CN113293089A - Prevent pasting wall fermenting installation based on combination stirring - Google Patents
Prevent pasting wall fermenting installation based on combination stirring Download PDFInfo
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- CN113293089A CN113293089A CN202110574824.XA CN202110574824A CN113293089A CN 113293089 A CN113293089 A CN 113293089A CN 202110574824 A CN202110574824 A CN 202110574824A CN 113293089 A CN113293089 A CN 113293089A
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- C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
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- 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
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Abstract
Aiming at the problems of a fermentation device for high-viscosity materials in the prior art, the invention provides an anti-sticking stirring system based on combined stirring. The wall sticking prevention fermentation device comprises a tank body, and a stirring device and a wall sticking prevention system which are arranged in the tank body. The stirring device comprises a stirring shaft and a stirring paddle; the stirring rake is the helical ribbon stirring rake, the helical ribbon stirring rake passes through the connecting rod and is connected with the agitator shaft. And the transmission rod and the guide rail of the adherence preventing system are both fixedly arranged at the top of the tank body. The upper end of the transmission rod is fixedly connected with the transmission gear, and the lower end of the transmission rod is provided with a bidirectional thread and is connected with the sliding block through the bidirectional thread. The slider is connected with the guide rail in a sliding mode, and the annular scraper is fixedly connected with the slider through a fixed support. The wall sticking prevention stirring system reduces the influence of shearing force and wall sticking in the fermentation process while improving the stirring efficiency of the fermentation tank, and solves the problem of low mass transfer efficiency in the fermentation of high-viscosity materials represented by filamentous fungi.
Description
Technical Field
The invention belongs to the technical field of fermentation engineering and equipment, relates to a fermentation device, and particularly relates to an anti-wall-sticking fermentation device based on combined stirring.
Background
Stirring is an important step of biological fermentation, and in a common stirring bioreactor, when the solid content is higher than 10%, problems in aspects of mixing, mass transfer, heat transfer, high energy consumption and the like occur, so that the defects of low conversion rate of final raw materials, low concentration of fermentation products and the like are caused. The fermentation liquor of high-viscosity materials is generally pasty and high in viscosity, so that a plurality of stirring blind areas exist, the difference of oxygen exchange effects of gas-liquid interfaces in different areas is large, and the axial movement and the radial movement of the fermentation liquor are greatly different in the stirring areas. Based on this, adopt current fermenting installation to stir high viscosity material zymotic fluid, often have because its ability to air break up, disperse is showing to reduce, leads to the problem that the area of contact of air and zymotic fluid reduces, dissolved oxygen in the zymotic fluid.
Among them, filamentous fungi are important microorganisms that produce various metabolites such as antibiotics, organic acids, enzymes, pigments, hormones, etc., and are one of the major contributors to industrial fermentation products; the fermentation product is widely applied to many fields of food, medicine, agriculture, environmental protection and the like. In the prior art, fermentation tank liquid fermentation is adopted. On one hand, in the process of hypha germination of filamentous fungi spores and hypha extension, the hyphae are mutually wound under the stirring action of spore aggregation and stirring blades to form flocculent hypha clusters; the mycelium pellet can increase the viscosity of fermentation liquor, reduce the transfer efficiency of substances and oxygen in the fermentation liquor and even in the mycelium pellet, and influence the yield of fermentation products. On the other hand, filamentous fungi thalli are easy to adhere to the inner wall of the fermentation tank and in the tube nest in the tank, and along with the increase of the fermentation time, the thalli gradually spread upwards along the inner wall of the fermentation tank, the more adherent thalli are accumulated, and because the adherent thalli can not draw the nutrition in the liquid culture medium, the mass transfer and the oxygen supply are greatly influenced, and the production efficiency of the product is reduced.
In order to solve the above problems, methods of increasing the power conditions, including increasing the stirring intensity and increasing the air flow rate, are generally used. Although the method can increase the mass transfer efficiency to a certain extent, the problem of adherent accumulation of thalli is relieved. But often leads to increased energy consumption, improves the production cost of the product, and is not suitable for large-scale popularization; and the enhancement of the stirring strength greatly improves the shearing force in the fermentation liquor, which is easy to cause hypha fracture and then form callus, thus causing the product accumulation to be influenced.
