CN220413355U - Online separation platform of perishable domestic waste resourceful carboxylic acid production and modularization - Google Patents
Online separation platform of perishable domestic waste resourceful carboxylic acid production and modularization Download PDFInfo
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The utility model provides a perishable household garbage recycling carboxylic acid production and modularized online separation platform, which comprises a continuous stirred tank reactor, an anaerobic membrane bioreactor, a filtrate buffer tank, a separation unit and a product collector which are sequentially connected, wherein the continuous stirred tank reactor is used for producing fermentation liquor containing carboxylic acid by utilizing perishable household garbage, the anaerobic membrane bioreactor is used for carrying out solid-liquid separation treatment on the fermentation liquor and producing filtrate rich in carboxylic acid, the filtrate buffer tank is used for collecting filtrate, the separation unit is used for separating and extracting short-chain carboxylic acid from the filtrate online, and the product collector is used for collecting the short-chain carboxylic acid; the separation unit comprises a bipolar membrane electrodialysis module and a membrane permeation module, wherein the bipolar membrane electrodialysis module is in a two-compartment configuration and can be used alone or in combination with the membrane permeation module. The platform achieves continuous production and on-line separation of short-chain carboxylic acids, and by continuously separating carboxylic acid products, inhibition caused by product accumulation is relieved to achieve higher carboxylic acid productivity.
Description
Technical Field
The utility model relates to the technical field of organic waste resource utilization, in particular to a perishable household garbage recycling carboxylic acid production and modularized online separation platform.
Background
After the classification of waste is carried out, a huge amount of biodegradable wet waste (or kitchen waste, perishable waste) needs to be effectively treated and recycled. The mainstream treatment mode is to recover energy in the form of methane while reducing biomass waste by an anaerobic digestion technology. However, the main problems faced by anaerobic digestion today are: the methane production stage is unstable, the effective utilization rate and the utilization value of methane are not high, and the transportation and storage of methane are inconvenient; methanogenic archaea are extremely sensitive to changes in environmental conditions, and when environmental conditions fluctuate, accumulation of organic acids, particularly short-chain volatile carboxylic acids, can be extremely prone to further inhibit methanogenic activity, and when severe, can cause reactor failure and even require restarting.
Short-chain carboxylic acid is an important 'building block' in the chemical industry, has wide application in the fields of food, chemical industry, medicine and the like, has higher market value than methane, is dependent on petrochemical industry at present, and the main obstacle of biological production is the lack of low-cost technology for separating the organic acid from anaerobic digestion liquid, and if the separation problem of the organic acid from the anaerobic digestion liquid is solved, the production of the organic acid from biomass waste by utilizing microorganisms has extremely high environmental benefit and competitiveness.
At present, the main stream method comprises solvent extraction and rectification, and the hydrophobic organic extractant has higher selectivity to organic acid. Chinese patent No. CN112479868A discloses a method and apparatus for extracting organic acid from mixed salt obtained by separating fermentation broth, wherein a hydrophobic organic solvent is used to extract organic acid from mixed salt obtained by separating fermentation broth, and the apparatus comprises an acid treatment unit, an extraction unit and a rectification unit which are connected; chinese patent No. CN106748734a discloses a method for extracting organic acids from fermentation broths, which uses ester-containing compounds or alkylamine compounds as extractant to extract organic acids from low pH fermentation broths. These operations are all based on offline batch operations; on the one hand, the lack of an effective method for stripping and separating organic acid from the extract requires very high energy consumption for rectification; on the other hand, the above-mentioned method cannot be used on line, the direct contact of the extractant and the fermentation broth can generate toxicity to microorganisms, and in addition, a low pH (1.5-3.5) is required to enable the organic acid in the fermentation broth to maintain molecular form so as to selectively extract the organic acid, so that the reactor cannot normally produce carboxylic acid at such a low pH.
The membrane-based separation and recovery method has higher potential in realizing continuous production and on-line recovery, low energy consumption required by membrane permeation, higher selectivity on free fatty acid at low pH (pH < 3) and capability of effectively avoiding transfer of other components, but in on-line application, the pH setting of a reactor is difficult to balance between separation efficiency and production efficiency, and under the higher pH condition favorable for microbial activity, the fatty acid mainly exists in an ionic form, so that the application effect of membrane permeation is poor; in addition, the absorbent liquid on the other side needs to be frequently replaced to maintain the recovered driving force. The electrochemical system based on the ion exchange membrane has the characteristics of high speed and high efficiency, is ideal choice for realizing online high-efficiency separation, but the traditional electrodialysis has no selectivity on ions, and a large amount of metal cations are simultaneously recovered while carboxylic anions are recovered, so that the purity of the product with overall current efficiency is reduced; in addition, the ion exchange membrane is easily affected by membrane pollution caused by organic matters, cannot be directly applied to reactor fermentation liquor, and lacks an on-line filtering means capable of filtering stably and high-flux under high organic load. Moreover, because short-chain carboxylic acids have different charged states at different pH states, different modules are suitable for different conditions, and a separation procedure which can be flexibly adjusted is lacking.
