CN210700032U - Microchannel gas-liquid reaction device - Google Patents
Microchannel gas-liquid reaction device Download PDFInfo
- Publication number
- CN210700032U CN210700032U CN201921079790.1U CN201921079790U CN210700032U CN 210700032 U CN210700032 U CN 210700032U CN 201921079790 U CN201921079790 U CN 201921079790U CN 210700032 U CN210700032 U CN 210700032U
- Authority
- CN
- China
- Prior art keywords
- reaction
- micro
- gas
- microchannel
- adipic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn - After Issue
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 276
- 239000007788 liquid Substances 0.000 title claims abstract description 47
- 239000012071 phase Substances 0.000 claims abstract description 44
- 239000007791 liquid phase Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 66
- 239000010432 diamond Substances 0.000 claims description 6
- 229910003460 diamond Inorganic materials 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 200
- 239000001361 adipic acid Substances 0.000 abstract description 100
- 235000011037 adipic acid Nutrition 0.000 abstract description 100
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 73
- 238000012546 transfer Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000006698 induction Effects 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 6
- 230000008676 import Effects 0.000 abstract 3
- 239000007792 gaseous phase Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 description 83
- 238000004458 analytical method Methods 0.000 description 33
- 239000007800 oxidant agent Substances 0.000 description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 230000001590 oxidative effect Effects 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 26
- 239000001301 oxygen Substances 0.000 description 26
- 229910052760 oxygen Inorganic materials 0.000 description 26
- 239000007789 gas Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000012530 fluid Substances 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229940011182 cobalt acetate Drugs 0.000 description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 230000011218 segmentation Effects 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- IJRNYIWWGDQEIY-UHFFFAOYSA-N (1,3-dioxoisoindol-2-yl) acetate Chemical compound C1=CC=C2C(=O)N(OC(=O)C)C(=O)C2=C1 IJRNYIWWGDQEIY-UHFFFAOYSA-N 0.000 description 2
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
The utility model relates to a microchannel reaction technical field discloses a microchannel gas-liquid reaction unit. The device includes from last roof, last heat transfer board, reaction plate and the heat transfer board down that stacks in proper order setting, wherein, the reaction plate includes the first little mixed structure that sets gradually according to the material trend, first little reaction channel, the little mixed structure of second, second little reaction channel and product export, liquid phase import and first gaseous phase import and the entry intercommunication of first little mixed structure, the export of second gaseous phase import and first little reaction channel and the entry intercommunication of the little mixed structure of second, first little reaction channel has different structures with second little reaction channel. Device can realize the serialization production of gas-liquid reaction, reduce induction phase side reaction's emergence, improve reaction efficiency, use device preparation adipic acid, the yield of cyclohexane conversion rate and adipic acid all obtains the improvement that is showing.
Description
Technical Field
The utility model relates to a microchannel reaction technical field, concretely relates to microchannel gas-liquid reaction unit.
Background
Adipic acid is an important aliphatic dicarboxylic acid, is mainly used for producing nylon 66 salt, further produces nylon 66 resin and fibers, polyester polyol, plasticizer and the like, and has wide application.
At present, methods for industrially producing adipic acid mainly comprise a KA oil (cyclohexanone, cyclohexanol) oxidation method and a cyclohexene hydrous nitric acid oxidation method. However, both of these methods use highly corrosive nitric acid as an oxidizing agent, and release a large amount of nitrogen oxides during the production process, which causes serious environmental pollution, and also has problems such as treatment of nitric acid vapor and spent acid solution. With the production idea of environmental protection, the substitution problem of nitric acid oxidation process is more and more emphasized.
The preparation of adipic acid by directly oxidizing cyclohexane with air or oxygen is a nitric acid substitution process with great application prospect. In 1940, the U.S. Pat. No. 2,185,3493 first proposed the preparation of adipic acid by one-step oxidation of cyclohexane with air as an oxidant, cobalt acetate as a catalyst and acetic acid as a solvent. The method successfully avoids the problems of nitrogen oxide generation and equipment corrosion caused by nitric acid in the traditional method. However, in order to prevent the formation of a large amount of by-products by deep oxidation, it is necessary to carry out the reaction at a low temperature and to control the conversion of cyclohexane, so that productivity and yield are not high. The Chinese patent CN1157605A improves the method and realizes the recycling of the catalyst. Chinese patents CN1247501C, CN1218922C and CN1231449C disclose methods for preparing adipic acid by air oxidation of cyclohexane using metalloporphyrin as a catalyst. Chinese patents CN101239899B and CN101337878B disclose methods for preparing adipic acid by using carbon material as a carrier to load a nano ruthenium dioxide catalyst or directly as a catalyst. However, the above-mentioned processes are either too costly or the adipic acid yield is too low. Chinese patent CN104109083A uses acetic acid as solvent, N-hydroxyphthalimide (NHPI) and N-acetoxyphthalimide (NAPI) as radical catalyst, cobalt acetate and manganese acetate as metal catalyst, crown ether as cocatalyst, and air as oxidant to oxidize cyclohexane to prepare adipic acid. The method obviously improves the conversion rate of cyclohexane, but has complex catalytic system and difficult catalyst recovery. The processes are all intermittent reaction processes, the gas-liquid contact efficiency is low, the reaction time is long, and continuous production is not realized.
