CN113546583A - Micro-interface preparation system and preparation method of DMC - Google Patents
Micro-interface preparation system and preparation method of DMC Download PDFInfo
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- CN113546583A CN113546583A CN202110804197.4A CN202110804197A CN113546583A CN 113546583 A CN113546583 A CN 113546583A CN 202110804197 A CN202110804197 A CN 202110804197A CN 113546583 A CN113546583 A CN 113546583A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 239000012071 phase Substances 0.000 claims description 25
- 239000007791 liquid phase Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000005810 carbonylation reaction Methods 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 230000006315 carbonylation Effects 0.000 claims description 2
- 238000007086 side reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 58
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 31
- 239000000047 product Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 230000008093 supporting effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
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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
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
-
- 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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/082—Controlling processes
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/085—Feeding reactive fluids
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/087—Heating or cooling the reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
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Abstract
The invention provides a micro-interface preparation system and a preparation method of DMC, comprising the following steps: a reaction tower; a gas phase inlet is formed in the side part of the reaction tower; the gas phase inlet is connected with a mixed gas pipeline; a first micro-interface generator and a second micro-interface generator are arranged in the reaction tower; the first micro-interface generator is arranged below the liquid level in the reaction tower, and the second micro-interface generator is arranged above the liquid level; the first micro-interface generator and the second micro-interface generator are both connected with the gas phase inlet, mixed gas enters the first micro-interface generator and the second micro-interface generator through the gas phase inlet, and micro-bubbles at the micron level are dispersed and crushed in the first micro-interface generator and the second micro-interface generator. The micro-interface preparation system of DMC of the present invention has the advantages of low reaction temperature and pressure, less side reaction, high methanol conversion rate, and wide popularization and application.
Description
Technical Field
The invention relates to the field of methanol carbonylation reaction preparation, in particular to a micro-interface preparation system and a micro-interface preparation method of DMC.
Background
A liquid-phase methanol oxidizing and carbonylating method based on CH3OH、O2And a method for synthesizing DMC (dimethyl carbonate) by CO under the action of catalyst.
The existing production process flow is generally carried out in two sets of reaction devices. Each set of reaction device consists of two parallel reactors and a gas-liquid separation tank. The reaction temperature is 115 ℃ and 120 ℃, and the reaction pressure is 2.2-2.5 MPaG. The normal operation liquid level of the gas-liquid separation tank is about 50 percent. The catalyst is cuprous chloride catalyst, the particle size of the catalyst particles is 200 meshes (74 mu m), the catalyst particles are in a pseudo-homogeneous state in the slurry, and the content is 1.5-3% (wt).
The liquid phase feeding of the reactor is fresh methanol and methanol circulated by the system, and the fresh methanol and the methanol are mixed and then enter a downcomer at the bottom of the gas-liquid separation tank to flow into the bottom of the reactor respectively. Fresh O in gas phase feed2And CO and circulating gas (mainly CO) are mixed and then respectively enter the two reactors in a bubbling mode through a distributor at the bottom of the two reactors. To ensure O2Fully reacting, and controlling O in the exhaust gas2The content is below the explosive limit and the oxygen concentration in the feed is < 5%. In the two reactors, the reaction mixture is fed into a reactor,O2and generating DMC and water by the CO and the methanol under the action of a catalyst. The top of the two reactors is connected with a gas-liquid separating tank through a pipeline, and the gas-liquid mixture on the upper part of the reactors enters the gas-liquid separating tank for separation. The separated gas phase mixture is sent to a downstream device, and the main components are CO, DMC, methanol and CO2And water. The liquid phase at the bottom of the separation tank is mixed with the raw material methanol from the downcomer and then circulates back to the bottoms of the two reactors.
The methanol oxidative carbonylation reaction is exothermic, the heat of reaction generated by 1mol of DMC is about 310kJ, the reaction material is discharged in a gas phase, and the latent heat of vaporization is 31 kJ/mol. Because the conversion per pass of the raw materials is low, the total exothermic amount of the reaction is relatively small, and the constant reaction temperature needs to be regulated by supplementing heat through a U-shaped heat exchanger inside the reactor. 4 heat exchangers are arranged in each reactor, and the steam consumption is about 0-10 t/h.
