CN104478519B - The device and method of nitrogen phosphorus is reclaimed with the supercritical water gasification product of blue-green algae algae solution - Google Patents
The device and method of nitrogen phosphorus is reclaimed with the supercritical water gasification product of blue-green algae algae solution Download PDFInfo
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- CN104478519B CN104478519B CN201410787213.3A CN201410787213A CN104478519B CN 104478519 B CN104478519 B CN 104478519B CN 201410787213 A CN201410787213 A CN 201410787213A CN 104478519 B CN104478519 B CN 104478519B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
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- 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
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- 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
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- 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
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Abstract
The present invention relates to the device and method that a kind of supercritical water gasification product with blue-green algae algae solution reclaims nitrogen phosphorus, belong to resource and environment filed.The present invention is directly carried out the blue-green algae algae solution for salvaging disembarkation after gasification process using the characteristic of supercritical water, a large amount of ammonia nitrogens, active phosphorus composition in the algae solution being enriched with reclaim liquid phase product, generation MAP crystal is applied as Crop fertilizer, the problems such as solving dehydration energy height, long processing period, recycling low SI in blue-green algae conventional processes, realizes that blue-green algae is effectively reclaimed after quickly handling.The method that the present invention is provided is realized two " synchronous to reclaim ", it is synchronous to reclaim nitrogen phosphorus in blue-green algae, and the synchronous P element reclaimed in supercritical water gasification liquid phase and solid phase, because many preservations of P element are in solid phase residual, the conversion of p-shaped state enters liquid phase in being remained by solid phase, and then can obtain 90% or so high recovery of nitrogen and phosphorus efficiency.
Description
Technical field
The invention belongs to resource and environment filed, and in particular to a kind of supercritical water gasification product with blue-green algae algae solution reclaims nitrogen
The device and method of phosphorus.
Background technology
Body eutrophication and break out blue-green algae formed wawter bloom serious harm is caused to China's environment.Salvaging is in eliminating
Land water bloom of water body pollutes important and common measure, is had been widely used in China Dian Chi, Taihu Lake, Chaohu etc..According to incompletely statistics,
970,000 tons of algae solution, nearly 300,000 tons of salvaging amount increase in than 2010 are salvaged from Taihu Lake is accumulative in Jiangsu Province in 2011.And in these salvagings
The algae solution of bank, how in time, quick harmless treatment with utilize, be bloom blue algae administer key.If to the algae solution of salvaging
Can not in time, effectively harmless treatment, algae solution rot it is smelly after, the nutrients release such as nitrogen, phosphorus enter water body and produce secondary
Environmental pollution so that lake bloom blue algae continuation breaks out.
At present, the Chinese patent of Application No. 200710025550.9 discloses one kind and fertilizer is prepared by raw material of bloom blue algae
The method of material, the patent will be dehydrated blue-green algae with composting mode and become thoroughly decomposed after processing, and organic fertilizer or compound organic and inorganic fertilizer is made, but will
The moisture content of dehydration blue-green algae is asked to reach 20~40% and treatment time is long, this is accomplished by expending substantial amounts of energy and place；Application
Number method and products thereof of blue-green algae biogas energyization fermentation a kind of is disclosed for 20061009.5 Chinese patent, the patent is proposed
Anaerobic fermentation method processing salvages blue-green algae and then obtains biogas, but the problems such as can not change treatment time length, inefficiency；
The Chinese patent of Application No. 201010520895.3 disclose a kind of utilization supercritical water oxidation method processing blue-green algae system and
Method, the patent to blue-green algae with supercritical water oxidation by way of handle, eventually form CO2And H2O, realize blue-green algae without
Evilization processing；And the nutrient discovery in algae solution is then entered liquid phase production by this patent using the water technology of supercritical water partial oxidation
Thing, then using the nitrogen phosphorus in MAP method high efficiente callback algae solutions, and breaks through the limitation that MAP methods are only applicable to liquid phase recovery, passes through acid
Wash concussion conversion and reclaim substantial amounts of P element in solids phase residue matter.
