CN207313361U - A kind of device for being used to prepare complex fertilizer - Google Patents
A kind of device for being used to prepare complex fertilizer Download PDFInfo
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- CN207313361U CN207313361U CN201720982239.2U CN201720982239U CN207313361U CN 207313361 U CN207313361 U CN 207313361U CN 201720982239 U CN201720982239 U CN 201720982239U CN 207313361 U CN207313361 U CN 207313361U
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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Abstract
The utility model discloses a kind of device for being used to prepare complex fertilizer, mainly include material box, moving bed membrane bioreactor, air pump, moving bed membrane bioreactor goes out water pot, 96 anion exchange resin reactors of SQD, sodium hydroxide solution tank, resin reaction device goes out water pot, cartridge filter, snakelike heat exchange tube, hollow fiber film assembly, hollow fibre membrane systems go out water pot, the absorption flow container of hollow fibre membrane systems, hydrochloric acid tank, the absorbing liquid circulating pump of hollow fibre membrane systems, resin eluant, eluent tank, resin reaction device thermostatic water-circulator bath pot, upper prop liquid adjusting hydrochloric acid tank, the hollow fibre membrane systems equipment such as thermostatic water-circulator bath pot.The utility model is combined resin technology using anaerobic sludge digestion liquid as raw material, using dual membrane system, prepares high-quality complex fertilizer, does not produce waste water and gas in preparation process, not only handled anaerobic sludge digestion liquid, but also realize utilization of waste as resource.
Description
Technical field
The utility model belongs to complex fertilizer preparing technical field, is related to the equipment that municipal sludge prepares complex fertilizer, tool
Body is related to a kind of device for being used to prepare complex fertilizer.
Background technology
Fertilizer is the material base of crop yield in agricultural, and developing agricultural production is called in China, ensures national food
The strategic materials of safety.China can be to account for the population that the world 21% has been supported in the arable land in the world 7%, with fertilizer particularly chemistry fertilizer
The a large amount of of material apply close relation.China since the 1950s apply complex fertilizer, applicating ratio also by
Year increase.
Complex fertilizer can need according to a certain regional soil and be configured to close rich in a variety of nutrients, nutrient formula economy
Reason, complex fertilizer with strong points.In addition complex fertilizer has good physical performance, is suitable for mechanized application, simplifies fertilising, section
Agricultural workforce is saved, a series of features such as effectiveness and function are more.
The production method of complex fertilizer mainly includes blending method, powder mixing granulation method, slurry granulation method, molten material and is granulated
Method, coating method etc..Wherein blending method refers to the mechanical mixture fertilizer of two or more nutriment, product design having powder
Shape and two kinds granular, its nutrient formula is determined according to crop species, target output, soil and weather conditions, can be met not
With the growth and development of crop.Such as 104973903 A of patent CN are pressed using stalk, animal wastes, cake fertilizer, amino acid waste liquid etc.
Certain proportion is blended to obtain organic composite fertilizer.And powder mixing granulation method is as needed, several fertilizer materials are selected
Dry powder is measured and mixed, using binding agent as cement the granulating in comminutor, such as 104150970 A of patent CN utilize
Disc granulation method produces ammonium magnesium phosphate slow-release fertilizer, by being closed to the powdered of ammonium magnesium phosphate material, granulation, drying, screening
The ammonium magnesium phosphate slow release fertilizer of lattice.The granulation of dry powder blend material needs to heat, and with plus water or add steam method increase amount of liquid phase,
Then the compound fertilizer granule of certain particle diameter is agglomerated into rotary drum in the case of rolling.Complex fertilizer is produced using slurry granulation method
Refer to the product by sulfuric acid, nitric acid, phosphoric acid or some mixed acid and ammonia reaction（Sometimes the product also reacted with acid with ground phosphate rock）
For nitrogen phosphorus slurry, sylvite is then added in slurry or directly sylvite is added in comminutor, then nitrogen phosphorus slurry is sprayed into and is granulated
In machine, reacted with sylvite N P and K ternary compound fertilizer is made at high temperature.Molten material be granulated rule be using melting urea or
Ammonium nitrate can form the characteristic of eutectic point compound with ammonium phosphate or potassium chloride, make its compound formed with suspended matter but have
The melt of mobility, then obtains granular compound fertilizer by granulating technique again.Such as by nitre in 1891678 A of patent CN
Sour ammonium is mixed with ammonium phosphate heating, and melting charge slurry is made, then adds sylvite thereto and fertilizer slurry, Ran Houzai is made with additive
It is granulated to obtain the compound fertilizer rich in N P and K.And coating method is the surface coating and cladding thin layer with physical method in fertilizer
The method of material, its property fertilizer more original with effect are improved to some extent and improved.
In conclusion it is primarily present problems with during the production of presented in compound fertilizer industry metaplasia：（1）The life of complex fertilizer at present
Production method be using all kinds of mineral resources as raw materials for production, and these mineral resources be often it is non-renewable, especially
It is that reserves of the phosphate rock resource in China are low, quality is not high；（2）Energy consumption is higher in traditional complex fertilizer preparation process, and raw material utilizes
Rate is not ideal enough；（3）The complex fertilizer quality of production is had a great influence by the control condition of preparation process；（4）Given birth in complex fertilizer
Waste water, exhaust gas can be produced during production, easily environment is polluted.
Utility model content
Goal of the invention：For a series of problems present in existing complex fertilizer production process, the purpose of this utility model
It is to provide a kind of device for being used to prepare complex fertilizer, using anaerobic sludge digestion liquid as raw material, is joined using resin and dual membrane system
With technology, the high-quality complex fertilizer of high Nitrogen-and Phosphorus-containing is prepared, waste water and gas is not produced in preparation process, has both handled sludge anaerobic
Digestive juice, and realize utilization of waste as resource.
