CN105063108B - A kind of intensifying method of biology electrodialysis production malic acid - Google Patents
A kind of intensifying method of biology electrodialysis production malic acid Download PDFInfo
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- CN105063108B CN105063108B CN201510456356.0A CN201510456356A CN105063108B CN 105063108 B CN105063108 B CN 105063108B CN 201510456356 A CN201510456356 A CN 201510456356A CN 105063108 B CN105063108 B CN 105063108B
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- 238000000909 electrodialysis Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 title claims abstract description 15
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 235000011090 malic acid Nutrition 0.000 title claims abstract description 15
- 239000001630 malic acid Substances 0.000 title claims abstract description 15
- 238000005265 energy consumption Methods 0.000 claims abstract description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 11
- 230000006872 improvement Effects 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 22
- 229940099690 malic acid Drugs 0.000 claims description 13
- 229940116298 l- malic acid Drugs 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000011033 desalting Methods 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 210000000952 spleen Anatomy 0.000 claims description 2
- 210000002784 stomach Anatomy 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims 1
- 235000011033 potassium malate Nutrition 0.000 claims 1
- 239000001415 potassium malate Substances 0.000 claims 1
- SVICABYXKQIXBM-UHFFFAOYSA-L potassium malate Chemical compound [K+].[K+].[O-]C(=O)C(O)CC([O-])=O SVICABYXKQIXBM-UHFFFAOYSA-L 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000002351 wastewater Substances 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 10
- 244000005700 microbiome Species 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of intensifying methods of biological electrodialytic technique production malic acid, belong to electrodialysis field, biological electrodialysis energy consumption can be further decreased, reduces internal resistance, improve current density by adding ion exchange resin using the continuous flow biology electrodialysis after improvement.
Description
Technical field
It the invention belongs to biological electrodialysis field, is further improved on the existing electrodialytic Research foundation of biology
Continuous flow biology electrodialysis, by addition ion exchange resin, further research reduction energy consumption, reduction internal resistance, raising electric current are close
The method of degree.
Background technique
Bioelectrochemical system is that a kind of biocatalyst i.e. microorganism carries out oxidation or reduction reaction on the electrode
Electro-chemical systems.Microorganism in this bioelectrochemical system carries out new old generation under the stimulation of bioelectricity reactor
It thanks, pollutant is handled with lower consumption in such a process, or carry out the electricity production of itself using pollutant as raw material.
Biological electrodialysis is a kind of novel bioelectrochemistry technology, microorganism is combined with electrodialytic technique, with this
Obtain the purpose that the production acid under low energy consumption produces alkali desalination.Microorganism produces electricity under the action of extra electric field, after electricity production with outside
Added electric field collective effect makes ion displacement in the electric field, so that all kinds of ion isolations in dope are produced acid production to reach
The purpose of alkali desalination.
Biological electrodialytic technique will make up that electrodialysis energy consumption is excessive, and the defect of biological production not enough power supply, it can pass through
It tames and is suitble to the microorganism of electrodialysis electric field to reduce energy consumption, improve coulombic efficiency, simultaneous hydrogen production gas, processing industrial chemical are useless
Water produces acid production alkali desalination, and consumes organic matter.
The industrial innovation with the development of science and technology of the preparation method of L MALIC ACID experienced and original press from fruit
Squeeze the industrialized production stage.Currently, the production method of L MALIC ACID is developed via the single extraction method of early stage including mentioning
Follow the example of production, chemical synthesis the preparation method, two-step fermentation and the solidification techniques such as enzyme or cell conversion process.From above four kinds
From the point of view of the preparation method of L MALIC ACID, the current methodology of malic acid all has its limitation, and conversion method and fermentation method are more suitable
In industrial development, product more abundant can be generated on the basis of safety, low cost.But it will be recognized that be such
Technique has that product is impure, type of acid-producing bacteria strain needs to be optimized culture, therefore finds a kind of safer
Effectively, the technique of the production malic acid of low energy is very necessary and great realistic meaning and value.
The present invention on the existing electrodialytic Research foundation of biology, is carried out continuous using L MALIC ACID as research object
The electrodialytic research of stream biology proposes high acid amount, and studies the electrodialytic critical operational parameters of continuous flow biology, passes through
The method that high yield production L MALIC ACID on the basis of reducing energy consumption is found in the research of these service conditions.
Summary of the invention
The purpose of the present invention is by the way that the electrodialytic improvement of continuous flow biology, acquisition, which further decreases internal resistance, reduces biology
The method of electrodialysis energy consumption, while in the research process to the biological electrodialysis service condition of improvement, find raising bioelectricity
The method of dialysis current density, to obtain high yield, low consumption, the continuous flow biology electrodialytic technique of high current density and its fortune
Row relevant parameter and improving technology.
