CN112010746A - External micro-interface strengthening system and method for preparing acetic acid through methanol carbonylation - Google Patents
External micro-interface strengthening system and method for preparing acetic acid through methanol carbonylation Download PDFInfo
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- CN112010746A CN112010746A CN202010831158.9A CN202010831158A CN112010746A CN 112010746 A CN112010746 A CN 112010746A CN 202010831158 A CN202010831158 A CN 202010831158A CN 112010746 A CN112010746 A CN 112010746A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 243
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 82
- 230000006315 carbonylation Effects 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000005728 strengthening Methods 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims description 32
- 239000007791 liquid phase Substances 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 23
- 239000002699 waste material Substances 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 31
- 239000007788 liquid Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides an external micro-interface strengthening system and method for preparing acetic acid by methanol carbonylation, which comprises the following steps: a carbonylation reaction kettle; the side wall of the carbonylation reaction kettle is provided with a first raw material inlet and a second raw material inlet, the first raw material inlet is provided with a first micro-interface generator for dispersing and crushing materials into micro-bubbles, and the second raw material inlet is provided with a second micro-interface generator for dispersing and crushing materials into micro-bubbles; according to the reaction system, the micro-interface reactor is arranged at the raw material inlet of the carbonylation reaction kettle, so that the problem of low reaction efficiency of the system due to the fact that carbon monoxide and methanol cannot be fully mixed in the reaction kettle in the prior art is solved.
Description
Technical Field
The invention relates to the technical field of preparation of acetic acid, in particular to an external micro-interface strengthening system and method for preparing acetic acid by methanol carbonylation.
Background
Acetic acid is one of important organic chemical raw materials, is mainly used for producing vinyl acetate, acetic anhydride, cellulose acetate, acetates, terephthalic acid, chloroacetic acid and the like, and can be widely used in the fields of chemical industry, light industry, textile, medicine, printing and dyeing and the like. Currently, the main methods for producing acetic acid include acetaldehyde oxidation, olefin direct oxidation, and methanol carbonylation. Among them, the methanol carbonylation method has the advantages of high conversion rate of methanol, small by-products and the like, and is gradually one of the main methods for producing acetic acid. In the prior art, the reaction for producing acetic acid by methanol carbonylation takes CO and methanol as raw materials, and the step for producing acetic acid by methanol carbonylation generally comprises the steps of feeding the methanol and CO into a reaction kettle to contact with a homogeneous catalyst solution, and feeding a mixture obtained after the contact into a flash tower. However, when acetic acid is produced using the existing carbonylation reaction system, the methanol liquid and the carbon monoxide gas are directly introduced into the carbonylation reaction kettle, and the methanol liquid and the carbon monoxide gas are not sufficiently mixed inside the carbonylation reaction kettle, thereby reducing the reaction efficiency of the system.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an external micro-interface strengthening system for preparing acetic acid by methanol carbonylation, which can disperse and break materials into micro bubbles on one hand after a micro-interface generator is arranged at a raw material inlet of a carbonylation reaction kettle, thereby increasing the phase interface area between a gas phase and a liquid phase, fully meeting mass transfer space, increasing the retention time of gas in the liquid phase, reducing energy consumption and improving reaction efficiency; on the other hand, the operation temperature and pressure in the carbonylation reaction kettle are reduced, and the safety and stability of the whole reaction system are improved.
The second purpose of the invention is to provide a method for preparing acetic acid by carbonylation by adopting the external micro-interface strengthening system, which is beneficial to reducing energy consumption and achieving better reaction effect than the prior art.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides an external micro-interface strengthening system for preparing acetic acid by methanol carbonylation, which comprises a carbonylation reaction kettle; the side wall of the carbonylation reaction kettle is provided with a first raw material inlet and a second raw material inlet, the first raw material inlet is provided with a first micro-interface generator for dispersing and crushing materials into micro-bubbles, and the second raw material inlet is provided with a second micro-interface generator for dispersing and crushing materials into micro-bubbles;
a product outlet is formed in the bottom of the carbonylation reaction kettle and connected with a flash tank to be used for carrying out flash evaporation on the carbonylation reaction product; the top of the flash tank is provided with a gas phase outlet, and the gas phase outlet is connected with a light component rectifying tower and is used for separating and rectifying a gas phase product obtained by flash evaporation; a side extraction port is arranged at the side part of the light component rectifying tower, the side extraction port is connected with a dehydrating tower to be used for dehydrating the product, and the dehydrated product enters the heavy component rectifying tower to be continuously separated and rectified; the side part of the heavy component rectifying tower is provided with an acetic acid outlet, the bottom part of the heavy component rectifying tower is provided with a heavy component outlet, and the heavy component outlet is connected with a waste acid stripping tower and used for carrying out superheated steam stripping on heavy components.
