CN112058184A - Preparation system and method of polyglycolic acid - Google Patents
Preparation system and method of polyglycolic acid Download PDFInfo
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- CN112058184A CN112058184A CN202010933482.1A CN202010933482A CN112058184A CN 112058184 A CN112058184 A CN 112058184A CN 202010933482 A CN202010933482 A CN 202010933482A CN 112058184 A CN112058184 A CN 112058184A
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 31
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 70
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 230000007062 hydrolysis Effects 0.000 claims abstract description 42
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 45
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003860 storage Methods 0.000 claims description 17
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- -1 glycolic acid ester Chemical class 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000413 hydrolysate Substances 0.000 claims description 3
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 abstract description 27
- 230000001965 increasing effect Effects 0.000 abstract description 9
- 239000012071 phase Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006053 organic reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
Abstract
The invention provides a preparation system and a preparation method of polyglycolic acid, wherein the preparation system comprises: a hydrogenation reactor, a hydrogen feeding pipeline, a hydrolysis reactor and a steam feeding pipeline; an oxalate feeding pipeline is arranged on the side wall of the hydrogenation reactor, a micro-interface unit is arranged in the hydrogenation reactor, and the micro-interface unit is formed by sequentially arranging a plurality of micro-interface generators from top to bottom; the hydrogen feeding pipeline penetrates through the side wall of the hydrogenation reactor and enters the inside of the micro interface unit, so that hydrogen is broken into micro bubbles in a micron level in the micro interface unit in advance before hydrogenation reaction. According to the preparation system, the micro-interface unit is arranged in the hydrogenation reactor, and the micro-interface generator is arranged in the hydrolysis reactor, so that hydrogen is crushed into micro bubbles before the hydrogen and dimethyl oxalate carry out hydrogenation reaction, the phase boundary mass transfer area between the hydrogen and the dimethyl oxalate is increased, and the phase boundary mass transfer area in the hydrolysis reaction process is increased.
Description
Technical Field
The invention relates to the field of polyglycolic acid preparation, and particularly relates to a polyglycolic acid preparation system and method.
Background
Polyglycolic acid is a common biodegradable polyester and is widely applied to high-added-value fields such as surgical sutures, drug carriers, bone materials and the like. Polyglycolic acid has a simple and regular linear molecular structure and is a simple linear aliphatic polyester. The polyglycolic acid with molecular weight over 10000 has strong mechanical strength and can be used for medical suture. The industrial production of high molecular weight polyglycolic acid generally employs a method of ring-opening polymerization of glycolide.
China is a country with less oil and more coal, and with the development of the industry of preparing ethylene glycol from coal in China, the development of the coal chemical industry can be further promoted by utilizing the intermediate product dimethyl oxalate to produce polyglycolic acid on a large scale. Preparing glycolate by hydrogenating dimethyl oxalate; glycolic acid is prepared by hydrolyzing glycollic acid ester; then preparing an intermediate product glycolide from the glycolic acid; the ring-opening polymerization of glycolide produces polyglycolic acid of high molecular weight.
When the existing dimethyl oxalate hydrogenation reaction system is used for preparing glycolate, dimethyl oxalate and hydrogen are mixed and then introduced into a reactor for hydrogenation reaction, and hydrogen and oxalic acid are usedThe dimethyl esters are not sufficiently mixed, so that the reaction needs to be carried out at a high hydrogen-ester ratio (hydrogen-ester ratio > 30:1) and a high hydrogen pressure (> 2.0MPa), and the production capacity of the reactor is limited (liquid hourly space velocity < 1.0 h)-1)。
Meanwhile, when the glycolic acid is prepared by the existing glycolate hydrolysis reaction system, glycolate and distilled water are directly introduced into a reaction kettle for hydrolysis reaction, and the water and glycolate cannot be fully mixed in the reaction kettle, so that the reaction efficiency is low.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a polyglycolic acid preparation system, which is characterized in that a micro-interface unit is arranged in a hydrogenation reactor, so that hydrogen is crushed into micro bubbles before the hydrogen and dimethyl oxalate carry out hydrogenation reaction, and the phase boundary mass transfer area between the hydrogen and the dimethyl oxalate is increased, thereby solving the problems of high reaction pressure, large hydrogen-ester ratio and low liquid hourly space velocity caused by insufficient mixing of the hydrogen and the dimethyl oxalate in the reactor in the prior art.
