CN110195008B - Bioreactor for improving mass transfer efficiency of reaction system by utilizing tail gas - Google Patents
Bioreactor for improving mass transfer efficiency of reaction system by utilizing tail gas Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 78
- 238000012546 transfer Methods 0.000 title abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 130
- 239000007789 gas Substances 0.000 claims description 130
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 238000009423 ventilation Methods 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 9
- 244000005700 microbiome Species 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 2
- 238000000855 fermentation Methods 0.000 description 56
- 230000004151 fermentation Effects 0.000 description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004364 calculation method Methods 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
- C12M27/02—Stirrer or mobile mixing elements
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/06—Nozzles; Sprayers; Spargers; Diffusers
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Abstract
The invention relates to a bioreactor for improving mass transfer efficiency of a reaction system by utilizing tail gas. The invention provides an external pneumatic stirring device which is reasonable in design and convenient to use, and the stirring device can be driven by utilizing the pressure energy of tail gas generated in the biological reaction process, so that the gas kinetic energy of the tail gas is fully recycled, the electric quantity consumed by electric driving stirring is reduced, and the production energy consumption required in the biological reaction process is effectively reduced.
Description
Technical Field
The invention belongs to the field of bioreactors, and in particular relates to a bioreactor for improving mass transfer efficiency of a reaction system by utilizing tail gas.
Background
With the increasing shortage of energy, energy conservation has been an important aspect of sustainable development, and many enterprises have also dug energy conservation as the most direct means of reducing cost and improving profits. In the field of microbial fermentation, along with the increasing expansion of microbial fermentation production scale, the bioreactor is increasingly developed to be large-scale and large-scale, and the volume of the bioreactor is increasingly large, so that the energy consumption is the maximum consumption except the raw materials. Among them, the energy consumption required for the fermentation production of microorganisms using an electrically driven stirred tank is very large.
Although in recent years, the person skilled in the art reduces the energy consumption by various measures such as installing a frequency conversion device, adjusting the property of the stirring device, and the like. In addition, new technology for replacing stirring paddles in a gas lifting and gas mixing mode is also developed in the field of microbial fermentation. The gas mixing method is classified into an airlift circulation type, a bubbling type, an air injection type, and the like. However, due to individual differences of fermented products and special requirements on mechanisms such as shearing, melt mixing and the like of gas-liquid flow in the fermentation process, the problems that the gas lift and gas mixing mode are difficult to overcome in the application process exist, and the stirring type fermentation tank is still currently the main stream equipment for biological fermentation production.
Therefore, it is a current concern to effectively reduce the energy consumption during the fermentation reaction while maintaining a good, mass transfer sufficient reaction.
Disclosure of Invention
The invention aims to provide a bioreactor for improving mass transfer efficiency of a reaction system by utilizing tail gas.
In a first aspect of the present invention, there is provided a bioreactor for increasing mass transfer efficiency of a reaction system using tail gas, the bioreactor comprising:
a bioreactor body (1);
a stirring device (2);
the pneumatic assembly (3) is positioned above the bioreactor and connected with the stirring rod of the stirring device (2), and generates kinetic energy by gas and drives the stirring rod to operate;
an intake pipe (4) for inputting a gas into a reaction system in the bioreactor;
one end of the ventilation pipe (5) is communicated with the bioreactor body (1), the other end of the ventilation pipe is communicated with the pneumatic assembly (3) and is used for outputting tail gas of the bioreactor to an air inlet (34) of the pneumatic assembly (3) to supply air for the pneumatic assembly (3);
and a discharge pipe (6) for outputting the gas flowing out of the pneumatic assembly (3).
In a preferred embodiment, the pneumatic assembly (3) comprises:
a closed bin (31);
an impeller (32);
and the impeller center (33) can be driven to rotate by the impeller (32), and is connected with the stirring rod of the stirring device (2) so as to drive the stirring device (2) to rotate.
In another preferred embodiment, the closed cabin (31) is a U-shaped closed cabin.
In another preferred embodiment, the closed chamber (31) comprises an air inlet and an air outlet, and the air inlet and the air outlet control the air inlet and the air outlet through valves.
In another preferred embodiment, the impeller center (33) is connected with the stirring rod of the stirring device (2) through the pneumatic assembly fixing frame (10).
In another preferred embodiment, the intake pipe (4) includes:
an intake valve (41);
a one-way check valve (43);
a gas flow meter (42).
In another preferred embodiment, the vent pipe (5) comprises an air inlet valve (51); preferably, the vent pipe (5) is further provided with an exhaust pipe, and an exhaust valve (52) is arranged on the exhaust pipe.
In another preferred embodiment, the air inlet pipe (4) extends into the lower space of the bioreactor and is communicated with the gas distributor (8).
In another preferred embodiment, the bottom of the bioreactor further comprises: the biological reaction liquid input and output pipeline also comprises a valve (9).
