CN114291987A - System and method for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance - Google Patents
System and method for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance Download PDFInfo
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Images
Classifications
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Treatment Of Sludge (AREA)
Abstract
The invention relates to the technical field of environmental pollution treatment and comprehensive utilization of solid wastes, in particular to a system and a method for recovering carbon and phosphorus resources in excess sludge by utilizing ultrasonic assistance. The system comprises: the system comprises a sludge pretreatment system, a carbon recovery system, a phosphorus recovery system and a sludge storage pool; wherein the sludge pretreatment system comprises an ultrasonic pretreatment reactor, Ca (OH)2A dissolving unit and an EDTA dissolving unit; the carbon recovery system comprises an anaerobic digestion tank, a biogas collecting device and a first centrifugal device; the phosphorus recovery system comprises a phosphorus recovery reaction tank,A medicament reservoir and a second centrifuge. The excess sludge recycling system disclosed by the invention is used for sludge disintegration by means of a comprehensive effect generated in the aspects of floc destruction and cell damage by combining an ultrasonic physical method and an alkaline agent. Compared with the traditional anaerobic digestion, the system improves the reaction efficiency, increases the release amount of carbon and phosphorus resources and reduces the treatment cost.
Description
Technical Field
The invention relates to the technical field of environmental pollution treatment and comprehensive utilization of solid wastes, in particular to a system and a method for recovering carbon and phosphorus resources in excess sludge by utilizing ultrasonic assistance.
Background
At present, the disposal method of excess sludge mainly includes a landfill method, a burning method, a land utilization method, an anaerobic digestion method, an aerobic composting method and the like. The landfill disposal method occupies a large land area and has the risk of polluting underground water and the like. The burning method has the defects of high energy consumption, high cost, easy generation of smoke pollution and the like. The soil utilization method has problems in biological safety, and is easy to cause the biochemical potential safety hazard caused by the transmission of toxic and harmful substances in the sludge along a biological chain. Both the anaerobic digestion method and the aerobic composting method of the sludge have the problems of complex process system, large floor area, landfill of a large amount of organic sludge as a byproduct and the like. Meanwhile, the generation amount of excess sludge has a sharp contradiction with the increasing trend, the shortage of sludge treatment capacity and the serious backward situation of treatment means, and the problem of treatment and disposal of the excess sludge becomes an unavoidable urban environment problem. Currently, a novel treatment method which is more economical, more environment-friendly, and capable of reducing sludge and recovering resources is urgently needed.
In recent years, many research reports about resource utilization of excess sludge are reported, remarkable effect is achieved, and certain theoretical guidance and technical support are provided for resource utilization of sludge. However, the development and utilization rate of excess sludge resources is not high in real life, and most of research reports that only one useful substance is obtained independently (such as only extracting phosphorus from excess sludge or only obtaining carbon from excess sludge), which causes the loss of other resources in the development process.
At present, the anaerobic digestion technology basically realizes the stabilization and reduction of excess sludge treatment, has certain superiority in the aspect of energy recovery, and becomes an effective way and a research hotspot for excess sludge treatment. However, in anaerobic digestion, the rate of hydrolysis is a decisive step in the rate of conversion of complex organic matter, so that the excess sludge is usually pretreated before anaerobic digestion. The combined treatment of the sonophysical method with the alkaline agent was best in numerous studies, but too many cations (such as Na) were present in combination+) Has inhibition effect on subsequent anaerobic digestion and the like, and is not solved at present.
The excess sludge is pretreated to release carbon and phosphorus resources, and simultaneously, metals in the sludge are released (such as Al)3+、Fe3+、Mg2+) Will be in contact with PO4 3-The reaction occurs to form insoluble matter, thereby reducing the recovery of phosphorus. The phosphorus recovery is carried out by using the calcium hydroxy phosphate precipitation technology, the recovery rate is not high, and the purity is lower. The treatment and disposal of the residual supernatant and the bottom sludge after the recovery cause resource waste. Therefore, a set of simple, economic, green and environment-friendly new process and new technology for efficiently utilizing the potential resources of the excess sludge are provided, which are important ways for solving the problems.
Disclosure of Invention
Based on the above, the invention provides a system and a method for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance. The system has reasonable design and convenient use, and can realize the reduction of excess sludge and the recycling of carbon and phosphorus resources. Compared with the traditional anaerobic digestion, the system improves the reaction efficiency, and compared with the traditional physical method, the ultrasonic physical method coupled with chemical agents increases the release amount of carbon and phosphorus resources and reduces the treatment cost.