The second purpose of the invention is to provide a method for preparing polyglycolic acid by adopting the preparation system, the polyglycolic acid obtained by reaction has high purity and wide application, the application range of the polyglycolic acid 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 polyglycolic acid preparation system, which comprises a hydrogenation reactor, a hydrogen feeding pipeline, a hydrolysis reactor and a steam feeding pipeline;
an oxalate feeding pipeline is arranged on the side wall of the hydrogenation reactor, a micro-interface unit is arranged in the hydrogenation reactor, and the micro-interface unit is formed by sequentially arranging a plurality of micro-interface generators from top to bottom; the hydrogen feeding pipeline penetrates through the side wall of the hydrogenation reactor and enters the inside of the micro interface unit, so that hydrogen is broken into micro bubbles at the micron level in the micro interface unit in advance before hydrogenation reaction;
the reaction product after hydrogenation reaction in the hydrogenation reactor enters a light component removal tower to remove light components, and then enters a rectifying tower to be rectified to obtain glycolic acid ester, glycolic acid is generated through the hydrolysis reactor, a micro-interface generator is arranged in the hydrolysis reactor, and the water vapor pipeline penetrates through the side wall of the hydrolysis reactor and enters the interior of the micro-interface generator, so that water vapor is pre-crushed into micro-bubbles in the micro-interface generator before hydrolysis reaction;
dehydrating the hydrolysate after the hydrolysis reaction in the hydrolysis reactor through a dehydrating tower, reacting in a first polymerization reaction kettle to obtain glycolide monomers, and polymerizing in a second polymerization reaction kettle to obtain polyglycolic acid.
Preferably, the micro-interface generator inside the hydrolysis reactor is single and is arranged at a lower position inside the hydrolysis reactor.
Preferably, the micro-interface unit comprises 3 micro-interface generators, a group of liquid reciprocal channels are arranged between every two adjacent micro-interface generators, and the liquid reciprocal channels realize the circulation of gas and liquid in the micro-interface generators.
Preferably, the water vapour feed line is connected to a distilled water storage tank to provide a source of feedstock for water vapour entering the hydrolysis reactor.
Preferably, the hydrogen feeding pipeline is connected with an external gas source channel to supply a gas source for hydrogen to enter the micro-interface unit.
Preferably, the oxalate feeding pipeline is connected with an oxalate storage tank to realize that a raw material source is provided for the oxalate entering the hydrogenation reactor.
The micro interface unit is arranged in the hydrogenation reactor and is arranged in a mode of being sequentially arranged from top to bottom, the oxalic ester enters the hydrogenation reactor from the oxalic ester storage tank through the oxalic ester feeding pipeline and can be closely contacted with the entering hydrogen as a medium after entering the hydrogenation reactor, thereby ensuring that the hydrogen can be fully dispersed and crushed in the micro-interface unit, equivalently forming a primary micro-interface system 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 bottommost part is closest to the gas phase feed inlet, therefore, the catalyst is used as a main dispersed and broken micro-interface system, and then the two micro-interface generators on the upper part form a secondary micro-interface system and a tertiary micro-interface system, thereby also playing a role in enhancing the hydrogenation reaction.
In addition, the liquid reciprocal channels are arranged between the adjacent micro-interface generators, the two liquid reciprocal channels are preferably arranged in bilateral symmetry, the gas phase crushing can be improved better because the mutual circulation of liquid is carried out between the micro-interface generators, the crushing needs power, the liquid reciprocal channels are correspondingly matched to provide power except that the microporous structures in the micro-interface generators provide power, and the best mode is that the liquid phase flow directions of the two liquid reciprocal channels are exactly opposite, so that the convection can be generated between the micro-interface generators, and the crushing effect is improved.
