylene glycol.
3. according to claim 1 water body dephosphorized dose of preparation method it is characterised in that hardening gel base described in step 3)
Body is 1000:2 ~ 1000:5 with the mass ratio of surfactant.
4. according to claim 1 water body dephosphorized dose of preparation method it is characterised in that by step 2) hardening gel that obtains
Matrix is placed in hydrothermal reaction kettle, carries out hydro-thermal reaction 10 ~ 150 min, obtain under conditions of 150 ~ 190 DEG C, 0.6 ~ 1.5mpa
To gelling matrix；Described gelling matrix is mixed with surfactant and carries out ball milling activation processing 2 ~ 10 min, is obtained described
Water body dephosphorized dose.
5. according to claim 4 water body dephosphorized dose of preparation method it is characterised in that under conditions of 180 DEG C, 1.0mpa
Carry out hydro-thermal reaction 120min.
6. a kind of water body dephosphorized method it is characterised in that will using the arbitrary methods described of claim 1 ~ 5 be obtained water body dephosphorized
Agent adds in staying water to be removed to the P elements in staying water；Wherein, described water body dephosphorized dose with treat
The mass volume ratio processing water body is 0.3 ~ 10 g:1000 ml.
7. according to claim 6 water body dephosphorized method it is characterised in that the described water body dephosphorized dose of matter with staying water
Amount volume ratio is 5 g:1000 ml.
8. according to claim 6 water body dephosphorized method it is characterised in that described water body dephosphorized dose is added into accessing pending water
In body, stirring reaction 15 ~ 60 min under the stir speed (S.S.) of 60 ~ 180 r/min.
9. according to claim 8 water body dephosphorized method it is characterised in that described stir speed (S.S.) be 140 r/min.
10. according to claim 8 water body dephosphorized method it is characterised in that stirring reaction time be 15 min.
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