CN117486684B - A kind of preparation method of diethylene glycol vinyl ether - Google Patents
A kind of preparation method of diethylene glycol vinyl ether Download PDFInfo
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- CN117486684B CN117486684B CN202311400355.5A CN202311400355A CN117486684B CN 117486684 B CN117486684 B CN 117486684B CN 202311400355 A CN202311400355 A CN 202311400355A CN 117486684 B CN117486684 B CN 117486684B
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- diethylene glycol
- alkali metal
- bubbling reactor
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- vinyl ether
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- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 205
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 230000005587 bubbling Effects 0.000 claims abstract description 76
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 64
- 239000002994 raw material Substances 0.000 claims abstract description 52
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 51
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 34
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 31
- -1 alkali metal alkoxides Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 25
- 238000012546 transfer Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000011344 liquid material Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 32
- 239000003054 catalyst Substances 0.000 description 22
- JFMADMRWGIJWGL-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;potassium Chemical compound [K].OCCOCCO JFMADMRWGIJWGL-UHFFFAOYSA-N 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229960000834 vinyl ether Drugs 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007793 non-solvation Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
- C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of diethylene glycol vinyl ether, and discloses a method for preparing diethylene glycol vinyl ether, which comprises the steps of (1) adding diethylene glycol raw materials containing alkali metal simple substances, alkali metal hydroxides or alkali metal alkoxides into a bubbling reactor, adjusting the atmosphere in the bubbling reactor to be inert atmosphere, heating, starting the diethylene glycol raw materials containing the alkali metal simple substances, the alkali metal hydroxides or the alkali metal alkoxides to circulate in a circulation pipeline of the bubbling reactor, wherein the circulation flow is 1600-3900L/h, and (2) crushing acetylene gas from the circulation pipeline into microbubbles, and then introducing the microbubbles into the bubbling reactor for reaction to obtain the diethylene glycol vinyl ether. According to the invention, the circulating liquid material is adopted to break the acetylene gas into micro bubbles, so that the mass transfer resistance is reduced, the reaction rate is accelerated, a better reaction effect than that in the traditional process is obtained under milder conditions, the cost is saved, and the productivity is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of diethylene glycol vinyl ether, and particularly relates to a preparation method of diethylene glycol vinyl ether.
Background
Diethylene glycol vinyl ether is an important chemical intermediate and polymeric monomer. According to the number of vinyl groups contained, two kinds of materials, diethylene glycol monovinyl ether and diethylene glycol divinyl ether, are classified. The diethylene glycol monovinyl ether can be used as a reactive diluent for UV curing coating, has the advantages of low viscosity, good dilution, complete non-solvation of the coating, high safety and the like compared with the traditional reactive diluent, and can also be used as a comonomer for polymer modification. Diethylene glycol divinyl ether can be used as a crosslinking agent, as a crosslinking comonomer for specialty resins, and the like. Homopolymers and copolymers of diethylene glycol vinyl ethers are widely used in many fields of adhesives, paints, lubricants, plasticizers, pesticides, surface protecting materials, and the like.
The vinyl ether synthesis method is commonly used in three ways, namely an acetylene method, a dehydrohalogenation method, an acetal thermal decomposition method and the like, wherein the acetylene method is most commonly used. The acetylene method is to directly react diethylene glycol with acetylene at a certain temperature and pressure to prepare diethylene glycol vinyl ether. The reaction of diethylene glycol and acetylene belongs to a gas-liquid heterogeneous reaction, the reaction rate is limited by gas-phase and liquid-phase mass transfer, and the reaction rate is slower.