The micro-interface generator in the hydrogenation reactor breaks hydrogen into micro-bubbles with micron scale, and releases the micro-bubbles into the reactor, so as to increase the phase boundary mass transfer area between the hydrogen and the dimethyl oxalate in the hydrogenation reaction process, so that the hydrogen is fully contacted with the dimethyl oxalate in the micro-bubble state, and the hydrogenation reaction is carried out.
Similarly, the micro-interface generator is arranged in the hydrolysis reactor, the single micro-interface generator can basically meet the reaction requirement, and the micro-interface generator is preferably arranged at a lower position in the reactor, so that the position of the micro-interface generator is closer to the position of the steam feeding pipeline, and the micro-interface generator can be fully dispersed and crushed in the micro-interface generator before steam enters the hydrolysis reactor to carry out hydrolysis reaction, thereby being more beneficial to the subsequent hydrolysis reaction, greatly increasing the dispersion and crushing effect by the arrangement position, and ensuring that the single micro-interface generator can achieve good dispersion effect.
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.
Preferably, the top of the lightness-removing column is provided with a light component outlet for discharging light components of methanol, methyl formate, ethylene glycol and dimethyl carbonate, and the bottom of the lightness-removing column is provided with a heavy component outlet communicated with the side wall of the rectifying column for further rectifying glycolic acid ester.
Preferably, the bottom of the rectifying tower is provided with a raw material circulating outlet, and the oxalic ester is returned to the hydrogenation reactor from the raw material circulating outlet to realize the recycling of the raw material.
Preferably, the top of the rectifying tower is provided with an overhead condenser, and a part of substances condensed from the overhead condenser is returned to the rectifying tower, and the other part of substances goes to a glycolate storage tank.
And conveying a reaction product after the reaction in the hydrogenation reactor to the inside of the light component removal tower, distilling out light components such as methanol, methyl formate, ethylene glycol and dimethyl carbonate from the top of the tower, and conveying the obtained heavy component to a subsequent rectifying tower.
The rectifying tower is used for rectifying heavy components in the light component removal tower, dimethyl oxalate left at the bottom of the rectifying tower is circulated to the interior of the hydrogenation reactor and is used for dimethyl oxalate hydrogenation reaction in the hydrogenation reactor again, one part of materials passing through a condenser at the top of the rectifying tower are returned to the rectifying tower, one part of distilled glycolic acid ester is conveyed to a glycolic acid ester storage tank, and the glycolic acid ester storage tank is connected with the top of the hydrolysis reactor. Filling an acidic hydrolysis catalyst into a hydrolysis reactor in advance, and conveying distilled water into a micro-interface generator in the hydrolysis reactor through a circulating pump; the glycolate is reacted with water in the hydrolysis reactor to produce the target product glycolic acid, and simultaneously methanol.
Then, a micro interface generator in the hydrolysis reactor breaks distilled water into micro liquid drops with micron scale, the micro liquid drops are released into the reactor to increase the mass transfer area of a phase boundary between the distilled water and the glycolate in the hydrolysis reaction process, so that the distilled water is fully contacted with the glycolate in a micro liquid drop state, the hydrolysis reaction is carried out, a hydrolysis reaction product is conveyed into a dehydration tower to obtain dewatered organic reaction liquid, and the organic reaction liquid is conveyed to a refining tower; rectifying the organic reaction liquid by the refining tower, circulating the glycolate left at the bottom of the refining tower into the hydrolysis reactor, reusing the glycolate in the hydrolysis reactor for hydrolysis reaction, distilling the methanol from the top of the tower, and conveying the distilled glycolic acid into a first polymerization reactor for glycolation, prepolymerization and depolymerization;
in the first polymerization reaction kettle, glycolic acid is subjected to esterification, prepolymerization and depolymerization to obtain a glycolide monomer crude product, and the glycolide monomer crude product is conveyed to a crystallization kettle; heating and dissolving the glycolide monomer crude product in a crystallization kettle, cooling and crystallizing to obtain a high-purity glycolide monomer, and conveying the high-purity glycolide monomer to a second polymerization kettle; and carrying out polymerization reaction on the high-purity glycolide monomer in a second polymerization kettle to finally obtain a polyglycolic acid product with high molecular weight.