In another preferred mode, a sealing ring is arranged at the connection position of the center of the impeller and the stirring rod, so that gas escape is avoided.
In another preferred mode, a sealing ring is arranged at the intersection of the bioreactor body (1) and the stirring rod, so that gas is prevented from escaping.
In another preferred embodiment, the aeration pipe (5) controls the gas flow among the bioreactor, the pneumatic assembly and the exhaust pipe through a tee joint.
In another aspect of the invention there is provided the use of the bioreactor for performing a biological reaction in which a gas is required to participate; preferably, the gas is a gas that provides carbon, hydrogen or oxygen to the biological reaction system; more preferably, the biological reaction is such that the aeration rate is not less than 4Nm 3 Biological reaction of/h.
In another aspect of the present invention, there is provided a method for performing a biological reaction using the bioreactor, the method comprising:
(a) Adding a biological reaction substrate (or reaction liquid) into the bioreactor body (1) and inoculating microorganisms;
(b) Introducing gas from an air inlet pipe (4) and inputting the gas into a reaction system in the bioreactor;
(c) Maintaining the communication of the vent pipe (5), and outputting the escaped tail gas to the pneumatic assembly (3) through the vent pipe (5) after the gas input in the step (b) flows through a reaction system consisting of microorganisms and reaction substrates, so that the pneumatic assembly (3) generates kinetic energy by the gas and drives a stirring rod of the stirring device (2) to operate; the inflow of the gas into the gas inlet pipe (4) is regulated according to the gas amount and stirring speed required by biological reaction.
In a preferred embodiment, the biological reaction is a biological reaction requiring the participation of a gas; when the reaction requiring stirring is carried out:
an air inlet valve (41) on the air inlet pipe (4) is in a communicating state;
the one-way check valve (43) on the air inlet pipe (4) is in a working state to prevent the air from flowing back;
an air inlet valve (51) on the air pipe (5) is in a communication state, and an exhaust valve (52) on the air pipe (5) is in a closed state;
when stirring is not needed:
an air inlet valve (41) on the air inlet pipe (4) is in a communicating state;
the one-way check valve (43) on the air inlet pipe (4) is in a working state to prevent the air from flowing back;
the air inlet valve (51) on the air pipe (5) is in a closed state, and the exhaust valve (52) on the air pipe (5) is in a communicated state.
In another preferred embodiment, the stirring rate of the stirring device (2) is constant or is constant.
Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
Drawings
FIG. 1 is a schematic structural view of a bioreactor according to example 1 of the present invention.
FIG. 2, left side view, is a schematic illustration of the structure of the pneumatic assembly (3) in the bioreactor of FIG. 1; the right diagram is a schematic diagram of the connection of the stirring device and the pneumatic assembly.
The reference numerals are as follows:
1: a bioreactor body;
2: a stirring device;
3: a pneumatic assembly; 31: closing the bin; 32: an impeller; 33: the center of the impeller; 34: an air inlet of the pneumatic assembly; 35: an air outlet of the pneumatic assembly;
4: an air inlet pipe; 41: an intake valve; 42: a gas flow meter; 43: a one-way check valve;
5: a vent pipe; 51: an intake valve; 52: an evacuation valve;
6: a discharge pipe;
7: an oxygen dissolving electrode;
8: a gas distributor;
9: a bioreactor bottom valve.
FIG. 3 shows a change curve of dissolved oxygen per unit time.
Fig. 4, acquisition of gas-liquid mass transfer coefficient KLa.
FIG. 5 is a graph showing the gas-liquid mass transfer coefficient measured by the exhaust method. Wherein A is dissolved oxygen concentration C; b is the slope calculation.
Fig. 6, solution of stirring power reference Np.
Detailed Description
The invention aims at researching the high-efficiency mass transfer of a bioreactor, and provides an external pneumatic stirring device which is reasonable in design and convenient to use on the basis of deep research, the stirring device can be driven by utilizing the pressure energy of tail gas generated in the biological reaction process, the gas kinetic energy of the tail gas is fully recycled, the electric quantity consumed by electric driving stirring is reduced, and the production energy consumption required in the biological reaction process is effectively reduced.
As used herein, the term "bioreactor" is used interchangeably with "fermenter".
Bioreactor
The invention provides a bioreactor for improving mass transfer efficiency of a reaction system by utilizing tail gas, which comprises the following components: a bioreactor body; a stirring device; the pneumatic assembly is positioned above the bioreactor and connected with the stirring rod of the stirring device, and generates kinetic energy by gas and drives the stirring rod to operate; an air inlet pipe for inputting gas into the reaction system in the bioreactor; one end of the vent pipe is communicated with the bioreactor body, the other end of the vent pipe is communicated with the pneumatic assembly and is used for outputting tail gas of the bioreactor to an air inlet of the pneumatic assembly to supply air for the pneumatic assembly; and the discharge pipe is used for outputting the gas flowing out of the pneumatic assembly.
