CN111961026A - Reinforced micro-interface preparation system and method for cyclic carbonate - Google Patents
Reinforced micro-interface preparation system and method for cyclic carbonate Download PDFInfo
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- CN111961026A CN111961026A CN202010863174.6A CN202010863174A CN111961026A CN 111961026 A CN111961026 A CN 111961026A CN 202010863174 A CN202010863174 A CN 202010863174A CN 111961026 A CN111961026 A CN 111961026A
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- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 120
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 118
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 34
- 239000007800 oxidant agent Substances 0.000 claims description 30
- 230000001590 oxidative effect Effects 0.000 claims description 25
- 238000003860 storage Methods 0.000 claims description 18
- 230000021523 carboxylation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 18
- 239000004593 Epoxy Substances 0.000 description 17
- 239000012071 phase Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- JCSHYFOSLVIDGY-UHFFFAOYSA-N imidazol-1-yl hydrogen carbonate Chemical compound OC(=O)ON1C=CN=C1 JCSHYFOSLVIDGY-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- -1 styrene cyclic carbonate Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000405 induce cancer Toxicity 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a system and a method for preparing an enhanced micro-interface of cyclic carbonate, wherein the preparation system comprises: the system comprises a stirring kettle, a first carboxylation reaction kettle and a second carboxylation reaction kettle, wherein ionic liquid catalysts are filled in the stirring kettle, the first carboxylation reaction kettle and the second carboxylation reaction kettle; the side of stirred tank is provided with little interface unit, little interface unit comprises a plurality of external little interface generator. The reinforced micro-interface preparation system increases the mass transfer area of the phase boundary between carbon dioxide and the in-situ generated cyclic carbonate in the carboxylation reaction process, and performs carboxylation reaction after full mixing, thereby solving the problem that the carbon dioxide and the cyclic carbonate can not be fully mixed in a reaction kettle in the prior art.
Description
Technical Field
The invention relates to the field of preparation of cyclic carbonate, in particular to a system and a method for preparing a reinforced micro interface of cyclic carbonate.
Background
The cyclic carbonate is an important chemical product, and has wide application in the fields of organic synthesis intermediates, polar aprotic solvents, lithium ion battery electrolytes, polymer monomers and the like. The cyclic carbonate is industrially synthesized by carboxylation of an epoxy compound with carbon dioxide. The process adopts metal halide and ammonium salt as catalysts, and realizes the synthesis of the cyclic carbonate from the epoxy compound and the carbon dioxide under the pressure of 2.0-5.0MPa and the temperature of 100-150 ℃.
However, most epoxy compounds are toxic and may induce cancer. Compared with epoxy compounds, the olefin has wider sources, lower price and lower toxicity. Olefins can be made into compounds by epoxidation reactions. Olefin and carbon dioxide are used as raw materials, imidazole bicarbonate ionic liquid is used as a bifunctional catalyst, and olefin epoxidation reaction and epoxy compound and carbon dioxide carboxylation reaction are connected in series to synthesize the cyclic carbonate in one step. The olefin and carbon dioxide oxidation carboxylation method for producing the cyclic carbonate can reduce the cost of raw materials, avoid the separation and storage of epoxy compounds and simplify the production flow.
Simultaneously, when current carbon dioxide carboxylation reaction system prepared cyclic carbonate, carry out the carboxylation reaction through directly letting in liquid raw materials and carbon dioxide gas in the reation kettle, because carbon dioxide gas and liquid raw materials can't obtain intensive mixing in reation kettle to lead to the reaction to go on under higher carbon dioxide operating pressure, reaction efficiency is low, and the reaction energy consumption is high.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a reinforced micro-interface preparation system of cyclic carbonate, which is based on a micro-interface reaction reinforcing technology, carbon dioxide is efficiently crushed into micron-sized bubbles by a micro-interface generator and is dispersed into a liquid raw material to form a micro-interface system, so that the gas-liquid phase interface area in a carboxylation reaction kettle is increased by tens of times, the mass transfer rate and the macroscopic hydrogenation rate of gas phase to reaction liquid are greatly increased, the cyclic carbonate is directly synthesized from olefin and carbon dioxide, and the problem of low efficiency of a reaction system caused by insufficient mixing of carbon dioxide and the liquid raw material in the reaction kettle in the prior art is solved.