The main problems of the existing DMC production process are as follows:
(1) the raw material gas mixture is initially distributed at the bottom of the reactor through a distributor and then is bubbled into a liquid phase. Because the opening of the distributor is in millimeter level (phi 5mm), the diameter of the generated bubbles is larger (8-15 mm), the gas-liquid interface area is smaller, the initially distributed bubbles are easy to coalesce in the rising process, the bubbles in the reactor are distributed unevenly, and in addition, the liquid circulation adopts a density difference circulation mode, the flow rate is slower (less than 0.1m/s), so that the gas-liquid mass transfer rate is lower, and the macroscopic reaction rate is seriously lower than the design expected value;
(2)O2the consumption is high, but the actual effective utilization rate is low;
(3) the single-pass conversion rate of CO is about 2-8%, and the feeding amount of CO is more, so that the power consumption of a fresh CO compressor and a circulating CO compressor is larger;
(4) because the product DMC stays in the system for too long time and undergoes hydrolysis reaction with water, CO is generated2With CO and O2Side reactions are easy to occur, and the factors greatly reduce the conversion rate of raw materials.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a micro-interface preparation system of DMC, the system disperses and breaks the mixed gas into micron-sized micro-bubbles through a first micro-interface generator and a second micro-interface generator arranged in the reactor, thus improving the phase boundary mass transfer area between methanol and the mixed gas, improving the reaction rate, reducing the retention time of the raw materials in the reactor and further reducing the occurrence of side reactions; meanwhile, the reaction energy consumption can be effectively reduced, and the reaction conversion rate can be improved.
The second purpose of the invention is to provide a preparation method adopting the system, the method is simple and convenient to operate, and by applying the system, the reaction energy consumption is reduced, and the single-pass conversion rate of methanol and the yield of DMC are improved.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a micro-interface preparation system of DMC, comprising: a reaction tower; a gas phase inlet is formed in the side part of the reaction tower; the gas phase inlet is connected with a mixed gas pipeline;
a first micro-interface generator and a second micro-interface generator are arranged in the reaction tower; the first micro-interface generator is arranged below the liquid level in the reaction tower, and the second micro-interface generator is arranged above the liquid level; the first micro-interface generator and the second micro-interface generator are both connected with the gas phase inlet, and mixed gas enters the first micro-interface generator and the second micro-interface generator through the gas phase inlet and is dispersed and crushed into micro-bubbles in the first micro-interface generator and the second micro-interface generator;
a micro-bubble outlet is arranged above the first micro-interface generator and clings to the first micro-interface generator; an outlet at the bottom of the second micro-interface generator is connected with a micro-bubble pipeline, and an outlet of the micro-bubble pipeline covers the upper part of the micro-bubble outlet;
a plurality of layers of sieve plates are arranged above the first micro-interface generator; a plurality of layers of fillers are arranged above the sieve plate; the filler is located below the liquid level.
In the prior art, the raw material gas mixture is arranged at the bottom of the reactorInitially distributed by a distributor and then bubbled into a liquid phase. Because the opening of the distributor is in millimeter level (phi 5mm), the diameter of the generated bubbles is larger (8-15 mm), the gas-liquid interface area is smaller, the initially distributed bubbles are easy to coalesce in the rising process, the bubbles in the reactor are not uniformly distributed, in addition, the liquid circulation adopts a density difference circulation mode, the flow rate is lower (less than 0.1m/s), so that the gas-liquid mass transfer rate is lower, the macroscopic reaction rate is seriously lower than the designed expected value, and because the product DMC stays in the system for too long time and undergoes hydrolysis reaction with water, CO is generated2With CO and O2Side reactions are easy to occur, and the factors greatly reduce the conversion rate of raw materials.
In order to solve the technical problems, the invention provides a micro-interface preparation system of DMC, the system disperses and breaks the mixed gas into micron-sized micro-bubbles through a first micro-interface generator and a second micro-interface generator which are arranged in a reactor, the phase boundary mass transfer area between methanol and the mixed gas is increased, the reaction rate is increased, the retention time of raw materials in the reactor is reduced, and thus the occurrence of side reactions is reduced; meanwhile, the reaction energy consumption can be effectively reduced, and the reaction conversion rate can be improved.
Preferably, the reaction tower is connected with a circulating pipeline; and the inlet of the circulating pipeline is positioned below the liquid level, and the outlet of the circulating pipeline penetrates through the reaction tower to be connected with the second micro-interface generator. Through setting up circulation pipeline with liquid circulation to the second micro-interface generator in, can improve crushing efficiency.
