CN112501014A - Oxygen circulation bioreactor for preparing L-glufosinate-ammonium - Google Patents
Oxygen circulation bioreactor for preparing L-glufosinate-ammonium Download PDFInfo
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- CN112501014A CN112501014A CN202010902352.1A CN202010902352A CN112501014A CN 112501014 A CN112501014 A CN 112501014A CN 202010902352 A CN202010902352 A CN 202010902352A CN 112501014 A CN112501014 A CN 112501014A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 239000001301 oxygen Substances 0.000 title claims abstract description 207
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 207
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000007789 gas Substances 0.000 claims abstract description 64
- 238000000746 purification Methods 0.000 claims abstract description 30
- 238000003860 storage Methods 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 239000000872 buffer Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
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- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 7
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- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000008055 phosphate buffer solution Substances 0.000 description 6
- 239000004009 herbicide Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 229930027917 kanamycin Natural products 0.000 description 4
- SBUJHOSQTJFQJX-NOAMYHISSA-N kanamycin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N SBUJHOSQTJFQJX-NOAMYHISSA-N 0.000 description 4
- 229960000318 kanamycin Drugs 0.000 description 4
- 229930182823 kanamycin A Natural products 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000005562 Glyphosate Substances 0.000 description 3
- 102000004316 Oxidoreductases Human genes 0.000 description 3
- 108090000854 Oxidoreductases Proteins 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 3
- 229940097068 glyphosate Drugs 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- WAXMRVDZHXIAHQ-UHFFFAOYSA-N COP(=O)(OO)CCC(C(=O)O)=C=O Chemical compound COP(=O)(OO)CCC(C(=O)O)=C=O WAXMRVDZHXIAHQ-UHFFFAOYSA-N 0.000 description 2
- 102000016938 Catalase Human genes 0.000 description 2
- 108010053835 Catalase Proteins 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- BPHPUYQFMNQIOC-NXRLNHOXSA-N isopropyl beta-D-thiogalactopyranoside Chemical compound CC(C)S[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O BPHPUYQFMNQIOC-NXRLNHOXSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- IAJOBQBIJHVGMQ-SCSAIBSYSA-N (2R)-glufosinate Chemical compound C[P@@](O)(=O)CC[C@@H](N)C(O)=O IAJOBQBIJHVGMQ-SCSAIBSYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005561 Glufosinate Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- UYQVCLAMCWIBKC-UHFFFAOYSA-N OOP(=O)(OC)CCC(N)C(=O)O Chemical group OOP(=O)(OC)CCC(N)C(=O)O UYQVCLAMCWIBKC-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 102000005396 glutamine synthetase Human genes 0.000 description 1
- 108020002326 glutamine synthetase Proteins 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/18—Apparatus specially designed for the use of free, immobilized or carrier-bound enzymes
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- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/24—Gas permeable parts
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- C12M27/02—Stirrer or mobile mixing elements
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- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/06—Nozzles; Sprayers; Spargers; Diffusers
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- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
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Abstract
An oxygen-recycling bioreactor for preparing L-glufosinate-ammonium, comprising: the inner cavity of the reactor tank body is divided into an upper part and a lower part by the oxygen permeable membrane; the bottom of the reactor tank body is provided with a water outlet; the top of the reactor tank body is provided with an oxygen outlet; the oxygen purification device is arranged in a reaction purification cavity of the reactor tank body and comprises a gas distributor and an oxygen guide pipe, and the gas distributor is laid at the bottom of the reaction purification cavity; the oxygen flow guide pipe is arranged in the inner cavity of the reactor tank body, and the lower end of the oxygen flow guide pipe is communicated with the gas inlet of the gas distributor; the upper end of the oxygen flow guide pipe penetrates out of the oxygen gas-permeable membrane and is arranged in the oxygen buffer cavity and communicated with the oxygen pump pipeline; and the oxygen storage device comprises an oxygen storage tank, an air outlet pipe and a pressure self-control valve. The invention has the beneficial effects that: the oxygen can be fully contacted with other reactants, the reaction efficiency (for example, the efficiency of preparing the L-glufosinate-ammonium) is improved, the oxygen in the reactor can be recycled, and the energy is saved.
