CN111484214A - Phosphorus recycling device and method - Google Patents
Phosphorus recycling device and method Download PDFInfo
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- CN111484214A CN111484214A CN202010493751.7A CN202010493751A CN111484214A CN 111484214 A CN111484214 A CN 111484214A CN 202010493751 A CN202010493751 A CN 202010493751A CN 111484214 A CN111484214 A CN 111484214A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000011574 phosphorus Substances 0.000 title claims abstract description 64
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 239000010802 sludge Substances 0.000 claims abstract description 157
- 208000005156 Dehydration Diseases 0.000 claims abstract description 28
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 28
- 230000018044 dehydration Effects 0.000 claims abstract description 26
- 230000007062 hydrolysis Effects 0.000 claims abstract description 25
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 25
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 23
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005185 salting out Methods 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 21
- 238000004062 sedimentation Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 239000010865 sewage Substances 0.000 claims description 14
- 230000000536 complexating effect Effects 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 238000001514 detection method Methods 0.000 claims description 11
- 230000020477 pH reduction Effects 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- -1 iron ions Chemical class 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 7
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 238000010668 complexation reaction Methods 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910001463 metal phosphate Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000002367 phosphate rock Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/08—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using sulfuric acid
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a phosphorus recycling device which comprises a sludge hydrolysis device, a dehydration treatment device, a complexation reaction device, a blow-off device and a precipitation crystallization device, wherein the sludge hydrolysis device is connected with the dehydration treatment device through a first sludge pump, the dehydration treatment device is connected with the complexation reaction device, the complexation reaction device is connected with the precipitation crystallization device through a second sludge pump, and the complexation reaction device is connected with a magnesium adding device. The phosphorus recycling device and method can efficiently recycle phosphorus from the concentrated sludge and remove heavy metals at the same time, and obtain the struvite product rich in phosphorus and capable of generating practical economic benefits.
Description
Technical Field
The invention relates to a phosphorus recycling device and method, and belongs to the field of phosphorus recycling.
Background
Phosphorus is an indispensable nutrient element for growth of animals and plants, and is almost a unidirectional cycle in nature. Phosphorus is also an irreplaceable raw material in many industrial fields. Only a few countries in the world have phosphorite which can be economically exploited and contains less pollutants, and phosphorus will become rare substances in the next decades. It is estimated that worldwide reserves of phosphate rock can only be maintained for about 100 years. Meanwhile, phosphorus is an important factor of water eutrophication, and threatens the water environment safety and the drinking water safety.
The advanced treatment process of sewage is adopted in most municipal sewage plants in China, and 90% of phosphorus enters sludge after the advanced treatment. The Chinese sewage treatment capacity reaches 1.78 billion cubic meters per day, and 5000 million tons of sludge with 80 percent of water content is produced every year. Therefore, phosphorus recovery from sludge is an important way to mitigate water pollution and phosphorus resource shortage. At present, the main process for phosphorus recovery is struvite (MAP chemical formula: MgNH)4PO4·6H2O), and the reclaimed struvite is a good slow-release fertilizer and can be applied to agricultural production. However, municipal sludge accumulates a lot of heavy metals and other harmful substances in the sewage treatment process, and the heavy metals are easy to form chelate bodies with organic matters, are included in phosphorus recovery products, are difficult to separate, are transferred in a food chain, and finally harm human health. In view of this, research on methods for efficiently recovering phosphorus from sludge and removing heavy metals has important application value for phosphorus recovery.
Disclosure of Invention
The invention aims to provide a phosphorus recycling device and a method, which can efficiently recycle phosphorus from sludge and remove heavy metals in the sludge.
In order to solve the technical problems, the invention adopts the following technical scheme: the utility model provides a phosphorus recycle device, includes sludge hydrolysis device, dehydration device, complex reaction device, blows and takes off the device and deposit the crystallization device, and sludge hydrolysis device is connected with dehydration device through first sludge pump, and dehydration device is connected with complex reaction device, and complex reaction device with deposit the crystallization device through second sludge pump and be connected, complex reaction device and magnesium add the device and be connected.