The second purpose of the invention is to provide a method for preparing cyclic carbonate by using the reinforced micro-interface preparation system, the cyclic carbonate obtained by the reaction has high purity and wide application, the application range of the cyclic carbonate is improved, and the method is worthy of wide popularization and application.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a reinforced micro-interface preparation system of cyclic carbonate, which comprises a stirring kettle, a first carboxylation reaction kettle and a second carboxylation reaction kettle, wherein ionic liquid catalysts are filled in the stirring kettle, the first carboxylation reaction kettle and the second carboxylation reaction kettle;
a micro-interface unit is arranged on the side surface of the stirring kettle, the micro-interface unit is composed of a plurality of external micro-interface generators, a main pipeline which is introduced into the micro-interface unit is simultaneously connected with an oxidant conveying pipeline and two branch pipelines of an olefin conveying pipeline, carbon dioxide is introduced into the micro-interface unit from the gas source conveying pipeline, and the carbon dioxide, the oxidant and the olefin enter the micro-interface unit to be used for crushing the carbon dioxide gas into micro-bubbles at the micron level;
a first reaction material liquid inlet is formed in the bottom of the first carboxylation reaction kettle and is communicated with the stirring kettle through an overflow pipe, two built-in micro-interface generators are arranged in the first carboxylation reaction kettle, a second reaction material liquid inlet is formed in the bottom of the second carboxylation reaction kettle and is communicated with the stirring kettle through the overflow pipe, and two micro-interface generators are also arranged in the second carboxylation reaction kettle;
each built-in micro interface generator is provided with a carbon dioxide feed inlet for dispersing and crushing carbon dioxide into micro bubbles under the condition that the reaction feed liquid is used as a medium;
and purifying the oxidation carboxylation reaction liquid which is reacted in the first carboxylation reaction kettle and the second carboxylation reaction kettle in sequence through a flash tank, a dehydration tower and a rectifying tower to obtain the cyclic carbonate product.
According to the reinforced micro-interface preparation system of the cyclic carbonate, the micro-interface unit is arranged in front of the stirring kettle, the micro-interface generators are arranged in the first carboxylation reaction kettle and the second carboxylation reaction kettle, and the entered carbon dioxide gas is dispersed and crushed into micro-bubbles, so that the mass transfer effect is improved, and the olefin solution, the oxidant aqueous solution and the reaction material liquid which are introduced into the micro-interface unit and the carboxylation reaction kettle are dispersed and crushed by matching with gas, which is equivalent to the action of a medium.
Preferably, the micro-interface generators arranged in the first carboxylation reaction kettle and the second carboxylation reaction kettle are arranged from top to bottom in sequence.
Preferably, a connecting channel is arranged between the first carboxylation reaction kettle and the second carboxylation reaction kettle for continuing carboxylation reaction in the second carboxylation reaction kettle.
Preferably, the external micro-interface generators are sequentially arranged from top to bottom along the vertical direction.
Preferably, the number of the external micro-interface generators is 3, and a connecting rod is connected between the bottom surface and the top surface between the adjacent micro-interface generators.
The micro interface unit of the invention is arranged at the outer side of the stirring kettle and is arranged in a mode of being sequentially arranged from top to bottom, and the oxidant, the olefin and the carbon dioxide are collected and then enter the micro-interface unit through the main pipeline, because the raw materials are added in a summarized mode, the fusion effect among the raw materials is improved, the carbon dioxide is added into each micro-interface generator in parallel, namely, a micro-interface system is formed in each micro-interface generator, so as to realize that the gas phase is fully dispersed and crushed in the micro interface generator on the premise of taking the liquid phase as a medium, the micro interface generator at the middle part is closest to the gas phase feed inlet, therefore, the micro-interface system is used as a micro-interface system for mainly dispersing and crushing, and then the two micro-interface generators on the upper part and the lower part form a secondary micro-interface system and a tertiary micro-interface system, and the effect of strengthening the carboxylation reaction is also achieved.