Description
Technical Field
The invention relates to an oxygen circulation bioreactor, in particular to an oxygen circulation bioreactor for producing refined glufosinate-ammonium by an oxidation-reduction coupling method, and belongs to the field of production of refined glufosinate-ammonium.
Background
Glufosinate-ammonium, whose chemical name is 4- [ hydroxy (methyl) phosphono ] -DL-homoalanine, is a herbicide resistant to the second major transgenic crop in the world, developed and produced by hester (bayer corporation after several times of mergers), also called glufosinate-ammonium salt, Basta, Buster, etc., and belongs to phosphonic acid herbicides, and a non-selective (biocidal) contact herbicide is a glutamine synthetase inhibitor.
It is well known that the biocidal herbicide market is huge. At present, three herbicides in the world are paraquat, glyphosate and glufosinate-ammonium respectively. In the aspect of market use, the glyphosate is exclusively used as a chelating agent, but due to long-term use, a large amount of weeds generate resistance, and the glyphosate also tends to lose effectiveness; the published bulletins of the department of agriculture in China show that the paraquat is listed in the Lute Te Dan convention because of the severe toxicity, the production of the paraquat is stopped at 7 and 1 months in 2014, and the paraquat is forbidden at 7 and 1 months in 2016; increasingly, countries worldwide are banned or restricted. At present, the glufosinate-ammonium has excellent weeding performance and small phytotoxicity side effect although the yield is small, and therefore the glufosinate-ammonium has great market potential in a future period.
Glufosinate has two optical isomers, L-glufosinate and D-glufosinate. But only the L-type has physiological activity (the molecular structure is shown in figure two), is easy to decompose in soil, has small toxicity to human and animals, has wide weeding spectrum and small destructive power to the environment.
Currently, glufosinate-ammonium is generally marketed as a racemic mixture. If the glufosinate-ammonium product can be used in the form of L-configuration pure optical isomer, the using amount of glufosinate-ammonium can be obviously reduced, and the method has important significance for improving atom economy, reducing use cost and relieving environmental pressure. In the preparation route of the refined glufosinate-ammonium (L-glufosinate-ammonium), the oxidation-reduction coupling method has the advantages of convenience, environmental protection, high conversion rate of production raw materials, high optical purity of products and the like due to the unique production process, and is more necessary for industrial application and large-scale popularization. The reaction principle of the oxidation stage is shown in fig. 4.
Since the reaction requires the presence of oxygen during the "oxidation" stage, reactor design for oxygen transfer becomes particularly important. Meanwhile, the reactor meets the requirements of stable oxygen supply, meets the economic and energy-saving standards, and is safe and reliable, so that the reaction is efficiently and stably carried out. The reactor on the market at present is mainly used for a common fermentation tank, oxygen can not be fully and uniformly contacted with other substrates, and the oxygen led into the tank can not be recycled, so that the reaction efficiency is greatly reduced, and the raw materials which are excessively consumed hinder the industrial production, thereby causing economic loss and resource waste.
Disclosure of Invention
The invention aims to provide an oxygen circulation bioreactor for preparing L-glufosinate-ammonium. The reactor designed by the invention can not only uniformly supply oxygen; the contact area of the reaction liquid and the oxygen is increased; meanwhile, the oxygen released by decomposing the byproduct hydrogen peroxide in the reaction can be recovered, purified and reused, thereby achieving the effect of recycling the oxygen.