Disclosure of Invention
The utility model aims to solve the problems, and aims to provide a perishable household garbage recycling carboxylic acid production and modularized online separation platform.
The utility model provides a perishable household garbage recycling carboxylic acid production and modularization online separation platform, which has the following characteristics: the device comprises a continuous stirring kettle type reactor, an anaerobic membrane bioreactor, a filtrate buffer tank, a separation unit and a product collector which are sequentially connected, wherein the continuous stirring kettle type reactor is used for producing fermentation liquor containing carboxylic acid by utilizing perishable household garbage, the anaerobic membrane bioreactor is used for carrying out solid-liquid separation treatment on the fermentation liquor and producing filtrate rich in carboxylic acid, the filtrate buffer tank is used for collecting the filtrate, the separation unit is used for separating and extracting short-chain carboxylic acid from the filtrate on line, and the product collector is used for collecting the short-chain carboxylic acid; the bottom of the continuous stirred tank reactor is communicated with the bottom of the anaerobic membrane bioreactor through a first circulating pump to realize internal liquid circulation, a negative pressure suction pump for suction filtration and filtrate conveying is arranged between the anaerobic membrane bioreactor and a filtrate buffer tank, the filtrate buffer tank is provided with an overflow port, the overflow port is communicated with a feed port of the continuous stirred tank reactor through a second circulating pump to realize overflow circulation, the separation unit comprises a bipolar membrane electrodialysis module and a membrane permeation module, the bipolar membrane electrodialysis module is in a two-compartment structure formed by alternately stacking bipolar membranes and anion exchange membranes, the bipolar membrane electrodialysis module is provided with an alkali chamber and an acid chamber, and the bipolar membrane electrodialysis module is singly used or combined with the membrane permeation module.
In the perishable household garbage recycling carboxylic acid production and modularized online separation platform provided by the utility model, the utility model can also have the following characteristics: further comprises: and the gas collector is communicated with the continuous stirred tank reactor, the anaerobic membrane bioreactor and the filtrate buffer tank and is used for balancing the internal gas pressure.
In the perishable household garbage recycling carboxylic acid production and modularized online separation platform provided by the utility model, the utility model can also have the following characteristics: the anaerobic membrane bioreactor is provided with a PVDF hollow fiber filter membrane, a back flush branch is arranged on a pipeline connected with the water inlet end of the negative pressure suction pump, the back flush branch is connected with the gas collector, and a back flush pump opposite to the conveying direction of the negative pressure suction pump is arranged on the back flush branch and is used for conveying gas in the gas collector to the anaerobic membrane bioreactor to carry out aeration flushing on the PVDF hollow fiber filter membrane.
In the perishable household garbage recycling carboxylic acid production and modularized online separation platform provided by the utility model, the utility model can also have the following characteristics: further comprises: the pH control device comprises a pH detector, a liquid adding pump and a neutralizer container which are sequentially connected, wherein the pH detector is arranged in the continuous stirring kettle type reactor, and the liquid adding pump is used for conveying the neutralizer into the continuous stirring kettle type reactor according to a feedback signal of the pH detector.
In the perishable household garbage recycling carboxylic acid production and modularized online separation platform provided by the utility model, the utility model can also have the following characteristics: the membrane permeation module comprises a polytetrafluoroethylene hydrophobic membrane.
In the perishable household garbage recycling carboxylic acid production and modularized online separation platform provided by the utility model, the utility model can also have the following characteristics: when the bipolar membrane electrodialysis module is used independently, filtrate circulation is carried out between the alkali chamber and the filtrate buffer tank, and acid collecting liquid circulation is carried out between the acid chamber and the product collector.
In the perishable household garbage recycling carboxylic acid production and modularized online separation platform provided by the utility model, the utility model can also have the following characteristics: when the bipolar membrane electrodialysis module is used in combination with the membrane permeation module, the bipolar membrane electrodialysis module is placed in front of or behind the membrane permeation module.
When the bipolar membrane electrodialysis module is arranged in front of the membrane osmosis module, filtrate circulation is carried out between the alkali chamber and the filtrate buffer tank, liquid circulation is carried out between the acid chamber and one side of the membrane osmosis module, and alkaline collecting liquid circulation is carried out between the other side of the membrane osmosis module and the product collector.
When the bipolar membrane electrodialysis module is arranged behind the membrane osmosis module, filtrate circulation is carried out between one side of the membrane osmosis module and the filtrate buffer tank, an alkaline absorption liquid container is arranged on the other side of the membrane osmosis module, alkaline absorption liquid circulation is carried out between the other side of the membrane osmosis module and the alkaline absorption liquid container, alkaline absorption liquid circulation is carried out between the alkaline chamber and the alkaline absorption liquid container, and acid collecting liquid circulation is carried out between the acid chamber and the product collector.