Disclosure of Invention
Aiming at the problems of a fermentation device for high-viscosity materials in the prior art, the invention provides an anti-sticking stirring system based on combined stirring. The wall sticking prevention stirring system reduces the influence of shearing force and wall sticking in the fermentation process while improving the stirring efficiency of the fermentation tank, and solves the problem of low mass transfer efficiency in the fermentation of high-viscosity materials represented by filamentous fungi.
The technical scheme of the invention is as follows:
prevent pasting wall fermenting installation based on combination stirring, including jar body and setting up agitating unit and prevent pasting wall system at jar internal portion. The stirring device comprises a stirring shaft and a stirring paddle; the stirring shaft is fixedly connected with a driving gear, and the driving gear is meshed with the transmission gear to obtain power. The stirring rake is the helical ribbon stirring rake, the helical ribbon stirring rake passes through the connecting rod and is connected with the agitator shaft. The length d of the connecting rod1Is 0.5-0.8 times of the radius R of the tank body. The width of the ribbon stirring paddle is 5-8 cm. The pitch d of the helical ribbon stirring paddle2Is 0.5-2 times of the diameter D of the ribbon; the rotating speed of the helical ribbon stirring paddle is 20-100 rpm. On one hand, the slowly rotating helical ribbon stirring paddle is turned over up and down in the fermentation liquor to form circulation flow, so that the materials or the fermentation liquor are fully mixed; on the other hand, the large bubbles escaping from the gas distributor are broken into small bubbles to be fully contacted with the surrounding fermentation liquor, thereby improving the dissolved oxygen in the fermentation liquor and greatly increasing the biomass and the yield of the product. In addition, the helical ribbon type stirring paddle greatly reduces the shearing force, reduces the breakage of mycelium and the formation of callus, and is beneficial to the accumulation of products.
The adherence preventing system consists of a transmission rod, a sliding block, a guide rail and an annular scraper. The transmission rod and the guide rail are both fixedly arranged at the top of the tank body. The upper end of the transmission rod is fixedly connected with the transmission gear, and the lower end of the transmission rod is provided with a bidirectional thread and is connected with the sliding block through the bidirectional thread. The slider is connected with the guide rail in a sliding mode, and the annular scraper is fixedly connected with the slider through a fixed support. One end of the sliding block, which is connected with the bidirectional thread, is provided with a threaded hole, and the other end of the sliding block, which is connected with the guide rail, is provided with a round hole. The radius R of the annular scraper is slightly smaller than the radius R of the tank body; the inclined direction of the annular scraper comprises an upward incline and a downward incline, and the angle between the cutting edge of the annular scraper and the side wall of the tank body is 30-45 degrees. The fixed support is in a hard columnar shape and is fixedly connected with the sliding block and the annular scraper. The annular scraper is driven by the sliding block to reciprocate up and down along the guide rail, so that mycelia or solid accumulated near the wall of the fermentation tank are knocked back into the fermentation liquid, and adherent adhesion of the mycelia or the solid on the wall of the fermentation tank is effectively reduced.
Wherein the radius ratio of the transmission gear to the driving gear is 0.5-20. The spiral belt type stirring paddle is provided with a plurality of circular holes with the diameter of 1-2cm, and the distance between every two adjacent circular holes is 30-40 cm. The ratio of the length of the bidirectional thread to the thread pitch is (200-10): 1; the distance between the cutting edge tip of the annular scraper and the side wall of the tank body is 1-2 cm.
The invention has the beneficial effects that:
(1) the wall sticking prevention fermentation device based on combined stirring not only has large dissolved oxygen amount and good mixing effect, but also has small shearing force, and also solves the problem of wall sticking of thalli.
(2) According to the wall sticking prevention fermentation device, the helical ribbon type stirring paddle with the round hole is adopted, so that the stirring efficiency of the fermentation tank is improved, the shearing force in the fermentation process is reduced, and the phenomenon that the accumulation of products is influenced due to the breakage of hyphae is avoided.
(3) The anti-sticking fermentation device adopts the annular scraper, has simple structure and low energy consumption, is particularly suitable for fermentation with high solid content, high viscosity or mycelium, and has important practical application value.