The invention relates to an oxygen circulation bioreactor for preparing L-glufosinate-ammonium, which is characterized by comprising the following components:
the inner cavity of the reactor tank body is divided into an upper part and a lower part by the oxygen permeable membrane, wherein the lower part is a reaction purification cavity used for purifying the introduced oxygen, and the lower part is an oxygen buffer cavity used for temporarily storing the purified oxygen; the bottom of the reactor tank body is provided with a water outlet which is communicated with the reaction purification cavity of the reactor tank body and used for discharging wastewater in the reaction purification cavity; the top of the reactor tank body is provided with an oxygen outlet which can be communicated with the oxygen collecting cavity, and the oxygen outlet is used for discharging the purified oxygen in the reactor tank body into the oxygen collecting device for storage;
the oxygen purification device is arranged in the reaction purification cavity of the reactor tank body and comprises a gas distributor and an oxygen guide pipe, wherein the gas distributor is laid at the bottom of the reaction purification cavity and used for distributing oxygen to each position in the reactor tank body; the oxygen flow guide pipe is arranged in the inner cavity of the reactor tank body, and the lower end of the oxygen flow guide pipe is used as an air outlet of the oxygen flow guide pipe and communicated with an air inlet of the gas distributor and used for introducing gas into the gas distributor; the upper end of the oxygen flow guide pipe is used as an air inlet of the oxygen flow guide pipe, penetrates out of the oxygen gas-permeable membrane, is arranged in the oxygen buffer cavity, is communicated with the oxygen pump pipeline and is used for introducing oxygen into the reaction purification cavity;
the oxygen storage device comprises an oxygen storage tank, an air outlet pipe and a pressure self-control valve, and the oxygen storage tank is communicated with an oxygen outlet pipeline of the reactor tank through the air outlet pipe; the pressure self-control valve is arranged at the joint of the gas outlet pipe and the reactor tank body, and the on-off of the pressure self-control valve is controlled by the pressure difference at the two ends of the pressure self-control valve; the oxygen supply device comprises an oxygen pump and a communicating pipe; the gas inlet of the oxygen pump is communicated with the gas outlet pipeline of the oxygen storage tank through a communicating pipe, the gas outlet of the oxygen pump is communicated with the gas inlet end of the gas distributor and the lower end of the oxygen flow guide pipe, the power of the oxygen pump can be freely assembled according to the size of a reaction system, oxygen is supplied to the reaction tank body through the oxygen pump, and then the oxygen is uniformly introduced into reaction liquid through the gas distributor.
The pressure self-control valve comprises a pushing part and a blocking part, the pushing part comprises a supporting seat and an upper push rod, and the supporting seat is arranged at an oxygen outlet of the reactor tank body and used for fixing the upper push rod; the upper end of the upper push rod is fixedly connected with the supporting seat and used for pushing the plugging part to control the plugging part to be switched on and off; the plugging part comprises a piston, a lower push rod, a valve plate and a spring, the piston is arranged at the end part of the air outlet pipe and is positioned below the upper push rod, and a vent hole is formed in the piston and used for realizing the communication of the upper side and the lower side of the piston; the lower push rod is arranged on the piston in a sliding manner, and the lower end of the lower push rod is connected with a valve plate which can be attached to the bottom surface of the piston; the valve plate is attached to the bottom surface of the piston and connected with the piston through a spring embedded in the bottom of the piston.
And a sealing ring is additionally arranged between the piston and the inner wall of the air outlet pipe, so that the piston is in sealing sliding connection with the air outlet pipe and is used for preventing oxygen from leaking in the sliding process of the piston.
The oxygen purification device also comprises a baffle group, wherein the baffle group comprises a plurality of baffles, and the baffles are horizontally arranged in the reaction purification cavity in a staggered manner.
The air inlet of the oxygen draft tube is an inverted cone-shaped opening, namely the diameter of the air inlet of the oxygen draft tube decreases progressively from top to bottom.
And the air inlet of the oxygen flow guide pipe is communicated with an external blower and used for pumping oxygen to be pressed into the gas distributor below.
The oxygen gas-permeable membrane is a waterproof gas-permeable membrane and consists of a non-woven fabric layer and a polyethylene high-molecular waterproof gas-permeable layer.
The gas distributor is connected with gas nozzles which are uniformly distributed, and the distance between every two gas nozzles is equal, so that the oxygen can be uniformly distributed to all positions in the reactor.
The gas distributor is in a regular polygon ring shape and is arranged at the whole bottom of the reactor tank body.
The first end part of the air outlet pipe is communicated with an air inlet of the oxygen storage tank, the second end part of the air outlet pipe is inserted into the ventilating hole of the reactor tank body and is connected with the ventilating hole in a sealing way, and the first end part of the air outlet pipe is provided with a storage tank valve capable of adjusting the flow rate in the pipe; the inner diameter of the first end part of the air outlet pipe is smaller than the inner diameter of the second end part of the air outlet pipe.
