CN1761507A - Method and apparatus for removing ion in fluid by crystallization - Google Patents
Method and apparatus for removing ion in fluid by crystallization Download PDFInfo
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- CN1761507A CN1761507A CN 200480007241 CN200480007241A CN1761507A CN 1761507 A CN1761507 A CN 1761507A CN 200480007241 CN200480007241 CN 200480007241 CN 200480007241 A CN200480007241 A CN 200480007241A CN 1761507 A CN1761507 A CN 1761507A
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- partial crystallization
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- 238000002425 crystallisation Methods 0.000 title claims abstract description 760
- 230000008025 crystallization Effects 0.000 title claims abstract description 760
- 238000000034 method Methods 0.000 title claims abstract description 178
- 239000012530 fluid Substances 0.000 title claims abstract description 102
- 239000002245 particle Substances 0.000 claims abstract description 251
- 238000006243 chemical reaction Methods 0.000 claims abstract description 135
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000011574 phosphorus Substances 0.000 claims abstract description 112
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 112
- 239000013078 crystal Substances 0.000 claims abstract description 76
- 239000000126 substance Substances 0.000 claims abstract description 76
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 855
- 229910001868 water Inorganic materials 0.000 claims description 855
- 239000007788 liquid Substances 0.000 claims description 347
- 239000003814 drug Substances 0.000 claims description 51
- 238000012546 transfer Methods 0.000 claims description 44
- 150000002500 ions Chemical class 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 28
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 25
- 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 description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 230000008676 import Effects 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 abstract description 90
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 318
- 239000004137 magnesium phosphate Substances 0.000 description 317
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 317
- 229960002261 magnesium phosphate Drugs 0.000 description 317
- 235000010994 magnesium phosphates Nutrition 0.000 description 317
- 239000011777 magnesium Substances 0.000 description 69
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 50
- 229910052749 magnesium Inorganic materials 0.000 description 50
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 150000002681 magnesium compounds Chemical class 0.000 description 42
- 238000012545 processing Methods 0.000 description 38
- 239000003513 alkali Substances 0.000 description 36
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 34
- 239000000347 magnesium hydroxide Substances 0.000 description 34
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 30
- 229910021529 ammonia Inorganic materials 0.000 description 25
- 239000002585 base Substances 0.000 description 24
- 239000003153 chemical reaction reagent Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 19
- 230000008859 change Effects 0.000 description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 239000002351 wastewater Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 11
- 230000029087 digestion Effects 0.000 description 11
- 229910001425 magnesium ion Inorganic materials 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229940043430 calcium compound Drugs 0.000 description 5
- 150000001674 calcium compounds Chemical class 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000008520 organization Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229940085991 phosphate ion Drugs 0.000 description 3
- 239000002367 phosphate rock Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- -1 hydroxyl magnesium carbonate Chemical compound 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000008141 laxative Substances 0.000 description 2
- 230000002475 laxative effect Effects 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 2
- 230000003442 weekly effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
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Abstract
The invention discloses a method and an apparatus for removing an ion to be removed in a fluid to be treated by the crystallization as crystal particles of a slightly soluble salt of the ion in a crystallization reaction vessel, characterized in that a chemical required for the crystallization is added to a part of a treated fluid flowing out from the crystallization reaction vessel and is dissolved therein and the resultant fluid is fed to the crystallization reaction vessel as a circulating fluid, wherein the fluid to be treated and the circulating fluid are introduced into the crystallization reaction vessel in the direction of the tangent to the cross section of the vessel. The method and the apparatus, which are embodiments of the present invention, can be used for improving the efficiency of the recovery of phosphorus.
Description
Technical field
The present invention relates to the method and the device that adopt crystallization from liquid, specific ion to be removed or reclaimed, particularly relate to by making chemical reactions such as phosphate ion contained in the various liquid, calcium ion, fluorine ion, carbonic acid ion, sulfate ion that the crystallization of the neat indissoluble salt of granularity is separated out, stablize these ions, efficiently remove and the method and the device of the goods crystallization that acquired character is stable.According to a preferred embodiment of the present invention, can from the sewage that contains high concentration N and phosphorus, remove, reclaim physical chemistry phosphorus.
Background technology
All the time, a kind of as the method for removing specific ion from liquid adopts crystallization.Crystallization be with processed liquid in contained specific ionic reaction, will add as medicament form the ion of indissoluble salt, and make the ion in the processed liquid become hypersaturated state by changing pH, make the crystallization that contains specific ion separate out the method for separation.
If the example of crystallization is shown, 2 times of following water are handled water or from the waste water such as the water that backflows of sludge treating system as processed water, in the occasion of removing phosphate ion wherein, add calcium, can make calcium phosphate (Ca
3(PO
4)
2) or hydroxyapatite (Ca
10(PO
4)
6(OH)
2): crystallization HAP) is separated out.In addition, it is more that the waste water of semiconductor factory contains the occasion of fluorine ion in a large number, in the occasion of handling this waste water, similarly makes calcirm-fluoride (CaF by adding the calcium source
2) crystallization separate out, can remove the fluorine in the waste water.Further,, rise, perhaps add carbonic acid calcium carbonate crystal is separated out by making pH removing with the occasion that makes the calcium ion in water, waste water, the rubbish leaching water of underground water as former water.Perhaps, for the hard water that contains the carbonic acid ion in a large number,, make calcium carbonate (CaCO equally by adding calcium ion
3) crystallization separate out, can reduce hardness.In addition can be with the impurity Mn in the sewer as manganese carbonate (MnCO by adding the carbonic acid ion
3) remove.Further,, contain the waste water of phosphate ion and ammonium ion in the liquid, add magnesium and can make magnesium phosphate (MgNH for the filtrate of anaerobic digested sludge or the waste water of fertilizer factory etc.
4PO
4: crystallization MAP) is separated out.
For example, the partial crystallization with MAP illustrates that as an example allegedly the magnesium in the liquid, ammonia, phosphorus, hydroxyl generate MAP by the reaction of following form.
In order to generate the condition of MAP, the product concentration of each molar concentration of phosphorus, ammonia, magnesium, hydroxyl (is called " ionic product ".[HPO
4 2-] [NH
4 +] [Mg
2+] [OH
-]; Unit in [] is mol/l) its concentration of ordinary dissolution at MAP is operated more than long-pending like that.In addition, the ammonia in the processed water, magnesium and phosphorus relatively be etc. mole or etc. exist like that more than the mole, phosphorus concentration is reduced.
The addition of magnesium is expressed as 1.2 times with mol ratio, the efficient height with respect to the phosphorus that flows into.The magnesium that adds, main material is magnesium chloride, magnesium hydroxide, magnesia, magnesium sulfate, dolomite.
In processed water, add calcium ion equally, react according to following form, generate calcium phosphate (hydroxyapatite: HAP) by making calcium ion, phosphorus, hydroxyl in the liquid.
In various crystallizations, MAP method particularly described above or HAP method are being studied just widely as removing the nitrogen contained in the decontaminated water or the method for phosphorus.
Nitrogen, phosphorus contained in the sewage are the reason materials of nutritiousization problem in river, ocean, the cistern etc., are desirably in the water treatment operation and can remove effectively.
As the method for handling the mud produce from the sewage disposal operation, have pair sludge dewatering to burn the but method of punishment today, makes the method for punishment such as dehydration after the sludge anaerobic digestion is further carried out drying again, burnt but, fusion.The separating liquid of discharging from such processing method (dehydration parting liquid) contains nitrogen (general 50-3000mg/l), the phosphorus (general 100-600mg/l) of high concentration, if they backflow in the sewage disposal system, so can not handle totally because the load of nitrogen, phosphorus uprises, become the reason that nitrogen, phosphorus concentration in the water of releasing become too high.Therefore, the expectation high efficiency method of removing the sewage of the nitrogen that contains high concentration, phosphorus.
In addition, phosphor resource is to be contemplated to exhausted material in 21 century.Most of dependence on import of Japan's phosphorus, the method for phosphorus is reclaimed in expectation now efficiently from organic waste and waste water.
As the method for from the sewage that contains phosphorus, removing dephosphorization, developed biology gradually and removed various methodologies such as method, coagulative precipitation method, crystallization, absorption method.Various processing methods all have merits and demerits, but crystallization does not have mud to produce basically, and the phosphorus of removing utilizes easily again, and can remove (recovery) with stable state.
Partial crystallization is made of the NUCLEATION PHENOMENA of the generation of accompanying crystallization nuclear and the growth phenomenon of nuclear increase.So just the nuclear that produces is necessary to reduce the water area load because the little sinking speed of particle diameter is slow, reactor makes very big.On the other hand, the nuclear of Cheng Changing is owing to there being enough sinking speed, so reactor volume can reduce to a certain degree.
As utilizing crystallization to remove or reclaim the method for the phosphorus in the waste water, the MAP method of having developed as described above the HAP method that phosphorus is reclaimed as hydroxyapatite gradually, phosphorus being reclaimed as ammonium magnesium phosphate.
By making the phosphorus in the processed water generate in the method remove as the ammonium magnesium phosphate partial crystallization, following 2 stage dephosphorization methods have been proposed, promptly, for the liquid that flows out from the groove top that has possessed importing processed water means to updraft 1 treatment trough, in 2 treatment troughs, add magnesium, the alkali composition, add processed water according to circumstances, reaction, behind the Separation of Solid and Liquid worker, the mud slurries that are accumulated in the Separation of Solid and Liquid zones of 2 treatment troughs bottom are returned to the mixing partial crystallization zone, bottom of aforementioned 1 treatment trough, improve the rate of recovery (spy opens the 2002-126761 communique) of MAP thus.
In addition, removing in the method for the frosting of phosphorus in making processed water by ammonium magnesium phosphate (MAP) particle that in reactive tank, flows, following dephosphorization method has been proposed, promptly, reclaim the fine MAP crystallization of separating out in the reactive tank with solid-liquid separation tank, by add former water, magnesium, as required alkali composition at digester, make the fine MAP crystalline growth of recovery, the MAP particle of growing up is returned to the bottom of previous reaction groove, in the previous reaction groove, becomes MAP particle (spy opens the 2002-326089 communique).
In the fluidized bed reactor, the speed that flows out from reactor in the crystallization that does not make in the reactor is with former water and the recirculated water of upwards circulating.Thus, the fluidized bed of crystalline particle is formed in the reactor, carries out the growth of crystalline particle at this.Such as described above, partial crystallization is made of NUCLEATION PHENOMENA and growth phenomenon, and the occasion of fluidized bed reactor by determining that operating condition makes the crystalline growth phenomenon only takes place in the reactor, can not produce fine nuclear, reclaims partial crystallization object material.By such operation, the volume of reactor is diminished.Here, only cause the growth phenomenon of crystallization in order not produce nuclear, do not become too high saturation state in the running of quasi-steady zone and get final product.In addition, the MAP particle of excessive growth becomes greatly owing to sinking speed, and crystallization is flowed and worsened, and contributes to long-pending minimizing of reacted surface etc. the rate of recovery is reduced.Therefore, the MAP particle diameter in the reactor is not preferably wanted excessive or too smallly and is turned round.
Use the phosphorous recovery of the MAP partial crystallization of fluidized bed reactor be subjected to following very big about, (1) the MAP crystallization in the reactor flows, and the mixing of (2) partial crystallization reaction relation material (phosphorus, ammonium nitrogen, magnesium, alkali), also have the contact condition of (3) reactor intercrystalline and partial crystallization reaction relation material in addition.Up to now, above-mentioned 3 discussion is also insufficient.The result, exist because the local degree of supersaturation that produces, producing fine nuclear causes phosphorous recovery to reduce, the heterogeneity of crystallization flows and produces the phosphorous recovery reduction that motionlessization of crystallization part (bringing the phosphorus load suitable with the crystallization packed space to increase) is brought, in addition, because the short path of former water and recirculated water, medicament causes the problems such as reduction of the phosphorous recovery that coring brings beyond crystal surface.
Therefore, the present invention's problem that will solve provides employing and can keep the particle in the crystallization withdrawal liquid of the high-recovery (90% or higher) that addresses the above problem and remove technology.The inventor with large-scale experimental facilities through for a long time to above-mentioned 3 checkings, found that the reduction of above-mentioned phosphorous recovery can solve by the mobile homogenization of the reaction relation material in the reactor, to such an extent as to finished the present invention based on this opinion.Particularly, in reaction system, add partial crystallization according to the present invention when reacting needed medicament, part by the processing water of will discharge in the partial crystallization reactive tank separately, supply in the partial crystallization reactive tank as recirculated water to wherein adding medicament dissolving back, simultaneously above-mentioned recirculated water and the processed water cross section with respect to the partial crystallization reactive tank is imported with tangential direction, reached the mobile homogenization of the reaction relation material in the partial crystallization reactive tank, the mixing of the abundant and homogeneous of processed water and medicament can be sought, the rate of recovery that is removed ion can be increased substantially thus.
Summary of the invention
Promptly, first embodiment of the present invention is, remove the method that is removed ion in the processed liquid by the crystalline particle partial crystallization that in the partial crystallization reactive tank, makes the indissoluble salt that is removed ion in the processed liquid, it is characterized in that, the medicament that the part of the treatment fluid that flows out from the partial crystallization reactive tank, adds the partial crystallization reaction needed, make its dissolving, it is supplied in the partial crystallization reactive tank as circulation fluid, at this moment, processed liquid and the circulation fluid cross section with respect to the partial crystallization reactive tank is imported with tangential direction.Here, so-called " medicament of partial crystallization reaction needed ", for example be meant magnesium compound in the occasion of removing the method for the phosphorus in the liquid by the partial crystallization reaction of MAP, be meant calcium compound in the occasion of removing the method for the phosphorus in the liquid by the partial crystallization reaction of HAP, be meant basic agent in the occasion that the calcium in the liquid is removed by rising pH as calcium carbonate in addition." medicament of partial crystallization reaction needed " is clearly to those skilled in the art in other various partial crystallization reactions.
In addition, in first embodiment of the present invention, by air is supplied with, near the core of the cross section of partial crystallization reactive tank, i.e. bubbling can promote the processed water in the reactive tank and the mixing of medicament more.Particularly reactive tank is the occasion of the container in big footpath, when processed liquid and circulation fluid are supplied to the tangential direction of cross section, liquid stream strengthens near the periphery of groove, but the liquid rheology is poor near the central part of the cross section of groove, and existence can not be carried out well-mixed situation.Therefore, stir, can more fully carry out the mixing of the liquid in the groove by cross-section center portion air supply (bubble) at groove.
In addition,, use the reactor of the cross section of the bottom shape littler, processed liquid and circulation fluid can be imported the bottom of this reactive tank than the cross section on top as the partial crystallization reactive tank.Use the big container applications in footpath as reactive tank, with before circulation fluid fully mixes, become upwelling in their each comfortable grooves and flow to the top, have the situation of admixture deterioration at processed liquid.Therefore, the shape littler than last cross section made in the bottom of reactive tank, that is, make the bottom of reactive tank thinner than top, by processed liquid and circulation fluid are supplied to this tiny part, can with the processed liquid that imports with become upwelling after circulation fluid fully mixes.For example, use the columnar reaction vessel with the level in the footpath also littler, the bottom of groove as the partial crystallization reactive tank than top.Also can use diminish the slowly reaction vessel of the such shape in footpath of the lower stage shape of groove in addition.In addition, also can use as shown in Figure 1, the foot of groove is the reaction vessel of the shape of inverted cone.
The simple declaration of accompanying drawing
Fig. 1 is the key diagram of longitudinal section of a concrete example of the associated partial crystallization reaction unit of expression first embodiment of the present invention.
Fig. 2 is the cross-sectional view of the inverted cone A-A ' face partly of the partial crystallization reaction unit among Fig. 1.
Fig. 3 is the oblique view of A-A ' face among Fig. 1.
Fig. 4 is the former water of expression in the comparative example 1 and the figure of the supply method of recirculated water.
Fig. 5 is the figure of configuration example of the phosphorus recovery device of expression preferred implementation of the present invention.
Fig. 6 is the horizontal sectional view of line A-A ' face of the partial crystallization reactive tank of Fig. 5.
Fig. 7 is the figure of the formation of the phosphorus recovery device of use among the expression embodiment 3.
Fig. 8 is the cross-sectional view of the inverted cone A-A ' face partly of the partial crystallization reaction unit among Fig. 7.
Fig. 9 is the figure of the formation of the phosphorus recovery device that uses of expression comparative example 3.
Figure 10 is the figure of the supply method of the former water that uses of expression comparative example 3 and recirculated water.
Figure 11 is the figure of a concrete example of the associated partial crystallization reaction unit of second embodiment of expression the present invention.
Figure 12 is the figure of the formation of the associated phosphorus recovery device of the preferred implementation isorrheic of the present invention of expression former water of consideration and recirculated water.
Figure 13 is the part enlarged drawing that expression specifies the isorrheic partial crystallization reactive tank top of Figure 12.
Figure 14 is the figure of the formation of the phosphorus recovery device that uses of expression comparative example 4.
Figure 15 is the figure of formation of the phosphorus recovery device of expression preferred implementation of the present invention.
Figure 16 is the figure of the formation of the associated phosphorus recovery device of the preferred implementation isorrheic of the present invention of expression former water of consideration and recirculated water.
Figure 17 is the part enlarged drawing that expression specifies the isorrheic partial crystallization reactive tank top of Figure 16.
Figure 18 is the figure of the formation of the phosphorus recovery device that uses of expression comparative example 5.
Figure 19 is the figure of the formation of the phosphorus recovery device that uses of expression comparative example 6.
Figure 20 is the figure of the formation of the 3rd phosphorus recovery device that embodiment is associated of expression the present invention.
Figure 21 is the figure that expression has designed the formation of the 3rd phosphorus recovery device that embodiment is associated of the present invention of adjusting groove.
Figure 22 is the figure that carries out the formation of the 3rd phosphorus recovery device that embodiment is associated of the present invention that pH adjusts 2 stages.
Figure 23 is the figure of the formation of the phosphorus recovery device that uses of expression embodiment 9.
Figure 24 is the figure of the formation of the phosphorus recovery device that uses of expression comparative example 7.
Figure 25 is the dependent figure of pH of the solubility of expression magnesium hydroxide.
The specific embodiment
With reference to accompanying drawing, the concrete example of the method for first embodiment of the present invention is described.The following description is the literal of a concrete example of explanation first embodiment of the present invention, but the present invention is not limited to these records.What relate to as concrete example in the following description in addition, is the explanation of removing, reclaiming the method and apparatus of phosphorus by the crystallization that generates ammonium magnesium phosphate (MAP) from phosphorous processed water.In each following accompanying drawing, the inscape with same function has prosign and describes.In addition, in each the description of the drawings, suitably omit its explanation for inscape with identical function.
Fig. 1 is the key diagram of longitudinal section of a concrete example of the associated partial crystallization reaction unit of expression first embodiment of the present invention.Fig. 2 is the cross-sectional view of the inverted cone A-A ' face partly of the partial crystallization reaction unit among Fig. 1.Fig. 3 is the oblique view of A-A ' face among Fig. 1.
In concrete example shown in Figure 1, show from the former water that contains phosphorus and remove, reclaim the process of the phosphorus in the former water by generating the MAP crystallization.The shape of partial crystallization reactive tank 1 has no particular limits, and as preferred mode, as shown in Figure 1, is the reactor of the bottom 2 cylindrical section shapes also thinner than top, and can use foot in addition is obconic reaction vessel.In the partial crystallization reactive tank 1, former water supplying pipe 12, recirculated water supply pipe 13, processing water effuser 16, crystallization take-off pipe 17 continue together.Further, in partial crystallization reactive tank 1, can continue as required alkali supply pipe 14, air supply pipe 15.