In addition, in order to play a good role in fixing, a connecting rod is specially arranged between the micro-interface generators so as to play a role in strengthening the fixing.
The reaction feed liquid after the addition reaction is carried out from the stirred tank enters into first carboxylation reation kettle and second carboxylation reation kettle from the overflow pipe through the feed liquid import of reaction after the liquid level to the cauldron top in, further carry out carboxylation oxidation reaction in first carboxylation reation kettle and second carboxylation reation kettle, every built-in micro interface generator side in the carboxylation reation kettle is provided with the carbon dioxide feed inlet, in order to make built-in micro interface generator more stable, the both sides of specially putting in micro interface generator are provided with the support, fix the inside at carboxylation reation kettle.
The micro-interface unit and the built-in micro-interface generator crush the carbon dioxide into micro-bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, so that the carbon dioxide contacts with the epoxy compound generated in situ in the state of the micro-bubbles to increase the phase boundary mass transfer area between the carbon dioxide and the epoxy compound generated in situ in the carboxylation reaction process, and the carbon dioxide and the epoxy compound are fully mixed and then subjected to carboxylation reaction, thereby solving the problem that the reaction efficiency of the system is reduced because the carbon dioxide and the epoxy compound cannot be fully mixed in a stirring kettle and a carboxylation reaction kettle in the prior art.
The external micro-interface generator and the internal micro-interface generator are of a pneumatic type, and carbon dioxide, olefin solution and oxidant solution are introduced into the micro-interface generator and then dispersed and crushed, so that the subsequent hydrogenation reaction is enhanced, impurities such as sulfur, nitrogen and the like are removed, and the mass transfer effect is improved.
Preferably, the oxidant conveying pipeline is connected with an oxidant storage tank, and tert-butyl hydroperoxide or hydrogen peroxide is stored in the oxidant storage tank. The first delivery pump is preferably arranged on the oxidant delivery line.
Preferably, the olefin conveying pipeline is connected with an olefin storage tank, and is used for conveying the olefin solution in the olefin storage tank to the micro interface unit through the olefin conveying pipeline. The olefin transfer line is preferably provided with a second transfer pump.
It will be appreciated by those skilled in the art that the micro-interface generator used in the present invention is described in the prior patents of the present inventor, such as the patents of application nos. CN201610641119.6, 201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN 207581700U. The detailed structure and operation principle of the micro bubble generator (i.e. micro interface generator) is described in detail in the prior patent CN201610641119.6, which describes that "the micro bubble generator comprises a body and a secondary crushing member, wherein the body is provided with a cavity, the body is provided with an inlet communicated with the cavity, the opposite first end and second end of the cavity are both open, and the cross-sectional area of the cavity decreases from the middle of the cavity to the first end and second end of the cavity; the secondary crushing member is disposed at least one of the first end and the second end of the cavity, a portion of the secondary crushing member is disposed within the cavity, and an annular passage is formed between the secondary crushing member and the through holes open at both ends of the cavity. The micron bubble generator also comprises an air inlet pipe and a liquid inlet pipe. "the specific working principle of the structure disclosed in the application document is as follows: liquid enters the micro-bubble generator tangentially through the liquid inlet pipe, and gas is rotated at a super high speed and cut to break gas bubbles into micro-bubbles at a micron level, so that the mass transfer area between a liquid phase and a gas phase is increased, and the micro-bubble generator in the patent belongs to a pneumatic micro-interface generator.
In addition, the first patent 201610641251.7 describes that the primary bubble breaker has a circulation liquid inlet, a circulation gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed inlet with the gas-liquid mixture outlet, which indicates that the bubble breakers all need to be mixed with gas and liquid, and in addition, as can be seen from the following drawings, the primary bubble breaker mainly uses the circulation liquid as power, so that the primary bubble breaker belongs to a hydraulic micro-interface generator, and the secondary bubble breaker simultaneously introduces the gas-liquid mixture into an elliptical rotating ball for rotation, thereby realizing bubble breaking in the rotating process, so that the secondary bubble breaker actually belongs to a gas-liquid linkage micro-interface generator. In fact, the micro-interface generator is a specific form of the micro-interface generator, whether it is a hydraulic micro-interface generator or a gas-liquid linkage micro-interface generator, however, the micro-interface generator adopted in the present invention is not limited to the above forms, and the specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can adopt.
