CN102336400A - Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method - Google Patents
Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method Download PDFInfo
- Publication number
- CN102336400A CN102336400A CN2010102330116A CN201010233011A CN102336400A CN 102336400 A CN102336400 A CN 102336400A CN 2010102330116 A CN2010102330116 A CN 2010102330116A CN 201010233011 A CN201010233011 A CN 201010233011A CN 102336400 A CN102336400 A CN 102336400A
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- calcium silicate
- sewage
- technology
- hydrated calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011574 phosphorus Substances 0.000 title claims abstract description 77
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 77
- 239000010865 sewage Substances 0.000 title claims abstract description 42
- 239000000378 calcium silicate Substances 0.000 title claims abstract description 36
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 36
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 13
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 11
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 4
- 238000002798 spectrophotometry method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 15
- 239000011591 potassium Substances 0.000 claims description 15
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- 239000002351 wastewater Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000011435 rock Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000002367 phosphate rock Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract 7
- 238000001035 drying Methods 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 239000001110 calcium chloride Substances 0.000 abstract 1
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 1
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000001514 detection method Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 12
- 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 7
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 235000010333 potassium nitrate Nutrition 0.000 description 6
- 239000004323 potassium nitrate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 238000010671 solid-state reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010435 syenite Substances 0.000 description 4
- 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 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910052567 struvite Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052641 aegirine Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- -1 ammonium nitrogen ion Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- YTCQFLFGFXZUSN-BAQGIRSFSA-N microline Chemical compound OC12OC3(C)COC2(O)C(C(/Cl)=C/C)=CC(=O)C21C3C2 YTCQFLFGFXZUSN-BAQGIRSFSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Removal Of Specific Substances (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a technology for recovering phosphor from sewage through a calcium silicate hydrate seed method. The technology comprises the following steps of 1, adjusting a pH value of phosphorus-containing sewage to a pH value of 8 to 9.5, and adding CaCl2 into the phosphorus-containing sewage until a molar ratio of Ca to P is in a range of 2 to 2.4, 2, adding the phosphorus-containing sewage obtained by the step 1 into calcium silicate hydrate powder, wherein a use amount of the calcium silicate hydrate powder is in range of 2 to 12g/L, 3, stirring the suspension liquid obtained by the step 2 at a temperature of 20 to 40 DEG C at a rate of 70 to 180r/min for 2 to 24 hours, standing for 2 to 24 hours, carrying out centrifugation, and recovering precipitates, 4, adding the phosphorus-containing sewage obtained by the step 1 into the precipitates obtained by the step 3, repeating the step 2 and the step 2, and carrying out x-ray diffraction (XRD) analysis detection of hydroxyapatite in the precipitates, and 5, drying the precipitates treated by the step 4 at a temperature of 105 to 110 DEG C for 24 hours, adding concentrated HNO3 into the dried precipitates to immerse it, heating at a temperature of 105 to 110 DEG C for 2 hours, placing the mixed solution indoors for 24 hours, determining concentration of phosphorus in the mixed solution by a phosphorus vanadium-molybdenum-yellow spectrophotometry, calculating content of P2O5, when the content of P2O5 in the precipitates is over 35% by mass, and drying the precipitates at a temperature of 105 DEG C to obtain recovered phosphorus-containing products as a succedaneum of industrial phosphate ore.
Description
Technical field
The present invention relates to the technology that a kind of hydrated calcium silicate crystal seed method reclaims phosphor in sewage.
Background technology
Phosphorus is the important element that causes body eutrophication, also is a kind of non-renewable and alternate resource.At present, the explored phosphorus ore reserves in the whole world only can be kept about 100 years.Though China's phosphorus reserves occupy the third place in the world, the phosphorus ore of higher-grade, low impurity content is estimated in following 10 years, will to have been exploited, and national departments concerned can not satisfy one of 20 kinds of mineral products of national economic development demand after classifying phosphorus ore as 2010 years already.Therefore, seek new phosphor resource, explore economically viable phosphorus recovery technology, have important economic value and social benefit for the Sustainable development that promotes China's agricultural and national economy.