In the prior art, the reaction for producing acetic acid by methanol carbonylation takes CO and methanol as raw materials, and the step for producing acetic acid by methanol carbonylation generally comprises the steps of feeding the methanol and CO into a reaction kettle to contact with a homogeneous catalyst solution, and feeding a mixture obtained after the contact into a flash tower. However, when acetic acid is produced using the existing carbonylation reaction system, the methanol liquid and the carbon monoxide gas are directly introduced into the carbonylation reaction kettle, and the methanol liquid and the carbon monoxide gas are not sufficiently mixed inside the carbonylation reaction kettle, thereby reducing the reaction efficiency of the system. The external micro-interface strengthening system for preparing acetic acid by methanol carbonylation can disperse and crush materials into micro bubbles on one hand, thereby increasing the phase interface area between a gas phase and a liquid phase, fully meeting mass transfer space, increasing the retention time of gas in the liquid phase, reducing energy consumption and improving reaction efficiency; on the other hand, the operation temperature and pressure in the carbonylation reaction kettle are reduced, and the safety and stability of the whole reaction system are improved.
The micro-interface generator is arranged at a raw material inlet of the carbonylation reaction kettle, carbon monoxide and methanol are simultaneously introduced into the micro-interface generator, the carbon monoxide is dispersed and crushed into micro-bubbles in the micro-interface generator and then fully emulsified with the methanol to form emulsion, and the emulsion enters the carbonylation reaction kettle for reaction. The applicant finds through a great deal of practice that the retention time of carbon monoxide in methanol can be prolonged by arranging the micro-interface generator at the position of a raw material inlet of the carbonylation reaction kettle, so that the raw material is fully emulsified before entering the reaction kettle, the gas-liquid reaction is strengthened, the mass transfer efficiency is improved, and the reaction efficiency is improved.
In order to improve the effect of the micro-interface, the number of the micro-interface generators is preferably set to be a plurality, the micro-interface generators can be sequentially arranged in parallel from top to bottom, when the micro-interface generators are arranged in parallel, bubbles generated by the upper micro-interface generator move downwards, bubbles generated by the lower micro-interface generator move upwards, and the bubbles collide with each other to generate smaller bubbles, so that the hedging is realized, the contact area is further increased, and the reaction efficiency is accelerated. Also the horizontal direction sets up in series in proper order, and when adopting the horizontal direction to set up in series in proper order, the microbubble that micro-interface generator produced before the setting reentrants the micro-interface generator that sets up after, and is further, the microbubble is broken into littleer microbubble, can prolong the dwell time of gas in the liquid phase moreover, fully improves mass transfer effect. The number of the micro-interface generators is preferably set to be 2, and the 2 micro-interface generators can ensure the effect of dispersive crushing.
Further, the micro-interface generator is selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
Further, a first gas phase inlet is formed in the side wall of the first micro-interface generator and used for introducing carbon monoxide, and a first liquid phase inlet is formed in the top of the first micro-interface generator and used for introducing raw material methanol; the side wall of the second micro-interface generator is provided with a second gas phase inlet for introducing carbon monoxide, and the bottom of the second micro-interface generator is provided with a second liquid phase inlet for introducing raw material methanol.
Carbon monoxide enters into the micro-interface generator from the horizontal lateral wall of micro-interface generator, can increase the inside pressure of micro-interface generator like this, make the gas-liquid two-phase emulsified substance that forms more easily, thereby increase the two-phase mass transfer area of gas-liquid, inside methanol after first preheater preheats gets into first micro-interface generator through the top of first micro-interface generator, inside methanol after second preheater preheats gets into second micro-interface generator through the bottom of second micro-interface generator, two way methanol can realize the offset through first pipeline and second pipeline, the inside gas of broken micro-interface generator after both fiercely collide, make it produce littleer bubble, further increased area of contact, and the reaction efficiency is accelerated.
Furthermore, the device also comprises a first pipeline and a second pipeline, wherein the first pipeline and the second pipeline both penetrate through the side wall of the first micro-interface generator and the side wall of the second micro-interface generator, and the material flow direction in the first pipeline and the material flow direction in the second pipeline are opposite to each other. Through setting up reverse pipeline, can realize the bubble downstream that first little interfacial surface generator produced, the bubble upward movement that the second little interfacial surface generator produced, both collide and produce littleer bubble, realize the offset, further increased area of contact for reaction efficiency.