In the foregoing phosphorus recycling device, the sludge hydrolysis device includes a first reactor, a first stirrer disposed in the first reactor, and a ph value detector disposed in the first reactor, wherein a detection electrode of the ph value detector is disposed above a stirring paddle of the first stirrer, and a discharge outlet of the first reactor is connected to a first sludge pump. A detection electrode end of the pH value detector is arranged above a stirring paddle of the first stirrer so as to ensure the accuracy of measured data after full stirring.
In the phosphorus recycling device, the dehydration treatment device includes a dehydrator, and the dehydrator is connected to the first sludge pump.
In the phosphorus recycling device, the complex reaction device comprises a second reactor, a second stirrer arranged in the second reactor and a pH detector arranged in the second reactor, wherein a detection electrode end of the pH detector is positioned above a stirring blade of the second stirrer, and a feed inlet of the second reactor is connected with a discharge outlet of the dehydrator.
In the phosphorus recycling device, the blowing-off device comprises an air compressor and an aeration head arranged at the bottom of the second reactor, and the aeration head is connected with the air compressor.
In the foregoing phosphorus recycling apparatus, the precipitation crystallization apparatus includes a precipitation tank and a dewatering tank, the precipitation tank is connected to the second sludge pump, the dewatering tank is connected to the precipitation tank, and a supernatant discharge port is provided on the precipitation tank.
In the phosphorus recovery and utilization apparatus, a polymer adding device is provided in a pipe between the dehydrator and the first sludge pump.
In the phosphorus recycling device, the first stirrer is provided with a foam removing device.
The phosphorus recycling device further comprises a first acid adding device, wherein the first acid adding device is connected with the first reactor; the sludge conveying pipe is connected with a sludge inlet at the bottom of the first reactor; the device also comprises a second acid adding device, and the second acid adding device is connected with the second reactor.
A phosphorus recovery treatment method comprises the following steps: step SO1 hydrolysis acidification sludge;
adding concentrated sludge of a municipal sewage plant into a first reactor as raw sludge, simultaneously adding sulfuric acid, opening a first stirrer to fully mix the raw sludge with the sulfuric acid, and stopping adding the raw sludge and the sulfuric acid when the pH value measured by a pH value detector reaches 4; wherein the concentration of sulfuric acid is 98%.
Step S02: dehydrating and hydrolyzing the acidified sludge;
when the pH value measured by the pH value detector reaches 4, starting a first sludge pump, adding a polymer into a pipeline between the first sludge pump and a desliming machine, fully mixing sludge subjected to hydrolytic acidification with the polymer, and then dehydrating the sludge added with the polymer in a dehydrator to obtain sludge filtrate and solid sludge cakes; the dewatered sludge filtrate is taken as a reclaimed material to be continuously treated;
step S03: complexing the sludge filtrate;
introducing the sludge filtrate as a reclaimed material into a second reactor, adding 50% citric acid, continuously stirring by a second stirrer, and reacting for 15-30 minutes after adding the citric acid to form a complex; the stoichiometric ratio of the amount of the added citric acid with the concentration of 50 percent to the sum of the metal ions contained in the sludge filtrate is 1: 1; the metal ions contained in the sludge filtrate are iron ions, aluminum ions, calcium ions and magnesium ions;
step S04: adding solid magnesium oxide into the sludge filtrate after the complexing treatment
After the complexing treatment, adding solid magnesium oxide powder into a second reactor; the stoichiometric ratio of magnesium to phosphorus is 1.5: 1; the dissolving time after adding the solid magnesium oxide powder is 30-60 minutes to obtain complex mixed liquor;
step S05: blowing-off treatment of complex mixed liquor
Adding compressed air at the bottom of the second reactor, blowing off carbon dioxide from the complex mixed solution to ensure that the pH value of the complex mixed solution is 8, and reacting in an alkaline environment: mg (magnesium)2++NH4 ++HPO4 2-+6H2O＝MgNH4PO4·6H2O+H+Reacting and crystallizing to generate small crystal struvite;
step S06: obtaining a recovered product;
after the pH value of the complex mixed liquid is determined to be 8 by the pH detector and the complex mixed liquid is stable, the complex mixed liquid is introduced into the sedimentation tank by the second sludge pump, the complex mixed liquid in the sedimentation tank continuously reacts and crystallizes for 1-2 hours, the small crystal struvite in the complex mixed liquid continuously forms large crystal struvite, then precipitate is obtained, the precipitate is led out to the dewatering box from the bottom of the sedimentation tank, the dewatering box is placed in the air statically, the precipitate in the dewatering box is dried, and a gray powder struvite product is obtained after the drying treatment is finished. The supernatant obtained by the sedimentation tank in the method of the invention is returned to the municipal sewage plant for utilization.