Usually, utilize membrane technique can obtain purified microcosmic salt, but cost is expensive; And the crystallization process cost is low, and it is obvious to reclaim the phosphorus effect, is that very promising phosphorus reclaims technology.Crystallization process reclaims phosphorus and mainly comprises magnesium ammonium phosphate method (struvite) and two kinds of technologies of calcium phosphate crystal method.The ammoniomagnesium phosphate crystal method can also remove the ammonium nitrogen ion of high density, but ammonium nitrogen concentration in the solution and orthophosphoric acid salt concentration need meet the formation condition of struvite, and this method only is applicable to the higher solution of phosphate concn (100～200mg/L) when removing dephosphorization.Adopt the calcium phosphate crystal method; Traditional way is that the B-grade sewage behind the removal suspended substance is incorporated in phosphate crystal or the animal bone ash; Make the phosphorus in the water be able to deposition; Because carbanion can be deposited in the crystallization that stops phosphorus on these seed crystals then, thereby need remove carbanion in advance.
In recent years; Because tobermorite has self hydroxide ion and calcium ion can be provided, and does not contain heavy metal and phosphorus, does not receive the restriction of organic concentration; Solubility in soil; Do not need to remove in advance the advantage of carbonic acid gas, become the good crystal seed of hydroxyl phosphate crystalline deposit, become the phosphorus salvage material of high-density phosphorus sewage (phosphorus concentration is greater than 20mg/L).
It is 200710178440.6 that the inventor has proposed number of patent application on November 30th, 2007; Invention and created name is the patented claim of " utilizing potassium rich rock to produce the method for agricultural mineral base saltpetre "; The solid state reaction product hydrated calcium silicate-aluminium of this application in the process of utilizing potassium rich rock production agricultural mineral base saltpetre is for tobermorite; This solid state reaction product is for the crystal formation fibrous hollow ball shape coacervate of tobermorite by aluminium; Process agricultural mineral base saltpetre as inorganic sustained release dosage solid support material and sylvite after compound, this solid state reaction product also can be used for the recovery of phosphorus-containing wastewater phosphorus in theory as the crystal seed of hydroxyl phosphate crystalline deposit.
Summary of the invention
The object of the present invention is to provide a kind of hydrated calcium silicate crystal seed method to reclaim the technology of phosphor in sewage, this technology reclaim phosphorus effective, be widely used, be convenient to implement to promote.
For achieving the above object, the present invention adopts following technical scheme:
A kind of hydrated calcium silicate crystal seed method reclaims the technology of phosphor in sewage, comprises the steps:
(1) with acid or alkali the pH of phosphorus-containing wastewater is transferred to 8～9.5, to wherein adding CaCl
2Mol ratio to Ca/P is 2～2.4;
(2) in hydration calcium silicate powder, add the phosphorus-containing wastewater that step (1) obtains, the consumption of this hydrated calcium silicate in this phosphorus-containing wastewater is 2～12g/L;
(3) suspension liquid that step (2) is obtained is in 20～40 ℃, stirs 2～24h with the speed of 70～180r/min, leaves standstill 0～2h, spinning, and inclining supernatant, reclaims throw out;
(4) in the throw out that reclaims, adding the pH that step (1) obtains is 8～9.5, and the mol ratio of Ca/P is 2～2.4 phosphorus-containing wastewater, repeating step (3), and utilize XRD analysis to detect the hydroxylapatite in the gained throw out;
(5) repeating step (4) takes by weighing throw out in 105～110 ℃ of oven dry 24h to the peak that can obviously detect hydroxylapatite repeatedly, adds dense HNO
3Submergence, once more in 105～110 ℃ of heat treated 2h, room temperature held 24h behind the zero(ppm) water constant volume, with the concentration of phosphorus in the yellow spectrophotometry solution of phosphorus molybdenum, calculates P
2O
5Content is treated P in the throw out
2O
5After mass content surpassed 35%, the phosphorous product that the throw out that obtains is obtained reclaiming in 105 ℃ of oven dry was as the substitute of industrial Rock Phosphate (72Min BPL).
In the said step (1) mol ratio of Ca/P is limited to 2～2.4 and can guarantees that enough calcium fully combines to generate hydroxylapatite with phosphorus in the sewage.
According to the mol ratio of the content and the Ca/P of phosphor in sewage, the consumption after hydrated calcium silicate adds in phosphorus-containing wastewater in the step (2) is preferably 2～12g/L.