Technical solution：In order to reach foregoing invention purpose, the technical solution adopted in the utility model is：
A kind of device for being used to prepare complex fertilizer, including material box, moving bed membrane bioreactor, air pump, movement
Bed membrane bioreactor goes out water pot, SQD-96 anion exchange resin reactor, sodium hydroxide solution tank, resin reaction device water outlet
Tank, cartridge filter, snakelike heat exchange tube, hollow fiber film assembly, hollow fibre membrane systems go out water pot, hollow fibre membrane systems
Absorb flow container, hydrochloric acid tank, the absorbing liquid circulating pump of hollow fibre membrane systems, resin eluant, eluent tank, the super perseverance of resin reaction device
Warm water bath, upper prop liquid adjusting hydrochloric acid tank, hollow fibre membrane systems thermostatic water-circulator bath pot；The material box and movement
Bed membrane bioreactor is connected；The air pump is connected with moving bed membrane bioreactor；The moving bed membrane bioreaction
Answer device to go out water pot with moving bed membrane bioreactor to be connected；The moving bed membrane bioreactor go out water pot and SQD-96 the moon from
Sub-exchange resin reactor is connected；The resin reaction device is anti-with thermostatic water-circulator bath pot and SQD-96 anion exchange resin
Device is answered to be connected；The upper prop liquid is connected with hydrochloric acid tank with SQD-96 anion exchange resin reactors；The SQD-96 is cloudy
Ion exchange resin reactor goes out water pot with resin reaction device and is connected；The sodium hydroxide solution tank and resin reaction device water outlet
Tank is connected；The resin reaction device goes out water pot and is connected by cartridge filter, snakelike heat exchange tube with hollow fiber film assembly；Institute
The hollow fibre membrane systems stated are connected with thermostatic water-circulator bath pot with snakelike heat exchange tube；The hollow fiber film assembly with it is hollow
Fiber membrane system goes out water pot and is connected, and hollow fiber film assembly is connected with the absorption flow container of hollow fibre membrane systems；The hydrochloric acid
Tank is connected with the absorption flow container of hollow fibre membrane systems；The resin eluant, eluent tank is reacted with SQD-96 anion exchange resin
Device is connected, and SQD-96 anion exchange resin reactor is connected with the absorption flow container of hollow fibre membrane systems.
Lower part in the moving bed membrane bioreactor sets floating stuffing, and top sets hydrophilic Kynoar
Pvdf membrane component, sets aeration head in moving bed membrane bioreactor, and bottom sets mud valve, and the material box passes through feed liquor
Pump, liquid inlet control valve be connected with moving bed membrane bioreactor, the air pump by gas control valve, spinner flowmeter with
Aeration head is connected.
The moving bed membrane bioreactor goes out water pot and is connected with vacuum pump.
SQD-96 anion exchange resin, the movement are set in the SQD-96 anion exchange resin reactors
Bed membrane bioreactor goes out water pot and passes through upper prop liquid pump, upper prop hydraulic control valve and SQD-96 anion exchange resin reactor phases
Even, the upper prop liquid with hydrochloric acid tank by the adjusting of upper prop liquid with hydrochloric acid add pump, upper prop liquid adjusting hydrochloric acid control valve with
SQD-96 anion exchange resin reactors are connected；The SQD-96 anion exchange resin reactor passes through resin reaction device
Outlet valve, resin reaction device water outlet pump go out water pot with resin reaction device and are connected；The resin eluant, eluent tank is eluted by resin
Agent adds pump, resin eluant, eluent control valve is connected with SQD-96 anion exchange resin reactors.
It is anti-that the sodium hydroxide solution tank by sodium hydroxide solution adds pump, sodium hydroxide solution control valve and resin
Answer device to go out water pot to be connected；The resin reaction device goes out liquid feeding pump, cartridge filter, snake of the water pot by hollow fibre membrane systems
Shape heat exchanger tube, hollow fibre membrane systems liquid inlet control valve, pressure gauge are connected with hollow fiber film assembly；Described SQD-96 the moon from
The water outlet of sub-exchange resin reactor goes out water pot with resin reaction device with magnetic stirring apparatus and is connected.
The snakelike heat exchange tube is connected with hollow fibre membrane systems with thermostatic water-circulator bath pot.
The hollow fiber film assembly passes through the absorbing liquid circulating pumps of hollow fibre membrane systems, hollow fibre membrane systems
Absorbing liquid circulation control valve is connected with the absorption flow container circulation of hollow fibre membrane systems.
The absorbing liquid is connected with magnetic stirring apparatus with the absorption flow container of hollow fibre membrane systems.
The hydrochloric acid tank adds pump by hydrochloric acid, hydrochloric acid control valve is connected with the absorption flow container of hollow fibre membrane systems.
The SQD-96 anion exchange resin reactor elutes hydraulic control valve and hollow fibre membrane systems by resin
Absorption flow container be connected.
Hydrophilic Pvdf Microporous Hollow Fiber Membrane, abbreviation PVDF hollow-fibre membranes, have good antifouling property, can
The processing procedures such as the filtering for sewage.
Hydrophobic type polypropylene hollow fiber membrane, abbreviation PP hollow-fibre membranes, since hydrophobic characteristic makes it to the trip in water
There is selective penetrated property from volatile materials such as amino molecules, and material soluble in water cannot then pass through membranous wall.
SQD-96 anion exchange resin belongs to the more amine ion exchange resin of alkalescent macropore polystyrene, to dissolubility
Orthophosphates SOP not only has ion exchange, also with hydrogen bond action, resin is had dissolubility orthophosphates SOP
Stronger compatibility, so as to add exchange capacity of the resin to phosphorus.