Compared with the prior art, the method has the advantages that the sludge hydrolysis device is used for hydrolyzing the concentrated sludge, the dehydration device is used for dehydrating the sludge after hydrolysis and acidification, the complex reaction device is used for carrying out complex reaction on phosphate ions in the obtained sludge filtrate and metal ions contained in the phosphate ions, the blowing-off device is used for obtaining acidic complex mixed liquid, and the precipitation crystallization device is used for finally obtaining a recovered struvite product; the phosphorus recycling device and the method can efficiently recycle phosphorus from the concentrated sludge and remove heavy metals, and the phosphorus recovery rate by using the method is more than 50 percent (relative to the total phosphorus content in the concentrated sludge of the municipal sewage plant); the phosphorus-rich struvite product is finally obtained by using the phosphorus recycling device and the method, heavy metals in the concentrated sludge can be effectively removed, and the struvite product capable of generating practical economic benefits can be obtained.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural diagram of an embodiment of the present invention.
Reference numerals: 1-sludge hydrolysis device, 101-first reactor, 102-first stirrer, 103-pH value detector, 2-dehydration treatment device, 201-dehydrator, 3-complex reaction device, 301-second reactor, 302-second stirrer, 303-pH detector, 4-magnesium adding device, 5-blowing device, 501-air compressor, 502-aeration head, 6-precipitation crystallization device, 601-sedimentation tank, 602-dehydration tank, 7-first sludge pump, 8-second sludge pump, 9-polymer adding device, 10-first acidification device, 11-sludge conveying pipe and 12-second acidification device.
The invention is further described with reference to the following figures and detailed description.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1 of the invention: the utility model provides a phosphorus recycle device, includes sludge hydrolysis device 1, dehydration treatment device 2, complex reaction device 3, blows and takes off device 5 and deposit crystallization device 6, sludge hydrolysis device 1 is connected with dehydration treatment device 2 through first sludge pump 7, dehydration treatment device 2 is connected with complex reaction device 3, complex reaction device 3 with through second sludge pump 8 with deposit crystallization device 6 and be connected, complex reaction device 3 adds 4 with magnesium and is connected.
Example 2 of the invention: the utility model provides a phosphorus recycle device, includes sludge hydrolysis device 1, dehydration treatment device 2, complex reaction device 3, blows and takes off device 5 and deposit crystallization device 6, sludge hydrolysis device 1 is connected with dehydration treatment device 2 through first sludge pump 7, dehydration treatment device 2 is connected with complex reaction device 3, complex reaction device 3 with through second sludge pump 8 with deposit crystallization device 6 and be connected, complex reaction device 3 adds 4 with magnesium and is connected. The sludge hydrolysis device 1 comprises a first reactor 101, a first stirrer 102 arranged in the first reactor 101 and a pH value detector 103 arranged in the first reactor 101, wherein a detection electrode end of the pH value detector 103 is positioned above a stirring paddle of the first stirrer 102, and a discharge outlet of the first reactor 101 is connected with a first sludge pump 7. A detection electrode end of the pH value detector is arranged above a stirring paddle of the first stirrer so as to ensure the accuracy of measured data after full stirring. Specifically, the dehydration treatment apparatus 2 includes a dehydrator 201, and the dehydrator 201 is connected to the first sludge pump 7. Specifically, the complex reaction device 3 includes a second reactor 301, a second stirrer 302 arranged in the second reactor 301, and a pH detector 303 arranged in the second reactor 301, wherein a detection electrode end of the pH detector 303 is positioned above a stirring blade of the second stirrer 302, and a feed inlet of the second reactor 301 is connected with a discharge outlet of the dehydrator 201.