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 applications CN201610641119.6, 201610641251.7,CN201710766435.0CN106187660, 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.
In addition, the prior patent201710766435.0The principle of the bubble breaker is described as high-speed jet flow to achieve mutual collision of gases, and the method can be used for a micro-interface strengthening reactor and verifies the relevance between the bubble breaker and a micro-interface generator; furthermore, the prior patent CN106187660 also describes the specific structure of the bubble breaker, specifically see [0031 ] in the specification]-[0041]The section, and the attached drawing part, it has detailed explanation to the concrete theory of operation of bubble breaker S-2, and the bubble breaker top is the import of liquid phase, and the side is the import of gaseous phase, provides entrainment power through the liquid phase that comes in from the top to reach the effect of smashing into superfine bubble, also can see in the attached drawing that the bubble breaker is the toper structure, and the diameter of upper portion is bigger than the diameter of lower part, also is for the liquid phase can be better provide entrainment power.
Since the micro-interfacial surface generator was just developed in the early stage of the prior patent application, it was named micro bubble generator (CN201610641119.6) and bubble breaker (C: (C))201710766435.0) And the micro-interface generator is called as a micro-interface generator in the later stage along with continuous technical improvement, and the micro-interface generator in the invention is equivalent to the prior micro-bubble generator, bubble breaker and the like, and is only named differently.
In summary, the micro-interface generator of the present invention belongs to the prior art, although some bubble breakers belong to the type of pneumatic bubble breakers, some bubble breakers belong to the type of hydraulic bubble breakers, and some bubble breakers belong to the type of gas-liquid linkage bubble breakers, the difference between the types is mainly selected according to the different specific working conditions, and in addition, the connection between the micro-interface generator and the reactor and other equipment, including the connection structure and the connection position, is determined according to the structure of the micro-interface generator, which is not limited.
Further, the device also comprises a first methanol preheater and a second methanol preheater which are used for preheating raw material methanol, wherein the first methanol preheater is connected with the first liquid phase inlet, and the second methanol preheater is connected with the second liquid phase inlet.
Further, the bottom of flash tank is provided with the catalyst export, the catalyst export with carbonylation reation kettle's bottom is connected in order to be used for the recycle of catalyst. The material containing the catalyst at the bottom of the flash tank returns to the carbonylation reaction kettle again through the catalyst outlet for recycling, so that the energy consumption is saved.
Further, a catalyst filter is connected to the catalyst outlet, and the bottom of the catalyst filter is connected with the bottom of the carbonylation reaction kettle so as to filter the catalyst and then return the catalyst for recycling. In order to separate the catalyst from the mixture, a catalyst filter is required, and the catalyst can be completely and independently separated by the catalyst filter, so that the catalyst can be returned to the carbonylation reaction kettle for reuse, and the activity of the catalyst is improved.
Furthermore, a return pipeline is arranged at the bottom of the light component rectifying tower and connected with the bottom of the flash tank so as to be used for continuously returning partial reflux materials to flash separation. Heavy components at the bottom of the light component rectifying tower contain a small amount of water, acetic acid and other high-boiling-point substances, and the heavy components are returned to the flash tank for further purification, so that resource waste is avoided.
Furthermore, a stripping outlet is formed in the top of the waste acid stripping tower, and the stripping outlet is connected with the side wall of the heavy component rectifying tower and used for returning steam containing acetic acid to be distilled for purification. The gas phase distilled from the waste acid stripping tower still contains a small amount of acetic acid, so that the acetic acid is returned to be purified to avoid waste.
In addition, the invention also provides a method for preparing acetic acid by methanol carbonylation by adopting the external micro-interface strengthening system, which comprises the following steps:
dispersing and crushing carbon monoxide into micro bubbles, and fully emulsifying the micro bubbles and methanol to form an emulsion;
carrying out carbonylation reaction on the emulsion to obtain a reaction product;
the reaction product is flashed and separated to obtain the acetic acid.