One of the technical schemes of the invention is a system for recovering carbon and phosphorus resources in excess sludge by utilizing ultrasonic assistance, which comprises a sludge pretreatment system, a carbon recovery system, a phosphorus recovery system and a sludge storage pool;
wherein saidThe sludge pretreatment system comprises an ultrasonic pretreatment reactor, Ca (OH)2A dissolving unit and an EDTA dissolving unit; the carbon recovery system comprises an anaerobic digestion tank, a biogas collecting device and a first centrifugal device; the phosphorus recovery system comprises a phosphorus recovery reaction tank, a medicament storage tank and a second centrifugal device;
the discharge hole of the sludge storage pool is communicated with the feed inlet of the ultrasonic pretreatment reactor, and Ca (OH)2The discharge ports of the dissolving unit and the EDTA dissolving unit are communicated with the feed port of the ultrasonic pretreatment reactor;
the discharge hole of the ultrasonic pretreatment reactor is communicated with the feed inlet of the anaerobic digestion tank, the upper end of the anaerobic digestion tank is communicated with the biogas collecting device, and the discharge hole of the anaerobic digestion tank is communicated with the feed inlet of the first centrifugal device;
the first centrifugal device liquid outlet with the retort feed inlet intercommunication is retrieved to phosphorus, medicament storage tank discharge gate with retort feed inlet intercommunication is retrieved to phosphorus, the retort discharge gate is retrieved to phosphorus with second centrifugal device feed inlet intercommunication.
Further, the sludge storage tank is provided with a submersible sewage pump and a first metering device;
further, a first stirring device, a first pH detector and a first index automatic detection device are arranged on the ultrasonic pretreatment reactor;
furthermore, a second metering device and a solution preparation device are arranged on the EDTA dissolution unit;
further, the Ca (OH)2The dissolving unit and the EDTA dissolving unit share a second metering device and a solution preparation device;
furthermore, a third metering device, a second pH tester, a nitrogen stripping device, a water bath shaking table device and a second index automatic detection device are arranged on the anaerobic digestion tank;
further, a third pH detection meter, a fourth metering device, a timing device, a third index automatic detection device and a second stirring device are arranged on the phosphorus recovery reaction tank;
further, the phosphorusThe recovery system also comprises a supernatant collecting tank and a phosphorus recovery collecting tank; the feed inlet of the supernatant collecting tank is communicated with the discharge outlet of the second centrifugal device, the discharge outlet of the supernatant collecting tank is communicated with the feed inlet of a recycling device, and the discharge outlet of the recycling device is Ca (OH)2The dissolving unit is communicated, and the recycling device and the EDTA dissolving unit share a solution preparation device;
furthermore, a history type fermentation pipe is arranged on the methane collecting device. The fermentation tube is filled with solution for absorbing acidic gas such as carbon dioxide and hydrogen sulfide.
According to the second technical scheme, calcium hydroxide and EDTA are added into the excess sludge, anaerobic digestion is carried out after ultrasonic pretreatment to obtain methane and anaerobic digestion products, the anaerobic digestion products are centrifuged to obtain supernatant, and the calcium hydroxide is continuously added into the supernatant to obtain phosphorus recovery products after solid-liquid separation.
Further, the method for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance utilizes the system for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance to recover excess sludge.
Further, the method specifically comprises the following steps:
(1) the excess sludge enters an ultrasonic pretreatment reactor through a sludge storage pool, and Ca (OH)2By Ca (OH)2The dissolving unit enters an ultrasonic pretreatment reactor, EDTA enters the ultrasonic pretreatment reactor through the EDTA dissolving unit, and the residual sludge is cracked under the ultrasonic condition to obtain pretreated residual sludge;
(2) the method comprises the following steps that pretreated residual sludge enters an anaerobic digestion tank and inoculated sludge are mixed for anaerobic digestion, generated methane is recycled through a methane collection device, and generated anaerobic digestion products enter a first centrifugal device for centrifugation to obtain bottom sludge and phosphorus-rich supernatant;
(3) and (3) allowing the phosphorus-rich supernatant to enter a phosphorus recovery reaction tank, allowing calcium hydroxide to enter the phosphorus recovery reaction tank through a medicament storage tank and mixing the phosphorus-rich supernatant with the calcium hydroxide to obtain a reaction solution, and allowing a product obtained after the reaction of the reaction solution to enter a second centrifugal device for centrifugal separation to obtain a supernatant and a phosphorus recovery product.