The content of the invention
The technical problem of solution：The purpose of the present invention overcomes the deficiencies in the prior art and provides a kind of with blue-green algae algae solution
Supercritical water gasification product reclaims the device and method of nitrogen phosphorus, using the characteristic of supercritical water that the blue-green algae algae solution for salvaging disembarkation is straight
Tap into after row gasification process, a large amount of ammonia nitrogens, active phosphorus composition in the algae solution being enriched with reclaim liquid phase product, generation MAP crystal is (again
Claim guanite) as being applied as Crop fertilizer, solve dehydration energy height in blue-green algae conventional processes, long processing period,
The problems such as recycling low SI, realize that blue-green algae is effectively reclaimed after quickly handling.
Technical scheme：
Contain substantial amounts of nitrogen P elements in the blue-green algae algae solution salvaged during by lake wawter bloom, be a kind of good resource.
The present invention handles algae solution by supercritical water gasification, the nitrogen phosphorus of wherein most is transferred in liquid product, then pass through MAP
Method generation MAP crystal carries out high efficiente callback utilization.
The device of nitrogen phosphorus, including hold-up tank, inlet valve, high-pressure plunger are reclaimed with the supercritical water gasification product of blue-green algae algae solution
Pump, outlet valve, heat exchanger, gas-liquid flow valve, gas-liquid separator tank, wet gas flow meter, fluid flowmeter, counterbalance valve,
Supercritical reaction device, MAP retort, stirring at low speed motor M, magnesium chloride storagetank, potassium dihydrogen phosphate storagetank, system pressure is adjusted
Valve is saved, magnesium chloride control valve, potassium dihydrogen phosphate controls valve, and magnesium chloride constant feeder D, potassium dihydrogen phosphate constant feeder D are done
Between baking, pH on-line computing models regulate and control pond, MAP crystal transfer valves, solid phase oscillator, acid solution storagetank, sour hydraulic control valve, acid solution
Quantitative scoring D, acid solution delivery valve；Wherein, the first efferent duct of hold-up tank pass sequentially through inlet valve, high-pressure plunger pump, outlet valve with
First input pipe of heat exchanger is connected, and the first efferent duct of heat exchanger passes through counterbalance valve and the input pipe of supercritical reaction device
Connection, the first efferent duct of supercritical reaction device is connected by system pressure regulating valve with the second input pipe of heat exchanger, is surpassed
Second efferent duct of critical reaction device is connected by controlling valve with the first input pipe of solid phase oscillator, and acid solution storagetank leads to successively
Peracid hydraulic control valve, acid solution quantitative scoring D are connected with the second input pipe of solid phase oscillator, and the first efferent duct of solid phase oscillator leads to
The input pipe that acid solution delivery valve is crossed with supercritical reaction device is connected, the second efferent duct output solid product of solid phase oscillator；
Second efferent duct of heat exchanger is connected by gas-liquid flow valve with the input pipe of gas-liquid separator tank, gas-liquid separation
First efferent duct of device tank is connected by the first input pipe between wet gas flow meter and dry dry, and the second of gas-liquid separator tank
Efferent duct is connected by fluid flowmeter with the input pipe of MAP retort, magnesium chloride storagetank pass sequentially through magnesium chloride control valve,
Magnesium chloride constant feeder D is connected with the input pipe of MAP retort, and potassium dihydrogen phosphate storagetank passes sequentially through potassium dihydrogen phosphate control
Valve processed, potassium dihydrogen phosphate constant feeder D are connected with the input pipe of MAP retort, and the first efferent duct of MAP retort passes through
The second input pipe between MAP crystal transfer valve and dry dry is connected, and does the first efferent duct output gas-phase product between drying, the second output
Pipe exports finished product fertilizer, the second efferent duct output supernatant of MAP retort, after pH on-line computing models are connected in parallel with regulation and control pond
Inserted by pipeline in MAP retort, stirring at low speed motor M flabellum is placed in MAP retort.