In the perishable household garbage recycling carboxylic acid production and modularized online separation platform provided by the utility model, the utility model can also have the following characteristics: the acid chamber is provided with 0.1M HCl as an initial solution, and the polar chamber of the bipolar membrane electrodialysis module is provided with 3 percent Na as the initial solution 2 SO 4 。
Effects and effects of the utility model
The utility model relates to a perishable household garbage recycling carboxylic acid production and modularized online separation platform, which comprises a continuous stirred tank reactor, an anaerobic membrane bioreactor, a filtrate buffer tank, a separation unit and a product collector. Wherein, the continuous stirred tank reactor and the anaerobic membrane bioreactor can produce short-chain carboxylic acid by continuously feeding perishable household garbage with high solid content, the anaerobic membrane bioreactor has high membrane pollution resistance, can stably filter fermentation liquor under the organic load rate of up to 6gVS/L/d and provide enough filtrate for a downstream separation unit; the separation unit can realize in-situ product separation, so that the time and labor consumption caused by batch operation are greatly avoided, and the inhibition of accumulation of carboxylic acid products on the production activity of microorganisms can be further relieved by separating and extracting the carboxylic acid products from filtrate on line; bipolar membrane electrodialysis modules can produce OH - For adjusting the pH of a continuously stirred tank reactor or for replenishing the alkaline absorption liquid of a membrane permeation module, H being produced simultaneously + Directly converting the recovered carboxylic acid product into a free form for further rectification and purification without additional adjustment of pH; the bipolar membrane electrodialysis module can be used as a separation unit singly or in combination with the membrane osmosis module, and when the bipolar membrane electrodialysis module is used in combination, the bipolar membrane electrodialysis module can be arranged in the membrane osmosis module in front or behind, so that the platform has flexible adaptability and can meet the application of producing carboxylic acid under different conditions and separating on lineA scene.
Drawings
FIG. 1 is a schematic diagram of the structure of the easy-to-decay domestic garbage recycling carboxylic acid production and modularized online separation platform of the utility model;
FIG. 2 is a schematic structural diagram of a carboxylic acid production and modularized online separation platform for recycling perishable household garbage in example 1 of the present utility model;
FIG. 3 is a schematic structural diagram of a carboxylic acid production and modularized online separation platform for recycling perishable household garbage in example 2 of the present utility model;
FIG. 4 is a graph showing the effect of carboxylic acid production and separation in examples 1 and 2 of the present utility model.
Reference numerals illustrate:
a separation unit; 1 a continuous stirred tank reactor; 2 an anaerobic membrane bioreactor; 3, a filtrate buffer tank; 301 overflow port; a bipolar membrane electrodialysis module; 401 bipolar membrane; 402 anion exchange membrane; 403 pole chambers; 404 an alkaline compartment; 405 acid chamber; 5 a product collector; 6 a pH control device; 601pH detector; 602 a neutralizer vessel; 603 a liquid adding pump; 7, a negative pressure suction pump; 8a gas collector; 9, back flushing the pump; 10 a first circulation pump; 11 a pressure sensor; a second circulation pump 12; 13 a third circulation pump; 14 a fourth circulation pump; 15 electrode liquid container; a fifth circulation pump 16; 17 membrane permeation module; 18 an alkaline absorption liquid container; 19 a sixth circulation pump; and 20 a seventh circulating pump.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purpose and the effect of the present utility model easy to understand, the present utility model is specifically described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a structure of a perishable household garbage-based carboxylic acid production and modular on-line separation platform.
The utility model provides a perishable household garbage recycling carboxylic acid production and modularized online separation platform which is used for realizing continuous production and online separation of short-chain carboxylic acid and mainly comprises a continuous stirring kettle type reactor 1, an anaerobic membrane bioreactor 2, a filtrate buffer tank 3, a separation module A and a product collector 5 which are connected in sequence. The following describes the embodiments of the present utility model in detail with reference to examples.
Example 1
FIG. 2 is a schematic structural diagram of a perishable household garbage-based carboxylic acid production and modular on-line separation platform.
As shown in fig. 2, the embodiment provides a perishable domestic waste recycling carboxylic acid production and modularized online separation platform, which is used for realizing continuous production and online separation of short-chain carboxylic acids, and mainly comprises a continuous stirred tank reactor 1, an anaerobic membrane bioreactor 2, a filtrate buffer tank 3, a bipolar membrane electrodialysis module 4, a product collector 5, a pH control device 6, a negative pressure suction pump 7, a gas collector 8, a backwash pump 9 and a plurality of circulating pumps. The following describes the respective parts in detail.