Further, in the step (1):
cracking reaction conditions: the ultrasonic sound energy density is 0.2-1.2W/mL, and the ultrasonic time is 30-60 min;
the mass ratio of the addition amount of EDTA to the excess sludge is 0.15 g: 10g, wherein the adding concentration of the EDTA is 0-20mmol/L (not zero);
Ca(OH)2the adding amount of the sludge is to adjust the pH value of the sludge to 10-12;
after the pH value of the pretreated excess sludge is adjusted to be neutral, the step (2) is carried out;
further, in the step (2):
the volume ratio of the pretreated residual sludge to the inoculated sludge is 4-6: 1;
the anaerobic digestion temperature is 33-37 ℃, and the anaerobic digestion time is 8-12 days;
first centrifuge centrifugation conditions: centrifuging at 6000r/min for 20-30 min;
further, in the step (3): the calcium-phosphorus ratio in the reaction liquid is 3-8:1, the pH value is 8.3-9.5, the reaction time is 10-20min, and the centrifugation conditions of a second centrifugal device are as follows: centrifuging at 6000r/min for 10-30 min.
Further, the supernatant obtained in the step (3) is returned to the calcium hydroxide dissolving unit through a recycling device.
Compared with the prior art, the invention has the beneficial effects that:
the excess sludge recycling system disclosed by the invention is used for breaking excess sludge in a mode of combining ultrasonic waves and an alkaline agent, so that the excess sludge can generate comprehensive effects on floc damage and cell damage. The difference from the existing mode of treating the excess sludge by combining ultrasound and alkali is that Ca (OH) is selected and used in the invention2The alkaline hydrolysis is carried out, while the alkaline agent used in the prior alkaline hydrolysis technology is NaOH mostly, although the NaOH is more Ca (OH)2The sludge breaking degree is higher, however, free sodium ions are easy to cause soil salinization, and the sodium ions have toxicity and can generate an inhibiting effect on anaerobic digestion. The advantage of the invention is that Ca (OH) is present at the same pH2The methane yield of the pretreated sludge is higher than that of NaOH pretreatment(ii) a Further, slaked lime (Ca (OH)2) Compared with sodium hydroxide, the method is cheaper and easily available, and the treatment cost is reduced.
In alkaline environment, the released metal ions (Al) are broken in the sludge3+、Fe3+、Ca2+、Mg2+) Insoluble matter is formed with phosphate radical, partial phosphate radical is consumed, and thus the phosphorus recovery rate is reduced and the purity is lower. In order to solve the problems, the invention discloses that EDTA complexing agent is added to form a stable complex with the metal ions, and the complexing sequence of EDTA to the metal ions is Al3+、Fe3+、Ca2+、Mg2+The consumption of phosphate radical is avoided, the recovery rate of phosphorus is further improved, the currently disclosed sludge cracking technology is mostly a technology combining NaOH strong base and a complexing agent, and compared with the following advantages: EDTA can be complexed with calcium ions, so that the loss of phosphate radicals is reduced, the recovery rate of the phosphate radicals is further improved, and the inhibition effect of adding metal cations on the subsequent anaerobic digestion unit is avoided; the phosphorus recovery technology adopts a calcium hydroxy phosphate precipitation technology to recover phosphorus (after anaerobic digestion, the pH of the supernatant is reduced, calcium hydroxide is added to adjust the pH to be within the range of 8.3-9.5, and phosphorus is recovered, at the moment, the concentration of calcium ions per se reaches the recovery amount, so that calcium ions do not need to be additionally added), calcium ions and phosphate radicals generate calcium hydroxy phosphate to be recovered and utilized.
The invention discloses an ultrasonic-assisted sludge breaking method by using the medicament, which aims to: the ultrasonic sound has certain cracking effect on the excess sludge, assists the alkaline agent and the complexing agent, and makes up for Ca (OH)2And the EDTA has insufficient sludge cracking degree, further releases more carbon and phosphorus resources and has higher recycling value. The overall advantage of the excess sludge recycling system disclosed by the invention is that the ultrasonic auxiliary alkaline agent (Ca (OH) is utilized2) The sludge is efficiently cracked by combining the EDTA complexing agent, and the release rate of carbon and phosphorus resources can reach more than 30%; and promotes the carbon recovery of the subsequent anaerobic digestion unit, and the yield of the produced methane in the anaerobic digestion unit is relatively highThe processing mode of the system can be improved by more than 45 percent; in the phosphorus recovery unit, the recovery rate of phosphorus can reach 80%, and the purity can reach more than 70%; under the treatment of low energy consumption, the carbon and phosphorus resources are efficiently recovered.
The system disclosed by the invention can recycle the residual supernatant discharged by the phosphorus recovery unit to the pretreatment unit for recycling the water dissolved by the medicament, so that the recycling of the system is realized, and the residual bottom mud can also be subjected to stabilization treatment and utilized.
The invention achieves the dual effects of environmental protection and resource recovery, on one hand, the final outlet of municipal excess sludge is expanded, carbon and phosphorus resources in sludge are recovered, and the reduction of excess sludge is realized; on the other hand, resources with great application prospects in the recovered excess sludge are changed into valuables.
