CN112808168A - Composite heating hydrothermal reaction device and composite heating method thereof - Google Patents
Composite heating hydrothermal reaction device and composite heating method thereof Download PDFInfo
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- CN112808168A CN112808168A CN202110273150.XA CN202110273150A CN112808168A CN 112808168 A CN112808168 A CN 112808168A CN 202110273150 A CN202110273150 A CN 202110273150A CN 112808168 A CN112808168 A CN 112808168A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/002—Component parts of these vessels not mentioned in B01J3/004, B01J3/006, B01J3/02 - B01J3/08; Measures taken in conjunction with the process to be carried out, e.g. safety measures
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F3/00—Fertilisers from human or animal excrements, e.g. manure
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a composite heating hydrothermal reaction device and a composite heating method thereof. The hydrothermal reaction tank comprises a tank body straight section, a tank body bottom and a tank body top, wherein a plurality of vertically arranged heat conduction oil heating pipes are arranged in the tank body straight section, and a heat conduction oil lower header is arranged at the bottom of the tank body and is connected with the high-temperature oil groove. Jar body bottom is provided with heat conduction oil coil pipe, presses close to around jar body bottom inner wall sets up, and its entry links to each other through low temperature oil pipe and high temperature oil pipe with low temperature oil groove and high temperature oil groove respectively, and is provided with low temperature oil valve and high temperature oil valve respectively and can switch. The hydrothermal reaction tank is also internally provided with steam heating pipes which are arranged from bottom to top in a surrounding way, and the inlets are connected with the steam distributing cylinder. According to the invention, through the compound heat exchange of the steam and the heat conducting oil, the material and the heat exchange tube can ensure enough heat exchange temperature difference to effectively heat the material, and simultaneously, the temperature difference between the material and the heat exchange tube can be effectively reduced, and the scabbing of the material on the outer wall surface of the heat exchange tube is avoided.
Description
Technical Field
The invention relates to a composite heating hydrothermal reaction device and a composite heating method thereof, in particular to a hydrothermal cracking reaction device for conditioning organic wastes such as livestock and poultry manure, straws, agricultural product processing residues, forestry wastes and the like, belonging to the field of environmental protection technology and pressure containers.
Background
On one hand, with the development of rural breeding industry, rural water, gas and soil pollution caused by breeding excrement is also concerned, and harmful substances such as germs, hormones, antibiotics and the like enter soil and water bodies in an agricultural mode through livestock excrement without being effectively treated, so that the harmful substances enter a food chain while forming deep threat to the environment to form a food safety problem. In-situ incineration of straw is one of the important causes of air pollution. On the other hand, the use of a large amount of chemical fertilizers in rural areas causes soil hardening and fertility reduction, and the chemical fertilizers remain in the rural areas, which is harmful to food safety, aggravates water and soil pollution and wastes a large amount of resources. With the increasing environmental importance of the public, the organic wastes such as the livestock and poultry manure, the straw and the agricultural product processing residues in the rural areas cannot be discarded or incinerated at any time, and the cost of the incineration disposal is relatively high when the wastes are collected. The organic wastes are autoclaved and hydrolyzed and then fermented to prepare the fertilizer, which is undoubtedly an effective recycling treatment way.
High-pressure water thermal cracking is an important link in the fertilizer preparation process. If the heating and pressurizing are realized by directly adding steam into the water thermal cracking device, the moisture of the materials in the device cannot be controlled. The single dividing wall type heat exchange mode often has large heating temperature difference, so that the material is excessively dehydrated and scabbed outside the heat exchange pipe, and the heat exchange is influenced.
Disclosure of Invention
One aspect of the invention aims to provide a hydrothermal reaction device for heating water vapor and heat conducting oil in a combined manner.
The invention is realized by the following technical scheme.