Phosphorus content in the said phosphorus-containing wastewater is greater than 10mg/L.When the phosphorus content in the phosphorus-containing wastewater during less than 10mg/L, utilize aforesaid method can reach the purpose of dephosphorization equally, the phosphorus content in the sewage is reduced to below the 0.5mg/L, reach the state sewage emission standard primary standard; When the phosphorus content in the phosphorus-containing wastewater during greater than 10mg/L, utilize aforesaid method can effectively reclaim the phosphorus in the sewage, reclaim the substitute that the phosphorus product can be used as industrial Rock Phosphate (72Min BPL).
Acid is hydrochloric acid described in the step (1), and said alkali is sodium hydroxide.
Said hydrochloric acid, sodium hydroxide are technical hydrochloric acid, industrial sodium hydroxide.
Described CaCl
2Be technical grade CaCl
2
The hydrated calcium silicate that uses in the said step (2) is 200710178440.6 as number of patent application; Invention and created name is the patented claim of " utilizing potassium rich rock to produce the method for agricultural mineral base saltpetre "; Solid state reaction product hydrated calcium silicate-aluminium in the process of utilizing potassium rich rock production agricultural mineral base saltpetre is for tobermorite, and the preparation of this hydrated calcium silicate may further comprise the steps:
1), makes the potassium felspar sand powder of granularity for-300 orders＞90% grade with grinding after potassium rich rock fragmentation, ore dressing, the removal of impurities;
2) in the potassium felspar sand powder: the lime quality ratio is 1: 0.80～0.85 ratio batching, puts into autoclave, adds entry, makes the solid-liquid mass ratio 1: 15～25, and mixes;
3) with the reaction kettle sealing, form closed environment, under 180～250 ℃ agitation condition, carry out hydro-thermal reaction, constant temperature 5～10 hours, reaction product is separated through filtering, and the solid phase that obtains is obtained hydrated calcium silicate 105 ℃ of oven dry.
Hydrated calcium silicate through aforesaid method obtains is different with natural tobermorite, and the part silicon in its lattice is replaced by aluminium, is called aluminium again for tobermorite, is long 5～10 μ m, the hollow ball shape coacervate of wide 0.1～1 μ m.
Technology of the present invention has following characteristics:
(1) reclaim crystal seed that phosphorus uses by product aquation Calucium Silicate powder, thereby tooling cost is low as hydrothermal decomposition potassium rich rock extraction potassium; Be applied to sewage phosphorus and reclaim, solved SiO in the potassium felspar sand effectively
2, Al
2O
3And K
2The problem of complex utilization of O component.
(2) because hydrated calcium silicate can discharge alkali and calcium ion in water; Can greatly promote phosphatic crystalline deposit; And make crystal seed with hydrated calcium silicate; Carbonate in the time of can overcoming traditional calcium phosphate crystal method technology and reclaim phosphorus, organism be to the interference of phosphate crystal, and have consistency with soil.
(3) compare with the natural snow rankinite, this synthetic hydration calcium silicate powder is the hollow ball shape coacervate, helps the recovery of phosphorus.The residual phosphorus concentration of sewage is reached below the state sewage emission standard primary standard, thereby when reclaiming phosphorus, realizing the qualified discharge of sewage phosphorus.
(4) crystal seed of this technology use can reuse, and reclaims the phosphorus product and can reach rich phosphorus ore standard, and main thing is a hydroxylapatite mutually, can be used as the substitute of industrial high-quality Rock Phosphate (72Min BPL).
Description of drawings
Fig. 1 reclaims the process flow sheet of phosphor in sewage for the hydrated calcium silicate crystal seed method.
Fig. 2 is the X-ray diffractogram of the phosphorus product of recovery among the embodiment 1.
Embodiment
The experimental water Calucium Silicate powder is that secondary rainbow brightness syenite low-temperature hydrothermal is decomposed the by product that extracts saltpetre, and this secondary rainbow brightness syenite chemical ingredients is (%) as follows:
SiO
2TiO
2Al
2O
3Fe
2O
3FeO MgO CaO Na
2O K
2O P
2O
5Burn and lose total amount
63.58?0.01?17.10?0.60 0.11?0.40?0.64?1.17 15.98?0.02?0.19?99.80
The electron probe microanalysis result of chemical composition analysis result, X ray powder crystal diffraction phase analysis and the essential mineral phase chemistry composition of comprehensive ore; The thing phase composite of this secondary rainbow brightness syenite is: microline 91.4%; Aegirine 4.5%, quartz 3.5%, phosphatic rock 0.1%.