Continuous flow biology electrodialysis plant is the reaction being connected in insulating box by the peristaltic pump and pipeline of multichannel
Device, so that the liquid in reactor flows.Reactor is that a kind of microorganism electrochemical system is mutually tied with bipolar membrane electrodialysis
Close novel system.While desalination, produces acid and produce alkali.It is altogether there are four reaction chamber, respectively anode chamber, acid from left to right
Room, desalting chamber and cathode chamber, since desalting chamber is in the centre of reactor, also known as middle room.Its volume ratio is 4: 1: 1
:2.It is spaced from each other between four Room with film, is Bipolar Membrane between anode chamber and acid compartment, is handed between acid compartment and desalting chamber for anion
Film is changed, is cation-exchange membrane between desalting chamber and cathode chamber.In anode and cathode both ends external dc power supply, and connect with 10 ohm
Resistance.Anode material is carbon brush, and cathode material uses three layers of rolling activated carbon cathode.Therefore in anode to cathode reactor
The external circuit formed by electron transmission by ion transport of portion's composition one.Hydrogen ion H is generated respectively in the two sides of Bipolar Membrane+
With hydroxide ion OH-, acid is formed in acid compartment and generates alkali in the cathodic compartment, therefore cathode chamber is also referred to as alkaline chamber.
Anode is located in anode chamber, and the anode of reaction system is made of the carbon brush for being attached with electricity-producing microorganism, and cathode uses
Carbon black, active carbon and ethyl alcohol production, yin-yang grade spacing is between 4-8 cm.
A kind of the advantages of intensifying method of biological electrodialysis production malic acid provided by the present invention, is: (1) common
The transformation of continuous flow is carried out on the basis of biological electrodialysis system, so that producing acid amount improves energy consumption decline, improves biological electric osmose
The operational efficiency and effect of analysis.(2) it is further improved on the basis of continuous flow biology electrodialysis system, passes through addition
The method of ion exchange resin declines the internal resistance of continuous flow biology electrodialysis system, and energy consumption is further decreased, further mentioned
High biological electrodialytic operational efficiency and effect.
Detailed description of the invention
Attached drawing 1 is intermittent biological electrodialysis system schematic diagram.
Attached drawing 2 is continuous flow-recycle stream dynamic formula bioelectricity electrodialysis system schematic diagram.
Attached drawing 3 is continuous flow-uniflow type biology electrodialysis system schematic diagram.
Attached drawing 4 is that continuous flow and common batch biology electrodialysis system produce electricity curve comparison schematic diagram.
Attached drawing 5 is that continuous flow and common batch biology electrodialysis system produce acid amount contrast schematic diagram.
Attached drawing 6 is continuous flow and common batch biology electrodialysis system energy consumption comparison schematic diagram.
Attached drawing 7 is production under different hydraulic detention times after continuous flow biology electrodialysis system addition ion exchange resin
Acid concentration contrast schematic diagram.
Attached drawing 8 is energy under different hydraulic detention times after continuous flow biology electrodialysis system addition ion exchange resin
Consume contrast schematic diagram.
Attached drawing 9 is that production acid under different applied voltages is dense after continuous flow biology electrodialysis system addition ion exchange resin
Spend contrast schematic diagram.
Attached drawing 10 is energy consumption under different applied voltages after continuous flow biology electrodialysis system addition ion exchange resin
Contrast schematic diagram.
Specific embodiment
As shown in Figure 1, 2, 3, continuous flow biology electrodialysis plant is connected to by the peristaltic pump and pipeline of multichannel
Reactor in insulating box, so that the liquid in reactor flows.Pipeline etc. is connected to wriggling under discontinuous state
Pump makes continuous flow biology electrodialysis stable operation until the plateau that reactor reaches discontinuous operation opens peristaltic pump,
Its cycle of operation is set as 24 hours.In the operational process of continuous flow, the continuous flow operational mode of four reaction chambers is different,
Middle-jiao yang, function of the spleen and stomach pole room is by the way of one-way flow, and its excess-three room is by the way of circulating.Wherein anode chamber's feed liquor is matrix,
The L MALIC ACID solution that acid compartment circulation fluid is the 0.04mol/L that total volume is 100mL, it is 250mL that middle room circulation fluid, which is total volume,
0.3mol/L L MALIC ACID potassium solution, the circulation fluid of alkaline chamber is the sodium chloride solution for the lmol/L that total volume is 100mL.