Drawings
FIG. 1 is a schematic structural diagram of a combined stirring-based anti-sticking fermentation device.
Wherein: 1. the spiral ribbon type stirring paddle comprises a spiral ribbon type stirring paddle, 2 parts of a connecting rod, 3 parts of a stirring shaft, 4 parts of a driving gear, 5 parts of a transmission gear, 6 parts of a transmission rod, 7 parts of a bidirectional thread, 8 parts of a sliding block, 9 parts of a guide rail, 10 parts of a fixed support and 11 parts of an annular scraper.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
prevent pasting wall fermenting installation based on combination stirring, including jar body and setting up agitating unit and prevent pasting wall system at jar internal portion. The radius R of the tank body is 1 m. The stirring device comprises a stirring shaft 3 and a stirring paddle; the stirring shaft 3 is fixedly connected with a driving gear 4, and the driving gear 4 is meshed with the transmission gear 5 to obtain power. The stirring rake is helical ribbon stirring rake 1, helical ribbon stirring rake 1 is connected with (mixing) shaft 3 through connecting rod 2. Length d of the connecting rod 21Is 0.8m (0.5-0.8 times of the radius R of the tank body). The width of the ribbon stirring paddle 1 is 8 cm. The pitch d of the helical ribbon stirring paddle 120.8m (0.5-2 times of D), and the diameter D of the stirring paddle is 1.6 m; the rotating speed of the ribbon agitating paddle 1 is 20-100 rpm.
The adherence preventing system consists of a transmission rod 6, a sliding block 8, a guide rail 9 and an annular scraper 11. The transmission rod 6 and the guide rail 9 are both fixedly arranged at the top of the tank body. The upper end of the transmission rod 6 is fixedly connected with the transmission gear 5, and the lower end of the transmission rod 6 is provided with a bidirectional thread 7 and is connected with the sliding block 8 through the bidirectional thread 7. The sliding block 8 is connected with the guide rail 9 in a sliding mode, and the annular scraper 11 is fixedly connected with the sliding block 8 through a fixing support 10. One end of the sliding block 8 connected with the bidirectional thread 7 is provided with a threaded hole, and the other end connected with the guide rail 9 is provided with a round hole. The radius R of the annular scraper 11 is slightly smaller than the radius R of the tank body; the annular scraper is inclined downwards in the vertical direction, and the angle between the cutting edge of the annular scraper 11 and the side wall of the tank body is 45 degrees. The fixed support 10 is in a hard columnar shape, and the fixed support 10 is fixedly connected with the sliding block 8 and the annular scraper 11. Wherein, the radius ratio of the transmission gear 5 and the driving gear 4 is 0.5. The spiral ribbon stirring paddle 1 is provided with a plurality of round holes with the diameter of 1.8cm, and the distance between every two adjacent round holes is 34 cm. The ratio of the length of the bidirectional thread 7 to the thread pitch is 200: 1; the distance between the cutting edge tip of the annular scraper 11 and the side wall of the tank body is 1 cm.
Example 2: in contrast to the embodiment 1, the process of the invention,
the radius R of the tank body of the wall-sticking prevention fermentation device based on combined stirring is 0.6 m. Length d of the connecting rod 21Is 0.48m (0.5-0.8 times of the radius R of the can body). The width of the ribbon stirring paddle 1 is 5 cm. The pitch d of the helical ribbon stirring paddle 121.92m (0.5-2 times the diameter D) and a diameter D of 0.96 m; the rotating speed of the ribbon agitating paddle 1 is 20-100 rpm.
The annular scraper blade is inclined upwards in the vertical direction, and the angle between the cutting edge of the annular scraper blade 11 and the side wall of the tank body is 30 degrees. The radius ratio of the transmission gear 5 to the driving gear 4 is 20. The spiral ribbon type stirring paddle 1 is provided with a plurality of round holes with the diameter of 2cm, and the distance between every two adjacent round holes is 30 cm. The ratio of the length of the bidirectional thread 7 to the thread pitch is 10: 1; the distance between the cutting edge tip of the annular scraper 11 and the side wall of the tank body is 2 cm.