Example 3 of the invention: the utility model provides a phosphorus recycle device, includes sludge hydrolysis device 1, dehydration treatment device 2, complex reaction device 3, blows and takes off device 5 and deposit crystallization device 6, sludge hydrolysis device 1 is connected with dehydration treatment device 2 through first sludge pump 7, dehydration treatment device 2 is connected with complex reaction device 3, complex reaction device 3 with through second sludge pump 8 with deposit crystallization device 6 and be connected, complex reaction device 3 adds 4 with magnesium and is connected. The sludge hydrolysis device 1 comprises a first reactor 101, a first stirrer 102 arranged in the first reactor 101 and a pH value detector 103 arranged in the first reactor 101, wherein a detection electrode end of the pH value detector 103 is positioned above a stirring paddle of the first stirrer 102, and a discharge outlet of the first reactor 101 is connected with a first sludge pump 7. A detection electrode end of the pH value detector is arranged above a stirring paddle of the first stirrer so as to ensure the accuracy of measured data after full stirring. Specifically, the dehydration treatment apparatus 2 includes a dehydrator 201, and the dehydrator 201 is connected to the first sludge pump 7. Specifically, the complex reaction device 3 includes a second reactor 301, a second stirrer 302 arranged in the second reactor 301, and a pH detector 303 arranged in the second reactor 301, wherein a detection electrode end of the pH detector 303 is positioned above a stirring blade of the second stirrer 302, and a feed inlet of the second reactor 301 is connected with a discharge outlet of the dehydrator 201. Specifically, the air stripping device 5 comprises an air compressor 501 and an aeration head 502 arranged at the bottom of the second reactor 301, and the aeration head 502 is connected with the air compressor 501. Specifically, the precipitation crystallization device 6 comprises a precipitation tank 601 and a dewatering tank 602, wherein the precipitation tank 601 is connected with the second sludge pump 8, the dewatering tank 602 is connected with the precipitation tank 601, and a supernatant discharge port is arranged on the precipitation tank 601. Further, a polymer adding device 9 is provided on a pipe between the dehydrator 201 and the first sludge pump 7. Further, a foam removing device is arranged on the first stirrer 102; the phosphorus recycling device also comprises a first acid adding device 10 connected with the first reactor 101, a sludge conveying pipe 11 connected with a sludge inlet at the bottom of the first reactor 101, and a second acid adding device 12 connected with the second reactor 301, wherein sulfuric acid is added into the first reactor 101 through the first acid adding device 10, and citric acid is added into the second reactor 301 through the second acid adding device 12.
The working process of the phosphorus recycling device comprises the following steps: concentrated sludge treated by a municipal sewage plant is conveyed into a first reactor 101 of a sludge hydrolysis device 1, sulfuric acid with the concentration of 98% is added into the first reactor 101, the sludge and the sulfuric acid added into the first reactor 101 at the same time are fully stirred by a first stirrer 102, metal phosphate in the sludge is redissolved into phosphate and metal ions by the added sulfuric acid, and the phosphate treated at the redissolution and the phosphate existing in the sludge can be used as raw materials for producing the bird droppings. In the process of hydrolyzing and acidifying sludge, a pH value detector 103 arranged in a first reactor 101 is used for detecting the pH value of a mixture of concentrated sludge and sulfuric acid in real time, when the pH value detected by the pH value detector is 4, a first sludge pump 7 is started, the sludge after hydrolysis and acidification enters a dehydrator 201 through the first sludge pump 7, the sludge added with polymers is dehydrated through the dehydrator 201 to obtain sludge filtrate and solid sludge cakes containing heavy metals, so that the aim of removing the heavy metals is fulfilled, the sludge filtrate obtained through dehydration treatment of the dehydrator 201 is conveyed into a second reactor 301, citric acid with the concentration of 50 percent is added into the second reactor 301, the sludge filtrate and the citric acid are fully stirred through a second stirrer 302 arranged in the second reactor 301, and metal ions (mainly iron ions, iron, Aluminum ions, calcium ions and magnesium ions) to form a complex, so as to prevent the metal ions from regenerating metal phosphate when the pH value is subsequently increased. Complexation reaction 1Adding solid magnesium oxide powder into the second reactor 301 after 5-30 minutes to ensure that enough magnesium ions can react with ammonium ions in the sludge filtrate, after adding the solid magnesium oxide for 30-60 minutes and ensuring that the solid magnesium oxide is fully dissolved, introducing compressed air into the second reactor 301 by using an air compressor 501, improving the pH value of the complex mixed solution in a blowing-off manner, detecting the pH value of the complex mixed solution in the second reactor 301 by using a pH detector 303, and starting to react Mg when the pH value displayed by the pH detector 303 is 72++NH4 ++HPO4 2-+6H2O＝MgNH4PO4·6H2O+H+Thereby, small crystal struvite begins to be generated, when the pH value detected by the pH detector 303 is 8 and reaches a stable value, the second sludge pump 8 is started, the complexing mixed liquid is conveyed into the sedimentation tank 601 through the second sludge pump 8, and Mg is contained in the sedimentation tank 6012++NH4 ++HPO4 2-+6H2O＝MgNH4PO4·6H2O+H+And (3) continuously reacting for 1-2 hours, crystallizing the small-crystal struvite into large-crystal struvite to obtain a precipitate, allowing the precipitate to come out of the bottom of the sedimentation tank 601 and then enter a dewatering box 602, and performing drying treatment in the dewatering box 602 to finally obtain a phosphorus-rich gray powder struvite product.
