CN111072598A - Process for producing epichlorohydrin by direct oxidation of titanium silicalite molecular sieve catalyst - Google Patents
Process for producing epichlorohydrin by direct oxidation of titanium silicalite molecular sieve catalyst Download PDFInfo
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- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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Abstract
The invention provides a process for producing epichlorohydrin by direct oxidation of a titanium-silicon molecular sieve catalyst, which comprises the steps of pumping prepared methanol catalyst mixed liquid and fresh chloropropene into a first mixer through a metering pump, mixing the methanol catalyst mixed liquid and the fresh chloropropene with hydrogen peroxide pumped into the first mixer, then feeding the mixture into a first tubular reactor for reaction, separating gas and liquid phases of reaction products through a separator, mixing the separated liquid phase part with the hydrogen peroxide fed into a second mixer, then feeding the mixture into a second tubular reactor for reaction, feeding the reaction products into a second separator for gas-liquid separation, feeding the finally formed reaction products into a separation tank for separating solid catalyst and liquid phase products, pumping catalyst slurry into a proportioning tank for re-proportioning, and taking the liquid products out from a filter at the upper part of the separation tank.
Description
Technical Field
The invention belongs to a process for producing epichlorohydrin by directly oxidizing titanium silicalite molecular sieve catalyst, belonging to the field of production process of chemical products.
Background
Epichlorohydrin is an organic synthetic raw material and an intermediate with extremely strong functionality, and has very wide application. Used for preparing epoxy resin, glycerol, polyether polyol and the like, and is an important raw material for producing glycerol and glycidyl derivatives. At present, the main method for preparing epichlorohydrin comprises the following steps: propylene high-temperature chlorination process, acrylic acetate process, glycerin process, etc. Although these processes are technically mature, they all have inevitable disadvantages, such as: the method has the advantages of serious corrosion to equipment, high energy consumption quota, high requirement on raw material purity, more byproducts, generation of a large amount of wastewater, serious damage to the environment and high device investment cost.
In order to overcome the above problems in the synthesis of epichlorohydrin, researchers developed a method for preparing epichlorohydrin by direct epoxidation of chloropropene.
US4833260 discloses a process for preparing epichlorohydrin by direct epoxidation of chloropropene using a titanium silicalite molecular sieve as a catalyst and hydrogen peroxide as an oxidant. However, the resulting epoxide will be partially subjected to ring-opening reaction due to the influence of the strongly polar compound present in the reaction system, which lowers the yield of the product. The epoxidation reaction of chloropropene is an exothermic reaction, if the released heat cannot be removed in time, the temperature of the system exceeds the control temperature, the ineffective decomposition of hydrogen peroxide is increased, and the effective utilization rate of the hydrogen peroxide is reduced. Based on this disadvantage, the 1999 patent CN1219536A added a solid inert diluent to the catalyst to delay the reaction so as to effectively control the reaction temperature, but the effective volume of the reactor would be significantly reduced.
CN201310211677.5 discloses a method for olefin oxidation, which is to make olefin and oxidant contact-react with catalyst on fixed bed under the condition of olefin oxidation reaction. The method can maintain the activity, oxidant conversion rate and target product selectivity of the catalyst at higher levels in the reaction contact process, and prolong the one-way running time of the catalyst, thereby delaying the deactivation of the catalyst and prolonging the service life of the catalyst. However, in the reaction process, the retention time of the reactants is insufficient, so that the effective contact area between the catalyst and the reactants is small, the reaction is incomplete, and the yield in unit time is low.
In order to improve the effective utilization rate of hydrogen peroxide, CN201110424544.7 discloses a method for continuously producing epichlorohydrin by direct epoxidation of chloropropene, wherein chloropropene, hydrogen peroxide, catalyst slurry and solvent are respectively conveyed into a reactor. The upper end of a discharge hole in the reactor is provided with a filter which can separate clear liquid containing products, and materials which are not filtered out by the lower end of the filter and contain catalyst and are not reacted completely are refluxed and conveyed to the reactor at the bottom end of the reactor. The catalyst does not need to be recovered in the continuous production process, the gas phase is condensed and refluxed through the condenser at the top of the reactor, and the jacketed heat exchange layers are arranged outside the condenser and the reactor in the device, so that heat generated by the reaction can be exchanged and taken away, and the effective utilization rate of the hydrogen peroxide is effectively improved. However, in the method, the hydrogen peroxide is fed once, and the conversion rate of chloropropene is not high, so that the yield of epichlorohydrin is low.