The invention not only can fully contact oxygen with other reactants and improve the reaction efficiency, but also designs a device for purifying, recovering and recycling the oxygen in a breakthrough manner, so that the oxygen in the reactor can be recycled, the energy is saved, and the economic benefit of the industrial production of the glufosinate-ammonium prepared by the oxidation-reduction coupling method is effectively improved.
The invention has the beneficial effects that:
(1) compared with the mode that the pressure relief valve fully relieves the pressure, the pressure self-control valve can be automatically closed in time after the pressure is reduced, the reaction in the reactor tank body is ensured to be continuously and efficiently carried out, the structure can automatically collect the overflowed redundant oxygen while realizing the self-circulation of the oxygen, and meanwhile, the reactor tank body does not need to be opened to collect the oxygen, the use is more convenient and fast, the process of opening the reactor is reduced, and a large amount of time cost and labor cost are saved. Compared with the reactor in the prior art, the oxygen self-circulation structure can realize real dead-angle-free stirring, overcomes the defect of small stirring area of the stirring paddle of the original reactor, and ensures that the reaction effect of the oxidation step reaction in the production process of the refined glufosinate ammonium is better and the working efficiency is higher;
(2) the air outlet pipe and the oxygen storage tank can directly collect redundant overflowed oxygen, so that the subsequent oxygen utilization is convenient in one step, the whole treatment process is simpler and faster, and the working efficiency is improved;
(3) the reactor tank body is internally provided with the baffle plate, so that three substances, namely solid, liquid and gas, can be disturbed, the contact time is longer, the contact area is larger, the stirring effect of oxygen is better, the oxidation reaction efficiency is improved, the oxidation reaction time is shortened, and the production efficiency of the final product, namely the glufosinate-ammonium is improved;
(4) the piston is connected with the sealing ring, so that the piston can be ensured not to leak gas while moving, the pressure automatic control valve can be ensured to realize the functions of opening and closing in time all the time, and the danger of oxygen leakage is avoided;
(5) the oxygen gas-permeable membrane is a waterproof gas-permeable membrane, and can prevent other reactants or products from being carried by oxygen to overflow while allowing oxygen to pass through, so that reaction substrates D, L-glufosinate-ammonium and amino acid oxidase can always stay in a reaction region to perform full reaction, the reaction efficiency is not reduced, the reaction is performed efficiently, and the production efficiency of preparing refined glufosinate-ammonium is improved;
(6) the gas distributor is in the shape of a regular polygon, the gas nozzles are connected on the gas distributor, oxygen can be uniformly distributed to all positions of the reactor tank body, so that the stirring effect of the oxygen on reaction liquid is better, compared with a stirring paddle of a traditional reactor, the gas moving speed of oxygen circulation is higher, stirring is more violent, and the production efficiency of the final product of the refined glufosinate-ammonium is greatly improved.
Drawings
FIG. 1 is a block diagram of the present invention.
Fig. 2 is a structural view of the pressure self-control valve of the present invention.
FIG. 3 is a diagram showing the molecular structure of L-glufosinate-ammonium.
FIG. 4 is a reaction scheme of preparing glufosinate-ammonium by oxidation-reduction coupling.