The stirring device comprises a part positioned inside the bioreactor and a part positioned outside the bioreactor, and the part is organically connected through a stirring rod penetrating the inside and the outside. The external part of the stirring device is connected with the pneumatic device, one end of the internal part of the stirring device is inserted into the reaction system of the biological reaction, and the stirring device can be operated with the improvement of the mass transfer efficiency of the reaction system.
The pneumatic assembly comprises: a closed bin and an impeller. The axial direction of the central position of the impeller is connected with a stirring rod of the stirring device, so that after gas (fermentation tail gas) is blown into the closed bin, the impeller rotates unidirectionally under the pushing of the gas, and the stirring device is driven to rotate.
The closed bin comprises an air inlet and an air outlet, the air inlet and the air outlet control the air to enter and output through valves, tail gas generated by biological reaction is input into the closed bin through the air inlet, and the air outlet of the closed bin discharges the air flowing through the impeller. The shape of the closed cabin can be various, and in general, a semi-ring shape and a U-shape are more suitable, and preferably, the closed cabin is a closed cabin with a U-shaped structure.
The center of the impeller is connected with a stirring rod of the stirring device through a pneumatic assembly fixing frame. It should be understood that a variety of fixation means may be employed in the present invention so long as fixation is achieved.
Since the stirring device has portions located inside as well as outside the bioreactor, a close combination of stirring device and bioreactor is important. Therefore, as a preferable mode of the invention, a sealing ring is arranged at the connecting position of the impeller center and the stirring rod; the bioreactor body and the crossing of puddler also be equipped with the sealing washer, avoid gaseous escape.
The air inlet pipe comprises an air inlet valve which is used for controlling whether the air inlet pipe is in air inlet or not and controlling the flow of air.
As a preferable mode of the invention, the air inlet pipe is also provided with a one-way check valve, so that the input air flows into the bioreactor in one way, and the energy consumption loss caused by air backflow is avoided.
In order to accurately understand the flow rate of the input gas, as a preferable mode of the invention, a gas flowmeter is further arranged on the air inlet pipe.
The air inlet pipe extends into the lower space of the bioreactor, so that the gas conveyed by the air inlet pipe can be discharged into the reaction system for the reaction system. As a preferred mode of the present invention, the gas fed from the gas feed pipe is communicated with a gas distributor, and the gas is distributed into the reaction system by the gas distributor, which is advantageous for more uniform utilization of the gas.
An air inlet valve is arranged on the vent pipe for outputting biological reaction tail gas; preferably, an exhaust pipe is also arranged, and an exhaust valve is arranged on the exhaust pipe; more preferably, the flow of gas between the bioreactor, the pneumatic assembly, the exhaust pipe is controlled by means of a tee.
The gas is continuously input into the reaction system at the gas inlet pipe, and after the reaction system is uniformly mixed with the gas and reacts, tail gas is continuously generated, so that the pressure of the gas above the liquid level of the reactor is increased, and the gas enters the gas inlet pipe and is conveyed into the pneumatic device.
It should be understood that other devices, such as a temperature detecting device, a humidity detecting device, a gas content analyzing device, a sampling device, etc., may be provided on the air inlet pipe or the air pipe in order to achieve good monitoring or to meet the requirements of different reactions on the gas, and it should be understood that these modifications are also covered in the scope of the present invention.
It will be appreciated that openable and sealable material inlets, material outlets, etc. may also be provided on the bioreactor to facilitate material addition, conversion, etc. and that valves may be used to provide good opening and sealing.
It should be understood that the off-gas flowing out of the pneumatic device according to the invention can be recycled in a cyclic manner by further feeding it back into the reactor through a pipe, if this is considered for further use of the off-gas.
Biological reaction method
The invention provides the application of the bioreactor, which is used for carrying out biological reaction, wherein the biological reaction is the biological reaction which needs gas to participate in; preferably, the gas is a gas that provides carbon, hydrogen or oxygen to the biological reaction system; more preferably, the biological reaction is such that the aeration rate is not less than 4Nm 3 Biological reaction of/h.
The invention provides a method for carrying out biological reaction by using the bioreactor, which comprises the following steps: (a) Adding a biological reaction substrate (or reaction liquid) into the bioreactor body and inoculating microorganisms; (b) Introducing gas from an air inlet pipe, and inputting the gas into a reaction system in the bioreactor; (c) And (c) keeping the vent pipe communicated, and outputting the escaped tail gas to the pneumatic assembly through the vent pipe after the gas input in the step (b) flows through a reaction system consisting of microorganisms and reaction substrates, so that the pneumatic assembly generates kinetic energy by the gas and drives a stirring rod of the stirring device to operate.