The device that the described supercritical water gasification product with blue-green algae algae solution reclaims nitrogen phosphorus reclaims nitrogen in bloom blue algae algae solution
The method of phosphorus, comprises the following steps：
1) the blue-green algae algae solution of disembarkation will be salvaged, supercritical reaction device is squeezed into by high-pressure plunger pump 3, stop is entered for 3-5 minutes
Water-filling gasification reaction；Product reclaims heat by heat exchanger, and the heat of recovery is used for the pre-heat treatment of next group blue-green algae sample introduction；
Product through over-heat-exchanger separates gas-liquid product after cooling step-down into gas-liquid separator tank, obtains the liquid of rich Nitrogen-and Phosphorus-containing
Phase product；Solid product enters solid phase oscillator under the regulation of control valve by the second efferent duct of supercritical reaction device 11
Afterwards, the acid solution in acid solution storagetank quantitatively enters supernatant after solid phase oscillator, concussion 8h through sour hydraulic control valve and acid solution quantitative scoring D
Liquid enters MAP retort；
2) supercritical fluid product is entered by conveyance conduit and reacted in MAP retort, passes through pH on-line computing models
With the acid or alkali environment in the regulation and control cell monitoring regulation MAP retort for filling alkali lye；
3) magnesium chloride and potassium dihydrogen phosphate dry powder are quantitatively given by magnesium chloride constant feeder D and potassium dihydrogen phosphate respectively
Material machine D is delivered into MAP retort, and by participating in MAP reactions after stirring at low speed motor M stirring and dissolvings；
4) second efferent duct discharge of the reacted supernatant through MAP retort, and being post-processed, the MAP of generation is brilliant
Body precipitation is entered between dry dry by the second input pipe of the first efferent duct of MAP retort between dry baking, by overcritical aqueous vapor
Change after the residual heat drying in the gas-phase product produced, gas-phase product is through the first efferent duct output between dry dry, and finished product fertilizer is through dry
The second efferent duct between baking is exported and collected to be applied as agricultural fertilizer.
The device that the described supercritical water gasification product with blue-green algae algae solution reclaims nitrogen phosphorus reclaims nitrogen in bloom blue algae algae solution
The method of phosphorus, wherein, step 1) pressure of mesohigh plunger pump is set as 22MPa.
The device that the described supercritical water gasification product with blue-green algae algae solution reclaims nitrogen phosphorus reclaims nitrogen in bloom blue algae algae solution
The method of phosphorus, wherein, step 1) in supercritical reaction device is warming up to 450~500 DEG C in advance.
The device that the described supercritical water gasification product with blue-green algae algae solution reclaims nitrogen phosphorus reclaims nitrogen in bloom blue algae algae solution
The method of phosphorus, wherein, step 2) in pH in MAP retort be 9.0~10.7.
The device that the above-mentioned supercritical water gasification product with blue-green algae algae solution reclaims nitrogen phosphorus reclaims nitrogen in bloom blue algae algae solution
The method of phosphorus, wherein, the acid solution stored in the acid solution storagetank is hydrochloric acid, and the solid phase oscillator uses sequencing batch operation side
Formula.
Beneficial effect
First, the present invention directly carries out the blue-green algae algae solution for salvaging the rich Nitrogen-and Phosphorus-containing of disembarkation after supercritical water gasification processing, greatly
Enter after the nitrogen phosphorus reaction of amount in liquid product, the nutrient discovery in liquid phase is improved into fertilizer efficiency into solid fertilizer using MAP reactions
And it is easy to follow-up transport and administration；
Second, the extra charge that the whole course of reaction of the present invention is brought without second dehydration and moisture regulation, and reacted
Without additionally adding oxidant in journey；
3rd, the present invention carries out MAP methods recovery nitrogen phosphorus after being handled by supercritical water gasification can greatly shorten the reaction time,
Realize efficient, quick blue-green algae processing；
4th, the method that the present invention is provided is realized two " synchronously reclaiming ", synchronous to reclaim nitrogen phosphorus in blue-green algae, and synchronous time
The P element in supercritical water gasification liquid phase and solid phase is received, because many preservations of P element are in solid phase residual, instant invention overcomes normal
The deficiency for the nitrogen P elements that recovery method can only be in reclaim liquid phase is advised, the conversion of p-shaped state enters liquid phase in being remained by solid phase, enters
And 90% or so high recovery of nitrogen and phosphorus efficiency can be obtained.
Brief description of the drawings
Fig. 1 reclaims the schematic device of nitrogen phosphorus in bloom blue algae algae solution for the present invention, wherein 1 is hold-up tank, 2 be import
Valve, 3 be high-pressure plunger pump, and 4 be outlet valve, and 5 be heat exchanger, and 6 be gas-liquid flow valve, and 7 be gas-liquid separator tank, and 8 be wet type
Gas flowmeter, 9 be fluid flowmeter, and 10 be counterbalance valve, and 11 be supercritical reaction device, and 12 be MAP retort, and 13 be that low speed is stirred
Motor M is mixed, 14 be magnesium chloride storagetank, and 15 be potassium dihydrogen phosphate storagetank, and 16 be system pressure regulating valve, and 17 be magnesium chloride control
Valve processed, 18 be potassium dihydrogen phosphate control valve, and 19 be magnesium chloride constant feeder D, and 20 be potassium dihydrogen phosphate constant feeder D, 21
It is that 22 be pH on-line computing models, and 23 be regulation and control pond, and 24 be MAP crystal transfer valves, and 25 be solid phase oscillator, and 26 be acid between dry dry
Liquid storagetank, 27 be sour hydraulic control valve, and 28 be acid solution quantitative scoring D, and 29 be acid solution delivery valve, and 30 be control valve.