CN200710046989.X discloses a method for producing epichlorohydrin, which is used for producing epichlorohydrin by catalytic oxidation of chloropropene under the catalytic action of a titanium-silicon molecular sieve and with hydrogen peroxide as an oxidant and a fixed bed as a reactor. The heat released in the reaction process is concentrated on the catalyst bed layer, cannot be transferred or converted in time, the reaction temperature is unstable, and the selectivity of the epichlorohydrin is easily reduced.
Disclosure of Invention
In view of the defects in the prior art, the technical problems to be solved by the invention are as follows: low effective utilization rate of hydrogen peroxide, difficult separation and recovery of catalyst, large load of process devices and the like. In order to realize the purpose, the invention provides a novel process method for producing epoxy chloropropane by directly oxidizing titanium silicalite molecular sieve catalyst, which has the characteristics of stable reaction temperature, simple process flow, high epoxy chloropropane yield, high effective utilization rate of hydrogen peroxide and the like.
The invention provides a device for producing epichlorohydrin, which comprises a first mixer, a first tubular reactor, a first separator, a second mixer, a second tubular reactor, a second separator, a separation tank and a filter, wherein the first mixer is arranged on the first tubular reactor;
the outlet of the first mixer is communicated with the feed inlet of the first tubular reactor through a pipeline;
the outlet of the first tubular reactor is communicated with the feed inlet of the first separator; the liquid phase outlet of the first separator is communicated with the feed inlet of the second mixer through a pipeline; the outlet of the second mixer is communicated with the feed inlet of the second tubular reactor through a pipeline; the outlet of the second tubular reactor is communicated with the feed inlet of the second separator; a liquid phase outlet of the second separator is communicated with a feed inlet of the separation tank;
a clear liquid discharge hole is formed in the upper part of the separation tank; the filter is arranged at the clear liquid outlet.
Based on the above technical solution, preferably, the apparatus further comprises a first condenser and a second condenser; the first condenser is arranged at the top of the first separator; the second condenser is arranged at the top of the second separator.
The invention also provides a process for producing epichlorohydrin by using the device and utilizing the titanium silicalite molecular sieve catalyst to directly oxidize:
(1) pumping fresh chloropropene and a solvent methanol added with a catalyst into a first mixer through a metering pump, uniformly mixing with an aqueous hydrogen peroxide solution pumped into the first mixer through the metering pump, mixing, and conveying to a first tubular reactor for reaction; the temperature of the first tubular reactor is 20-70 ℃, and the retention time is 1-7 h;
(2) the material reacted in the first tubular reactor enters a first separator through an outlet, and nitrogen is introduced into the first separator, so that the pressure of the first separator is kept at 0.1-0.8 MPa; the gas phase part enters a first condenser for condensation and reflux, the liquid phase part is conveyed to a second mixer through an outlet by a pump, and the hydrogen peroxide water solution is added into the second mixer again; conveying the reaction materials in the second mixer to a second tubular reactor for reaction; setting the temperature of the second tubular reactor to be 20-70 ℃ and the retention time to be 1-7 h;
(3) feeding the material reacted in the second tubular reactor into a second separator, introducing nitrogen into the second separator to keep the pressure of the second separator at 0.1-0.8MPa, and feeding the gas phase part in the second separator into a condenser above the second separator for condensation and reflux;
(4) the final reaction product is pumped into a separation tank through a metering pump, a built-in filter is arranged at the upper part of the separation tank, the solid catalyst and the liquid phase product can be separated, the catalyst slurry is pumped into a proportioning tank through a pump for proportioning again, and the liquid product is extracted from the filter at the upper part of a settling tank.
Based on the technical scheme, the tubular reactor is preferably a metal hollow tube with a smooth inner wall, the inner diameter of the metal hollow tube is 10-500mm, and the length of the metal hollow tube is 1-100 m.