The continuous stirred tank reactor 1, the anaerobic membrane bioreactor 2, the filtrate buffer tank 3, the bipolar membrane electrodialysis module 4 and the product collector 5 are connected in sequence. Wherein, continuous stirred tank reactor 1 is used for utilizing perishable domestic waste to produce the zymotic fluid that contains the carboxylic acid, and anaerobic membrane bioreactor 2 is used for carrying out solid-liquid separation to the zymotic fluid to produce the filtrate that is rich in the carboxylic acid, filtrate buffer tank 3 is used for collecting the filtrate, and bipolar membrane electrodialysis module 4 is used for extracting the short chain carboxylic acid in the filtrate on line, and product collector 5 is used for collecting the short chain carboxylic acid.
The inoculum and substrate were added to the continuous stirred tank reactor 1. In this example, the inoculum was anaerobic granular sludge collected from an upflow anaerobic sludge blanket of a paper mill, which was acclimatized in the laboratory with kitchen waste; the substrate is prepared from vegetable waste collected from vegetable market, potato waste rich in starch is manually selected from the vegetable waste, crushed and homogenized by a crusher, stored in a refrigerator at-40 ℃, and thawed in a refrigerator at 4 ℃ before use; the basic properties of inoculum and substrate are as follows: inoculum TS:11.23% ± 0.07%, VS:70.55% ± 0.16% ts; substrate TS:18.08% ± 0.88%, VS:95.72% + -0.24% TS.
The pH control device 6 is used for controlling the pH value in the continuous stirred tank reactor 1, and comprises a pH detector 601, a neutralizer container 602 and a liquid adding pump 603, wherein the pH detector 601 is arranged in the continuous stirred tank reactor 1, the neutralizer container 602, the liquid adding pump 603 and the continuous stirred tank reactor 1 are sequentially connected, the neutralizer container 602 contains a neutralizer, and the liquid adding pump 603 conveys the neutralizer into the continuous stirred tank reactor 1 according to a feedback signal of the pH detector 601. In this embodiment, the neutralizing agent is NaOH.
The side surface of the anaerobic membrane bioreactor 2 is communicated with the side surface of the continuous stirred tank reactor 1, and an immersed hydrophilic PVDF hollow fiber filter membrane for filtering fermentation liquor is arranged in the anaerobic membrane bioreactor 2. According to the scale of the continuous stirred tank reactor and the anaerobic membrane bioreactor, the effective filtration area of the PVDF hollow fiber filter membrane is not less than 100cm 2 Respectively circulating fermentation liquor and pH at two sides of PVDF hollow fiber filter membrane>10. The bottom of the anaerobic membrane bioreactor 2 is also communicated with the bottom of the continuous stirred tank reactor 1 through a first circulating pump 10, so that the continuous circulation of liquid in the anaerobic membrane bioreactor and the continuous stirred tank reactor is realized.
In the embodiment, the total volume of the continuous stirred tank reactor 1 and the anaerobic membrane bioreactor 2 is 12L, and the effective working volume is 10L, wherein the effective working volume of the continuous stirred tank reactor 1 is 8L and accounts for 80 percent, and the effective working volume of the anaerobic membrane bioreactor 2 is 2L and accounts for 20 percent; the aperture of the PVDF hollow fiber filter membrane is 0.22 mu m, the outer diameter is 1.73mm, and the effective filtering area is 1148cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The first circulation pump 10 is a peristaltic pump.
The continuous stirred tank reactor 1 was started at an inoculum to substrate ratio of 2:1, and operated at a reaction temperature of 40℃and a pH of 4.5 to 7.5 with a hydraulic residence time of 4 days. The organic load rate was gradually increased from 2gVS/L/d to 8gVS/L/d during the start-up phase, the carboxylic acid product stabilized at 6gVS/L/d after starting to accumulate, and the substrate was diluted with nutrient salt solution for each feed to achieve a hydraulic retention time of 4 days, and a corresponding volume of effluent was discharged from the outlet at the bottom before each feed. Wherein the diluent at the start-up comprises nutrient salt and phosphate buffer, and the pH inside the continuous stirred tank reactor 1 is not adjusted in the start-up stage until the pH is controlled by the pH control device 6 after acidification enters the carboxylic acid accumulation stage. When the pH in the continuous stirred tank reactor 1 drops below 4.4, the liquid adding pump 603 is operated to supplement the additional NaOH to maintain the pH in the continuous stirred tank reactor 1 at 4.4-4.8 to direct the substrate reaction to carboxylic acid rather than methane, while avoiding the peracid environment to divert the biological process to lactic acid fermentation. When the start-up phase is over, the continuous stirred tank reactor 1 can stably produce a fermentation broth containing carboxylic acid.
