CN108395061A - Phosphorus recovery system in phosphorous biomass based on supercritical oxidation technology and method - Google Patents

Phosphorus recovery system in phosphorous biomass based on supercritical oxidation technology and method Download PDF

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Publication number
CN108395061A
CN108395061A CN201810448260.3A CN201810448260A CN108395061A CN 108395061 A CN108395061 A CN 108395061A CN 201810448260 A CN201810448260 A CN 201810448260A CN 108395061 A CN108395061 A CN 108395061A
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phosphorous
phosphorus
supercritical oxidation
dephosphorization agent
unit
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CN108395061B (en
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王树众
雷杰
徐甜甜
杨闯
宋文瀚
李建娜
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Li Li (suzhou) Environmental Protection Technology Co Ltd
Xian Jiaotong University
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Li Li (suzhou) Environmental Protection Technology Co Ltd
Xian Jiaotong University
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • 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
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular 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
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses the phosphorus recovery systems and method in a kind of phosphorous biomass based on supercritical oxidation technology, and the system comprises supercritical oxidation unit, ammonia still process unit, phosphorus recovery unit, biological processing unit, MVR evaporation elements.The present invention takes full advantage of supercritical oxidation technology and discharges the phosphorus in phosphorous biomass in the liquid phase in the form of phosphate from biomass to greatest extent；Phosphate in liquid phase, by adding dephosphorization agent, realizes that phosphorus recycles in phosphorus recovery system in the form of calcium phosphate precipitation；Inclined-tube sedimentation tank, which is equipped with deflector, realizes fluid flow fields optimization in association control precipitation, enhances separating effect of the phosphorous precipitation with water；Inclined-tube sedimentation tank is equipped with assistant sludge discharge device, avoid it is phosphorous be deposited in inclined-tube sedimentation tank due to arranging defeated unsmooth accumulation；Using biomass phosphorus as phosphorus source, the recycling phosphate of maximum conversion rate, the recycling of phosphorus opens up new way in this biomass, to promoting the sustainable use of phosphor resource to have very important significance.

Description

Phosphorus recovery system in phosphorous biomass based on supercritical oxidation technology and method
Technical field
The invention belongs to chemical industry and environmental technology fields, and in particular to a kind of phosphorous biology based on supercritical oxidation technology Phosphorus recovery system in matter and method.
Background technology
Supercritical Water Oxidation Technology is possessed under supercriticality (Tc=374 DEG C, Pc=22.1MPa) based on water Special nature makes organic matter and oxidant be completely dissolved in supercritical water, and homogeneous oxidizing reaction occurs rapidly, rapid, thorough Phosphatic form is converted to by the process of oxidation operation, while by organophosphor.
Phosphorus is the indispensable element of the various biological life activities of nature, to energy as a kind of non-renewable resources The synthesis of the phosphorous matrix such as the transmission and storage of amount, protein also plays critical effect.Current whole world rock phosphate in powder is only about It can use 100 years or so, and the demand of phosphorus increases increasingly with the development of mankind's industrial or agricultural, while phosphorus is typically to deposit Property endless form recycled in the ecosystem, phosphatic form is deposited in water body last part, formed bed mud, phosphorus The imbalance between supply and demand that will more aggravate of this One Direction Transfer mode, the limiting factor of the following various vital movements will be become.
It is less about the technique for extracting phosphorus from biomass at present, while based on the conversion ratio of phosphorus in other technique biomass It is not high, while organic matter material content is higher in liquid phase, the phosphorus product purity after recycling is not high enough, and resource utilization efficiency is low.
Therefore, it is highly desirable to develop a kind of phosphorous biology based on supercritical oxidation technology using biomass phosphorus as phosphorus source Phosphorus recovery system in matter.
Invention content
It is an object of the invention to overcome the above-mentioned prior art, a kind of containing based on supercritical oxidation technology is provided Phosphorus recovery system in phosphorus biomass and method reduce dephosphorization system dephosphorization agent, lye adds；Improve UTILIZATION OF VESIDUAL HEAT IN effect Rate reduces MVR vapo(u)rization system energy inputs, realizes and is utilized by the biomass phosphor resourceization of core of supercritical technology；This life The recycling of phosphorus opens up new way in substance, to promoting the sustainable use of phosphor resource to have very important significance.