Drawings
FIG. 1 is a process flow chart of a system for recovering carbon and phosphorus resources from excess sludge by ultrasonic wave assistance, which is used in example 1 of the present invention;
FIG. 2 is a partial enlarged view of a sludge pretreatment system in a process flow diagram of a system for recovering carbon and phosphorus resources from excess sludge with the aid of ultrasonic waves, which is used in example 1 of the present invention;
FIG. 3 is a partial enlarged view of a carbon recovery system in a process flow chart of a system for ultrasonic-assisted recovery of carbon and phosphorus resources in excess sludge, which is used in example 1 of the present invention;
FIG. 4 is a partial enlarged view of a phosphorus recovery system in a process flow diagram of a system for ultrasonic-assisted recovery of carbon and phosphorus resources in excess sludge, which is used in example 1 of the present invention;
in the figures 1-4, 1, a sludge pretreatment system, 2, a carbon recovery system, 3, a phosphorus recovery system, 4, a sludge storage tank, 5, a first metering device, 6, an ultrasonic pretreatment reactor, 7, an EDTA dissolution unit, 8, Ca (OH)2The device comprises a dissolving unit, 9, a second metering device, 10, a solution preparation device, 11, a first stirring device, 12, a first pH tester, 13, a first index automatic detection device, 14, an anaerobic digestion tank, 15, a biogas collection device, 16, a first centrifugal device, 17, a third metering device, 18, a second pH tester, 19, a nitrogen stripping device, 20, a water bath shaking table device, 21, a second stirring device, a third stirring device, a fourth stirring device, a fifth stirring device, a sixth stirring device, a fifth stirring device, a sixth stirring device, a fifth stirring device, a sixth stirring device, a third stirring device, a fourth stirring device, a third stirring device, a fourth stirring device, a third stirring device, a fourth stirring device, a second stirring device, a third stirring device, a fourth stirring device, a third device, a second stirring device, a third stirring device, a third device, a second stirring device, a third device, a fourth stirring device, a third device, a fourth stirring device, a third device, a,The device comprises a second index automatic detection device, a bottom sediment discharge tank, a phosphorus recovery reaction tank, a reagent storage tank, a second centrifugal device, a supernatant collection tank, a phosphorus recovery material collection tank, a recycling device, a third pH tester, a fourth metering device, a timing device, a third index automatic detection device, a second stirring device, a reagent storage tank, a second centrifugal device, a supernatant collection tank, a second phosphorus recovery material collection tank, a third pH tester, a fourth metering device, a timing device, a third index automatic detection device and a second stirring device.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
FIG. 1 is a process flow chart of a system for recovering carbon and phosphorus resources from excess sludge by ultrasonic wave assistance, which is used in example 1 of the present invention; FIG. 2 is a partial enlarged view of a sludge pretreatment system in a process flow diagram of a system for recovering carbon and phosphorus resources from excess sludge with the aid of ultrasonic waves, which is used in example 1 of the present invention; FIG. 3 is a partial enlarged view of a carbon recovery system in a process flow chart of a system for ultrasonic-assisted recovery of carbon and phosphorus resources in excess sludge, which is used in example 1 of the present invention; FIG. 4 is a partial enlarged view of a phosphorus recovery system in a process flow diagram of a system for recovering carbon and phosphorus resources in excess sludge by ultrasonic assistance, which is used in example 1 of the present invention.
The method specifically comprises the following steps: 1 is a sludge pretreatment system, 2 is a carbon recovery system, 3 is a phosphorus recovery system, 4 is a sludge storage tank, 5 is a first metering device, 6 is an ultrasonic pretreatment reactor, 7 is an EDTA dissolution unit, 8 is Ca (OH)2The system comprises a dissolving unit, 9 is a second metering device, 10 is a solution preparation device, 11 is a first stirring device, 12 is a first pH tester, 13 is a first index automatic detection device, 14 is an anaerobic digestion tank, 15 is a biogas collection device, 16 is a first centrifugal device, 17 is a third metering device, 18 is a second pH tester, 19 is a nitrogen gas stripping device, 20 is a water bath shaking table device, 21 is a second index automatic detection device, 22 and a bottom mud discharge tank, 23 is a phosphorus recovery reaction tank, 24 is a medicament storage tank, 25 is a second centrifugal device, 26 is a supernatant collection tank, 27 is a phosphorus recovery material collection tank, 28 is a recycling device, 29 is a third pH tester, 30 is a fourth metering device, 31 is a timing device, 32 is a third index automatic detection device, and 33 is a second stirring device.