FIG. 5 is a schematic diagram showing the conversion curve of the reaction system of the reactor of the present invention compared with that of a conventional reactor.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
With reference to the accompanying drawings:
example 1 an oxygen recycle bioreactor for the production of L-glufosinate according to the invention comprises:
the inner cavity of the reactor tank body 3 is divided into an upper part and a lower part by an oxygen permeable membrane, wherein the lower part is a reaction purification cavity used for purifying the introduced oxygen, and the lower part is an oxygen buffer cavity used for temporarily storing the purified oxygen; the bottom of the reactor tank body 3 is provided with a water outlet 8, and the water outlet 8 is communicated with the reaction purification cavity of the reactor tank body 3 and is used for discharging wastewater in the reaction purification cavity; the top of the reactor tank body 3 is provided with an oxygen outlet which can be communicated with the oxygen collecting cavity and is used for discharging the purified oxygen in the reactor tank body into an oxygen collecting device for storage;
the oxygen purification device is arranged in a reaction purification cavity of the reactor tank body and comprises a gas distributor 10 and an oxygen guide pipe 7, wherein the gas distributor 10 is laid at the bottom of the reaction purification cavity and used for distributing oxygen to each position in the reactor tank body; the oxygen flow guide pipe 7 is arranged in the inner cavity of the reactor tank body, and the lower end of the oxygen flow guide pipe 7 is used as an air outlet of the oxygen flow guide pipe and communicated with an air inlet of the gas distributor 10 and used for introducing gas into the gas distributor; the upper end of the oxygen draft tube 7 is used as an air outlet of the oxygen draft tube, penetrates out of the oxygen permeable membrane, is arranged in the oxygen buffer cavity, is communicated with the oxygen pump pipeline and is used for introducing oxygen into the reaction purification cavity;
the oxygen storage device comprises an oxygen storage tank 12, an air outlet pipe 1 and a pressure automatic control valve 2, and the oxygen storage tank 12 is communicated with an oxygen outlet pipeline of the reactor tank 3 through the air outlet pipe 1; the pressure automatic control valve 2 is arranged at the joint of the gas outlet pipe 1 and the reactor tank body 3, and the on-off of the pressure automatic control valve is controlled through the pressure difference at the two ends of the pressure automatic control valve; the oxygen supply device comprises an oxygen pump 13 and a communicating pipe; the gas inlet of the oxygen pump is communicated with the gas outlet pipeline of the oxygen storage tank 12 through a communicating pipe, the gas outlet of the oxygen pump is communicated with the gas inlet end of the gas distributor 10, the power of the oxygen pump can be freely assembled according to the size of a reaction system, oxygen is supplied to the reaction tank body 3 through the oxygen pump, and then the oxygen is uniformly introduced into reaction liquid through the gas distributor 10.
The pressure self-control valve 2 comprises a pushing part and a blocking part, the pushing part comprises a supporting seat 14 and an upper push rod 15, and the supporting seat 14 is arranged at an oxygen outlet of the reactor tank body 3 and used for fixing the upper push rod 15; the upper end of the upper push rod 15 is fixedly connected with the supporting seat 14 and used for pushing the plugging part to control the plugging part to be switched on and off; the plugging part comprises a piston 17, a lower push rod 16, a valve plate 18 and a spring 20, the piston 17 is arranged at the end part of the air outlet pipe 1 and is positioned below the upper push rod 15, and a vent hole 21 is formed in the piston 17 and used for realizing the communication between the upper side and the lower side of the piston; the lower push rod 16 is arranged on the piston 17 in a sliding manner, and the lower end of the lower push rod is connected with a valve plate 18 which can be attached to the bottom surface of the piston; the valve plate 18 is attached to the bottom surface of the piston 17 and connected thereto by a spring 20 embedded in the bottom of the piston 17.
Compared with the mode that the pressure of the common pressure release valve is fully released, the pressure self-control valve 2 can be automatically closed in time after the pressure is reduced, the reaction in the reactor tank body 3 is ensured to be continuously and efficiently carried out, the structure can automatically collect overflowed redundant oxygen while realizing the self-circulation of the oxygen, and meanwhile, the reactor tank body 3 does not need to be opened to collect the oxygen without stopping working, so that the use is more convenient and fast, the process of opening the reactor is reduced, and a large amount of time cost and labor cost are saved. Compared with the reaction fermentation tank in the prior art, the oxygen self-circulation structure can realize true dead-angle-free stirring, overcomes the defect that part of D, L-glufosinate-ammonium and bacteria liquid in the oxygen-introducing reaction circulation structure can not enter circulation convection all the time, and ensures that the glufosinate-ammonium production process has higher efficiency and better effect.
Example 4 this example focuses on the improvement compared to the above examples, and the same parts will not be described again, in this example, the reactor tank 3 below the oxygen permeable membrane 5 is installed with the baffle plates 6 in the horizontal staggered arrangement. The baffle plates are divided into two types, the first type of baffle plates surround the oxygen flow guide pipe, and a gap is reserved between the outer edge of the first type of baffle plates and the inner wall of the reactor tank body; the outer edge of the second baffle plate is fixedly connected with the inner wall of the reactor tank body, a gap is reserved between the inner edge and the oxygen guide pipe, the first baffle plate and the second baffle plate are arranged in the reaction purification cavity of the reactor tank body in an up-and-down staggered mode, and the gap between the first baffle plate and the adjacent second baffle plate is kept in a staggered arrangement. The reactor tank body 3 of the embodiment is internally provided with the baffle plate 6, so that three substances of solid, liquid and gas can be disturbed, the contact time of the three substances is longer, the stirring effect of oxygen is better, and the contact area of the oxygen and amino acid oxidase is increased, thereby greatly improving the reaction efficiency of an oxidation stage.