In order to achieve the above objectives, the present invention is achieved by the following scheme：
A kind of phosphorus recovery system in phosphorous biomass based on supercritical oxidation technology, including supercritical oxidation unit, Ammonia still process unit, phosphorus recovery unit, biological processing unit and MVR evaporation elements；Phosphorous biomass enter supercritical oxidation unit into Row oxidation；The supercritical oxidation water outlet of supercritical oxidation unit enters phosphorus recovery unit through ammonia still process unit, and afterheat steam inputs MVR Evaporation element is as heat source of supply；After phosphorus recovery unit is discharged progress dephosphorization and flocculation treatment to supercritical oxidation, on Clear liquid discharges after entering biochemical treatment unit reprocessing, and the sediment of generation enters sludge pump, and a sediment part is back to phosphorus Recovery unit, another part form solid powder by MVR evaporation element evaporative crystallizations.
The present invention, which further improves, to be：
Phosphorus recovery unit include regulating reservoir, dephosphorization agent mixing pit, dephosphorization agent reaction tank, flocculant concentration reaction tank, help it is solidifying Agent adds reaction tank, adding of agent system and inclined-tube sedimentation tank；
The entrance of regulating reservoir is connected with the outlet of ammonia still process unit, and outlet is connected with the entrance of dephosphorization agent mixing pit, removes Phosphorus agent mixing pit is connected with the top of dephosphorization agent reaction tank, and dephosphorization agent reaction tank is connected with the bottom of flocculant concentration reaction tank Logical, the top that flocculant concentration reaction tank adds reaction tank with flocculation aid is connected；Dephosphorization agent mixing pit and three reaction tanks are equal It is provided with corresponding agitating device and dosing mouth；Flocculation aid adds the outlet of reaction tank and is connected with the entrance of inclined-tube sedimentation tank, The outlet at bottom of inclined-tube sedimentation tank is connected with sludge pump, and top is connected by effluent weir with biochemical treatment unit.
A part of sediment blowback dephosphorization agent reaction tank, another part are pumped into MVR evaporation elements by sludge pump.
It is equipped with deflector along pool wall in the middle part of inclined-tube sedimentation tank pool wall, bottom is equipped with assistant sludge discharge device.
Flowmeter, inclined-tube sedimentation tank and biochemical treatment unit are provided on pipeline between regulating reservoir and dephosphorization agent mixing pit Between pipeline be equipped with phosphorus on-line detector.
Adding of agent system includes dephosphorization agent quantitative feeder, flocculant storage tank and flocculation aid storage tank；Dephosphorization agent is quantitative Throwing device is connected with dephosphorization agent mixing pit, and flocculant storage tank is anti-by flocculant concentration frequency conversion metering pump and flocculant concentration Ying Chi is connected, and flocculation aid storage tank, which by flocculation aid adds frequency conversion metering pump and adds reaction tank with flocculation aid, to be connected；Dephosphorization agent Quantitative feeder is associated with flowmeter；Flocculant concentration frequency conversion metering pump is associated with flowmeter；Flocculation aid adds Frequency conversion metering pump is associated with flowmeter.
Flocculant in flocculant storage tank is 4-10%PFC solution, dosage 100-200ppm；In flocculation aid storage tank Flocculation aid is 0.1-0.4%PAM solution, dosage 10-20ppm.
The inlet flow-patterm of phosphorus recovery unit is 10-11, and temperature is 35 ± 5 DEG C.