The microchannel reaction technology is a novel process strengthening technology for carrying out chemical reaction, heat exchange, mixing, separation and control in a three-dimensional process fluid channel with the characteristic dimension of 10-1000 mu m, and the core of the microchannel reactor is a microchannel reactor. Compared with the conventional reactor, the microchannel reactor has extremely small mass and heat transfer distance, can obviously improve the heat and mass transfer efficiency and the space utilization rate, realizes the accurate control of the reaction temperature, the reaction time and the material proportion, and has intrinsic safety. Chinese patent CN102746111A discloses a method for preparing a mixture of cyclohexanol, cyclohexanone and adipic acid by oxidizing cyclohexane with oxygen or air in a microchannel. The reaction temperature is 150 ℃ and 200 ℃, the pressure is 1.5-8MPa, and the molar ratio of oxygen or air to cyclohexane is (0.15-0.5): 1. however, in this method, the gas-liquid ratio is too low, resulting in incomplete reaction, low selectivity of adipic acid in the product, and a large amount of by-products need to be separated, resulting in increased energy consumption.
It follows that simply combining a conventional batch process with a microchannel reactor does not achieve good reaction results. This is because, for the microchannel reactor, if the atmospheric liquid ratio consistent with the conventional process is adopted, a large amount of bubbles will be generated in the microchannel, which will result in poor gas-liquid contact and decrease of the actual residence time of the material, and even cause the reaction not to be initiated (chem.eng.res.des.,2010, 88: 255-); on the other hand, if the low gas-liquid ratio in the chinese patent CN102746111A is adopted, good contact can be ensured, but the reaction degree is low, and a large amount of side reactions occur, resulting in poor reaction selectivity. Therefore, the key point for developing the technology is to select a proper air inlet mode and achieve reasonable matching with the microchannel reactor.
SUMMERY OF THE UTILITY MODEL
The utility model aims at overcoming the intermittent type reaction technology gas-liquid contact inefficiency that prior art exists, reaction selectivity is poor big, and a large amount of accessory substances need separate, make the problem that the energy consumption increases, a microchannel gas-liquid reaction device and the method of strengthening gas-liquid reaction and preparation adipic acid are provided, the utility model discloses a microchannel device carries out gas-liquid reaction and carries out serialization production, through the technology of segmentation oxidation, will induce phase and reaction phase to go on respectively, through the good matching between gas-liquid mass transfer rate and the reaction rate, reduce the emergence of induction phase side reaction, improve reaction efficiency, belong to a low carbon environmental protection, energy saving and emission reduction's process route.
In order to achieve the above objects, one aspect of the present invention provides a microchannel gas-liquid reactor, which comprises a top plate, an upper heat exchange plate, a reaction plate and a lower heat exchange plate, which are sequentially stacked from top to bottom,
the reaction plate comprises a first micro-mixing structure, a first micro-reaction channel, a second micro-mixing structure, a second micro-reaction channel and a product outlet which are sequentially arranged according to the material trend, a liquid phase inlet and a first gas phase inlet are communicated with an inlet of the first micro-mixing structure, a second gas phase inlet is communicated with an outlet of the first micro-reaction channel and an inlet of the second micro-mixing structure, and the first micro-reaction channel and the second micro-reaction channel have different structures.
Preferably, the first micro-reaction channel has a structure of zigzag, linear or wave-shaped periodically arranged, more preferably zigzag.
Preferably, the equivalent diameter D of the first micro-reaction channel1Is 50-3000 μm, more preferably 200-1000 μm.
Preferably, the distance between two adjacent periodically arranged structural units is 5-50D1More preferably 10-20D1。
Preferably, the second micro reaction channel has a structure of a circle, a triangle, a diamond, or a rectangle, which are periodically arranged, and more preferably, a circle or a diamond.
Preferably, the equivalent diameter D of the second micro-reaction channel2At 50-3000 μm, more preferably at 200-1000 μm.
Preferably, the equivalent diameter of the periodically arranged structural units of the second micro-reaction channel is 1 to 5D2More preferably 2-3D2。
Preferably, the distance between two adjacent periodically arranged structural units is 5-20D2More preferably 5-10D2。
Preferably, the first micro-hybrid structure and the second micro-hybrid structure are both T-type hybrid structures or Y-type hybrid structures, more preferably T-type hybrid structures.
Preferably, the equivalent diameters of the first and second micro-mixing structures are both 50-500 μm, more preferably 100-300 μm.
Preferably, a heat exchange medium inlet and a heat exchange medium outlet are arranged on the top plate, and a heat exchange medium enters the upper heat exchange plate and the lower heat exchange plate from the heat exchange medium inlet, exchanges heat with the reaction plate, and flows out from the heat exchange medium outlet.
A second aspect of the present invention provides a method of enhancing a gas-liquid reaction, the method being carried out using a microchannel apparatus as described hereinbefore, the method comprising the steps of:
(1) the liquid phase raw material entering through the liquid phase inlet is in mixed contact with the first gas phase raw material entering through the first gas phase inlet at the first micro-mixing structure;
(2) the fluid obtained from the outlet of the first micro-mixing structure enters a first micro-reaction channel to carry out a first-stage reaction;
(3) the fluid obtained from the outlet of the first micro-reaction channel is in mixed contact with a second gas-phase raw material entering through a second gas-phase inlet at a second micro-mixing structure;
(4) and the fluid obtained from the outlet of the second micro-mixing structure enters a second micro-reaction channel to carry out second-stage reaction, and the obtained product is discharged through a product outlet.