Former water supplying pipe 12 and recirculated water supply pipe 13 continue and make on the obconic part 11 in the bottom of partial crystallization reactive tank 1, and the recirculated water 3 that a former water 2 and a discharge part are handled water 6 is imported into.Recirculated water 3 be branch process water a part, to wherein add as the ionogenic magnesium compound of Mg and the dissolving water.As shown in Figure 1,, also a part of handling water temporarily can be stored in earlier in the Mg dissolving tank 8, add magnesium compound 9 dissolvings from Mg supply pipe 19 at this in recirculated water, adding magnesium compound and dissolving.Supply in the partial crystallization reactive tank 1 by recirculated water former water, the dissolving of Mg ion, produce upwelling in the partial crystallization reactive tank 1, form the fluidized bed of MAP crystalline particle, Mg ion and phosphorus in the liquid react on the surface of MAP crystalline particle, and the MAP crystalline particle is grown up.
Fig. 2 of the cross-sectional view of the water flowing direction of former water and recirculated water such as turbination part and oblique view are tangential direction with respect to the cross section B of partial crystallization reactive tank 1 as shown in Figure 3, and former water supplying pipe 12 is connected with recirculated water supply pipe 13.By former water supplying pipe 12 is connected in the tangential direction with respect to partial crystallization reactive tank cross section with circulating water treatment pipe 13, the force of the liquid stream by supplying with former water 2 and recirculated water 3, form the eddy current that former water and recirculated water produce, thus, liquid in the partial crystallization reactive tank and crystalline particle homogeneous flow.In this occasion, mobile being meant of so-called homogeneous do not produce the interior liquid of partial crystallization reactive tank and the flow regime in the immobilising dead zone of crystalline particle.By forming such homogeneous state that surges, mixing and these hazardous substances of the material related with the partial crystallization reaction become fairly good with contacting of crystal surface.
Flowing velocity stall, the liquid rheology of former water 2 and the horizontal direction of recirculated water 3 is the time of upwelling to the inventor in the presence of the crystalline particle of 0.2-1.0mm by detecting, the result draws that the chances are 0.1-0.3 second.Therefore, flow and recirculated water 3 mobile of former at least water 2 be combined in 1 second kind flow velocity (m/s) if the 3-10 of the periphery of the cross section B at the place that continues of former water and recirculated water supply pipe 12 and 13 doubly, it is mobile that all crystalline particles on the cross section of importing place of former water and recirculated water just form homogeneous.As a result, the whole of the crystalline particle in the reactive tank 1 can contribute to the partial crystallization reaction, promote the partial crystallization reaction.
Further, as the result that former water 2 and recirculated water 3 are imported in tangential direction, liquid is owing to rise with the stream that circles round, so the reaction time is elongated, reaction atmosphere just can make to react and carry out up to enough low degree of supersaturation.
If former water 2 and recirculated water 3 are supplied with in tangential direction, in the big partial crystallization reactive tank 1 of diameter, near the side of partial crystallization reactive tank 1, be near the periphery flow good, but the mobile variation of the central part of partial crystallization reactive tank.Therefore, in such occasion, preferably by air supply pipe 15 air supplies 5 that continue of the central part at the cross section of partial crystallization reactive tank 1, the mixing of the liquid in the partial crystallization reactive tank obtains promoting.The position of air supply pipe 15, the position of the lower end of supply pipe gets final product in position arbitrarily especially, is preferably placed in the fluidized bed of crystalline particle.Further, in order not hinder circling round of liquid mobile, make the lower end of air supply pipe be positioned at the supply pipe 12 of former water and recirculated water and the top of 13 splice locations at least.
The supply pipe 19 of magnesium compound 9 is connected on the pipeline from the recirculated water 3 of a part of branch of the processing water 6 of partial crystallization reactive tank 1.By magnesium compound 9 being supplied with the pipeline of recirculated water 3, even occasion in the magnesium compound stoste of adding high concentration, supply in the reactive tank 1 after can being diluted to enough low concentration by recirculated water 3, can prevent to form in the partial crystallization reactive tank 1 local high hypersaturated state.
All can in the groove (Mg dissolving tank) 8 of temporary transient storage recirculated water 3 in the pipe arrangement 13 of recirculated water in the supply position of magnesium compound 9.The magnesium compound 9 that adds can be an ionic condition, also can be the compound state, particularly, can use magnesium chloride, magnesium hydroxide, magnesia, magnesium sulfate etc.
In addition, the pH by pH meter 10 is measured in the partial crystallization reactive tank 1 adds base reagent 4 by alkali supply pipe 14 as required, makes reaction atmosphere keep suitable pH, so preferred.Base reagent 4 can supply in former water 2 or the partial crystallization reactive tank 1.Occasion in base reagent being supplied to former water 2, adding the place can also can be in former water supplying pipe 12 at former tank.Add base reagent in the partial crystallization reactive tank 1 occasion, preferably supply to supply position in former water 2 and/or the recirculated water 3 near.Under this occasion, dilute by former water when flowing in the partial crystallization reactive tank 1, so also can prevent the local hypersaturated state of formation in the partial crystallization reactive tank 1 owing to base reagent.As base reagent 4, can use caustic soda, magnesium hydroxide, calcium hydroxide etc.The interpolation of base reagent 4 can by each control method running alkali inflow pump such as on-off control, proportion control, carry out the pH value that reaches desired according to the pH value of measuring in the partial crystallization reactive tank 1.So-called desired pH value, preferably change setting value according to the ammonia concentration in the former water, phosphorus concentration, magnesium density etc., for example handle ammonia concentration and be the occasion of 1000mg/L or higher former water, making pH is 7.0-8.0, handling the occasion that ammonia concentration is 300mg/L or lower former water, making pH is that 8.0-9.5 is such, and preferably kind and the change in concentration according to former water changes setting value.
As the method for taking out the MAP crystalline particle 7 of growing up in the partial crystallization reactive tank 1, the method for using the switch of pump to take out from the bottom of partial crystallization reactive tank 1 is arranged, but the trouble of bringing is many when pump is inaccessible.In an embodiment of the invention as shown in Figure 1,, solved the problem of the troubles such as obturation etc. of pump, can well crystallization have been taken out by using air lift 17.
Here, so-called air lift is meant following such pump, promptly, be configured in the lower end in the liquid of tank, the bottom of the pipe (air-lift unit pipe) that the upper end is provided with being configured above liquid level, by being blown into air, make the apparent specific gravity of the bubble mixed liquor of carrying in the stalk littler than the proportion of the liquid outside the pipe, the liquid level of carrying thus in the stalk also rises with respect to the liquid level of tank, the liquid level that exceeds tank, can use the liquid in the tank to get a promotion, such pump is used for the discharge of the precipitating sludge of dung urine purification tank more, the discharge of the mud in the setting pot, field from the Solid Conveying and Melting in high depth seabed etc.
As previously mentioned, the crystalline particle homogeneous in the partial crystallization reactive tank 1 flows, and particularly flow regime is fairly good near the place that continues of former water and recirculated water supply pipe 12 and 13.Because magnesium compound 9 and base reagent 4 supply to the good part of such flow regime, are fully mixed immediately, do not cause that the metastable zone that nuclear produces forms immediately.Because the crystalline particle homogeneous flows,, react based on the partial crystallization of the developmental process of crystalline particle and to obtain promotion in addition so the contacting efficiency of partial crystallization reaction relation material and crystalline particle is good.
In addition, in first embodiment of above-mentioned explanation, except the partial crystallization reactive tank, also can dispose kind of the brilliant groove that generates, the fine crystal particle that taking-up is contained in the interior liquid of partial crystallization reactive tank supplies to kind of the brilliant groove that generates, generate formation kind of the crystalline substance of growing up in the groove by kind of a crystalline substance, the kind crystalline substance of this growth is turned back in the partial crystallization reactive tank.By adopting such formation, can prevent from that the fine crystal particle that generates is blended into to handle in the water to be discharged from the partial crystallization reactive tank, can improve the rate of removing, the rate of recovery that are removed ion.
In this embodiment, kind of brilliant a generation in the groove, the same about partial crystallization reactive tank and above-mentioned explanation supplies air near the central part of kind brilliant cross section that generates groove, can promote kind of the liquid that brilliant generation groove is interior and the mixing of crystalline particle more.In addition, the same as kind of the brilliant groove that generates with the partial crystallization reactive tank, use the reaction vessel of the cross section of the bottom shape littler than the cross section on top, processed liquid and circulation fluid can be imported the lower part of this reactive tank.Further, can use diminish the slowly reaction vessel of the such shape in footpath of the lower stage shape of groove, perhaps as Fig. 5 31 shown in the foot of such groove be that the reaction vessel of obconic shape is as kind of the brilliant groove that generates.
Followingly describe with reference to the concrete example of accompanying drawing to this embodiment.Same with Fig. 1-Fig. 3, in the following description,, describe about generating method and the device of from phosphorous processed water, removing, reclaim phosphorus by the crystallization that makes ammonium magnesium phosphate (MAP) as concrete example.In addition, in each accompanying drawing, the inscape with identical function has same symbol, suitably omits the explanation to it.
Fig. 5 is the configuration example of phosphorus recovery device of the optimal way of the present invention of the above-mentioned explanation of expression.Fig. 6 is the cross-sectional view of line A-A ' face of the partial crystallization reactive tank of Fig. 5.
Partial crystallization reaction unit shown in Figure 5 possesses partial crystallization reactive tank 1 and plants the brilliant groove 31 that generates.
Planting the brilliant groove 31 that generates generates expeditiously for kind of a crystalline substance, top from partial crystallization reactive tank 1, perhaps always from the outflow water of partial crystallization reactive tank 1, reclaim fine MAP crystallization with fine crystal retracting device (diagram is omitted), the fine MAP that reclaims is transplanted on kind of the brilliant groove 31 that generates by fine crystal transfer tube 37, kind of brilliant a generation fine MAP crystalline particle is grown up, generate crystallization thus.As the fine crystal retracting device, can use known all retracting devices in this technology, for example can use liquid cyclone separator (cyclone), simple stillpot etc.
Kind of brilliant the generation in the groove 31 added the recirculated water 3 of former water 2 and magnesium compound by supply, by making the frosting of the material relevant with the partial crystallization reaction at fine MAP crystalline particle, makes its growth.Former water can supply to crystal seed and generate groove 31 by the branched pipe 32 to the former water supplying pipe 12 of partial crystallization reactive tank 1, recirculated water can supply to kind of the brilliant groove 31 that generates by the branched pipe 33 to the recirculated water supply pipe 13 of partial crystallization reactive tank 1.The kind crystalline substance of growing up can be returned to partial crystallization reactive tank 1 in due course.Kind of the brilliant foldback of growing up for example can use air-lift unit pipe 38 to carry out.Kind of the brilliant foldback of growing up may be carried out batchwise, and also can carry out continuously.Set kind of a brilliant foldback frequency and the foldback amount of growing up, make the value of the average grain diameter of the crystalline particle in the partial crystallization reactive tank 1 for expectation.For example, if take out the MAP goods crystallization 80kg of average grain diameter 0.6mm in the partial crystallization reactive tank 1 every day, but from kind of brilliant groove 31 foldback average grain diameter 0.3mm (1/2 of the particle diameters of goods crystalline particle that generate, volume 1/8) kind be 10kg/d in brilliant 1 day, but perhaps 3 days each 30kg of the kind of foldback average grain diameter 0.3mm crystalline substance in partial crystallization reactive tank 1.Kind of the brilliant discharge pipe 40 that generates the outflow water 39 of groove 31 can be connected on the discharge pipe 16 of outflow water 6 of partial crystallization reactive tank 1 as shown in Figure 5.
In partial crystallization reactive tank 1, kind of a crystalline substance is further grown up.Same with kind of brilliant generation groove 31, arrive partial crystallization reactive tank 1 by supplying with former water 2 with the recirculated water 3 that contains magnesium compound, make the partial crystallization reactive material at kind of a brilliant frosting, make its growth.Can be used as goods crystallization 7 from the part of the crystalline particle of kind of polycrystalline growing suitably takes out.The removing method of crystalline particle has the method for taking out by the switch pump from partial crystallization reactive tank 1 bottom, but the trouble that the pump obturation is brought is many.In the mode shown in Figure 5, solved the problem of trouble etc. of the obturation etc. of pump, can take out the goods crystallization well by using air lift 17.
Below be elaborated for each groove.
Plant the brilliant shape that generates groove 31 and/or partial crystallization reactive tank 1 and be not particularly limited, in preferred embodiment, as shown in Figure 5, can use foot to make obconic mobile stratotype reaction vessel.In each reactive tank, the supply pipe 12,32 of former water 2, supply pipe 13,33 with recirculated water 3, the supply pipe 14 of basic agent 4, handle the stream place pipe 16 of water 6, the supply pipe 15,36 of air 5,35, the transfer tube 37 of fine MAP crystallization, the take-off pipe 17 of goods crystallization is planted brilliant transfer tube 38 and is continued as required respectively.
The recirculated water 3 that a former water 2 and a part that take out to handle water 6 have been added magnesium compound 9 supplies to the bottom of partial crystallization reactive tank 1 and makes obconic part.The water flowing direction is tangential direction ground with respect to the cross section of partial crystallization reactive tank 1 former water supplying pipe 12, recirculated water supply pipe 13 is connected in the partial crystallization reactive tank 1 as shown in Figure 6.Being tangential direction ground by the cross section with respect to the partial crystallization reactive tank connects former water supplying pipe 12, recirculated water supply pipe 13, owing to supply with the force of the liquid stream of former water 2 and recirculated water 3, form the eddy current that former water and recirculated water produce, thus, liquid in the partial crystallization reactive tank and crystalline particle homogeneous flow.At this moment, the mobile flow regime that is meant that liquid in the partial crystallization reactive tank and the immobilising dead zone of crystalline particle do not take place of so-called homogeneous.By reaching the flow regime of such homogeneous, mixing, these related substances of the material relevant with the partial crystallization reaction are all fairly good with contacting of crystal surface.
The inventor has studied the flowing velocity stall of the horizontal direction of in the presence of the crystalline particle of 0.2-1.0mm former water 2 and recirculated water 3, and the time of liquid rheology for upwards flowing, the result learns the second into about 0.1-0.3.Therefore, when the flow velocity (m/s) with 1 second kind of the mobile merging of recirculated water 3 of flowing of former at least water 2 was 3-10 times of periphery of cross section at the place that continues of former water and recirculated water supply pipe 12 and 13, it is mobile that the crystalline particle on the cross section of importing place of former water and recirculated water all just becomes homogeneous.As a result, the whole of the crystalline particle in the reactive tank can have contribution to the partial crystallization reaction, and the partial crystallization reaction is promoted.
Further, as the result who imports former water 2 and recirculated water 3 in tangential direction, liquid rises in the partial crystallization reactive tank 1 with the stream that circles round, so the reaction time is elongated, can make reaction atmosphere arrive the very low degree of saturation of crossing and react.
If supply with former water 2 and recirculated water 3 in tangential direction, in the big reactive tank of diameter, near the flowing medial surface of reactive tank is good, the mobile deterioration of the central part of reactive tank.Therefore, in such occasion, preferably air supply pipe 15 is connected to the central part of the cross section of partial crystallization reactive tank 1, air supply 5 promotes the mixing of the liquid in the partial crystallization reactive tank.The position of the lower end of the position of air supply pipe 15, particularly supply pipe can be in position arbitrarily, but preferably is located in the fluidized bed of crystalline particle.Further, in order not hinder circling round of liquid mobile, preferably make the lower end of air supply pipe 15 be positioned at top at least than the link position of the supply pipe 12 of former water and recirculated water and 13.
The supply pipe 19 of magnesium compound is connected on the pipeline of the recirculated water 3 of the processing water branch of autoreaction groove in the future.By magnesium compound 9 being supplied to the pipeline of recirculated water 3, even occasion in the magnesium compound stoste of adding high concentration, can dilute for enough low concentration supplies in the reactive tank by recirculated water 3, can prevent to form in the reactive tank local too high saturation state.
The supply position of magnesium compound 9 can also can temporarily stored in the groove 8 of recirculated water 3 in the pipe arrangement 13 of recirculated water.The magnesium compound 9 that adds can be an ionic condition, also can be the compound state, particularly, can use magnesium chloride, magnesium hydroxide, magnesia, magnesium sulfate etc.
In addition, the pH with pH meter 10 is measured in the partial crystallization reactive tank 1 preferably makes reaction atmosphere keep suitable pH by adding base reagent 4 as required.Base reagent 4 can supply in former water 2 or the partial crystallization reactive tank 1.Base reagent 4 is supplied to the occasion of former water 2, and adding the place can be in former tank, also can be in former water supplying pipe 12.Base reagent 4 is supplied to occasion in the partial crystallization reactive tank 1, preferably supply to former water 2 with and/or the supply position of recirculated water 3 near.Under this occasion, diluted when flowing into partial crystallization reactive tanks 1 by former water owing to base reagent 4, so can prevent the formation of the local hypersaturated state in the partial crystallization reactive tank 1.As base reagent 4, can use caustic soda, magnesium hydroxide, calcium hydroxide etc.The interpolation of base reagent 4 for the pH value that obtains expecting, adopts each control method running alkali injection pump (not illustrating among the figure) such as on-off control, proportion control to carry out according to the value of measuring the pH in the partial crystallization reactive tank 1.The pH value of so-called expectation, preferably change setting value according to the ammonia concentration in the former water, phosphorus concentration, magnesium density etc., for example preferably handling the occasion that ammonia concentration is 1000mg/L or higher former water, pH is 7.0-8.0, handling the occasion that ammonia concentration is 300mg/L or lower former water, pH is that 8.0-9.5 changes setting value according to the kind and the concentration change of former water like that.
As described above, the crystalline particle homogeneous in the partial crystallization reactive tank 1 flows, and especially, near the coupling part of former water supplying pipe 12 and recirculated water supply pipe 13, flow regime is extremely good.Because magnesium compound 9 and base reagent 4 supply to the good part of such flow regime, are fully mixed immediately, do not cause that the metastable zone that nuclear produces forms immediately.Because the crystalline particle homogeneous flows,, react based on the partial crystallization of the developmental process of crystalline particle and to obtain promotion in addition so the contacting efficiency of partial crystallization reaction relation material and crystalline particle is good.
In addition, in mode shown in Figure 5,, also can adopt the formation same as described above with partial crystallization reactive tank 1 about kind of the brilliant groove 31 that generates.That is,, can import processed water and recirculated water in tangential direction, can supply air to the central part of the cross section of partial crystallization reactive tank in addition with respect to kind of a brilliant cross section that generates groove kind of brilliant a generation in the groove 31.In addition, as kind of the brilliant groove 31 that generates, can use the reaction vessel of the cross section of the bottom shape littler than the cross section on top, further, can also use foot is the reaction vessel of obconic shape.
In addition, in the partial crystallization reaction unit, exist in the fine crystal that generates in the reactive tank and sneak into the problem that is discharged from the treatment fluid.