Based on the technical scheme, preferably, the solid content percentage of the catalyst in the reaction liquid in the tubular reactor is 0.1-30 percent; the mole numbers of the hydrogen peroxide aqueous solution added into the first mixer and the second mixer are 1/8-1 of the mole number of the chloropropene, and the amount of the hydrogen peroxide aqueous solution added twice can be the same or different; the chloropropene mass concentration is more than 98%, the hydrogen peroxide water solution mass concentration is 27% -70%, and the mass ratio of the solvent methanol to the chloropropene is 0.1-5: 1.
Based on the technical scheme, preferably, the filter is a ceramic membrane filter or a polytetrafluoroethylene filter element, and the pore size of the filter is 2-10 μm smaller than the particle size of the catalyst; the filter is connected with the clear liquid discharge port in a detachable pipeline manner.
Based on the technical scheme, preferably, the filter is a polytetrafluoroethylene filter element; the pore space of the polytetrafluoroethylene filter element is 1-50 μm, the filter is composed of 1-100 polytetrafluoroethylene filter elements, and the polytetrafluoroethylene filter element is in the shape of a solid cylinder.
Based on the technical scheme, preferably, the first condenser, the second condenser, the first tubular reactor and the second tubular reactor are externally provided with jacket heat exchange layers.
Based on the technical scheme, preferably, the raw materials of the method also comprise an additive M2CO3Or MHCO3M is K+、Na+、NH4 +。
Advantageous effects
(1) The front part of each tubular reactor is connected with a mixer, and the reaction materials in the tubular reactors are fully and uniformly mixed by the mixers before entering, so that the catalysts are ensured to be fully contacted with the reaction materials, and the catalytic reaction is favorably carried out. Compared with the stirring kettle type reaction, the method of the invention reduces the energy consumption of the mixed material and has stable reaction.
(2) The hydrogen peroxide aqueous solution is divided into two steps and enters the reaction materials respectively, so that the free regulation and control of the mole ratio of chloropropene and hydrogen peroxide can be realized, the self-decomposition reaction of hydrogen peroxide in the presence of a catalyst is reduced, the effective utilization rate of hydrogen peroxide is improved, the production cost is reduced, and the working efficiency is improved.
(3) The invention designs two tubular reactors, which can effectively control the reaction temperature and the chloropropene conversion rate and increase the reaction safety.
(4) The separating tank is favorable for separating the catalyst so as to facilitate the extraction of the liquid phase through the filter element, and the sedimentation of the solid catalyst can effectively reduce the load of the filter element and is favorable for separating the catalyst.
(5) The fresh chloropropene feeding pipeline is added, the load of the whole process device can be adjusted, and the influence on the reaction process is reduced by adjusting the reaction time. The invention has potential market value.
Drawings
FIG. 1 is a schematic view of the process flow for producing epichlorohydrin,
FIG. 2 is a schematic process flow diagram for epichlorohydrin production in contrast to the present invention; wherein: p-1, P-2, P-3, P-4 and P-5 are metering pumps, M-1 is a first mixer, R-1 is a first tubular reactor, V-1 is a first separator, L-1 is a first condenser, V-2 is a second separator, L-2 is a second condenser, M-2 is a second mixer, R-2 is a second tubular reactor, C is a separation tank and F is a filter.
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to the examples.
Detailed Description
The catalyst used in the present invention was a titanium silicalite catalyst prepared using the method disclosed in 201711344584.4. According to the method, solid metatitanic acid and solid orthotitanic acid are used as titanium sources to synthesize TS-1, alcohol substances are not required to be added in the process of introducing new titanium, certain burden is reduced for the subsequent alcohol removal step, the metatitanic acid and the orthotitanic acid are low in price, the synthesis cost can be reduced, and the production cost of the method is further saved.
Comparative example 1
The epichlorohydrin production process shown in figure 1 is carried out.
The device is provided with two tubular reactors which are both provided with heat exchange jacket layers so as to exchange heat and take away heat generated by the reaction; the front parts of the two tubular reactors are respectively provided with a mixer so as to fully mix the raw materials; reflux condensers are arranged at the tops of the two separators.