Further, carbon monoxide and methanol are introduced into the micro-interface generator, the carbon monoxide is broken into micro bubbles with the diameter of more than or equal to 1 mu m and less than 1mm and then fully emulsified with the methanol and then introduced into the carbonylation reaction kettle, the mass transfer area of a phase boundary between the carbon monoxide and the methanol in the carbonylation reaction process is increased, the carbon monoxide is fully contacted with the methanol in a micro bubble state, the carbonylation reaction is carried out, the obtained carbonylation reaction product enters a flash evaporation tank for flash evaporation, the liquid phase product containing the catalyst obtained by flash evaporation returns to the hydroxylation reaction kettle again, the gas phase product obtained by flash evaporation enters a light component rectifying tower for separation and rectification, the separated heavy component part of backflow material continuously returns to the flash evaporation tank for separation and purification, the side line of the aqueous acetic acid is discharged and then enters a dehydration tower for dehydration treatment, the dehydrated product enters a medium heavy component rectifying tower for continuous separation and rectification, and the product acetic acid is collected from an acetic acid extraction outlet at the side part, heavy component materials at the bottom of the tower enter a waste acid stripping tower for superheated steam stripping, waste materials are discharged from the bottom of the waste acid stripping tower, and steam containing acetic acid, which is evaporated from a stripping outlet at the top of the tower, returns to the heavy component rectifying tower for re-purification and utilization.
Further, the carbonylation reaction temperature was 168-171 ℃.
Further, the pressure of the carbonylation reaction is 2.2-3.9 MPa.
Compared with the prior art, the invention has the beneficial effects that:
according to the external micro-interface strengthening system for preparing acetic acid by methanol carbonylation, after the micro-interface generator is arranged at the raw material inlet of the carbonylation reaction kettle, on one hand, the material can be dispersed and crushed into micro bubbles, so that the phase interface area between a gas phase and a liquid phase is increased, the mass transfer space is fully satisfied, the retention time of the gas in the liquid phase is increased, the energy consumption is reduced, and the reaction efficiency is improved; on the other hand, the operation temperature and pressure in the carbonylation reaction kettle are reduced, and the safety and stability of the whole reaction system are improved.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a schematic structural diagram of an external micro-interface enhancement system for preparing acetic acid by carbonylation of methanol according to the present invention in embodiment 1.
Description of the drawings:
1-a carbonylation reaction kettle; 11-a first feedstock inlet;
12-a second feedstock inlet; 13-product outlet;
101-a first micro-interface generator; 102-a second micro-interface generator;
1010 — a first vapor phase inlet; 1011-first liquid phase inlet;
1020-a second gas phase inlet; 1021-a second liquid phase inlet;
21-a first methanol preheater; 22-a second methanol preheater;
3-a flash tank; 4-a catalyst filter;
5-a light component rectifying tower; 51-a return line;
52-a side draw; 6-a dehydration column;
7-heavy ends rectifying tower; 71-acetic acid extraction outlet;
72-a heavies outlet; 8-a spent acid stripper;
81-stripping outlet.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Examples
Referring to fig. 1, the external micro-interface strengthening system for preparing acetic acid by methanol carbonylation according to the present invention comprises a carbonylation reaction kettle 1; the side wall of the carbonylation reaction kettle 1 is provided with a first raw material inlet 11 and a second raw material inlet 12, the first raw material inlet 11 is provided with a first micro-interface generator 101 for dispersing the crushed material into micro-bubbles, the second raw material inlet 12 is provided with a second micro-interface generator 102 for dispersing the crushed material into micro-bubbles, it can be understood that the first micro-interface generator 101 and the first raw material inlet 11 are not specifically limited in the connection relationship between the second micro-interface generator 102 and the second raw material inlet 12, as long as the first micro-interface generator 101 can be fixed at the first raw material outlet 11, and the second micro-interface generator 102 can be fixed at the second raw material outlet 12.
Specifically, the side wall of the first micro-interface generator 101 is provided with a first gas phase inlet 1010 for introducing carbon monoxide, and the top of the first micro-interface generator 101 is provided with a first liquid phase inlet 1011 for introducing raw material methanol; the sidewall of the second micro-interface generator 102 is provided with a second gas phase inlet 1020 for introducing carbon monoxide, and the bottom of the second micro-interface generator 102 is provided with a second liquid phase inlet 1021 for introducing raw material methanol. In this embodiment, the device further comprises a first methanol preheater 21 and a second methanol preheater 22 for preheating the raw material methanol, wherein the first methanol preheater 21 is connected with the first liquid phase inlet 1011, the second methanol preheater 22 is connected with the second liquid phase inlet 1021, and the first methanol preheater 21 and the second methanol preheater 22 are used for preheating the raw material methanol and then feeding the preheated raw material methanol into the micro-interface generator to emulsify carbon monoxide. In this embodiment, the device further includes a first pipeline 91 and a second pipeline 92, the first pipeline 91 and the second pipeline 92 both penetrate through a side wall of the first micro-interface generator 101 and a side wall of the second micro-interface generator 102, and a material flow direction in the first pipeline 91 and a material flow direction in the second pipeline 92 are opposite to each other.