In order to address this problem, granulation dephosphorization device (spy opens flat 8-155469 communique, the spy opens the 2001-9472 communique) has been proposed, it is characterized in that, in the MAP granulation tower and establish the liquid cyclone separator that separates the MAP solids the processing water that the MAP solids supplied with from the processing water supplying pipe by the MAP granulation tower sneak into.As the problem points under this occasion, to compare with the MAP particle that in granulation dephosphorization device, reclaims, the MAP particle diameter that reclaims in the liquid cyclone separator is very thin, exists to be difficult to remove anhydrate to wait dehydration difficult.In addition, be sent in the liquid cyclone separator after handling in the tank because the processing water of reactor temporarily is stored in, so be difficult to obtain water balance.
In addition, open in the 2002-326089 communique the spy, motion a kind of phosphorus remove means, be that fine crystal is grown up in digester, use as the kind in the reactive tank is brilliant by the crystallization of will grow up, can remove the stable means of removing phosphorus in the processed water of rate with height.
In the fluidized bed reactor, the speed of not coming out from reactor stream with the crystallization in the reactor is with former water and the recirculated water of upwards circulating.Thus, the fluidized bed of crystalline particle is formed in the reactor, carries out the growth of crystalline particle at this.Such as described above, partial crystallization is made up of NUCLEATION PHENOMENA and growth phenomenon, in the occasion of fluidized bed reactor, makes the growth phenomenon that only causes crystallization in reactor by the decision operating condition, can not produce fine nuclei and reclaim partial crystallization object material.By such operation, the volume of reactor is reduced.At this, take place in order not cause nuclear, only cause the growth phenomenon of crystallization, can be in order not form too high saturation state in the running of inferior stable region.
But many fine crystallizations generate and flow out in the reality.Especially, the concentration at (a) former water has change, the local occasion of crossing the high saturation generation; (b) heterogeneity by crystallization flows and the generation of motionlessization of crystallization part the occasion that the phosphorus load suitable with the crystallization packed space increases; And (c) occasion of former water and recirculated water, medicament short path (short pass), the generation of fine nuclei is remarkable especially.In the past, in order to prevent the outflow of these fine crystals, the water surface load on the top of reactor was reduced.Especially, reactor top is main thing by the separation of partial crystallization reaction fine crystal, if it is many to handle the water yield, exists the maximization of device, original cost to increase, install running and becomes problems such as difficulty.
Therefore, other mode purposes of the present invention are phosphorus recovery method and the devices that can keep high yield (90% or higher) in order to address the above problem a little, to provide.
The inventor has carried out long-term checking for above-mentioned 3 by large-scale experiment factory.Found that, the outflow that prevents above-mentioned fine crystal is by following realization, promptly in the part of the outflow water of liquid cyclone separator, add as behind the Mg of necessary medicament or the calcium compound this medicament annex solution being returned to the partial crystallization reactive tank, plant polycrystalline growing and do not produce nuclear crystalline growth takes place only to cause.
Promptly, the 2nd kind of embodiment of the present invention is to use the device that comprises partial crystallization reactive tank and liquid cyclone separator, in the partial crystallization reactive tank, make the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid, remove the method that is removed ion in the processed liquid thus, it is characterized in that, to react the treat liquid importing liquid cyclone separator of concentrated flow from partial crystallization, in the liquid cyclone separator, separate, fine crystal particle in the recycle process fluids, part or all of the fine crystal particle that reclaims is returned to the partial crystallization reactive tank, the medicament that while adds in the part of the outflow water of liquid cyclone separator partial crystallization reaction necessity makes its dissolving, and it is supplied in the partial crystallization reactive tank as circulation fluid.
That is, the most important place of the 2nd mode of the present invention is that the relevant medicament of interpolation and partial crystallization reaction grows up fine crystal in the partial crystallization reactive tank fully the recirculated water that is returned to the partial crystallization reactive tank from the liquid cyclone separator.
Be elaborated with reference to the example of accompanying drawing to the specific embodiment of the 2nd mode of the present invention.In the following accompanying drawing, the inscape that has same function with the inscape of previously described accompanying drawing has prosign, suitably omits its explanation.In addition, in the following description, as concrete example, to from phosphorous processing water, describing by making ammonium magnesium phosphate (MAP) crystallization generate method and the device of removing and reclaim phosphorus.
Figure 11 is a concrete example of the expression partial crystallization reaction unit relevant with the 2nd embodiment of the present invention.Partial crystallization reaction unit shown in Figure 11 has MAP partial crystallization reactive tank 1 and liquid cyclone separator 51.
In MAP partial crystallization reactive tank 1, make kind of a polycrystalline growing.The kind crystalline substance of so-called this occasion, expression can make the particle of new MAP partial crystallization on its surface, and the MAP particle of partial crystallization means the particle etc. that covers product at the sand that adds from the outside etc.The shape of MAP crystallization reaction groove 1 has no particular limits, but in preferred embodiment, turbination can be made in the bottom of straight torso portion as shown in Figure 11.Be connected at the take-off pipe 17 of MAP partial crystallization reactive tank 1 Central Plains water supplying pipe 12 with recirculated water supply pipe 13, processing water transfer tube 52, goods crystallization 7.Handle water transfer tube 52 and be preferably placed at the also high position, position of fluidized bed MAP partial crystallization reactive tank 1, ratio formation MAP crystalline particle, and be connected below with respect to the liquid level in the MAP partial crystallization reactive tank 1.The occasion that the SS of former water is high is perhaps wanted to promote the occasion that flows of the crystalline particle in the partial crystallization reactive tank air 5 to be supplied in the MAP partial crystallization reactive tank 1 by air supply pipe 15.The position of air supply 5 can be position arbitrarily, and is preferred not in the side of partial crystallization reactive tank, but at the central part in cross section, in addition, the bottom of air supply pipe 15 is preferably placed in the fluidized bed that is formed on the MAP crystalline particle in the groove.
Preferably in MAP partial crystallization reactive tank, often be pre-existing in kind of a crystalline substance, make kind of the brilliant above fluidized bed of Desired Height that forms.
The recirculated water 3 of the part of former water 2 and taking-up liquid cyclone separator outflow water 56 supplies to the bottom (forming obconic part among Figure 11) of partial crystallization reactive tank 1.The water flowing direction of former water and recirculated water has no particular limits, and the cross section that preferred mode can be relative partial crystallization reactive tank is tangential direction and connects inflow pipe 12 and 13 like that.Import former water 2 and recirculated water 3 by the cross section with respect to reactive tank in tangential direction, utilize the force of the liquid of supplying with former water and recirculated water, form the eddy current that former water and recirculated water produce, thus, liquid in the partial crystallization reactive tank 1 and crystalline particle homogeneous flow.At this moment, so-called homogeneous flows, and is meant the interior liquid of partial crystallization reactive tank and the flow regime in the immobilising dead zone of crystalline particle do not take place.By reaching such homogeneous flow regime, the mixing of the material relevant with the partial crystallization reaction, these concern that material is all fairly good with contacting of crystal surface.
The medicament 9 that partial crystallization reaction is necessary promptly supplies to partial crystallization reactive tank 1 in the occasion magnesium compound of MAP partial crystallization device adds a part of recirculated water 3 as the outflow water of liquid cyclone separator 51 to by medicament supply pipe 19.Phosphorus concentration in the outflow water 56 of liquid cyclone separator 51 reduces, even add magnesium compound, hypersaturated state takes place hardly also, and the generation of MAP is few.Therefore, even high concentration magnesium compound stoste by adopting the as above supply method of explanation, can be passed through and supply with partial crystallization reactive tank 1 after recirculated water be diluted to enough low concentration, can prevent from partial crystallization reactive tank 1, to form local too high saturation state.Can prevent the reduction of phosphorous recovery thus.
The magnesium compound that adds can be an ionic condition, also can be the compound state, particularly, can use magnesium chloride, magnesium hydroxide, magnesia, magnesium sulfate etc.
Can obtain goods crystallization 7 after taking out a part of proper time of the crystalline particle that generates in MAP partial crystallization reactive tank 1.The removing method of crystallization has the method for using the switch of pump to take out from the bottom of partial crystallization reactive tank 1, but the trouble of bringing when pump is inaccessible is many.In an embodiment of the invention as shown in figure 11,, solved the problem of the troubles such as obturation etc. of pump, can well crystallization have been taken out by using air lift 17.When taking out the goods crystalline particle, stop in partial crystallization reactive tank 1, to supply with and stir,, can select to reclaim the big MAP particle of particle diameter thus the crystallization classification with air 5 by air-lift unit.Preferred air lift carries out in the rinse air riser when finishing.Washing methods is that MAP crystalline particle water or air residual in the riser are flowed back in the reactive tank.By carrying out the washing of air-lift unit pipe like this, can prevent the obturation in the air-lift unit pipe.
If the excessive growth of MAP crystalline particle in the partial crystallization reactive tank 1, phosphorous recovery reduces.At this moment, take out the full dose of the crystalline particle that is comprised in the groove, can newly add the little kind crystalline substance of particle diameter, also can be in good time or be added on the kind crystalline substance that other reactive tank generates continuously.
As handling the inflow method of water, can adopt pump handover, spontaneous current laxative remedy etc. from MAP partial crystallization reactive tank 1 to liquid cyclone separator 51.In pump is transferred, pump (diagram is omitted) is set in handling water transfer tube 52 ways, thus can be with in the feeding liquid under pressure liquid cyclone separator 51 in the partial crystallization reactive tank 1.The fluid flow that is transplanted on liquid cyclone separator 51 by transfer tube 52 can be set arbitrarily according to the amount of the fine MAP crystalline particle of wanting to reclaim.While causing that bumpy flow descends, the fine MAP crystalline particle that is contained in thus in the liquid is concentrated by the side surface side that action of centrifugal force concentrates on the below processing water along the wall of the turbination part of liquid cyclone separator in liquid cyclone separator 51.Part or all of the fine MAP crystalline particle that concentrates divides discharge pipe 54 to be returned in the MAP partial crystallization reactive tank 1 can further to grow up by concentrating solid shape.In addition, the part of the fine MAP crystalline particle of Nong Suoing also can reclaim.
In addition, be returned to occasion in the MAP partial crystallization reactive tank 1, preferably be returned to the top of partial crystallization reactive tank at outflow water with liquid cyclone separator 51.With reference to Figure 12 and Figure 13 this mode is described.
The inflow water yield of processing water and the former water in the MAP partial crystallization reactive tank 12 worsen with the water balance of the total water yield of recirculated water 3 in liquid separator 51, existence overflows from the water or the fine crystal particle of partial crystallization reactive tank 1, perhaps the water level reduction air in the partial crystallization reactive tank 1 enters in the pump, can not bring into play the situation of the pump performance of regulation.At this moment, consider in MAP partial crystallization reactive tank 1, the water level meter to be set the rotary speed of control liquid cyclone separator inflow pump (diagram is omitted) or the method for gauge tap.But, need frequently washing for fear of polluting the water level meter or stopping up switch etc.
In preferred implementation of the present invention, such shown in Figure 12 (detailed figure is Figure 13), part 61 by the outflow water that will separate at liquid cyclone separator 51 is returned to the top of MAP partial crystallization reactive tank 1 or is returned to the place ahead of the processing water efflux pump (diagram is omitted) to the liquid cyclone separator, can address these problems.Promptly, make the amount of the liquid cyclone separator outflow water that is returned to partial crystallization reactive tank 1 more by (1) than the total water yield of former water 2 in the MAP partial crystallization reactive tank 1 and recirculated water 3, (2) the liquid cyclone separator is flowed out the top that water supplies to MAP partial crystallization reactive tank 1, in the top of MAP partial crystallization reactive tank 1, cause that towards the current of the flow export of liquid cyclone separator residual conduct is handled water and is discharged to outside the system.For example, will be to the quantity delivered of the former water of MAP partial crystallization reactive tank 1 and recirculated water as 1Q, to flow out the foldback amount of MAP crystallization reaction groove 1 of water as 2Q to the liquid cyclone separator, top 1Q at MAP partial crystallization reactive tank 1 flows to the flow export towards the liquid cyclone separator, and residual 1Q discharges as handling water.Like this, overflow from the top of MAP partial crystallization reactive tank 1 with amount, can keep the water level of the water surface of MAP partial crystallization reactive tank 1 thus with the quantity delivered of former water, recirculated water.In addition, as follows at the embodiment shown in Figure 12 and 13, a top that supplies to partial crystallization reactive tank 1 of the outflow water of liquid cyclone separator 51, the residual fraction that liquid cyclone separator 51 flows out water supplies to and adds the bottom of having dissolved regulation medicament 9 partial crystallization reactive tank 1 afterwards, will take out by discharge pipe 16 from the processing water 6 of partial crystallization reactive tank 1.
In the past, the reduction of the phosphorous recovery that brings for the generation that prevents fine crystal and outflow, the result that the water area load is reduced is to have the tendency that the fluidized bed reactor increases.According to the 2nd embodiment of the present invention, work hard on interpolation medicament method by (1), and the employing of the high efficiency of (2) liquid cyclone separator, can very big contribution be arranged to the miniaturization and the phosphorous recovery of reactor.
In addition, in the 2nd embodiment of the present invention, also disposed and planted crystalline substance generation groove, can make at least a portion of the fine crystal particle that reclaims by the liquid cyclone separator supply with a partial crystallization reactive tank after a groove grows into kind of crystalline substance kind of brilliant a generation.
Method for this embodiment describes with reference to accompanying drawing.With above-mentioned same, the inscape that has same function in each accompanying drawing has prosign, suitably omits its explanation.
Figure 15 represents the configuration example of the partial crystallization reaction unit of aforesaid way.Below, to by making the MAP crystallization separate out the method for the phosphorus in the recycle process fluids and the system of device carries out the aftermentioned explanation.
The described partial crystallization reaction unit of Figure 15 possesses partial crystallization reactive tank that the MAP crystalline particle is grown up (below, be called " MAP partial crystallization reactive tank 1 ") 1, plants brilliant groove 31 and the liquid cyclone separator 51 of generating.
In the MAP partial crystallization reactive tank 1, make kind of polycrystalline growing form the MAP crystalline particle.The shape of MAP crystallization reaction groove 1 has no particular limits, but in preferred embodiment, can adopt as shown in Figure 15 obconic shape is made in the bottom of straight torso portion.Can be in MAP partial crystallization reactive tank 1 with former water supplying pipe 12 with recirculated water supply pipe 13, be connected to the processing water transfer tube (fine crystal pipe) 52 of liquid cyclone separator, the take-off pipe 17 of goods crystallization 7 etc.Processing water transfer tube 52 preferred positions more than the fluidized bed height of the MAP particle that MAP partial crystallization reactive tank 1 forms to the liquid cyclone separator, and be connected below with respect to the liquid level in the MAP partial crystallization reactive tank, by the liquid transporting that contains the fine crystal particle in this processing water effuser 52MAP partial crystallization reactive tank 1 in liquid cyclone separator 51.The occasion that the SS of former water is high is perhaps wanted to promote the occasion that flows of the crystallization in the partial crystallization reactive tank 1 air 5 to be supplied in the MAP partial crystallization reactive tank 1 by air supply pipe 15.The position of air supply 5 can be position arbitrarily, and is preferred not near the sidewall of partial crystallization reactive tank, but at the central part in cross section, in addition, preferably in the fluidized bed of the MAP crystalline particle that above-below direction forms in groove.
In MAP partial crystallization reactive tank,, preferably be pre-existing in kind of a crystalline substance usually in order to make kind of crystalline substance more than the packed layer height of hope.
Former water 2 and the obconic part of formation that the recirculated water 3 that the part that the liquid cyclone separator flows out water (processing water) 55 is carried out branch is supplied to the bottom of partial crystallization reactive tank 1.The water flowing direction has no particular limits, and the cross section that preferred mode can be relative partial crystallization reactive tank is tangential direction and connects each inflow pipe like that.Import former water 2 and recirculated water 3 by cross section in tangential direction with respect to the partial crystallization reactive tank, utilize the force of the liquid of supplying with former water and recirculated water, form the eddy current that former water and recirculated water produce, thus, liquid in the partial crystallization reactive tank and crystalline particle homogeneous flow.At this moment, so-called homogeneous flows, be meant that former water 2 and/or recirculated water 3 supplies with at least as outer week Monday of the cross section that is connected with recirculated water supply pipe 13 around former water supplying pipe 12, do not produce the flow regime in liquid and the immobilising dead zone of crystalline particle.By reaching such flow regime, the mixing of the material relevant with the partial crystallization reaction (occasion of MAP partial crystallization reaction, phosphorus, ammonia, magnesium, potassium), these concern that material is all fairly good with contacting of crystal surface.
In addition, the medicament that partial crystallization reaction is necessary, for example at the occasion magnesium compound 9 of MAP partial crystallization reaction as shown in Figure 15, a part that supplies to the outflow water of liquid cyclone separator 51 is returned to partial crystallization reactive tank 1 as recirculated water 3.Phosphorus concentration in the outflow water of liquid cyclone separator 51 reduces, even add magnesium compound, hypersaturated state takes place hardly also, and the generation of MAP is few.Therefore, even high concentration magnesium compound stoste by adopting the as above supply method of explanation, can be passed through and supply with partial crystallization reactive tank 1 after recirculated water 3 be diluted to enough low concentration, can prevent from partial crystallization reactive tank 1, to form local too high saturation state.The magnesium compound that adds can be an ionic condition, also can be the compound state, particularly, can use magnesium chloride, magnesium hydroxide, magnesia, magnesium sulfate etc.
PH with pH meter 10 is measured in the partial crystallization reactive tank 1 preferably makes reaction atmosphere keep suitable pH by adding base reagent 4 as required.Base reagent 4 can supply in former water 2 or the partial crystallization reactive tank 1.Base reagent 4 is supplied to the occasion of former water 2, and adding the place can be former tank (illustrating among the figure), can be in former water supplying pipe 12 yet.Base reagent 4 is supplied to occasion in the partial crystallization reactive tank 1, preferably supply to former water 2 with and/or the supply position of recirculated water 3 near.Under this occasion, diluted when flowing into partial crystallization reactive tanks 1 by former water owing to base reagent 4, so also can prevent the formation of the local hypersaturated state in the partial crystallization reactive tank 1.As base reagent 4, can use caustic soda, magnesium hydroxide, calcium hydroxide etc.The interpolation of base reagent 4 is measured in the partial crystallization reactive tank 1 by pH analyzer 10, according to this pH value, for the pH value that obtains expecting, adopts each control method running alkali injection pump (not illustrating among the figure) such as on-off control, proportion control to carry out.The pH value of so-called expectation, preferably change setting value according to the ammonia concentration in the former water, phosphorus concentration, magnesium density etc., for example preferably handling the occasion that ammonia concentration is 1000mg/L or higher former water, pH is 7.0-8.0, handling the occasion that ammonia concentration is 300mg/L or lower former water, pH is that 8.0-9.5 changes setting value according to the kind and the concentration change of former water (processed liquid) like that.
As being transplanted on the method for liquid cyclone separator 51, can adopt pump handover, spontaneous current laxative remedy etc. from the processing water of MAP partial crystallization reactive tank 1.In pump is transferred, in the way of handling water transfer tube 52, pump P (with reference to Figure 17) is set, the processing hydraulic pressure in the partial crystallization reactive tank 1 can be delivered to liquid cyclone separator 51 thus.The flow that is transplanted on the processing water of liquid cyclone separator 51 can be set arbitrarily according to the amount of the fine MAP crystalline particle of wanting to reclaim.In liquid cyclone separator 51, while causing that bumpy flow descends, fine thus MAP crystalline particle is concentrated by the side surface side that action of centrifugal force concentrates on the below processing water that contains fine MAP crystalline particle along the wall of the turbination part of liquid cyclone separator.Part or all of the fine MAP crystalline particle that concentrates is returned to kind of a brilliant groove 31 or the MAP partial crystallization reactive tank 1 of generating by concentrating fine crystal discharge pipe 72.Usually the preferred fine MAP crystalline particle that reclaims in liquid cyclone separator 51 is supplied with kind of the brilliant groove 31 that generates.Suitably, by opening the pump of MAP partial crystallization reactive tank 1 side, also fine MAP crystalline particle can be transplanted in the MAP partial crystallization reactive tank 1.Fine MAP crystalline particle often can be supplied with MAP partial crystallization reactive tank 1 in addition, also fine MAP crystalline particle full dose can be supplied with MAP partial crystallization reactive tank 1.In addition, also can be recovered in the part of the fine MAP crystalline particle that reclaims in the liquid cyclone separator 51.