The invention also provides a preparation method of polyglycolic acid, which comprises the following steps:
carrying out hydrogenation reaction after the mixed micro interface of the oxalate and hydrogen is dispersed and crushed, and then carrying out dehydrogenation and rectification to obtain glycolic acid ester for collection;
and (3) after the glycolic acid ester is subjected to hydrolysis reaction and dehydration, the glycolide monomer is obtained through esterification, prepolymerization and depolymerization, and the polyglycolic acid is obtained through polymerization.
Preferably, the temperature of the hydrogenation reaction is 200 ℃ to 300 ℃, and the pressure of the carboxylation reaction is 0.1 to 2 MPa.
Preferably, the temperature of the hydrolysis reaction is 60-100 ℃.
Preferably, in the hydrolysis reaction, n (glycolate): n (H)2O) is 1:1.5-1: 4.
Specifically, the preparation method comprises the steps of arranging the micro-interface generator connected with the hydrogen feeding pipeline in the hydrogenation reactor, enabling the micro-interface generator to break the hydrogen into micro-bubbles with the diameter of more than or equal to 1 mu m and less than 1mm before the hydrogen and the dimethyl oxalate carry out hydrogenation reaction, enabling the hydrogen to be in contact with the dimethyl oxalate in the micro-bubble state, increasing the mass transfer area of a phase boundary between the hydrogen and the dimethyl oxalate in the hydrogenation reaction process, fully mixing the hydrogen and the dimethyl oxalate, and then carrying out the hydrogenation reaction, so that the problems of high reaction pressure, large hydrogen-ester ratio and low liquid hourly space velocity caused by the fact that the hydrogen and the dimethyl oxalate cannot be fully mixed in the reactor in the prior art are solved.
The scheme of the invention has the advantages that the micro interface generator connected with the distilled water storage tank is arranged in the hydrolysis reactor, so that before the distilled water and the glycollate are subjected to hydrolysis reaction, the distilled water is crushed into micro liquid drops with the diameter of more than or equal to 1 mu m and less than 1mm by the micro interface generator, the distilled water is contacted with the glycollate in a micro liquid drop state, the phase boundary mass transfer area between the distilled water and the glycollate in the hydrolysis reaction process is increased, the consumption of the distilled water is reduced, the reaction efficiency is improved, and the operation cost of product dehydration is reduced.
The polyglycolic acid product obtained by the reaction method of the invention has good quality and high yield. And the preparation method has low reaction temperature, greatly reduced pressure and high liquid hourly space velocity, which is equivalent to improving the productivity.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation system of the polyglycolic acid, the micro-interface unit is arranged in the hydrogenation reactor, so that hydrogen is crushed into micro bubbles before the hydrogen and dimethyl oxalate carry out hydrogenation reaction, and the phase boundary mass transfer area between the hydrogen and the dimethyl oxalate is increased, so that the problems of high reaction pressure, large hydrogen-ester ratio and low liquid hourly space velocity caused by the fact that the hydrogen and the dimethyl oxalate cannot be fully mixed in the reactor in the prior art are solved;
(2) according to the invention, the micro-interface generator is arranged in the hydrolysis reactor and is used for receiving the distilled water before the hydrolysis reaction, and the distilled water is crushed into micro-droplets with the diameter of micron level before the hydrolysis reaction, so that the mass transfer area of the phase boundary between the distilled water and the glycolate in the hydrolysis reaction process is increased, and the reaction efficiency of the glycolate hydrolysis is enhanced.