Furthermore, the prior patent 201710766435.0 states that the principle of the bubble breaker is that high-speed jet flows are used to achieve mutual collision of gases, and also states that the bubble breaker can be used in a micro-interface strengthening reactor to verify the correlation between the bubble breaker and the micro-interface generator; moreover, in the prior patent CN106187660, there is a related description on the specific structure of the bubble breaker, see paragraphs [0031] to [0041] in the specification, and the accompanying drawings, which illustrate the specific working principle of the bubble breaker S-2 in detail, the top of the bubble breaker is a liquid phase inlet, and the side of the bubble breaker is a gas phase inlet, and the liquid phase coming from the top provides the entrainment power, so as to achieve the effect of breaking into ultra-fine bubbles, and in the accompanying drawings, the bubble breaker is also seen to be of a tapered structure, and the diameter of the upper part is larger than that of the lower part, and also for better providing the entrainment power for the liquid phase. Since the micro-interface generator was just developed in the early stage of the prior patent application, the micro-interface generator was named as a micro-bubble generator (CN201610641119.6), a bubble breaker (201710766435.0) and the like in the early stage, and is named as a micro-interface generator in the later stage along with the continuous technical improvement, and the micro-interface generator in the present invention is equivalent to the micro-bubble generator, the bubble breaker and the like in the prior art, and has different names.
In summary, the micro-interface generator of the present invention belongs to the prior art, although some bubble breakers belong to the type of pneumatic bubble breakers, some bubble breakers belong to the type of hydraulic bubble breakers, and some bubble breakers belong to the type of gas-liquid linkage bubble breakers, the difference between the types is mainly selected according to the different specific working conditions, and in addition, the connection between the micro-interface generator and the reactor and other equipment, including the connection structure and the connection position, is determined according to the structure of the micro-interface generator, which is not limited.
The liquid catalyst is a bifunctional catalyst of imidazole bicarbonate ionic liquid, the type of the oxidizing agent is t-butyl peroxygen aqueous solution (the mass fraction of t-butyl hydroperoxide is 70%), and the type of the catalyst is not limited as long as the oxidative carboxylation reaction can be smoothly performed.
Preferably, the oxidation carboxylation reaction liquid enters from the side wall of the flash tank, a flash product outlet is arranged at the top of the flash tank, a catalyst outlet is arranged at the bottom of the flash tank, the catalyst outlet is connected with the side wall of the carboxylation reaction kettle and used for returning the ionic liquid catalyst, and the flash product outlet is connected with the dehydration tower and used for dehydrating the flash product.
The oxidation carboxylation reaction liquid is conveyed to the inside of the flash tank for flash evaporation treatment, the ionic liquid catalyst after flash evaporation treatment is circularly returned to the inside of the carboxylation reaction kettle for being used for the oxidation carboxylation reaction in the reaction kettle again, and flash evaporation products obtained by flash evaporation are conveyed to the product purification unit (a dehydration tower and a rectification tower). And the product purification unit is used for sequentially dehydrating and rectifying other products obtained by flash evaporation to finally obtain the product cyclic carbonate.
Preferably, the dehydration product from the dehydration tower enters the rectification tower for rectification, the obtained product is stored in a finished product tank, the finally obtained product is collected and stored in the finished product tank, and the product is generally extracted from the side line of the rectification tower. And other components generated in the reaction process are removed from the system. For example, the gas phase from the top of the rectifying tower returns to the gas source conveying pipeline again to be used as raw materials.
The invention also provides a preparation method of the cyclic carbonate reinforced micro-interface preparation system, which comprises the following steps:
and (3) dispersing and crushing a mixed micro interface of the olefin solution and the carbon dioxide, performing carboxylation reaction, and performing flash evaporation, dehydration and rectification to obtain a product for collection.
Preferably, the temperature of the carboxylation reaction is 50-80 ℃, and the pressure of the carboxylation reaction is 0.1-1 MPa.
