CN110228887B - Synchronous recovery system and method for carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste - Google Patents

Synchronous recovery system and method for carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste Download PDF

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CN110228887B
CN110228887B CN201910578302.XA CN201910578302A CN110228887B CN 110228887 B CN110228887 B CN 110228887B CN 201910578302 A CN201910578302 A CN 201910578302A CN 110228887 B CN110228887 B CN 110228887B
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anaerobic fermentation
kitchen waste
biogas slurry
carbon
nitrogen
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CN110228887A (en
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周涛
赵由才
武舒娅
伍娜
耿晓梦
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/26—Carbonates or bicarbonates of ammonium
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P9/00—Preparation of organic compounds containing a metal or atom other than H, N, C, O, S or halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • 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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Abstract

The invention relates to a system and a method for synchronously recovering carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste, wherein the method comprises the following steps: (1) adjusting the pH value of the anaerobic fermentation biogas slurry of the kitchen waste to 9-10; (2) in N2Stirring in an atmosphere and dropwise adding Mg2+Solution and Al3+A solution; (3) after the precipitation appears, carrying out hydrothermal treatment on the suspension, and after the reaction is finished, washing and collecting the precipitate to obtain a carbon resource product; (4) the generated gas carries NH in the process3Reacting it with CO2React to form NH4HCO3Crystallizing and separating out the product to obtain a nitrogen resource product. Compared with the prior art, the method has the advantages of simple synchronous carbon and nitrogen recovery process, low cost, capability of efficiently recovering carbon and nitrogen resources in the kitchen waste fermentation biogas slurry, and higher economic and social environmental benefits.