In kind of brilliant generation groove 31,, the fine MAP crystalline particle that reclaims forms kind of a crystalline substance in liquid cyclone separator 51 by being grown up.Plant the brilliant groove 31 that generates and turbination can be made in the bottom of straight torso portion as shown in Figure 15.Kind brilliant generate the former water supplying pipe 75 that can connect in the groove 31 from former water supplying pipe 12 branches, from the recirculated water supply pipe 33 of recirculated water supply pipe 13 branches, handle water effuser 40, from the brilliant transfer tube 72 of the kind of liquid cyclone separator 51.Kind of brilliant a generation in the groove 31, equally also can be connected the supply pipe 36 of air 35 with MAP partial crystallization reactive tank 1.
Kind of brilliant a generation in the groove 31, supply with the recirculated water 3 that former water 2 and magnesium compound 9 have been dissolved in interpolation, make the surperficial crystallization of the material relevant at fine MAP crystalline particle with the partial crystallization reaction, fine MAP crystalline particle is grown up form kind of a crystalline substance.The kind crystalline substance of growing up suitably is returned to MAP partial crystallization reactive tank 1.As kind of the foldback means of crystal orientation MAP partial crystallization reactive tank of growing up, can consider the blocked operation of various pumps, switch, can use air lift 38 in the mode as shown in figure 15.Kind of the brilliant foldback of growing up may be carried out batchwise, and also can carry out continuously.Set kind of a brilliant foldback frequency and the foldback amount of growing up, make the value of the average grain diameter of the MAP crystalline particle in the MAP partial crystallization reactive tank 1 for expectation.For example, if take out the MAP goods crystallization 6 of 80kg average grain diameter 0.6mm in the partial crystallization reactive tank 1 every day, but from kind of brilliant groove 31 foldback average grain diameter 0.3mm (1/2 of the particle diameters of goods crystalline particle that generate, volume 1/8) kind be 10kg/d in brilliant 1 day, but perhaps 3 days each 30kg of the kind of foldback average grain diameter 0.3mm crystalline substance in partial crystallization reactive tank 1.
In partial crystallization reactive tank 1, the part of the crystalline particle of growing up be can be used as goods crystallization 7 suitably take out.The removing method of crystalline particle has the method for taking out by the switch pump from partial crystallization reactive tank 1 bottom, but the trouble that the pump obturation is brought is many.In the mode shown in Figure 15, solved the problem of trouble etc. of the obturation etc. of pump, can take out the goods crystallization well by using air lift 17.When goods crystallization 7 is taken out, stop air supply 5 in reactive tank 1,, can select to reclaim the big MAP crystalline particle of particle diameter thus the crystallization classification.Preferred air lift carries out in the rinse air riser when finishing.The washing of riser can be by flowing back to MAP water or air residual in the riser in the reactive tank.By such washing, can prevent the obturation in the air-lift unit pipe.
By supplying with the little MAP crystalline particle of particle diameters (planting brilliant) and select the bigger MAP crystalline particle of recovery, can make the average grain diameter of the crystalline particle in the MAP partial crystallization reactive tank 1 not stablize processing from kind of a brilliant generation groove 31 with changing.
Same with the mode shown in Figure 12,13, when the outflow water with liquid cyclone separator 51 was returned to MAP partial crystallization reactive tank 1 with the outflow water of planting brilliant generation groove 31, preferred at least a portion was returned to the top of partial crystallization reactive tank 1.With reference to Figure 16 and Figure 17 this mode is described.
To liquid separator 51, handle the words that the water balance of the inflow water yield of water and the former water in the MAP partial crystallization reactive tank 12 and the total water yield of recirculated water 3 worsens from partial crystallization reactive tank 1, existence overflows from the water or the fine crystal particle of partial crystallization reactive tank 1, perhaps the water level reduction air in the partial crystallization reactive tank 1 enters in the pump, can not bring into play the situation of the pump performance of regulation.At this moment, consider in MAP partial crystallization reactive tank 1 the water level meter to be set, control is to the rotation number of the processing water inflow pump (diagram is omitted) of liquid cyclone separator or the method for gauge tap.But, need frequently washing for fear of polluting the water level meter or stopping up switch etc.
In preferred implementation of the present invention, such shown in Figure 16 (detailed figure is Figure 17), part by the outflow water 55 that will separate at liquid cyclone separator 51 and be returned to the top of MAP partial crystallization reactive tank 1 by top supply pipe 62 or be returned to the place ahead of the processing water efflux pump (diagram is omitted) to the liquid cyclone separator from kind of a brilliant part that generates the outflow water 40 of groove 31 can address these problems.Promptly, make the amount of the liquid cyclone separator outflow water that is returned to partial crystallization reactive tank 1 more by (1) than the total water yield of former water 2 in the MAP partial crystallization reactive tank 1 and recirculated water 3, (2) water surface by making MAP partial crystallization reactive tank 1 and the liquid cyclone separator that imports the partial crystallization reactive tank water surface that flows out water is with one side, the outflow water 61 of liquid cyclone separator 51 produces towards the mobile circular flow of the direction of MAP partial crystallization reactive tank 1, can address the above problem.In addition, the mode of representing in Figure 16 is as follows, with liquid cyclone separator 51 and plant the top that a brilliant part that generates the outflow water of groove 31 supplies to partial crystallization reactive tank 1, the brilliant residual fraction that generates the outflow water of groove 31 of liquid cyclone separator 51 and kind supplies to and adds the bottom of having dissolved regulation medicament 9 partial crystallization reactive tank 1 afterwards, will pass through discharge pipe 16 from the processing water 6 of partial crystallization reactive tank 1 and take out.
In the 2nd embodiment of the present invention, also same as the 1st embodiment of the present invention that had illustrated, in partial crystallization reactive tank and/or the brilliant generation of kind groove, processed liquid and recirculated water can be imported tangential direction with respect to the cross section of groove, further, can supply air to the brilliant central part that generates the cross section of groove of partial crystallization reactive tank and/or kind.Further,, the reactor of the cross section of the bottom shape littler can be used, in addition, the reactor of foot can be used as the shape of inverted cone than the cross section on top as partial crystallization reactive tank and/or the brilliant groove that generates of kind.
Variety of way of the present invention according to the above description can efficiently be carried out the partial crystallization course of reaction.In addition, according to other embodiments of the present invention, can solve because the problem of the reduction of the formation of the fine crystal particle that causes with the high concentration state of partial crystallization reaction related substance and the rate of recovery.
For example, react as partial crystallization, by making phosphorus in the former water as the insoluble occasion of carrying out the dephosphorization treatment of former water of MAP, can use and be provided with the partial crystallization reactive tank that the MAP crystalline particle is generated, with the means of phosphorous former water being supplied with in the partial crystallization reactive tank, and supply with magnesium compound at the equipment of the periphery of partial crystallization reactive tank or partial crystallization reactive tank as required, pH adjusts the dephosphorization treatment device of the means of agent and ammonia, make phosphorus, ammonia, magnesium, each molar concentration product concentration of alkali is operated more than the MAP solubility product, and makes ammonia with respect to the phosphorus in the former water, mole such as magnesium, perhaps waiting the above existence of mole to handle like that.
When MAP was separated out, the pH that finds to respond was high more, and the amount of separating out of MAP is big more, handles the tendency that the phosphorus concentration in the water reduces.But, if under too high alkaline atmosphere, react, the own nucleation of fine MAP, these MAP come out along with handling current, and water quality treatment worsens.Therefore, reaction pH at 7.5-10, preferably handles in the scope of 7.5-9 according to the ammonia concentration in the former water, magnesium density and different.
In the past, with respect to the phosphorus in the processed water, the superfluous former water that exists of ammonia, the water etc. that backflows that for example carries out the disengaging liquid of anaerobic digestion, takes place by the decontamination treatment process, with respect to the phosphorus in the processed water, the content of magnesium is few, generates groove or its peripheral equipment interpolation magnesium compound at MAP.In addition, also can add alkali composition (for example caustic soda) as required.
Add magnesium compound and generate the occasion of MAP in phosphorous processed water, the magnesium compound as adding uses magnesium chloride usually, with respect to the phosphorus in the processed water for etc. add like that more than the mole.Magnesium chloride is ease of solubility, maneuverable material.But because magnesium unit price height, the expense that the magnesium chloride in the dephosphorization device needs is the suitable amount of money, so it is excessive to handle the operation cost that needs.Further, mostly magnesium chloride is hexahydrate, so lacking of the content of magnesium of every weight about 12% uses quantitative change many.
From the above fact, the spy opens the 2002-18448 communique and has proposed to use unit price content of magnesium about 42% cheap, every weight the magnesium hydroxide of many slightly solubilities like this for the additive that generates MAP.In the method that proposes, to have set forth in order preventing and to have generated fine MAP by the dissolving pH rising of magnesium hydroxide, use the processing water of dephosphorization treatment that the magnesium hydroxide of pulpous state is dissolved, will contain deliquescent magnesium ion concentration and supply in the partial crystallization reactive tank than the water of handling the high magnesium ion of water.
But, even like this, the high occasion of ammonia concentration in the former water, there are the following problems: (1) causes separating out of fine MAP because the interior pH of partial crystallization reactive tank rises; (2) influence of a part of undissolved magnesium hydroxide reduces phosphorous recovery.
In addition, open in the 2002-326089 communique the spy, dephosphorization method and device have been proposed, described method is: in the dephosphorization apparatus that possesses partial crystallization reactive tank and digester, by using the MAP crystalline particle in digester, grow up, remove phosphorus in the former water with the high stabilised efficiency of removing as the kind crystalline substance in the partial crystallization reactive tank.
But, to record and narrate to some extent for the dispensing means of former water, each all possesses in each groove for the supply pipe of alkali, the supply pipe of magnesium compound, pH determinator, exists processing procedure and running control numerous and diverse, the problem of equipment cost increase etc.
According to the third embodiment of the present invention, by to the part of the treatment fluid that flows out from the partial crystallization reactive tank, adding the insoluble chemical compound and the acid of pulpous state, it is supplied with the partial crystallization reactive tank as circulation fluid, the problems referred to above are solved.
Promptly, the third embodiment of the present invention relates to a kind of method, be by making the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid in the partial crystallization reactive tank, remove the method that is removed ion in the processed liquid, it is characterized in that, use the medicament of the insoluble chemical compound of pulpous state, the part of the treatment fluid that flows out from the partial crystallization reactive tank, add the insoluble chemical compound and the acid of this pulpous state, it is supplied with in the partial crystallization reactive tank as circulation fluid as the partial crystallization reaction needed.
In addition, in the third embodiment of the present invention, also other modes as described above are same, can adopt the brilliant groove that generates of further configuration kind, fine crystal particle in the partial crystallization reactive tank is transplanted on kind of brilliant a generation in the groove, it is grown up form kind of a crystalline substance, it is returned to form such in the partial crystallization reactive tank.
Below, describe with reference to the form of accompanying drawing the third embodiment of the present invention.Below, describe for using the partial crystallization reactive tank and planting the brilliant form that generates groove.In addition, below, for from the former water (processed water) that contains phosphorus and ammonium-nitrogen, making ammonium magnesium phosphate (MAP) partial crystallization, remove the phosphorus in the former water thus, and the method that reclaims describes.With same before record, in each following accompanying drawing, have prosign with the inscape with same function of former explanation, suitably omit its explanation.
Figure 20 is a form of the water treatment facilities of expression the third embodiment of the present invention.Treating apparatus shown in Figure 20 possesses MAP partial crystallization reactive tank 1, plants brilliant groove 31, the recirculated water adjustment groove 82 of generating.
The medicament that adds in the recirculated water is the slightly solubility magnesium compound and the acid of pulpous state.All materials can be enumerated as the slightly solubility magnesium compound that can use, but, wherein, magnesia, magnesium hydroxide, magnesium carbonate, hydroxyl magnesium carbonate etc. can be suitably used as the slightly solubility magnesium compound of the cheap pulpous state of unit price from price.In the embodiment of following explanation, use magnesium hydroxide as magnesium compound.In addition, as acid, can use sulfuric acid, hydrochloric acid etc.Below in Shuo Ming the embodiment, use sulfuric acid.
In MAP partial crystallization reactive tank 1, the former water supplying pipe 12 that continues, recirculated water supply pipe 13, the effuser 16 of handling water, fine MAP crystalline particle are to kind of the transfer tube 37 of brilliant generation groove, goods crystallization discharge piping 17 etc.Kind of brilliant a generation in the groove 31, continue from the former water supplying pipe 32 of former water supplying pipe 12 branches, from the recirculated water supply pipe 33 of recirculated water supply pipe 13 branches, from kind brilliant transfer tube 12 that generates the effuser 40 of the processing water of groove, fine MAP crystalline particle, plant a brilliant transfer tube 38 etc.In recirculated water is adjusted groove 82, the supply pipe 13 of the inlet tube 81 that will handle a part of branch of water 6 of can continuing, magnesium hydroxide supply pipe 84, sulfuric acid supply pipe 86, pH meter 10, recirculated water etc.
In MAP partial crystallization reactive tank 1, be pre-charged with the MAP crystalline particle of average grain diameter 0.1-3mm, make it become the height of regulation.With former water 2 and recirculated water 3 from the bottom of MAP partial crystallization reactive tank 1 with to the continuous water flowing in upper reaches.Former water 2 is by in the MAP partial crystallization reactive tank 1 time, and by phosphorus in the former water and ammonia, with the reactive magnesium in the recirculated water, MAP is at kind of a brilliant frosting, and the phosphorus in the former water is removed.Part by the MAP crystalline particle 7 that will grow up in MAP partial crystallization reactive tank 1 is suitably taken out, and reclaims the MAP crystalline particle.At this moment, make the packed height of the fluidized bed of the MAP particle that forms in the partial crystallization reactive tank 1 not become low.Among Figure 20, as the recovery method of growth MAP crystalline particle, show the method for utilizing air lift 17, but also can reclaim from reactor bottom.
In recirculated water is adjusted groove 82, in a part of handling water, add magnesium hydroxide 83 and sulfuric acid 85, with the mixed liquor that obtains as recirculated water 3.Recirculated water 3 is supplied with partial crystallization reactive tank 1 respectively by pipe arrangement 13 and 33 and is planted the brilliant groove 31 that generates.
The solubility of magnesium hydroxide is 0.9mg/100g (chemical voluminous dictionary, upright altogether publishing house's (strain)), very indissoluble.Magnesian in addition solubility is 0.62mg/100g (chemical voluminous dictionary, upright altogether publishing house's (strain)), the solubility of magnesium carbonate is 10.6mg/100g (chemical voluminous dictionary, upright altogether publishing house's (strain)), hydroxyl magnesium carbonate is 25mg/100g (chemical voluminous dictionary, upright altogether publishing house's (strain)), each equal slightly solubility.
In the former method, in recirculated water adjustment groove 82, only add magnesium hydroxide.PH in the liquid is at once more than 9 as a result, by undissolved magnesium compound and be accompanied by the hypogeal fine MAP crystallization of pH etc., can not carry out stable treated.
The solubility of above-mentioned slightly solubility magnesium compound depends on pH, the low more dissolving more of pH.As an example, the solubility of magnesium hydroxide and the relation of pH are shown in Figure 25 (with solubility product 1.2 * 10
11Calculate).The solubility of magnesium hydroxide is about 7g/L when pH9, be about 700g/L when pH8, and is high 100 times.
In the third embodiment of the present invention, add in the recirculated water of branch process water by slightly solubility magnesium compound pulpous state, add the rising that acid suppresses pH simultaneously, undissolved magnesium compound and fine MAP crystallization are swum.As a result, can carry out stable treated.
Add sulfuric acid in recirculated water, adjust the pH that the pH meter 10 in the groove 82 is measured according to being arranged on recirculated water, the interpolation sulfuric acid amount makes and becomes desired pH.Control can be undertaken by on-off control or proportion control etc.As desired pH, preferably change setting value according to the ammonia concentration in the former water, phosphorus concentration, magnesium density, for example handling the occasion that ammonia concentration is 1000mg/L or higher former water, making pH is 7.0-8.0, handling the occasion that ammonia concentration is 300mg/L or lower former water, making pH is that 8.0-9.5 is such, can change setting value according to the kind and the concentration change of processed liquid.
The phosphorus concentration of the processing water preferred dissolution of interpolation magnesium hydroxide and sulfuric acid is at 20mg/L or lower, more preferably at 10mg/L or lower.The deliquescent phosphorus concentration of waste water of digestion disengaging liquid etc. is the such high concentration of 100-600mg/L, forms degree of supersaturation when adding magnesium hydroxide in such waste water easily, generates fine MAP crystalline particle.On the other hand, making the phosphorus concentration in the processing water behind the MAP partial crystallization is 20mg/L or lower low concentration, even also form degree of supersaturation hardly so in such processing water, add magnesium hydroxide, do not generate fine MAP crystalline particle, can prevent that the rate of recovery from descending.
In addition, as using other advantages that make the magnesium hydroxide dissolving from the processing water of partial crystallization reactive tank, can enumerate for waste water such as the disengaging liquid of anaerobic digestion or the water that backflows, with city's water and secondary or handle the water ratios for three times and have cushioning effect, suppress the effect that pH rises.
After making the slightly solubility magnesium compound of pulpous state and acid be dissolved in the recirculated water, supply to advantage in the partial crystallization reactive tank 1 as recirculated water 3, can enumerate with the situation that in the past such magnesium with high concentration (1-10%) directly injects the partial crystallization reactive tank and compare, can fully make magnesium density reduce the back and inject (0.1% or lower).As a result, in the partial crystallization reactive tank, do not form local too high saturation state, suppress separating out of fine MAP crystalline particle, can prevent the reduction of the rate of recovery.
The addition of magnesium hydroxide is with respect to the input (kg-P/hr) of the phosphorus of time per unit supply, and preferred interpolation is as 0.5-1.5 times (kg-Mg/hr) of magnesium.
Adjusting the recirculated water 3 of having adjusted pH and magnesium density in the groove 82 at recirculated water can supply to MAP partial crystallization reactive tank 1 and plant brilliant the generation in the groove 31 with the dispensing ratio of stipulating.At this moment, preferably to the dispensing ratio of each groove of former water 2 with to the dispensing of recirculated water 3 each groove than identical.Like this, the ratio of the phosphorus of supply, ammonia, Mg is identical in each groove, there is no need to control respectively each groove, can make between processing procedure and running control just.In addition, counting of machine subdued, and reduces equipment cost.