Specifically, the preparation method comprises the steps of smashing carbon dioxide into micro-bubbles with micron scale through a micro interface, releasing the micro-bubbles into the carboxylation reaction kettle, so as to increase the mass transfer area of a phase boundary between the carbon dioxide and the in-situ generated cyclic carbonate in the carboxylation reaction process, fully contacting the carbon dioxide with the in-situ generated epoxy compound in a micro-bubble state, and carrying out carboxylation reaction.
The product obtained by the cyclic carbonate reaction has good quality and high yield. The preparation method of the cyclic carbonate has low reaction temperature, greatly reduced pressure and high liquid hourly space velocity, which is equivalent to improving the productivity.
Before starting the system, firstly, filling an ionic liquid catalyst into a stirring kettle and a carboxylation reaction kettle, filling olefin into an olefin storage tank, filling tert-butyl hydroperoxide/hydrogen peroxide into an oxidant storage tank, feeding carbon dioxide into the system from a gas source conveying pipeline, starting the system, and quantitatively conveying the olefin, the oxidant and the carbon dioxide into a micro-interface unit.
After the olefin and the oxidant are dispersed and crushed by the micro interface unit, the olefin and the oxidant are subjected to oxidation reaction in the stirring kettle to generate an epoxy compound, the epoxy compound and carbon dioxide are subjected to carboxylation reaction to generate cyclic carbonate, in addition, a built-in micro interface generator positioned in the carboxylation reaction kettle is used for crushing the carbon dioxide into micro bubbles with a micron scale and releasing the micro bubbles into the reaction kettle so as to increase the mass transfer area of a phase boundary between the carbon dioxide and the epoxy compound in the carboxylation reaction process, so that the carbon dioxide is fully contacted with the epoxy compound in a micro bubble state and subjected to carboxylation reaction.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the reinforced micro-interface preparation system of the cyclic carbonate, before the carboxylation reaction of carbon dioxide and an epoxy compound generated in situ is carried out, the micro-interface generator breaks the carbon dioxide into micro bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, so that the carbon dioxide is contacted with the cyclic carbonate generated in situ in the state of the micro bubbles to increase the phase boundary mass transfer area between the carbon dioxide and the cyclic carbonate generated in situ in the carboxylation reaction process, and the carbon dioxide and the cyclic carbonate are fully mixed and then subjected to the carboxylation reaction, thereby solving the problem that the reaction efficiency of the system is reduced because the carboxylation reaction of the carbon dioxide and the cyclic carbonate cannot be fully mixed in a reaction kettle in the prior art;
(2) the reinforced micro-interface preparation system of the invention returns the carbon dioxide and the catalyst obtained by final separation to be recycled, thereby further saving the production cost;
(3) according to the reinforced reaction process for preparing the cyclic carbonate through the oxidation carboxylation reaction of the low-pressure olefin and the carbon dioxide, the imidazole bicarbonate ionic liquid is used as the bifunctional catalyst, so that the olefin and the carbon dioxide are directly subjected to the oxidation carboxylation reaction to prepare the cyclic carbonate, the raw material cost is reduced, the separation and storage of epoxy compounds are avoided, and the production flow is simplified.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a schematic structural diagram of an enhanced micro-interface preparation system for cyclic carbonate according to an embodiment of the present invention.
Description of the drawings:
11-an olefin storage tank; 12-an oxidant storage tank;
13-gas source delivery line; 14-a first carboxylation reaction kettle;
15-a flash tank; 16-a dehydration column;
17-a rectification column; 18-finished product tank;
19-external micro-interface generator; 20-a stirred tank;
21-built-in micro-interface generator; 22-a second carboxylation reaction kettle;
a 23-olefin transfer conduit; 24-an oxidant delivery conduit;
25-main pipe; 26-a first reaction feed liquid inlet;
27-an overflow pipe; 28-a first delivery pump;
29-a second delivery pump; 30-second reaction feed liquid inlet.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Examples
Referring to fig. 1, the system for preparing an enhanced micro-interface of cyclic carbonate according to an embodiment of the present invention mainly includes a stirring kettle 20, a first carboxylation reaction kettle 14, and a second carboxylation reaction kettle 22, wherein a micro-interface unit is disposed on a side surface of the stirring kettle 20, the micro-interface unit is composed of a plurality of external micro-interface generators 19, the external micro-interface generators 19 are sequentially disposed along a vertical direction from top to bottom, connecting rods for fixing are connected between bottom surfaces and top surfaces between adjacent external micro-interface generators 19, and the number of the external micro-interface generators 19 is preferably 3.