Description

Synchronous recovery system and method for carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a system and a method for synchronously recovering carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste.
Background
Anaerobic fermentation can realize degradation and resource utilization of organic matters in the kitchen waste, is also a common energy regeneration technology for the kitchen waste at present, but the problem of secondary pollution of fermentation liquor is urgently needed to be solved. The anaerobic fermentation biogas slurry of the kitchen waste is brownish yellow in apparent color, is acidic, high in suspended matter and high in concentration organic waste liquid, and has high nitrogen and phosphorus contents and high carbon-nitrogen ratio; metallic element and inorganic anion with K+、Na+、Cl-、SO4 2-The common ions in food are mainly ions, the organic matter is mainly aromatic protein analogues, which account for about 80% of the organic matter content, and the volatile organic matter isVolatile acids and alcohols are the main.
The anaerobic fermentation liquid of kitchen waste contains rich nutrients including C source (such as VFAs and alcohols) and N source (such as NH)4 +) Etc. can provide nutrients for plant and microbial growth, such as providing necessary C and N source for soil and enhancing soil fertility. However, high salinity and low pH in anaerobic fermentation broth, as well as heavy metals and other harmful substances, can lead to salinization and acidification of the soil, and if the fermentation broth is directly irrigated, it can be difficult to control the effective dosage and application rate of the external C and N sources. Therefore, more and more attention is paid to a safe method for effectively separating and utilizing the anaerobic fermentation liquor of the kitchen waste.
The anaerobic fermentation biogas slurry of the kitchen waste contains rich nutrient resources, and the resource utilization of the anaerobic fermentation biogas slurry mainly shows that the anaerobic fermentation biogas slurry of the kitchen waste serves as a carbon source in wastewater treatment to strengthen denitrification, improve polluted soil, improve the growth environment of animals and plants and the like. But the content of NH is high no matter the carbon source is used as a microorganism denitrification carbon source or the soil is irrigated to realize soil improvement3The threat of-N and salt, which limits the use of the fermentation broth. The invention aims at high VFA and NH in anaerobic fermentation biogas slurry of kitchen waste3And (4) developing C, N synchronous recovery technology for the N concentration, and further applying the technology to soil improvement, wherein the technical method is not reported.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a system and a method for synchronously recovering carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for synchronously recovering carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste, which comprises the following steps:
(1) adjusting the pH value of the anaerobic fermentation biogas slurry of the kitchen waste to 9-10;
(2) in N2Stirring in an atmosphere and dropwise adding Mg2+Solution and Al3+A solution;
(3) after the precipitation appears, carrying out hydrothermal treatment on the suspension, and after the reaction is finished, washing and collecting the precipitate to obtain a carbon resource product;
(4) the generated gas carries NH in the process3Reacting it with CO2React to form NH4HCO3Crystallizing and separating out the product to obtain a nitrogen resource product.
Preferably, in the step (1), the anaerobic fermentation biogas slurry of the kitchen waste is obtained by separating fermentation residues (by using analysis filter paper) after anaerobic fermentation of the kitchen waste.
Preferably, the anaerobic fermentation method of the kitchen waste comprises the following steps: pulping the kitchen waste and deionized water according to the mass ratio of 1:1, then carrying out anaerobic fermentation, controlling the temperature to 35 ℃ in the fermentation process, and adjusting and controlling the pH value to 5.0-6.0; naturally fermenting, wherein no sludge is inoculated in the process, and the reaction time is 3 d.
Preferably, the adjustment of the pH is carried out with 4M NaOH or 4M HCl.
Preferably, in step (2), Mg2+The solution is Mg (NO)3)2Solution of Al3+The solution is Al (NO)3)3A solution; mg (magnesium)2+Mg in solution2+Ions, Al3+Al in solution3+The dosage ratio of the ions to the anaerobic fermentation biogas slurry of the kitchen waste is 0.3mol:0.15mol: 5L.
Preferably, the stirring rate in step (2) is 100 rpm.
Preferably, the hydrothermal treatment in step (3) means hydrothermal treatment at 70 ℃ for 24 hours.
Preferably, the carbon resource product obtained in step (3) is an organic acid-based double metal hydroxide (VFA-LDH).
The invention also provides a system for synchronously recovering carbon and nitrogen resources in the anaerobic fermentation biogas slurry of the kitchen waste, which is used for the recovery method and comprises a full-automatic anaerobic fermentation tank and an ammonia recovery device;
the full-automatic anaerobic fermentation tank comprises a tank body, a stirrer arranged on the tank body, a discharge hole, a feed inlet, a pH monitor, a temperature sensor and N2The inlet, the outlet, a plurality of automatic liquid medicine adding mechanisms and a water bath heating sleeve arranged around the tank body;
the ammonia recovery device comprises an ammonia recovery deviceRecovery reactor, CO2The ammonia recovery reactor is respectively connected with the gas outlet of the full-automatic anaerobic fermentation tank and CO2The gas supply mechanism is connected, and the condenser is used for condensing NH carried in the gas outlet of the full-automatic anaerobic fermentation tank3。
Preferably, the plurality of automatic chemical liquid adding mechanisms are Mg2+Solution feeder, Al3+A solution adder, an acid solution adder (for adding 4M HCl) and a lye adder (for adding 4M NaOH).
Preferably, said CO is2The gas supply mechanism is CO2Gas cylinders.
Preferably, said N2The inlet is connected with a nitrogen-air integrated machine to keep N in the reaction process2Atmosphere; and N is2The inlet is connected with N which leads to the bottom of the tank body2A conduit, which is used for extending into the kitchen waste anaerobic fermentation biogas slurry in the reaction process to form N2Simultaneously stripping NH generated in the reaction process in the atmosphere3。