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 a system for preparing glycolate from oxalate according to an embodiment of the present invention.
Description of the drawings:
11-oxalate storage tank; 12-an external gas source channel;
13-a hydrogenation reactor; 131-a micro-interface generator;
132-liquid reciprocal channel; 14-a light component removal tower;
141-light fraction outlet; 142-a heavy ends outlet;
15-a rectification column; 151-overhead condenser;
152-a raw material recycle outlet; a 16-glycolate storage tank;
17-a first delivery pump; 18-a second delivery pump;
19-a hydrolysis reactor; 20-a steam feed line;
21-distilled water storage tank; 22-a third delivery pump;
23-a hydrogen feed line; 24-a dehydration column;
25-a first polymerization reactor; 26-second polymerization reaction kettle.
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, a polyglycolic acid preparation system according to an embodiment of the present invention mainly includes a hydrogenation reactor 13, a hydrogen gas feed pipe 23, a hydrolysis reactor 19, and a steam feed pipe 20, wherein 1kg of a hydrogenation catalyst is pre-filled in the hydrogenation reactor 13, an oxalate feed pipe is further disposed on a side wall of the hydrogenation reactor 13, a micro interface unit is disposed in the hydrogenation reactor 13, the micro interface unit is formed by sequentially arranging a plurality of micro interface generators 131 from top to bottom, preferably 3 micro interface generators 131, a group of liquid reciprocal channels 132 is disposed between adjacent micro interface generators 131, and the liquid reciprocal channels 132 realize gas-liquid circulation in the micro interface generators 131. In this way, the hydrogen feeding pipe 23 passes through the side wall of the hydrogenation reactor 13 into the inside of the micro interface unit to realize the breaking of hydrogen into micro bubbles in micron level in advance in the inside of the micro interface unit before hydrogenation reaction.
The hydrogen feeding pipeline 23 is connected with an external gas source channel 12 to provide a gas source for hydrogen entering the micro interface unit, the oxalate feeding pipeline is connected with an oxalate storage tank 11 to provide a raw material source for oxalate entering the hydrogenation reactor 13, 50kg of dimethyl oxalate is filled into the oxalate storage tank 11 in advance and is conveyed into the hydrogenation reactor 13 through a first conveying pump 17, the external gas source channel 12 is connected with a sufficient hydrogen gas source, the system is started, the temperature of the hydrogenation reactor 13 is set to be 200 ℃, the pressure is set to be 1.0MPa, the dimethyl oxalate is conveyed into the hydrogenation reactor 13, and meanwhile, hydrogen is conveyed into each micro interface generator 131 of the micro interface unit through the hydrogen feeding pipeline 23.
The micro-interface generator 131 breaks the hydrogen into micro-bubbles with micron-scale dimensions, and releases the micro-bubbles into the reactor, so that the hydrogen is fully contacted with dimethyl oxalate in the micro-bubble state, and the dimethyl oxalate reacts with the hydrogen under the catalysis of the hydrogenation catalyst to generate glycolate, and meanwhile, byproducts such as methanol, methyl formate, ethylene glycol, dimethyl carbonate and the like are also generated.
The hydrogenated reaction product is conveyed to a light component removal tower 14 to remove light components, the light components and heavy components are separated, the light components such as methanol, methyl formate and the like are distilled out from a light component outlet 141 at the top of the tower, the heavy components such as dimethyl oxalate, glycollate and the like are left at the bottom of the tower, and the heavy component is sent out from the heavy component outlet 142 to the rectifying tower 15, the dimethyl oxalate is left at the bottom of the rectifying tower 15 and is sent out from a raw material circulating outlet 152 arranged at the bottom of the rectifying tower 15, the glycolate is conveyed back to the hydrogenation reactor 13 through a second conveying pump 18 to be recycled, the glycolate is distilled from the top of the rectifying tower 15, one part of the glycolate is refluxed through an overhead condenser 151, the other part of the glycolate is directly extracted to a glycolate storage tank 16 to be stored, the glycolate storage tank 16 is connected with the top of the hydrolysis reactor 19, and the glycolate is conveyed into the hydrolysis reactor 19 to be subjected to hydrolysis reaction.