Municipal sewage plant's residual active sludge obtains anaerobic sludge digestion liquid through anaerobic digestion, rich in nitrogen and phosphorus member
Element, at the same time containing partial organic substances and a small amount of potassium sodium plasma.Wherein COD concentration is 122.71 ~ 461.54mg/L, total phosphorus concentration
For 137.66 ~ 209.41mg/L, dissolubility orthophosphates SOP concentration is 118.36 ~ 253.26mg/L, total nitrogen concentration 295.53
~ 670.31mg/L, ammonia nitrogen concentration are 277.51 ~ 651.89mg/L, and potassium concentration is 21.74 ~ 31.75mg/L, and sodium ion is dense
Spend for 31.95 ~ 32.19mg/L.Feed liquor of the anaerobic sludge digestion liquid after centrifugal treating as moving bed membrane bioreactor.
SQD-96 anion exchange resin carries out the dissolubility orthophosphates SOP in moving bed membrane bioreactor water outlet
Concentration and separation, mainly make use of ion exchange of the anion exchange resin to phosphate radical, and key reaction can be represented by the formula：
In formula, a, b are respectively ion A, the charge number of B.The anion exchange resin of A types can dissociate in the solution it is cloudy from
Sub- A-, these anion A-It is diffused into from resin among solution system.At the same time, in solution same type B-Ion also can
In the space net structure for enough moving to resin.As anion B-In the solution with resin there are concentration difference it is very big when（Solution
In account for a large amount of, minimal amount on resin）, anion B will be caused using concentration difference as motive force-Occur between resin and solution
Exchange reaction.The resin that sodium hydroxide solution has adsorbed phosphorus for eluent is used to obtain rich phosphorus eluent.
After SQD-96 anion exchange resin carries out concentration and separation to dissolubility orthophosphates SOP in anaerobic sludge digestion liquid
Water outlet, carry out ammonia nitrogen concentration and separation into hollow fibre membrane systems, and resin eluent is used as doughnut after being acidified with acid
The absorbing liquid of membranous system.Due to hydrophobic type polypropylene PP hollow-fibre membranes by SQD-96 the moon ion-exchanges change the water outlet of resin reaction device with
The absorbing liquid of empty fiber membrane system is separated, and SQD-96 the moon ion-exchanges change the ammonia nitrogen molecule to dissociate in resin reaction device water outlet can be
Film both sides concentration difference is converted into vapor phase ammonia as the micropore that the hydrophobic layer that membrane interface is passed through under the action of motive force enters on membranous wall
Molecule, then move in the gas phase of absorbing liquid side of hollow fibre membrane systems, then with the absorbing liquid of hollow fibre membrane systems
Middle hydrogen ion reaction is so as to form ammonium ion.As long as the absorbing liquid of hollow fibre membrane systems has sufficient acidity, film both sides will
This concentration difference is maintained always so that the separation process of ammonia nitrogen carries out always, so that ammonia nitrogen is in hollow fibre membrane systems
It is enriched with absorbing liquid, main process can be represented by the formula：
Obtained ammonium salt species is determined by species sour in absorbing liquid, is to richness in the utility model using hydrochloric acid
The resin eluent of phosphorus is acidified.
The absorbing liquid for being enriched with the hollow fiber film assembly for concentrating high concentration N-P contains sodium ion and chlorion at the same time, by
It is small in the solubility with temperature amplitude of variation of sodium chloride, and the solubility with temperature amplitude of variation of phosphate and ammonium salt is big, therefore
First sodium chloride is separated using evaporative crystallization using the difference of solubility, high Nitrogen-and Phosphorus-containing is then prepared using crystallisation by cooling
Complex fertilizer.
Beneficial effect：Compared with existing complex fertilizer production technology, the utility model has following remarkable advantage：
（1）Anaerobic sludge digestion liquid is pre-processed using moving bed membrane bioreactor, the resin of rich phosphorus is eluted
Liquid adds hydrochloric acid acidifying to be used as the absorbing liquid of hollow fibre membrane systems ammonia nitrogen UF membrane, organically gives birth to resin and moving bed film
Thing reactor and hollow fibre membrane systems combine, and realize that synchronous nitrogen and phosphorus concentrates, and will not in complex fertilizer production process
Pollution is produced to environment.
（2）Anaerobic sludge digestion liquid is pre-processed using moving bed membrane bioreactor system, selective removal has
Retained nitrogen phosphorus while machine thing, and reduce adverse effect of the suspended matter in anaerobic sludge digestion liquid to subsequent production process.
（3）While complex fertilizer is prepared, anaerobic sludge digestion liquid is handled, final outflow water reaches sewage discharge mark
It is accurate.
（4）Rich Nitrogen-and Phosphorus-containing, has effectively recycled nutrient therein, has realized the money of discarded object in anaerobic sludge digestion liquid
Sourceization utilizes.
Brief description of the drawings
Fig. 1 is the structure diagram of device.
Embodiment
The utility model is described further with specific embodiment below in conjunction with the accompanying drawings.