Preferably, a filter screen is arranged at the communication position of the inlet of the circulating pipeline and the reaction tower. Through setting up the filter screen, can prevent effectively that the catalyst from flowing into circulation pipeline and causing the jam, can prevent the waste of catalyst simultaneously, practice thrift the cost.
Preferably, the microbubble outlet is oriented horizontally or vertically upwards. When the micro-bubble outlet is vertically upward, a 180-degree corner is formed in the flow direction of bubbles at the outlet of the second micro-interface generator, and at the moment, the bubbles at the outlet of the top of the first micro-interface generator and the bubbles flowing down from the second micro-interface generator form collision flow, so that the crushing effect is further enhanced.
Preferably, the top of the second micro-interface generator is connected with a gas collecting pipe. Through setting up the gas collecting pipe, can collect the unreacted gas in reaction tower top, improve the utilization ratio and the conversion of raw materials.
Preferably, the first micro-interface generator is a pneumatic micro-interface generator, and the second micro-interface generator is a gas-liquid linkage micro-interface generator or a hydraulic micro-interface generator.
The reaction tower is internally provided with the first micro-interface generator and the second micro-interface generator, and the mixed gas is dispersed and crushed into micro-bubbles through the two micro-interface generators, so that the phase boundary mass transfer area between the mixed gas and methanol can be effectively increased, and the reaction efficiency is improved; during reaction, the mixed gas is dispersed and crushed into micro bubbles through the first micro interface generator and the second micro interface generator, and then is subjected to carbonylation reaction with methanol under the participation of the catalyst. In the invention, the outlet of the second micro-interface generator is connected with the first micro-interface generator through a specific structure, the two micro-interface generators need to be combined into a whole and are not arranged independently, and the two micro-interface generators are combined to form a hybrid micro-interface unit SBBS, thereby improving the application effect of the independent micro-interface generator. On one hand, collision flow can be formed between the first micro-interface generator and the second micro-interface generator, and bubbles are further dispersed and crushed; on the other hand, when the first micro interface generator is internally blocked, the bubble flow of the second micro interface generator can flush the inside of the first micro interface generator, so that the blockage is prevented. And set up like this and can also improve fixed effect, play the supporting effect to the second micro-interface generator through the pipeline between first micro-interface generator and the second micro-interface generator. The space in the reaction tower is narrower itself, if the setting of micro-interface generator too disperse and also can influence the normal work of reaction tower, the design also shortens each micro-interface generator's distance for holistic structure in addition, strengthens the cooperation ability each other between each part, through the broken bubble collision impact back each other of micro-interface to improve dispersion crushing effect.
In addition, in the scheme of the invention, the first micro-interface generator and the second micro-interface generator are connected into a whole through a micro-bubble pipeline, the micro-bubble pipeline is directly communicated with a micro-bubble outlet arranged at the upper part of the first micro-interface generator, the micro-bubble outlet is an outlet of micro-bubbles formed after the first micro-interface generator is dispersed and crushed, and power is provided for materials discharged from the micro-bubble outlet through the guiding effect of a micro-bubble channel. In addition, this microbubble export can set up to along horizontal direction or perpendicular direction up, and the horizontal direction is the direct injection away just, and perpendicular ascending direction is equivalent to set up 180 back bending in the exit to promote the circulation energy of gas-liquid emulsion more, also can drive the material that is located the mixing effect difference on upper portion and carry out the backmixing and break again.
According to the preparation system, the multilayer sieve plate is arranged above the first micro-interface generator, and the completely mixed flow with violent reaction is changed into the plug flow through the blocking effect of the multilayer sieve plate, so that the side reaction of the product DMC and water can be prevented, and the product yield is ensured. In addition, the filler is arranged below the liquid level, the filler can perform the gas-liquid separation effect, mixed liquid in product gas is primarily separated, and the product purity is improved.
The top of the second micro-interface generator is also connected with a gas collecting pipe, and the gas collecting pipe can effectively collect the mixed gas overflowing to the top of the reaction tower by utilizing the entrainment effect in the second micro-interface generator, so that the utilization rate and the conversion rate of raw materials are improved. Therefore, the effect of independently applying the micro-interface generator is improved by applying the hybrid micro-interface unit SBBS and combining the sieve plate, the filler, the gas collecting pipe and the like.