In the device of Figure 20, kind of brilliant a generation in the groove 31, the fine MAP crystalline particle that swims is transplanted in the MAP partial crystallization reactive tank 1, fine MAP crystalline particle is grown up, generation is planted brilliant.Can be with former water 2 and recirculated water 3 from kind brilliant bottom that generates groove 31 with to the continuous water flowing in upper reaches.Former water 2 is brilliant when generating in the groove 31 by the MAP kind, and by the reactive magnesium in the phosphorus in the former water, ammonia and the recirculated water, MAP is at the frosting of fine MAP crystalline particle, fine MAP crystalline growth.Can suitably be transplanted in the MAP partial crystallization reactive tank 1 at kind of the brilliant kind crystalline substance of growing up in the groove 31 that generates.Among Figure 20, to the method for transporting of the kind crystalline substance of partial crystallization reactive tank 1, the system that utilizes air lift 38 has been shown from kind of the brilliant groove 31 that generates.From the discharge pipe 40 of kind brilliant outflow water that generates groove 31 as shown in figure 20, can be connected on the discharge pipe 16 of outflow water 6 of partial crystallization reactive tank 1.
Former water can generate in the groove 31 with kind is brilliant than supplying with MAP partial crystallization reactive tank 1 with the dispensing of regulation.
Figure 21 is the example that has designed medicament adjustment groove 91.Medicament is adjusted in the groove 91, mixes magnesium hydroxide 83 and sulfuric acid 85, adjusts to the concentration and the pH that become regulation.The soup of adjusting adds in the recirculated water 3 of a part of branch process water 6, with recirculated water 3 dispensings in each groove.Other operation as above-mentioned explanations relevant with Figure 20.
Among Figure 22, the method for carrying out the pH adjustment with 2 stages has been described.Adjust in the groove 92 at the pH of phase I, add magnesium hydroxide 83 and sulfuric acid 85.Sulfuric acid 85 can be ratio ground with the addition of magnesium hydroxide 83 to be added, and pH meter (not illustrating among the figure) also can be set add according to the pH setting value.In the pH of second stage inching groove 93, add sulfuric acid 85 in order to carry out the pH inching.Same with phase I adjustment groove 92, sulfuric acid 85 can be ratio ground with the addition of magnesium hydroxide to be added, and pH meter 10 preferably is set adds according to the pH setting value.In addition, in the low excessively occasion of pH, also can add base reagent in addition.About other method, with the above-mentioned explanation relevant with Figure 20.
In the third embodiment of the present invention, also same with first embodiment of the present invention that has illustrated, in partial crystallization reactive tank and/or the brilliant generation of kind groove, can import processed liquid and recirculated water with tangential direction with respect to the cross section of groove, can also supply air to the partial crystallization reactive tank and/or plant the brilliant central part that generates the cross section of groove.Further, as partial crystallization reactive tank and/or the brilliant groove that generates of kind, can use the reaction vessel of the cross section of the bottom shape littler than the cross section on top, in addition, can use foot is the reaction vessel of obconic shape.
In addition, in the explanation of above-mentioned concrete mode, for being illustrated, use said method that hydroxyapatite (HAP) partial crystallization is gone out except that dephosphorization by the method that from the processed liquid that contains phosphorus and ammonium-nitrogen, makes ammonium magnesium phosphate (MAP) partial crystallization remove dephosphorization.At this moment, as the necessary medicament of partial crystallization reaction, add calcium compound.In addition, same, according to the present invention, by from containing the processed water of fluorine ion, for example the waste water from semiconductor factory makes the calcirm-fluoride partial crystallization, can remove fluorine.In this occasion,, add calcium compound as medicament to the partial crystallization reaction needed.In addition,, make the calcium carbonate partial crystallization, processed hardness of water is reduced by in the hard water of carbon containing acid ion, adding calcium compound according to the present invention.Or interpolation carbonic acid ion makes the calcium carbonate partial crystallization in containing the processed liquid of calcium, can remove calcium ion from processed water.In addition, according to the present invention,, can remove as the manganese carbonate partial crystallization by making the impurity manganese in the water pipe water by in water pipe water, adding the carbonic acid ion.
The invention still further relates to the device that is used to the method implementing as above to illustrate.Below represent variety of way of the present invention.
1. in the partial crystallization reactive tank, remove the method that is removed ion in the processed liquid for one kind by the crystalline particle partial crystallization that makes the indissoluble salt that is removed ion in the processed liquid, it is characterized in that, the medicament that adds the partial crystallization reaction needed the part of the treatment fluid that flows out from the partial crystallization reactive tank makes its dissolving, it is supplied with the partial crystallization reactive tank as circulation fluid, at this moment, the cross section with respect to the partial crystallization reactive tank imports processed liquid and circulation fluid in tangential direction.
2. the method for above-mentioned the 1st record, wherein, to the central part air supply of the cross section of partial crystallization reactive tank.
3. the method for above-mentioned the 1st or the 2nd record, wherein, as the partial crystallization reactive tank, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top is with the bottom of processed liquid and circulation fluid importing reactive tank.
4. the method for each above-mentioned the 1st the-the 3rd record wherein, as the partial crystallization reactive tank, is used the reaction vessel of foot as the inverted cone shape.
5. the method for each above-mentioned the 1st the-the 4th record, wherein, use the partial crystallization reactive tank and plant the brilliant groove that generates, processed liquid and circulation fluid are supplied to kind of the brilliant groove that generates, the fine crystal particle that takes out the liquid from the partial crystallization reactive tank is supplied with kind of the brilliant groove that generates simultaneously, in kind of crystalline substance generation groove, the fine crystal particle is grown up, form kind of a crystalline substance thus, will generate the brilliant partial crystallization reactive tank of supplying with of the kind that grow up in the groove at kind of crystalline substance.
6. the method for above-mentioned the 5th record wherein, imports with respect to kind of a brilliant cross section that generates groove fine crystal particle, processed liquid and circulation fluid with tangential direction.
7. the method for above-mentioned the 5th or the 6th record, wherein, to the central part air supply of the cross section of partial crystallization reactive tank.
8. the method for above-mentioned the 5th the-the 7th record, wherein, as the partial crystallization reactive tank, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top is with the bottom of processed liquid and circulation fluid importing reactive tank.
9. the method for each above-mentioned the 5th the-the 8th record wherein, as the partial crystallization reactive tank, is used the reaction vessel of foot as the inverted cone shape.
10. device that contains partial crystallization reactive tank and liquid cyclone separator by use, in the partial crystallization reactive tank, make the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the method that is removed ion in the processed liquid, it is characterized in that, to import the liquid cyclone separator from the treatment fluid that the partial crystallization reactive tank flows out, in the liquid cyclone separator, separate, fine crystal particle in the recycle process fluids, part or all of the fine crystal particle that reclaims is returned in the partial crystallization reactive tank, while adds the medicament of partial crystallization reaction needed in the part of the outflow water of liquid cyclone separator, make its dissolving, it is supplied to the partial crystallization reactive tank as circulation fluid.
11. the method for above-mentioned the 10th record wherein, supplies to the part of the outflow water of liquid cyclone separator on the top of partial crystallization reactive tank.
12. the method for above-mentioned the 10th or the 11st record, wherein, also use kind of the brilliant groove that generates, part or all of the fine crystal particle that will reclaim with the liquid cyclone separator supplies to kind of the brilliant groove that generates, kind of brilliant a generation fine crystal particle is grown up, form kind of a crystalline substance, will be at kind of the brilliant brilliant partial crystallization reactive tank of supplying with of the kind of growing up in the groove that generates, simultaneously, at the outflow water of liquid cyclone separator with plant the medicament that adds the partial crystallization reaction needed in the brilliant part that generates the concentrated flow water outlet, make its dissolving, it is supplied to the partial crystallization reactive tank as circulation fluid.
13. the method for each above-mentioned the 10th the-the 12nd record is characterized in that, processed liquid and the circulation fluid cross section with respect to the partial crystallization reactive tank is imported with tangential direction.
14. the method for each above-mentioned the 10th the-the 13rd record wherein, is supplied with air the central part in the cross section of partial crystallization reactive tank.
15. the method for each above-mentioned the 10th the-the 14th record, wherein, as the partial crystallization reactive tank, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top is with the bottom of processed liquid and circulation fluid importing reactive tank.
16. the method for each above-mentioned the 10th the-the 15th record wherein, as the partial crystallization reactive tank, is used the reaction vessel of foot as the inverted cone shape.
17. the method for each above-mentioned the 12nd the-the 16th record wherein, imports with respect to kind of a brilliant cross section that generates groove fine crystal particle, processed liquid and circulation fluid with tangential direction.
18. the method for each above-mentioned the 12nd the-the 17th record wherein, is supplied with kind of a brilliant central part that generates the cross section of groove with air.
19. the method for each above-mentioned the 12nd the-the 18th record, wherein, as kind of the brilliant groove that generates, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top imports kind of a brilliant bottom that generates groove with fine crystal particle, processed liquid and circulation fluid.
20. the method for each above-mentioned the 12nd the-the 19th record wherein, as kind of the brilliant groove that generates, is used the reaction vessel of foot as the inverted cone shape.
21. crystalline particle partial crystallization by the indissoluble salt that is removed ion in the processed liquid in making the partial crystallization reactive tank, remove the method that is removed ion in the processed liquid, it is characterized in that, use the medicament of the insoluble chemical compound of pulpous state as the partial crystallization reaction needed, the part of the treatment fluid that flows out from the partial crystallization reactive tank, add the insoluble chemical compound and the acid of this pulpous state, it is supplied with in the partial crystallization reactive tank as circulation fluid.
22. the method for above-mentioned the 21st record, wherein, use partial crystallization reactive tank and kind crystalline substance to generate groove processed liquid and circulation fluid are supplied with kind of a crystalline substance generation groove, the fine crystal particle that takes out the liquid from the partial crystallization reactive tank is supplied with kind of the brilliant groove that generates simultaneously, brilliant by the growth formation in kind of brilliant generation groove of fine crystal particle is planted, the kind crystalline substance supply partial crystallization reactive tank that will in kind of crystalline substance generation groove, grow up.
23. the method for above-mentioned the 22nd record wherein, makes from kind of the brilliant outflow liquid of groove and the treatment fluid interflow of flowing out from the partial crystallization reactive tank of generating.
24. the method for each above-mentioned the 21st the-the 23rd record is characterized in that, processed liquid and the circulation fluid cross section with respect to the partial crystallization reactive tank is imported with tangential direction.
25. the method for each above-mentioned the 21st the-the 24th record wherein, is supplied with air the central part in the cross section of partial crystallization reactive tank.
26. the method for each above-mentioned the 21st the-the 24th record, wherein, as the partial crystallization reactive tank, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top is with the bottom of processed liquid and circulation fluid importing reactive tank.
27. the method for each above-mentioned the 21st the-the 26th record wherein, as the partial crystallization reactive tank, is used the reaction vessel of foot as the inverted cone shape.
28. the method for each above-mentioned the 22nd the-the 27th record wherein, imports fine crystal particle, processed liquid and the circulation fluid cross section with respect to kind of brilliant reactive tank with tangential direction.
29. the method for each above-mentioned the 22nd the-the 28th record wherein, is supplied with kind of a brilliant central part that generates the cross section of groove with air.
30. the method for each above-mentioned the 22nd the-the 29th record, wherein, as kind of a brilliant reactive tank, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top imports kind of a brilliant bottom that generates groove with fine crystal particle, processed liquid and circulation fluid.
31. the method for each above-mentioned the 22nd the-the 30th record wherein, as kind of a brilliant reactive tank, is used the reaction vessel of foot as the inverted cone shape.
32. the method for each above-mentioned the 1st the-the 31st record wherein, by making the ammonium magnesium phosphate partial crystallization, is removed dephosphorization from processed liquid from the processed liquid that contains phosphorus and ammonium-nitrogen.
33. the method for each above-mentioned the 1st the-the 31st record wherein, by making the hydroxyapatite partial crystallization, is removed dephosphorization from processed liquid from the processed liquid that contains phosphorus.
34. the method for each above-mentioned the 1st the-the 31st record wherein, by making the calcirm-fluoride partial crystallization, is removed fluorine from processed liquid from the processed liquid that contains fluorine ion.
35. the method for each above-mentioned the 1st the-the 31st record wherein, by making the calcium carbonate partial crystallization, is removed calcium from processed liquid from the processed liquid that contains calcium ion.
36. the method for each above-mentioned the 1st the-the 31st record wherein, by making the calcium carbonate partial crystallization, is removed the carbonic acid ion from processed liquid from the processed liquid that contains the carbonic acid ion.
37. one kind makes the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the device that is removed ion in the processed liquid thus by partial crystallization reaction, it is characterized in that, possesses the partial crystallization reactive tank, processed liquid is supplied with the processed liquid supply pipe of partial crystallization reactive tank, the treatment fluid discharge pipe that to induce from the treatment fluid that the partial crystallization reactive tank flows out, the recirculated water supply pipe that treatment fluid is returned to the partial crystallization reactive tank from treatment fluid discharge pipe branch, the medicament of partial crystallization reaction needed is supplied with the medicament supply mean of recirculated water, and processed liquid supply pipe and recirculated water supply pipe are connected on the partial crystallization reactive tank with tangential direction with respect to the cross section of reactive tank.
38. the device of above-mentioned the 37th record also possesses the air supply pipe of central part of air being supplied with the cross section of partial crystallization reactive tank.
39. the device of above-mentioned the 37th or the 38th record, wherein, the partial crystallization reactive tank is the reaction vessel of the cross section of the bottom shape littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe with the partial crystallization reactive tank.
40. the device of each above-mentioned the 37th the-the 39th record, wherein, the partial crystallization reactive tank is that foot is the container of inverted cone shape.
41. the device of each above-mentioned the 37th the-the 40th record, wherein, also possesses kind of the brilliant groove that generates, wherein, processed liquid supply pipe also is connected with kind of the brilliant groove that generates with the recirculated water supply pipe, also possess from the partial crystallization reactive tank fine crystal particle in the groove is transplanted on kind a brilliant fine crystal particle transfer tube that generates groove, will generate the brilliant transfer tube of kind that the kind crystalline substance that grow up in the groove is transplanted on the partial crystallization reactive tank kind brilliant.
42. the device of above-mentioned the 41st record, wherein, fine crystal particle transfer tube, processed liquid supply pipe, recirculated water supply pipe are connected to kind of brilliant a generation on the groove with respect to the cross section of groove with tangential direction respectively.
43. the device of above-mentioned the 41st or the 42nd record also possesses the air supply pipe of central part of air being supplied with the cross section of partial crystallization reactive tank.
44. the device of each above-mentioned the 41st the-the 43rd record, wherein, the partial crystallization reactive tank is the reaction vessel of the cross section of the bottom shape littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe with the partial crystallization reactive tank.
45. the device of each above-mentioned the 41st the-the 44th record, wherein, the partial crystallization reactive tank is that foot is the container of inverted cone shape.
46. the device of each above-mentioned the 37th the-the 45th record wherein, possesses the crystallization recovering means that the crystalline particle that will grow up reclaims from the partial crystallization reactive tank.
47. one kind makes the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the device that is removed ion in the processed liquid thus by partial crystallization reaction, it is characterized in that possessing the partial crystallization reactive tank, the liquid cyclone separator, with the processed liquid supply pipe in the processed liquid supply partial crystallization reactive tank, to be induced to the treatment fluid transfer tube of liquid cyclone separator from the treatment fluid that the partial crystallization reactive tank flows out, the treatment fluid discharge pipe that the outflow water of liquid cyclone separator is induced, the recirculated water supply pipe that treatment fluid is returned to the partial crystallization reactive tank from treatment fluid discharge pipe branch, supply with the solid shape of concentrating of partial crystallization reactive tank at the fine crystal particle of liquid cyclone separator concentrating and separating and divide transfer tube, the medicament of partial crystallization reaction needed is supplied with the medicament supply mean of recirculated water.
48. the device of above-mentioned the 47th record wherein, possesses the liquid cyclone separator that the part of the outflow water of liquid cyclone separator is supplied with the top of partial crystallization reactive tank and flows out the water transfer tube.
49. the device of above-mentioned the 47th or the 48th record, wherein, also possesses kind of the brilliant groove that generates, wherein, processed liquid supply pipe also is connected with kind of the brilliant groove that generates with the recirculated water supply pipe, the fine crystal particle that also possesses concentrating and separating on the liquid cyclone separator is transplanted on kind of a brilliant fine crystal particle transfer tube that generates groove, and the kind crystalline substance that will grow up in kind of brilliant generation groove is transplanted on the brilliant transfer tube of kind of partial crystallization reactive tank.
50. the device of above-mentioned the 47th the-the 49th each record, wherein, processed liquid supply pipe, recirculated water supply pipe are connected on the partial crystallization reactive tank with tangential direction with respect to the cross section of partial crystallization reactive tank respectively.
51. the device of each above-mentioned the 47th the-the 50th record also possesses the air supply pipe of central part of air being supplied with the cross section of partial crystallization reactive tank.
52. the device of each above-mentioned the 47th the-the 51st record, wherein, the partial crystallization reactive tank is the reaction vessel of the cross section of the bottom shape littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe with the partial crystallization reactive tank.
53. the device of each above-mentioned the 47th the-the 52nd record, wherein, the partial crystallization reactive tank is that foot is the container of inverted cone shape.
54. the device of each above-mentioned the 47th the-the 53rd record, wherein, processed liquid supply pipe and recirculated water supply pipe are connected to kind of brilliant a generation on the groove with respect to kind of a brilliant cross section that generates groove with tangential direction.
55. the device of each above-mentioned the 47th the-the 54th record also possesses air is supplied with kind of the air supply pipe of the central part of the cross section of brilliant generation groove.
56. the device of each above-mentioned the 47th the-the 55th record, wherein, the brilliant generation of kind groove is the reaction vessel of the cross section of the bottom shape littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe and the brilliant generation of kind groove.
57. the device of each above-mentioned the 47th the-the 56th record, wherein, planting brilliant generation groove is that foot is the container of inverted cone shape.
58. the device of each above-mentioned the 47th the-the 57th record wherein, possesses the crystallization recovering means that the crystalline particle that will grow up reclaims from the partial crystallization reactive tank.
59. one kind makes the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the device that is removed ion in the processed liquid thus by partial crystallization reaction, it is characterized in that the medicament supply mean that possesses the partial crystallization reactive tank, processed liquid is supplied with processed liquid supply pipe in the partial crystallization reactive tank, the treatment fluid discharge pipe that will induce from the treatment fluid that the partial crystallization reactive tank flows out, supplied with recirculated water from the recirculated water supply pipe that treatment fluid is returned to the partial crystallization reactive tank of treatment fluid discharge pipe branch, with the medicament and the acid of partial crystallization reaction needed.
60. the device of above-mentioned the 59th record wherein, possesses and will temporarily accept to supply with the adjustment groove of partial crystallization reactive tank from the recirculated water of treatment fluid branch, and the medicament and the acid of partial crystallization reaction needed is supplied to the adjustment groove.
61. the device of above-mentioned the 59th or the 60th record, wherein, also possesses kind of the brilliant groove that generates, wherein, processed liquid supply pipe also is connected with kind of the brilliant groove that generates with the recirculated water supply pipe, also possess from the partial crystallization reactive tank fine crystal particle in the groove is transplanted on kind a brilliant fine crystal particle transfer tube that generates groove, will generate the brilliant transfer tube of kind that the kind crystalline substance that grow up in the groove is transplanted on the partial crystallization reactive tank kind brilliant.
62. the device of above-mentioned the 59th the-the 61st each record, wherein, processed liquid supply pipe, recirculated water supply pipe are connected on the partial crystallization reactive tank with tangential direction with respect to the cross section of partial crystallization reactive tank respectively.
63. the device of each above-mentioned the 59th the-the 62nd record also possesses the air supply pipe of central part of air being supplied with the cross section of partial crystallization reactive tank.