Embodiment
The present invention is described in further detail below by specific embodiment, wherein the solid phase oscillator 25 uses sequence
The batch method of operation.
Embodiment 1
With reference to Fig. 1, the device of nitrogen phosphorus, including hold-up tank 1, inlet valve are reclaimed with the supercritical water gasification product of blue-green algae algae solution
2, high-pressure plunger pump 3, outlet valve 4, heat exchanger 5, gas-liquid flow valve 6, gas-liquid separator tank 7, wet gas flow meter 8, liquid
Flowmeter body 9, counterbalance valve 10, supercritical reaction device 11, MAP retort 12, stirring at low speed motor M13, magnesium chloride storagetank 14,
Potassium dihydrogen phosphate storagetank 15, system pressure regulating valve 16, magnesium chloride control valve 17, potassium dihydrogen phosphate control valve 18, magnesium chloride
Constant feeder D19, potassium dihydrogen phosphate constant feeder D20, do 21, pH on-line computing models 22 between drying, and regulate and control pond 23, and MAP is brilliant
Body transfer valve 24, solid phase oscillator 25, acid solution storagetank 26, sour hydraulic control valve 27, acid solution quantitative scoring D28, acid solution delivery valve 29；
Wherein, the first efferent duct of hold-up tank 1 passes sequentially through the first of inlet valve 2, high-pressure plunger pump 3, outlet valve 4 and heat exchanger 5
Input pipe is connected, and the first efferent duct of heat exchanger 5 is connected by counterbalance valve 10 with the input pipe of supercritical reaction device 11, super to face
First efferent duct of boundary's reactor 11 is connected by system pressure regulating valve 16 with the second input pipe of heat exchanger 5, overcritical
Second efferent duct of reactor 11 is connected by controlling valve 30 with the first input pipe of solid phase oscillator 25, acid solution storagetank 26 according to
It is secondary to be connected by sour hydraulic control valve 27, acid solution quantitative scoring D28 with the second input pipe of solid phase oscillator 25, solid phase oscillator 25
First efferent duct is connected by acid solution delivery valve 29 with the input pipe of supercritical reaction device 11, the second output of solid phase oscillator 25
Pipe exports solid product；
Second efferent duct of heat exchanger 5 is connected by gas-liquid flow valve 6 with the input pipe of gas-liquid separator tank 7, gas-liquid
First efferent duct of separator pot 7 is connected by between wet gas flow meter 8 and dry dry 21 the first input pipe, gas-liquid separator
Second efferent duct of tank 7 is connected by fluid flowmeter 9 with the input pipe of MAP retort 12, and magnesium chloride storagetank 14 leads to successively
Superchlorination magnesium control valve 17, magnesium chloride constant feeder D19 are connected with the input pipe of MAP retort 12, potassium dihydrogen phosphate storage
Groove 15 passes sequentially through potassium dihydrogen phosphate control valve 18, the input pipe phase of potassium dihydrogen phosphate constant feeder D20 and MAP retort 12
Even, the first efferent duct of MAP retort 12 is connected by between MAP crystal transfer valve 24 and dry dry 21 the second input pipe, is done and is dried
Between 21 the first efferent duct output gas-phase product, the second efferent duct output finished product fertilizer, the second efferent duct of MAP retort 12 is defeated
Go out supernatant, pH on-line computing models 22 are inserted in MAP retort 12 after being connected in parallel with regulation and control pond 23 by pipeline, stirring at low speed
Motor M13 flabellum is placed in MAP retort 12.
Embodiment 2
The device for reclaiming nitrogen phosphorus with the supercritical water gasification product of blue-green algae algae solution reclaims the side of nitrogen phosphorus in bloom blue algae algae solution
Method, comprises the following steps：
1) the blue-green algae algae solution (moisture content 98%~99%) for salvaging disembarkation enters hold-up tank 1, pending after the separation of algae water.