A kind of phosphorus recovery method in the phosphorous biomass based on supercritical oxidation technology of phosphorus recovery system, including it is following Step：
1) oxidation operation is CO by supercritical oxidation unit by phosphorous biomass2, organophosphor switchs to
2) supercritical oxidation water outlet is input to ammonia still process unit by supercritical oxidation unit, is generated afterheat steam and is evaporated for MVR Unit inputs institute's calorific requirement；
3) the supercritical oxidation water outlet after ammonia still process cell processing enters regulating reservoir, and gravity flow later enters dephosphorization agent and mixes Pond is mixed with the dephosphorization agent quantitatively added from dephosphorization agent dry powder at the top of dephosphorization agent mixing pit, using being arranged at middle part Agitating device is tentatively mixed；The water outlet of dephosphorization agent mixing pit into dephosphorization agent reaction tank, flocculant concentration reaction tank and helps successively Solidifying agent adds reaction tank, is stirred using agitating device in the middle part of pond body, and phosphate generates phosphorus with dephosphorization agent by reaction in water Hydrochlorate precipitates, and sediment is formed by the mixing coagulating sedimentation of flocculant, flocculation aid；Subsequently into the water inlet of inclined-tube sedimentation tank Pipe, the precipitation of hydroxyapatite object for reacting generation sink to inclined-tube sedimentation tank lower part, are entered by sludge pipe under the effect of gravity Sludge pump, the reflux of portion phosphate precipitation pass through MVR evaporation element evaporative crystallizations in dephosphorization agent mixing pit, portion phosphate precipitation Form phosphorous solid product；Supernatant in inclined-tube sedimentation tank enters biochemical treatment list by overfalling weir, outlet pipe and connecting tube Outer row after member reprocessing.
In step 2), the pH value of supercritical oxidation water outlet is adjusted to 10.5-11, while the temperature that supercritical oxidation is discharged Ammonia still process unit is inputted after being down to 80-90 DEG C.
Compared with prior art, the invention has the advantages that：
The present invention is based on the phosphorus recovery systems in the phosphorous biomass of supercritical oxidation technology, take full advantage of overcritical oxygen Change technology discharges the phosphorus in biomass in the liquid phase in the form of phosphate；Phosphate in liquid phase leads in phosphorus recovery system It crosses and adds dephosphorization agent, realize that phosphorus recycles in the form of calcium phosphate precipitation, waste water enters biochemical unit realization waste water after phosphorus recycling Qualified discharge；It is thorough to organic matter degradation under certain operating mode to phosphorous biomass that this system combines supercritical oxidation system Bottom, organophosphor are fully released to the characteristic of liquid phase, realize using biomass phosphorus as phosphorus source, the recycling phosphate of maximum conversion rate, tool There are good environmental benefit and economic benefit；
Further, the present invention is steamed using the steam that the UTILIZATION OF VESIDUAL HEAT IN unit of supercritical water oxidation system generates towards MVR Bill member is dried crystallization to phosphate, reduces the energy input and operating cost of MVR evaporation elements；
Further, dephosphorization agent mixing pit up-conversion dephosphorization agent quantitative feeder of the present invention is associated with flowmeter； Flocculant concentration frequency conversion metering pump is associated with flowmeter；Flocculation aid adds frequency conversion metering pump and is associated with flowmeter；Most The automation for realizing phosphorus recovery unit of big conversion ratio；
Further, inclined-tube sedimentation tank portion phosphate of the present invention precipitation by spoil disposal pump reflux in dephosphorization agent reaction tank, Reduce Dephosphorization reagent dosage, while conducive to the formation of calcium phosphate precipitation；
Further, prolong pool wall in the middle part of inclined-tube sedimentation tank pool wall of the present invention and be equipped with deflector, can control inclined-tube sedimentation tank stream Body flow field, calcium phosphate precipitation is the same as the bad phenomenon of the separating effect of water caused by preventing the short stream of fluid；Bottom is equipped with auxiliary sludge discharging Device prevents phosphate sludge due to the unsmooth accumulation in inclined-tube sedimentation tank of spoil disposal, it is ensured that inclined-tube sedimentation tank calcium phosphate precipitation is same Water good separation；
Further, dephosphorization unit inlet flow-patterm of the present invention is 10-11, and temperature is 35 ± 5 DEG C；Flocculant is 4-10%PFC Solution, dosage 100-200ppm；Flocculation aid 0.1-0.4%PAM solution, dosage 10-20ppm；Ammonia steaming system is discharged PH is 10.5-11, and chemical phosphorus removal system, which is not required to increase, throws lye maintenance optimum response pH, and phosphate forms hydroxyl with calcium ion in water Apatite has rapid reaction, generates the small stabilization of precipitation solubility product, closely knit, free settling；Take full advantage of supercritical oxidation system System, ammonia steaming system, dephosphorization system are discharged and the optimum response pH operating modes of each unit, improves reaction efficiency, and lye utilizes effect Rate, reduce ammonia steaming system, chemical phosphorus removal system operating cost.