64. the device of each above-mentioned the 59th the-the 63rd record, wherein, the partial crystallization reactive tank is the reaction vessel of the cross section of the bottom shape littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe with the partial crystallization reactive tank.
65. the device of each above-mentioned the 59th the-the 64th record, wherein, the partial crystallization reactive tank is that foot is the container of inverted cone shape.
66. the device of each above-mentioned the 61st the-the 65th record, wherein, processed liquid supply pipe and recirculated water supply pipe are connected to kind of brilliant a generation on the groove with respect to kind of a brilliant cross section that generates groove with tangential direction.
67. the device of each above-mentioned the 61st the-the 66th record also possesses air is supplied with kind of the air supply pipe of the central part of the cross section of brilliant generation groove.
68. the device of each above-mentioned the 61st the-the 67th record, wherein, the brilliant generation of kind groove is the reaction vessel of the cross section of the bottom shape littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe and the brilliant generation of kind groove.
69. the device of each above-mentioned the 61st the-the 68th record, wherein, planting brilliant generation groove is that foot is the container of inverted cone shape.
70. the device of each above-mentioned the 59th the-the 69th record wherein, possesses the crystallization recovering means that the crystalline particle that will grow up reclaims from the partial crystallization reactive tank.
71. the device of each above-mentioned the 37th the-the 70th record wherein, by making the ammonium magnesium phosphate partial crystallization, removes dephosphorization from processed liquid from the processed liquid that contains phosphorus and ammonium-nitrogen.
72. the device of each above-mentioned the 37th the-the 70th record wherein, by making the hydroxyapatite partial crystallization, removes dephosphorization from processed liquid from the processed liquid that contains phosphorus.
73. the device of each above-mentioned the 37th the-the 70th record wherein, by making the calcirm-fluoride partial crystallization, is removed fluorine from processed liquid from the processed liquid that contains fluorine ion.
74. the device of each above-mentioned the 37th the-the 70th record wherein, by making the calcium carbonate partial crystallization, is removed calcium from processed liquid from the processed liquid that contains calcium ion.
75. the device of each above-mentioned the 37th the-the 70th record wherein, by making the calcium carbonate partial crystallization, is removed the carbonic acid ion from processed liquid from the processed liquid that contains the carbonic acid ion.
Below, according to embodiment various forms of the present invention are described in more detail.
In the present embodiment, use handling process shown in Figure 1, by from the dehydration filtrate of anaerobic digestion (below, be called " former water "), generating the experiment that the MAP crystalline particle reclaims phosphorus.The treating apparatus that uses in the present embodiment possesses partial crystallization reactive tank 1 and handles water storagetank 8.Partial crystallization reactive tank 1 is the shape with reacting part (bottom is the little part of obconic part and footpath) and precipitation portion (top is the big part in footpath).
The operating condition of table 1 expression dephosphorizing process, the water quality of former water 2 of table 2 expression and processing water 6.In addition, use acrylic resin system, can confirm the device of the flow regime of the crystalline particle in the partial crystallization reactive tank at experimental provision.
The lower end position of air supply pipe 15 is the position from the top 25cm of the link position of the supply pipe of former water and recirculated water.The air supply amount is 10L/min.
With respect to former water T-P280mg/L, the T-P that handles water is 25mg/L, and asking the phosphorous recovery of calculation from water quality is 91%, has shown well and has reclaimed.The flow regime of the crystalline particle in the reactor is good, and whole homogeneous of the crystalline particle on the cross section of importing place of former water and recirculated water flow, and do not find the dead zone.Operating condition and water quality are like shown in table 1 and the table 2.
Table 1: operating condition
| ＜reactor apperance 〉 | |||
| Reacting part | Diameter | mm | 350 |
| Highly | m | 2 | |
| Precipitation portion | Diameter | mm | 800 |
| Highly | m | 1 | |
| Former water supplying pipe | Diameter | mm | 20 |
| The recirculated water supply pipe | Diameter | mm | 20 |
| ＜water flowing condition 〉 | |||
| Raw water flow | m 3/hr | 0.5 | |
| Quantity of circulating water | m 3/hr | 2.5 | |
| LV | Reacting part | m/hr | 30 |
| Precipitation portion | m/hr | 8 | |
| Air capacity | L/ | 10 | |
| The MAP particle diameter | mm | 0.5 | |
| Packed height | m | 1.2 | |
Table 2: water quality (embodiment 1)
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 280 | 25 | |
| PO 4-P | mg/L | 260 | 8 | |
| NH 4-N | mg/L | 1000 | 880 | |
| | ％ | 91 |
Comparative example 1
With handling process similarly to Example 1, use to change the groove of the structure of partial crystallization reactive tank, and carry out water test under the same condition of table 1.In the partial crystallization reactive tank, as shown in Figure 4, the closure of former water supplying pipe 12 and recirculated water supply pipe 13 is the right angle with respect to partial crystallization reactive tank cross section all.That is, former water supplying pipe 12 and recirculated water supply pipe 13 connect towards the center of partial crystallization reactive tank, and connection angle is 180 degree.Similarly to Example 1, the diameter of former water supplying pipe 12 and recirculated water supply pipe 13 is 20mm, the former water=0.44m/s (0.5m of supply line speed
3/ hr), recirculated water 2.2m/s (2.5m
3/ hr).Former water supplying pipe 12 and recirculated water supply pipe 13 are connected on the same cross section, and the diameter of the cross section of the partial crystallization reactive tank of junction is 150mm.
The supply conditions of magnesium component and alkali similarly to Example 1.Do not carry out the supply of air.
Water quality treatment is as shown in table 3.With respect to former water T-P280mg/L, the T-P that handles water is 70mg/L.In addition, asking the phosphorous recovery of calculation from water quality is 75%, has reduced by 16 points than embodiment 1.Crystalline particle in the partial crystallization reactive tank 1 does not flow in 90 degree directions from the closure of former water supplying pipe 12 and recirculated water supply pipe 13, forms the dead zone, is the state that heterogeneity flows.
Table 3: water quality (comparative example 1)
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 280 | 70 | |
| PO 4-P | mg/L | 260 | 7 | |
| NH 4-N | mg/L | 1000 | 860 | |
| | ％ | 75 |
Comparative example 2
In comparative example 2, under the water flowing condition of comparative example 1, carry out the supply of air 5.The quantity delivered of air is 10L/min.Other conditions are identical with comparative example 1.
Fig. 4 represents water quality treatment.With respect to former water T-P280mg/L, the T-P that handles water is 50mg/L, and asking the phosphorous recovery of calculation from water quality is 82%, though than comparative example 17 points that risen, reduced by 9 points than embodiment 1.Same with comparative example 1, the crystalline particle in the partial crystallization reactive tank 1 does not flow in 90 degree directions from the closure of former water supplying pipe 12 and recirculated water supply pipe 13, forms the dead zone, is the state that heterogeneity flows.
Table 4: water quality (comparative example 2)
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 280 | 50 | |
| PO 4-P | mg/L | 260 | 8 | |
| NH 4-N | mg/L | 1000 | 870 | |
| | ％ | 82 |
In the present embodiment, use handling process as shown in Figure 5, generate the recovery test that carries out phosphorus by from the dehydration filtrate (former water) of anaerobic digestion, making MAP.Treating apparatus possesses kind of brilliant groove 31, MAP partial crystallization reactive tank 1, the Mg dissolving tank 8 of generating.
The operating condition of table 5 expression dephosphorizing process, the table 6 former water 2 of expression and the water quality of handling water 6.In addition,, use acrylic resin system, can confirm the device of the flow regime of the crystalline particle in the partial crystallization reactive tank as experimental provision.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank 1, making packed height is 2.0m.
Method of operation after the steady running is as follows.
To once be transplanted on kind of brilliant a generation in the groove 31 at the fine MAP crystalline particle that swims in the top of MAP partial crystallization reactive tank 1 in 3 days by fine MAP crystallization transfer tube 37.In the time of the handover of fine MAP crystalline particle, will to generate the kind that groove 31 generates brilliant all by being arranged on the air lift 38 in kind of the brilliant generation groove 31 kind brilliant, be returned in the MAP partial crystallization reactive tank 1.In the MAP partial crystallization reactive tank 1, once reclaimed goods crystallization 7 in 17,1 days by the air lift that is arranged on MAP partial crystallization reactive tank 1.
In MAP partial crystallization reactive tank 1, former water 2 and will handle the recirculated water 3 that the part of water extracts, as shown in Figure 6, supply with in the obconic part of partial crystallization reactive tank with tangential direction at cross section with respect to groove.The diameter of former water supplying pipe 12 and recirculated water supply pipe 13 is 20mm, the former water=0.44m/s (0.5m of supply line speed
3/ hr), recirculated water 2.2m/s (2.5m
3/ hr).Former water supplying pipe 12 and recirculated water supply pipe 13 are connected on the same cross section of partial crystallization reactive tank 1 (diameter of cross section is 150mm).The linear velocity in 1 second that former water 2 and recirculated water 3 adds up to is 5.2 times of periphery distance of the cross section of junction.As shown in Figure 6, the connection angle between former water supplying pipe 12 and the recirculated water supply pipe 13 is 180 degree.
The exit position of air supply pipe 15 is the position from the top 25cm of the link position of former water supplying pipe 12 and recirculated water supply pipe.The air supply amount is 10L/min.
Average water quality between running beginning back 1-2 month is, with respect to former water T-P300mg/L, the T-P that handles water is 25mg/L, and asking the phosphorous recovery of calculation from water quality is 92%, has shown well to reclaim.Be about 0.3mm from kind of the average grain diameter that brilliant generation groove 31 is returned to the kind crystalline substance of MAP partial crystallization reactive tank 1, the particle diameter of goods crystallization 7 is about 0.6mm, does not also have big change, and particle diameter is stable.In addition, the flow regime of the crystalline particle in the partial crystallization reactive tank 1 is good, and the whole homogeneous that are connected the crystalline particle on the cross section of former water 2 and recirculated water 3 flow, and do not find the dead zone.
Table 5: device apperance and operating condition
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | m | 2 | ||
| Precipitation portion | Diameter | mm | 800 | |
| Highly | m | 1 | ||
| Former water supplying pipe | Diameter | mm | 20 | |
| The recirculated water supply pipe | Diameter | mm | 20 | |
| Plant the brilliant groove that generates | ||||
| Reacting part (the precipitation portion of holding concurrently) | Diameter | mm | 250 | |
| Highly | m | 2 | ||
| Former water supplying | Diameter | mm | 10 | |
| The recirculated water supply | Diameter | mm | 10 | |
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Air capacity | L/ | 10 | ||
| The MAP particle diameter | mm | 0.5 | ||
| Packed | m | 2 | ||
| Plant the brilliant groove that generates | ||||
| Raw water flow | m 3/hr | 0.1 | ||
| Quantity of circulating water | m 3/hr | 0.2 | ||
| Air capacity | L/ | 1 | ||
Table 6: water quality
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 300 | 25 | |
| PO 4-P | mg/L | 285 | 9 | |
| NH 4-N | mg/L | 1100 | 980 | |
| | ％ | 92 |
In the present embodiment, use handling process as shown in Figure 7, generate the recovery test that carries out phosphorus by from the filtrate (former water) of anaerobic digestion, making MAP.Treating apparatus possesses MAP partial crystallization reactive tank 1, plants brilliant groove 31, the fine MAP crystallization accumulator tank 42 of generating.
The operating condition of table 7 expression dephosphorizing process, the table 8 former water 2 of expression and the water quality of handling water 6.In addition,, use acrylic resin system, can confirm the device of the flow regime of the crystalline particle in the partial crystallization reactive tank as experimental provision.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank, making packed height is 2.0m.
Method of operation after the steady running is as follows.
The fine MAP crystallization that to flow out on the top of MAP partial crystallization reactive tank 1 is reclaimed by being deposited in merely in the fine MAP crystallization accumulator tank 42.The fine MAP crystalline particle that reclaims is transplanted on kind of a crystalline substance by transfer tube 43 weekly and generates in the groove 31,, generates kind of a crystalline substance by fine MAP crystalline particle is grown up here.The kind crystalline substance that generates is returned in the MAP partial crystallization reactive tank 1 weekly.Utilize the Mohno pump that fine MAP crystalline particle is transplanted on kind of the brilliant groove 31 that generates from fine MAP crystallization accumulator tank 42.Take out goods crystallization 7 use air lifts 17,38 from kind of the foldback of the kind crystalline substance of brilliant generation groove 31 to MAP partial crystallization reactive tanks 1 and from MAP partial crystallization reactive tank.
Similarly to Example 2, former water 2 and will handle the recirculated water 3 that the part of water extracts, as shown in Figure 8, supply with in the obconic part of partial crystallization reactive tank with tangential direction at cross section with respect to groove.The diameter of former water supplying pipe 12 and recirculated water supply pipe 13 is 20mm, the former water=0.44m/s (0.5m of supply line speed
3/ hr), recirculated water=2.2m/s (2.5m
3/ hr).Former water supplying pipe 12 and recirculated water supply pipe 13 are connected on the same cross section, and the diameter of cross section is 150mm.The linear velocity in 1 second that former water 2 and recirculated water 3 adds up to is 5.2 times of periphery distance of the cross section of junction.As shown in Figure 8, the connection angle between former water supplying pipe 12 and the recirculated water supply pipe 13 is 180 degree.
The position of air supply pipe 15 is the position from the top 25cm of the link position of former water supplying pipe 12 and recirculated water supply pipe 13.The air supply amount is 10L/min.
Average water quality between 2 months of running beginning back 1-3 month is, with respect to former water T-P270mg/L, the T-P that handles water is 20mg/L, and asking the phosphorous recovery of calculation from water quality is 92%, has reclaimed phosphorus well.Be about 0.4mm from kind of the average grain diameter that brilliant generation groove 31 is returned to the kind crystalline substance of MAP partial crystallization reactive tank 1, the particle diameter of goods crystallization 7 is about 0.8mm, does not also have big change, and particle diameter is stable.In addition, the flow regime of the crystalline particle in the partial crystallization reactive tank 1 is good, and the whole homogeneous that are connected the crystalline particle on the cross section of former water supplying pipe 12 and recirculated water supply pipe 13 flow, and do not find the dead zone.
Table 7: device apperance and operating condition
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part (the precipitation portion of holding concurrently) | Diameter | mm | 350 | |
| Highly | m | 4 | ||
| Former water supplying pipe | Diameter | mm | 20 | |
| The recirculated water supply pipe | Diameter | mm | 20 | |
| Plant the brilliant groove that generates | ||||
| Reacting part (the precipitation portion of holding concurrently) | Diameter | mm | 250 | |
| Highly | m | 2 | ||
| Former water supplying | Diameter | mm | 10 | |
| The recirculated water supply | Diameter | mm | 10 | |
| Fine MAP crystallization accumulator tank | ||||
| Diameter | m | 1.5 | ||
| Highly | m | 1.5 | ||
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Air capacity | L/ | 10 | ||
| The MAP particle diameter | mm | 0.5 | ||
| Packed | m | 2 | ||
| Plant the brilliant groove that generates | ||||
| Raw water flow | m 3/hr | 0.1 | ||
| Quantity of circulating water | m 3/hr | 0.2 | ||
| Air capacity | L/ | 1 | ||
Table 8: water quality
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 270 | 20 | |
| PO 4-P | mg/L | 255 | 9 | |
| NH 4-N | mg/L | 1000 | 900 | |
| | ％ | 93 |
Comparative example 3
In this comparative example, use handling process as shown in Figure 9, generate the recovery test that carries out phosphorus by from the dehydration filtrate (former water) of anaerobic digestion, making MAP.Treating apparatus possesses MAP partial crystallization reactive tank 1, the Mg dissolving tank 8 that comprises reacting part and precipitation portion.
The operating condition of table 9 expression dephosphorizing process, the table 10 former water 2 of expression and the water quality of handling water 3.In addition,, use acrylic resin system, can confirm the device of the flow regime of the crystalline particle in the partial crystallization reactive tank 1 as experimental provision.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank 1, making packed height is 2.0m.Reclaim goods crystallization 7 17, one days 1 time by the air lift that is arranged in the MAP partial crystallization reactive tank 1 in the MAP partial crystallization reactive tank 1.
As shown in Figure 10, the closure of former water supplying pipe 12 and recirculated water supply pipe 13 all is that central shaft with respect to the cross section of partial crystallization reactive tank becomes the right angle.Former water supplying pipe 12 and recirculated water supply pipe 13 are connected the direction of the central part of cross section, and connection angle is 180 degree.Same with embodiment 2 and 3, the diameter of former water supplying pipe 12 and recirculated water supply pipe 13 is 20mm, the former water=0.44m/s (0.5m of supply line speed
3/ hr), recirculated water=2.2m/s (2.5m
3/ hr).Former water supplying pipe 12 and recirculated water supply pipe 13 are connected on the same cross section, and the diameter of cross section is 150mm.
The supply condition of magnesium component 9, alkali 4 and air 5 similarly to Example 2.The exit position of air supply pipe is the position from the top 25cm of the link position of former water supplying pipe 12 and recirculated water supply pipe 13.The air supply amount is 10L/min.
Average water quality after the running beginning between 1 month of 1-2 month is that with respect to former water T-P290mg/L, the T-P that handles water is 70mg/L.Asking the phosphorous recovery of calculation from water quality is 76%, compares 16 points that descended than embodiment 1.The equal particle diameter of kind Jinping of filling is 0.5mm, and the running beginning grew to 1.0mm after 1 month, and the running beginning grows to 2.5mm after back 2 months.Crystalline particle in the partial crystallization reactive tank does not flow in 90 directions from the closure of former water supplying pipe 12 and recirculated water supply pipe 13, forms the dead zone, is the state that heterogeneity flows.
Table 9: device apperance and operating condition
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | m | 2 | ||
| Precipitation portion | Diameter | mm | 800 | |
| Highly | m | 1 | ||
| Former water supplying pipe | Diameter | mm | 20 | |
| The recirculated water supply pipe | Diameter | mm | 20 | |
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Air capacity | L/ | 10 | ||
| The MAP particle diameter | mm | 0.5 | ||
| Packed | m | 2 | ||
Table 10: water quality
| Former water | Handle water | ||
| pH | - | 8.0 | 8.0 |
| T-P | mg/L | 290 | 70 |
| PO 4-P | mg/L | 270 | 8 |
| NH 4-N | mg/L | 1100 | 980 |
| Phosphorous recovery | ％ | 76 |
In the present embodiment, use handling process as shown in figure 11, generate the recovery test that carries out phosphorus by from the dehydration filtrate (former water) of anaerobic digestion, making MAP.Treating apparatus possesses MAP partial crystallization reactive tank 1, liquid cyclone separator 51.The operating condition of table 11 expression dephosphorizing process.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank 1, making packed height is 2.0m.
Method of operation after the steady running is as follows.
Water level meter (omitting diagram) is set on the top of MAP partial crystallization reactive tank 1, and the water level one in the partial crystallization reactive tank 1 reduces, and with regard to stop liquid cyclone separator inflow pump, water level is restarted pump once rising.
Table 12 former water 2 of expression and the water quality of handling water 6.
The running beginning back average water quality between 2 weeks is, with respect to former water T-P300mg/L, the T-P that handles water is 25mg/L, and asking the phosphorous recovery of calculation from water quality is 92%, has reclaimed phosphorus well.Average grain diameter=the 0.5mm of the MAP crystalline particle of filling with respect to the initial stage, the particle diameter of the MAP crystalline particle after 2 weeks is 0.8mm.