A composite heating hydrothermal reaction device comprises a hydrothermal reaction tank, a steam distributing cylinder, a high-temperature oil groove and a low-temperature oil groove; the hydrothermal reaction tank comprises a tank body straight section, a tank body bottom and a tank body top, wherein the tank body bottom is in a cone hopper shape, a discharge hole is formed in the cone hopper-shaped bottom, and a feed hole is formed in the tank body top; a plurality of vertically arranged heat conduction oil heating pipes are arranged in the straight section of the tank body, and heat conduction oil lower headers are arranged at the bottoms of the plurality of heat conduction oil heating pipes and connected with each other, so that high-temperature heat conduction oil can be introduced; the bottom of the tank body is provided with a heat conduction oil coil pipe, the heat conduction oil coil pipe is arranged around the inner wall close to the bottom of the tank body, a low-temperature oil pipe and a high-temperature oil pipe are respectively arranged at the inlet of the heat conduction oil coil pipe, low-temperature heat conduction oil and high-temperature heat conduction oil can be respectively introduced to serve as heat media, and a low-temperature oil valve and a high-temperature oil valve are respectively arranged on the low-temperature oil pipe and the high-temperature oil pipe to enable the heat media in the heat; and the hydrothermal reaction tank is also internally provided with steam heating pipes which are arranged from bottom to top in a surrounding manner and can be filled with steam.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the steam heating pipe includes a lower section of steam pipes disposed around the bottom space of the tank body and an upper section of steam pipes disposed adjacent to the inner wall of the straight section of the tank body, and an inlet of the lower section of steam pipes is connected to the gas-distributing cylinder.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the apparatus further includes a gas distribution cylinder, a high temperature oil tank, and a low temperature oil tank, which are respectively used for distributing steam, high temperature heat transfer oil, and low temperature heat transfer oil; the steam distributing cylinder is connected with an inlet of the steam heating pipe; the high-temperature oil groove is communicated with the heat-conducting oil lower header; the low-temperature oil groove, the high-temperature oil groove and the inlet of the heat conducting oil coil are connected through a low-temperature oil pipe and a high-temperature oil pipe respectively.
A composite heating method of a hydrothermal reaction device comprises the following steps:
starting a charging process, enabling the materials to enter the hydrothermal reaction tank through the feeding hole, starting steam heating and low-temperature heat conduction oil heating at the moment, enabling the steam to enter from an inlet of the steam heating pipe through the steam distributing cylinder, heating from the bottom of a tank body of the hydrothermal reaction tank upwards, and leading out from the top of the steam heating pipe after heat exchange and cooling of the steam; and meanwhile, low-temperature heat conduction oil in the low-temperature oil groove enters from the inlet of the heat conduction oil coil to heat the bottom of the tank body.
Finishing the charging process after the materials in the hydrothermal reaction tank reach a preset material level; when the temperature of the materials in the hydrothermal reaction tank reaches more than 100 ℃, stopping steam feeding and heating; closing the low-temperature oil valve and opening the high-temperature oil valve to switch low-temperature oil heat conduction oil in the heat conduction oil pan pipe into high-temperature heat conduction oil in the high-temperature oil groove, so that the bottom of the tank body is switched from low-temperature heat conduction oil heating to high-temperature heat conduction oil heating; and simultaneously, introducing high-temperature heat conduction oil into the heat conduction oil heating pipe from the high-temperature heat conduction oil groove to heat the materials in the straight section of the tank body at high temperature until the materials in the hydrothermal reaction tank complete the hydrothermal reaction process.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the temperature of the high-temperature heat-conducting oil is 280-300 ℃; the temperature of the low-temperature heat conduction oil is 150-180 ℃.
Optionally, according to an embodiment of the present invention, in the foregoing technical solution, the material includes any one of livestock and poultry manure, crop straw, or a mixture thereof.
The advantages and beneficial effects of the invention include: during low temperature, steam up exchanges heat from the bottom, and low temperature conduction oil is used as an intensive heating measure at the bottom, so that the bottom material can be heated as far as possible and can be continuously heated to enter the material. And when the temperature of the materials in the tank reaches above 100 ℃, the steam heat exchange is cut off, the heating is replaced by the high-temperature heat conducting oil in the straight section of the tank body, and meanwhile, the heating of the low-temperature heat conducting oil at the bottom of the tank body is switched to the heating of the high-temperature heat conducting oil. The materials are heated by the low-temperature heat medium (steam and low-temperature heat transfer oil) and the high-temperature heat medium (high-temperature heat transfer oil) firstly, so that not only can the necessary heat exchange temperature difference be kept, but also the problem that the materials are scabbed outside the heat exchange pipe quickly due to too large heat exchange temperature difference so as to influence effective heat exchange is avoided.
Drawings
FIG. 1 is a schematic view of a hydrothermal reaction apparatus with combined heating according to one embodiment of the present invention.
In the figure: 1-a hydrothermal reaction tank; 2-steam heating pipe; 3-heat conducting oil coil pipe; 4-a heat conducting oil heating pipe.
Detailed Description
The following describes the embodiments and operation of the present invention with reference to the accompanying drawings.
The terms of orientation such as up, down, left, right, front, and rear in the present specification are established based on the positional relationship shown in the drawings. The corresponding positional relationship may also vary depending on the drawings, and therefore, should not be construed as limiting the scope of protection.