Description of the drawings
Fig. 1 is the overall structure diagram of present system；
Wherein, 1- supercritical oxidations unit；2- ammonia still process units；3- regulating reservoirs；4- flowmeters；5- dephosphorization agent mixing pits；6- Dephosphorization agent reaction tank；7- flocculant concentration reaction tanks；8- flocculation aids add reaction tank；9- calcium phosphate precipitation return valves；10- phosphoric acid Salt precipitates dump valve；11- sludge pumps；12- inclined-tube sedimentation tanks；13-MVR evaporation elements；14- assistant sludge discharge devices；15- water conservancy diversion Plate；16- phosphorus on-line detectors；17- biological processing units；18- dephosphorization agent quantitative feeders；19- flocculant storage tanks；20- wads a quilt with cotton Solidifying agent adds frequency conversion metering pump；21- flocculation aid storage tanks；22- flocculation aids add frequency conversion metering pump.
Specific implementation mode
The present invention is described in further detail below in conjunction with the accompanying drawings：
Referring to Fig. 1, the present invention is based on the phosphorus recovery system in the phosphorous biomass of supercritical oxidation technology, including it is overcritical Oxidation unit 1, ammonia still process unit 2, phosphorus recovery unit, biological processing unit 17, MVR evaporation elements 13.
Phosphorus recovery unit include regulating reservoir 3, dephosphorization agent mixing pit 5, dephosphorization agent reaction tank 6, flocculant concentration reaction tank 7, Flocculation aid adds reaction tank 8, inclined-tube sedimentation tank 12, medicament addition device and MVR evaporation elements 13；Dephosphorization agent mixing pit 5, dephosphorization Agent reaction tank 6, flocculant concentration reaction tank 7, flocculation aid add reaction tank 8 and contain inlet and outlet channel, agitating device and dosing mouth； Dephosphorization agent mixing pit 5 also contains dephosphorization agent quantitative feeder 18；Inclined-tube sedimentation tank 12 containing water inlet cloth water flow passage, effluent weir, Inclined tube filler, sludge pump 11, including deflector 15 and assistant sludge discharge device 14；It is set on regulating reservoir 3 to 5 pipeline of dephosphorization agent mixing pit There is flowmeter 4；Inclined-tube sedimentation tank outlet conduit is equipped with phosphorus on-line detector 16；Adding of agent system include flocculant storage tank 19, Flocculant concentration frequency conversion metering pump 20, flocculation aid storage tank 21, flocculation aid add frequency conversion metering pump 22.
5 up-conversion dephosphorization agent quantitative feeder 18 of dephosphorization agent mixing pit is associated with flowmeter 4；Flocculant concentration becomes Frequency metering pump 20 is associated with flowmeter 4；Flocculation aid adds frequency conversion metering pump 22 and is associated with flowmeter 4；Dephosphorization unit Inlet flow-patterm is 10-11, and temperature is 35 ± 5 DEG C.
A part of calcium phosphate precipitation is flowed back by sludge pump 11 in dephosphorization agent reaction tank 6 in inclined-tube sedimentation tank 12；Another portion Calcium phosphate precipitation is divided to pass through the conveying of sludge pump 11 and MVR evaporation elements 13；MVR institute's calorific requirements are provided by 1 waste heat of overcritical unit； Prolong pool wall in the middle part of 12 pool wall of inclined-tube sedimentation tank and be equipped with deflector 15, bottom is equipped with assistant sludge discharge device 14.