Bubbling reactors employed in current research are largely divided into conventional bubbling reactors, fixed bed reactors and tubular reactors. From the aspect of reaction pressure, the method can be divided into normal pressure process, low pressure process (about 0.6 MPa) and high pressure process (higher than 6 MPa), and the reaction temperature is generally controlled between 165 ℃ and 185 ℃. The pressurizing process is favorable for improving the solubility of acetylene in a liquid phase, can accelerate the reaction rate, but has higher requirements on equipment and increases the risk of acetylene explosion. The reaction temperature is increased, and the reaction rate can be accelerated, but the occurrence of side reactions is also aggravated, and the difficulty of product separation and purification is increased. Meanwhile, in the traditional reactor such as a bubbling reactor, the bubble diameter is larger, the bubble diameter is generally between 10 mm and 20mm, the gas-liquid phase interfacial area is small, the mass transfer efficiency is low, the reaction rate is slow, the reaction time is long, the equipment volume is large, the productivity is low, and the production efficiency is low.
Disclosure of Invention
In order to overcome the above defects or improvement demands of the prior art, the invention prepares diethylene glycol vinyl ether by controlling the circulation flow of diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide in a bubbling reactor, crushing acetylene gas into micro bubbles and then reacting the micro bubbles with diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide. The preparation method of the invention solves the problems of higher reaction pressure, higher temperature and lower mass transfer efficiency of the diethylene glycol vinyl ether in the bubbling reactor, and further improves the production efficiency and the productivity of the diethylene glycol vinyl ether.
In order to achieve the above object, the present invention provides a method for preparing diethylene glycol vinyl ether, comprising the steps of:
(1) Adding diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide into a bubbling reactor, adjusting the atmosphere in the bubbling reactor to be inert atmosphere, and heating; starting the diethylene glycol raw material containing the alkali metal simple substance, the alkali metal hydroxide or the alkali metal alkoxide to circulate in a circulation pipeline of the bubbling reactor, wherein the circulation flow rate of the diethylene glycol raw material containing the alkali metal simple substance, the alkali metal hydroxide or the alkali metal alkoxide in the bubbling reactor is 1600-3900L/h;
(2) Acetylene gas is crushed into micro bubbles from the circulating pipeline and then is introduced into the bubbling reactor for reaction, and diethylene glycol vinyl ether is obtained through the reaction.
In the present invention, the mass ratio of alkali metal or alkali metal hydroxide to diethylene glycol in the diethylene glycol raw material containing an alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide is preferably (2 to 10): 100.
As the preferable mode of the invention, the feeding flow rate of the acetylene during the feeding is 169L/h-394L/h.
In the present invention, the size of the microbubbles is preferably 50 μm to 500. Mu.m.
Preferably, the reaction temperature is 130 ℃ to 150 ℃.
Preferably, the reaction pressure is 0.1 to 0.4MPa.
Preferably, the reaction time is 1 to 9 hours.
Preferably, in the step (2), the acetylene gas is crushed into microbubbles from the circulating pipeline through a microbubble generator, wherein the microbubble generator comprises a mixing pipe for performing primary liquid shearing crushing, and a secondary bubble crusher accommodating cavity for performing secondary liquid shearing crushing.
Preferably, the microbubble generator is arranged at a gas inlet of the bubbling reactor and is communicated with the circulating pipeline, so that the acetylene gas is sheared and crushed into microbubbles by liquid in the circulating pipeline, and a gas-liquid mixture is formed and enters the bubbling reactor.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) According to the invention, acetylene gas entering the bubbling reactor is crushed into micron-sized bubbles to enter the circulating liquid raw material, and the micron-sized bubbles greatly increase the gas-liquid phase interface area and the volume mass transfer coefficient, so that the reaction rate is accelerated, the reaction pressure and the reaction temperature are reduced, and the reaction efficiency and the productivity are improved.
In the embodiment of the invention, acetylene gas is crushed into bubbles with the size of 50-500 mu m, the size of the bubbles is reduced by 2-3 orders of magnitude, and the interface volume and the volume mass transfer coefficient of gas-liquid phases are greatly increased by the bubbles with the size of microns. Preferably, acetylene gas is passed through a bubbling reactor with a microbubble generator arranged at a gas inlet of the bubbling reactor and communicated with a circulating pipeline of the liquid raw material, so that the gas is crushed into bubbles with a micrometer scale and then combined with the liquid to form a continuous reaction flow, and the improvement of the reaction efficiency is further facilitated.