With grinding after the fragmentation of above-mentioned secondary rainbow brightness syenite, ore dressing, the removal of impurities, make the potassium felspar sand powder of granularity for-300 orders＞90% grade; In the potassium felspar sand powder: the lime quality ratio is 1: 0.80～0.85 ratio batching, puts into autoclave, adds entry, makes the solid-liquid mass ratio 1: 15～25, and mixes; With the reaction kettle sealing, form closed environment, under 180～250 ℃ agitation condition, carry out hydro-thermal reaction, constant temperature 5～10 hours, reaction product is separated through filtering, and the solid phase that obtains is obtained hydrated calcium silicate 105 ℃ of oven dry.According to X ray powder crystal diffraction analysis result, the aluminium that this synthetic hydrated calcium silicate is the well-crystallized is for tobermorite.According to the sem test result, its pattern is for being about 5-10 μ m, the spherical hollow coacervate of wide about 0.1-1 μ m.Chemical composition analysis result such as table 1.
Chemical composition analysis result (the w of table 1 experimental water Calucium Silicate powder
B/ %)
To utilize the effect of hydrated calcium silicate for crystal seed recovery phosphorus in order verifying, at first to adopt the phosphorous aqueous solution (water distribution) through chemical pure material preparation to replace phosphorus-containing wastewater to make an experiment, detailed process is following:
(1) getting phosphorus concentration is 25mg/L, and calcium concn is the water distribution 3L of 64mg/L, and the pH that regulates water distribution is 8, in water distribution, adds 36g hydration calcium silicate powder (amount of seed is 12g/L).Room temperature (25 ℃) down 140r/min stirred 2 hours, leave standstill after 2 hours centrifugally, inclining supernatant, records that phosphorus concentration is 1.12mg/L in the supernatant, and obtains moistening throw out;
(2) in moistening throw out, continuing to add phosphorus concentration is 25mg/L; Calcium concn is 64mg/L, and the pH value is 8 water distribution 3L, and 140r/min stirred 2 hours under room temperature (25 ℃); Leave standstill after 2 hours centrifugal; Inclining supernatant, records that phosphorus concentration is 3.39mg/L in the supernatant, and utilizes XRD analysis to detect the hydroxylapatite in the gained throw out;
(3) repeating step is (2) 55 times, and average dephosphorizing rate reaches 82%.Get a certain amount of throw out in 105～110 ℃ of oven dry 24h, add dense HNO
3Submergence, once more in 105～110 ℃ of heat treated 2h, room temperature held 24h with the concentration of phosphorus in the yellow spectrophotometry solution of phosphorus molybdenum, calculates P
2O
5Content obtains reclaiming the phosphorus content (P of phosphorus product
2O
5Be 35.02% %), meet rich phosphorus ore standard;
(4) throw out that obtains is obtained the phosphorous product that 68.73g reclaims in 105 ℃ of oven dry.
Reclaim phosphorus product X x ray diffration pattern x such as Fig. 2; Wherein 1 be the X ray diffracting spectrum of pure hydroxylapatite; 2 is the X ray diffracting spectrum of the phosphorous product of recovery; 3 is the X ray diffracting spectrum of natural snow rankinite, contrasts the high preferred orientation intensity CPS value of various materials in three kinds of collection of illustrative plates, can know that reclaiming the main thing of phosphorus product is hydroxylapatite mutually.Calculate, hydroxylapatite content is 82.54% in this product, and hydrated calcium silicate content only accounts for 17.46%, can be used as the substitute of industrial high-quality Rock Phosphate (72Min BPL).
What use in the present embodiment is certain pig farm sewage, through filtering, removes its staple such as table 2 behind the impurity.