A main pipeline 25 which is led into the micro-interface unit is simultaneously connected with two branch pipelines of an oxidant conveying pipeline 24 and an olefin conveying pipeline 23 and is simultaneously connected with a gas source conveying pipeline 13, carbon dioxide, oxidant and olefin enter the interior of the micro-interface generator to be used for breaking carbon dioxide gas into micro-bubbles with micron level, and 200g of imidazole bicarbonate ionic liquid catalyst is filled in the stirring kettle 20, the first carboxylation reaction kettle 14 and the second carboxylation reaction kettle 22; the olefin storage tank 11 is connected to an olefin transfer pipe 23 for transferring 1kg of styrene stored in the olefin storage tank 11 into the stirred tank 20 through the olefin transfer pipe 23, and a second transfer pump 29 is provided in the olefin transfer pipe 23 for transferring the styrene by a second circulation pump in order to increase the transfer power. The oxidizer storage tank 12 is connected to an oxidizer delivery pipe 24 for delivering 2kg of a tert-butyl hydroperoxide aqueous solution (the mass fraction of tert-butyl hydroperoxide is 70%) in the oxidizer storage tank 12 into the stirred tank 20 through the oxidizer delivery pipe 24, and in order to improve the power transmission, a first delivery pump 28 is provided in the oxidizer delivery pipe 24 for delivering the aqueous solution by a first circulation pump. In addition, the gas source conveying pipeline 13 ensures that a sufficient amount of carbon dioxide gas source exists, the system is started, the temperature of the system is set to be 50 ℃, and the pressure is set to be 1.0 MPa.
In the stirring kettle 20, the gas phase dispersed and crushed by the micro interface unit is easier to perform cycloaddition reaction with the raw material and the oxidant, the stirring kettle 20 is provided with a condensing coil of a speed-adjustable motor, and the condensing coil is heated by a jacket. The reaction liquid level reaches the overflow pipe 27 and enters the first carboxylation reaction kettle 14 and the second carboxylation reaction kettle 22 from the first reaction liquid inlet 26 and the second reaction liquid inlet 30 at the bottom of the first carboxylation reaction kettle 14 and the second carboxylation reaction kettle 22 through the pipeline, and the reaction is further completed. Two micro-interface generators 21 are arranged in the first carboxylation reaction kettle 14, and two micro-interface generators 21 are arranged in the second carboxylation reaction kettle 22.
In the first carboxylation reaction kettle 14 and the second carboxylation reaction kettle 22, styrene is oxidized by tert-butyl hydroperoxide to generate styrene oxide under the catalysis of imidazole bicarbonate ionic liquid, meanwhile, each built-in micro-interface generator is provided with a carbon dioxide feed port, the built-in micro-interface generator 21 breaks carbon dioxide into micro-bubbles with micrometer scale, and the micro-bubbles are released into the first carboxylation reaction kettle 14 and the second carboxylation reaction kettle 22, so that the carbon dioxide is fully contacted with the in-situ generated styrene oxide in the micro-bubble state, and carboxylation reaction is carried out.
The micro-interface generators 21 arranged in the first carboxylation reactor 14 and the second carboxylation reactor 22 are sequentially arranged from top to bottom, and a connecting channel is arranged between the first carboxylation reactor 14 and the second carboxylation reactor 22 for continuing carboxylation reaction in the second carboxylation reactor 22.
The oxidation carboxylation reaction liquid which is subjected to carboxylation reaction is conveyed to a flash tank 15, a flash product outlet is formed in the top of the flash tank 15, a catalyst outlet is formed in the bottom of the flash tank 15, the oxidation carboxylation reaction liquid is subjected to flash evaporation treatment, after the flash evaporation is finished, the ionic liquid catalyst in the flash product is discharged through the catalyst outlet and then circulated to the interior of the carboxylation reaction kettle 14 for the oxidation carboxylation reaction in the interior of the carboxylation reaction kettle 14 again, and the flash product except the catalyst is conveyed to a subsequent product purification unit.