(2) In the present invention, the present invention has the advantage of controlling the circulation flow rate of the diethylene glycol feed containing the alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide by providing sufficient energy for shearing broken bubbles to form microbubbles. The bubbles in the traditional bubbling reactor are mainly generated through sieve holes, liquid materials can flow circularly or not, the size of the bubbles is not influenced obviously, the size of the bubbles generated through the sieve hole structure is large, the size of the bubbles is generally between 10 mm and 20mm, the gas-liquid phase interface area is small, the mass transfer efficiency is low, and the reaction rate is low.
Further, the invention controls the feeding flow rate when acetylene is introduced, and combines the circulating flow rate of diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide, so that the circulating liquid raw material shears and breaks acetylene gas to form micro bubbles.
(3) In the invention, the reaction temperature is controlled to be 130-150 ℃ and the reaction pressure is controlled to be 0.1-0.4 MPa, and compared with the traditional preparation method of diethylene glycol vinyl ether by using a bubbling reactor, the preparation method has the advantages of milder temperature and pressure conditions, lower requirements on equipment strength and lower product cost. The gas and liquid materials interact in the microbubble generator, so that the generated bubbles are smaller, the phase boundary area is larger, the volume mass transfer coefficient is larger, and the reaction rate is accelerated.
In conclusion, the invention adopts the circulating liquid material to break the material of the acetylene gas into micro bubbles, reduces mass transfer resistance, accelerates reaction rate, obtains better reaction effect than the traditional process under milder reaction conditions, saves cost and improves productivity.
Drawings
FIG. 1 is a schematic diagram of a column bubbling reaction system for preparing diethylene glycol vinyl ether, as exemplified in the examples of the present invention;
FIG. 2 is an image of microbubbles at a mirror measured using a USB high definition digital microscope, as an example in an embodiment of the invention;
fig. 3 is a schematic structural diagram of an exemplary microbubble generator according to an embodiment of the present invention.
The reference numerals show 1-material storage tank, 2-micro bubble generator, 3-centrifugal pump, 4-sampling port, 5-bubbling reactor, 6-bottom valve, 7-sight glass, 8-external circulation pipeline, 9-condenser, 10-gas-liquid separator, 11-condensate, 12-tail gas, 21-liquid inlet, 22-jet pipe, 23-suction chamber, 24-nozzle, 25-gas inlet, 26-pressure gauge, 27-mixing pipe, 28-connecting pipe, 29-secondary bubble breaker containing cavity, 210-discharge port, 211-secondary bubble breaker pipe box, 212-secondary bubble breaker, 213-pipe box connecting pipe, 214-sight glass and 215-bubbling reactor wall.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In an embodiment of the present invention, a process for preparing diethylene glycol vinyl ether by reacting diethylene glycol with acetylene,
Referring to fig. 1, a schematic diagram of a tower type bubbling reaction system for preparing diethylene glycol vinyl ether according to the present invention is shown, wherein 1 is a raw material storage tank, 2 is a microbubble generator, 3 is a centrifugal pump, 4 is a sampling port, 5 is a bubbling reactor, 6 is a bottom valve, 7 is a sight glass, 8 is an external circulation pipeline, 9 is a condenser, 10 is a gas-liquid separator, 11 is condensate, and 12 is tail gas.
In an embodiment of the invention, the preparation of diethylene glycol vinyl ether comprises the following steps:
Adding diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide into a bubbling reactor 5, introducing inert gas to replace air, such as N 2, heating diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide, starting condensation circulation of a condenser 9, starting a centrifugal pump 3 of the bubbling reactor after the temperature of the diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide reaches a first preset temperature, pumping the diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide out of the bubbling reactor, entering an external circulation pipeline 8, and entering the bubbling reactor 5 from a liquid inlet, so that the diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide circularly flows in the bubbling reactor 5 and the external circulation pipeline 8.