The oxygen draft tube 7 divides the whole tank body into two parts and is used for fixing the part of the baffle plate 6, so that the introduced oxygen baffling path is longer, the contact area of the reaction liquid and the oxygen is larger, and the reaction airflow is stirred more uniformly. When the oxygen pump 13 is led out, the oxygen gas passes through the oxygen gas guide pipe 7 and the gas distributor 10, and the oxygen gas guide pipe 7 has a larger inner diameter, so that the oxygen gas can play a role in air pressure balance and buffering, and is beneficial to selecting the power of the oxygen pump. Meanwhile, the oxygen enters the purification cavity through the oxygen draft tube 7 to be recycled, so that the condition that the oxygen generated by decomposing the byproduct hydrogen peroxide in the reaction process is insufficient can be compensated.
Embodiment 5 focuses on the improvement of the above embodiment, and the same parts are not described again, in this embodiment, the side surface of the piston 17 is connected to the sealing ring 19. The piston 17 of this embodiment is connected with sealing washer 19, can guarantee that piston 17 can not reveal gas when removing to guarantee that pressure automatic control valve 2 can realize in time opening and closed function all the time, avoid oxygen to reveal and take place danger.
Example 6 this example focuses on the improvement of the above examples, and the same parts are not repeated, in this example, the oxygen permeable membrane 5 is a waterproof permeable membrane, and is composed of a nonwoven fabric layer and a polyethylene polymer waterproof permeable layer, and the pore diameter of the pore only allows oxygen molecules to pass through. The oxygen is allowed to pass through, and simultaneously, the anti-reaction liquid and other byproducts can be carried by the oxygen to overflow, so that the reaction raw materials can be always kept in the reaction area for full reaction, the high-efficiency utilization rate of the raw materials D, L-glufosinate-ammonium and the amino acid oxidase is ensured, the reaction is carried out efficiently, and the working efficiency of the reactor is improved.
Embodiment 7 this embodiment focuses on the improvement of the above embodiment, and the same parts are not repeated, in this embodiment, the gas distributor 10 is connected with the gas nozzles 9 which are uniformly arranged and distributed, and the gas distributor 10 is in the shape of a regular polygon ring, preferably a regular octagon ring. The gas distributor 10 of this embodiment is regular polygon, and the higher authority is connected with air nozzle 9, can be with each position of oxygen evenly distributed to the reactor jar body 3 for the oxygen air current is better to the stirring effect of reaction liquid, compares in sewage cycle's mode, and oxygen endless gas moving speed is faster, stirs more acutely, has improved the work efficiency of reactor.
Example 8 this example illustrates the simultaneous use of a reactor according to the present invention and a conventional reactor for a 500ml reaction solution system to perform the oxidation stage reaction in the preparation of glufosinate-ammonium. In the case of the same reaction conditions except for the reactor, this example can show the reaction effect of the reactor of the present invention and the case of no dead-angle aeration stirring.
(1) Engineering bacteria E.coli BL21(DE3)/pET28b-CeDAAO-I16F-R54H-Y57N-R219K-N312H were inoculated into LB liquid medium containing 50. mu.g/mL kanamycin, cultured at 37 ℃ and 200rpm for 12 hours, further inoculated into fresh LB liquid medium containing 50. mu.g/mL kanamycin resistance in an inoculum size of 1% (v/v), and cultured at 37 ℃ and 150rpm until the bacterial body OD is reached600Reaching 0.6-0.8, adding IPTG with final concentration of 24 μ g/mL, inducing culture at 28 deg.C for 14h, centrifuging at 4 deg.C and 8000rpm for 20min, discarding supernatant, collecting precipitate, and washing twice with Phosphate Buffer Solution (PBS) with pH of 7.5 and 20mM to obtain wet thallus.