Staple in the sewage of table 2 pig farm
The pH value of above-mentioned sewage is adjusted to 8, to wherein adding CaCl
2Ca/P (mol ratio) wherein is adjusted to 2.Get this sewage 50mL, add the hydration calcium silicate powder of preparation among the 0.6g embodiment 1, promptly amount of seed is 12g/L.With the speed oscillation of 140r/min 4 hours, centrifugal under room temperature (25 ℃), record that phosphorus concentration is 9.91mg/L in the supernatant, dephosphorizing rate is 89.08%; The 140r/min vibration is after 24 hours down in room temperature (25 ℃), and centrifugal, phosphorus concentration is 0.45mg/L in the supernatant, reaches below the state sewage emission standard primary standard (0.5mg/L).
What use in the present embodiment is staple sewage as shown in table 2.
Staple in table 3 sewage
Wherein, TP representes that total phosphorus content, the COD in the sewage representes COD, and DO representes dissolved oxygen amount.
Because this sewage phosphorus content is lower, in sewage, add analytical pure KH
2PO
4Make the total P concentration of sewage bring up to 25mg/L.PH value with above-mentioned sewage is adjusted to 9.5 then, to wherein adding CaCl
2Ca/P (mol ratio) wherein is adjusted to 2.Get this sewage 50mL, add the hydration calcium silicate powder of preparation among the 0.12g embodiment 1, promptly amount of seed is 2.4g/L.With the speed oscillation of 140r/min 4 hours, centrifugal under room temperature (25 ℃), record that phosphorus concentration is 2.83mg/L in the supernatant; The 140r/min vibration is after 24 hours down in room temperature (25 ℃), and centrifugal, phosphorus concentration is 0.38mg/L in the supernatant, reaches below the state sewage emission standard primary standard (0.5mg/L).
Claims (6)
1. the technology of a hydrated calcium silicate crystal seed method recovery phosphor in sewage is characterized in that, comprises the steps:
(1) with acid or alkali the pH of phosphorus-containing wastewater is transferred to 8～9.5, to wherein adding CaCl
2Mol ratio to Ca/P is 2～2.4;
(2) in hydration calcium silicate powder, add the phosphorus-containing wastewater that step (1) obtains, the consumption of this hydrated calcium silicate in this phosphorus-containing wastewater is 2～12g/L;
(3) suspension liquid that step (2) is obtained is in 20～40 ℃, stirs 2～24h with the speed of 70～180r/min, leaves standstill 0～2h, spinning, and inclining supernatant, reclaims throw out;
(4) in the throw out that reclaims, adding the pH that step (1) obtains is 8～9.5, and the mol ratio of Ca/P is 2～2.4 phosphorus-containing wastewater, repeating step (3), and utilize XRD analysis to detect the hydroxylapatite in the gained throw out;
(5) repeating step (4) is got a certain amount of throw out in 105～110 ℃ of oven dry 24h to the peak that can obviously detect hydroxylapatite repeatedly, adds dense HNO
3Submergence, once more in 105～110 ℃ of heat treated 2h, room temperature held 24h behind the zero(ppm) water constant volume, with the concentration of phosphorus in the yellow spectrophotometry solution of phosphorus molybdenum, calculates P
2O
5Content is treated P in the throw out
2O
5After mass content surpassed 35%, the phosphorous product that the throw out that obtains is obtained reclaiming in 105 ℃ of oven dry was as the substitute of industrial Rock Phosphate (72Min BPL).
2. hydrated calcium silicate crystal seed method according to claim 1 reclaims the technology of phosphor in sewage, it is characterized in that the phosphorus content described in the step (1) in the phosphorus-containing wastewater is greater than 10mg/L.
3. hydrated calcium silicate crystal seed method according to claim 1 reclaims the technology of phosphor in sewage, it is characterized in that acid is hydrochloric acid described in the step (1), and said alkali is sodium hydroxide.
4. hydrated calcium silicate crystal seed method according to claim 1 reclaims the technology of phosphor in sewage, it is characterized in that said hydrochloric acid, sodium hydroxide are technical hydrochloric acid, industrial sodium hydroxide.