Preferably, the diethylene glycol feed containing the alkali metal element, alkali metal hydroxide or alkali metal alkoxide is withdrawn from the bubbling reactor, introduced into the external circulation line 8, and introduced into the bubbling reactor 5 again from the liquid inlet of the microbubble generator 2.
Wherein, alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide is dissolved into diethylene glycol to obtain diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide. For example, the simple alkali metal is Na or K, the hydroxide of alkali metal is NaOH or KOH, and the alkoxide of alkali metal is potassium diglycol or sodium diglycol.
Wherein the mass ratio of the alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide to diethylene glycol is (2-10): 100, preferably (8-10): 100, more preferably 8:100.
Wherein, after diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide is stably circulated in the bubbling reactor, the circulation flow rate is adjusted to 1600L/h-3900L/h, preferably 3900L/h.
And after the diethylene glycol raw material temperature containing the alkali metal simple substance, the alkali metal hydroxide or the alkali metal alkoxide reaches a first preset temperature, starting the external circulation of the bubbling reactor. The first preset temperature is 60-100 ℃, which is mainly set according to the liquid level observed in the sight glass 7, and the liquid level is generally ensured to be positioned in the middle of the sight glass so as to facilitate the circulation flow of the logistics.
Step two, after the diethylene glycol raw material containing the alkali metal simple substance, the alkali metal hydroxide or the alkali metal alkoxide is heated to the reaction temperature, acetylene is introduced, and the diethylene glycol raw material containing the alkali metal simple substance, the alkali metal hydroxide or the alkali metal alkoxide is mixed with the diethylene glycol raw material containing the alkali metal simple substance, the alkali metal hydroxide or the alkali metal alkoxide and enters a bubbling reactor 5.
Wherein acetylene is introduced into the microbubble generator 2 and is crushed into bubbles of 50-500 mu m through the shearing action of liquid. The acetylene feed rate is controlled to be 169L/h-394L/h, preferably 282L/h.
And thirdly, reacting for 1-9 h after the reaction pressure in the bubbling reactor 5 is 0.1-0.4 MPa, preferably 0.35MPa, and the reaction temperature is 130-150 ℃, preferably 140 ℃.
In the embodiment of the invention, the acetylene gas is crushed by the micro-bubble generator 2, specifically, the acetylene gas is sheared into bubbles with a certain size for the first time by the liquid moving at a high speed through the mixing pipe 27 in the micro-bubble generator 2, and further enters the accommodating cavity 29 of the secondary bubble crusher to rotate along the wall at a high speed and is sheared into smaller bubbles by the second further compression of the liquid.
As shown in FIG. 2, in order to measure the bubble image at the sight glass by using the USB high-definition digital microscope, most of bubbles in the visible image are distributed uniformly, the larger bubble size is about 350 μm, the small bubble size is about 100 μm, and the bubble size is between 50 μm and 500 μm.
As shown in fig. 3, the microbubble generator 2 comprises a liquid inlet 21, a jet pipe 22, an air suction chamber 23, a nozzle 24, an air inlet 25, a pressure gauge 26 and a mixing pipe 27, a connecting pipe 28, a secondary bubble breaker accommodating cavity 29, a discharge port 210, a secondary bubble breaker pipe box 211, a secondary bubble breaker 212, a pipe box connecting pipe 213, a sight glass 214 and a bubbling reactor wall 215.
The liquid inlet is connected with the injection pipe 22 and the nozzle 24 in sequence, and the injection pipe 22 is positioned in the air suction chamber 23. The liquid material enters the injection pipe 22 at a certain flow rate and then is ejected at a high speed at the nozzle 24, and because of the high flow rate of the liquid at the nozzle, a negative pressure is generated in the suction chamber, so that acetylene gas enters the suction chamber 23.