As shown in fig. 1, the hydrothermal reaction device with combined heating comprises a hydrothermal reaction tank, a steam distributing cylinder, a high-temperature oil tank, a low-temperature oil tank and the like. As an embodiment, the device further comprises a heat conduction oil furnace, wherein part of straws are used as fuel to heat and respectively generate low-temperature heat conduction oil (150-.
The hydrothermal reaction tank is a high-pressure container, is used for producing organic fertilizer by using livestock manure (including cow manure, pig manure and chicken manure), crop straws and other rural wastes, and comprises a tank body straight section, a tank body bottom and a tank body top. The top of the tank body is in a conventional arrangement mode of a pressure container, namely the top of a semicircular tank body, and the bottom of the tank body is in a conical hopper shape, so that the discharging can be smoother. The feed inlet is arranged in the center of the top, the discharge outlet is arranged in the center of the bottom, namely the conical bottom, and valves are arranged on the feed inlet and the discharge outlet, and the inlet and the outlet of materials such as straws, excrement and the like are controlled by opening and closing the valves.
A plurality of heat conducting oil heating pipes 4 are arranged in the straight section of the tank body, the heat conducting oil heating pipes 4 are vertically arranged at large intervals, and heat conducting oil headers are arranged at the bottom and the top of the heat conducting oil heating pipes and connected with each other. In the embodiment shown in fig. 1, these conduction oil heating pipes are preferably connected by two sets of conduction oil headers, respectively. Each group of heat transfer oil header comprises a heat transfer oil lower header (inlet header) and a heat transfer oil upper header (outlet header). And a connecting pipe is arranged between the high-temperature oil groove and the heat-conducting oil lower header, and a high-temperature oil valve is arranged on the connecting pipe. The high-temperature oil groove stores high-temperature heat conduction oil with the temperature of 280 and 300 ℃. High-temperature heat conduction oil enters the heat conduction oil heating pipe from bottom to top to heat the hydrothermal reaction tank, and the heat conduction oil after heat exchange is collected by the heat conduction oil upper header and then led out, and returns to the heat conduction oil furnace to be heated for cyclic utilization.
Steam pipes (fig. 1 only schematically shows the encircling connection of part of the steam pipes, and in fact, the steam pipes are communicated and spirally upwards arranged in an encircling way) are arranged in the straight section of the tank body in an encircling way and are arranged close to the inner wall of the straight section of the tank body. The bottom of the tank body is internally provided with a steam heating pipe 2, and the steam heating pipe 2 is arranged in the material instead of being arranged along the wall. The bottom of the steam heating pipe 2 is an inlet, the top of the steam heating pipe is an outlet, the outlet of the steam heating pipe 2 is communicated with a steam pipe, and the inlet is connected with a steam distributing cylinder, so that the steam is communicated with the surrounding heating from the bottom to the upper part of the hydrothermal reaction tank.
The bottom of the tank body is also provided with a heat conduction oil coil pipe 3, and the heat conduction oil coil pipe 3 is arranged around the inner wall close to the bottom of the tank body. And a low-temperature oil pipe and a high-temperature oil pipe are respectively arranged between the inlet of the heat conducting oil coil 3 and the low-temperature oil tank and between the inlet of the heat conducting oil coil 3 and the high-temperature oil tank. And the low-temperature oil valve and the high-temperature oil valve are respectively arranged on the low-temperature oil pipe and the high-temperature oil pipe, and the low-temperature oil valve and the high-temperature oil valve are opened and closed through switching, so that the bottom of the tank body can realize switching between low-temperature heat transfer oil heating and high-temperature heat transfer oil heating.
Starting a charging process, enabling rural wastes such as livestock manure (including cow manure, pig manure and chicken manure) and crop straws to enter a hydrothermal reaction tank as materials through a feed inlet, and starting steam heating and low-temperature heat conduction oil heating at the moment. The feeding device is arranged according to requirements, such as a feces feeding device, a straw feeding device and a clear liquid feeding device which are arranged in parallel. The excrement feeding device comprises an excrement tank and an excrement pump, the straw feeding device comprises a straw bin and a feeder, and the clear liquid feeding device is used for supplementing clear liquid, so that the excrement and/or the straw can reach moisture (usually 70% -80%) required by hydrothermal cracking.
Steam heating: steam (143-165 ℃) with gauge pressure of 0.3-0.6 MPa enters from an inlet of the steam heating pipe 2 through the steam distributing cylinder, is heated from the bottom of the hydrothermal reaction tank upwards through the steam heating pipe and the steam pipe in sequence, and is changed into saturated water or superheated water after heat exchange and cooling, and is led out from the upper part of the steam pipe.