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 numbers CN201610641119.6, CN201610641251.7, 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.
Preferably, a liquid phase inlet is arranged at the bottom of the reaction tower; the liquid phase inlet is connected with a methanol pipeline.
Preferably, the top of the reaction tower is provided with a gas outlet, and the side part of the reaction tower is provided with a product outlet; the product outlet is positioned below the liquid level; the product outlet is connected with a gas-liquid separator, a gas-phase outlet of the gas-liquid separator is connected with a production pipeline, and a liquid-phase outlet is connected with the reaction tower.
The invention also provides a preparation method of the micro-interface preparation system adopting the DMC, which comprises the following steps:
crushing the mixed gas through a micro interface, mixing the crushed mixed gas with methanol and a catalyst for carbonylation, and performing gas-liquid separation to obtain a product DMC; the catalyst is cuprous chloride.
Preferably, the carbonylation reaction temperature is 108 ℃ and 113 ℃, and the pressure is 1.3-1.8 MPa.
The DMC obtained by the reaction method of the invention has high yield. And the preparation method has the advantages of low reaction temperature, greatly reduced pressure and remarkably reduced cost.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the micro-interface preparation system of DMC, the first micro-interface generator and the second micro-interface generator which are arranged in the reactor are used for dispersing and crushing the mixed gas into micron-sized micro bubbles, so that the phase boundary mass transfer area between methanol and the mixed gas is increased, the reaction rate is increased, the retention time of the raw materials in the reactor is reduced, and the occurrence of side reactions is reduced; meanwhile, the reaction energy consumption can be effectively reduced, and the reaction conversion rate is improved;
(2) the two micro-interface generators are combined to form the hybrid micro-interface unit SBBS, so that the application effect of the single micro-interface generator is improved. On one hand, collision flow can be formed between the first micro-interface generator and the second micro-interface generator, and bubbles are further dispersed and crushed; on the other hand, when the first micro interface generator is internally blocked, the bubble flow of the second micro interface generator can flush the inside of the first micro interface generator, so that the blockage is prevented. The fixing effect can be improved, and the second micro-interface generator is supported by the pipeline between the first micro-interface generator and the second micro-interface generator;
(3) through setting up the filter screen, can prevent effectively that the catalyst from leading to the fact the jam in flowing into the circulating line, avoid the waste of catalyst.
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 a micro interface of DMC according to embodiment 1 of the present invention.
Wherein:
10-methanol line; 20-a reaction tower;
201-liquid phase inlet; 202-a first micro-interface generator;
203-gas phase inlet; 204-a filter screen;
205-sieve plate; 206-a filler;
207-micro bubble pipeline; 208-a second micro-interface generator;
209-a gas collecting pipe; 210-a gas outlet;
211-product outlet; 30-a mixed gas line;
40-a circulation line; 50-a gas-liquid separator;
60-production line.
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.
Example 1
Referring to fig. 1, the present embodiment provides a system for preparing a micro interface of DMC, comprising: a reaction tower 20; the side part of the reaction tower 20 is provided with a gas phase inlet 203; the gas phase inlet 203 is connected with a mixed gas pipeline 30; the bottom of the reaction tower 20 is provided with a liquid phase inlet 201; the liquid phase inlet 201 is connected with a methanol pipeline 10. The top of the reaction tower 20 is provided with a gas outlet 210, and the side part is provided with a product outlet 211; a liquid level is arranged in the reaction tower 20; the product outlet 211 is located below the liquid level; the product outlet 211 is connected with a gas-liquid separator 50, the liquid phase outlet of the gas-liquid separator 50 is connected with the reaction tower 20, the gas phase outlet is connected with a production pipeline 60, and during actual use, DMC is obtained from the production pipeline 60. In order to improve the purity of the product, the product can be further purified by rectification, phase separation and other modes.