Table 11: operating condition and water quality treatment
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | | 4 | ||
| The liquid cyclone separator | ||||
| Handle the water inflow | Diameter | mm | 51 | |
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Air capacity | L/ | 10 | ||
| Packed | m | 2 | ||
| The liquid cyclone separator | ||||
| Flow | m
3/ | 3 | ||
Table 12: water quality
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 300 | 25 | |
| PO 4-P | mg/L | 280 | 10 | |
| NH 4-N | mg/L | 1000 | 860 | |
| | ％ | 92 |
In the present embodiment, use treating apparatus as shown in figure 12, generate the recovery test that carries out phosphorus by from the dehydration filtrate (former water) of anaerobic digestion, making MAP.Treating apparatus possesses MAP partial crystallization reactive tank 1, liquid cyclone separator 51.The operating condition of table 13 expression dephosphorizing process.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank 1, making packed height is 2.0m.
Method of operation after the steady running is as follows.
With the pars intermedia feed fluid cyclone separator 52 of the liquid in the MAP partial crystallization reactive tank 1 from MAP partial crystallization reactive tank 1.The part of liquid cyclone separator outflow water 56 is returned in the MAP partial crystallization reactive tank 1 after adding magnesium solutions 9 as recirculated water 3.In addition, the part by the liquid cyclone separator being flowed out water 56 is returned to the top of MAP partial crystallization reactive tank 1 by transfer tube 61, and the part of foldback water is overflowed often, prevents that water level from reducing.And the part that will flow out is taken out as handling water 6.
The fine MAP crystalline particle that concentrates at liquid cyclone separator 51 is returned to MAP partial crystallization reactive tank 1 by transfer tube 54.
The water quality of former water 2 of table 14 expression and processing water 6.
The running beginning back average water quality between 2 weeks is, with respect to former water T-P300mg/L, the T-P that handles water is 20mg/L, and asking the phosphorous recovery of calculation from water quality is 93%, has reclaimed phosphorus well.With respect to the average grain diameter 0.5mm of the MAP crystalline particle of filling, the particle diameter of the MAP crystalline particle in the partial crystallization reactive tank 1 after between 2 weeks is 0.8mm.
Table 13: operating condition and water quality treatment
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | | 4 | ||
| The liquid cyclone separator | ||||
| Handle the water inflow | Diameter | mm | 51 | |
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Air capacity | L/ | 10 | ||
| The MAP particle diameter | mm | 0.5 | ||
| Packed | m | 2 | ||
| The liquid cyclone separator | ||||
| Flow | m
3/ | 4 | ||
Table 14: water quality
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 300 | 20 | |
| PO 4-P | mg/L | 280 | 10 | |
| NH 4-N | mg/L | 1000 | 860 | |
| | ％ | 93 |
Comparative example 4 (comparative example of embodiment 4)
In this comparative example, use the treating apparatus that does not have the liquid cyclone separator as shown in figure 14, by being generated, MAP carries out the recovery of phosphorus.
Treating apparatus is made of MAP partial crystallization reactive tank 1 basically.Except not using the liquid cyclone separator, conditional operation similarly to Example 4.
Table 15 former water 2 of expression and the water quality of handling water 6.
The running beginning back average water quality between 2 weeks is, with respect to former water T-P300mg/L, the T-P that handles water is 65mg/L, and asking the phosphorous recovery of calculation from water quality is 78%.Handle water T-P and handle water PO
4The difference of-P mainly is the P among the MAP, is 55mg/L, and is many.
Table 15: water quality
| Former water | Handle water | ||
| pH | - | 8.0 | 8.0 |
| T-P | mg/L | 300 | 65 |
| PO 4-P | mg/L | 280 | 10 |
| NH 4-N | mg/L | 1000 | 860 |
| Phosphorous recovery | ％ | 78 |
In the present embodiment, use treating apparatus as shown in figure 15, carry out the recovery of phosphorus by MAP is generated.Treating apparatus possesses MAP partial crystallization reactive tank 1, plants brilliant separating tank 31, liquid cyclone separator 51.The operating condition of table 16 expression dephosphorizing process.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank 1, making packed height is 2.0m.
Method of operation after the steady running is as follows.
Supply with former water 2 and recirculated water 3 and air 35 in the groove 31 kind of brilliant a generation.Kind of brilliant a generation fine MAP crystalline particle is grown up, generation is planted brilliant thus.Kinds brilliant 1 time/3 days be returned to MAP partial crystallization reactive tank 1 by transfer tube 38.
Table 17 former water 2 of expression and the water quality of handling water 6.
Average water quality between 1 month of the running beginning back 1-2 month is, with respect to former water T-P300mg/L, the T-P that handles water is 22mg/L, and asking the phosphorous recovery of calculation from water quality is 93%, has reclaimed phosphorus well.Generate the about 0.3mm of average grain diameter that groove 31 is returned to the kind crystalline substance of MAP partial crystallization reactive tank 1 from kind of a crystalline substance, the about 0.6mm of the average grain diameter of goods crystallization 7 does not have big change, and particle diameter is stable.
Table 16: operating condition and water quality treatment
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | | 4 | ||
| The liquid cyclone separator | ||||
| Handle the water inflow | Diameter | mm | 51 | |
| Plant the brilliant groove that generates | ||||
| Reacting part (the precipitation portion of holding concurrently) | Diameter | mm | 250 | |
| Highly | m | 2 | ||
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Air capacity | L/ | 10 | ||
| Packed | m | 2 | ||
| Plant the brilliant groove that generates | ||||
| Raw water flow | m 3/hr | 0.1 | ||
| Quantity of circulating water | m 3/hr | 0.2 | ||
| Air capacity | L/ | 1 | ||
| The liquid cyclone separator | ||||
| Flow | m
3/ | 3 | ||
Table 17: water quality
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 300 | 22 | |
| PO 4-P | mg/L | 280 | 10 | |
| NH 4-N | mg/L | 1000 | 800 | |
| | ％ | 93 |
In the present embodiment, use treating apparatus as shown in figure 16, carry out the recovery of phosphorus by MAP is generated.Treating apparatus possesses MAP partial crystallization reactive tank 1, plants brilliant groove 31, the liquid cyclone separator 51 of generating.The operating condition of table 18 expression dephosphorizing process.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank, making packed height is 2.0m.
Method of operation after the steady running is as follows.
Table 19 former water 2 of expression and the water quality of handling water 6.
Average water quality between 1 month of the running beginning back 1-2 month is, with respect to former water T-P300mg/L, the T-P that handles water is 20mg/L, and asking the phosphorous recovery of calculation from water quality is 93%, has reclaimed phosphorus well.Generate the about 0.3mm of average grain diameter that groove 31 is returned to the kind crystalline substance of MAP partial crystallization reactive tank 1 from kind of a crystalline substance, the about 0.6mm of the average grain diameter of goods crystallization 7 does not have big change, and particle diameter is stable.
Table 18: operating condition and water quality treatment
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | | 4 | ||
| The liquid cyclone separator | ||||
| Handle the water inflow | Diameter | mm | 51 | |
| Plant the brilliant groove that generates | ||||
| Reacting part (the precipitation portion of holding concurrently) | Diameter | mm | 250 | |
| Highly | m | 2 | ||
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Handle water foldback amount | m
3/ | 1 | ||
| Air capacity | L/ | 10 | ||
| The MAP particle diameter | mm | 0.5 | ||
| Packed | m | 2 | ||
| Plant the brilliant groove that generates | ||||
| Raw water flow | m 3/hr | 0.1 | ||
| Quantity of circulating water | m 3/hr | 0.2 | ||
| Air capacity | L/ | 1 | ||
| The liquid cyclone separator | ||||
| Flow | m
3/ | 4 | ||
Table 19: water quality
| Former water | Handle water | |||
| pH | - | 8.0 | 8.0 | |
| T-P | mg/L | 300 | 20 | |
| PO 4-P | mg/L | 280 | 8 | |
| NH 4-N | mg/L | 1000 | 800 | |
| | ％ | 93 |
Embodiment 8
In the present embodiment, use treating apparatus as shown in figure 15, carry out the recovery of phosphorus by HAP is generated.Treating apparatus possesses HAP partial crystallization reactive tank 1, plants brilliant groove 31, the liquid cyclone separator 51 of generating.The operating condition of table 20 expression dephosphorizing process.
In when beginning running, the kind crystalline substance (rock phosphate in powder) of pre-prepd average grain diameter 0.2mm is filled in the HAP partial crystallization reactive tank, making packed height is 2.0m.
Method of operation after the steady running is as follows.
Table 21 former water 2 of expression and the water quality of handling water 6.
Average water quality between 2 months of the running beginning back 2-4 month is, with respect to former water T-P100mg/L, the T-P that handles water is 15mg/L, and asking the phosphorous recovery of calculation from water quality is 85%, has reclaimed phosphorus well.Generate the about 0.1mm of average grain diameter that groove 31 is returned to the kind crystalline substance of HAP partial crystallization reactive tank 1 from kind of a crystalline substance, the about 0.25mm of the average grain diameter of goods crystallization 7 does not have big change, and particle diameter is stable.
Table 20: operating condition and water quality treatment
| ＜device apperance 〉 | ||||
| HAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | | 4 | ||
| The liquid cyclone separator | ||||
| Handle the water inflow | Diameter | mm | 51 | |
| Plant the brilliant groove that generates | ||||
| Reacting part (the precipitation portion of holding concurrently) | Diameter | mm | 250 | |
| Highly | m | 2 | ||
| ＜water flowing condition 〉 | ||||
| HAP partial crystallization reactive tank | ||||
| Raw water flow | m 3/hr | 0.5 | ||
| Quantity of circulating water | m 3/hr | 2.5 | ||
| Air capacity | L/ | 10 | ||
| The rock phosphate in powder particle diameter | mm | 0.2 | ||
| Packed | m | 2 | ||
| Plant the brilliant groove that generates | ||||
| Raw water flow | m 3/hr | 0.1 | ||
| Quantity of circulating water | m 3/hr | 0.2 | ||
| Air capacity | L/ | 1 | ||
| The liquid cyclone separator | ||||
| Flow | m
3/ | 3 | ||
Table 21: water quality
| Former water | Handle water | |||
| pH | - | 7.3 | 9.0 | |
| T-P | mg/L | 100 | 15 | |
| PO 4-P | mg/L | 90 | 2 | |
| | ％ | 85 |
Comparative example 5 (comparative example of embodiment 6)
In this comparative example, use treating apparatus as shown in figure 18, by being generated, MAP carries out the recovery of phosphorus.Treating apparatus possesses MAP partial crystallization reactive tank 1, plants brilliant separating tank 31.Except the liquid cyclone separator, conditional operation similarly to Example 6.
Table 22 former water 2 of expression and the water quality of handling water 6.
Average water quality between 1 month of running beginning back 1-2 month is, with respect to former water T-P300mg/L, the T-P that handles water is 70mg/L, and asking the phosphorous recovery of calculation from water quality is 77%.Handle water T-P and handle water PO
4The difference of-P mainly is the P among the fine MAP, is 60mg/L, and is many.
Table 22: water quality
| Former water | Handle water | ||
| pH | - | 8.0 | 8.0 |
| T-P | mg/L | 300 | 70 |
| PO 4-P | mg/L | 280 | 10 |
| NH 4-N | mg/L | 1000 | 800 |
| Phosphorous recovery | ％ | 77 |
Comparative example 6 (comparative example of embodiment 6)
In this comparative example, use treating apparatus as shown in figure 19, by being generated, MAP carries out the recovery of phosphorus.Treating apparatus possesses the MAP partial crystallization reactive tank 1 that comprises reacting part (bottom is footpath little part and obconic part) and precipitation portion (top is the big part in footpath).The diameter of the reacting part of partial crystallization reactive tank 1 is 350mm, and the diameter of precipitation portion is 800mm.
The operating condition of table 23 expression dephosphorizing process.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank 1, making packed height is 2.0m.In MAP partial crystallization reactive tank 1, reclaim goods crystallization 7 17,1 days 1 time by the air lift that is arranged in the partial crystallization reactive tank 1.Supply with magnesium component 9, alkali 4 and air 5 similarly to Example 6.The lower end position of air supply pipe 15 is the position from the top 25cm of the link position of former water supplying pipe and recirculated water supply pipe 13.The quantity delivered of air 5 is 10L/min.
Table 24 former water 2 of expression and the water quality of handling water 6.
Average water quality between 1 month of running beginning back 1-2 month is, with respect to former water T-P300mg/L, the T-P that handles water is 60mg/L, and asking the phosphorous recovery of calculation from water quality is 80%, compares with embodiment 6 and has reduced by 13 points.The average grain diameter of the kind crystalline substance of filling is 0.5mm, and the running beginning grew to 2.3mm after 2 months.The diameter of the MAP partial crystallization reactive tank 1 of embodiment 6 is 0.35m, and the diameter of the MAP partial crystallization reactive tank 1 of this comparative example 6 is 0.8m, although the big rate of recovery of device reduces.
Table 23: operating condition and water quality treatment
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | m | 2 | ||
| Precipitation portion | Diameter | mm | 800 | |
| Highly | m | 1 | ||
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m
3/ | 1 | ||
| Quantity of circulating water | m
3/ | 2 | ||
| Air capacity | L/ | 10 | ||
| The MAP particle diameter | mm | 0.5 | ||
| Packed | m | 2 | ||
Table 24: water quality
| Former water | Handle water | ||
| pH | - | 8.0 | 8.0 |
| T-P | mg/L | 300 | 60 |
| PO 4-P | mg/L | 280 | 8 |
| NH 4-N | mg/L | 1000 | 800 |
| Phosphorous recovery | ％ | 80 |
In present embodiment 9, use treating apparatus as shown in figure 23, generate the recovery test that carries out phosphorus by from the dehydration filtrate (former water) of anaerobic digestion, making MAP.Treating apparatus possesses MAP partial crystallization reactive tank 1, recirculated water is adjusted groove 82.The operating condition of table 25 expression dephosphorizing process, the water quality of former water 2 of table 26 expression and processing water 6.Use magnesium hydroxide as magnesium component 83, use sulfuric acid as acid 85.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank 1, making packed height is 2.0m.
Method of operation after the steady running is as described below.
With former water 2 and recirculated water 3 from the bottom of MAP partial crystallization reactive tank 1 with the water that upwards circulates.The MAP crystalline particle 7 of growing up in MAP partial crystallization reactive tank 1 uses air lift 17 suitably to reclaim.The addition of the magnesium hydroxide 83 in the recirculated water adjustment groove 82 is adjusted to and is made former water PO
4-P/ adds Mg weight ratio=1.0.In addition, in recirculated water adjustment groove 82, pH meter 10 is set, according to the power output on-off interpolation sulfuric acid 85 of pH meter 10.The setting value of pH is 8.0.
Average water quality between running beginning 2 weeks of back is shown in table 26 like that, and with respect to former water T-P300mg/L, the T-P that handles water is 32mg/L, and asking the phosphorous recovery of calculation from water quality is 89%; Reclaimed phosphorus well.
Table 25: operating condition and water quality treatment
| ＜device apperance 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Reacting part | Diameter | mm | 350 | |
| Highly | m | 4 | ||
| Precipitation portion | Diameter | mm | 800 | |
| Highly | m | 1 | ||
| PH adjusts groove | Volume | m 3 | 0.3 | |
| ＜water flowing condition 〉 | ||||
| MAP partial crystallization reactive tank | ||||
| Raw water flow | m 3/hr | 0.8 | ||
| Quantity of circulating water | m 3/hr | 1.6 | ||
| The MAP particle diameter | mm | 0.5 | ||
| Packed | m | 2 | ||
| PH adjusts groove | ||||
| Former water addition | The former water of mg/L- | 680 | ||
Table 26: water quality
| Former water | Handle water | ||
| pH | - | 8.0 | 8.0 |
| T-P | mg/L | 300 | 32 |
| PO 4-P | mg/L | 280 | 11 |
| NH 4-N | mg/L | 1000 | 870 |
| Phosphorous recovery | ％ | 89 |
In present embodiment 10, use treating apparatus as shown in figure 20, by being generated, MAP carries out the recovery of phosphorus.Treating apparatus possesses MAP partial crystallization reactive tank 1, plants brilliant groove 31, the recirculated water adjustment groove 82 of generating.The operating condition of table 27 expression dephosphorizing process, the water quality of former water 2 of table 28 expression and processing water 6.Use magnesium hydroxide as magnesium component 83, use sulfuric acid as acid 85.
In when beginning running, the kind crystalline substance (MAP particle) of pre-prepd average grain diameter 0.5mm is filled in the MAP partial crystallization reactive tank, making packed height is 2.0m.
Method of operation after the steady running is as described below.
To once be transplanted on kind of brilliant a generation in the groove 31 at the fine MAP crystalline particle that swims in the top of MAP partial crystallization reactive tank 1 in 3 days by fine MAP crystallization transfer tube 37.In the time of the handover of fine MAP crystalline particle, will to generate the kind that groove 31 generates brilliant all by being arranged on the air lift 38 in kind of the brilliant generation groove 31 kind brilliant, be returned in the MAP partial crystallization reactive tank 1.In the MAP partial crystallization reactive tank 1, once reclaimed goods crystallization 7 in 17,1 days by the air lift that is arranged on MAP partial crystallization reactive tank 1.
The quantity delivered of former water 2 is a MAP partial crystallization reactive tank: plant the brilliant groove=0.5m of generation
3/ hr: 0.06m
3/ hr, the quantity delivered of recirculated water 3 is a MAP partial crystallization reactive tank: plant the brilliant groove=1.0m of generation
3/ hr: 0.12m
3/ hr.
The addition of magnesium hydroxide 83 is adjusted into and makes former water PO
4-P/ adds Mg weight ratio=1.0.In addition, in recirculated water adjustment groove 82, pH meter 10 is set, according to the power output on-off interpolation sulfuric acid 85 of pH meter 10.The setting value of pH is 8.0.
The average water quality that running begins between back 1 month is shown in table 28 like that, and with respect to former water T-P300mg/L, the T-P that handles water is 30mg/L, and asking the phosphorous recovery of calculation from water quality is 90%; Reclaimed phosphorus well.
Table 27: operating condition and water quality treatment
| ＜device apperance 〉 | |||||
| MAP partial crystallization reactive tank | |||||
| Reacting part | Diameter | mm | 350 | ||
| Highly | m | 2 | |||
| Precipitation portion | Diameter | mm | 800 | ||
| Highly | m | 1 | |||
| Plant the brilliant groove that generates | |||||
| Reacting part (the precipitation portion of holding concurrently) | Diameter | mm | 250 | ||
| Highly | m | 2 | |||
| PH adjusts groove | Volume | m 3 | 0.3 | ||
| ＜water flowing condition 〉 | |||||
| MAP partial crystallization reactive tank | |||||
| Raw water flow | m 3/hr | 0.5 | |||
| Quantity of circulating water | m 3/hr | 1.0 | |||
| The MAP particle diameter | mm | 0.5 | |||
| Packed | m | 2 | |||
| Plant the brilliant groove that generates | |||||
| Raw water flow | m 3/hr | 0.06 | |||
| Quantity of circulating water | m 3/hr | 0.12 | |||
| PH adjusts groove | |||||
| Mg(OH) 2Addition | The former water of mg/L- | 680 | |||
Table 28: water quality
| Former water | Handle water | ||
| pH | - | 8.0 | 8.0 |
| T-P | mg/L | 300 | 30 |
| PO 4-P | mg/L | 280 | 10 |
| NH 4-N | mg/L | 1000 | 880 |
| Phosphorous recovery | ％ | 90 |
Comparative example 7
In this comparative example 7, use treating apparatus as shown in figure 24, by being generated, MAP carries out the recovery of phosphorus.Compare with embodiment 9, except not having sulfuric acid interpolation equipment, all identical with embodiment 9.