2) during on-test, the inlet valve 2 of high-pressure plunger pump is opened, high-pressure plunger pump 3 is opened, and open heat exchanger 5
Heater, its temperature is risen to 300 DEG C or so, open supercritical reaction device 11, be warming up to 500 DEG C.
3) algae solution outlet valve 4 is opened, the algae solution after the separation of algae water is entered heat exchanger 5, is warming up to by heat exchanger
250℃；Then supercritical reaction device 11 is entered by counterbalance valve 10, temperature is reached 400 DEG C in reactor, pressure 25Mpa,
Supercriticality is reached, stops 3 minutes and carries out water reaction；After reaction terminates, system pressure regulating valve 16 is opened, makes gas-liquid
Mixed phase product enters heat exchanger 5, and the pending algae solution of next stage is warming up into 250 DEG C, and process by heat exchanger
In cause the reduction of gas-liquid mixed phase product temperatur, open gas-liquid flow valve 6 and enter gas-liquid separator tank 7, obtained after gas-liquid separation
The liquid product of fuel gas and rich Nitrogen-and Phosphorus-containing, and by wet gas flow meter 8, the gas-phase product being had surplus heat using band is in dry
Finished product is made in the fertilizer drying subsequently obtained by 21 between baking.
4) after supercritical reaction terminates, inorganic solid phase product is discharged into solid phase oscillator by the bottom of supercritical reaction device 11
25, sour hydraulic control valve 27 is opened, hydrochloric acid solution is quantitatively inputted by acid solution quantitative scoring D28, concussion is stopped after 8h, opens acid solution defeated
Go out valve 29, the solid product residue periodic cleaning row for making supernatant enter in the hybrid reaction of MAP retort 12, solid phase oscillator 25
Go out.
5) liquid product enters MAP retort 12 through fluid flowmeter 9, by pH on-line computing models 22 and fills alkali lye
Regulate and control the acid or alkali environment in the monitoring of pond 23 regulation MAP retort 12, it is 9.0 to maintain the pH in MAP retort；By magnesium chloride and phosphorus
It is anti-that acid dihydride potassium dry powder delivers into MAP by magnesium chloride constant feeder D19 and potassium dihydrogen phosphate constant feeder D20 respectively
Answer in tank 12, and by participating in MAP reactions after stirring at low speed motor M13 stirring and dissolvings.
Embodiment 3
The device for reclaiming nitrogen phosphorus with the supercritical water gasification product of blue-green algae algae solution reclaims the side of nitrogen phosphorus in bloom blue algae algae solution
Method, comprises the following steps：
1) the blue-green algae algae solution (moisture content 98%~99%) for salvaging disembarkation enters hold-up tank 1, pending after the separation of algae water.
2) during on-test, the inlet valve 2 of high-pressure plunger pump is opened, high-pressure plunger pump 3 is opened, and open heat exchanger 5
Heater, its temperature is risen to 300 DEG C or so, open supercritical reaction device 11, be warming up to 500 DEG C.
3) algae solution outlet valve 4 is opened, the algae solution after the separation of algae water is entered heat exchanger 5, is warming up to by heat exchanger
250℃；Then supercritical reaction device 11 is entered by counterbalance valve 10, temperature is reached 500 DEG C in reactor, pressure 22Mpa,
Supercriticality is reached, stops 5 minutes and carries out water reaction；After reaction terminates, system pressure regulating valve 16 is opened, makes gas-liquid
Mixed phase product enters heat exchanger 5, and the pending algae solution of next stage is warming up into 250 DEG C, and process by heat exchanger
In cause the reduction of gas-liquid mixed phase product temperatur, open gas-liquid flow valve 6 and enter gas-liquid separator tank 7, obtained after gas-liquid separation
The liquid product of fuel gas and rich Nitrogen-and Phosphorus-containing, and by wet gas flow meter 8, the gas-phase product being had surplus heat using band is in dry
Finished product is made in the fertilizer drying subsequently obtained by 21 between baking.
4) after supercritical reaction terminates, inorganic solid phase product is discharged into solid phase oscillator by the bottom of supercritical reaction device 11
25, sour hydraulic control valve 27 is opened, hydrochloric acid solution is quantitatively inputted by acid solution quantitative scoring D 28, concussion is stopped after 8h, opens acid solution
Delivery valve 29, the solid product residue periodic cleaning for making supernatant enter in the hybrid reaction of MAP retort 12, solid phase oscillator 25
Discharge.