Example 4 of the invention: a phosphorus recovery treatment method comprises the following steps:
step SO1 hydrolysis acidification sludge;
adding concentrated sludge of a municipal sewage plant into a first reactor as raw sludge, simultaneously adding sulfuric acid, opening a first stirrer to fully mix the raw sludge with the sulfuric acid, and stopping adding the raw sludge and the sulfuric acid when the pH value measured by a pH value detector reaches 4; wherein the concentration of sulfuric acid is 98%. The amount of phosphate that can be redissolved by adding sulfuric acid depends on the pH value achieved and the types of iron and aluminum salts of the phosphorus removal agent used for chemical phosphorus removal in sewage plants. More metal phosphate will dissolve out as the pH is lowered, but too low a pH means increased chemical input and the sludge will become more difficult to dewater. Therefore, the pH value reached by adding acid was set to 4 in consideration of the recovery rate and the economic efficiency. The addition of acid produces strong foam, and in order to avoid an increase in the running time due to waiting for the foam to be eliminated, it is necessary to add sulfuric acid simultaneously with the addition of raw sludge to the first reactor.
Step S02: dehydrating and hydrolyzing the acidified sludge;
when the pH value measured by the pH value detector reaches 4, starting a first sludge pump, adding a polymer into a pipeline between the first sludge pump and a desliming machine, fully mixing sludge subjected to hydrolytic acidification with the polymer, and then dehydrating the sludge added with the polymer in a dehydrator to obtain sludge filtrate and solid sludge cakes; the dewatered sludge filtrate is taken as a reclaimed material to be continuously treated; because the pH value of the sludge is lower after the acid is added, the sludge is difficult to dehydrate, and a plate-and-frame filter press made of plastic materials can be used for dehydration. The solid sludge cake after dehydration by the dehydrator contains a lot of heavy metal substances. Therefore, the important function of the step can also remove a plurality of heavy metal substances such as cadmium, chromium, lead, copper, zinc and uranium in the sludge, and most of the heavy metal substances such as cadmium, chromium, lead, copper, zinc and uranium are removed from the whole process along with the solid sludge cake, wherein the content of the heavy metal substances is more than 95 percent. And the content of heavy metals in the obtained sludge filtrate is very low.
Step S03: complexing the sludge filtrate;
introducing the sludge filtrate as a reclaimed material into a second reactor, adding 50% citric acid, continuously stirring by a second stirrer, and reacting for 15-30 minutes after adding the citric acid to form a complex; the stoichiometric ratio of the amount of the added citric acid with the concentration of 50 percent to the sum of the metal ions contained in the sludge filtrate is 1: 1; the metal ions contained in the sludge filtrate are iron ions, aluminum ions, calcium ions and magnesium ions; the sludge filtrate obtained after hydrolysis and acidification contains not only phosphate ions, but also metal ions mainly including Fe, Al, Ca and Mg. The citric acid is added to form a complex reaction, and the complex reaction is complexed with other metal ions to form a complex, so that the metal ions are prevented from generating metal phosphate again when the pH value is increased subsequently. The amount of citric acid added depends on the amount of metal ions contained in the sludge filtrate, and generally the stoichiometric ratio of the amount of citric acid to the sum of the metals Fe, Al, Ca, Mg is 1: 1.