The water quality of former water 2 of table 29 expression and processing water 6.
The average water quality that running begins between back 1 month is shown in table 29 like that, and with respect to former water T-P=300mg/L, the T-P that handles water is 70mg/L, and asking the phosphorous recovery of calculation from water quality is 77%.PH in the partial crystallization reactive tank 1 rises to 8.8, finds most block SS, and a part has flowed.SS composition to bulk is investigated, and finds it mainly is MAP.Infer that having generated most fine MAP crystalline particles becomes bulk because pH rises.
Table 29: water quality
| Former water | Handle water | ||
| pH | - | 8.0 | 8.0 |
| T-P | mg/L | 300 | 70 |
| PO 4-P | mg/L | 280 | 10 |
| NH 4-N | mg/L | 1000 | 880 |
| Phosphorous recovery | ％ | 77 |
Utilizability on the industry
The first kind of way according to the present invention, in the method that is removed ion and device of removing by the partial crystallization reaction in the processed liquid, the part of the treatment fluid that flows out from the partial crystallization reactive tank, add the medicament of partial crystallization reaction needed, make its dissolving, it is supplied with the partial crystallization reactive tank as circulation fluid, at this moment, by processed liquid and the circulation fluid cross section with respect to the partial crystallization reactive tank is imported with tangential direction, crystalline particle homogeneous in the partial crystallization reactive tank flows, mixing between the reaction relation material and reaction relation material are all extremely good with contacting of crystal surface, promote the partial crystallization reaction of developmental process as leading take crystalline particle.
In addition, according to the second embodiment of the present invention, in the method that is removed ion and device of removing by the partial crystallization reaction in the processed liquid, use comprises the device of partial crystallization reactive tank and liquid cyclone separator, to import the liquid cyclone separator from the treat liquid that the partial crystallization reactive tank flows out, fine crystal particle in the liquid cyclone separator in separation, the recycle process fluids, part or all of the fine crystal particle that reclaims is returned to the partial crystallization reactive tank, the medicament that while adds in the part of the outflow water of liquid cyclone separator partial crystallization reaction necessity makes its dissolving, it is supplied in the partial crystallization reactive tank as circulation fluid, thus the fine crystal particle is discharged to the outside from the partial crystallization reactive tank, and the fine crystal particle is further grown up at the partial crystallization reactive tank, the amount that reclaims as the goods crystallization is increased, the result, the rate of recovery of phosphorus is high, and can make device compact.
In addition, be recycled to the top of partial crystallization reactive tank by a part that the liquid cyclone separator is flowed out water, make the water balance of the total water yield of former water in the partial crystallization reactive tank and recirculated water good, reduce the change of the liquid level of partial crystallization reactive tank, the liquid that easily will contain the fine crystal particle is delivered to the liquid cyclone separator from the partial crystallization reactive tank, do not cause the fault of transferring with pump, the setting that can omit in addition water-level gauge.
In addition, according to the third embodiment of the present invention, in the method that is removed ion and device of removing by the partial crystallization reaction in the processed liquid, use the medicament of the insoluble chemical compound of pulpous state as the partial crystallization reaction needed, the insoluble chemical compound and the acid that the part of the treatment fluid that flows out from the partial crystallization reactive tank, add this pulpous state, it is supplied with in the partial crystallization reactive tank as circulation fluid, thus, by using cheap insoluble chemical compound, it is easily dissolved, improve the concentration that is removed particle in the liquid, recovery method that is removed ion and device that handling property is reduced can be provided.
Claims (51)
1. in the partial crystallization reactive tank, remove the method that is removed ion in the processed liquid for one kind by the crystalline particle partial crystallization that makes the indissoluble salt that is removed ion in the processed liquid, it is characterized in that, the medicament that adds the partial crystallization reaction needed the part of the treatment fluid that flows out from the partial crystallization reactive tank makes its dissolving, it is supplied with the partial crystallization reactive tank as circulation fluid, at this moment, the cross section with respect to the partial crystallization reactive tank imports processed liquid and circulation fluid in tangential direction.
2. the method for claim 1 record, wherein, to the central part air supply of the cross section of partial crystallization reactive tank.
3. the methods of claim 1 or 2 records wherein, as the partial crystallization reactive tank, are used the reaction vessel of the cross section of the bottom shape littler than the cross section on top, processed liquid and circulation fluid are imported the bottom of reactive tank.
4. the method for each record of claim 1-3 wherein, as the partial crystallization reactive tank, is used the reaction vessel of foot as the inverted cone shape.
5. the method for each record of claim 1-4, wherein, use the partial crystallization reactive tank and plant the brilliant groove that generates, processed liquid and circulation fluid are supplied to kind of the brilliant groove that generates, the fine crystal particle that takes out the liquid from the partial crystallization reactive tank is supplied with kind of the brilliant groove that generates simultaneously, generate a groove at kind of a crystalline substance fine crystal particle is grown up, form kind of a crystalline substance thus, will be at kind of the brilliant brilliant partial crystallization reactive tank of supplying with of the kind that grow up in the groove that generates.
6. device that comprises partial crystallization reactive tank and liquid cyclone separator by use, in the partial crystallization reactive tank, make the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the method that is removed ion in the processed liquid, it is characterized in that, to import the liquid cyclone separator from the treatment fluid that the partial crystallization reactive tank flows out, in the liquid cyclone separator, separate, fine crystal particle in the recycle process fluids, part or all of the fine crystal particle that reclaims is returned in the partial crystallization reactive tank, while adds the medicament of partial crystallization reaction needed in the part of the outflow water of liquid cyclone separator, make its dissolving, it is supplied to the partial crystallization reactive tank as circulation fluid.
7. the method for claim 6 record wherein, supplies to the part of the outflow water of liquid cyclone separator on the top of partial crystallization reactive tank.
Claim 6 or 7 the record methods, wherein, also use kind of the brilliant groove that generates, part or all of the fine crystal particle that will reclaim at the liquid cyclone separator supplies to kind of the brilliant groove that generates, kind of brilliant a generation fine crystal particle is grown up, form kind of a crystalline substance, will be at kind of the brilliant brilliant partial crystallization reactive tank of supplying with of the kind of growing up in the groove that generates, simultaneously, at the outflow water of liquid cyclone separator with plant the medicament that adds the partial crystallization reaction needed in the brilliant part that generates the concentrated flow water outlet, make its dissolving, it is supplied to the partial crystallization reactive tank as circulation fluid.
9. the method for each record of claim 6-8 is characterized in that, processed liquid and the circulation fluid cross section with respect to the partial crystallization reactive tank is imported with tangential direction.
10. the method for each record of claim 6-9 wherein, is supplied with air the central part in the cross section of partial crystallization reactive tank.
11. the method for each record of claim 6-10, wherein, as the partial crystallization reactive tank, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top is with the bottom of processed liquid and circulation fluid importing reactive tank.
12. the method for each record of claim 6-11 wherein, as the partial crystallization reactive tank, is used the reaction vessel of foot as the inverted cone shape.
13. one kind by making the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid in the partial crystallization reactive tank, remove the method that is removed ion in the processed liquid, it is characterized in that, use the medicament of the insoluble chemical compound of pulpous state as the partial crystallization reaction needed, the part of the treatment fluid that flows out from the partial crystallization reactive tank, add the insoluble chemical compound and the acid of this pulpous state, it is supplied with in the partial crystallization reactive tank as circulation fluid.
14. the method for claim 13 record, wherein, use the partial crystallization reactive tank and plant the brilliant groove that generates, processed liquid and circulation fluid are supplied with kind of the brilliant groove that generates, the fine crystal particle that takes out the liquid from the partial crystallization reactive tank is supplied with kind of the brilliant groove that generates simultaneously, brilliant by the growth formation in kind of brilliant generation groove of fine crystal particle is planted, the kind crystalline substance supply partial crystallization reactive tank that will in kind of crystalline substance generation groove, grow up.
15. the method for claim 14 record wherein, makes from kind of the brilliant outflow liquid of groove and the treatment fluid interflow of flowing out from the partial crystallization reactive tank of generating.
16. the method for each record of claim 13-15 is characterized in that, processed liquid and the circulation fluid cross section with respect to the partial crystallization reactive tank is imported with tangential direction.
17. the method for each record of claim 13-16 wherein, is supplied with air the central part in the cross section of partial crystallization reactive tank.
18. the method for each record of claim 13-17, wherein, as the partial crystallization reactive tank, the reaction vessel of the shape that the cross section of use bottom is littler than the cross section on top is with the bottom of processed liquid and circulation fluid importing reactive tank.
19. the method for each record of claim 13-18 wherein, as the partial crystallization reactive tank, is used the reaction vessel of foot as the inverted cone shape.
20. the method for each record of claim 1-19 wherein, by making the ammonium magnesium phosphate partial crystallization, is removed dephosphorization from processed liquid from the processed liquid that contains phosphorus and ammonium-nitrogen.
21. the method for each record of claim 1-19 wherein, by making the hydroxyapatite partial crystallization, is removed dephosphorization from processed liquid from the processed liquid that contains phosphorus.
22. the method for each record of claim 1-19 wherein, by making the calcirm-fluoride partial crystallization, is removed fluorine from processed liquid from the processed liquid that contains fluorine ion.
23. the method for each record of claim 1-19 wherein, by making the calcium carbonate partial crystallization, is removed calcium from processed liquid from the processed liquid that contains calcium ion.
24. the method for each record of claim 1-19 wherein, by making the calcium carbonate partial crystallization, is removed the carbonic acid ion from processed liquid from the processed liquid that contains the carbonic acid ion.
25. one kind makes the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the device that is removed ion in the processed liquid thus by partial crystallization reaction, it is characterized in that, possesses the partial crystallization reactive tank, with the processed liquid supply pipe in the processed liquid supply partial crystallization reactive tank, the treatment fluid discharge pipe that to induce from the treatment fluid that the partial crystallization reactive tank flows out, the recirculated water supply pipe that treatment fluid is returned to the partial crystallization reactive tank from treatment fluid discharge pipe branch, the medicament of partial crystallization reaction needed is supplied with the medicament supply mean of recirculated water, and processed liquid supply pipe and recirculated water supply pipe are connected on the partial crystallization reactive tank with tangential direction with respect to the cross section of reactive tank.
26. the device of claim 25 record also possesses the air supply pipe of central part of air being supplied with the cross section of partial crystallization reactive tank.
27. the device of claim 25 or 26 records, wherein, the partial crystallization reactive tank is the reaction vessel of the cross section of the bottom shape littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe with the partial crystallization reactive tank.
28. the device of each record of claim 25-27, wherein, the partial crystallization reactive tank is that foot is the container of inverted cone shape.
29. the device of each record of claim 25-28, wherein, also possesses kind of the brilliant groove that generates, processed liquid supply pipe also is connected with kind of the brilliant groove that generates with the recirculated water supply pipe, also possess from the partial crystallization reactive tank fine crystal particle in the groove is transplanted on kind a brilliant fine crystal particle transfer tube that generates groove, will generate the brilliant transfer tube of kind that the kind crystalline substance that grow up in the groove is transplanted on the partial crystallization reactive tank kind brilliant.
30. the sharp device that requires each record of 25-29 wherein, possesses the crystallization recovering means that the crystalline particle that will grow up reclaims from the partial crystallization reactive tank.
31. one kind makes the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the device that is removed ion in the processed liquid thus by partial crystallization reaction, it is characterized in that possessing the partial crystallization reactive tank, the liquid cyclone separator, with the processed liquid supply pipe in the processed liquid supply partial crystallization reactive tank, to be induced to the treatment fluid transfer tube of liquid cyclone separator from the treatment fluid that the partial crystallization reactive tank flows out, the treatment fluid discharge pipe that to induce from the outflow water of liquid cyclone separator, the recirculated water supply pipe that treatment fluid is returned to the partial crystallization reactive tank from treatment fluid discharge pipe branch, supply with the solid shape of concentrating of partial crystallization reactive tank at the fine crystal particle of liquid cyclone separator concentrating and separating and divide transfer tube, the medicament of partial crystallization reaction needed is supplied with the medicament supply mean of recirculated water.
32. the device of claim 31 record wherein, possesses the liquid cyclone separator that the part of the outflow water of liquid cyclone separator is supplied with the top of partial crystallization reactive tank and flows out the water transfer tube.
33. the device of claim 31 or 32 records, wherein, also possesses kind of the brilliant groove that generates, processed liquid supply pipe also is connected with kind of the brilliant groove that generates with the recirculated water supply pipe, the fine crystal particle that also possesses liquid cyclone separator concentrating and separating is transplanted on kind of a brilliant fine crystal particle transfer tube that generates groove, and the kind crystalline substance that will grow up in kind of brilliant generation groove is transplanted on the brilliant transfer tube of kind of partial crystallization reactive tank.
34. the device of each record of claim 31-33, wherein, processed liquid supply pipe, recirculated water supply pipe are connected on the partial crystallization reactive tank with tangential direction with respect to the cross section of partial crystallization reactive tank.
35. the device of each record of claim 31-34 also possesses the air supply pipe of central part of air being supplied with the cross section of partial crystallization reactive tank.
36. the device of each record of claim 31-35, wherein, the partial crystallization reactive tank is the cross section of the bottom shapes of containers littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe with the partial crystallization reactive tank.
37. the device of each record of claim 31-36, wherein, the partial crystallization reactive tank is that foot is the container of inverted cone shape.
38. the device of each record of claim 31-37 wherein, possesses the crystallization recovering means that the crystalline particle that will grow up reclaims from the partial crystallization reactive tank.
39. one kind makes the crystalline particle partial crystallization of the indissoluble salt that is removed ion in the processed liquid remove the device that is removed ion in the processed liquid thus by partial crystallization reaction, it is characterized in that the medicament supply mean that possesses the partial crystallization reactive tank, processed liquid is supplied with processed liquid supply pipe in the partial crystallization reactive tank, the treatment fluid discharge pipe that will induce from the treatment fluid that the partial crystallization reactive tank flows out, supplied with recirculated water from the recirculated water supply pipe that treatment fluid is returned to the partial crystallization reactive tank of treatment fluid discharge pipe branch, with the medicament and the acid of partial crystallization reaction needed.
40. the device of claim 39 record wherein, possesses and will temporarily accept to supply with the adjustment groove of partial crystallization reactive tank from the recirculated water of treatment fluid branch, and the medicament and the acid of partial crystallization reaction needed is supplied to the adjustment groove.
41. the device of claim 39 or 40 records, wherein, also possesses kind of the brilliant groove that generates, processed liquid supply pipe also is connected with kind of the brilliant groove that generates with the recirculated water supply pipe, also possess from the partial crystallization reactive tank fine crystal particle in the groove is transplanted on kind a brilliant fine crystal particle transfer tube that generates groove, will generate the brilliant transfer tube of kind that the kind crystalline substance that grow up in the groove is transplanted on the partial crystallization reactive tank kind brilliant.
42. the device of each record of claim 39-41 item, wherein, processed liquid supply pipe, recirculated water supply pipe are connected on the partial crystallization reactive tank with tangential direction with respect to the cross section of partial crystallization reactive tank.
43. the device of each record of claim 39-41 also possesses the air supply pipe of central part of air being supplied with the cross section of partial crystallization reactive tank.
44. the device of each record of claim 39-43, wherein, the partial crystallization reactive tank is the cross section of the bottom shapes of containers littler than the cross section on top, and processed liquid supply pipe is connected with the bottom of recirculated water supply pipe with the partial crystallization reactive tank.
45. the device of each record of claim 39-44, wherein, the partial crystallization reactive tank is that foot is the container of inverted cone shape.
46. the device of each record of claim 39-45 wherein, possesses the crystallization recovering means that the crystalline particle that will grow up reclaims from the partial crystallization reactive tank.
47. the device of each record of claim 25-46 wherein, by making the ammonium magnesium phosphate partial crystallization, removes dephosphorization from processed liquid from the processed liquid that contains phosphorus and ammonium-nitrogen.
48. the device of each record of claim 25-46 wherein, by making the hydroxyapatite partial crystallization, removes dephosphorization from processed liquid from the processed liquid that contains phosphorus.
49. the device of each record of claim 25-46 wherein, by making the calcirm-fluoride partial crystallization, is removed fluorine from processed liquid from the processed liquid that contains fluorine ion.
50. the device of each record of claim 25-46 wherein, by making the calcium carbonate partial crystallization, is removed calcium from processed liquid from the processed liquid that contains calcium ion.
51. the device of each record of claim 25-46 wherein, by making the calcium carbonate partial crystallization, is removed the carbonic acid ion from processed liquid from the processed liquid that contains the carbonic acid ion.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP023841/2003 | 2003-01-31 | ||
| JP2003023841 | 2003-01-31 | ||
| JP043104/2003 | 2003-02-20 | ||
| JP080974/2003 | 2003-03-24 | ||
| JP110406/2003 | 2003-04-15 | ||
| JP142115/2003 | 2003-05-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1761507A true CN1761507A (en) | 2006-04-19 |
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ID=36707302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480007241 Pending CN1761507A (en) | 2003-01-31 | 2004-01-20 | Method and apparatus for removing ion in fluid by crystallization |
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| CN (1) | CN1761507A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249494A (en) * | 2011-06-23 | 2011-11-23 | 南京大学 | Method for improving activity of methanogens while reducing high-concentration ammonia nitrogen in anaerobic process |
| CN102728094A (en) * | 2011-03-31 | 2012-10-17 | 海法化学工业公司 | Crystallization apparatus |
| CN102803154A (en) * | 2009-06-29 | 2012-11-28 | 纳尔科公司 | Fluid Treatment Reactor |
| CN103011453A (en) * | 2012-12-08 | 2013-04-03 | 北京国环清华环境工程设计研究院有限公司 | Processing method for fluoride waste water in production of solar cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102803154A (en) * | 2009-06-29 | 2012-11-28 | 纳尔科公司 | Fluid Treatment Reactor |
| CN102803154B (en) * | 2009-06-29 | 2014-07-09 | 纳尔科公司 | Fluid Treatment Reactor |
| CN102728094A (en) * | 2011-03-31 | 2012-10-17 | 海法化学工业公司 | Crystallization apparatus |
| CN102728094B (en) * | 2011-03-31 | 2015-08-12 | 海法化学工业公司 | Crystallization apparatus |
| CN102249494A (en) * | 2011-06-23 | 2011-11-23 | 南京大学 | Method for improving activity of methanogens while reducing high-concentration ammonia nitrogen in anaerobic process |
| CN102249494B (en) * | 2011-06-23 | 2012-11-28 | 南京大学 | Method for improving activity of methanogens while reducing high-concentration ammonia nitrogen in anaerobic process |
| CN104024221A (en) * | 2011-12-28 | 2014-09-03 | 住友化学株式会社 | Method for producing high-quality epsilon-caprolactam |
| CN104024221B (en) * | 2011-12-28 | 2016-06-22 | 住友化学株式会社 | The manufacture method of high-quality epsilon-caprolactams |
| CN103011453A (en) * | 2012-12-08 | 2013-04-03 | 北京国环清华环境工程设计研究院有限公司 | Processing method for fluoride waste water in production of solar cells |
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