As shown in fig. 2, a negative pressure suction pump 7 is connected between the anaerobic membrane bioreactor 2 and the filtrate buffer tank 3, provides a negative pressure of 30-50kPa, is used for filtering and conveying the filtrate produced by the anaerobic membrane bioreactor 2 into the filtrate buffer tank 3, and a pressure sensor 11 is further arranged between the anaerobic membrane bioreactor 2 and the filtrate buffer tank 3. The filtrate buffer tank 3 has an overflow 301, and the overflow 301 communicates with the continuous stirred tank reactor 1 via a second circulation pump 12. When the filtrate in the filtrate buffer tank 3 reaches the storage volume, the filtrate overflows from the overflow port 301 and circulates back into the continuous stirred tank reactor 1 under the conveyance of the second circulation pump 12. In this example, the negative pressure suction pump 7 performs negative pressure suction filtration at a filtration flow rate of 20mL/min, and the filtrate is collected in the filtrate buffer tank 3 having a volume of 1.5L.
The gas collector 8 is connected with the tops of the continuous stirred tank reactor 1, the anaerobic membrane bioreactor 2 and the filtrate buffer tank 3 and is used for balancing the top air pressure of the three, and the gas components collected in the gas collector 8 are mainly initial N 2 And a small amount of biogas. In this embodiment, the gas collector 8 is an aluminum gas bag connected to the tops of the continuous stirred tank reactor 1, the anaerobic membrane bioreactor 2 and the filtrate buffer tank 3 through a silica gel hose, respectively.
A back flush branch is arranged on a pipeline connected with the water inlet end of the negative pressure suction pump 7, the back flush branch is connected with the gas collector 8, a back flush pump 9 is arranged on the back flush branch, and the conveying direction of the back flush pump 9 is opposite to the conveying direction of the negative pressure suction pump 7. When the filtration performance of the PVDF hollow fiber filter membrane of the anaerobic membrane bioreactor 2 is reduced, the backwash pump 9 conveys the gas in the gas collector 8 to the anaerobic membrane bioreactor 2, and the PVDF hollow fiber filter membrane is subjected to aeration flushing to recover the membrane performance.
The separation unit a in this embodiment is a bipolar membrane electrodialysis module 4. Bipolar membrane electrodialysis module 4 is a two-compartment configuration formed by alternately stacking bipolar membranes 401 and anion exchange membranes 402, and bipolar membranes 401 and anion exchange membranes 402 alternately stacked divide a space between cathode compartment 403 and anode compartment 403 into a base compartment 404 and an acid compartment 405. The two compartment configuration is simplified in layout, type of circulating fluid required and number of containers required compared to the driven three compartment configuration. The bipolar membrane electrodialysis module 4 is not provided with a cation exchange membrane, so that cation nutrient salts such as ammonium, calcium and the like can be kept in filtrate to facilitate the movement of acidogenic bacteria, and the loss of cations to current is avoided.
Wherein, realize the filtrate circulation through pipeline and third circulating pump 13 between alkali room 404 and the filtrate buffer tank 3, acid room 405 and product collector 5 realize the acid collection liquid circulation through pipeline and fourth circulating pump 14, realize the electrode liquid circulation through pipeline and fifth circulating pump 16 between electrode room 403 and the electrode liquid container 15. The filtrate in the filtrate buffer tank 3 enters an alkali chamber 404 under the action of a third circulating pump 13, carboxylic acid is ionized into carboxylate anions under the action of bipolar membrane electrodialysis, and the carboxylate anions are transferred to an acid chamber 405 through an anion exchange membrane 402, so that OH is generated on the cathode side of the bipolar membrane 401 - OH produced - The filtrate is circulated back to the filtrate buffer tank 3, OH under the action of the third circulating pump 13 - The overflow port 301 of the filtrate buffer tank 3 is circulated back to the continuous stirred tank reactor 1 under the action of the second circulating pump 12, so that the alkali required for regulating the pH in the continuous stirred tank reactor 1 is compensated. In the acid chamber 405, the anode side of the bipolar membrane 401 generates H + H produced + And carboxylate anions are combined into free carboxylic acid and collected into the product collector 5 under the action of the fourth circulation pump 14 for further rectification.
In this embodiment, the bipolar membranes 401 and the anion exchange membranes 402 alternately stacked have five pairs, and the effective area of each membrane is 150cm 2 (20.8X7.2 cm), the middle is separated by a polypropylene water distribution plate with the thickness of 0.7mm, and the electrode material is titanium ruthenium-iridium plating; bipolar membrane electrodialysis module 4 further comprises an additional bipolar membrane 401 for protecting the polar compartment 403; acid chamberThe initial solution in 405 was 0.1M HCl and the initial solution in pole chamber 403 was 3% Na 2 SO 4 The initial volumes are all 1L; the third circulating pump 13, the fourth circulating pump 14 and the fifth circulating pump 15 are peristaltic pumps and circulate at a flow rate of 200 mL/min; the bipolar membrane electrodialysis module 4 is powered by a direct current power supply and operates in a constant current mode, and the current density is based on the current density of OH in the continuous stirred tank reactor 1 - Is adjusted.
FIG. 4 is a graph showing the effect of carboxylic acid production and separation.