Preferably, the fully automatic control anaerobic fermentation tank is a commercial available BIOTECH-5 JGZ-7000. The fermentation tank can realize automatic pH and temperature adjustment. At the same time, two additional samples (Mg) can be ensured2+Solution and Al3+Solution) is automatically added at a constant speed, and the stirring is mechanical stirring.
Compared with the prior art, the method has the advantages of simple synchronous carbon and nitrogen recovery process, low cost, capability of efficiently recovering carbon and nitrogen resources in the kitchen waste fermentation biogas slurry, and higher economic and social environmental benefits.
Drawings
FIG. 1 is a schematic view of a synchronous carbon and nitrogen recovery system of anaerobic fermentation biogas slurry of kitchen waste in embodiment 1;
FIG. 2 is a graph showing changes in COD and ammonia nitrogen concentration in anaerobic fermentation biogas slurry of kitchen waste in example 1. Wherein, fig. 2(a) represents the concentration change before and after the Chemical Oxygen Demand (COD) in the fermented biogas slurry; FIG. 2(b) represents the concentration change before and after ammonia nitrogen in the fermented biogas slurry.
In the figure, 1 is a tank body, 2 is a stirrer, 3 is a discharge port, and 4 is feedingMouth, 5 as pH monitor, 6 as temperature sensor, 7 as N2Inlet, outlet 8, Al 93+Solution adder, 10 is Mg2+A solution adder, 11 is an alkali liquor adder, 12 is an acid liquor adder, 13 is a water bath heating jacket, 14 is a water inlet, 15 is a water outlet, 16 is a thermocouple, and 17 is an ammonia recovery device.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The utility model provides a synchronous recovery system of carbon nitrogen resource in kitchen garbage anaerobic fermentation natural pond liquid, as shown in figure 1, including full-automatic anaerobic fermentation jar and ammonia recovery unit 17, wherein: the full-automatic anaerobic fermentation tank comprises a tank body 1, a stirrer 2 arranged on the tank body 1, a discharge hole 3, a feed inlet 4, a pH monitor 5, a temperature sensor 6 and N2An inlet 7, an outlet 8 and a plurality of automatic liquid medicine adding mechanisms (Al)3+ Solution adder 9, Mg2+A solution adding device 10, an alkali liquor adding device 11 (for adding 4M NaOH) and an acid liquor adding device 12 (for adding 4M HCl)), and a water bath heating jacket 13 arranged around the tank body 1, wherein the water bath heating jacket 13 is provided with a water inlet 14 and a water outlet 15, and is provided with a thermocouple 16; the ammonia recovery device 17 comprises an ammonia recovery reactor and CO2The gas supply mechanism, the condenser and the ammonia recovery reactor are respectively connected with the gas outlet of the full-automatic anaerobic fermentation tank and CO2The gas supply mechanism is connected, and the condenser is used for condensing NH carried in the gas outlet of the full-automatic anaerobic fermentation tank3。
More specifically, the fully automated controlled anaerobic fermentor is commercially available BIOTECH-5 JGZ-7000. The volume was 7L. The fermentation tank can realize automatic pH and temperature adjustment. At the same time, two additional samples (Mg) can be ensured2+Solution and Al3+Solution) is automatically added at a constant speed, and the stirring is mechanical stirring. N is a radical of2The inlet is connected with a nitrogen-air integrated machine to keep N in the reaction process2Atmosphere; and N is2The inlet is connected with N which leads to the bottom of the tank body2A conduit, which is used for extending into the kitchen waste anaerobic fermentation biogas slurry in the reaction process to form N2Of the atmosphereSimultaneously stripping off NH generated in the reaction process3。
In this embodiment, this system can realize automatically regulated pH, temperature. Meanwhile, automatic dripping of two additional samples can be ensured, and stirring is mechanical stirring; the dropping rate and stirring rate of the added sample can be set. To ensure the double metal hydroxide (VFA-LDH) and NH in the fermentation liquor system4HCO3The full-automatic anaerobic fermentation tank is combined with the nitrogen-air integrated machine to ensure the N of the system2Atmosphere; the ammonia recovery device adopts a simple ammonia recovery tower consisting of a water bath condenser, a 100mL three-neck flask and CO2Gas cylinder composition, blown off NH3Recycling to an ammonia recovery unit, and finally, CO2Reaction to form NH4HCO3。
The method for synchronously recovering carbon and nitrogen resources in the anaerobic fermentation biogas slurry of the kitchen waste in the embodiment comprises the following steps:
(1) 5.0L of anaerobic fermentation biogas slurry of the kitchen waste, which is fermented in advance and separated by filter paper, is placed in the synchronous carbon and nitrogen recovery system, and the pH is adjusted to 9-10 (about 9.5 is selected in the embodiment) by using 4M NaOH or 4M HCl;
(2) in N2The constant stirring rate in the atmosphere was 100rpm, and 0.30mol of Mg was added2+Solution (150mL) and 0.15mol Al3+The solution (150mL) was added dropwise to the reactor;
(3) after precipitation had occurred, the suspension was hydrothermally treated at 70 ℃ for 24 h. After the reaction is finished, washing the precipitate for 3 times by using deionized water and centrifugally collecting to obtain a carbon resource product VFA-LDH;
(4) NH carried by the exhaust gas in the process3The gas outlet is connected with an ammonia recovery device and introduces CO2And NH3React to form NH4HCO3Crystallizing and separating out the product to obtain a nitrogen resource product.
In this example, Mg2+Solution and Al3+The solution is composed of Mg (NO)3)2And Al (NO)3)3Is configured to form. NaOH, HCl, Mg (NO)3)2And Al (NO)3)3Are all purchased from Shanghai AladdinBiochemical technology, Inc., are all analytically pure.
In this embodiment, the changes of the concentrations of COD and ammonia nitrogen in the fermentation broth after simultaneous recovery of carbon and nitrogen are compared, as shown in fig. 2. FIG. 2(a) shows COD concentration changes in anaerobic fermentation biogas slurry before and after reaction. As can be seen from the figure, the COD concentration in the biogas slurry after treatment is reduced from 15,400mg/L to 7,800mg/L, and the total removal efficiency is about 49.4%; FIG. 2(b) shows NH in fermentation broth before and after treatment3-N concentration variation. NH (NH)3N concentration decreased from 710.9 to 401.1mg/L, NH after treatment3The removal efficiency was about 43.6%.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (9)