Fresh chloropropene and methanol added with a catalyst are pumped into a first mixer M-1 through a metering pump P-1, are mixed with hydrogen peroxide pumped into the first mixer M-1 through a metering pump P-2, are uniformly mixed and are conveyed to a first tubular reactor R-1 for reaction. The mass ratio of the methanol to the chloropropene is 1:1, the mole number of the hydrogen peroxide in the hydrogen peroxide is 1/6 of the chloropropene, the mass concentration of the hydrogen peroxide is 50%, the weight solid content of the catalyst is 10%, no additive is added into the catalyst, and the feeding flow is 5L/h.
The method comprises the following steps that materials reacted in a first tubular reactor R-1 enter a first separator V-1, nitrogen is introduced from the outside above a liquid phase of the first separator V-1 to keep the pressure of the first separator V-1 at 0.4MPa, a gas phase part enters a first condenser L-1 at the top of the first separator V-1 to be condensed and refluxed, a liquid phase part is conveyed to a second mixer M-2 through a metering pump P-3 and is conveyed to the second mixer M-2 together with hydrogen peroxide pumped into the second mixer M-2 through the metering pump P-4 to be mixed, the mixture is uniformly mixed and then is pumped into the second tubular reactor R-2 to react, and the mole number of hydrogen peroxide in the hydrogen peroxide is 1/6 of chloropropene.
The material reacted in the second tubular reactor R-2 enters a second separator V-2, nitrogen is introduced from the outside above the liquid phase of the second separator V-2 to maintain the pressure in the second separator V-2 at 0.4MPa, and the gas phase part in the second separator V-2 enters a second condenser L-2 above the second separator V-2 for condensation and reflux.
The materials pumped out by the second separator V-2 are pumped into a separation tank C through a metering pump P-5, a built-in filter F is arranged at the upper part of the separation tank C and can separate the solid catalyst and the liquid phase products, the catalyst slurry is pumped into a proportioning tank through a pump to be proportioned again, and the liquid products are extracted from the filter F at the upper part of the separation tank C.
The reaction was continued for 1000 hours, and the separated clear solution was analyzed to obtain the selectivity of epichlorohydrin and the effective utilization of hydrogen peroxide, as shown in table 1.
Table 1 part of the reaction conditions and the results of the reaction of comparative example 1
Comparative example 2
The epichlorohydrin production process shown in figure 2 is carried out.
The device is provided with two tubular reactors which are both provided with heat exchange jacket layers so as to exchange heat and take away heat generated by the reaction; the front parts of the two tubular reactors are respectively provided with a mixer so as to fully mix the raw materials; reflux condensers are arranged at the tops of the two separators.
Fresh chloropropene and methanol added with a catalyst are pumped into a first mixer M-1 through a metering pump P-1, are mixed with hydrogen peroxide pumped into the first mixer M-1 through a metering pump P-2, are uniformly mixed and are conveyed to a first tubular reactor R-1 for reaction. The mass ratio of the methanol to the chloropropene is 1:1, the molar ratio of the chloropropene to the hydrogen peroxide is 3:1, the mass concentration of the hydrogen peroxide is 50%, the solid content of the catalyst is 10%, and the additive Na2CO3The dosage of the catalyst is 15ppm of the dosage of the mixed solution, and the feed flow is 5L/h.
The material reacted in the first tubular reactor R-1 enters a first separator V-1, nitrogen is introduced from the outside above the liquid phase of the first separator V-1 to keep the pressure of the first separator V-1 at 0.4MPa, the gas phase part enters a first condenser L-1 at the top of the first separator V-1 for condensation and reflux, and the liquid phase part is conveyed to a second tubular reactor R-2 through a metering pump P-3. .
The material of the second tubular reactor R-2 enters a second separator V-2, nitrogen is introduced from the outside above the liquid phase of the second separator V-2, the pressure inside the second separator V-2 is maintained at 0.4MPa, and the gas phase part in the second separator V-2 enters a second condenser L-2 above the second separator V-2 for condensation and reflux.
The materials pumped out by the second separator V-2 are pumped into a separation tank C through a metering pump P-5, a built-in filter F is arranged at the upper part of the separation tank C and can separate the solid catalyst and the liquid phase products, the catalyst slurry is pumped into a proportioning tank through a pump to be proportioned again, and the liquid products are extracted from the filter F at the upper part of the separation tank C.