5) liquid product enters MAP retort 12 through fluid flowmeter 9, by pH on-line computing models 22 and fills alkali lye
Regulate and control the acid or alkali environment in the monitoring of pond 23 regulation MAP retort 12, it is 10.7 to maintain the pH in MAP retort；By magnesium chloride and
Potassium dihydrogen phosphate dry powder delivers into MAP by magnesium chloride constant feeder D19 and potassium dihydrogen phosphate constant feeder D20 respectively
In retort 12, and by participating in MAP reactions after stirring at low speed motor M13 stirring and dissolvings.
Embodiment 4
The device for reclaiming nitrogen phosphorus with the supercritical water gasification product of blue-green algae algae solution reclaims the side of nitrogen phosphorus in bloom blue algae algae solution
Method, comprises the following steps：
1) the blue-green algae algae solution (moisture content 98%~99%) for salvaging disembarkation enters hold-up tank 1, pending after the separation of algae water.
2) during on-test, the inlet valve 2 of high-pressure plunger pump is opened, high-pressure plunger pump 3 is opened, and open heat exchanger 5
Heater, its temperature is risen to 300 DEG C or so, open supercritical reaction device 11, be warming up to 500 DEG C.
3) algae solution outlet valve 4 is opened, the algae solution after the separation of algae water is entered heat exchanger 5, is warming up to by heat exchanger
250℃；Then supercritical reaction device 11 is entered by counterbalance valve 10, temperature is reached 450 DEG C in reactor, pressure 22Mpa,
Supercriticality is reached, stops 5 minutes and carries out water reaction；After reaction terminates, system pressure regulating valve 16 is opened, makes gas-liquid
Mixed phase product enters heat exchanger 5, and the pending algae solution of next stage is warming up into 250 DEG C, and process by heat exchanger
In cause the reduction of gas-liquid mixed phase product temperatur, open gas-liquid flow valve 6 and enter gas-liquid separator tank 7, obtained after gas-liquid separation
The liquid product of fuel gas and rich Nitrogen-and Phosphorus-containing, and by wet gas flow meter 8, the gas-phase product being had surplus heat using band is in dry
Finished product is made in the fertilizer drying subsequently obtained by 21 between baking.
4) after supercritical reaction terminates, inorganic solid phase product is discharged into solid phase oscillator by the bottom of supercritical reaction device 11
25, sour hydraulic control valve 27 is opened, hydrochloric acid solution is quantitatively inputted by acid solution quantitative scoring D 28, concussion is stopped after 8h, opens acid solution
Delivery valve 29, the solid product residue periodic cleaning for making supernatant enter in the hybrid reaction of MAP retort 12, solid phase oscillator 25
Discharge.
5) liquid product enters MAP retort 12 through fluid flowmeter 9, by pH on-line computing models 22 and fills alkali lye
Regulate and control the acid or alkali environment in the monitoring of pond 23 regulation MAP retort 12, it is 9.0~10.7 to maintain the pH in MAP retort；By chlorination
Magnesium and potassium dihydrogen phosphate dry powder respectively by magnesium chloride constant feeder D19 and potassium dihydrogen phosphate constant feeder D20 convey into
Enter in MAP retort 12, and by participating in MAP reactions after stirring at low speed motor M13 stirring and dissolvings.
Application examples 1
Taihu Lake is salvaged to the entrance algae moisture debarked algae solution leaving from station, moisture content is that 96%, TN and TP concentration is respectively
3268mg/L, 180.63mg/L, are reacted after 500 DEG C, 5min supercritical water gasification processing into MAP retort,
Stopped 10 minutes after being sufficiently stirred for, it is as shown in table 1 that precipitation obtains finished product fertilizer property into after being dried between dry dry.
Application examples 2
Taihu Lake is salvaged to the entrance algae moisture debarked algae solution leaving from station, it is dense by dehydration device progress dehydration concentration algae solution
Degree, moisture content is reduced to 86%, TN and TP concentration is respectively 10008mg/L, 544.93mg/L, faces by 500 DEG C, the super of 5min
Reacted, stopped 20 minutes after being sufficiently stirred for into MAP retort after the water processing in boundary, precipitation between dry dry into after being dried
Obtain finished product fertilizer property as shown in table 1.