The air inlet 25 is connected to the suction chamber 23, the mixing pipe 27, the connection pipe 28, and the secondary bubble breaker 212 in this order.
Wherein gas is simultaneously pumped from the compressor into the suction chamber 23 through the gas inlet 25. Then, the liquid ejected from the nozzle and the gas introduced from the suction chamber are mixed in the mixing pipe 27, where the gas is sheared into bubbles of a certain size for the first time by the liquid moving at a high speed.
The secondary bubble breaker 212 consists of a containing cavity 29, a connecting pipe 28 and a discharge hole 210, wherein the containing cavity 29 is in a rotator shape, a rotation generatrix is a curve formed by a straight line parallel to the axis of the containing cavity and two arcs, the straight line is tangential to the arcs at the intersection, the secondary bubble breaker 212 is positioned in a secondary bubble breaker pipe box 211, and the secondary bubble breaker pipe box 211 is connected with the bubbling reactor 5 through a pipe box connecting pipe 213. The gas-liquid mixture enters the secondary bubble generator housing chamber 29 from the mixing pipe 27 through the connecting pipe 28, and the gas-liquid mixture rotates at a high speed along the wall in the housing chamber 29 because the length direction of the connecting pipe 28 is tangential to the circumferential direction of the housing chamber 29. Due to the density difference, the gas mainly gathers near the axis of the accommodation chamber 29 and is sheared into bubbles of 50 μm size by the second further compression of the liquid.
The gas-liquid mixture containing the microbubbles leaves the secondary microbubble generator 212 from the discharge port into the secondary bubble breaker tube box 211 and enters the bubbling reactor 5 from the tube box connection tube 213.
In the present example, the diethylene glycol vinyl ether was prepared according to the method in the above example, by feeding the gas-liquid raw material into the column bubbling reaction system through the gas inlet 25 and the liquid inlet 21 of the microbubble generator 2, respectively.
The bubbling reactor 5 is connected with an external circulation pipeline 8, a centrifugal pump 3 and a microbubble generator 2 in sequence, so that diethylene glycol raw material containing alkali metal simple substance, alkali metal hydroxide or alkali metal alkoxide circularly flows in the bubbling reactor 5 and the external circulation pipeline 8.
Further, a sampling port 4 is provided in the discharge pipe of the centrifugal pump for collecting a liquid sample during the reaction for gas chromatography, and a raw material tank 1 is provided above the bubble breaker for storing the diethylene glycol raw material containing an alkali metal element, an alkali metal hydroxide, or an alkali metal alkoxide.
Further, a bottom valve 6 in the bubble reaction system is used to discharge the liquid crude product from the bubble reactor 5.
The bubbling reactor 5, the condenser 9 and the gas-liquid separator 10 are connected in this order to separate the liquid product carried out by the unreacted acetylene from the gas and collect the crude liquid product.
The raw material storage tank 1 is connected with a centrifugal pump 3.
A sight glass 7 is positioned at the top of the bubble reactor for observing the liquid level in the bubble reactor.
The following is a specific example to further illustrate the embodiments of the present invention and the benefits achieved.
Example 1
Based on the bubbling reactor, and acetylene gas is introduced into the bubbling reactor through a microbubble generator, diethylene glycol vinyl ether is prepared at different catalyst dosages as follows, and the method comprises the following steps:
(1) Adding 0.44kg KOH and 22kg diglycol into a stirring kettle, completely dissolving KOH into diglycol to obtain raw materials containing catalyst diglycol potassium, adding the raw materials into a raw material storage tank, pumping the raw materials into a bubbling reactor by a pump, introducing N 2 into the bubbling reactor to replace air for three times, heating the raw materials containing catalyst diglycol potassium, starting condensation circulation of a condenser, starting an external circulating pump of the bubbling reactor after the temperature of reaction materials reaches a first preset temperature of 80 ℃, pumping the raw materials containing catalyst diglycol potassium out of the bubbling reactor, entering an external circulating pipeline 8, and entering the bubbling reactor 5 from a liquid inlet of a microbubble generator 2, so that the raw materials containing catalyst diglycol potassium circularly flow in the bubbling reactor 5 and the external circulating pipeline 8. The circulating flow rate of the catalyst-containing potassium diglycol raw material is controlled to be 3900L/h.