Wherein the sludge pretreatment system 1 comprises an ultrasonic pretreatment reactor 6, an EDTA dissolution unit 7 and Ca (OH)2A dissolving unit 8; the feed inlet of the ultrasonic pretreatment reactor 6 is connected with the outlet of the sludge storage tank 4 through a submersible sewage pump; the ultrasonic pretreatment reactorThe discharge hole of the 6 is connected with the feed inlet of the anaerobic digestion tank 14 through a conveying pipe 1-2; the sludge storage tank 4 is provided with a first metering device 5; the ultrasonic pretreatment reactor 6 is sequentially provided with a first stirring device 11, a first pH tester 12 and a first index automatic detection device 13; the EDTA dissolution unit 7 is connected with a feed inlet of the ultrasonic pretreatment reactor 6 through a conveying pipe 1-3, and a second metering device 9 and a solution preparation device 10 are sequentially arranged on the EDTA dissolution unit 7; the Ca (OH)2The dissolving unit 8 is connected with a feed inlet of the ultrasonic pretreatment reactor 6 through a conveying pipe 1-4, and shares a second metering device 9 and a solution preparation device 10 with the EDTA dissolving unit 7; the sludge enters an ultrasonic pretreatment reactor 6 from a sludge storage tank 4 through a 1-1 conveying pipe, passes through an EDTA dissolving unit 7 and Ca (OH)2The dissolving unit 8 is added with a medicament, sludge is cracked under the combined action of the first stirring device 11, carbon and phosphorus resources in the sludge are released, data are recorded through the first pH tester 12 and the first index automatic detection device 13, and the effect of resource release is analyzed. The pretreated sludge mixed liquor enters a carbon recovery system 2 through a conveying pipe 1-2.
The carbon recovery system 2 comprises an anaerobic digestion tank 14, a biogas collection device 15 and a first centrifugal device 16. The feed inlet of the anaerobic digestion tank 14 is connected with the discharge outlet of the ultrasonic pretreatment reactor 6 through a conveying pipe 1-2; the discharge hole of the anaerobic digestion tank 14 is connected with the inlet of a first centrifugal device 16 through a conveying pipe 2-1; the anaerobic digestion tank 14 is provided with a third metering device 17, a second pH tester 18, a nitrogen stripping device 19, a water bath shaking table device 20 and a second index automatic detection device 21; the inlet of the methane collecting device 15 is connected with the discharge hole of the anaerobic digestion tank 14 through a gas transmission pipe 2-2. A history type fermentation pipe (not shown in the figure) filled with NaCl saturated solution of NaOH with the concentration of 5mol/L is arranged on the methane collection device 15 and is used for absorbing acid gases such as carbon dioxide, hydrogen sulfide and the like; the pretreated sludge mixed liquor is conveyed to an anaerobic digestion tank 14 through a conveying pipe 1-2, and the sludge is subjected to reactions in three stages of anaerobic digestion by adjusting the second pH tester 18, the nitrogen stripping device 19 and the water bath shaking table device 20 under the optimal conditions (35 +/-1 ℃) so that resources in the sludge are recycled to a methane collection device 15 in the form of methane gas. The inlet of the first centrifugal device 16 is connected with the discharge hole of the anaerobic digestion tank 14 through a conveying pipe 2-1; the centrifuged bottom mud enters a bottom mud discharge tank 22 for stable discharge; the supernatant rich in phosphorus after centrifugation enters a phosphorus recovery system 3 for phosphorus recovery.
The phosphorus recovery system 3 comprises a phosphorus recovery reaction tank 23, a medicament storage tank 24, a second centrifugal device 25, a supernatant collection tank 26, a phosphorus recovery collection tank 27 and a recycling device 28. The feed inlet of the phosphorus recovery reaction tank 23 is connected with the upper end of the first centrifugal device 16 through a conveying pipe 3-1; the discharge port of the phosphorus recovery reaction tank 23 is connected with the inlet of a second centrifugal device 25 through a conveying pipe 3-2; the phosphorus recovery reaction tank 23 is provided with a third pH tester 29, a fourth metering device 30, a timing device 31, a third index automatic detection device 32 and a second stirring device 33; the outlet of the medicament storage tank 24 is connected with the inlet of the phosphorus recovery reaction tank 23 through a delivery pipe 3-3 for adding the medicament; the supernatant rich in phosphorus after the first centrifugation enters a phosphorus recovery reaction tank 23, and phosphorus recovery is carried out under the combined action of the optimum pH, the calcium-phosphorus ratio and the reaction time (the pH is 9.5, the calcium-phosphorus ratio is 3: 1; the reaction time is 20 min); the mixture of HAP pellet and supernatant is transferred to the inlet of the second centrifugal device 25 through the transfer pipe 3-2.