The property for the finished product fertilizer that table 1 is obtained
After supercritical water treatment, the method for salvaging nitrogen phosphorus in algae solution is reclaimed using MAP methods, it is on the one hand rich for reduction
Nitrogen, phosphorus recycling level in nutrient laden lake, solve the problem of outlet for salvaging blue-green algae, extremely short reacting treatment time and stop
Yield huge during Blue-green Algae Fast Growth can more be tackled freely by staying the time, and 2011 accumulative from Taihu Lake salvaging moisture content 98% or so
970,000 tons of blue-green algae, equivalent to directly from lake body take out nearly 500 tons of nitrogen, 100 tons of phosphorus, supercritical water gasification processing after carry out MAP
The harmless treatment for salvaging blue-green algae and recycling can rapidly and efficiently be realized by reclaiming the method for nitrogen phosphorus；
On the other hand, the present invention is by the nutrient discovery salvaged in blue-green algae into available agricultural fertilizer, and transformation efficiency is quick
Efficiently, transformation efficiency is up to 90%, far above the P element recovery method in existing only reclaim liquid phase product, alleviates nitrogen phosphorus fertilizer
Economic gain, environmental pollution in material production process, and increasingly exhausted phosphorus ore resource, if Taihu Lake in 2011 is salvaged
Blue-green algae in nitrogen phosphorus all carry out MAP recovery, can about obtain 8500 tons of MAP crystal fertilizer；Reduce river lake internal contamination load
Meanwhile, certain economic benefit is realized, the environmental pollution in the exhaustion and fertilizer process of P ore resources is alleviated.
Claims (4)
1. the device of nitrogen phosphorus is reclaimed with the supercritical water gasification product of blue-green algae algae solution, it is characterised in that including hold-up tank（1）, enter
Mouth valve（2）, high-pressure plunger pump（3）, outlet valve（4）, heat exchanger（5）, gas-liquid flow valve（6）, gas-liquid separator tank（7）, it is wet
Formula gas flowmeter（8）, fluid flowmeter（9）, counterbalance valve（10）, supercritical reaction device（11）, MAP retort（12）, low speed
Stirring motor M（13）, magnesium chloride storagetank（14）, potassium dihydrogen phosphate storagetank（15）, system pressure regulating valve（16）, magnesium chloride
Control valve（17）, potassium dihydrogen phosphate control valve（18）, magnesium chloride constant feeder D（19）, potassium dihydrogen phosphate constant feeder D
（20）, do between drying（21）, pH on-line computing models（22）, regulate and control pond（23）, MAP crystal transfer valves（24）, solid phase oscillator（25）,
Acid solution storagetank（26）, sour hydraulic control valve（27）, acid solution quantitative scoring D（28）, acid solution delivery valve（29）, control valve（30）；Wherein,
Hold-up tank（1）The first efferent duct pass sequentially through inlet valve（2）, high-pressure plunger pump（3）, outlet valve（4）With heat exchanger（5）'s
First input pipe is connected, heat exchanger（5）The first efferent duct pass through counterbalance valve（10）With supercritical reaction device（11）Input
Pipe is connected, supercritical reaction device（11）The first efferent duct pass through system pressure regulating valve（16）With heat exchanger（5）Second
Input pipe is connected, supercritical reaction device（11）The second efferent duct by controlling valve（30）With solid phase oscillator（25）It is first defeated
Enter pipe to be connected, acid solution storagetank（26）Pass sequentially through sour hydraulic control valve（27）, acid solution quantitative scoring D（28）With solid phase oscillator（25）
The second input pipe be connected, solid phase oscillator（25）The first efferent duct pass through acid solution delivery valve（29）With supercritical reaction device
（11）Input pipe be connected, solid phase oscillator（25）The second efferent duct output solid product；
Heat exchanger（5）The second efferent duct pass through gas-liquid flow valve（6）With gas-liquid separator tank（7）Input pipe be connected, gas
Liquid/gas separator tank（7）The first efferent duct pass through wet gas flow meter（8）Between dry baking（21）The first input pipe be connected, gas
Liquid/gas separator tank（7）The second efferent duct pass through fluid flowmeter（9）With MAP retort（12）Input pipe be connected, magnesium chloride
Storagetank（14）Pass sequentially through magnesium chloride control valve（17）, magnesium chloride constant feeder D（19）With MAP retort（12）Input
Pipe is connected, potassium dihydrogen phosphate storagetank（15）Pass sequentially through potassium dihydrogen phosphate control valve（18）, potassium dihydrogen phosphate constant feeder D
（20）With MAP retort（12）Input pipe be connected, MAP retort（12）The first efferent duct pass through MAP crystal transfer valves
（24）Between dry baking（21）The second input pipe be connected, do dry between（21）The first efferent duct output gas-phase product, second output
Pipe exports finished product fertilizer, MAP retort（12）The second efferent duct output supernatant, pH on-line computing models（22）With regulation and control pond
（23）MAP retort is inserted by pipeline after being connected in parallel（12）It is interior, stirring at low speed motor M（13）Flabellum be placed in MAP reaction
Tank（12）It is interior.