Example 3: in contrast to the embodiment 1, the process of the invention,
the radius R of the tank body of the wall-sticking prevention fermentation device based on combined stirring is 1.5 m. Length d of the connecting rod 21Is 1 m. The width of the ribbon stirring paddle 1 is 7 cm. The pitch d of the helical ribbon stirring paddle 121.2m (0.5-2 times of D), diameter D2 m; the rotating speed of the ribbon agitating paddle 1 is 20-100 rpm.
The annular scraper is inclined upwards in the vertical direction, and the angle between the cutting edge of the annular scraper 11 and the side wall of the tank body is 35 degrees. The radius ratio of the transmission gear 5 to the driving gear 4 is 2. The spiral ribbon type stirring paddle 1 is provided with a plurality of round holes with the diameter of 1cm, and the distance between every two adjacent round holes is 38 cm. The ratio of the length of the bidirectional thread 7 to the thread pitch is 50: 1; the distance between the cutting edge tip of the annular scraper 11 and the side wall of the tank body is 1.8 cm.
Example 4: in contrast to the embodiment 1, the process of the invention,
prevent pasting wall fermenting installation's jar based on combination stirringThe bulk radius R is 0.2 m. Length d of the connecting rod 21Is 0.12 m. The width of the ribbon stirring paddle 1 is 6 cm. The pitch d of the helical ribbon stirring paddle 120.2m (0.5-2 times of D), diameter D0.24 m; the rotating speed of the ribbon agitating paddle 1 is 20-100 rpm.
The annular scraper is inclined upwards in the vertical direction, and the angle between the cutting edge of the annular scraper 11 and the side wall of the tank body is 30-45 degrees. The radius ratio of the transmission gear 5 to the driving gear 4 is 10. The spiral ribbon stirring paddle 1 is provided with a plurality of round holes with the diameter of 1.4cm, and the distance between every two adjacent round holes is 40 cm. The ratio of the length of the bidirectional thread 7 to the thread pitch is 100: 1; the distance between the blade tip of the annular scraper 11 and the side wall of the tank body is 1.5 cm.
Example 5: the liquid state fermentation of Mortierella alpina for ARA production was performed by using the anti-adherence fermentation apparatuses described in examples 1 and 3
Mortierella alpina SD003 was inoculated into PDA slant culture medium and cultured at 25 ℃ for one week. The slant mycelia and spores were washed with sterile water and inoculated into a shake flask. The culture medium comprises the following components in percentage by mass: 2% of glucose, 1% of yeast extract and the balance of water, wherein the pH is natural, and the liquid filling amount is as follows: a250 ml shake flask was filled with 50ml of medium, and the medium was incubated at 25 ℃ for 3 days with the rotation speed of the shaker at 100rpm to form a seed culture. Inoculating the seed culture solution into a fermentation culture medium according to the proportion of 10%. The fermentation medium comprises the following components in percentage by mass: 8% of glucose, 0.3% of yeast powder, 0.6% of corn steep liquor, 0.3% of monopotassium phosphate, 0.03% of magnesium sulfate heptahydrate, 0.3% of sodium nitrate and the balance of water. Fermenting at 25 deg.C and pH6.0 for 7 days. After the fermentation was completed, the results are shown in Table 1.
TABLE 1 comparison of Mortierella biomass and ARA yields in different devices
As can be seen from Table 1, the biomass of the liquid fermentation of Mortierella alpina for ARA production by the conventional apparatus was 38.02g/L, and the ARA production was 9.9 g/L. The biomass of the Mortierella alpina liquid-state fermentation device adopting the wall-sticking prevention fermentation device in embodiment 1 of the application for producing ARA is 50.87g/L, which is improved by 33.8% compared with the traditional device; the yield of ARA is 11.4g/L, which is improved by 27.7 percent compared with the traditional device. When the wall sticking prevention fermentation device in the embodiment 3 is adopted for liquid fermentation of Mortierella alpina for ARA production, the biomass is 48.55g/L, which is improved by 15.2% compared with the traditional device; the yield of ARA is 12.5g/L, which is improved by 26.3 percent compared with the traditional device.