5. hydrated calcium silicate crystal seed method according to claim 1 reclaims the technology of phosphor in sewage, it is characterized in that described CaCl
2Be technical grade CaCl
2
6. hydrated calcium silicate crystal seed method according to claim 1 reclaims the technology of phosphor in sewage, it is characterized in that, the hydrated calcium silicate that uses in the said step (2) prepares through following method:
1), makes the potassium felspar sand powder of granularity for-300 orders＞90% grade with grinding after potassium rich rock fragmentation, ore dressing, the removal of impurities;
2) in the potassium felspar sand powder: the lime quality ratio is 1: 0.80～0.85 ratio batching, puts into autoclave, adds entry, makes the solid-liquid mass ratio 1: 15～25, and mixes;
3) with the reaction kettle sealing, form closed environment, under 180～250 ℃ agitation condition, carry out hydro-thermal reaction, constant temperature 5～10 hours, reaction product is separated through filtering, and the solid phase that obtains is obtained hydrated calcium silicate 105 ℃ of oven dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102330116A CN102336400B (en) | 2010-07-21 | 2010-07-21 | Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102330116A CN102336400B (en) | 2010-07-21 | 2010-07-21 | Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102336400A true CN102336400A (en) | 2012-02-01 |
| CN102336400B CN102336400B (en) | 2012-11-21 |
Family
ID=45512409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102330116A Expired - Fee Related CN102336400B (en) | 2010-07-21 | 2010-07-21 | Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102336400B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104487404A (en) * | 2012-05-25 | 2015-04-01 | 太平洋水泥株式会社 | Method for producing phosphorous fertilizer |
| CN104785198A (en) * | 2015-04-08 | 2015-07-22 | 陕西科技大学 | Carbonate hydroxyapatite/glass powder composite material as well as preparation method and application thereof |
| CN105174528A (en) * | 2015-07-18 | 2015-12-23 | 常州市鼎日环保科技有限公司 | Method for recovering phosphorus in culturing farm biogas slurry |
| CN108499547A (en) * | 2018-05-23 | 2018-09-07 | 常州清流环保科技有限公司 | A kind of adsorbent and its methods and applications prepared using polyaluminium chloride lime scum |
| CN109722264A (en) * | 2019-03-05 | 2019-05-07 | 重庆大学 | A kind of method of feces of livestock and poultry hydrothermal carbonization recycling phosphorus |
| CN110227411A (en) * | 2019-05-30 | 2019-09-13 | 南通大学 | The method of preparation and the processing sewage containing cadmium with pH self-adjusting ability material |
| CN110373199A (en) * | 2019-06-21 | 2019-10-25 | 湖南大学 | A kind of composite soil renovation agent and preparation method thereof and restorative procedure |
| CN113104856A (en) * | 2021-05-08 | 2021-07-13 | 中南大学 | Preparation method, product and application of water body phosphorus removal material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008122621A1 (en) * | 2007-04-05 | 2008-10-16 | Solvay (Société Anonyme) | High-purity calcium compounds |
| CN101585522A (en) * | 2009-06-18 | 2009-11-25 | 南京林业大学 | Method for recovering phosphorus from urban mud anaerobic digestion solution |
| CN101734778A (en) * | 2008-11-24 | 2010-06-16 | 江苏工业学院 | Quantitative application process for removing phosphorous from phosphorous-enriched water by natural minerals |
| CN101774669A (en) * | 2010-02-26 | 2010-07-14 | 江苏工业学院 | Composite dephosphorizing agent for treating acidic wastewater containing phosphorus and preparation and application methods thereof |
-
2010
- 2010-07-21 CN CN2010102330116A patent/CN102336400B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008122621A1 (en) * | 2007-04-05 | 2008-10-16 | Solvay (Société Anonyme) | High-purity calcium compounds |
| CN101734778A (en) * | 2008-11-24 | 2010-06-16 | 江苏工业学院 | Quantitative application process for removing phosphorous from phosphorous-enriched water by natural minerals |
| CN101585522A (en) * | 2009-06-18 | 2009-11-25 | 南京林业大学 | Method for recovering phosphorus from urban mud anaerobic digestion solution |
| CN101774669A (en) * | 2010-02-26 | 2010-07-14 | 江苏工业学院 | Composite dephosphorizing agent for treating acidic wastewater containing phosphorus and preparation and application methods thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104487404A (en) * | 2012-05-25 | 2015-04-01 | 太平洋水泥株式会社 | Method for producing phosphorous fertilizer |