As shown in FIG. 4, when the bipolar membrane electrodialysis module 4 is not connected, the reactor of the stage (referred to as a continuous stirred tank reactor 1+anaerobic membrane bioreactor 2, the same applies hereinafter) can stably produce short-chain carboxylic acid and obtain a yield of 315.4 mg/gVS.
When bipolar membrane electrodialysis module 4 was connected, see BPED extraction stage in the figure, the carboxylic acid concentration in the reactor effluent rapidly dropped to 116.9mM on day 17 and to a minimum value of 69.67mM on day 22, indicating that the carboxylic acid in the broth was effectively recovered into the acid extract. In this example, bipolar membrane electrodialysis module 4 alone was used as separation unit A, and the average recovery rate of bipolar membrane electrodialysis module 4 was 38.63% and up to 53.76%, and it was possible to separate about 150mmol of carboxylic acid product from anaerobic digestion solution on average per day, and about 8800mg/d. The bipolar membrane electrodialysis module 4 has higher selectivity to short-chain acetic acid, and the average recovery rate of each acid is respectively: 41.68% of acetic acid, 34.69% of propionic acid, 34.80% of butyric acid, 24.30% of valeric acid and 19.44% of caproic acid.
In the BPED extraction stage, the organic matter fermentation efficiency is improved, the highest carboxylic acid yield reaches 475.2mg/gVS, the average yield of the whole stage reaches 379.3mg/gVS, and compared with a control stage (the average yield of 23d-60d is 315.4 mg/gVS) when the bipolar membrane electrodialysis module 4 is not connected, the inhibition of product accumulation on the production process is relieved. Furthermore, the base used in this stage to adjust the pH in the continuous stirred tank reactor 1 is entirely generated by the bipolar membrane 401, completely counteracting the external lye addition used to adjust the pH.
Example 2
FIG. 3 is a schematic diagram of the structure of a perishable household garbage-based carboxylic acid production and modular on-line separation platform.
As shown in fig. 3, this embodiment provides a perishable domestic waste recycling carboxylic acid production and modularized online separation platform, which is different from embodiment 1 in that the system further comprises a membrane permeation module 17, wherein the membrane permeation module 17 is connected between the filtrate buffer tank 3 and the bipolar membrane electrodialysis module 4, in other words, the membrane permeation module 17 is disposed upstream of the bipolar membrane electrodialysis module 4. The membrane permeation module 17 and the bipolar membrane electrodialysis module 4 together serve as a separation unit a in the present embodiment for extracting the product.
The membrane permeation module 17 comprises a polytetrafluoroethylene hydrophobic membrane which is supported by a polypropylene supporting layer and is fixed by adopting an acrylic plate and a rubber gasket which are the same as those of the bipolar membrane electrodialysis module 4, and the pore diameter of the polytetrafluoroethylene hydrophobic membrane is 0.1-0.45 mu m. One side of the membrane permeation module 17 and the filtrate buffer tank 3 realize liquid circulation through a pipeline and a sixth circulating pump 19, and the other side of the membrane permeation module 17 and the alkaline absorption liquid container 18 realize liquid circulation through a pipeline and a seventh circulating pump 20. Because of the volatility of the short chain carboxylic acid, when the filtrate is circulated on one side of membrane permeation module 17, the carboxylic acid will diffuse across the polytetrafluoroethylene hydrophobic membrane and be captured by the alkaline absorption liquid on the other side, wherein the presence of a pH gradient provides a driving force for diffusion transfer of the carboxylic acid, while the hydrophobicity of the polytetrafluoroethylene hydrophobic membrane ensures that other non-volatile solutes will not transfer, allowing for the pre-extraction of higher purity carboxylates. The liquid circulation is realized between the alkaline absorption liquid container 18 and the alkaline chamber 404 of the bipolar membrane electrodialysis module 4 through the pipeline and the third circulation pump 13, and the rest of the arrangement is kept the same as in the embodiment 1.
In this example, the polytetrafluoroethylene hydrophobic membrane had a pore size of 0.22 μm and an effective filtration area of 150cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The sixth circulating pump 19 and the seventh circulating pump 20 are peristaltic pumps, and perform liquid circulation at a flow rate of 80 mL/min; the alkaline absorption liquid is a 0.1M NaOH solution with the pH value of more than 10.
The current of the bipolar membrane electrodialysis module 4 can be based on the OH generated by it - Flexible selection and adjustment: if OH is - For adjusting the pH in the reactor 1 of the continuous stirred tank reactor, according to the continuous stirred tank reactorThe current applied by pH adjustment in the reactor 1, if OH - The alkaline absorption liquid used to supplement the membrane permeation module 17 can adjust the applied current according to the pH of the alkaline absorption liquid.
FIG. 4 is a graph showing the effect of carboxylic acid production and separation.