(2) After the temperature of the catalyst-containing potassium diglycol raw material is raised to 140 ℃, acetylene is directly introduced from the air inlet of the microbubble generator 2 and mixed with the catalyst-containing potassium diglycol raw material to enter the bubbling reactor 5, wherein acetylene gas is crushed into microbubbles by the shearing action of liquid in the microbubble generator 2 and then enters the bubbling reactor. And after the pressure in the bubbling reactor reaches the set value of 0.4MPa, adjusting the acetylene flow to 226L/h.
(3) In the reaction process, sampling is carried out at the sampling port 4 every 2 hours, and gas chromatography is adopted for analysis. The reaction reaches the set reaction time of 9 hours, and the prepared diethylene glycol vinyl ether crude product is obtained after the reaction is finished in the bubbling reactor 5. The reaction product was discharged in its entirety, weighed, and sampled for analysis. The final product mass composition is 40.23% diethylene glycol monovinyl ether, 5.03% diethylene glycol divinyl ether, 52.99% diethylene glycol, and the balance other impurities. Calculated, the conversion of diethylene glycol was 43.66%, the yield of diethylene glycol monovinyl ether was 34.35%, and the yield of total vinyl ether was 37.93%.
The effect of catalyst amount was examined by changing the amount of KOH as a catalyst precursor in the above procedure, and the reaction results obtained are shown in Table 1. It can be seen that the preferred mass ratio of catalyst precursor KOH to diethylene glycol is 8:100 and 10:100, more preferably 8:100.
TABLE 1 influence of the KOH content of the catalyst precursor according to the invention
Example 2
Based on the above-mentioned bubbling reactor, and acetylene gas was introduced into the bubbling reactor through a microbubble generator, diethylene glycol vinyl ether was produced at different circulation flow rates of the raw materials as follows, and reference was made to example 1 for specific procedures.
Wherein, 1.76kg KOH and 22kg diethylene glycol were added to a stirred tank to dissolve KOH completely into diethylene glycol, to obtain a catalyst-containing potassium diethylene glycol raw material.
Wherein, the pressure in the bubbling reactor reaches the set value of 0.35MPa, and the acetylene flow is regulated to 339L/h after the reaction temperature is 140 ℃.
Based on the above steps, two experiments were conducted by changing the circulation flow rate of the catalyst-containing potassium diglycol feedstock to 1600L/h and 3900L/h.
In the reaction process, sampling is carried out at the sampling port 4 every 2 hours, and gas chromatography is adopted for analysis. The reaction reaches the set reaction time of 9 hours, and the prepared diethylene glycol vinyl ether crude product is obtained after the reaction is finished in the bubbling reactor 5. The reaction product was discharged in its entirety, weighed, and sampled for analysis.
In the same way, two experiments were carried out by changing the circulation flow rate of the catalyst-containing potassium diglycol raw material to 1600L/h and 3900L/h. The reaction results obtained are shown in Table 2 and are specifically as follows:
TABLE 2 influence of the circulation flow of the catalyst Potassium diethylene glycol feedstock according to the invention
Example 3
Based on the above-mentioned bubbling reactor, and acetylene gas was introduced into the bubbling reactor through a microbubble generator, diethylene glycol vinyl ether was produced at different acetylene feed rates as follows, for specific procedures, reference example 1.
Wherein, 1.76kg KOH and 22kg diethylene glycol were added to a stirred tank to dissolve KOH completely into diethylene glycol, to obtain a catalyst-containing potassium diethylene glycol raw material.
Wherein, the circulation flow rate of the reaction raw material containing catalyst diethylene glycol potassium is 3900L/h.