The reaction was continued for 1000 hours, and the separated clear solution was analyzed to obtain the selectivity of epichlorohydrin and the effective utilization of hydrogen peroxide, as shown in table 2.
Table 2 part of the reaction conditions and the results of the reaction of comparative example 2
Example 1
The epichlorohydrin production process shown in figure 1 is carried out.
The device is provided with two tubular reactors which are both provided with heat exchange jacket layers so as to exchange heat and take away heat generated by the reaction; the front parts of the two tubular reactors are respectively provided with a mixer so as to fully mix the raw materials; reflux condensers are arranged at the tops of the two separators.
Fresh chloropropene and methanol added with a catalyst are pumped into a first mixer M-1 through a metering pump P-1, are mixed with hydrogen peroxide pumped into the first mixer M-1 through a metering pump P-2, are uniformly mixed and are conveyed to a first tubular reactor R-1 for reaction. The mass ratio of the methanol to the chloropropene is 1:1, the mole number of the hydrogen peroxide in the hydrogen peroxide is 1/6 of the chloropropene, the mass concentration of the hydrogen peroxide is 50%, the weight solid content of the catalyst is 10%, and the additive Na is2CO3The dosage of the catalyst is 15ppm of the dosage of the mixed solution, and the feed flow is 5L/h.
The method comprises the following steps that materials reacted in a first tubular reactor R-1 enter a first separator V-1, nitrogen is introduced from the outside above a liquid phase of the first separator V-1 to keep the pressure of the first separator V-1 at 0.4MPa, a gas phase part enters a first condenser L-1 at the top of the first separator V-1 to be condensed and refluxed, a liquid phase part is conveyed to a second mixer M-2 through a metering pump P-3 and is conveyed to the second mixer M-2 together with hydrogen peroxide pumped into the second mixer M-2 through the metering pump P-4 to be mixed, the mixture is uniformly mixed and then is pumped into the second tubular reactor R-2 to react, and the mole number of hydrogen peroxide in the hydrogen peroxide is 1/6 of chloropropene.
The material reacted in the second tubular reactor R-2 enters a second separator V-2, nitrogen is introduced from the outside above the liquid phase of the second separator V-2 to maintain the pressure in the second separator V-2 at 0.4MPa, and the gas phase part in the second separator V-2 enters a second condenser L-2 above the second separator V-2 for condensation and reflux.
The materials pumped out by the second separator V-2 are pumped into a separation tank C through a metering pump P-5, a built-in filter F is arranged at the upper part of the separation tank C and can separate the solid catalyst and the liquid phase products, the catalyst slurry is pumped into a proportioning tank through a pump to be proportioned again, and the liquid products are extracted from the filter F at the upper part of the separation tank C.
The reaction was continued for 1000 hours, and the separated clear solution was analyzed to obtain the selectivity of epichlorohydrin and the effective utilization rate of hydrogen peroxide, as shown in table 3.
Table 3 part of the reaction conditions of example 1 and the reaction results thereof
By comparing the results in tables 1 and 3, it can be seen that additive Na2CO3The activity of the catalyst can be improved. The continuous reaction is carried out for 1000 hours, the selectivity of the epichlorohydrin is kept about 99 percent, the highest value reaches 99.6 percent, and the selectivity is improved compared with the case without the additive; the effective utilization rate of the hydrogen peroxide is kept above 98 percent, and the maximum value reaches 98.7 percent. The catalyst has high activity and stability under the condition of adding the additive.
As can be seen from a comparison of the results in tables 2 and 3, the effective utilization of hydrogen peroxide can be significantly improved by adding hydrogen peroxide twice. The reaction is continued for 1000 hours, the effective utilization rate of the hydrogen peroxide is kept above 98 percent, and the maximum value reaches 98.7 percent. Compared with the one-time adding of all hydrogen peroxide, the two-time adding of hydrogen peroxide obviously improves the selectivity of the epichlorohydrin and the effective utilization rate of the hydrogen peroxide.
The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention in any way.