A third aspect of the present invention provides a process for the preparation of adipic acid, the process being carried out using a microchannel apparatus as described hereinbefore, the process comprising the steps of:
(1) the liquid-phase raw material entering through the liquid-phase inlet is in mixed contact with the first gas oxidant entering through the first gas-phase inlet at the first micro-mixing structure, wherein the liquid-phase raw material contains a catalyst, a solvent and cyclohexane;
(2) the fluid obtained from the outlet of the first micro-mixing structure enters a first micro-reaction channel to carry out a first-stage reaction;
(3) the fluid obtained from the outlet of the first micro-reaction channel is in mixed contact with a second gas-phase oxidant entering through a second gas-phase inlet at a second micro-mixing structure;
(4) the fluid obtained from the outlet of the second micro-mixing structure enters a second micro-reaction channel to carry out second-stage reaction, and the obtained product is discharged through a product outlet;
preferably, the catalyst is at least one of cobalt oxide, cobalt hydroxide or cobalt salt of oxyacid, more preferably cobalt acetate;
preferably, the solvent is at least one of acetic acid, acetonitrile and ethyl acetate, and more preferably acetic acid;
preferably, the first gas phase oxidant and the second gas phase oxidant are the same or different and are each air, oxygen or ozone, preferably oxygen or ozone.
Preferably, in step (1), the molar ratio of the catalyst, solvent and cyclohexane is (0.0001-0.1): (0.1-10): 1;
preferably, in the first stage reaction, the molar ratio of the first gas-phase oxidant to cyclohexane is 0.01 to 0.2, more preferably 0.02 to 0.1;
preferably, in the second stage reaction, the molar ratio of the second gaseous oxidant to cyclohexane is from 0.02 to 10, more preferably from 0.05 to 5;
preferably, the reaction time of the first stage reaction is 0.1-10min, more preferably 0.5-2 min;
preferably, the reaction time of the second stage reaction is 0.5-50min, more preferably 1.5-10 min;
preferably, the reaction time of the first stage reaction and the second stage reaction is 70-150 ℃, more preferably 110-130 ℃;
preferably, the reaction pressure of the first stage reaction and the second stage reaction is 1 to 10MPa, more preferably 3 to 7 MPa.
Microchannel gas-liquid reaction unit can realize the serialization production of gas-liquid reaction, through the technology of segmentation oxidation, separately go on first section reaction and second section reaction, be about to induction phase and reaction phase and go on respectively. Through the good matching between the gas-liquid mass transfer rate and the reaction rate, the occurrence of side reaction in the induction period is reduced, the reaction efficiency is improved, the reaction retention time is shortened from several hours to several minutes, and the contradiction between the conversion rate and the reaction selectivity is effectively solved. Use microchannel gas-liquid reaction unit prepare adipic acid, the yield of cyclohexane conversion rate and adipic acid all is showing and is improving, through microchannel gas-liquid reaction unit realize the serialization production of gas-liquid reaction, belong to a low carbon environmental protection, energy saving and emission reduction's process route.
Drawings
FIG. 1 is a view of a microchannel gas-liquid reaction apparatus;
FIG. 2 is a schematic view of a microchannel reaction plate;
FIG. 3 is a schematic diagram of the features of a first micro-reaction channel and a second micro-reaction channel.
Description of the reference numerals
1 top plate 2 upper heat exchange plate
3 reaction plate 4 lower heat exchange plate
5 liquid phase inlet 6 first gas phase inlet
7 second gas phase inlet 8 product outlet
9 heat exchange medium inlet and 10 heat exchange medium outlet
11 first micro-mixing structure 12 first micro-reaction channel
13 second micro-mixing structure 14 second micro-reaction channel
Detailed Description
The following detailed description of the embodiments of the present invention will be made with reference to the accompanying drawings. It is to be understood that the description of the embodiments herein is for purposes of illustration and explanation only and is not intended to limit the invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The utility model provides a micro-channel gas-liquid reaction device, as shown in figure 1-2, which comprises a top plate 1, an upper heat exchange plate 2, a reaction plate 3 and a lower heat exchange plate 4 which are sequentially overlapped from top to bottom, wherein,
the reaction plate 3 comprises a first micro-mixing structure 11, a first micro-reaction channel 12, a second micro-mixing structure 13, a second micro-reaction channel 14 and a product outlet 8 which are sequentially arranged according to the material trend, a liquid phase inlet 5 and a first gas phase inlet 6 are communicated with an inlet of the first micro-mixing structure 11, a second gas phase inlet 7 is communicated with an outlet of the first micro-reaction channel 12 and an inlet of the second micro-mixing structure 13, and the first micro-reaction channel 12 and the second micro-reaction channel 14 have different structures.
Microchannel gas-liquid reaction unit can realize the serialization production of gas-liquid reaction, through the technology of segmentation oxidation, will induce phase and reaction phase and go on respectively, through the good matching between gas-liquid mass transfer rate and the reaction rate, reduce the emergence of induction phase side reaction, improve reaction efficiency. Through microchannel gas-liquid reaction unit can shorten reaction dwell time to several minutes by several hours, effectively solved the contradiction between conversion rate and the reaction selectivity, belong to a low carbon environmental protection, energy saving and emission reduction's process route.
In the device of the present invention, as shown in FIG. 3, the structure of the first micro reaction channel 12 may be a zigzag, linear or wave shape arranged periodically, preferably a zigzag shape.
In the device of the present invention, the equivalent diameter D of the first micro reaction channel 121Is 50-3000 μm, preferably 200-1000 μm.
In the device of the present invention, the distance between two adjacent periodically arranged structural units is 5-50D1Preferably 10-20D1。
In the device of the present invention, as shown in FIG. 3, the structure of the second micro reaction channel 14 may be a circle, a triangle, a diamond or a rectangle, preferably a circle or a diamond, which are periodically arranged.
In the device of the present invention, the equivalent diameter D of the second micro reaction channel 142At 50-3000 μm, preferably 200-1000 μm.