Wherein, the pressure in the bubbling reactor reaches the set value of 0.4MPa, and after the reaction temperature is 140 ℃, the diethylene glycol vinyl ether is prepared by adjusting acetylene at different flow rates.
The reaction reaches the set reaction time of 9 hours, and the prepared diethylene glycol vinyl ether crude product is obtained in the bubbling reactor after the reaction is finished. The reaction product was discharged in its entirety, weighed, and sampled for analysis.
In the same manner as above, the acetylene feed rate was changed, and the effect of the acetylene feed rate was examined, and the obtained reaction results are shown in Table 3. As can be seen from Table 3, the preferred acetylene feed flow is 282L/h.
TABLE 3 influence of acetylene feed flow according to the invention
Example 4
Based on the above-mentioned bubbling reactor, and acetylene gas was introduced into the bubbling reactor through a microbubble generator, diethylene glycol vinyl ether was produced at different reaction pressures as follows, and reference example 1 was made for specific procedures.
Wherein, 1.76kg KOH and 22kg diethylene glycol were added to a stirred tank to dissolve KOH completely into diethylene glycol, to obtain a catalyst-containing potassium diethylene glycol raw material.
Wherein, the circulation flow rate of the reaction raw material containing catalyst diethylene glycol potassium is 3900L/h.
Wherein, the pressure in the bubbling reactor reaches a set value, and after the reaction temperature is 140 ℃, the flow of acetylene is regulated to 339L/h.
The reaction reaches the set reaction time of 9 hours, and the prepared diethylene glycol vinyl ether crude product is obtained in the bubbling reactor after the reaction is finished. The reaction product was discharged in its entirety, weighed, and sampled for analysis.
The reaction pressure was varied in the same manner as above, and the influence of the reaction pressure was examined, and the obtained reaction results are shown in Table 4. As can be seen from Table 4, the preferred reaction pressure is 0.35MPa.
TABLE 4 influence of the pressure in the reaction system according to the invention
Example 5
Based on the above-mentioned bubble reactor, and acetylene gas was introduced into the bubble reactor through a microbubble generator, diethylene glycol vinyl ether was produced at different reaction temperatures as follows, for specific procedures with reference to example 1.
Wherein, 1.76kg KOH and 22kg diethylene glycol were added to a stirred tank to dissolve KOH completely into diethylene glycol, to obtain a catalyst-containing potassium diethylene glycol raw material.
Wherein, the circulation flow rate of the reaction raw material containing catalyst diethylene glycol potassium is 3900L/h.
Wherein, the pressure in the bubbling reactor reaches the set value of 0.4MPa, and after the reaction temperature reaches the preset temperature, the flow rate of acetylene is adjusted to the set value of 282L/h.
The reaction reaches the set reaction time of 9 hours, and the prepared diethylene glycol vinyl ether crude product is obtained in the bubbling reactor after the reaction is finished. The reaction product was discharged in its entirety, weighed, and sampled for analysis.
The reaction temperature was changed in the same manner as above, and the influence of the reaction temperature was examined, and the obtained reaction results are shown in Table 5. As can be seen from Table 5, the preferred reaction temperature is 140 ℃.
TABLE 5 influence of reaction temperature
Comparative example 1
The microbubble generator is replaced by a traditional sieve mesh bubble generator uniformly arranged along the air inlet pipe, and the diameter of the sieve mesh is 3mm. Experimental procedure referring to example 1, specific experimental conditions were set at a KOH/diethylene glycol mass ratio of 8:100, an acetylene feed flow of 339L/h, a catalyst-containing potassium diethylene glycol feed circulation flow of 3900L/h, a reaction pressure of 0.4MPa, and a reaction temperature of 140 ℃.
At the end of the experiment, a diethylene glycol conversion of 86.98%, a diethylene glycol monovinyl ether yield of 45.78% and a total vinyl ether yield of 73.35% was obtained. The microbubble generator of the present invention was used under the same conditions, and the resulting diethylene glycol conversion was 93.75%, diethylene glycol monovinyl ether yield was 46.75%, and total vinyl ether yield was 83.77%. Therefore, the reaction effect is obviously better by adopting the microbubble generator.