Low-temperature heat conduction oil heating: so that the low-temperature heat conducting oil in the low-temperature oil groove enters from the inlet of the heat conducting oil coil 3 to heat the bottom of the tank body.
And when the material in the hydrothermal reaction tank reaches a preset material level, ending the charging process and closing the feed inlet valve. A plurality of temperature measuring devices are arranged in the hydrothermal reaction tank, and when the temperature of the materials in the hydrothermal reaction tank reaches 100 ℃, the steam feeding and heating are stopped. And simultaneously, high-temperature heat conduction oil is led into the heat conduction oil heating pipe from the high-temperature heat conduction oil groove to heat the materials in the straight section of the tank body at high temperature. And the low-temperature oil valve is closed, and the high-temperature oil valve is opened, so that the low-temperature oil heat conduction oil in the heat conduction oil tray pipe is switched to high-temperature heat conduction oil in the high-temperature oil groove, the bottom of the tank body is switched to be heated by the high-temperature heat conduction oil from the low-temperature heat conduction oil, and the high-temperature heating requirement is met. And keeping the high-temperature heat-conducting oil to be heated until the materials in the hydrothermal reaction tank complete the high-pressure hydrothermal reaction process. And opening a discharge port valve to discharge after the preset retention time is reached.
The materials entering the hydrothermal reaction tank fall under the action of gravity and are gradually accumulated from the bottom to the top, so that the bottom enhanced heating is important for the hydrothermal reaction. Also consequently, during low temperature, steam from the bottom up heat transfer, the bottom is low temperature conduction oil as intensive heating measure in addition simultaneously, can guarantee that the bottom material is heated as far as possible and the material that gets into after constantly heating. And when the temperature of the materials in the tank reaches above 100 ℃, the steam heat exchange is cut off, the heating is replaced by the high-temperature heat conducting oil in the straight section of the tank body, and meanwhile, the heating of the low-temperature heat conducting oil at the bottom of the tank body is switched to the heating of the high-temperature heat conducting oil. The materials are heated by the low-temperature heat medium (steam and low-temperature heat transfer oil) and the high-temperature heat medium (high-temperature heat transfer oil) firstly, so that not only can the necessary heat exchange temperature difference be kept, but also the problem that the materials are scabbed outside the heat exchange pipe quickly due to too large heat exchange temperature difference so as to influence the heat exchange process is avoided.
Whether the steam heating pipe, the heat conducting oil heating pipe or the heat conducting oil coil pipe penetrates through the wall surface of the hydrothermal reaction tank serving as the pressure container, the sealing arrangement is adopted, and the sealing arrangement can be understood and imagined by a person skilled in the art and is not described in detail herein. And the forced circulation arrangement is adopted for both high-temperature and low-temperature heat conduction oil and steam, and the arrangement can be understood and imagined by those skilled in the art.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The hydrothermal reaction device with composite heating is characterized by comprising a hydrothermal reaction tank, wherein the hydrothermal reaction tank (1) comprises a tank body straight section, a tank body bottom and a tank body top, the tank body bottom is in a cone bucket shape, a discharge hole is formed in the cone bucket shape bottom, and a feed hole is formed in the tank body top; a plurality of vertically arranged heat conduction oil heating pipes (4) are arranged in the straight section of the tank body, and heat conduction oil lower headers are arranged at the bottoms of the plurality of heat conduction oil heating pipes and connected with each other, so that high-temperature heat conduction oil can be introduced; the bottom of the tank body is provided with a heat-conducting oil coil pipe (3), the heat-conducting oil coil pipe (3) is arranged around the inner wall close to the bottom of the tank body, the inlet of the heat-conducting oil coil pipe (3) is respectively provided with a low-temperature oil pipe and a high-temperature oil pipe which can be respectively introduced with low-temperature heat-conducting oil and high-temperature heat-conducting oil, and the low-temperature oil pipe and the high-temperature oil pipe are respectively provided with a low-temperature oil valve and a; and the hydrothermal reaction tank is also internally provided with steam heating pipes (2) which are arranged from bottom to top in a surrounding manner and can be filled with steam.
2. The complex-heated hydrothermal reaction device according to claim 1, wherein the steam heating pipe (2) includes a lower section surrounding a space in the bottom of the tank and an upper section disposed adjacent to the inner wall of the straight section of the tank, and an inlet of the lower section is connected to the gas-distributing cylinder.