The acidic hydrolysis catalyst is filled into the hydrolysis reactor 19 in advance, distilled water in a distilled water storage tank is sent into the hydrolysis reactor 19 through a third circulating pump 22 arranged on a water vapor feeding pipeline 20, a single micro-interface generator is arranged at the lower part in the hydrolysis reactor 19, the temperature of the hydrolysis reactor 19 is set to be 60 ℃, and the feeding molar ratio is prepared as follows: n (glycolate): n (H)2O) ═ 1:2, the micro interface generator 131 located inside the hydrolysis reactor 19 breaks up the distilled water into micro droplets with micron-scale dimensions, and releases the micro droplets into the hydrolysis reactor 19, so that the distilled water is fully contacted with glycolate in a micro-bubble state, the glycolate reacts with the distilled water under the catalysis of the hydrolysis catalyst to generate glycolic acid and methanol, and the hydrolysis reaction liquid is conveyed to the dehydration tower 24 for dehydration.
Dehydrating the hydrolysate in a dehydrating tower 24 to obtain dehydrated glycolate hydrolysis reaction liquid, then sending the glycolate hydrolysis reaction liquid to a first polymerization reaction kettle 25 for glycolation, prepolymerization and depolymerization, firstly carrying out esterification at 80 ℃, and vacuumizing for dehydration; then the temperature of the first polymerization reaction kettle 25 is raised to 140 ℃ until the materials in the first polymerization reaction kettle 25 are polymerized to be solidified; heating the first polymerization reactor 25 to 175 ℃, and keeping the temperature for 4 hours; after the heat preservation is finished, the temperature of the first polymerization reaction kettle 25 is continuously raised to 320 ℃, and the crude product of the glycolide monomer is distilled out by cracking the materials under the vacuum-pumping condition.
The distilled crude glycolide monomer is transferred to the second polymerization reactor 26. 20g of catalyst is added into the second polymerization reactor 26, the temperature of the second polymerization reactor 26 is set to be 200 ℃, the glycolide ring-opening polymerization is carried out to obtain 26.7kg of polyglycolic acid product, and the molecular weight of the polyglycolic acid is detected to be over 10000.
In the above embodiment, the micro-interface generator 131 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 1 μm or more and a diameter of less than 1mm, and the micro-bubbles are divided into the pneumatic micro-interface generator 131, the hydraulic micro-interface generator 131 and the gas-liquid linkage micro-interface generator 131 according to the energy input mode or the gas-liquid ratio, wherein the pneumatic micro-interface generator 131 is driven by gas, and the input gas amount is much larger than the liquid amount; the hydraulic micro-interface generator 131 is driven by liquid, and the input gas amount is generally smaller than the liquid amount; the gas-liquid linkage type micro-interface generator 131 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 131 is selected from one or more of a pneumatic micro-interface generator 131, a hydraulic micro-interface generator 131 and a gas-liquid linkage micro-interface generator 131.
In order to increase the dispersion and mass transfer effects, additional micro-interface generators 131 can be additionally arranged, the installation positions are not limited, the micro-interface generators can be externally or internally arranged, and the micro-interface generators can be arranged on the side wall in the kettle in a relative mode when the micro-interface generators are internally arranged, so that micro-bubbles discharged from the outlets of the micro-interface generators 131 are opposite.
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 hydrogenation reaction temperature was set at 220 ℃, the pressure was set at 0.5 MPa.
In the above examples, other operating conditions were unchanged, and when the hydrogenation reaction temperature was set at 260 ℃, the pressure was set at 1 MPa.
In the above examples, other operating conditions were unchanged, and when the hydrogenation reaction temperature was set at 300 ℃, the pressure was set at 0.1 MPa.