The feed inlet of the second centrifugal device 25 is connected with the outlet of the phosphorus recovery reaction tank 23; the centrifuged HAP sediment enters a phosphorus recovery material collecting tank 27 to obtain sludge phosphorus recovery material; the residual supernatant after centrifugation enters a supernatant collecting tank 26 through a conveying pipe 3-4; the inlet of the supernatant collecting tank 26 is connected with the upper end of the second centrifugal device 25; the outlet of the supernatant collecting tank 26 is connected with the inlet of a recycling device 28 through a 3-5 conveying pipe for recycling; the inlet of the recycling device 28 is connected with the outlet of the supernatant collecting tank 26; the outlet of the recycling device 28 is communicated with Ca (OH) through a conveying pipe2The dissolving unit 8 is connected; the recycling device 28 is provided with a solution preparation device and an EDTA dissolution unit 7 which share one device.
The excess sludge is obtained from a sewage treatment plant in Changchun city and is taken backThe sludge is sieved by using a 2mm multiplied by 2mm screen mesh, is put into a sludge storage tank 4 for natural sedimentation, is taken out for standby after being placed for 24 hours, and various indexes of the raw sludge are measured by using a detection device as follows: pH of 6.8-7.1, water content of 97% (after filtration and precipitation, solid content reaches 2% -3%), PO4 3-14.2-16.6 mg/L of P, 32.5-37.2 mg/L of TP, 13256-24587 mg/L of TCOD, 718.8-1333 mg/L of SCOD, 20533-24290 mg/L of TS, 14116-17320 mg/L of VS, 13380-16400 mg/L of VSS and 18944-22400 mg/L of TSS. The following treatments were performed using the above apparatus:
(1) the excess sludge is measured by a sludge storage tank 4 through a first metering device 5 to obtain 200mL of sludge, the 200mL sludge enters an ultrasonic pretreatment reactor 6 through a submersible sewage pump, and Ca (OH)2The dissolving units 8 are respectively 1mol/L Ca (OH)2And H2SO4The pH of the sludge is adjusted to 12 by the mixed alkaline agent, EDTA is weighed to be 0.15g/10g (sludge) in an EDTA dissolution unit 7, 15mmol/L concentration is prepared and added into the sludge, an ultrasonic pretreatment reactor 6 is opened, ultrasonic time is set for 30min under the conditions that the frequency is 20kHz, the power is 100W and the ultrasonic sound energy density is ensured to be 0.5W/mL, after the pretreatment is finished, various indexes of the pretreated sludge are measured by a detection device, the VS/TS in the original sludge is 64.7 percent, the content of organic matters is high, and the requirement of anaerobic digestion is basically met; after pretreatment, the TSS and the VSS of the sludge are respectively 16221.2mg/L and 11426.0mg/L, and the reduction rate of the TSS and the VSS reaches 24.2 percent and 21.2 percent, which shows that the pretreatment system and the method greatly promote the conversion of the solid granular substances of the sludge to soluble substances; the increase of SCOD is 4568mg/L, and the release amount is 5.35 times of that of the excess sludge. The dissolution rate of SCOD can reach 30.1%; the TP was determined to be 48.75mg/L, PO4 3-21.9mg/L, the release rate is up to 50 percent, which is 1.5 times of the original excess sludge; the pH value of the pretreated sludge mixed liquor is 4.39, and alkali is properly added to adjust the pH value to be neutral, and the pretreated sludge mixed liquor enters the anaerobic digestion tank 14.
(2) The pretreated sludge mixed liquor enters a carbon recovery system 2 through a conveying pipe 1-2, pretreated sludge (sludge treated under the optimal condition, the condition of the step (1)) and inoculated sludge are taken according to the volume ratio of 5: 1, mixing, entering an anaerobic digestion tank 14, introducing nitrogen to blow off for 1min, sealing, placing in a water bath shaking table at 35 +/-1 ℃, and periodically sampling and detecting. Carrying out anaerobic fermentation for 10 days, respectively recording the index data of the samples at 1, 2, 3, 4, 6, 8, 9 and 10, and analyzing the yield of methane under the optimal condition; and (3) directly carrying out the treatment of the step (2) on the original excess sludge which is not subjected to the treatment of the step (1) to be used as a control group.