As shown in Figure 1, be the device for being used to prepare complex fertilizer of the utility model, including material box 1, liquid feeding pump 2, into
Hydraulic control valve 3, mud valve 4, aeration head 5, floating stuffing 6, moving bed membrane bioreactor 7, hydrophilic Kynoar PVDF
Hollow fiber film assembly 8, air pump 9, gas control valve 10, spinner flowmeter 11, moving bed membrane bioreactor go out water pot 12,
Vacuum pump 13, upper prop liquid pump 14, upper prop hydraulic control valve 15, SQD-96 anion exchange resin reactor 16, SQD-96 anion
Exchanger resin 17, resin reaction device outlet valve 18, resin reaction device water outlet pump 19, sodium hydroxide solution tank 20, sodium hydroxide are molten
Liquid adds pump 21, sodium hydroxide solution control valve 22, resin reaction device and goes out water pot 23, SQD-96 anion exchange resin reactors
Water outlet magnetic stirring apparatus 24, the liquid feeding pump 25 of hollow fibre membrane systems, cartridge filter 26, snakelike heat exchange tube 27, hollow fibre
Dimension membranous system liquid inlet control valve 28, pressure gauge 29, hollow fiber film assembly 30, hollow fibre membrane systems go out water pot 31, hollow fibre
Tie up the absorption flow container 32 of membranous system, absorbing liquid with magnetic stirring apparatus 33, hydrochloric acid tank 34, hydrochloric acid add pump 35, hydrochloric acid control valve 36,
The absorbing liquid circulating pump 37 of hollow fibre membrane systems, the absorbing liquid circulation control valve 38 of hollow fibre membrane systems, resin eluant, eluent
Tank 39, resin eluant, eluent add pump 40, resin eluant, eluent control valve 41, resin elution hydraulic control valve 42, resin reaction device and use and surpass
Level thermostat water bath 43, the adjusting of upper prop liquid add pump 45, upper prop liquid adjusting hydrochloric acid with hydrochloric acid tank 44, the adjusting of upper prop liquid with hydrochloric acid
Control valve 46, hollow fibre membrane systems thermostatic water-circulator bath pot 47.The device is by liquid feeding pump 2 by anaerobic sludge digestion liquid pump
Enter in moving bed membrane bioreactor 7, by hydrophilic Kynoar PVDF hollow fiber film assemblies 8, periodically suction is gone out
Water, the air that air pump 9 supplies are aerated into moving bed membrane bioreactor 7 after the metering of spinner flowmeter 11, are promoted
The growth of microorganism on floating stuffing 6.7 water outlet of moving bed membrane bioreactor enters by the use of after salt acid for adjusting pH as upper prop liquid
SQD-96 anion exchange resin reactor 16 simultaneously passes through resin reaction device 43 controlling reaction temperature of thermostatic water-circulator bath pot, tree
Fat reactor water outlet pump 19 controls water flow.The resin reaction device water outlet that inflow resin reaction device goes out water pot 23 uses hydroxide
Sodium solution passes through the tube side for entering hollow fiber film assembly 30 by cartridge filter 26 and snakelike heat exchange tube 27 after adjusting pH, in utilization
Empty fiber membrane system controls the operation temperature of hollow fibre membrane systems, the suction of hollow fibre membrane systems with thermostatic water-circulator bath pot 47
Receive the shell side that the absorbing liquid in flow container 32 enters hollow fiber film assembly 30 after adding hydrochloric acid to adjust acidity.Hollow fiber film assembly
Ammonia nitrogen in 30 separation water inlets, water outlet go out water pot 31 into hollow fibre membrane systems.Using sodium hydroxide solution as eluent
The SQD-96 anion exchange resin of phosphorus is adsorbed in SQD-96 anion exchange resin reactor 16, the eluent of rich phosphorus enters
The absorption flow container 32 of hollow fibre membrane systems.The absorbing liquid for being enriched with the hollow fiber film assembly for concentrating high concentration N-P is crystallizing
The complex fertilizer of high Nitrogen-and Phosphorus-containing is obtained afterwards.
SQD-96 anion exchange resin used in following embodiments is the limited public affairs of Jiangsu Su Qing engineering of water treatment group
Take charge of the polystyrene polyethylene polyamine class weak-base anion-exchange resin product of production.
Berthelot spectrophotometry, molybdenum-antimony anti-spectrophotometric method, potassium dichromate method and the chromatography of ions is respectively adopted to survey
Ammonia nitrogen concentration, dissolubility orthophosphates SOP concentration, COD concentration and Na in fixed following embodiment+With K+Plasma concentration.
In following embodiment, ammonia nitrogen removal frank, dissolubility orthophosphates SOP removal rates, SOP points of dissolubility orthophosphates
It is described as follows from rate and ammonia nitrogen separation rate calculating process：
To moving bed membrane bioreactor, the concentration of ammonia nitrogen and dissolubility orthophosphates SOP are divided in anaerobic sludge digestion liquid
Wei not C1Mg/L and C2mg/L；The concentration of ammonia nitrogen and dissolubility orthophosphates SOP are distinguished in moving bed membrane bioreactor water outlet
For C3Mg/L and C4mg/L；The concentration of dissolubility orthophosphates SOP is C in SQD-96 anion exchange resin reactor water outlets5
Mg/L, the concentration of ammonia nitrogen is C in hollow fibre membrane systems water outlet6 mg/L。
Removal rate=[(C of moving bed membrane bioreactor ammonia nitrogen1- C3)÷C1]×100%；
Removal rate=[(C of moving bed membrane bioreactor dissolubility orthophosphates SOP2- C4)÷C2]×100%；
Separation rate=[(C of SQD-96 resin anion (R.A.) reactor dissolubility orthophosphates SOP4- C5)÷C4]×100%；
Ammonia nitrogen separation rate=[(C of hollow fibre membrane systems3- C6)÷C3]×100%。
Embodiment 1
Municipal sludge obtains anaerobic sludge digestion liquid after anaerobic digestion, measured after centrifugation COD concentration for 122.71 ~
461.54mg/L, total phosphorus concentration are 137.66 ~ 209.41mg/L, dissolubility orthophosphates SOP concentration for 118.36 ~
253.26mg/L, total nitrogen concentration are 295.53 ~ 670.31mg/L, and ammonia nitrogen concentration is 277.51 ~ 651.89mg/L, potassium concentration
For 21.74 ~ 31.75mg/L, Na ion concentration is 31.95 ~ 32.19mg/L.