When the reaction requiring stirring is carried out, an air inlet valve on the air inlet pipe is in a communicating state; the one-way check valve on the air inlet pipe is in a working state, so that the air is prevented from flowing back; the air inlet valve on the vent pipe is in a communication state, and the exhaust valve on the vent pipe is in a closed state. When stirring is not needed, an air inlet valve on the air inlet pipe is in a communication state; the one-way check valve on the air inlet pipe is in a working state, so that the air is prevented from flowing back; the air inlet valve on the vent pipe is in a closed state, and the exhaust valve on the vent pipe is in a communicated state.
The bioreactor of the invention can adjust the gas inflow of the air inlet pipe according to the gas amount and stirring speed required by biological reaction; the stirring can be changed in different reaction stages according to the reaction requirement. The stirring rate of the stirring device may be a constant value or an indefinite value.
K is used for gas-liquid mass transfer coefficient (or volumetric mass transfer coefficient) L a represents K L The size of a is an important index for evaluating the aeration performance of the fermentation tank and the mixing speed of gas and liquid. Under the same fermentation condition, the gas-liquid mass transfer coefficient K L The larger the value of a, the mass transfer speed and effect of the gas dissolved in the liquid are demonstratedThe higher the rate. Fermentors of different forms, obtaining the same K L a the energy consumed is very different.
The resulting data in the examples of the present invention uses the volumetric gas-liquid mass transfer coefficient (K L a) To highlight the experimental effect of the present invention. K (K) L a is a very important concept in fermentation engineering, and is also an important reference factor for the ability of dissolved gas in the fermentation process, and is generally used for controlling in the actual fermentation process. Generally, K L a is closely related to the equipment parameters, operating conditions and fermentation broth properties.
Wherein K is L a is the total mass transfer coefficient (unit m/h) taking the difference between the gas solubility and the actual gas concentration as the total driving force, and a is the specific surface area (unit m 2 /m 3 ) Since the specific surface area a of the gas-liquid is difficult to measure, K is generally used in the gas-liquid mass transfer process L a is treated together as a factor, and the product of the former and the latter represents the mass transfer rate in the biochemical reaction process.
K L a is measured and calculated in a number of ways, where K is measured by the usual exhaust method L a is illustrated. And obtaining the gas-liquid mass transfer coefficient K by measuring the dissolution rate of oxygen in the fermentation tank L a。
In the fermentation equipment to be measured, nitrogen is firstly used for driving away dissolved oxygen in the liquid, then air is introduced, sampling is carried out at fixed time, the concentration of the dissolved oxygen in the fermentation liquid is measured by using a dissolved oxygen detector, and the change condition of the concentration of the dissolved oxygen in the solution along with time is recorded. The saturated dissolved oxygen concentration C in the solution can be obtained by plotting the obtained curve with the time t as the abscissa and the oxygen concentration of the solution as the ordinate, as shown in fig. 5A.
Under this condition, the mass transfer rate at which oxygen diffuses from the main stream of gas to the main stream of liquid can be expressed by the following formula.
Wherein K is L a-gas-liquid mass transfer coefficient with concentration difference as driving force, h -1 ;
C-concentration of oxygen in equilibrium with partial pressure of oxygen in the gas phase p, kmol/m 3 ;
C L Oxygen concentration in the liquid phase and at the gas phase interface kmol/m 3 。
When t=0, C should be L =0, and the above equation is integrated to obtain equation (2).
To be used forPlotting the time t on the coordinate can obtain a straight line with the slope of-K L a, see fig. 5B.
The bioreactor is characterized in that a gas loop is arranged, a pneumatic device is used for driving the stirring paddle in the bioreactor by utilizing the residual pressure of tail gas, and the bioreactor has a simple structure and is convenient to operate, and the mixing degree of gas and liquid in microbial fermentation liquid can be improved under the condition that the energy consumption of electric stirring is not increased additionally.
In the prior art, the stirring technology in the microbial industry almost adopts an electric stirring mode, so that the problem of overlarge electric energy consumption exists in the production process, the production cost is increased, and the economic benefit is reduced; although the airlift method is used for replacing the mechanical stirring mode, the condition of insufficient dissolved air exists, the yield of fermentation production is affected, and therefore the economic benefit is also affected. The device and the method provided by the invention take the defects of two traditional modes into consideration to the maximum extent, and skillfully utilize the residual pressure of the tail gas in the tank to solve the energy consumption trouble existing in the current two ways of increasing the dissolved gas quantity.
The main advantages of the technical scheme of the invention are as follows:
(1) The structure is simple, the transformation difficulty is low, and the operation mode is simple, convenient and quick;
(2) The electric energy consumption used by a large amount of mechanical stirring is reduced, the whole fermentation production cost is saved, and the profit margin is improved;
(3) By skillfully combining the airlift type and the stirring type, the air dissolving amount of the fermentation liquid is increased on the premise of reducing the energy consumption, the rapid fermentation is promoted, and the fermentation period is shortened;
(4) The exhaust gas to be discharged is perfectly utilized, and the exhaust gas is recycled through simple and ingenious transformation, so that the environment-friendly recycling concept is realized.