The flash evaporation product conveyed to the product purification unit is sequentially dehydrated and rectified through a dehydrating tower 16 and a rectifying tower 17, the dehydrating tower 16 is used for dehydrating the flash evaporation product, the rectifying tower 17 is used for rectifying the dehydration product, and finally the styrene cyclic carbonate product is obtained and collected and stored in a finished product tank 18. Other components generated in the reaction process are removed by a system, the yield of the styrene cyclic carbonate is about 85 percent when the styrene cyclic carbonate is detected, and the gas phase discharged from the top of the rectifying tower 17 is returned to the gas source conveying pipeline 13 for recycling.
In the above embodiment, the micro-interface generator converts the pressure energy of the gas and/or the kinetic energy of the liquid into the surface energy of the bubbles and transmits the surface energy of the bubbles to the bubbles, so that the bubbles are broken into micro-bubbles with a diameter of more than or equal to 1 μm and less than 1mm, and the micro-bubbles are divided into a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator according to an energy input mode or a gas-liquid ratio, wherein the pneumatic micro-interface generator is driven by gas, and the input gas amount is far greater than the liquid amount; the hydraulic micro-interface generator is driven by liquid, and the input air quantity is generally smaller than the liquid quantity; the gas-liquid linkage type micro-interface generator is driven by gas and liquid at the same time, and the input gas amount is close to the liquid amount. The micro-interface generator is one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
In order to increase the dispersion and mass transfer effects, an additional micro-interface generator can be additionally arranged, the installation position is not limited actually, the micro-interface generator can be arranged externally or internally, and the micro-interface generator can be arranged on the side wall in the kettle in a relative mode when the micro-interface generator is arranged internally so as to realize the opposite flushing of micro-bubbles discharged from the outlet of the micro-interface generator.
In the above embodiment, the number of the pump bodies is not specifically required, and the pump bodies may be arranged at corresponding positions as required.
In the above examples, other operating conditions were unchanged, and when the reaction temperature was set to 65 ℃ and the pressure was set to 0.5MPa, the yield was 88%.
In the above examples, other operating conditions were unchanged, and when the reaction temperature was set at 80 ℃ and the pressure was set at 0.1MPa, the yield was 92%.
In addition, the pressure and the temperature in the carboxylation reaction kettle 14 are reduced by laying the micro-interface generator, and the energy consumption is sufficiently reduced.
In a word, compared with the reinforced micro-interface preparation system of the cyclic carbonate in the prior art, the reinforced micro-interface preparation system of the cyclic carbonate has the advantages of fewer equipment components, small occupied area, low energy consumption, low cost, high safety, controllable reaction and high raw material conversion rate, is equivalent to providing a reinforced micro-interface preparation system with stronger operability for the field of the cyclic carbonate, and is worthy of wide popularization and application.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The system for preparing the enhanced micro-interface of the cyclic carbonate is characterized by comprising a stirring kettle, a first carboxylation reaction kettle and a second carboxylation reaction kettle, wherein ionic liquid catalysts are filled in the stirring kettle, the first carboxylation reaction kettle and the second carboxylation reaction kettle;
a micro-interface unit is arranged on the side surface of the stirring kettle, the micro-interface unit is composed of a plurality of external micro-interface generators, a main pipeline which is introduced into the micro-interface unit is simultaneously connected with an oxidant conveying pipeline and two branch pipelines of an olefin conveying pipeline, carbon dioxide is introduced into the micro-interface unit from the gas source conveying pipeline, and the carbon dioxide, the oxidant and the olefin enter the micro-interface unit to be used for crushing the carbon dioxide gas into micro-bubbles at the micron level;
a first reaction material liquid inlet is formed in the bottom of the first carboxylation reaction kettle and is communicated with the stirring kettle through an overflow pipe, two built-in micro-interface generators are arranged in the first carboxylation reaction kettle, a second reaction material liquid inlet is formed in the bottom of the second carboxylation reaction kettle and is communicated with the stirring kettle through the overflow pipe, and two micro-interface generators are also arranged in the second carboxylation reaction kettle;
each built-in micro interface generator is provided with a carbon dioxide feed inlet for dispersing and crushing carbon dioxide into micro bubbles under the condition that the reaction feed liquid is used as a medium;
and purifying the oxidation carboxylation reaction liquid which is reacted in the first carboxylation reaction kettle and the second carboxylation reaction kettle in sequence through a flash tank, a dehydration tower and a rectifying tower to obtain the cyclic carbonate product.