In the above examples, other operating conditions were not changed, and the temperature of the hydrolysis reaction was 70 ℃, 80 ℃, 90 ℃ and 100 ℃.
In a word, compared with the preparation system of polyglycolic acid in the prior art, the preparation system provided by the invention 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 preparation system with stronger operability for the field of glycolic acid ester preparation, 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. A polyglycolic acid production system, comprising: a hydrogenation reactor, a hydrogen feeding pipeline, a hydrolysis reactor and a steam feeding pipeline;
an oxalate feeding pipeline is arranged on the side wall of the hydrogenation reactor, a micro-interface unit is arranged in the hydrogenation reactor, and the micro-interface unit is formed by sequentially arranging a plurality of micro-interface generators from top to bottom; the hydrogen feeding pipeline penetrates through the side wall of the hydrogenation reactor and enters the inside of the micro interface unit, so that hydrogen is broken into micro bubbles at the micron level in the micro interface unit in advance before hydrogenation reaction;
the reaction product after hydrogenation reaction in the hydrogenation reactor enters a light component removal tower to remove light components, and then enters a rectifying tower to be rectified to obtain glycolic acid ester, glycolic acid is generated through the hydrolysis reactor, a micro-interface generator is arranged in the hydrolysis reactor, and the water vapor pipeline penetrates through the side wall of the hydrolysis reactor and enters the interior of the micro-interface generator, so that water vapor is pre-crushed into micro-bubbles in the micro-interface generator before hydrolysis reaction;
dehydrating the hydrolysate after the hydrolysis reaction in the hydrolysis reactor through a dehydrating tower, reacting in a first polymerization reaction kettle to obtain glycolide monomers, and polymerizing in a second polymerization reaction kettle to obtain polyglycolic acid.
2. The system of claim 1, wherein the steam feed line is connected to a distilled water storage tank to provide a source of feedstock for steam entering the hydrolysis reactor.
3. The preparation system of claim 1, wherein the micro-interface unit comprises 3 micro-interface generators, a set of liquid-reciprocal channels is arranged between the adjacent micro-interface generators, and the liquid-reciprocal channels realize the circulation of gas and liquid in the micro-interface generators.
4. The system for preparing a polymer according to claim 1, wherein the micro-interfacial generator inside the hydrolysis reactor is single and is disposed at a lower position inside the hydrolysis reactor.
5. The preparation system of any one of claims 1 to 4, wherein the top of the lightness-removing column is provided with a light component outlet for discharging light components of methanol, methyl formate, ethylene glycol and dimethyl carbonate, and the bottom of the lightness-removing column is provided with a heavy component outlet communicated with the side wall of the rectification column for further rectifying glycolic acid ester.
6. The preparation system according to any one of claims 1 to 4, wherein a raw material circulating outlet is arranged at the bottom of the rectifying tower, and the oxalic ester is returned to the hydrogenation reactor from the raw material circulating outlet to realize the recycling of the raw material.
7. A production system according to any one of claims 1 to 4, wherein an overhead condenser is provided at the top of the rectifying tower, and a part of the material condensed from the overhead condenser is returned to the rectifying tower and another part is sent to a glycolate storage tank connected to the top of the hydrolysis reactor.
8. The method for producing polyglycolic acid using the system for producing polyglycolic acid according to any one of claims 1 to 7, comprising the steps of:
carrying out hydrogenation reaction after the mixed micro interface of the oxalate and hydrogen is dispersed and crushed, and then carrying out dehydrogenation and rectification to obtain glycolic acid ester for collection;
and (3) after the glycolic acid ester is subjected to hydrolysis reaction and dehydration, the glycolide monomer is obtained through esterification, prepolymerization and depolymerization, and the polyglycolic acid is obtained through polymerization.
9. The reaction process as claimed in claim 8, wherein the temperature of the hydrogenation reaction is 200 ℃ and the pressure of the carboxylation reaction is 0.1 to 2 MPa.
10. The reaction process according to claim 8, wherein the temperature of the hydrolysis reaction is 60-100 ℃.
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