The invention will be illustrated by way of specific examples. It is to be understood that these examples are illustrative only and are not limiting of the invention. Unless otherwise indicated, all numbers expressing quantities of liquid loading, aeration flow, dissolved oxygen values, and aeration times used in the specification, claims, and embodiments are not to be understood as being absolute precise values, which are within the limits of the tolerance of known techniques as understood by those skilled in the art.
Example 1, microorganism stirring type fermentation tank example
In this example, a 5L scale microorganism stirring fermenter apparatus was provided.
The device is further described with reference to fig. 1 and 2, said device comprising:
the bioreactor body 1 is a balun 5L microbial stirred tank fermenter.
And a stirring device 2, one part of which is inserted into the middle lower part of the fermentation tank body, and the other part of which extends out of the upper part of the tank body, wherein the part of the stirring device penetrating through the tank body is sealed by a sealing ring.
And a pneumatic assembly 3 which is positioned above the bioreactor body 1 and is connected with a stirring rod of the stirring device 2. The pneumatic assembly 3 comprises: the closed bin 31 is a U-shaped closed bin and comprises an air inlet and an air outlet, and the air inlet and the air outlet control the air to enter and output through valves; an impeller 32; an impeller center 33, which can be driven in rotation by the impeller 32, is connected in the axial direction to the stirring rod of the stirring device 2. The impeller center 33 is connected with the stirring rod of the stirring device 2 through the pneumatic assembly fixing frame 10.
An air inlet pipe 4 inserted into a lower space of the bioreactor; an intake valve 41, a one-way check valve 43, and a gas flow meter 42 are provided thereon. The end of the air inlet pipe 4 is communicated with a gas distributor 8.
A breather pipe 5, one end of which is communicated with the bioreactor body 1, and the other end of which is communicated with the pneumatic assembly 3; an intake valve 51 is provided thereon; an exhaust pipe is also provided, on which an exhaust valve 52 is provided. The gas flow among the bioreactor, the pneumatic component and the exhaust pipe is controlled by a tee joint.
The pneumatic assembly further comprises a discharge pipe 6 for outputting the gas flowing out of the pneumatic assembly 3.
The bottom of the bioreactor body 1 also comprises a biological reaction liquid input and output pipeline and a valve 9.
An OxyFerm FDA VP 225 dissolved oxygen electrode is also arranged in the bioreactor body 1.
EXAMPLE 2 relationship of aeration to stirring shaft Power
1. First hypothesis
Stirring shaft power calculation (5L tank as an example)
1. The fermentation broth is a low concentration fermentation broth and can be considered as a newtonian fluid.
Calculating Rem:
Rem=(D 2 Nρ)/μ
d: paddle diameter, d=0.1m (assumed value)
N: paddle rotation speed, n=240 r/60 s=4r/s (assumed value)
ρ: fermentation broth density, ρ=1000 Kg/m 3 (near water, in terms of water density)
Mu: viscosity of fermentation broth, μ= 0.8004 ×10 -3 (30 ℃ C., look-up table)
Substituting the formula:
Rem=5×10 4 >10 4
from the obtained Rem result, it can be seen that the fermentation broth is in a turbulent state, and the stirring power quasi-number np=4.7. As in fig. 6.
2. Calculating stirring shaft power P in case of no ventilation 0
P 0 =N P N 3 D 5 ρ
N P : its value is 4.7 when in turbulent stirring state
N: stirring speed, 4r/s
D: diameter of stirring paddle, d=0.1 m
ρ: fermentation broth density, ρ=1000 Kg/m 3
Substituting the formula:
P 0 ’=3.008W
stirring at two steps:
P 0 =2P 0 ’=6.016W
when the ventilation volume does work on the pneumatic device and is larger than the power of the stirring shaft, the pneumatic device can be driven to perform stirring operation by a certain ventilation volume.
The existing options for pneumatic motors are as follows in table 1:
TABLE 1
WM0014 type, WM0004 type, etc., are selected, that is, when the intake air amount is 67.9L/min (. Apprxeq.4 m) 3 /h), the maximum power is 35W.
I.e., 35W > 6.016W;
namely P Pneumatic element >P 0 ;
Therefore, the following description is made: when the air inflow is more than or equal to 4m 3 And (3) during the time of/h, the air inflow can drive the pneumatic device to stir.
2. Second hypothesis
Stirring shaft power calculation (5L tank, assume layer flow regime)
As shown in the graph, to make the fermentation liquid in a laminar flow state, the reynolds number Rem needs to satisfy: rem is more than 1 and less than 10; the readable range of the stirring power quasi-number Np at this time is: 5 < Np < 40. Based on this range, the following parameter assumptions are made:
1. the fermentation broth is a low concentration fermentation broth and can be considered as a newtonian fluid.