In the device of the present invention, the equivalent diameter of the periodically arranged structural units of the second micro reaction channel 14 is 1 to 5D2Preferably 2-3D2。
In the device of the present invention, the distance between two adjacent periodically arranged structural units is 5-20D2Preferably 5-10D2。
In the device of the present invention, the first micro-mixing structure 11 and the second micro-mixing structure 12 are T-type mixing structure or Y-type mixing structure, preferably T-type mixing structure.
In the device of the present invention, the equivalent diameters of the first micro-mixing structure 11 and the second micro-mixing structure 13 are both 50-500 μm, preferably 100-300 μm.
In the device of the present invention, as shown in fig. 1, a heat exchange medium inlet 9 and a heat exchange medium outlet 10 are provided on the top plate 1, and the heat exchange medium is passed through the heat exchange medium inlet 9, enters the upper heat exchange plate 2 and the lower heat exchange plate 4, exchanges heat with the reaction plate 3, and is passed through the heat exchange medium outlet 10.
The second aspect of the present invention provides a method for enhancing a gas-liquid reaction, which is carried out by the microchannel apparatus described above, the method comprising the steps of:
(1) the liquid phase raw material entering through the liquid phase inlet 5 is in mixing contact with the first gas phase raw material entering through the first gas phase inlet 6 at the first micro-mixing structure 11;
(2) the fluid obtained from the outlet of the first micro-mixing structure 11 enters the first micro-reaction channel 12 to perform a first stage reaction;
(3) the fluid obtained from the outlet of the first micro-reaction channel 12 is mixed and contacted with the second gas-phase raw material entering through the second gas-phase inlet 7 at the second micro-mixing structure 13;
(4) the fluid obtained from the outlet of the second micro-mixing structure 13 enters the second micro-reaction channel 14 for second-stage reaction, and the obtained product is discharged through the product outlet 8.
The utility model provides a method of strengthening gas-liquid reaction based on microchannel technique has better suitability, is applicable to the serialization production that has the induced phase of reaction's multiple different gas-liquid reaction processes, especially to cyclohexane oxidation preparation adipic acid process, and the effect is more obvious.
A third aspect of the present invention provides a process for the preparation of adipic acid, the process being carried out using a microchannel apparatus as described hereinbefore, the process comprising the steps of:
(1) a liquid-phase raw material entering through a liquid-phase inlet 5 is in mixed contact with a first gaseous oxidant entering through a first gas-phase inlet 6 at a first micro-mixing structure 11, wherein the liquid-phase raw material contains a catalyst, a solvent and cyclohexane;
(2) the fluid obtained from the outlet of the first micro-mixing structure 11 enters the first micro-reaction channel 12 to perform a first stage reaction;
(3) the resulting fluid at the outlet of the first micro-reaction channel 12 is brought into mixing contact with the second gas-phase oxidant entering through the second gas-phase inlet 7 at the second micro-mixing structure 13.
(4) The fluid obtained from the outlet of the second micro-mixing structure 13 enters the second micro-reaction channel 14 for second-stage reaction, and the obtained product is discharged through the product outlet 8.
The utility model provides a microchannel device and method of preparation adipic acid have adopted gas oxidants such as cleaner oxygen to replace the nitric acid oxidant in the traditional handicraft, have reduced the three wastes and have discharged, have simplified process flow, have avoided cyclohexane and oxygen to form the possibility of explosive gas mixture, have guaranteed that process flow has good security.
In the method for preparing adipic acid of the present invention, the catalyst is at least one of cobalt oxide, cobalt hydroxide or cobalt salt of oxyacid, preferably cobalt acetate.
In the method for preparing adipic acid of the present invention, the solvent is at least one of acetic acid, acetonitrile and ethyl acetate, preferably acetic acid.
In the method for preparing adipic acid of the present invention, the first gas-phase oxidizing agent and the second gas-phase oxidizing agent are the same or different and are each air, oxygen or ozone. The first gas phase oxidant is preferably oxygen or ozone and the second gas phase oxidant is preferably oxygen.
In the method for preparing adipic acid according to the present invention, in the step (1), the molar ratio of the catalyst, the solvent and cyclohexane is (0.0001-0.1): (0.1-10): 1, preferably (0.002-0.05): (0.6-8): 1, more preferably (0.008-0.09): (1-7): 1.
in the method for preparing adipic acid of the present invention, in the first stage reaction, the molar ratio of the first gas-phase oxidant to cyclohexane is 0.01 to 0.2, preferably 0.02 to 0.1.
In the method for preparing adipic acid of the present invention, in the second stage reaction, the molar ratio of the second gaseous oxidant to cyclohexane is 0.02 to 10, preferably 0.05 to 5.
In the method for preparing adipic acid of the present invention, the reaction time of the first stage reaction is 0.1-10min, preferably 0.5-2 min.
In the method for preparing adipic acid of the present invention, the reaction time of the second stage reaction is 0.5-50min, preferably 1.5-10 min.
In the method for preparing adipic acid of the present invention, the reaction time of the first stage reaction and the second stage reaction is 70-150 ℃, preferably 110-.
In the method for preparing adipic acid of the present invention, the reaction pressure of the first stage reaction and the second stage reaction is 1 to 10MPa, preferably 3 to 7 MPa.