The working process of the separation unit A comprises the following steps: as the carboxylic acid in the filtrate is continuously transferred to the alkaline absorption liquid in the membrane permeation module 17, the pH of the alkaline absorption liquid is continuously reduced, when the pH of the alkaline absorption liquid is reduced to be below 10, the bipolar membrane electrodialysis module 4 is started, and part of carboxylate captured by the alkaline absorption liquid is transported to the acid chamber 405 and is connected with H generated by the bipolar membrane 401 + The combination of free carboxylic acid, the negative charge deficiency after carboxylate transfer will be OH generated by base compartment 404 - And compensating, so that the alkaline absorption liquid is regenerated.
After the pH has risen back to 13, bipolar membrane electrodialysis module 4 is suspended for three bipolar membrane electrodialysis operations coupled together throughout the membrane permeation separation period, as shown in the mp+bped extraction stage of fig. 4, on days 69, 78, and 85, respectively. This has the advantage that the polytetrafluoroethylene hydrophobic membrane isolates almost all components that may contaminate the bipolar membrane 401 and the anion exchange membrane 402, especially divalent cations and complex organics, while reducing competition for other extraneous ions for current efficiency in the electrodialysis process.
After 18 days of on-line separation, 150.9mmol of carboxylic acid product is accumulated and extracted in the extracting solution, the average acidification efficiency of the stage is obviously improved (+8.9%) compared with that of a comparison stage, the polytetrafluoroethylene hydrophobic membrane shows high resistance to membrane pollution, the carboxylic acid extraction flux is not obviously influenced after continuous use for a plurality of days, and the average acidification efficiency is always maintained at 0.1mol m -2 h -1 In the vicinity, limited by the membrane area, the average recovery of carboxylic acid produced in the reactor at this stage is only 4.52%, and further improvement of separation efficiency by increasing the membrane area or using a membrane stack design like electrodialysis can be considered in full-scale industrial application. The bipolar membrane electrodialysis module 4 is provided with a front membrane permeation module 17 which has higher selectivity on long-chain caproic acid, and the average recovery rate of each acid is respectively as follows: acetic acid3.93%, 4.69% propionic acid, 5.35% butyric acid, 4.72% valeric acid and 5.57% caproic acid.
In addition, the front bipolar membrane electrodialysis module is overlapped with the rear membrane osmosis module, so that the following effects can be achieved: the bipolar membrane electrodialysis module can recover acid carboxylic acid solution mixed with other salt ions, the acid pH can ensure mass transfer efficiency of subsequent membrane permeation, and the membrane permeation module can further purify the harvested carboxylic acid and reduce the content of other salt ions. This solution is not illustrated by way of example.
In addition, the bipolar membrane electrodialysis module and the membrane permeation module can be flexibly selected as separation units according to the pH of the anaerobic digestion solution, the clarification degree of filtrate and the carbon chain length of the target carboxylic acid to be obtained: if the short chain carboxylic acids of three carbon atoms and below are preferentially recovered, a bipolar membrane electrodialysis module is preferred; if the recovery of short chain carboxylic acids of four carbon atoms and above is preferred, membrane permeation modules are preferred; if the pH of the fermentation broth is close to neutral, a bipolar membrane electrodialysis module is preferred; if the fermentation broth is pH-slightly acidic, a membrane permeation module is preferred.
Effects and effects of the examples
The online separation platform for producing and modularizing the carboxylic acid by utilizing the perishable household garbage according to the embodiment comprises a continuous stirred tank reactor, an anaerobic membrane bioreactor, a filtrate buffer tank, a separation unit and a product collector. Wherein, the continuous stirred tank reactor and the anaerobic membrane bioreactor can produce short-chain carboxylic acid by continuously feeding perishable household garbage with high solid content, the anaerobic membrane bioreactor has high membrane pollution resistance, can stably filter fermentation liquor under the organic load rate of up to 6gVS/L/d and provide enough filtrate for a downstream separation unit; the separation unit can realize in-situ product separation, so that the time and labor consumption caused by batch operation are greatly avoided, and the inhibition of accumulation of carboxylic acid products on the production activity of microorganisms can be further relieved by separating and extracting the carboxylic acid products from filtrate on line; bipolar membrane electrodialysis modules can produce OH - For adjusting the pH of a continuously stirred tank reactor or for replenishing the alkaline absorption liquid of a membrane permeation module, H being produced simultaneously + The recovered carboxylic acid product is directly usedThe mixture is converted into a free form so as to be further rectified and purified without additional adjustment of pH; the bipolar membrane electrodialysis module can be used as a separation unit singly or in combination with the membrane osmosis module, and when the bipolar membrane electrodialysis module is used in combination, the bipolar membrane electrodialysis module can be arranged in the membrane osmosis module in front or behind, so that the platform has flexible suitability and can meet the application scenes of carboxylic acid production and online separation under different conditions.
The above embodiments are preferred examples of the present utility model, and are not intended to limit the scope of the present utility model.