Calculating Rem:
Rem=(D 2 Nρ)/μ
d: paddle diameter, d=0.03 m (assuming minimum reasonable value)
ρ: fermentation broth density, ρ=1000 Kg/m 3 (in terms of water density)
Mu: viscosity of fermentation broth, μ= 0.8004 ×10 -3 (30 ℃ C., look-up table)
According to the range of 1 < Rem < 10, the range of the reverse calculation stirring paddle rotating speed N is as follows:
0.89×10 -3 r/s<N<0.89×10 -2 r/s
at this time, the stirring paddle rotates very slowly.
Continuing to count down:
according to the condition that the fermentation liquid is regarded as a laminar flow state, the stirring power standard number is 5 < Np < 40.
2. Calculating stirring shaft power P in case of no ventilation 0
P 0 =N P N 3 D 5 ρ
N P : in turbulent stirring state, the value is 5 < Np < 40
N: stirring rotation speed of 0.89×10 -3 r/s<N<0.89×10 -2 r/s
D: diameter of stirring paddle, d=0.03 m
ρ: fermentation broth density, ρ=1000 Kg/m 3
Substituting the formula:
P 0 ’<<<3.008W
stirring at two steps:
P 0 =2P 0 ’<<<6.016W
when the ventilation volume does work on the pneumatic device and is larger than the power of the stirring shaft, the pneumatic device can be driven to perform stirring operation by a certain ventilation volume.
According to the existing option of the air motor (Table 1), WM0014 type, WM0004 type, etc. are selected, that is, when the intake air amount is 67.9L/min (. Apprxeq.4 m) 3 /h), the maximum power is 35W.
I.e., 35W > 6.016W
Namely P Pneumatic element >>>P 0
So it proves that: when the exhaust gas quantity is more than or equal to 4m 3 And at the time of/h, the exhaust gas can drive the pneumatic device to stir.
Therefore, the stirring can still be carried out normally under the laminar flow state.
3. Third hypothesis
The mode of this assumption is similar to the first assumption, the fixed value method.
Stirring shaft power calculation (5L tank as an example)
1. The fermentation broth is a low concentration fermentation broth and can be considered as a newtonian fluid.
Calculating Rem:
Rem=(D 2 Nρ)/μ
d: paddle diameter, d=0.03 m (assuming minimum reasonable value)
ρ: fermentation broth density, ρ=1000 Kg/m 3 (in terms of water density) (constant value)
Mu: viscosity of fermentation broth, μ= 0.8004 ×10 -3 (30 ℃ C., table look-up available) (constant value)
Reynolds number rem=1000
Substituting the above formula and back calculating the stirring rotating speed N=0.89 r/s
From the graph, np.apprxeq.4.7 (Table lookup)
2. Calculating stirring shaft power P in case of no ventilation 0
P 0 =N P N 3 D 5 ρ
N P : its value is 4.7 when in turbulent stirring state
N: stirring rotation speed of 0.89r/s
D: diameter of stirring paddle, d=0.03 m
ρ: fermentation broth density, ρ=1000 Kg/m 3
Substituting the formula:
P 0 ’=8×10 -5 W
stirring at two steps:
P 0 =2P 0 ’=16×10 -5 W
WM0014 type, WM0004 type, etc., are selected, that is, when the intake air amount is 67.9L/min (. Apprxeq.4 m) 3 /h), maximum power35W.
I.e., 35W > 16X 10 -5 W
Namely P Pneumatic element >>>P 0
So it proves that: when the exhaust gas quantity is more than or equal to 4m 3 And at the time of/h, the exhaust gas can drive the pneumatic device to stir.
Taken together, according to the above results of the present example, at a ventilation of 4m or more at three representative Reynolds numbers 3 And at the time of/h, the pneumatic component can normally operate.
Example 3 fermentation Using the microorganism-stirred tank fermentation tank of example 1
1. Experimental reagent and raw materials
Distilled water is used as fermentation liquor.
For providing a gas: nitrogen bottle 1, oxygen bottle 1.