Example 6: liquid fermentation for producing ethanol by fermenting lignocellulose raw material by adopting the anti-sticking fermentation device in the embodiment 2 and the embodiment 4
The proportion of the pretreated lignocellulose raw material in the fermentation system is 12 percent, 5 percent of cellulose degrading bacteria are inoculated under the anaerobic condition for anaerobic fermentation, and the mixture is cultured for three days at 55 ℃. The ethanol yield results after fermentation are shown in table 2.
TABLE 2 comparison of ethanol yields in different plants
As can be seen from Table 2, the ethanol yield was 28.9g/L when the conventional apparatus was used to ferment lignocellulosic feedstocks to produce ethanol. And adopt the prevent pasting wall fermenting installation of this application embodiment 2 to carry out lignocellulose raw materials fermentation production ethanol, ethanol output is 36.5g/L, compares with traditional device, promotes 26.3%. Adopt the prevent pasting wall fermenting installation carry out lignocellulose raw materials fermentation production ethanol, ethanol output is 38.5g/L, compares with traditional device, promotes 33.2%.
In summary, the anti-sticking fermentation device based on combined stirring is compared with the existing fermentation device, and the fermentation yield is remarkably improved under the same condition. Fully prove, through the combination of the spiral shell belt stirring paddle and the annular scraper that set up the round hole, not only effectual adherence adhesion of reduction thalli at the fermentation cylinder wall improves the stirring efficiency of fermentation cylinder moreover, has reduced the shearing force in the fermentation process, has avoided the hypha fracture to influence the result accumulation, has important industry application prospect.
Claims (10)
1. The wall sticking prevention fermentation device based on combined stirring comprises a tank body, a stirring device and a wall sticking prevention system, wherein the stirring device and the wall sticking prevention system are arranged in the tank body, the stirring device comprises a stirring shaft (3) and a stirring paddle, and the stirring shaft (3) obtains power through a transmission gear (5); the method is characterized in that: the adherence preventing system consists of a transmission rod (6), a sliding block (8), a guide rail (9) and an annular scraper (11), wherein the transmission rod (6) and the guide rail (9) are fixedly arranged at the top of the tank body; the upper end of the transmission rod (6) is fixedly connected with the transmission gear (5), and the lower end of the transmission rod (6) is provided with a bidirectional thread (7) and is connected with the sliding block (8) through the bidirectional thread (7); the sliding block (8) is in sliding connection with the guide rail (9), and the annular scraper (11) is fixedly connected with the sliding block (8) through a fixed support (10).
2. The wall-sticking prevention fermentation device based on the combined stirring of claim 1, wherein: radius of the annular scraperrSlightly smaller than the radius of the tank bodyR(ii) a The angle between the cutting edge of the annular scraper (11) and the side wall of the tank body is 30-45 degrees, and the distance between the tip of the cutting edge of the annular scraper (11) and the side wall of the tank body is 1-2 cm.
3. The wall-sticking prevention fermentation device based on the combined stirring of claim 2, wherein: the stirring paddle is a helical ribbon stirring paddle (1), and the helical ribbon stirring paddle (1) is connected with the stirring shaft (3) through a connecting rod (2); the width of the ribbon stirring paddle (1) is 5-8 cm.
4. The wall-sticking prevention fermentation device based on the combined stirring of claim 3, wherein: length of the connecting rod (2)d 1Is the radius of the tank bodyR0.5-0.8 times of; the spiral ribbon type stirring paddle (1) is provided with a plurality of round holes with the diameter of 1-2cm, and the distance between every two adjacent round holes is 30-40 cm.
5. The wall-sticking prevention fermentation device based on the combined stirring of claim 3, wherein: the screw pitch of the helical ribbon stirring paddle (1)d 2Is 0.5-2 times of the diameter D of the ribbon; the rotating speed of the ribbon stirring paddle (1) is 20-100 rpm.
6. The wall-sticking prevention fermentation device based on the combined stirring of claim 2, wherein: one end of the sliding block (8) connected with the bidirectional thread (7) is provided with a threaded hole, and one end connected with the guide rail (9) is provided with a round hole.
7. The wall-sticking prevention fermentation device based on the combined stirring of claim 2, wherein: the ratio of the length to the thread pitch of the bidirectional thread (7) is (200-10): 1.