The utility model provides a method for preparing adipic acid in microchannel realizes the serialization production of cyclohexane direct oxidation system adipic acid, process through the sectional oxidation, go on induction phase and reaction respectively, through the good matching between gas-liquid mass transfer rate and the reaction rate, the emergence of induction phase side reaction has been reduced, the reaction efficiency has been improved, shorten reaction dwell time to several minutes by several hours, effectively solved the contradiction between conversion rate and the reaction selectivity, the yield of cyclohexane conversion rate and adipic acid all is showing and is improving, belong to a low carbon environmental protection, energy saving and emission reduction's process route.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
Example 1
This example was carried out using the microchannel gas-liquid reactor shown in FIGS. 1 to 2. As shown in fig. 1, the microchannel gas-liquid reaction device comprises a top plate 1, an upper heat exchange plate 2, a reaction plate 3 and a lower heat exchange plate 4 which are sequentially stacked from top to bottom, wherein,
as shown in fig. 2, the reaction plate 3 includes a first micro-mixing structure 11, a first micro-reaction channel 12, a second micro-mixing structure 13, a second micro-reaction channel 14 and a product outlet 8, which are arranged in sequence according to the material direction, the liquid phase inlet 5 and the first gas phase inlet 6 are communicated with the inlet of the first micro-mixing structure 11, and the second gas phase inlet 7 and the outlet of the first micro-reaction channel 12 are communicated with the inlet of the second micro-mixing structure 13;
a heat exchange medium inlet 9 and a heat exchange medium outlet 10 are arranged on the top plate 1, and a heat exchange medium enters the upper heat exchange plate 2 and the lower heat exchange plate 4 from the heat exchange medium inlet 9, exchanges heat with the reaction plate 3 and flows out from the heat exchange medium outlet 10;
wherein the first micro reaction channel 12 has a zigzag structure with a periodic arrangement, and the equivalent diameter D of the first micro reaction channel 121At 400 μm, the distance between two adjacent periodically arranged structural units of the first micro-reaction channel 12 is 15D1；
The structure of the second micro reaction channel 14 is a circle arranged periodically, and the equivalent diameter D of the second micro reaction channel 142400 μm, the equivalent diameter of the periodically arranged structural units of the second micro reaction channel 14 being 3D2The distance between two adjacent structural units arranged periodically of the second micro-reaction channel 14 is 5D2；
The first micro-hybrid structure 11 and the second micro-hybrid structure 13 are both T-shaped hybrid structures, and the equivalent diameters of the first micro-hybrid structure 11 and the second micro-hybrid structure 13 are both 200 μm.
An experiment for preparing adipic acid by cyclohexane step-by-step oxidation is carried out in the microchannel gas-liquid reaction device, and the method comprises the following steps: the heat conducting oil is introduced to control the reaction temperature of the micro reaction (the first stage reaction and the second stage reaction) to be 120 ℃, and the pressure of the system (the first stage reaction and the second stage reaction) to be 5MPa is controlled by a back pressure valve connected with an outlet pipeline. Mixing cobalt acetate, acetic acid and cyclohexane according to a molar ratio of 0.0025:3:1 to prepare a liquid-phase raw material, and controlling the molar ratio of oxygen (a first gas oxidant) to cyclohexane to be 0.05; the liquid phase raw material reaction material and oxygen are mixed in the first micro-mixing structure 11 and then enter the first micro-reaction channel 12 to carry out initiation reaction (first stage reaction), and the reaction time is 1 min; the reaction liquid flowing out of the first micro reaction channel 12 is mixed with another oxygen (second gas oxidant) feed in a second micro mixing structure 13, and the molar ratio of the oxygen (second gas oxidant) to the cyclohexane is controlled to be 3; after mixing, the mixture enters a second micro reaction channel 14 for reaction (second stage reaction), the reaction time is 3min, and products are collected at an outlet. And cooling and crystallizing the reaction product, then carrying out suction filtration, washing twice with dilute hydrochloric acid, washing twice with cold deionized water, and airing to obtain adipic acid. Analysis gave a cyclohexane conversion of 22.2% and an adipic acid selectivity of 95.1%.
Example 2
Adipic acid was prepared according to the apparatus and method described in example 1, except that first micro-hybrid structure 11 and second micro-hybrid structure 13 were each Y-type hybrid structures and that first micro-hybrid structure 11 and second micro-hybrid structure 13 each had an equivalent diameter of 400 μm. Analysis gave a cyclohexane conversion of 20.2% and an adipic acid selectivity of 88.6%.
Example 3
Adipic acid was prepared according to the apparatus and method described in example 1, except that first micro-hybrid structure 11 was a T-type hybrid structure, and the equivalent diameters of first micro-hybrid structure 11 were all 200 μm; the second mixing structures 13 are all Y-shaped mixing structures, and the equivalent diameter of the second micro-mixing structure 13 is 400 μm. Analysis gave a cyclohexane conversion of 13.7% and an adipic acid selectivity of 75.5%.
Example 4
Adipic acid was prepared according to the apparatus and method described in example 1, except that the equivalent diameters of the first micro-mixing structures 11 were all 500 μm; the equivalent diameter of the first micro reaction channel 12 is 1000. mu.m. Analysis gave a cyclohexane conversion of 17.2% and an adipic acid selectivity of 84.8%.
Example 5
Adipic acid was prepared according to the apparatus and method described in example 1, except that the equivalent diameters of the first micro-mixing structures 11 were all 500 μm; the equivalent diameter of the first micro reaction channel 12 is 2000. mu.m. Analysis gave a cyclohexane conversion of 13.1% and an adipic acid selectivity of 77.7%.
Example 6
Adipic acid was prepared according to the apparatus and method described in example 1, except that the equivalent diameters of the first micro-mixing structures 11 were all 100 μm; the equivalent diameter of the first micro reaction channel 12 is 100. mu.m. Analysis gave a cyclohexane conversion of 14.6% and an adipic acid selectivity of 67.2%.