ColiBL21(DE3)/pET28b-CeDAAO-I16F-R54H-Y57N-R219K-N312H wet cell was added in an amount of 10g, and then a phosphate buffer solution of D, L-glufosinate-ammonium at a final concentration of 600mM and catalase (3000U/mg) at a final concentration of 0.1g/L and pH 8.0 (20mM) was added to prepare 500mL of a reaction system. The 500mL of the reaction mixture was charged into the reactor of the present invention, the reaction was carried out at 30 ℃ with an air flow of 1L/min, and ammonia was fed to maintain the pH of the reaction mixture at 8.0. FIG. 5 is a graph showing the reaction progress of the concentration of the product 2-carbonyl-4- [ hydroxy (methyl) phosphono ] butanoic acid during the reaction, as measured by a liquid phase method.
(2) Engineering bacteria E.coli BL21(DE3)/pET28b-CeDAAO-I16F-R54H-Y57N-R219K-N312H were inoculated into LB liquid medium containing 50. mu.g/mL kanamycin, cultured at 37 ℃ and 200rpm for 12 hours, further inoculated into fresh LB liquid medium containing 50. mu.g/mL kanamycin resistance in an inoculum size of 1% (v/v), and cultured at 37 ℃ and 150rpm until the bacterial body OD is reached600Reaching 0.6-0.8, adding IPTG with final concentration of 24 μ g/mL, inducing culture at 28 deg.C for 14h, centrifuging at 4 deg.C and 8000rpm for 20min, discarding supernatant, collecting precipitate, and washing twice with Phosphate Buffer Solution (PBS) with pH of 7.5 and 20mM to obtain wet thallus.
Coli BL21(DE3)/pET28b-CeDAAO-I16F-R54H-Y57N-R219K-N312H wet cell addition amount was 10g, and 500mL of a reaction system was constituted by adding thereto a phosphate buffer solution of D, L-glufosinate-ammonium at a final concentration of 600mM, and catalase (3000U/mg) at a final concentration of 0.1g/L and pH 8.0 (20 mM). The 500mL reaction solution was added to a conventional reactor with an aeration rate of 1L/min, and the reaction was carried out at 30 ℃ and a magnetic stirring speed of 600rpm, and ammonia was fed to maintain the pH of the reaction solution at 8.0. FIG. 5 is a graph showing the reaction progress of the concentration of the product 2-carbonyl-4- [ hydroxy (methyl) phosphono ] butanoic acid during the reaction, as measured by a liquid phase method.
As can be seen from FIG. 5, when the reaction proceeded to 8 hours, the conversion rate of the reaction system using the reactor of the present invention could reach 97.2%, while the conversion rate of the reaction solution in the conventional reactor was only 62% under the same reaction conditions and the same reaction time.
The embodiments described in this specification are merely illustrative of implementations of the inventive concept and the scope of the present invention should not be considered limited to the specific forms set forth in the embodiments but includes equivalent technical means as would be recognized by those skilled in the art based on the inventive concept.