The invention also discloses the phosphorus recovery methods in a kind of phosphorous biomass based on supercritical oxidation technology, including with Lower step：
1) oxidation operation is CO by supercritical oxidation unit by phosphorous biomass2, organophosphor switchs to
2) supercritical oxidation water outlet pH is 10.5-11, and water outlet is down to 30-35 DEG C via temperature after heat exchanger, generates waste heat Steam inputs institute's calorific requirement for MVR evaporation elements 13；
3) supercritical oxidation water outlet via after heat exchange enter regulating reservoir, later gravity flow enter dephosphorization agent mixing pit 5, with from The dephosphorization agent that 5 top dephosphorization agent dry powder of dephosphorization agent mixing pit quantitatively adds is mixed, and the agitating device being arranged at middle part is utilized It is tentatively mixed, takes water inlet line flow meter chain with the frequency converter of dephosphorization agent quantitative feeder, realize calcium hydroxide Quantify and add；The water outlet of dephosphorization agent mixing pit 5 is added into dephosphorization agent reaction tank 6, flocculant concentration reaction tank 7 and flocculation aid successively Reaction tank 8 is stirred using agitating device in the middle part of pond body, phosphate same dephosphorization agent under conditions of pH is 10.5-11 in water Calcium phosphate precipitation is generated by reaction, big and closely knit sediment is formed by the mixing coagulating sedimentation of flocculant, flocculation aid；So The water inlet pipe for entering inclined-tube sedimentation tank 12 afterwards, reacting the precipitation of hydroxyapatite object of generation, to sink to inclined tube under the effect of gravity heavy 12 lower part of shallow lake pond enters sludge pump 11 by sludge pipe, and portion phosphate precipitation reflux is in dephosphorization agent mixing pit 5, part phosphoric acid Salt precipitation forms phosphorous solid product by 13 evaporative crystallization of MVR evaporation elements；Supernatant passes through overfalling weir, outlet pipe and connection Pipe enters the reprocessing of biochemical treatment unit 17, final qualified discharge；
Embodiment 1
It is CO by oxidation operation 1. phosphorous biomass is by supercritical oxidation unit2, organophosphor switchs to
2. it is 10.5-11 that supercritical oxidation, which is discharged pH, water outlet is down to 80-85 DEG C via temperature after heat exchanger, generates waste heat Steam inputs institute's calorific requirement for MVR units；
3. supercritical oxidation water outlet via after heat exchange enter regulating reservoir, later gravity flow enter dephosphorization agent mixing pit, in from The dephosphorization agent that top dephosphorization agent dry powder quantitatively adds is mixed, and it is theoretical dosage that dephosphorization agent, which selects Ca (OH) 2, dosage, 1.1~1.3 times；
4. flocculant is 4-10%PFC solution, dosage 100-200ppm；Flocculation aid 0.1-0.4%PAM solution is thrown Dosage is 10-20ppm；
5. calcium phosphate precipitation return sludge ratio is 10~30%；
Embodiment 2
It is CO by oxidation operation 1. phosphorous biomass is by supercritical oxidation unit2, organophosphor switchs to
2. it is 10.5-11 that supercritical oxidation, which is discharged pH, water outlet is down to 30-35 DEG C via temperature after heat exchanger, generates waste heat Steam inputs institute's calorific requirement for MVR units；
3. supercritical oxidation water outlet via after heat exchange enter regulating reservoir, later gravity flow enter dephosphorization agent mixing pit, in from The dephosphorization agent that top dephosphorization agent dry powder quantitatively adds is mixed, and it is the 1.1~1.3 of theoretical dosage that dephosphorization agent, which selects CaCl2, Times；
4. flocculant is 4-10%PAC liquid, dosage 80-160ppm, flocculation aid 0.1-0.4%PAM solution, dosage For 10-20ppm；
5. calcium phosphate precipitation return sludge ratio is 10~30%；
Embodiment 3
It is CO by oxidation operation 1. phosphorous biomass is by supercritical oxidation unit2, organophosphor switchs to
2. supercritical oxidation water outlet pH is adjusted to 6~8, water outlet is down to 30-35 DEG C via temperature after heat exchanger, generates waste heat Steam inputs institute's calorific requirement for MVR units；
3. supercritical oxidation water outlet via after heat exchange enter regulating reservoir, later gravity flow enter dephosphorization agent mixing pit, in from The dephosphorization agent that top dephosphorization agent dry powder quantitatively adds is mixed, and dephosphorization agent is selectedMg2+；Molar ratio is 1.3：1:(1.05~1.3)：1：1.2；
4. flocculant is 4-10%PAC liquid, dosage 80-160ppm, flocculation aid 0.1-0.4%PAM solution, dosage For 10-20ppm；
5. calcium phosphate precipitation return sludge ratio is 15~40%；
The above content is merely illustrative of the invention's technical idea, and protection scope of the present invention cannot be limited with this, every to press According to technological thought proposed by the present invention, any change done on the basis of technical solution each falls within claims of the present invention Protection domain within.