Example 7
Adipic acid was prepared by the apparatus and method as described in example 1, except that the structure of the first micro reaction channel 12 was a wave shape periodically arranged. Analysis gave a cyclohexane conversion of 17.5% and an adipic acid selectivity of 88.4%.
Example 8
Adipic acid was prepared by the apparatus and method as described in example 1, except that the structure of the first micro reaction channel 12 was a periodically arranged step-like structure. Analysis gave a cyclohexane conversion of 12.2% and an adipic acid selectivity of 80.6%.
Example 9
Adipic acid was prepared by the apparatus and method as described in example 1, except that the structure of the first micro reaction channel 12 was a zigzag shape periodically arranged; the distance between two adjacent structural units which are arranged periodically of the first micro-reaction channel 12 is 5D1. Analysis gave a cyclohexane conversion of 15.3% and an adipic acid selectivity of 77.1%.
Example 10
Adipic acid was prepared by the apparatus and method as described in example 1, except that the structure of the first micro reaction channel 12 was a zigzag shape periodically arranged; the distance between two adjacent structural units arranged periodically of the first micro-reaction channel 12 is 30D1. Analysis gave a cyclohexane conversion of 16.6% and an adipic acid selectivity of 87.2%.
Example 11
Adipic acid was prepared according to the apparatus and method described in example 1, except thatThat is, the structure of the second micro reaction channel 14 is a circle periodically arranged; the equivalent diameter D of the second micro-reaction-channel 142And 200 μm. Analysis gave a cyclohexane conversion of 14.7% and an adipic acid selectivity of 74.8%.
Example 12
Adipic acid was prepared according to the apparatus and method described in example 1, except that the second micro-hybrid structure 13 was a T-type hybrid structure, and the equivalent diameter of the second micro-hybrid structure 13 was 500 μm; the structure of the second micro reaction channel 14 is a circle arranged periodically, and the equivalent diameter D of the second micro reaction channel 142And 1500 μm. Analysis gave a cyclohexane conversion of 12.6% and an adipic acid selectivity of 72.2%.
Example 13
Adipic acid was prepared by the apparatus and method as described in example 1, except that the structure of the second micro-reaction channel 14 was a periodically arranged circle, and the equivalent diameter D of the second micro-reaction channel 142Is 400 μm; the equivalent diameter of the periodically arranged structural units of the second micro-reaction channel 14 is 5D2(ii) a The distance between two adjacent structural units arranged periodically of the second micro-reaction channel 14 is 10D2. Analysis gave a cyclohexane conversion of 18.2% and an adipic acid selectivity of 88.6%.
Example 14
Adipic acid was prepared by the apparatus and method as described in example 1, except that the second micro reaction channel 14 had a structure of periodically arranged diamonds. Analysis gave 21.7% conversion of cyclohexane and 85.4% selectivity to adipic acid.
Example 15
Adipic acid was prepared by the apparatus and method as described in example 1, except that the structure of the second micro reaction channel 14 was a periodically arranged rectangle. Analysis gave a cyclohexane conversion of 17.1% and an adipic acid selectivity of 80.8%.
Example 16
Adipic acid was prepared by the apparatus and method as described in example 1, except that the structure of the second micro reaction channel 14 was a periodically arranged triangle. Analysis gave a cyclohexane conversion of 18.1% and an adipic acid selectivity of 75.4%.
Example 17
Adipic acid was prepared according to the apparatus and method described in example 1, except that the molar ratio of oxygen (first gaseous oxidant) to cyclohexane fed into the first micro-reaction channel was controlled to be 0.05. Analysis gave a cyclohexane conversion of 20.7% and an adipic acid selectivity of 91.3%.
Example 18
Adipic acid was prepared according to the apparatus and method described in example 1, except that the molar ratio of oxygen (first gaseous oxidant) to cyclohexane fed into the first micro-reaction channel was controlled to be 0.01. Analysis gave 10.4% conversion of cyclohexane and 75.4% selectivity to adipic acid.
Example 19
Adipic acid was prepared according to the apparatus and method described in example 1, except that the molar ratio of oxygen (first gaseous oxidant) to cyclohexane fed into the first micro-reaction channel was controlled to be 0.2. Analysis gave a cyclohexane conversion of 17.2% and an adipic acid selectivity of 82.0%.
Example 20
Adipic acid was produced by the apparatus and method as described in example 1, except that the system pressure (first-stage reaction and second-stage reaction) was controlled to be 8MPa by a back pressure valve connected to the outlet line; the molar ratio of oxygen (first gaseous oxidant) to cyclohexane entering the first micro-reaction channel was controlled to 0.1. Analysis gave a cyclohexane conversion of 27.8% and an adipic acid selectivity of 71.8%.
Example 21
Adipic acid was produced by the apparatus and method as described in example 1, except that the system pressure (first-stage reaction and second-stage reaction) was controlled to 2MPa by a back pressure valve connected to the outlet line; the molar ratio of oxygen (first gaseous oxidant) to cyclohexane entering the first micro-reaction channel was controlled to 0.02. Analysis gave 10.6% conversion of cyclohexane and 88.2% selectivity to adipic acid.
Example 22
Adipic acid was prepared by the apparatus and method as described in example 1, except that heat transfer oil was introduced to control the reaction temperature of the micro-reactions (first stage reaction and second stage reaction) to 90 ℃. Analysis gave a cyclohexane conversion of 7.2% and an adipic acid selectivity of 83.1%.