2. the device that the supercritical water gasification product with blue-green algae algae solution described in claim 1 reclaims nitrogen phosphorus reclaims bloom blue algae algae
The method of nitrogen phosphorus in liquid, it is characterised in that comprise the following steps：
1）The blue-green algae algae solution of moisture content 98% ~ 99% for salvaging disembarkation is entered into hold-up tank（1）, it is pending after the separation of algae water；
2）The inlet valve of high-pressure plunger pump is opened during on-test（2）, high-pressure plunger pump is opened, and open heat exchanger（5）'s
Heater, 300 DEG C are risen to by its temperature, open supercritical reaction device（11）It is warming up to 450 ~ 500 DEG C；
3）Open algae solution outlet valve（4）, the algae solution after the separation of algae water is entered heat exchanger（5）, it is warming up to by heat exchanger
250℃；Then counterbalance valve is passed through（10）Into supercritical reaction device（11）, 400 ~ 500 DEG C, pressure are reached in reactor temperature
22 ~ 25Mpa, reaches supercriticality, stops 3 ~ 5 minutes laggard water-filling gasification reactions；After reaction terminates, open system pressure and adjust
Save valve（16）, gas-liquid mixed phase product is entered heat exchanger（5）, by heat exchanger by the pending algae solution liter of next stage
Temperature to 250 DEG C, and during cause gas-liquid mixed phase product temperatur reduction, open gas-liquid flow valve（6）Into gas-liquid separator
Tank（7）, the liquid product of fuel gas and rich Nitrogen-and Phosphorus-containing is obtained after gas-liquid separation, and pass through wet gas flow meter（8）, utilize
Gas-phase product that band has surplus heat and it is dry dry between（21）Finished product is made in the fertilizer drying subsequently obtained；
4）After supercritical reaction terminates, inorganic solid phase product is by supercritical reaction device（11）Bottom is discharged into solid phase oscillator
（25）, open sour hydraulic control valve（27）, pass through acid solution quantitative scoring D（28）Hydrochloric acid solution is quantitatively inputted, concussion is stopped after 8h, is opened
Acid solution delivery valve（29）, supernatant is entered MAP retort（12）Hybrid reaction, solid phase oscillator（25）In solid product it is residual
Slag periodic cleaning is discharged；
5）Liquid product is through fluid flowmeter（9）Into MAP retort（12）, pass through pH on-line computing models（22）With fill alkali lye
Regulation and control pond（23）Monitoring regulation MAP retort（12）In acid or alkali environment, maintain MAP retort in pH be 9.0 ~ 10.7；
Magnesium chloride and potassium dihydrogen phosphate dry powder are passed through into magnesium chloride constant feeder D respectively（19）With potassium dihydrogen phosphate constant feeder D
（20）Deliver into MAP retort（12）In, and by stirring at low speed motor M（13）MAP reactions are participated in after stirring and dissolving.
3. the supercritical water gasification product according to claim 2 with blue-green algae algae solution reclaims the device recycle-water Chinese blue of nitrogen phosphorus
The method of nitrogen phosphorus in algae algae solution, it is characterised in that the acid solution storagetank（26）The acid solution of middle storage is hydrochloric acid.
4. the supercritical water gasification product with blue-green algae algae solution according to Claims 2 or 3 reclaims the device recycle-water of nitrogen phosphorus
The method of nitrogen phosphorus in Chinese blue algae algae solution, it is characterised in that the solid phase oscillator（25）Using sequencing batch operation mode.
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