It is the startup stage of moving bed membrane bioreactor first, by seed sludge with anaerobic sludge digestion liquid by volume
1:1 inserts in reactor.0.25L muddy water mixed solutions are released from reactor bottom after using aeration quantity as 2L/h continuous aerations 24h, then
0.25L anaerobic sludge digestion liquid is added, is just started after continuous aeration 24h again with the continuous feed liquor operation of anaerobic sludge digestion liquid.
After the completion of moving bed membrane bioreactor startup stage, continuously run using anaerobic sludge digestion liquid as feed liquor, into
COD concentration is 149.65 ~ 391.74mg/L in liquid, ammonia nitrogen concentration is 277.51 ~ 388.85mg/L, dissolubility orthophosphates SOP
Concentration is 144.67 ~ 242.51mg/L.Moving bed membrane bioreactor is run under conditions of HRT is 18h, gas-water ratio is 20,
Water outlet goes out water pot into moving bed membrane bioreactor, and it is 62.38mg/L to measure COD mean concentrations in water outlet, and ammonia nitrogen is average dense
It is 138.30mg/L to spend for 185.13mg/L, SOP mean concentrations.Moving bed membrane bioreactor ammonia nitrogen and dissolubility orthophosphates
The removal rate of SOP is respectively 33.68% and 8.79%.
Embodiment 2
Continuously run using anaerobic sludge digestion liquid as moving bed membrane bioreactor feed liquor, COD concentration is in feed liquor
310.98 ~ 367.59mg/L, ammonia nitrogen concentration are 285.63 ~ 372.75mg/L, dissolubility orthophosphates SOP concentration be 141.72 ~
183.67mg/L.The HRT for adjusting moving bed membrane bioreactor is 18h, gas-water ratio 10, and water outlet enters moving bed membrane bioreaction
Device is answered to go out water pot, it is 72.12mg/L to measure COD mean concentrations in water outlet, and ammonia nitrogen mean concentration is 192.17mg/L, and dissolubility is just
Phosphate SOP mean concentrations are 165.86mg/L.The removal of moving bed membrane bioreactor ammonia nitrogen and dissolubility orthophosphates SOP
Rate is respectively 25.82% and 5.13%.
Embodiment 3
Continuously run using anaerobic sludge digestion liquid as moving bed membrane bioreactor feed liquor, COD concentration is in feed liquor
195.45 ~ 360.61mg/L, ammonia nitrogen concentration are 296.57 ~ 364.77mg/L, dissolubility orthophosphates SOP concentration be 156.31 ~
196.83mg/L.The HRT for adjusting moving bed membrane bioreactor is 18h, gas-water ratio 5, and water outlet enters moving bed membrane bioreaction
Device is answered to go out water pot, it is 77.19mg/L to measure COD mean concentrations in water outlet, and ammonia nitrogen mean concentration is 249.09mg/L, and dissolubility is just
Phosphate SOP mean concentrations are 170.00mg/L.The removal of moving bed membrane bioreactor ammonia nitrogen and dissolubility orthophosphates SOP
Rate is respectively 17.58% and 11.59%.
Embodiment 4
Continuously run using anaerobic sludge digestion liquid as moving bed membrane bioreactor feed liquor, COD concentration is in feed liquor
145.99 ~ 424.44mg/L, ammonia nitrogen concentration are 310.14 ~ 370.69mg/L, dissolubility orthophosphates SOP concentration be 165.32 ~
225.14mg/L.The HRT for adjusting moving bed membrane bioreactor is 12h, gas-water ratio 5, and water outlet enters moving bed membrane bioreaction
Device is answered to go out water pot, it is 63.67mg/L to measure COD mean concentrations in water outlet, and ammonia nitrogen mean concentration is 272.59mg/L, and dissolubility is just
Phosphate SOP mean concentrations are 167.66mg/L.The removal of moving bed membrane bioreactor ammonia nitrogen and dissolubility orthophosphates SOP
Rate is respectively 17.07% and 8.73%.
Embodiment 5
The water outlet of moving bed membrane bioreactor is used as SQD-96 anion exchange resin reactors by the use of in embodiment 4
Upper prop liquid, wherein COD mean concentrations are 63.67mg/L, and total average nitrogen concentration is 286.33mg/L, and ammonia nitrogen mean concentration is
272.59mg/L, total phosphorus mean concentration are 167.70mg/L, and dissolubility orthophosphates SOP mean concentrations are 167.66mg/L.
SQD-96 anion exchange resin reactor is 25 DEG C in adsorption temp, does not change upper prop liquid pH（7.3）Condition
Under the dissolubility orthophosphates SOP in upper prop liquid is adsorbed, when SQD-96 anion exchange resin is to dissolubility orthophosphoric acid
The absorption of salt SOP stops absorption when reaching breakthrough point.Upper prop flow velocity is respectively 1BV/h, 2BV/h and 4BV/h（BV is resin bed
Layer volume）When, phosphorus concentration meets in resin reaction device water outlet《Urban wastewater treatment firm pollutant emission standard》（GB 18918—
2002）In to the maximum processing volume integral of resin reaction device of total phosphorus level-one emission standard A limit value requirement not Wei 36BV, 32BV and
28BV, dissolubility orthophosphates SOP separation rates reach more than 99%.
Embodiment 6
The water outlet of moving bed membrane bioreactor is used as SQD-96 anion exchange resin reactors by the use of in embodiment 4
Upper prop liquid, wherein COD mean concentrations are 63.67mg/L, and total average nitrogen concentration is 286.33mg/L, and ammonia nitrogen mean concentration is
272.59mg/L, total phosphorus mean concentration are 167.70mg/L, and dissolubility orthophosphates SOP mean concentrations are 167.66mg/L.