The result shows that the removal rate of TCOD of the residual sludge treated by ultrasonic treatment for 30min after the medicament is added in the step (1) is 20.84 percent after 10 days of anaerobic fermentation, and is improved by 42.0 percent compared with the anaerobic digestion of a control group; the removal rate of SCOD under the same condition is 35.17%; the removal rate of VS was 20.5%; the VSS removal rate is improved to 23.21 percent, and is improved by 59.0 percent compared with a control group which is not treated; under the condition that the pH value is 12, the maximum gas production appears on the 5 th day and the 6 th day of anaerobic digestion, and the gas production of the reactor is in a lower level by the 10 th day of digestion, the average daily gas production can reach 132.5mL/d, the gas production is improved by 45 percent compared with the traditional pretreatment, and can be improved by 75 percent compared with the gas production without the pretreatment. And (3) feeding the sludge mixed liquor after the reaction in the anaerobic digestion tank 14 into a first centrifugal device 16 for solid-liquid separation, and centrifuging the sludge for 20min under the condition of 6000r/min to finish the solid-liquid separation. And (4) enabling the supernatant to enter a phosphorus recovery system 3, and enabling the residual bottom sludge to enter a bottom sludge discharge tank 33 for stabilizing incineration treatment.
(3) The phosphorus-rich supernatant after centrifugation by the first centrifuge 16 is fed into a phosphorus recovery system 3 for phosphorus recovery, and the supernatant is subjected to pH measurement (pH, TP, PO)4 3-P), considering the recovery of calcium hydroxy phosphate precipitant (after centrifugation, the supernatant enters the phosphorus recovery reaction tank 23 for phosphorus recovery, and the step is to continue adding calcium hydroxide reagent for the adaptation condition of adjusting pH for phosphorus recovery), the ratio of calcium to phosphorus is adjusted in the optimum ratio of 3: 1. after the reaction is carried out for 10min under the condition that the pH value is 9.5, the recovery rate of the phosphorus can reach more than 80 percent, and the purity can reach more than 70 percent. And (3) performing solid-liquid separation on the sludge mixed liquor after the reaction in the phosphorus recovery reaction tank 23, and centrifuging the sludge for 20min under the condition of 6000r/min to finish the solid-liquid separation. The centrifuged HAP sediment enters a phosphorus recovery material collecting tank 27 to obtain sludge phosphorus recovery material for utilization; the residual supernatant after centrifugation enters a supernatant collecting tank 26 through a conveying pipe 3-4; collecting supernatantThe outlet of the tank 26 is connected with the inlet of a recycling device 28 through a 3-5 conveying pipe for recycling; metering the solution required for the preparation in the recycling apparatus 28, adding Ca (OH)2The dissolving unit 8 recycles the water for dissolving the medicament.
In the above, the recovery rate of phosphorus: the ratio of the difference between the concentration of phosphorus released from the sludge into the supernatant and the concentration of phosphorus remaining in the supernatant after recovery to the concentration of phosphorus in the sludge.
Purity: p in calcium hydroxy phosphate2O5The calculation of (2): drying a certain amount of precipitate in a constant temperature drying oven at 105 deg.C to constant weight, dissolving the precipitate with 1mol/LHCL, transferring into a 100ml volumetric flask, and metering to marked volume, P2O5(％)＝(Cp×141.94)/(m×30.97×2)×104×100％
CpThe concentration of phosphorus in the volumetric flask is mg/L; 30.97 is the relative atomic mass of P, g/mol; 141.94 is P2O5Molar mass of (a), g/mol; m is the mass of the precipitate taken, g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A system for recovering carbon and phosphorus resources in excess sludge by utilizing ultrasonic assistance is characterized by comprising a sludge pretreatment system, a carbon recovery system, a phosphorus recovery system and a sludge storage pool;
wherein the sludge pretreatment system comprises an ultrasonic pretreatment reactor, Ca (OH)2A dissolving unit and an EDTA dissolving unit; the carbon recovery system comprises an anaerobic digestion tank, a biogas collecting device and a first centrifugal device; the phosphorus recovery system comprises a phosphorus recovery reaction tank, a medicament storage tank and a second centrifugal device;
the discharge hole of the sludge storage pool is communicated with the feed inlet of the ultrasonic pretreatment reactor, and Ca (OH)2The discharge ports of the dissolving unit and the EDTA dissolving unit are communicated with the feed port of the ultrasonic pretreatment reactor;
the discharge hole of the ultrasonic pretreatment reactor is communicated with the feed inlet of the anaerobic digestion tank, the upper end of the anaerobic digestion tank is communicated with the biogas collecting device, and the discharge hole of the anaerobic digestion tank is communicated with the feed inlet of the first centrifugal device;
the first centrifugal device liquid outlet with the retort feed inlet intercommunication is retrieved to phosphorus, medicament storage tank discharge gate with retort feed inlet intercommunication is retrieved to phosphorus, the retort discharge gate is retrieved to phosphorus with second centrifugal device feed inlet intercommunication.