Example 23
Adipic acid was prepared by the apparatus and method as described in example 1, except that heat transfer oil was introduced to control the reaction temperature of the micro-reactions (first stage reaction and second stage reaction) to 150 ℃. Analysis gave a cyclohexane conversion of 25.6% and an adipic acid selectivity of 66.3%.
Example 24
Adipic acid was prepared according to the apparatus and method described in example 1, except that the molar ratio of oxygen (second gaseous oxidant) to cyclohexane in the second micro-reaction channel was controlled to be 1. Analysis gave a cyclohexane conversion of 13.6% and an adipic acid selectivity of 80.3%.
Example 25
Adipic acid was prepared according to the apparatus and method described in example 1, except that the molar ratio of oxygen (second gaseous oxidant) to cyclohexane in the second micro-reaction channel was controlled to be 8. Analysis gave 10.3% conversion of cyclohexane and 85.5% selectivity to adipic acid.
Example 26
Adipic acid was prepared according to the apparatus and method described in example 1, except that the liquid phase raw material reactant and oxygen were mixed in the first micro-mixing structure 11 and then introduced into the first micro-reaction channel 12 for initiation reaction (first stage reaction) for 5 min. Analysis gave a cyclohexane conversion of 24.7% and an adipic acid selectivity of 80.6%.
Example 27
Adipic acid was prepared according to the apparatus and method described in example 1, except that the liquid phase raw material reactant and oxygen were mixed in the first micro-mixing structure 11 and then introduced into the first micro-reaction channel 12 for the initiation reaction (first stage reaction) for 0.2 min. Analysis gave a cyclohexane conversion of 7.3% and an adipic acid selectivity of 78.4%.
Example 28
Adipic acid was prepared by the apparatus and method as described in example 1, except that the reaction time for the reaction in the second micro reaction channel 14 after mixing was 1 min. Analysis gave 10.8% conversion of cyclohexane and 92.6% selectivity to adipic acid.
Example 29
Adipic acid was prepared according to the apparatus and method described in example 1, except that the reaction time for the reaction in the second micro reaction channel 14 after mixing was 20 min. Analysis gave a cyclohexane conversion of 28.3% and an adipic acid selectivity of 65.5%.
Example 30
Adipic acid was prepared by the apparatus and method as described in example 1, except that cobalt acetate, acetic acid and cyclohexane were mixed at a molar ratio of 0.005:5:1 to prepare a liquid phase raw material. Analysis gave a cyclohexane conversion of 18.7% and an adipic acid selectivity of 75.2%.
Comparative example 1
A T-shaped micro-channel mixer with the equivalent diameter of 200 mu m and a micro-tube reactor with the inner diameter of 400 mu m are connected in series to form a micro-channel reaction system. An experiment for preparing adipic acid by cyclohexane oxidation was carried out in the microchannel reactor described above. The temperature of the micro reaction is controlled to be 120 ℃ by introducing heat conducting oil, and the system pressure is controlled to be 5MPa by a back pressure valve connected with an outlet pipeline. Cobalt acetate, acetic acid and cyclohexane are mixed according to a molar ratio of 0.0025:3:1 to prepare a liquid phase raw material. The molar ratio of oxygen to cyclohexane was controlled to 0.05. Mixing the liquid phase raw material reaction material and oxygen in a T-shaped microchannel mixer, then feeding the mixture into a microchannel reactor for reaction, wherein the reaction time is 30min, and collecting the product at an outlet. Analysis gave a cyclohexane conversion of 3.2% and an adipic acid selectivity of 60.1%.
Comparative example 2
An experiment for preparing adipic acid by oxidation of cyclohexane was carried out in accordance with the microchannel reactor described in comparative example 1, except that the molar ratio of oxygen to cyclohexane was controlled to be 3. Analysis gave a cyclohexane conversion of 5.2% and an adipic acid selectivity of 35.2%.
Test example
The cyclohexane conversion and adipic acid selectivity obtained in examples 1 to 30 and comparative examples 1 to 2 were analyzed, and the results of the analysis are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the microchannel gas-liquid reactor of the present invention can be used for continuous production of adipic acid, and the conversion rate of cyclohexane and the selectivity of adipic acid are significantly improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. In the technical idea scope of the present invention, it can be right to the technical solution of the present invention perform multiple simple modifications, including each technical feature combined in any other suitable manner, these simple modifications and combinations should be regarded as the disclosed content of the present invention, and all belong to the protection scope of the present invention.
Claims (10)
1. A micro-channel gas-liquid reaction device comprises a top plate (1), an upper heat exchange plate (2), a reaction plate (3) and a lower heat exchange plate (4) which are sequentially overlapped from top to bottom, wherein,
the reaction plate (3) comprises a first micro-mixing structure (11), a first micro-reaction channel (12), a second micro-mixing structure (13), a second micro-reaction channel (14) and a product outlet (8) which are sequentially arranged according to the material trend, a liquid phase inlet (5) and a first gas phase inlet (6) are communicated with an inlet of the first micro-mixing structure (11), a second gas phase inlet (7) is communicated with an outlet of the first micro-reaction channel (12) and an inlet of the second micro-mixing structure (13), and the first micro-reaction channel (12) and the second micro-reaction channel (14) have different structures.
2. The microchannel gas-liquid reaction device as set forth in claim 1, wherein the first microchannel (12) has a zigzag, linear or wavy structure in a periodic arrangement.
3. The microchannel gas-liquid reaction device as set forth in claim 1 or 2, wherein the equivalent diameter D of the first microchannel (12)1Is 50-3000 μm.
4. The microchannel gas-liquid reaction device as set forth in claim 1, wherein the second microchannel (14) has a structure of a circle, a triangle, a diamond or a rectangle periodically arranged.