SQD-96 anion exchange resin reactor is 2BV/h in upper prop flow velocity, does not change upper prop liquid pH（7.3）Bar
The dissolubility orthophosphates SOP in upper prop liquid is adsorbed under part, when SQD-96 anion exchange resin is to the positive phosphorus of dissolubility
The absorption of hydrochlorate SOP stops absorption when reaching breakthrough point.When adsorption temp is respectively 15 DEG C, 25 DEG C and 35 DEG C, resin reaction device
Phosphorus concentration meets in water outlet《Urban wastewater treatment firm pollutant emission standard》（GB 18918—2002）In to total phosphorus level-one A arrange
Put the maximum processing volume integral of resin reaction device of standard limited value requirement not Wei 40BV, 40BV and 36BV, dissolubility orthophosphates SOP
Separation rate reaches more than 99%.
Embodiment 7
The water outlet of moving bed membrane bioreactor is used as SQD-96 anion exchange resin reactors by the use of in embodiment 4
Upper prop liquid, wherein COD mean concentrations are 63.67mg/L, and total average nitrogen concentration is 286.33mg/L, and ammonia nitrogen mean concentration is
272.59mg/L, total phosphorus mean concentration are 167.70mg/L, and dissolubility orthophosphates SOP mean concentrations are 167.66mg/L.
SQD-96 anion exchange resin reactor is 25 DEG C in adsorption temp, under conditions of upper prop flow velocity is 2BV/h
Dissolubility orthophosphates SOP in upper prop liquid is adsorbed, when SQD-96 anion exchange resin is to dissolubility orthophosphates
The absorption of SOP stops absorption when reaching breakthrough point.It is respectively 6.0 and 6.5 using 5% hydrochloric acid adjusting upper prop liquid pH and does not adjust
pH（7.3）When, phosphorus concentration meets in resin reaction device water outlet《Urban wastewater treatment firm pollutant emission standard》（GB 18918—
2002）In to the maximum processing volume integral of resin reaction device of total phosphorus level-one emission standard A limit value requirement not Wei 52BV and 40BV with
And 32BV, dissolubility orthophosphates SOP separation rates reach more than 99%.
Embodiment 8
When upper prop liquid pH is 6.0 in embodiment 7, when SQD-96 anion exchange resin is to dissolubility orthophosphates SOP
Absorption reach breakthrough point after, use sodium hydroxide solution to be eluted for eluant, eluent to SQD-96 anion exchange resin.
Elution flow rate is 0.5BV/h, and eluting temperature is 35 DEG C, and eluant, eluent concentration of sodium hydroxide solution is respectively 2%, 3% and 4% condition
Under eluted, in eluent dissolubility orthophosphates SOP concentration be respectively 4142.51mg/L, 5013.54mg/L and
5685.11mg/L。
Embodiment 9
When upper prop liquid pH is 6.0 in Example 7, SQD-96 anion exchange resin reactor water outlets are with sodium hydroxide
Solution is passed through by the feeding liquid of cartridge filter and snakelike heat exchange tube as hollow fibre membrane systems, wherein COD concentration after adjusting pH
Less than 50mg/L, ammonia nitrogen mean concentration is 265.19mg/L, and dissolubility orthophosphates SOP mean concentrations are less than 0.5mg/L.Take reality
The rich phosphorus eluent obtained when using 4% sodium hydroxide solution as eluant, eluent in example 8 is applied, adding hydrochloric acid wherein makes at acidifying
Concentration of hydrochloric acid reaches 1mol/L and is used as the absorbing liquid of hollow fiber film assembly separation ammonia nitrogen in rich phosphorus eluent after reason.
It is 10min in the HRT of hollow fiber film assembly, under conditions of operation temperature is 25 DEG C, with 10% sodium hydroxide solution
Feeding liquid pH is adjusted when being respectively 10.0,11.0 and 12.0, the ammonia nitrogen separation rates of hollow fibre membrane systems is respectively 52.60%,
75.24% and 77.88%, in hollow fibre membrane systems water outlet ammonia nitrogen concentration be respectively 125.70mg/L, 65.66mg/L and
58.66mg/L。
Embodiment 10
When upper prop liquid pH is 6.0 in Example 7, SQD-96 anion exchange resin reactor water outlets are with sodium hydroxide
Solution is passed through by the feeding liquid of cartridge filter and snakelike heat exchange tube as hollow fibre membrane systems, wherein COD concentration after adjusting pH
Less than 50mg/L, ammonia nitrogen mean concentration is 265.19mg/L, and dissolubility orthophosphates SOP mean concentrations are less than 0.5mg/L.Take reality
The rich phosphorus eluent obtained when using 4% sodium hydroxide solution as eluant, eluent in example 8 is applied, adding hydrochloric acid wherein makes at acidifying
Concentration of hydrochloric acid reaches 1mol/L and is used as the absorbing liquid of hollow fiber film assembly separation ammonia nitrogen in rich phosphorus eluent after reason.
It is 10min in the HRT of hollow fiber film assembly, under conditions of feeding liquid pH is 11.0, operation temperature is respectively 25
DEG C, 30 DEG C and at 35 DEG C, the ammonia nitrogen separation rate of hollow fibre membrane systems is respectively 75.24%, 80.47% and 84.54%, hollow fibre
It is respectively 65.66mg/L, 51.79mg/L and 50.00mg/L to tie up ammonia nitrogen concentration in membranous system water outlet.
Embodiment 11
When upper prop liquid pH is 6.0 in Example 7, SQD-96 anion exchange resin reactor water outlets are with sodium hydroxide
Solution is passed through by the feeding liquid of cartridge filter and snakelike heat exchange tube as hollow fibre membrane systems, wherein COD concentration after adjusting pH
Less than 50mg/L, ammonia nitrogen mean concentration is 265.19mg/L, and dissolubility orthophosphates SOP mean concentrations are less than 0.5mg/L.Take reality
The rich phosphorus eluent obtained when using 4% sodium hydroxide solution as eluant, eluent in example 8 is applied, adding hydrochloric acid wherein makes at acidifying
Concentration of hydrochloric acid reaches 1mol/L and is used as the absorbing liquid of hollow fibre membrane systems separation ammonia nitrogen in rich phosphorus eluent after reason.