2. The system of claim 1, wherein the micro-interface generators disposed inside the first carboxylation reactor and the second carboxylation reactor are arranged in sequence from top to bottom.
3. The system of claim 2, wherein a connecting channel is provided between the first carboxylation reaction kettle and the second carboxylation reaction kettle for proceeding carboxylation reaction in the second carboxylation reaction kettle.
4. The system for preparing the enhanced micro-interface according to any one of claims 1 to 3, wherein the oxidant delivery pipeline is connected with an oxidant storage tank, and tert-butyl hydroperoxide or hydrogen peroxide is stored in the oxidant storage tank.
5. The system of claim 4, wherein the oxidant delivery conduit is provided with a first delivery pump.
6. The system of any one of claims 1-3, wherein an olefin storage tank is connected to the olefin transfer line for transferring the olefin solution in the olefin storage tank to the micro-interface unit through the olefin transfer line.
7. The system of claim 6, wherein a second transfer pump is disposed on the olefin transfer line.
8. The system as claimed in claim 7, wherein the oxidation and carboxylation reaction liquid enters from the side wall of the flash tank, the top of the flash tank is provided with a flash product outlet, the bottom of the flash tank is provided with a catalyst outlet, the catalyst outlet is connected with the side wall of the carboxylation reaction kettle and used for returning the ionic liquid catalyst, and the flash product outlet is connected with the dehydration tower and used for dehydrating the flash product.
9. A method for preparing an enhanced micro-interface preparation system using the cyclic carbonate according to any one of claims 1 to 8, comprising:
and (3) dispersing and crushing a mixed micro interface of the olefin solution and the carbon dioxide, performing carboxylation reaction, and performing flash evaporation, dehydration and rectification to obtain a product for collection.
10. The method according to claim 9, wherein the temperature of the carboxylation reaction is 50 to 80 ℃ and the pressure of the carboxylation reaction is 0.1 to 1 MPa.
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| CN202010863174.6A CN111961026A (en) | 2020-08-25 | 2020-08-25 | Reinforced micro-interface preparation system and method for cyclic carbonate |
| PCT/CN2020/122807 WO2022041425A1 (en) | 2020-08-25 | 2020-10-22 | Reinforced micro-interface preparation system and method for cyclic carbonate |
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| CN112062943A (en) * | 2020-09-08 | 2020-12-11 | 南京延长反应技术研究院有限公司 | Micro-interface preparation system and method for polyglycolic acid |
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| CN114507133A (en) * | 2022-03-03 | 2022-05-17 | 南京延长反应技术研究院有限公司 | Enhanced micro-interface system and method for preparing dimethyl maleate |
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| CN112156731A (en) * | 2020-09-08 | 2021-01-01 | 南京延长反应技术研究院有限公司 | Reinforced micro-interface preparation system and method for polyglycolic acid |
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| CN112933630A (en) * | 2021-01-29 | 2021-06-11 | 南京华基塔业有限公司 | Intelligent micro-interface reaction system and method for preparing lactide from lactic acid |
| CN114409628A (en) * | 2022-01-19 | 2022-04-29 | 南京延长反应技术研究院有限公司 | Method and system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition |
| WO2023138074A1 (en) * | 2022-01-19 | 2023-07-27 | 南京延长反应技术研究院有限公司 | Method and system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition |
| CN114507133A (en) * | 2022-03-03 | 2022-05-17 | 南京延长反应技术研究院有限公司 | Enhanced micro-interface system and method for preparing dimethyl maleate |
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