Claims (10)

1. the phosphorus recovery system in a kind of phosphorous biomass based on supercritical oxidation technology, which is characterized in that including overcritical Oxidation unit (1), ammonia still process unit (2), phosphorus recovery unit, biological processing unit (17) and MVR evaporation elements (13)；Phosphorous biology Matter enters supercritical oxidation unit (1) and is aoxidized；The supercritical oxidation of supercritical oxidation unit (1) is discharged through ammonia still process unit (2) enter phosphorus recovery unit, afterheat steam inputs MVR evaporation elements (13) and is used as heat source of supply；By phosphorus recovery unit pair After supercritical oxidation water outlet carries out dephosphorization and flocculation treatment, supernatant discharges after entering biochemical treatment unit (17) reprocessing, raw At sediment enter sludge pump (11), a sediment part is back to phosphorus recovery unit, and another part passes through MVR evaporation elements (13) evaporative crystallization forms solid powder.
2. the phosphorus recovery system in the phosphorous biomass according to claim 1 based on supercritical oxidation technology, feature It is, phosphorus recovery unit includes regulating reservoir (3), dephosphorization agent mixing pit (5), dephosphorization agent reaction tank (6), flocculant concentration reaction tank (7), flocculation aid adds reaction tank (8), adding of agent system and inclined-tube sedimentation tank (12)；
The entrance of regulating reservoir (3) is connected with the outlet of ammonia still process unit (2), and outlet is connected with the entrance of dephosphorization agent mixing pit (5) Logical, dephosphorization agent mixing pit (5) is connected with the top of dephosphorization agent reaction tank (6), and dephosphorization agent reaction tank (6) and flocculant concentration are anti- The bottom of Ying Chi (7) is connected, and the top that flocculant concentration reaction tank (7) adds reaction tank (8) with flocculation aid is connected；Dephosphorization Agent mixing pit (5) is both provided with corresponding agitating device and dosing mouth with three reaction tanks；Flocculation aid adds going out for reaction tank (8) Mouth is connected with the entrance of inclined-tube sedimentation tank (12), and the outlet at bottom of inclined-tube sedimentation tank (12) is connected with sludge pump (11), top It is connected with biochemical treatment unit (17) by effluent weir.
3. the phosphorus recovery system in the phosphorous biomass according to claim 2 based on supercritical oxidation technology, feature It is, a part of sediment blowback dephosphorization agent reaction tank (6), another part are pumped into MVR evaporation elements (13) by sludge pump (11).
4. the phosphorus recovery system in the phosphorous biomass according to claim 2 based on supercritical oxidation technology, feature It is, be equipped with deflector (15) along pool wall in the middle part of inclined-tube sedimentation tank (12) pool wall, bottom is equipped with assistant sludge discharge device (14).
5. the phosphorus recovery system in the phosphorous biomass according to claim 2 based on supercritical oxidation technology, feature It is, flowmeter (4), inclined-tube sedimentation tank (12) and life is provided on the pipeline between regulating reservoir (3) and dephosphorization agent mixing pit (5) The pipeline changed between processing unit (17) is equipped with phosphorus on-line detector (16).
6. the phosphorus recovery system in the phosphorous biomass according to claim 5 based on supercritical oxidation technology, feature It is, adding of agent system includes dephosphorization agent quantitative feeder (18), flocculant storage tank (19) and flocculation aid storage tank (21)；It removes Phosphorus agent quantitative feeder (18) is connected with dephosphorization agent mixing pit (5), and flocculant storage tank (19) passes through flocculant concentration frequency conversion Metering pump (20) is connected with flocculant concentration reaction tank (7), and flocculation aid storage tank (21) adds frequency conversion metering pump by flocculation aid (22) reaction tank (8) is added with flocculation aid to be connected；Dephosphorization agent quantitative feeder (18) same to flowmeter (4) is associated；Wadding Solidifying agent adds frequency conversion metering pump (20) same to flowmeter (4) and is associated；Flocculation aid adds frequency conversion metering pump (22) same to flowmeter (4) It is associated.