Step S04: adding solid magnesium oxide into the sludge filtrate after the complexing treatment;
after the complexing treatment, adding solid magnesium oxide powder into a second reactor; the stoichiometric ratio of the amount of magnesium to phosphorus is 1.5: 1; the dissolving time after adding the solid magnesium oxide powder is 30-60 minutes to obtain complex mixed liquor; enough ammonium ions are already in sludge of municipal sewage plants, and enough magnesium ions need to be added for generating MAP, in the method, enough magnesium ions are added by adding solid magnesium oxide MgO, the adding amount of the solid magnesium oxide depends on the content of phosphorus in sludge filtrate as a reclaimed material, the stoichiometric ratio of the amount of magnesium to the amount of phosphorus can be 1.5:1, and the adding of solid magnesium oxide powder needs to be carried out in an acid environment to ensure sufficient dissolving effect.
Step S05: blowing off the complex mixed solution;
adding compressed air at the bottom of the second reactor, blowing off carbon dioxide from the complex mixed solution to ensure that the pH value of the complex mixed solution is 8, and reacting in an alkaline environment: mg (magnesium)2++NH4 ++HPO4 2-+6H2O＝MgNH4PO4·6H2O+H+Reacting and crystallizing to generate small crystal struvite; the carbon dioxide is blown off from the complexing mixed liquor by the added compressed air, and the pH value of the complexing mixed liquor is increased. The crystallization reaction of struvite MAP is about to start at pH 7, large crystals are gradually formed from the starting small crystals, and the large crystals are easily precipitated.
Step S06: obtaining a recovered product;
after the pH value of the complex mixed liquid is determined to be 8 by the pH detector and the complex mixed liquid is stable, the complex mixed liquid is introduced into the sedimentation tank by the second sludge pump, the complex mixed liquid in the sedimentation tank continuously reacts and crystallizes for 1-2 hours, the small crystal struvite in the complex mixed liquid continuously forms large crystal struvite, then precipitate is obtained, the precipitate is led out to the dewatering box from the bottom of the sedimentation tank, the dewatering box is placed in the air statically, the precipitate in the dewatering box is dried, and a gray powder struvite product is obtained after the drying treatment is finished.
The supernatant obtained by the sedimentation tank in the method of the invention is returned to the municipal sewage plant for utilization. The recovery rate of phosphorus in the concentrated sludge treated by the device and the method is more than 50 percent, and the recovery rate is relative to the total phosphorus content in the concentrated sludge of the municipal sewage plant.
Claims (10)
1. The utility model provides a phosphorus recycle device, its characterized in that, includes sludge hydrolysis device (1), dehydration device (2), complex reaction device (3), blows off device (5) and deposits crystallization device (6), sludge hydrolysis device (1) is connected with dehydration device (2) through first sludge pump (7), dehydration device (2) are connected with complex reaction device (3), complex reaction device (3) with through second sludge pump (8) with deposit crystallization device (6) be connected, complex reaction device (3) add device (4) with magnesium and be connected.
2. The phosphorus recycling device according to claim 1, wherein the sludge hydrolysis device (1) comprises a first reactor (101), a first stirrer (102) arranged in the first reactor (101), and a pH value detector (103) arranged in the first reactor (101), wherein a detection electrode end of the pH value detector (103) is positioned above a stirring paddle of the first stirrer (102), and a discharge port of the first reactor (101) is connected with a first sludge pump (7).
3. The phosphorus recovery apparatus according to claim 2, wherein the dehydration treatment apparatus (2) comprises a dehydrator (201), and the dehydrator (201) is connected to the first sludge pump (7).
4. The phosphorus recycling device according to claim 3, wherein the complexing reaction device (3) comprises a second reactor (301), a second stirrer (302) arranged in the second reactor (301), and a pH detector (303) arranged in the second reactor (301), wherein a detection electrode end of the pH detector (303) is positioned above a stirring blade of the second stirrer (302), and a feeding hole of the second reactor (301) is connected with a discharging hole of the dehydrator (201); a polymer adding device (9) is arranged on a pipeline between the dehydrator (201) and the first sludge pump (7).