Hollow fibre membrane systems are 11.0 in feeding liquid pH, and operation temperature is respectively under conditions of 35 DEG C, and HRT is respectively
When 5min, 10min and 15min, the ammonia nitrogen separation rate of hollow fibre membrane systems is respectively 68.89%, 84.54% and 90.95%, in
Ammonia nitrogen concentration is respectively 82.50mg/L, 50.00mg/L and 24.00mg/L in empty fiber membrane system water outlet.
In summary, COD concentration is less than 100mg/L in system final outflow water in optimal conditions, and ammonia nitrogen concentration is less than
25mg/L, meets《Urban wastewater treatment firm pollutant emission standard》（GB 18918—2002）In to the two level of COD and ammonia nitrogen
Limited value of discharge standard requirement；Phosphorus concentration is less than 0.5mg/L in water outlet, meets《Urban wastewater treatment firm pollutant emission standard》
（GB 18918—2002）In to the requirement of the level-one emission standard A limit value of total phosphorus.
Embodiment 12
Under conditions of HRT is 12, gas-water ratio is 5, using moving bed membrane bioreactor to anaerobic sludge digestion liquid into
Row pretreatment, COD concentration be 204.10 ~ 461.54mg/L wherein in anaerobic sludge digestion liquid, total phosphorus concentration is 137.66 ~
209.41mg/L, dissolubility orthophosphates SOP concentration are 118.36 ~ 208.41mg/L, total nitrogen concentration for 295.53 ~
670.31mg/L, ammonia nitrogen concentration are 277.51 ~ 651.89mg/L, and COD concentration is less than in moving bed membrane bioreactor water outlet
The removal rate of 100mg/L, ammonia nitrogen and SOP are respectively lower than 25% and 15%.
Enter SQD-96 anion exchange resin reactors using the water outlet of moving bed membrane bioreactor as upper prop liquid, its
COD mean concentrations are 63.67mg/L in middle upper prop liquid, and total average nitrogen concentration is 286.33mg/L, and ammonia nitrogen mean concentration is
272.59mg/L, total phosphorus mean concentration are 167.70mg/L, and dissolubility orthophosphates SOP mean concentrations are 167.66mg/L.
Upper prop flow velocity is 2BV/h, and adsorption temp is 25 DEG C, under conditions of upper prop liquid pH is 6.0, SQD-96 anion exchange resin pair
The breakthrough point of dissolubility orthophosphates SOP absorption is 52BV, and the separation rate of dissolubility orthophosphates SOP in upper prop liquid is exceeded
99%.Eluting temperature be 35 DEG C, elution flow rate be 0.5BV/h under conditions of, use 4% sodium hydroxide solution for eluant, eluent to suction
The SQD-96 anion exchange resin of attached phosphorus is eluted, and dissolubility orthophosphates SOP concentration is more than 5000mg/ in eluent
L。
Using SQD-96 anion exchange resin reactor water outlets as the feeding liquid of hollow fibre membrane systems, in 4% hydroxide
Hydrochloric acid is added in the rich phosphorus eluent obtained when sodium solution is as eluant, eluent makes hydrochloric acid in the rich phosphorus eluent after acidification dense
Degree reaches absorbing liquids of the 1mol/L as hollow fibre membrane systems separation ammonia nitrogen, is 11.0 in feeding liquid pH, operation temperature 35
DEG C, under conditions of HRT is 15min, ammonia nitrogen concentration is less than 25mg/L in hollow fibre membrane systems water outlet, hollow fiber film assembly
Ammonia nitrogen concentration in absorbing liquid is then more than 10000mg/L, and dissolubility orthophosphates SOP concentration is then more than 5000mg/L.
Ammonia nitrogen containing high concentration and soluble orthophosphates SOP in the absorbing liquid of hollow fiber film assembly, while also contain
There are substantial amounts of sodium ion and chlorion.Since the solubility with temperature of sodium chloride varies less, and sodium ascorbyl phosphate, ammonium phosphate salt and
The solubility of ammonium chloride etc. is proportionate with temperature change, therefore first separates hollow fiber film assembly using the method for evaporative crystallization
Sodium chloride in absorbing liquid, then the absorbing liquid of hollow fiber film assembly of the method after sodium chloride has been separated using crystallisation by cooling
Middle acquisition complex fertilizer, without adding medicine.
After measured, most of sodium ion in the absorbing liquid of hollow fiber film assembly passes through evaporative crystallization as sodium chloride
Separated from the absorbing liquid of hollow fiber film assembly, and in the obtained crystal of evaporative crystallization sodium chloride content nearly 90%.
And after having separated the absorbing liquid crystallisation by cooling of the hollow fiber film assembly after sodium chloride, the total nutrient content of crystallized product（P2O5%+
NH4 +-N%+K2O%）More than 40%, reach《Complex fertilizer》（GB 15063—2009）The quality requirement of middle and high concentration total nutrient.