1. A method for synchronously recovering carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste is characterized by comprising the following steps:
(1) adjusting the pH value of the anaerobic fermentation biogas slurry of the kitchen waste to 9-10;
(2) in N2Stirring in an atmosphere and dropwise adding Mg2+Solution and Al3+A solution;
(3) after the precipitation appears, carrying out hydrothermal treatment on the suspension, and after the reaction is finished, washing and collecting the precipitate to obtain a carbon resource product;
(4) the generated gas carries NH in the process3Reacting it with CO2React to form NH4HCO3Crystallizing and separating out the product to obtain a nitrogen resource product.
2. The method for synchronously recycling carbon and nitrogen resources in the anaerobic fermentation biogas slurry of kitchen waste according to claim 1, wherein in the step (1), the anaerobic fermentation biogas slurry of kitchen waste is obtained by separating fermentation residues after the anaerobic fermentation of kitchen waste.
3. The method for synchronously recycling carbon and nitrogen resources in the anaerobic fermentation biogas slurry of kitchen waste according to claim 2, is characterized in that the anaerobic fermentation method of kitchen waste comprises the following steps: pulping the kitchen waste and deionized water according to the mass ratio of 1:1, then carrying out anaerobic fermentation, controlling the temperature to 35 ℃ in the fermentation process, and adjusting and controlling the pH value to 5.0-6.0; naturally fermenting, wherein no sludge is inoculated in the process, and the reaction time is 3 d.
4. The method for synchronously recovering carbon and nitrogen resources in the anaerobic fermentation biogas slurry of kitchen waste according to claim 1 or 3, characterized in that pH is adjusted by using 4M NaOH or 4M HCl.
5. The method for synchronously recycling carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste according to claim 1, characterized in that in the step (2), Mg2+The solution is Mg (NO)3)2Solution of Al3+The solution is Al (NO)3)3A solution; mg (magnesium)2+Mg in solution2+Ions, Al3+Al in solution3+The dosage ratio of the ions to the anaerobic fermentation biogas slurry of the kitchen waste is 0.3mol:0.15mol: 5L.
6. The method for synchronously recovering carbon and nitrogen resources in the anaerobic fermentation biogas slurry of kitchen waste according to claim 1, characterized in that the hydrothermal treatment in the step (3) is hydrothermal treatment at 70 ℃ for 24 hours.
7. The method for synchronously recycling carbon and nitrogen resources in the anaerobic fermentation biogas slurry of kitchen waste according to claim 1, characterized in that the carbon resource product obtained in the step (3) is organic acid-based bimetallic hydroxide.
8. A synchronous recovery system for carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste is characterized by being used for the recovery method of any one of claims 1 to 7 and comprising a full-automatic anaerobic fermentation tank and an ammonia recovery device;
the full-automatic anaerobic fermentation tank comprises a tank body, a stirrer arranged on the tank body, a discharge hole, a feed inlet, a pH monitor, a temperature sensor and N2The inlet, the outlet, a plurality of automatic liquid medicine adding mechanisms and a water bath heating sleeve arranged around the tank body;
said N2The inlet is connected with a nitrogen-air integrated machine to keep N in the reaction process2Atmosphere; and N is2The inlet is connected with N which leads to the bottom of the tank body2A conduit, which is used for extending into the kitchen waste anaerobic fermentation biogas slurry in the reaction process to form N2Simultaneously stripping NH generated in the reaction process in the atmosphere3；
The air outlet is arranged at the top of the tank body;
the ammonia recovery device comprises an ammonia recovery reactor and CO2The ammonia recovery reactor is respectively connected with the gas outlet of the full-automatic anaerobic fermentation tank and CO2The gas supply mechanism is connected, and the condenser is used for condensing NH carried in the gas outlet of the full-automatic anaerobic fermentation tank3。
9. The system for synchronously recycling carbon and nitrogen resources in the anaerobic fermentation biogas slurry of kitchen waste according to claim 8, is characterized in that the fully-automatically controlled anaerobic fermentation tank is a commercial available BIOTECH-5 JGZ-7000.
CN201910578302.XA 2019-06-28 2019-06-28 Synchronous recovery system and method for carbon and nitrogen resources in anaerobic fermentation biogas slurry of kitchen waste Active CN110228887B (en)

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CN106992287A (en) * 2017-03-24 2017-07-28 武汉纺织大学 A kind of novel lamellar carbon electrode material and preparation method thereof
CN206985832U (en) * 2017-04-07 2018-02-09 清华大学深圳研究生院 A kind of sewage disposal device based on carbon nitrogen energy recovery
CN108928880A (en) * 2018-08-10 2018-12-04 南华大学 A kind of processing method of the waste water containing radioactive element
CN109455885A (en) * 2018-12-21 2019-03-12 上海市政工程设计研究总院（集团）有限公司 A kind of nitrogen resource thermal extraction recovery method

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CN106992287A (en) * 2017-03-24 2017-07-28 武汉纺织大学 A kind of novel lamellar carbon electrode material and preparation method thereof
CN206985832U (en) * 2017-04-07 2018-02-09 清华大学深圳研究生院 A kind of sewage disposal device based on carbon nitrogen energy recovery
CN108928880A (en) * 2018-08-10 2018-12-04 南华大学 A kind of processing method of the waste water containing radioactive element
CN109455885A (en) * 2018-12-21 2019-03-12 上海市政工程设计研究总院（集团）有限公司 A kind of nitrogen resource thermal extraction recovery method

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