5. The phosphorus recycling device of claim 4, wherein the blowing-off device (5) comprises an air compressor (501) and an aeration head (502) arranged at the bottom of the second reactor (301), and the aeration head (502) is connected with the air compressor (501).
6. The phosphorus recycling device according to claim 5, wherein the precipitation crystallization device (6) comprises a sedimentation tank (601) and a dewatering tank (602), the sedimentation tank (601) is connected with the second sludge pump (8), the dewatering tank (602) is connected with the sedimentation tank (601), and a supernatant discharge port is arranged on the sedimentation tank (601).
7. A phosphorus recycling apparatus according to claim 6, further comprising a first acid adding device (10), wherein said first acid adding device (10) is connected to the first reactor (101); the system also comprises a sludge conveying pipe (11), wherein the sludge conveying pipe (11) is connected with a sludge inlet at the bottom of the first reactor (101); the device also comprises a second acid adding device (12), wherein the second acid adding device (12) is connected with the second reactor (301).
8. A phosphorus recovery and utilization apparatus according to claim 6, wherein the first stirrer (102) is provided with a foam removing device.
9. The method for recycling phosphorus of the phosphorus recycling apparatus according to any one of claims 1 to 7, comprising the steps of:
step SO1 hydrolysis acidification sludge;
adding concentrated sludge of a municipal sewage plant into a first reactor as raw sludge, simultaneously adding sulfuric acid, opening a first stirrer to fully mix the raw sludge with the sulfuric acid, and stopping adding the raw sludge and the sulfuric acid when the pH value measured by a pH value detector reaches 4;
step S02: dewatering and hydrolyzing the acidified sludge:
when the pH value measured by the pH value detector reaches 4, starting a first sludge pump, adding a polymer into a pipeline between the first sludge pump and a desliming machine, fully mixing sludge subjected to hydrolytic acidification with the polymer, and then dehydrating the sludge added with the polymer in a dehydrator to obtain sludge filtrate and solid sludge cakes; the dewatered sludge filtrate is taken as a reclaimed material to be continuously treated;
step S03: complexing sludge filtrate
Introducing the sludge filtrate as a reclaimed material into a second reactor, adding 50% citric acid, continuously stirring by a second stirrer, and reacting for 15-30 minutes after adding the citric acid to form a complex; the stoichiometric ratio of the amount of the added citric acid with the concentration of 50 percent to the sum of the metal ions contained in the sludge filtrate is 1: 1; the metal ions contained in the sludge filtrate are iron ions, aluminum ions, calcium ions and magnesium ions;
step S04: adding solid magnesium oxide into the sludge filtrate after the complexing treatment
After the complexing treatment, adding solid magnesium oxide powder into a second reactor; the stoichiometric ratio of magnesium to phosphorus is 1.5: 1; the dissolving time after adding the solid magnesium oxide powder is 30-60 minutes to obtain complex mixed liquor;
step S05: blowing-off treatment of complex mixed liquor
Adding compressed air at the bottom of the second reactor, blowing off carbon dioxide from the complex mixed solution to ensure that the pH value of the complex mixed solution is 8, and reacting in an alkaline environment: mg (magnesium)2++NH4 ++HPO4 2-+6H2O＝MgNH4PO4·6H2O+H+Reacting and crystallizing to generate small crystal struvite;
step S06: obtaining a recovered product;
after the pH value of the complex mixed liquid is determined to be 8 by the pH detector and the complex mixed liquid is stable, the complex mixed liquid is introduced into the sedimentation tank by the second sludge pump, the complex mixed liquid in the sedimentation tank continuously reacts and crystallizes for 1-2 hours, the small crystal struvite in the complex mixed liquid continuously forms large crystal struvite, then precipitate is obtained, the precipitate is led out to the dewatering box from the bottom of the sedimentation tank, the dewatering box is placed in the air statically, the precipitate in the dewatering box is dried, and a gray powder struvite product is obtained after the drying treatment is finished.
10. The phosphorus recovery and utilization method of claim 6, wherein the concentration of sulfuric acid is 98%.
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