Claims (10)
- A kind of 1. device for being used to prepare complex fertilizer, it is characterised in that：Including material box（1）, moving bed membrane bioreactor （7）, air pump（9）, moving bed membrane bioreactor go out water pot（12）, SQD-96 anion exchange resin reactors（16）, hydrogen Sodium hydroxide solution tank（20）, resin reaction device go out water pot（23）, cartridge filter（26）, snakelike heat exchange tube（27）, doughnut Membrane module（30）, hollow fibre membrane systems go out water pot（31）, hollow fibre membrane systems absorption flow container（32）, hydrochloric acid tank（34）、 The absorbing liquid circulating pump of hollow fibre membrane systems（37）, resin eluant, eluent tank（39）, resin reaction device thermostatic water-circulator bath pot （43）, upper prop liquid adjusting hydrochloric acid tank（44）, hollow fibre membrane systems thermostatic water-circulator bath pot（47）；The material box （1）With moving bed membrane bioreactor（7）It is connected；The air pump（9）With moving bed membrane bioreactor（7）It is connected；Institute The moving bed membrane bioreactor stated（7）Go out water pot with moving bed membrane bioreactor（12）It is connected；The moving bed film life Thing reactor goes out water pot（12）With SQD-96 anion exchange resin reactors（16）It is connected；The resin reaction device is with super Thermostat water bath（43）With SQD-96 anion exchange resin reactors（16）It is connected；The upper prop liquid hydrochloric acid tank（44）With SQD-96 anion exchange resin reactors（16）It is connected；The SQD-96 anion exchange resin reactors（16）With resin Reactor goes out water pot（23）It is connected；The sodium hydroxide solution tank（20）Go out water pot with resin reaction device（23）It is connected；It is described Resin reaction device go out water pot（23）Pass through cartridge filter（26）, snakelike heat exchange tube（27）With hollow fiber film assembly（30）Phase Even；Hollow fibre membrane systems thermostatic water-circulator bath pot（47）With snakelike heat exchange tube（27）It is connected；The hollow fibre Tie up membrane module（30）Go out water pot with hollow fibre membrane systems（31）It is connected, hollow fiber film assembly（30）With hollow fibre membrane systems Absorption flow container（32）It is connected；The hydrochloric acid tank（34）With the absorption flow container of hollow fibre membrane systems（32）It is connected；Described Resin eluant, eluent tank（39）With SQD-96 anion exchange resin reactors（16）It is connected, the reaction of SQD-96 anion exchange resin Device（16）With the absorption flow container of hollow fibre membrane systems（32）It is connected.
- 2. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：Given birth in the moving bed film Thing reactor（7）Interior lower part sets floating stuffing（6）, top sets hydrophilic Kynoar pvdf membrane component（8）, in moving bed Membrane bioreactor（7）Inside set aeration head（5）, bottom sets mud valve（4）, the material box（1）Pass through liquid feeding pump（2）, into Hydraulic control valve（3）With moving bed membrane bioreactor（7）It is connected, the air pump（9）Pass through gas control valve（10）, rotor Flowmeter（11）With aeration head（5）It is connected.
- 3. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：The moving bed film biology Reactor goes out water pot（12）With vacuum pump（13）It is connected.
- 4. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：Described SQD-96 the moon from Sub-exchange resin reactor（16）Inside set SQD-96 anion exchange resin（17）, the moving bed membrane bioreactor water outlet Tank（12）Pass through upper prop liquid pump（14）, upper prop hydraulic control valve（15）With SQD-96 anion exchange resin reactors（16）It is connected, The upper prop liquid hydrochloric acid tank（44）Pump is added with hydrochloric acid by the adjusting of upper prop liquid（45）, upper prop liquid adjust use hydrochloric acid control valve （46）With SQD-96 anion exchange resin reactors（16）It is connected；The SQD-96 anion exchange resin reactors（16） Pass through resin reaction device outlet valve（18）, resin reaction device water outlet pump（19）Go out water pot with resin reaction device（23）It is connected；It is described Resin eluant, eluent tank（39）Pump is added by resin eluant, eluent（40）, resin eluant, eluent control valve（41）With SQD-96 anion Exchanger resin reactor（16）It is connected.
- 5. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：The sodium hydroxide solution Tank（20）Pump is added by sodium hydroxide solution（21）, sodium hydroxide solution control valve（22）Go out water pot with resin reaction device（23） It is connected；The resin reaction device goes out water pot（23）Pass through the liquid feeding pump of hollow fibre membrane systems（25）, cartridge filter（26）、 Snakelike heat exchange tube（27）, hollow fibre membrane systems liquid inlet control valve（28）, pressure gauge（29）With hollow fiber film assembly（30）Phase Even；The SQD-96 anion exchange resin reactor water outlet magnetic stirring apparatus（24）Go out water pot with resin reaction device（23） It is connected.
- 6. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：The snakelike heat exchange tube （27）With hollow fibre membrane systems thermostatic water-circulator bath pot（47）It is connected.
- 7. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：The hollow-fibre membrane group Part（30）Pass through the absorbing liquid circulating pump of hollow fibre membrane systems（37）, hollow fibre membrane systems absorbing liquid circulation control valve （38）With the absorption flow container of hollow fibre membrane systems（32）Circulation is connected.
- 8. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：The absorbing liquid magnetic force Blender（33）With the absorption flow container of hollow fibre membrane systems（32）It is connected.
- 9. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：The hydrochloric acid tank（34）It is logical Persalt adds pump（35）, hydrochloric acid control valve（36）With the absorption flow container of hollow fibre membrane systems（32）It is connected.
- 10. the device according to claim 1 for being used to prepare complex fertilizer, it is characterised in that：Described SQD-96 the moon from Sub-exchange resin reactor（16）Hydraulic control valve is eluted by resin（42）With the absorption flow container of hollow fibre membrane systems（32）Phase Even.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112876314A (en) * | 2021-01-29 | 2021-06-01 | 宁夏茂原生物科技有限公司 | Humic acid compound fertilizer/blended fertilizer shared production system and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112876314A (en) * | 2021-01-29 | 2021-06-01 | 宁夏茂原生物科技有限公司 | Humic acid compound fertilizer/blended fertilizer shared production system and use method thereof |
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