Claims (10)
1. The utility model provides a perishable domestic waste resourceful carboxylic acid production and modularization on-line separation platform which characterized in that: comprises a continuous stirred tank reactor, an anaerobic membrane bioreactor, a filtrate buffer tank, a separation unit and a product collector which are connected in sequence,
the continuous stirred tank reactor is used for producing fermentation liquor containing carboxylic acid by utilizing the perishable household garbage,
the anaerobic membrane bioreactor is used for carrying out solid-liquid separation treatment on the fermentation liquor and producing filtrate rich in carboxylic acid,
the filtrate buffer tank is used for collecting filtrate,
the separation unit is used for separating and extracting short-chain carboxylic acid from the filtrate on line,
the product collector is used for collecting the short-chain carboxylic acid;
wherein the bottom parts of the continuous stirred tank reactor and the anaerobic membrane bioreactor are communicated through a first circulating pump to realize internal liquid circulation,
a negative pressure suction pump for suction filtration and conveying of the filtrate is arranged between the anaerobic membrane bioreactor and the filtrate buffer tank,
the filtrate buffer tank is provided with an overflow port, the overflow port is communicated with the feed port of the continuous stirred tank reactor through a second circulating pump to realize overflow circulation,
the separation unit comprises a bipolar membrane electrodialysis module and a membrane permeation module,
the bipolar membrane electrodialysis module is a two-compartment configuration formed by alternately stacking bipolar membranes and anion exchange membranes and is provided with an alkali chamber and an acid chamber, and the bipolar membrane electrodialysis module is used alone or in combination with the membrane permeation module.
2. The perishable household garbage-based carboxylic acid production and modular on-line separation platform of claim 1, further comprising:
and the gas collector is communicated with the continuous stirred tank reactor, the anaerobic membrane bioreactor and the filtrate buffer tank and is used for balancing the internal gas pressure.
3. The perishable household garbage-based carboxylic acid production and modular on-line separation platform of claim 2, wherein:
wherein the anaerobic membrane bioreactor is provided with a PVDF hollow fiber filter membrane,
a back flushing branch circuit is arranged on a pipeline connected with the water inlet end of the negative pressure suction pump, the back flushing branch circuit is connected with the gas collector, a back flushing pump with the opposite conveying direction to the negative pressure suction pump is arranged on the back flushing branch circuit,
the back flushing pump is used for conveying the gas in the gas collector to the anaerobic membrane bioreactor to perform aeration flushing on the PVDF hollow fiber filter membrane.
4. The perishable household garbage-based carboxylic acid production and modular on-line separation platform of claim 1, further comprising:
the pH control device comprises a pH detector, a liquid adding pump and a neutralizer container which are connected in sequence,
the pH detector is arranged in the continuous stirred tank reactor,
and the liquid adding pump conveys the neutralizing agent into the continuous stirred tank reactor according to the feedback signal of the pH detector.
5. The perishable household garbage-based carboxylic acid production and modular on-line separation platform of claim 1, wherein:
wherein the membrane permeation module comprises a polytetrafluoroethylene hydrophobic membrane.
6. The perishable household garbage recycling carboxylic acid production and modular on-line separation platform of any one of claims 1 to 5, characterized in that:
when the bipolar membrane electrodialysis module is used independently, filtrate circulation is carried out between the alkali chamber and the filtrate buffer tank, and acid collecting liquid circulation is carried out between the acid chamber and the product collector.
7. The perishable household garbage recycling carboxylic acid production and modular on-line separation platform of any one of claims 1 to 5, characterized in that:
wherein, when the bipolar membrane electrodialysis module is used in combination with the membrane permeation module, the bipolar membrane electrodialysis module is arranged in front of or behind the membrane permeation module.
8. The perishable household garbage-based carboxylic acid production and modular on-line separation platform of claim 7, wherein:
when the bipolar membrane electrodialysis module is arranged in front of the membrane osmosis module, filtrate circulation is carried out between the alkali chamber and the filtrate buffer tank, liquid circulation is carried out between the acid chamber and one side of the membrane osmosis module, and alkaline collecting liquid circulation is carried out between the other side of the membrane osmosis module and the product collector.
9. The perishable household garbage-based carboxylic acid production and modular on-line separation platform of claim 7, wherein:
when the bipolar membrane electrodialysis module is arranged behind the membrane osmosis module, filtrate circulation is carried out between one side of the membrane osmosis module and the filtrate buffer tank, an alkaline absorption liquid container is arranged on the other side of the membrane osmosis module, alkaline absorption liquid circulation is carried out between the other side of the membrane osmosis module and the alkaline absorption liquid container, alkaline absorption liquid circulation is carried out between the alkaline chamber and the alkaline absorption liquid container, and acid collecting liquid circulation is carried out between the acid chamber and the product collector.
10. The perishable household garbage-based carboxylic acid production and modular on-line separation platform of claim 1, wherein:
wherein the acid chamber is internally provided with 0.1M HCl as an initial solution, and the polar chamber of the bipolar membrane electrodialysis module is internally provided with 3 percent Na as the initial solution 2 SO 4 。
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