Wherein, a first micro-interface generator 202 and a second micro-interface generator 208 are arranged in the reaction tower 20; the first micro-interface generator 202 is arranged below the liquid level in the reaction tower 20, and the second micro-interface generator 208 is arranged at the liquid level; the first micro-interface generator 202 and the second micro-interface generator 208 are both connected with the gas phase inlet 203, the mixed gas enters the first micro-interface generator 202 and the second micro-interface generator 208 through the gas phase inlet 203, and is dispersed and broken into micro-bubbles in the micron level in the first micro-interface generator 202 and the second micro-interface generator 208; the first micro-interface generator 202 is a pneumatic micro-interface generator, and the second micro-interface generator 208 is a gas-liquid linkage micro-interface generator or a hydraulic micro-interface generator.
Specifically, a microbubble outlet is arranged above the first micro-interface generator 202 and clings to the first micro-interface generator 202; the outlet at the bottom of the second micro interface generator 208 is connected with a micro-bubble pipeline 207, and the outlet of the micro-bubble pipeline 207 covers the upper part of the micro-bubble outlet; the outlet of the microbubble channel 207 communicates with the microbubble outlet. The microbubble outlet direction may be horizontal or vertical. In this embodiment, the outlets of the microbubbles are vertically upward. In effect, the upper and left and right sidewalls of the first micro-interfacial surface generator 202 are all full of outlets. When the micro-bubble outlet is vertically upward, a 180-degree corner is formed with the flow direction of the bubbles at the outlet of the second micro-interface generator 208, and meanwhile, the bubbles flowing down from the second micro-interface generator 208 collide with the micro-bubbles generated by the first micro-interface generator 202 to form an impinging stream, so that further dispersion and fragmentation can be realized. Although not explicitly shown in the drawings, the detailed structure of the microbubble outlet will be clear from the description of the present invention.
In addition, a multilayer sieve plate 205 is arranged above the first micro-interface generator 202; a plurality of layers of filler 206 are arranged above the sieve plate 205; the fill material 206 is located below the liquid level. The packing 206 is filled with regular packing, which may be wire mesh packing or corrugated plate packing. During the reaction, the filler in the filler 206 can perform primary gas-liquid separation on the rising product gas flow, thereby improving the product purity.
In this embodiment, a gas header 209 is connected to the top of the second micro-interface generator 208. During the reaction, the liquid circulated in the circulation line 40 forms entrainment in the second micro-interface generator 208, and the gas overflowing from the top of the reaction tower 20 is collected by the gas collecting pipe 209 for the liquid to return to the reaction tower 20 together to continue to participate in the reaction.
In this embodiment, the reaction tower 20 is connected with a circulation line 40; the inlet of the circulation line 40 is located below the liquid level and the outlet is connected to a second micro-interface generator 208 through the reaction column 20. A filter screen 204 is arranged at the position where the inlet of the circulating pipeline 40 is communicated with the reaction tower 20. In order to ensure the circulation effect, the circulation pipeline 40 is correspondingly provided with a circulation pump, a one-way valve and a control valve. During the reaction, the filter screen 204 can effectively prevent the catalyst from blocking up due to flowing into the circulation pipeline 40, and can prevent the waste of the catalyst, thereby saving the cost.
During reaction, methanol and mixed gas are simultaneously introduced into the reaction tower, the mixed gas is dispersed into micro bubbles through the first micro interface generator and the second micro interface generator, then the micro bubbles react with the methanol under the participation of a catalyst, and a reaction product is separated through a gas-liquid separator to obtain a product DMC.
Wherein, the specific process parameters of the reaction are as follows:
methanol conversion-mol of methanol converted/mol of methanol fed,
DMC yield is the molar flow rate of DMC produced per molar amount of methanol fed.
As can be seen from the above table, the conversion per pass of methanol reached 20.92% (typically 10-15% for the prior art) and the DMC yield reached 17.46% (typically 8-12% for the prior art). The reaction temperature is 108 ℃ and the pressure is 1.3MPa, while the existing reaction temperature is generally 120 ℃ and 125 ℃ and the pressure is 2.2-2.5MPa, thus the system of the embodiment has obviously reduced temperature and pressure compared with the existing process.
Example 2
This example is different from example 1 only in terms of process parameters, and the specific process parameters are as follows:
wherein the reaction temperature is 110 ℃ and the pressure is 1.5 MPa.
Through calculation, the single-pass conversion rate of the methanol reaches 20.48 percent, and the yield of the DMC reaches 17.48 percent. It can be seen that the system of the present embodiment has a significant reduction in temperature and pressure relative to existing processes.