Claims (9)
1. The device for producing the epichlorohydrin is characterized by comprising a first mixer, a first tubular reactor, a first separator, a second mixer, a second tubular reactor, a second separator, a separation tank and a filter;
the outlet of the first mixer is communicated with the feed inlet of the first tubular reactor through a pipeline;
the outlet of the first tubular reactor is communicated with the feed inlet of the first separator; the liquid phase outlet of the first separator is communicated with the feed inlet of the second mixer through a pipeline; the outlet of the second mixer is communicated with the feed inlet of the second tubular reactor through a pipeline; the outlet of the second tubular reactor is communicated with the feed inlet of the second separator; a liquid phase outlet of the second separator is communicated with a feed inlet of the separation tank;
a clear liquid discharge hole is formed in the upper part of the separation tank; the filter is arranged at the clear liquid outlet.
2. The apparatus of claim 1, further comprising a first condenser and a second condenser; the first condenser is arranged at the top of the first separator; the second condenser is arranged at the top of the second separator.
3. Process for manufacturing epichlorohydrin, characterized in that it uses the device of claim 1 or 2, comprising the following steps:
(1) pumping fresh chloropropene and a solvent methanol added with a catalyst into a first mixer through a metering pump, uniformly mixing with an aqueous hydrogen peroxide solution pumped into the first mixer through the metering pump, mixing, and conveying to a first tubular reactor for reaction; setting the reaction temperature of the first tubular reactor to be 20-70 ℃ and the retention time to be 1-7 h;
(2) the reaction material in the first tubular reactor enters a first separator through an outlet, and nitrogen is introduced into the first separator, so that the pressure of the first separator is kept at 0.1-0.8 MPa; the gas phase part enters a first condenser for condensation and reflux, the liquid phase part is conveyed to a second mixer through an outlet by a pump, hydrogen peroxide water solution is added into the second mixer again, the reaction materials in the second mixer are conveyed to a second tubular reactor for reaction, the reaction temperature of the second tubular reactor is set to be 20-70 ℃, and the retention time is 1-7 h; the reacted reaction material enters a second separator through an outlet, and nitrogen is introduced into the second separator, so that the pressure of the second separator is kept between 0.1 and 0.8 MPa; the gas phase part enters a second condenser for condensation and reflux, the liquid phase part is conveyed to a separation tank through an outlet by a pump, and clear liquid containing products is separated out through a filter at a clear liquid discharge port.
4. The process according to claim 3, wherein the tubular reactor is a metal hollow tube having a smooth inner wall, an inner diameter of 10 to 500mm and a length of 1 to 100 m.
5. The process of claim 3, wherein the reaction liquid in the tubular reactor has a catalyst weight solids percentage of 0.1 to 30%; adding 1/8-1 mol number of hydrogen peroxide in the hydrogen peroxide aqueous solution into the first mixer and the second mixer, wherein the two times of adding the hydrogen peroxide aqueous solution can be the same or different; the chloropropene mass concentration is more than 98%, the hydrogen peroxide water solution mass concentration is 27% -70%, and the mass ratio of the solvent methanol to the chloropropene is 0.1-5: 1.
6. The method of claim 3, wherein the filter is a ceramic membrane filter or a polytetrafluro filter cartridge, and the pore size of the filter is 2 to 10 μm smaller than the particle size of the catalyst; the filter is connected with the clear liquid discharge port in a detachable pipeline manner.
7. The method of claim 3, wherein said filter is a polytetraflouroethylene filter element; the pore space of the polytetrafluoroethylene filter element is 1-50 μm, the filter is composed of 1-100 polytetrafluoroethylene filter elements, and the polytetrafluoroethylene filter element is in the shape of a solid cylinder.
8. The method of claim 3, wherein the first condenser, the second condenser, the first tubular reactor and the second tubular reactor are externally provided with jacket heat exchange layers.
9. The method according to claim 3, characterized in that the raw material of the method further comprises an additive M2CO3Or MHCO3M is K+、Na+、NH4 +。
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| CN115197171A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Method and system for producing propylene oxide |
| CN115894400A (en) * | 2022-12-01 | 2023-04-04 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane by directly oxidizing chloropropene by using liquid-solid circulating fluidized bed reactor |
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| CN211771015U (en) | 2020-10-27 |
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