5. The microchannel gas-liquid reaction device as claimed in claim 1 or 4, wherein the equivalent diameter D of the second microchannel (14)2At 50-3000 μm.
6. The microchannel gas-liquid reaction device as set forth in claim 4, wherein the equivalent diameter of the periodically arranged structural units of the second microchannel (14) is 1 to 5D2。
7. The microchannel gas-liquid reaction apparatus as set forth in claim 6, wherein the distance between two adjacent periodically arranged structural units is 5 to 20D2。
8. The microchannel gas-liquid reaction device of claim 1, wherein the first micro-mixing structure (11) and the second micro-mixing structure (13) are both T-type mixing structures or Y-type mixing structures.
9. The microchannel gas-liquid reaction device according to claim 1 or 8, wherein the equivalent diameters of the first micro-mixing structure (11) and the second micro-mixing structure (13) are each 50 to 500 μm.
10. The microchannel gas-liquid reactor as recited in claim 1, wherein the top plate (1) is provided with a heat exchange medium inlet (9) and a heat exchange medium outlet (10), and a heat exchange medium enters the upper heat exchange plate (2) and the lower heat exchange plate (4) from the heat exchange medium inlet (9), exchanges heat with the reaction plate (3), and flows out from the heat exchange medium outlet (10).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201921079790.1U CN210700032U (en) | 2019-07-10 | 2019-07-10 | Microchannel gas-liquid reaction device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201921079790.1U CN210700032U (en) | 2019-07-10 | 2019-07-10 | Microchannel gas-liquid reaction device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN210700032U true CN210700032U (en) | 2020-06-09 |
Family
ID=70956980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201921079790.1U Withdrawn - After Issue CN210700032U (en) | 2019-07-10 | 2019-07-10 | Microchannel gas-liquid reaction device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN210700032U (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112206727A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Micro-channel gas-liquid reaction device, gas-liquid reaction strengthening method and adipic acid preparation method |
| CN112221444A (en) * | 2020-10-19 | 2021-01-15 | 中国科学院大连化学物理研究所 | System and method for continuously synthesizing clethodim |
-
2019
- 2019-07-10 CN CN201921079790.1U patent/CN210700032U/en not_active Withdrawn - After Issue
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112206727A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Micro-channel gas-liquid reaction device, gas-liquid reaction strengthening method and adipic acid preparation method |
| CN112206727B (en) * | 2019-07-10 | 2024-01-05 | 中国石油化工股份有限公司 | Microchannel gas-liquid reaction device and method for strengthening gas-liquid reaction and method for preparing adipic acid |
| CN112221444A (en) * | 2020-10-19 | 2021-01-15 | 中国科学院大连化学物理研究所 | System and method for continuously synthesizing clethodim |
| CN112221444B (en) * | 2020-10-19 | 2021-11-02 | 中国科学院大连化学物理研究所 | System and method for continuously synthesizing clethodim |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103936559B (en) | The method of continuous prodution Resorcinol | |
| CN210700032U (en) | Microchannel gas-liquid reaction device | |
| CN109456167A (en) | A method of using micro passage reaction by cyclohexanone synthesizing adipic acid | |
| CN112206727A (en) | Micro-channel gas-liquid reaction device, gas-liquid reaction strengthening method and adipic acid preparation method | |
| CN106380375B (en) | A kind of method of the continuous synthesizing adipic acid of micro passage reaction | |
| CN103254060A (en) | Method for preparing adipic acid through co-catalytic oxidation of six-carbon oxygenated compound and cyclohexane | |
| CN103724315A (en) | Method used for synthesizing cyclic carbonate in enhanced microreactor system | |
| CN105601588A (en) | Method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production | |
| CN112300033B (en) | Device and method for fully continuously synthesizing 2-nitro-4-methylsulfonyl benzoic acid from 4-methylsulfonyl toluene | |
| CN102219698B (en) | Method for producing C1-C4 alkyl nitrite ester | |
| CN112499592A (en) | System and process for preparing hydrogen peroxide based on anthraquinone method | |
| CN113967454A (en) | Device and method for high-selectivity continuous synthesis of mixed dinitrobenzene | |
| CN102746111A (en) | Cosynthesis device and method of cyclohexanol, cyclohexanone and adipic acid in microchannels | |
| CN107056670A (en) | A kind of preparation method of two tertiary base peroxide | |
| CN102266794B (en) | Method for producing magnetic-loaded titanium silicon molecular sieve catalyst and specialized colliding ultrasonic micro hybrid reactor | |
| CN104418752A (en) | Method for synthesizing single nitro-o-xylene employing catalytic nitration in micro-reactor | |
| CN1982273A (en) | Production of anone by cyclohexane liquid-phase oxidation | |
| CN112209816B (en) | Preparation method of adipic acid | |
| CN112358392B (en) | Method for efficiently synthesizing refined adipic acid by using tubular reactor | |
| CN110903181A (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN114956981A (en) | System and process for continuously producing butyric acid | |
| Luo et al. | Integrated microreaction systems of microdevices with conventional equipment | |
| US20110160447A1 (en) | Method for synthesizing acrolein | |
| CN220056681U (en) | System for isononanoic acid is prepared in isononanal oxidation | |
| CN114702521B (en) | Method for preparing high-purity triethyl phosphate by using green low-carbon micro-reaction synthesis technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| AV01 | Patent right actively abandoned | ||
| AV01 | Patent right actively abandoned | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20200609 Effective date of abandoning: 20240105 |
|
| AV01 | Patent right actively abandoned |
Granted publication date: 20200609 Effective date of abandoning: 20240105 |