| CN104785198A (en) * | 2015-04-08 | 2015-07-22 | 陕西科技大学 | Carbonate hydroxyapatite/glass powder composite material as well as preparation method and application thereof |
| CN105174528A (en) * | 2015-07-18 | 2015-12-23 | 常州市鼎日环保科技有限公司 | Method for recovering phosphorus in culturing farm biogas slurry |
| CN108499547A (en) * | 2018-05-23 | 2018-09-07 | 常州清流环保科技有限公司 | A kind of adsorbent and its methods and applications prepared using polyaluminium chloride lime scum |
| CN109722264A (en) * | 2019-03-05 | 2019-05-07 | 重庆大学 | A kind of method of feces of livestock and poultry hydrothermal carbonization recycling phosphorus |
| CN110227411A (en) * | 2019-05-30 | 2019-09-13 | 南通大学 | The method of preparation and the processing sewage containing cadmium with pH self-adjusting ability material |
| CN110373199A (en) * | 2019-06-21 | 2019-10-25 | 湖南大学 | A kind of composite soil renovation agent and preparation method thereof and restorative procedure |
| CN110373199B (en) * | 2019-06-21 | 2021-10-01 | 湖南大学 | Composite soil repairing agent and preparation method and repairing method thereof |
| CN113104856A (en) * | 2021-05-08 | 2021-07-13 | 中南大学 | Preparation method, product and application of water body phosphorus removal material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102336400B (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102336400B (en) | Technology for recovering phosphorus from sewage through calcium silicate hydrate seed method | |
| Musyoka et al. | Synthesis of zeolites from coal fly ash using mine waters | |
| Huang et al. | Recovery of phosphate and ammonia nitrogen from the anaerobic digestion supernatant of activated sludge by chemical precipitation | |
| Xuechu et al. | Phosphate removal and recovery through crystallization of hydroxyapatite using xonotlite as seed crystal | |
| Yu et al. | Phosphate removal by hydrothermally modified fumed silica and pulverized oyster shell | |
| Kirinovic et al. | Spectroscopic and microscopic identification of the reaction products and intermediates during the struvite (MgNH4PO4· 6H2O) formation from magnesium oxide (MgO) and magnesium carbonate (MgCO3) microparticles | |
| JP5201454B2 (en) | Phosphorus recovery material and phosphorus recovery method | |
| CN104258804B (en) | A kind of method of comprehensive utilization of gangue | |
| CN101774669B (en) | Composite dephosphorizing agent for treating acidic wastewater containing phosphorus and preparation and application methods thereof | |
| Chen et al. | Capture and recycling of ammonium by dolomite-aided struvite precipitation and thermolysis | |
| Kuwahara et al. | Removal of phosphate from aqueous solution using layered double hydroxide prepared from waste iron-making slag | |
| CN107210432A (en) | The method for producing lithium metal phosphates | |
| CN103998633A (en) | Method for extraction of lithium from lithium bearing solution | |
| CN101585522B (en) | Method for recovering phosphorus from urban mud anaerobic digestion solution | |
| CN102674516A (en) | Method for circularly treating nitrogen-phosphorus wastewater | |
| CN102432083B (en) | Method for removing and recovering phosphate in waste water | |
| Belibagli et al. | Phosphate recovery from waste fish bones ash by acidic leaching method and iron phosphate production using electrocoagulation method | |
| CN107879321A (en) | A kind of method of phosphorus ore de-magging co-production prodan and magnesium sulfate | |
| Liu et al. | Hydrothermal reaction of K‐feldspar powder in NaOH Ca (OH) 2 mixed medium | |
| CN101830553B (en) | Dephosphorizing crystal seed for sewage treatment and preparation method thereof | |
| US7670405B2 (en) | Process for the manufacture of a bio-release fertilizer of an anionic micro nutrient viz molybdenum | |
| CN102442655B (en) | Method for preparing potassium dihydrogen phosphate with phosphorus recovery product in sewage | |
| CN105329974B (en) | A kind of method that fluorine is reclaimed from fluoride waste | |
| JP2009256172A (en) | Method of producing aluminum phosphate | |
| JP2014000487A (en) | Phosphorus recovery material and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121121 |