Using a kind of intensifying method of biological electrodialysis production malic acid of the invention, continuous flow biology electrodialysis is compared
In common batch biology electrodialysis, the acid production rate of malic acid is doubled, and is increased to 0.203mol/L from 0.108mol/L,
Energy consumption drops to original 80%, is a kind of more optimal biological electrodialysis continuous-flow system.
The optimum operation hydraulic detention time of continuous flow biology electrodialysis system is 12 hours, is run under this service condition
Effect is best, and production malic acid concentration is 0.203mol/L, energy consumption 1.0kWh/kg.
It is a kind of more superior continuous flow biology electrodialysis that continuous flow, which adds ion exchange resin biology electrodialysis system,
System is successful improvement project, and compared to general continuous flow biology electrodialysis system, reactor internal resistance reduces half, from
260 Ω are reduced to 140 Ω, produce acid amount and improve by about one time；It is dropped to compared to common biological electrodialysis system energy consumption original
16.7%.
Continuous flow adds the applied voltage that the optimum operating condition of ion exchange resin biology electrodialysis system is 1V, and 12 is small
When hydraulic detention time, operational effect is best under this service condition, and energy consumption is only 0.183kWh/kg.
Claims (6)
1. a kind of intensifying method of biology electrodialysis production malic acid, which is characterized in that the system is improvement continuous flow bioelectricity
Dialysis, specific as follows: including anode chamber, acid compartment, desalting chamber and alkaline chamber, the continuous flow operational mode of four reaction chambers is different,
Middle-jiao yang, function of the spleen and stomach pole room is by the way of one-way flow, and its excess-three room is by the way of circulating；Cation exchange is added in acid compartment
Resin adds anion exchange resin in alkaline chamber, and chamber volume ratio and addition ion exchange resin volume ratio are 1: 1, acid
Room circulation fluid is L MALIC ACID solution, and middle room circulation fluid is L MALIC ACID potassium solution, and the circulation fluid of alkaline chamber is sodium chloride solution；Into
The method that one step reduces energy consumption, reduces internal resistance, improves current density.
2. the method according to claim 1, wherein for recycling malic acid from the waste water containing potassium malate.
3. according to claim 1, which is characterized in that control anode chamber's feed liquor is matrix, and acid compartment circulation fluid is 0.04mol/L's
L MALIC ACID solution, middle room circulation fluid are the L MALIC ACID potassium solution of 0.1-0.5mol/L, and the circulation fluid of alkaline chamber is 1mol/L's
Sodium chloride solution.
4. according to claim 1, which is characterized in that system internal resistance can be reduced, after ion exchange resin is added, system internal resistance is
120-160 ohm.
5. according to claim 1, which is characterized in that the hydraulic detention time of system operation is 9-15h, produces malic acid concentration and is
0.05-0.12mol/L, the energy consumption for producing malic acid is 0.18-0.34kWh/kg.
6. according to claim 1, which is characterized in that for system under 1.0-1.4V applied voltage, production malic acid concentration is 0.06-
0.12mol/L, the energy consumption for producing malic acid is 0.18-0.41kWh/kg.
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| CN105483165B (en) * | 2016-01-19 | 2020-09-04 | 安徽雪郎生物科技股份有限公司 | Preparation method of L-malic acid |
| CN106145312A (en) * | 2016-07-20 | 2016-11-23 | 中山大学 | The processing method of reverse osmosis concentrated water in a kind of municipal wastewater treatment plant effluent reuse |
| CN110937679A (en) * | 2019-10-30 | 2020-03-31 | 同济大学 | System and method for producing hydrogen by recovering nitrogen and phosphorus in sewage through bioelectrochemistry and synchronously fixing carbon |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234961A (en) * | 2008-03-04 | 2008-08-06 | 江苏道森生物化学有限公司 | Method for preparing lactic acid by applying double pole film electrodialysis technique |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234961A (en) * | 2008-03-04 | 2008-08-06 | 江苏道森生物化学有限公司 | Method for preparing lactic acid by applying double pole film electrodialysis technique |
Non-Patent Citations (2)
| Title |
|---|
| "Malic acid production using a biological electrodialysis with bipolar membrane";Guangli Liu等;《Journal of Membrane Science》;20141231(第471期);摘要，材料和方法 |
| "双极膜电渗析从发酵废液回收柠檬酸";董恒等;《第四届中国膜科学与技术报告会论文集》;20110614;摘要，第1页左栏第1段-右栏第1段，1实验部分 |
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