8. the wall-sticking prevention fermentation device based on the combined stirring of claim 2, wherein: the fixed support (10) is in a hard columnar shape, and the fixed support (10) is fixedly connected with the sliding block (8) and the annular scraper (11).
9. The wall-sticking prevention fermentation device based on the combined stirring of any one of claims 1 to 8, wherein: the stirring shaft (3) is fixedly connected with a driving gear (4), and the driving gear (4) is meshed with the transmission gear (5).
10. The wall-sticking prevention fermentation device based on the combined stirring of claim 9, wherein: the radius ratio of the transmission gear (5) to the driving gear (4) is 0.5-20.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110574824.XA CN113293089A (en) | 2021-05-26 | 2021-05-26 | Prevent pasting wall fermenting installation based on combination stirring |
| CN202221278196.7U CN218404137U (en) | 2021-05-26 | 2022-05-25 | Prevent pasting wall fermenting installation based on combination stirring |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110574824.XA CN113293089A (en) | 2021-05-26 | 2021-05-26 | Prevent pasting wall fermenting installation based on combination stirring |
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| CN202221278196.7U Active CN218404137U (en) | 2021-05-26 | 2022-05-25 | Prevent pasting wall fermenting installation based on combination stirring |
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| CN108793669A (en) * | 2016-11-21 | 2018-11-13 | 黄种继 | A kind of sludge quick drying apparatus |
| CN208287891U (en) * | 2018-05-02 | 2018-12-28 | 福州合农农业科技有限公司 | Agitating device is used in a kind of production and processing of mushroom |
| CN209810133U (en) * | 2019-03-29 | 2019-12-20 | 海南希睿达生物技术有限公司 | Novel silica gel production device |
| CN209865875U (en) * | 2019-02-19 | 2019-12-31 | 江苏美天奶业有限公司 | High-speed mixing tank for yoghourt processing |
| CN211518042U (en) * | 2019-12-30 | 2020-09-18 | 永铭集团有限公司 | Mortar mixer |
| CN211620481U (en) * | 2019-12-25 | 2020-10-02 | 北京科尔沁乳业有限公司 | Fermentation cylinder that production cereal milk used |
| CN212732156U (en) * | 2020-07-29 | 2021-03-19 | 定远县尚时新材料有限公司 | Reation kettle belt cleaning device is used in p-phenylenediamine production |
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2021
- 2021-05-26 CN CN202110574824.XA patent/CN113293089A/en not_active Withdrawn
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2022
- 2022-05-25 CN CN202221278196.7U patent/CN218404137U/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101408302B1 (en) * | 2014-01-29 | 2014-06-17 | 엔텍스 주식회사 | Hydraulic screw stirrer type anaerobic digestion unit for organic waste |
| CN108793669A (en) * | 2016-11-21 | 2018-11-13 | 黄种继 | A kind of sludge quick drying apparatus |
| CN206576188U (en) * | 2016-12-06 | 2017-10-24 | 徐亮 | A kind of efficient Yoghourt processing agitating device |
| CN107446798A (en) * | 2017-08-08 | 2017-12-08 | 上海本优机械有限公司 | A kind of pulvis solid-state biological fermentation equipment |
| CN208287891U (en) * | 2018-05-02 | 2018-12-28 | 福州合农农业科技有限公司 | Agitating device is used in a kind of production and processing of mushroom |
| CN209865875U (en) * | 2019-02-19 | 2019-12-31 | 江苏美天奶业有限公司 | High-speed mixing tank for yoghourt processing |
| CN209810133U (en) * | 2019-03-29 | 2019-12-20 | 海南希睿达生物技术有限公司 | Novel silica gel production device |
| CN211620481U (en) * | 2019-12-25 | 2020-10-02 | 北京科尔沁乳业有限公司 | Fermentation cylinder that production cereal milk used |
| CN211518042U (en) * | 2019-12-30 | 2020-09-18 | 永铭集团有限公司 | Mortar mixer |
| CN212732156U (en) * | 2020-07-29 | 2021-03-19 | 定远县尚时新材料有限公司 | Reation kettle belt cleaning device is used in p-phenylenediamine production |
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| CN218404137U (en) | 2023-01-31 |
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Application publication date: 20210824 |