Claims (10)
1. An oxygen-recycling bioreactor for preparing L-glufosinate-ammonium, comprising:
the inner cavity of the reactor tank body is divided into an upper part and a lower part by the oxygen permeable membrane, wherein the lower part is a reaction purification cavity used for purifying the introduced oxygen, and the lower part is an oxygen buffer cavity used for temporarily storing the purified oxygen; the bottom of the reactor tank body is provided with a water outlet which is communicated with the reaction purification cavity of the reactor tank body and used for discharging wastewater in the reaction purification cavity; the top of the reactor tank body is provided with an oxygen outlet which can be communicated with the oxygen collecting cavity, and the oxygen outlet is used for discharging the purified oxygen in the reactor tank body into the oxygen collecting device for storage;
the oxygen purification device is arranged in the reaction purification cavity of the reactor tank body and comprises a gas distributor and an oxygen guide pipe, wherein the gas distributor is laid at the bottom of the reaction purification cavity and used for distributing oxygen to each position in the reactor tank body; the oxygen flow guide pipe is arranged in the inner cavity of the reactor tank body, and the lower end of the oxygen flow guide pipe is used as an air outlet of the oxygen flow guide pipe and communicated with an air inlet of the gas distributor and used for introducing gas into the gas distributor; the upper end of the oxygen flow guide pipe is used as an air inlet of the oxygen flow guide pipe, penetrates out of the oxygen gas-permeable membrane, is arranged in the oxygen buffer cavity, is communicated with the oxygen pump pipeline and is used for introducing oxygen into the reaction purification cavity;
the oxygen storage device comprises an oxygen storage tank, an air outlet pipe and a pressure self-control valve, and the oxygen storage tank is communicated with an oxygen outlet pipeline of the reactor tank through the air outlet pipe; the pressure self-control valve is arranged at the joint of the gas outlet pipe and the reactor tank body, and the on-off of the pressure self-control valve is controlled by the pressure difference at the two ends of the pressure self-control valve; the oxygen supply device comprises an oxygen pump and a communicating pipe; the gas inlet of the oxygen pump is communicated with the gas outlet pipeline of the oxygen storage tank through a communicating pipe, and the gas outlet of the oxygen pump is communicated with the gas inlet end of the gas distributor and the lower end of the oxygen flow guide pipe.
2. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium of claim 1, wherein: the pressure self-control valve comprises a pushing part and a blocking part, the pushing part comprises a supporting seat and an upper push rod, and the supporting seat is arranged at an oxygen outlet of the reactor tank body and used for fixing the upper push rod; the upper end of the upper push rod is fixedly connected with the supporting seat and used for pushing the plugging part to control the plugging part to be switched on and off; the plugging part comprises a piston, a lower push rod, a valve plate and a spring, the piston is arranged at the end part of the air outlet pipe and is positioned below the upper push rod, and a vent hole is formed in the piston and used for realizing the communication of the upper side and the lower side of the piston; the lower push rod is arranged on the piston in a sliding manner, and the lower end of the lower push rod is connected with a valve plate which can be attached to the bottom surface of the piston; the valve plate is attached to the bottom surface of the piston and connected with the piston through a spring embedded in the bottom of the piston.
3. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium of claim 2, wherein: and a sealing ring is additionally arranged between the piston and the inner wall of the air outlet pipe, so that the piston is in sealing sliding connection with the air outlet pipe and is used for preventing oxygen from leaking in the sliding process of the piston.
4. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium of claim 1, wherein: the oxygen purification device also comprises a baffle group, wherein the baffle group comprises a plurality of baffles, and the baffles are horizontally arranged in the reaction purification cavity in a staggered manner.
5. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium according to claim 4, wherein: the air inlet of the oxygen draft tube is an inverted cone-shaped opening, namely the diameter of the air inlet of the oxygen draft tube decreases progressively from top to bottom.
6. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium of claim 5, wherein: and the air inlet of the oxygen flow guide pipe is communicated with an external blower and used for pumping oxygen to be pressed into the gas distributor below.
7. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium of claim 1, wherein: the oxygen gas-permeable membrane is a waterproof gas-permeable membrane and consists of a non-woven fabric layer and a polyethylene high-molecular waterproof gas-permeable layer.
8. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium of claim 5, wherein: the gas distributor is connected with gas nozzles which are uniformly distributed, and the distance between every two gas nozzles is equal, so that the oxygen can be uniformly distributed to all positions in the reactor.
9. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium of claim 8, wherein: the gas distributor is in a regular polygon ring shape and is arranged at the whole bottom of the reactor tank body.
10. The oxygen-recycling bioreactor for preparing L-glufosinate-ammonium according to claim 3, wherein: the first end part of the air outlet pipe is communicated with an air inlet of the oxygen storage tank, the second end part of the air outlet pipe is inserted into the ventilating hole of the reactor tank body and is connected with the ventilating hole in a sealing way, and the first end part of the air outlet pipe is provided with a storage tank valve capable of adjusting the flow rate in the pipe; the inner diameter of the first end part of the air outlet pipe is smaller than the inner diameter of the second end part of the air outlet pipe.
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| CN105413590A (en) * | 2015-12-02 | 2016-03-23 | 青岛迈特达新材料有限公司 | Butane catalytic oxidation reaction device |
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