7. the phosphorus recovery system in the phosphorous biomass according to claim 6 based on supercritical oxidation technology, feature It is, the flocculant in flocculant storage tank (19) is 4-10%PFC solution, dosage 100-200ppm；Flocculation aid storage tank (21) flocculation aid in is 0.1-0.4%PAM solution, dosage 10-20ppm.
8. the phosphorus recovery system in the phosphorous biomass according to claim 1 or 2 based on supercritical oxidation technology, special Sign is that the inlet flow-patterm of phosphorus recovery unit is 10-11, and temperature is 35 ± 5 DEG C.
9. a kind of phosphorous biology based on supercritical oxidation technology using phosphorus recovery system described in claim 2-8 any one Phosphorus recovery method in matter, which is characterized in that include the following steps：
1) oxidation operation is CO by supercritical oxidation unit (1) by phosphorous biomass2, organophosphor switchs to
2) supercritical oxidation water outlet is input to ammonia still process unit (2) by supercritical oxidation unit (1), is generated afterheat steam and is steamed for MVR Bill member (13) input institute calorific requirement；
3) pass through ammonia still process unit (2) treated supercritical oxidation water outlet and enter regulating reservoir, gravity flow later enters dephosphorization agent and mixes Pond (5) is mixed with the dephosphorization agent quantitatively added from dephosphorization agent dry powder at the top of dephosphorization agent mixing pit (5), is existed using setting The agitating device at middle part is tentatively mixed；Dephosphorization agent mixing pit (5) water outlet is thrown into dephosphorization agent reaction tank (6), flocculant successively Add reaction tank (7) and flocculation aid to add reaction tank (8), be stirred using agitating device in the middle part of pond body, phosphate is same in water removes Phosphorus agent generates calcium phosphate precipitation by reaction, and sediment is formed by the mixing coagulating sedimentation of flocculant, flocculation aid；Subsequently into The water inlet pipe of inclined-tube sedimentation tank (12), the precipitation of hydroxyapatite object for reacting generation sink to inclined-tube sedimentation tank under the effect of gravity (12) lower part enters sludge pump (11) by sludge pipe, and portion phosphate precipitation reflux is in dephosphorization agent mixing pit (5), part phosphorus Hydrochlorate precipitation forms phosphorous solid product by MVR evaporation elements (13) evaporative crystallization；Supernatant in inclined-tube sedimentation tank (12) Enter outer row after biochemical treatment unit (17) is reprocessed by overfalling weir, outlet pipe and connecting tube.
10. the phosphorus recovery method in the phosphorous biomass according to claim 9 based on supercritical oxidation technology, feature It is, in step 2), adjusts the pH value of supercritical oxidation water outlet to 10.5-11, while the temperature of supercritical oxidation water outlet being dropped Ammonia still process unit (2) is inputted after to 80-85 DEG C.
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CN113045022A (en) * 2021-04-21 2021-06-29 新地环保技术有限公司 Supercritical water oxidation treatment phosphorus-containing waste and phosphorus recovery method

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CN106915878A (en) * 2017-03-24 2017-07-04 博天环境集团股份有限公司 The recovery method of phosphorus in a kind of phosphorus containing sludge

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Publication number Priority date Publication date Assignee Title
CN106915878A (en) * 2017-03-24 2017-07-04 博天环境集团股份有限公司 The recovery method of phosphorus in a kind of phosphorus containing sludge

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113045022A (en) * 2021-04-21 2021-06-29 新地环保技术有限公司 Supercritical water oxidation treatment phosphorus-containing waste and phosphorus recovery method
CN113045022B (en) * 2021-04-21 2022-11-15 新地环保技术有限公司 Supercritical water oxidation treatment phosphorus-containing waste and phosphorus recovery method

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