2. Experimental procedure
(1) The 5L stirring type fermentation tank and the components thereof are installed;
(2) Installing an oxygen dissolving electrode in a 5L stirring type fermentation tank and calibrating the oxygen dissolving electrode;
(3) Adding 2L of distilled water into a 5L stirring type fermentation tank, opening an air inlet valve 1 and an air exhaust valve 12, closing an air inlet valve 13 of a pneumatic assembly, and starting to continuously introduce a large amount of nitrogen for deoxidization operation; closing the air inlet valve 1 and the air exhaust valve 12 and closing the air inlet valve 13 of the pneumatic assembly until the oxygen dissolving electrode indication number is 0;
(4) Opening the intake valve 1 starts to continuously feed 4m 3 Oxygen per h and opening the purge valve 12, keeping the pneumatic assembly intake valve 13 closed;
(5) Recording the number of dissolved oxygen electrodes per minute, stopping counting when the number of dissolved oxygen electrodes approaches to be stable, and calculating Kla (2L);
(6) Completely discharging the liquid in the 5L stirring type fermentation tank, adding 2L distilled water into the stirring type fermentation tank, opening the air inlet valve 1 and the air exhaust valve 12, closing the air inlet valve 13 of the pneumatic assembly, and starting to continuously introduce a large amount of nitrogen to perform deoxidization operation; closing the air inlet valve 1 and the air exhaust valve 12 and closing the air inlet valve 13 of the pneumatic assembly until the oxygen dissolving electrode indication number is 0;
(7) Opening the intake valve 1 starts to continuously feed 4m 3 Oxygen per h and opening the pneumatic assembly inlet valve 13, keeping the evacuation valve 12 closed;
(8) Recording the number of dissolved oxygen electrodes per minute, stopping counting when the number of dissolved oxygen electrodes approaches to be stable, and calculating Kla (2L pneumatic);
taking distilled water with a liquid loading of 2L as an example, the aeration rate is 4m 3 In the case of/h, the gas was directly evacuated without treatment (2L) and after treatment with a pneumatic stirring assembly (2L pneumatic), the change curve of dissolved oxygen per unit time was obtained as shown in FIG. 3.
According to the calculation formula of gas-liquid mass transfer coefficient KLa
To be used forPlotting the time t on a coordinate gives a straight line with a slope of-KLa. Wherein c—oxygen saturation value; c (C) L Oxygen concentration per unit time t. As shown in fig. 4.
According to DO data and K L a data shows that the experiment through the pneumatic stirring assembly is shown as K in FIG. 4 L a has a value of 0.31h at a 2L loading -1 The method comprises the steps of carrying out a first treatment on the surface of the K not passing through pneumatic stirring assembly under the condition of 2L of liquid loading L a=0.17h -1 The improvement is 82% under the same other conditions. The result shows that the dissolved oxygen speed of the fermentation broth is faster after the fermentation broth is pneumatically stirred by the residual pressure of the tail gas.
This example shows that, after using pneumatic means, this system has recycled the energy of tail gas residual pressure, has increased mass transfer rate, has saved the energy consumption that fermentation production required, has greatly reduced the inherent cost of fermentation trade.
All documents mentioned in this application are incorporated by reference as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (2)
1. A method of performing a biological reaction using a bioreactor, the method comprising:
(a) Adding a biological reaction substrate (or reaction liquid) into the bioreactor body (1) and inoculating microorganisms;
(b) Introducing gas from an air inlet pipe (4) and inputting the gas into a reaction system in the bioreactor;
(c) Maintaining the communication of the vent pipe (5), and outputting the escaped tail gas to the pneumatic assembly (3) through the vent pipe (5) after the gas input in the step (b) flows through a reaction system consisting of microorganisms and reaction substrates, so that the pneumatic assembly (3) generates kinetic energy by the gas and drives a stirring rod of the stirring device (2) to operate; adjusting the inflow amount of the gas in the gas inlet pipe (4) according to the amount of the gas required by the biological reaction and the stirring speed; the biological reaction is a biological reaction requiring gas participation; the gas is used for providing carbon, hydrogen or oxygen for a biological reaction system; the biological reaction is that the aeration rate is more than or equal to 4Nm 3 Biological reaction of/h;
wherein the bioreactor comprises:
a bioreactor body (1);
a stirring device (2); the stirring device comprises a part positioned inside the bioreactor and a part positioned outside the bioreactor, and is connected through a stirring rod penetrating through the inside and the outside; the external part of the stirring device is connected with the pneumatic device, and one end of the internal part of the stirring device is inserted into the reaction system of the biological reaction;