3. The complex-heated hydrothermal reaction device according to claim 1, further comprising a gas-distributing cylinder, a high-temperature oil tank and a low-temperature oil tank for distributing steam, high-temperature heat transfer oil and low-temperature heat transfer oil, respectively; the steam distributing cylinder is connected with an inlet of the steam heating pipe (2); the high-temperature oil groove is communicated with the heat-conducting oil lower header; the low-temperature oil groove, the high-temperature oil groove and the inlet of the heat conducting oil coil (3) are connected through a low-temperature oil pipe and a high-temperature oil pipe respectively.
4. A combined heating method for a hydrothermal reaction apparatus using the hydrothermal reaction apparatus according to any one of claims 1 to 3, comprising:
starting a charging process, enabling the materials to enter the hydrothermal reaction tank through the feeding hole, starting steam heating and low-temperature heat conduction oil heating at the moment, enabling the steam to enter from an inlet of the steam heating pipe (2) through the steam distributing cylinder, heating from the bottom of a tank body of the hydrothermal reaction tank upwards, and leading out from the top of the steam heating pipe after the steam is cooled through heat exchange; meanwhile, low-temperature heat conduction oil enters from an inlet of the heat conduction oil coil (3) to heat the bottom of the tank body;
finishing the charging process after the materials in the hydrothermal reaction tank reach a preset material level; when the temperature of the materials in the hydrothermal reaction tank reaches more than 100 ℃, stopping steam feeding and heating; closing the low-temperature oil valve and opening the high-temperature oil valve to switch the low-temperature oil heat conduction oil in the heat conduction oil pan pipe into high-temperature heat conduction oil, so that the bottom of the tank body is switched from low-temperature heat conduction oil heating to high-temperature heat conduction oil heating; and simultaneously, introducing high-temperature heat conduction oil into the heat conduction oil heating pipe to heat the materials in the straight section of the tank body at high temperature until the materials in the hydrothermal reaction tank complete the hydrothermal reaction process.
5. The composite heating method of the hydrothermal reaction device as set forth in claim 4, wherein the temperature of the high-temperature heat transfer oil is 280-300 ℃; the temperature of the low-temperature heat-conducting oil is 150-180 ℃.
6. The combined heating method of a hydrothermal reaction unit as set forth in claim 4, wherein the material includes any one of livestock and poultry manure, crop straw, or a mixture thereof.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110273150.XA CN112808168B (en) | 2021-03-14 | 2021-03-14 | Composite heating hydrothermal reaction device and composite heating method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110273150.XA CN112808168B (en) | 2021-03-14 | 2021-03-14 | Composite heating hydrothermal reaction device and composite heating method thereof |
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| CN112808168A true CN112808168A (en) | 2021-05-18 |
| CN112808168B CN112808168B (en) | 2022-07-26 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201719862U (en) * | 2010-07-09 | 2011-01-26 | 许累峰 | Dewatering and degreasing diffuser |
| CN202427432U (en) * | 2011-12-13 | 2012-09-12 | 天津市大邱庄津姿涂料有限公司 | Temperature regulation system for reaction kettle |
| WO2014161396A1 (en) * | 2013-04-03 | 2014-10-09 | 清华大学 | Circulating bed organic heat carrier furnace for co-producing hot oil and water vapour |
| CN108211994A (en) * | 2018-02-07 | 2018-06-29 | 北京环清环境科技有限公司 | A kind of organic fertilizer hydrolysis device |
| CN208742517U (en) * | 2018-04-18 | 2019-04-16 | 青岛蓝帆新材料有限公司 | A kind of polymerization technique reaction kettle |
-
2021
- 2021-03-14 CN CN202110273150.XA patent/CN112808168B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201719862U (en) * | 2010-07-09 | 2011-01-26 | 许累峰 | Dewatering and degreasing diffuser |
| CN202427432U (en) * | 2011-12-13 | 2012-09-12 | 天津市大邱庄津姿涂料有限公司 | Temperature regulation system for reaction kettle |
| WO2014161396A1 (en) * | 2013-04-03 | 2014-10-09 | 清华大学 | Circulating bed organic heat carrier furnace for co-producing hot oil and water vapour |
| CN108211994A (en) * | 2018-02-07 | 2018-06-29 | 北京环清环境科技有限公司 | A kind of organic fertilizer hydrolysis device |
| CN208742517U (en) * | 2018-04-18 | 2019-04-16 | 青岛蓝帆新材料有限公司 | A kind of polymerization technique reaction kettle |
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| CN112808168B (en) | 2022-07-26 |
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