Example 3
This example is different from example 1 only in terms of process parameters, and the specific process parameters are as follows:
wherein the reaction temperature is 113 ℃ and the pressure is 1.8 MPa.
Through calculation, the single-pass conversion rate of the methanol reaches 20.08 percent, and the yield of the DMC reaches 17.26 percent. It can be seen that the system of the present embodiment has a significant reduction in temperature and pressure relative to existing processes.
Comparative example 1
The difference between this example and example 1 is that a hybrid micro-interfacial surface generator in which a first micro-interfacial surface generator and a second micro-interfacial surface generator are combined is not used. The feed materials were the same as in example 1.
The methanol conversion per pass was calculated to be 10% and the DMC yield was calculated to be 9%.
Comparative example 2
The difference between this example and example 1 is that the hybrid micro-interfacial surface generator, which is a combination of a first micro-interfacial surface generator and a second micro-interfacial surface generator, is replaced by a pneumatic micro-interfacial surface generator. The feed materials were the same as in example 1.
The methanol conversion per pass was calculated to be 14% and the DMC yield was calculated to be 13%.
In conclusion, compared with the prior art, the micro-interface preparation system of DMC disclosed by the invention has the advantages of low reaction temperature and pressure, less side reaction, high methanol conversion rate and wide popularization and application value.
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 system for preparing a DMC micro-interface, comprising: a reaction tower; a gas phase inlet is formed in the side part of the reaction tower; the gas phase inlet is connected with a mixed gas pipeline;
a first micro-interface generator and a second micro-interface generator are arranged in the reaction tower; the first micro-interface generator is arranged below the liquid level in the reaction tower, and the second micro-interface generator is arranged above the liquid level; the first micro-interface generator and the second micro-interface generator are both connected with the gas phase inlet, and mixed gas enters the first micro-interface generator and the second micro-interface generator through the gas phase inlet and is dispersed and crushed into micro-bubbles in the first micro-interface generator and the second micro-interface generator;
a micro-bubble outlet is arranged above the first micro-interface generator and clings to the first micro-interface generator; an outlet at the bottom of the second micro-interface generator is connected with a micro-bubble pipeline, and an outlet of the micro-bubble pipeline covers the upper part of the micro-bubble outlet;
a plurality of layers of sieve plates are arranged above the first micro-interface generator; a plurality of layers of fillers are arranged above the sieve plate; the filler is located below the liquid level.
2. The system for the micro-interface preparation of DMC of claim 1, wherein said reaction column is connected to a circulation line; and the inlet of the circulating pipeline is positioned below the liquid level, and the outlet of the circulating pipeline penetrates through the reaction tower to be connected with the second micro-interface generator.
3. The system for micro-interface preparation of DMC according to claim 2, characterized by that, the inlet of the circulation pipeline is connected to the reaction tower and a filter screen is installed.
4. The system for the micro-interfacial production of DMC of claim 1, wherein said microbubble outlet direction is horizontally or vertically upward.
5. The system for the micro-interface preparation of DMC of claim 1, wherein a gas header is attached to the top of said second micro-interface generator.
6. The system for the micro-interface preparation of DMC of claim 1, wherein said first micro-interface generator is a pneumatic micro-interface generator and said second micro-interface generator is a gas-liquid linkage micro-interface generator or a hydraulic micro-interface generator.
7. The system for the micro-interfacial production of DMC of claim 1, wherein said reaction column is provided with a liquid phase inlet at the bottom; the liquid phase inlet is connected with a methanol pipeline.
8. The system for the micro-interface preparation of DMC of claim 1, wherein said reaction column is provided with a gas outlet at the top and a product outlet at the side; the product outlet is positioned below the liquid level; the product outlet is connected with a gas-liquid separator, a gas-phase outlet of the gas-liquid separator is connected with a production pipeline, and a liquid-phase outlet is connected with the reaction tower.
9. Method for the preparation of a system for the micro-interfacial preparation of DMC according to any of claims 1 to 8, comprising the steps of:
crushing the mixed gas through a micro interface, mixing the crushed mixed gas with methanol and a catalyst for carbonylation, and performing gas-liquid separation to obtain a product DMC; the catalyst is cuprous chloride.
10. The process according to claim 9, wherein the carbonylation reaction temperature is 108 ℃ and 113 ℃ and the pressure is 1.3 to 1.8 MPa.
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