Table 6 shows the change in mass content of diethylene glycol over time during the reaction of comparative example 1, and it can be seen that the concentration of diethylene glycol decreases significantly faster after the microbubble generator of the present invention is installed, indicating a significantly faster reaction rate.
TABLE 6 comparison of the mass content of diethylene glycol with time
Comparative example 2
The microbubble generator is replaced by a traditional sieve mesh bubble generator uniformly arranged along the air inlet pipe, and the diameter of the sieve mesh is 3mm. The experimental procedure is the same as in example 1, the experimental conditions are set to have a mass ratio of KOH to diethylene glycol of 8:100, an acetylene feed flow of 282L/h, a catalyst-containing diethylene glycol potassium feed circulation flow of 3900L/h, a reaction pressure of 0.4MPa and a reaction temperature of 140 ℃.
At the end of the experiment, a diethylene glycol conversion of 84.93%, a diethylene glycol monovinyl ether yield of 48.38% and a total vinyl ether yield of 70.4% was obtained. The microbubble generator of the present invention was used under the same conditions, and the resulting diethylene glycol conversion was 87.19%, diethylene glycol monovinyl ether yield was 65.93%, and total vinyl ether yield was 84.35%. Therefore, the reaction effect is obviously better by adopting the microbubble generator.
Table 7 shows the mass content of diethylene glycol as a function of time during the reaction, and it can be seen that the concentration of diethylene glycol decreases significantly faster after the microbubble generator of the present invention is installed, indicating a significantly faster reaction rate.
TABLE 7 comparison of the mass content of diethylene glycol with time
Comparative example 3
The microbubble generator is replaced by a traditional sieve mesh bubble generator uniformly arranged along the air inlet pipe, and the diameter of the sieve mesh is 3mm. The experimental procedure is the same as in example 1, the experimental conditions are set to have a mass ratio of KOH to diethylene glycol of 8:100, an acetylene feed flow of 169L/h, a catalyst-containing diethylene glycol potassium feed circulation flow of 3900L/h, a reaction pressure of 0.4MPa and a reaction temperature of 140 ℃.
At the end of the experiment, a diethylene glycol conversion of 60.36% was obtained, the diethylene glycol monovinyl ether yield of 44.53% and the total vinyl ether yield of 54.02%. The results obtained using the microbubble generator of the present invention under the same conditions were a diethylene glycol conversion of 75.17%, a diethylene glycol monovinyl ether yield of 47.4% and a total vinyl ether yield of 69.69%. Therefore, the reaction effect is obviously better by adopting the microbubble generator.
Table 8 shows the mass content of diethylene glycol as a function of time during the reaction, and it can be seen that the concentration of diethylene glycol decreases significantly faster after the microbubble generator of the present invention is installed, indicating a significantly faster reaction rate.
TABLE 8 comparison of the mass content of diethylene glycol with time
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
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| CN102051207A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for enhancing mass transfer through suspension bed hydrogenation technology |
| CN109550418A (en) * | 2018-12-04 | 2019-04-02 | 浙江大学 | A kind of cyclone-type microbubble generator and gas-liquid reactor |
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| CN114950173B (en) * | 2022-05-09 | 2023-06-16 | 中国石油化工股份有限公司 | Microbubble cold hydrogen mass transfer mechanism and catalytic hydrogenation reactor |
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| CN102051207A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for enhancing mass transfer through suspension bed hydrogenation technology |
| CN109550418A (en) * | 2018-12-04 | 2019-04-02 | 浙江大学 | A kind of cyclone-type microbubble generator and gas-liquid reactor |
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| 二甘醇乙烯基醚合成常压鼓泡床工艺研究;赵飞;张钰;张吉波;蒋巍;;吉林化工学院学报;20130315(03);第6-9页 * |
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