2. The system for recovering carbon and phosphorus resources in excess sludge by using ultrasonic assistance according to claim 1, wherein the sludge storage tank is provided with a submersible sewage pump and a first metering device;
the ultrasonic pretreatment reactor is provided with a first stirring device, a first pH detector and a first index automatic detection device;
the EDTA dissolving unit is provided with a second metering device and a solution preparation device;
the Ca (OH)2The dissolving unit and the EDTA dissolving unit share a second metering device and a solution preparation device;
a third metering device, a second pH tester, a nitrogen stripping device, a water bath shaking table device and a second index automatic detection device are arranged on the anaerobic digestion tank;
the phosphorus recovery reaction tank is provided with a third pH detector, a fourth metering device, a timing device, a third index automatic detection device and a second stirring device;
the phosphorus recovery system also comprises a supernatant collecting tank and a phosphorus recovery collecting tank; the feed inlet of the supernatant collecting tank is communicated with the discharge outlet of the second centrifugal device, the discharge outlet of the supernatant collecting tank is communicated with the feed inlet of a recycling device, and the discharge outlet of the recycling device is communicated with Ca (OH)2The dissolving unit is communicated, and the recycling device and the EDTA dissolving unit share a solution preparation device;
the methane collecting device is provided with a history type fermentation pipe.
3. A method for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance is characterized in that calcium hydroxide and EDTA are added into the excess sludge, anaerobic digestion is carried out after ultrasonic pretreatment to obtain methane and anaerobic digestion products, the anaerobic digestion products are centrifuged to obtain supernatant, and the calcium hydroxide is continuously added into the supernatant to carry out solid-liquid separation to obtain phosphorus recovery products.
4. The method for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance according to claim 3, wherein the system for recovering carbon and phosphorus resources in excess sludge by using ultrasonic wave assistance according to any one of claims 1 to 2 is used for recovering excess sludge.
5. The method for recovering carbon and phosphorus resources in excess sludge with the assistance of ultrasonic waves according to claim 4 is characterized by comprising the following steps:
(1) the excess sludge enters an ultrasonic pretreatment reactor through a sludge storage pool, and Ca (OH)2By Ca (OH)2Dissolving the EDTA in the dissolving unit, then feeding the EDTA into an ultrasonic pretreatment reactor through the EDTA dissolving unit, and performing cracking reaction on the excess sludge under an ultrasonic condition to obtain pretreated excess sludge;
(2) the method comprises the following steps that pretreated residual sludge enters an anaerobic digestion tank and inoculated sludge are mixed for anaerobic digestion, generated methane is recycled through a methane collection device, and generated anaerobic digestion products enter a first centrifugal device for centrifugation to obtain bottom sludge and phosphorus-rich supernatant;
(3) and (3) allowing the phosphorus-rich supernatant to enter a phosphorus recovery reaction tank, allowing calcium hydroxide to enter the phosphorus recovery reaction tank through a medicament storage tank and mixing the phosphorus-rich supernatant with the calcium hydroxide to obtain a reaction solution, and allowing a product obtained after the reaction of the reaction solution to enter a second centrifugal device for centrifugal separation to obtain a supernatant and a phosphorus recovery product.
6. The method for recovering carbon and phosphorus resources in excess sludge with the assistance of ultrasonic waves according to claim 5, wherein in the step (1):
cracking reaction conditions: the ultrasonic sound energy density is 0.2-1.2W/mL, and the ultrasonic time is 30-60 min;
the addition concentration of the EDTA is 0-20 mmol/L;
Ca(OH)2the adding amount of the sludge is to adjust the pH value of the sludge to 10-12;
and (3) after the pH value of the pretreated residual sludge is adjusted to be neutral, performing the step (2).
7. The method for recovering carbon and phosphorus resources in excess sludge with the assistance of ultrasonic waves according to claim 5, wherein in the step (2):
the volume ratio of the pretreated residual sludge to the inoculated sludge is 4-6: 1;
the anaerobic digestion temperature is 33-37 ℃, and the anaerobic digestion time is 8-12 days;
first centrifuge centrifugation conditions: centrifuging at 6000r/min for 20-30 min.
8. The method for recovering carbon and phosphorus resources in excess sludge with the assistance of ultrasonic waves according to claim 5, wherein in the step (3): the calcium-phosphorus ratio in the reaction liquid is 3-8:1, the pH value is 8.3-9.5, the reaction time is 10-20min, and the centrifugation conditions of a second centrifugal device are as follows: centrifuging at 6000r/min for 10-30 min.
9. The method for recovering carbon and phosphorus resources in excess sludge with the assistance of ultrasonic waves according to claim 5, wherein the supernatant obtained in the step (3) is returned to the calcium hydroxide dissolving unit through a recycling device.
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