the pneumatic assembly (3) is positioned above the bioreactor and connected with the stirring rod of the stirring device (2), and generates kinetic energy by gas and drives the stirring rod to operate; the pneumatic assembly (3) comprises: the stirring device comprises a closed bin (31), an impeller (32) and an impeller center (33), wherein the impeller center (33) is driven to rotate by the impeller (32), and the impeller center (33) is connected with a stirring rod of the stirring device (2) so as to drive the stirring device (2) to rotate, and the closed bin is a U-shaped closed bin; the pneumatic assembly (3) comprises an air inlet (34) and an air outlet (35), the pneumatic assembly (3) is provided with the air inlet (34) and the air outlet (35) which are both connected with the closed bin (31), and the air inlet (34) and the air outlet (35) of the pneumatic assembly (3) are both upward so that the closed bin is a U-shaped closed bin; wherein a sealing ring is arranged at the connection position of the center of the impeller and the stirring rod; a sealing ring is also arranged at the intersection of the bioreactor body and the stirring rod;
an intake pipe (4) for inputting a gas into a reaction system in the bioreactor; the air inlet pipe comprises an air inlet valve; the air inlet pipe is also provided with a one-way check valve; the air inlet pipe is also provided with an air flowmeter; the gas conveyed by the gas inlet pipe is communicated with a gas distributor, and the gas is distributed into the reaction system through the gas distributor;
one end of the ventilation pipe (5) is communicated with the bioreactor body (1), the other end of the ventilation pipe is communicated with the pneumatic assembly (3) and is used for outputting tail gas of the bioreactor to an air inlet (34) of the pneumatic assembly (3) to supply air for the pneumatic assembly (3); an air inlet valve is arranged on the vent pipe; the vent pipe is also provided with an exhaust pipe, and an exhaust valve is arranged on the exhaust pipe; the gas flow among the bioreactor, the pneumatic assembly and the exhaust pipe is controlled through a tee joint;
a discharge pipe (6) for outputting the gas flowing out of the pneumatic assembly (3);
the gas is continuously input into the reaction system at the gas inlet pipe, and tail gas is continuously generated after the reaction system is uniformly mixed with the gas and reacts, so that the gas above the liquid level of the reactor enters the vent pipe and is conveyed into the pneumatic device; the tail gas flowing out through the pneumatic device is returned to the reactor through a pipeline and recycled in a circulating mode; wherein the air inflow of the air inlet pipe is more than or equal to 4m 3 And/h, the exhaust volume of the exhaust pipe is more than or equal to 4m 3 /h。
2. The method of performing a biological reaction according to claim 1, wherein the biological reaction is a biological reaction requiring participation of a gas; when the reaction requiring stirring is carried out:
an air inlet valve (41) on the air inlet pipe (4) is in a communicating state;
the one-way check valve (43) on the air inlet pipe (4) is in a working state to prevent the air from flowing back;
an air inlet valve (51) on the air pipe (5) is in a communication state, and an exhaust valve (52) on the air pipe (5) is in a closed state;
when stirring is not needed:
an air inlet valve (41) on the air inlet pipe (4) is in a communicating state;
the one-way check valve (43) on the air inlet pipe (4) is in a working state to prevent the air from flowing back;
the air inlet valve (51) on the air pipe (5) is in a closed state, and the exhaust valve (52) on the air pipe (5) is in a communicated state.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101210222A (en) * | 2007-12-21 | 2008-07-02 | 王曼丹 | Ventilation fermentation tank tail gas energy turbine reclaiming method |
CN201276562Y (en) * | 2008-10-22 | 2009-07-22 | 方民 | Aerobic biofermentation tank for recycling tail gas |
JP2009289465A (en) * | 2008-05-27 | 2009-12-10 | Toshiba Fuel Cell Power Systems Corp | Liquid fuel desulfurizer and liquid fuel desulfurizing method, and fuel cell power generation system |
CN103045472A (en) * | 2013-01-25 | 2013-04-17 | 李明忠 | Pneumatic stirring machine for biological fermentation |
CN103184145A (en) * | 2013-04-15 | 2013-07-03 | 清华大学 | Photosynthesis-fermentation mixed culture device and application thereof in culturing of oil-containing microalgae |
CN203594474U (en) * | 2013-12-03 | 2014-05-14 | 湖北傲林液压有限公司 | Pneumatic motor with rotation impeller |
CN203648421U (en) * | 2013-11-13 | 2014-06-18 | 刘现梅 | Pneumatic agitator for bucket |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180010082A1 (en) * | 2016-06-03 | 2018-01-11 | Lonza Ltd | Bioreactor With Higher Agitation Rates |
-
2018
- 2018-02-24 CN CN201810157288.1A patent/CN110195008B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101210222A (en) * | 2007-12-21 | 2008-07-02 | 王曼丹 | Ventilation fermentation tank tail gas energy turbine reclaiming method |
JP2009289465A (en) * | 2008-05-27 | 2009-12-10 | Toshiba Fuel Cell Power Systems Corp | Liquid fuel desulfurizer and liquid fuel desulfurizing method, and fuel cell power generation system |
CN201276562Y (en) * | 2008-10-22 | 2009-07-22 | 方民 | Aerobic biofermentation tank for recycling tail gas |
CN103045472A (en) * | 2013-01-25 | 2013-04-17 | 李明忠 | Pneumatic stirring machine for biological fermentation |
CN103184145A (en) * | 2013-04-15 | 2013-07-03 | 清华大学 | Photosynthesis-fermentation mixed culture device and application thereof in culturing of oil-containing microalgae |
CN203648421U (en) * | 2013-11-13 | 2014-06-18 | 刘现梅 | Pneumatic agitator for bucket |
CN203594474U (en) * | 2013-12-03 | 2014-05-14 | 湖北傲林液压有限公司 | Pneumatic motor with rotation impeller |
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