A product outlet 13 is formed in the bottom of the carbonylation reaction kettle 1, and the product outlet 13 is connected with a flash tank 3 and is used for carrying out flash evaporation on the carbonylation reaction product; the bottom of flash tank 3 is provided with catalyst outlet 31, and the catalyst outlet is connected with catalyst filter 4, and the bottom of catalyst filter 4 and the bottom of carbonylation reation kettle 1 are connected in order to return the reuse after being used for filtering the catalyst. The top of the flash tank 3 is provided with a gas phase outlet 32, and the gas phase outlet is connected with a light component rectifying tower 5 for separating and rectifying a gas phase product obtained by flash evaporation;
wherein, the bottom of the light component rectifying tower 5 is provided with a return pipeline 51, and the return pipeline 51 is connected with the bottom of the flash tank 3 to be used for continuously returning partial reflux materials to flash separation; the side wall of the light component rectifying tower 5 is provided with a side line extraction outlet 52, the side line extraction outlet 52 is connected with the dehydrating tower 6 for dehydrating the product, and the dehydrated product enters the heavy component rectifying tower 7 for continuous separation and rectification.
The side of the heavy component rectifying tower 7 is provided with an acetic acid outlet 71 for collecting final product acetic acid, the bottom is provided with a heavy component outlet 72, and the heavy component outlet 72 is connected with the waste acid stripping tower 8 for carrying out superheated steam stripping on heavy components. The top of the waste acid stripping tower 8 is provided with a stripping outlet 81, and the stripping outlet 81 is connected with the side wall of the heavy component rectifying tower 7 for the steam containing acetic acid which is distilled out to return to the purification again.
In the above embodiment, the number of the micro-interface generators is not limited, and in order to increase the dispersion and mass transfer effects, additional micro-interface generators may be additionally provided, especially, the installation position of the micro-interface generator is not limited, and the micro-interface generator may be external or internal, and when the micro-interface generator is internal, the micro-interface generator may be installed on the side wall in the kettle in a manner of being oppositely arranged, so as to realize the opposite flushing of micro-bubbles coming out from the outlet of the micro-interface generator.
The working process and principle of the external micro-interface strengthening system for preparing acetic acid by methanol carbonylation according to the present invention are briefly described as follows:
introducing carbon monoxide and methanol into the interior of a first micro-interface generator 101 and a second micro-interface generator 102, crushing the carbon monoxide into micro-bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, fully emulsifying the micro-bubbles and the methanol, introducing the micro-bubbles and the methanol into the interior of a carbonylation reaction kettle 1, increasing the mass transfer area of a phase boundary between the carbon monoxide and the methanol in the carbonylation reaction process, enabling the carbon monoxide to fully contact with the methanol in a micro-bubble state, carrying out the carbonylation reaction, introducing the obtained carbonylation reaction product into a flash tank 3 for flash evaporation, returning the liquid-phase product containing the catalyst obtained by flash evaporation into the carbonylation reaction kettle 1 again, introducing the gas-phase product obtained by flash evaporation into a light component rectifying tower 5 for separation and rectification, continuously returning the separated heavy component part of reflux material into the flash tank 3 for separation and purification, discharging the aqueous acetic acid from a side stream outlet 52, and then introducing the, and (3) the dehydrated product enters a medium and heavy component rectifying tower 7 to be continuously separated and rectified, the product acetic acid is collected from an acetic acid extraction port 71 at the side part, the heavy component material at the bottom of the tower enters a waste acid stripping tower 8 to be subjected to superheated steam stripping, waste materials are discharged from the bottom of the waste acid stripping tower 8, and the steam containing the acetic acid and evaporated from a stripping port 81 at the top of the tower returns to the heavy component rectifying tower 7 to be purified and utilized again.
In the process, the carbonylation reaction temperature in the carbonylation reaction kettle 1 is 168-171 ℃, and the carbonylation reaction pressure is 2.2-3.9 MPa.
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. An external micro-interface strengthening system for preparing acetic acid by methanol carbonylation is characterized by comprising a carbonylation reaction kettle; the side wall of the carbonylation reaction kettle is provided with a first raw material inlet and a second raw material inlet, the first raw material inlet is provided with a first micro-interface generator for dispersing and crushing materials into micro-bubbles, and the second raw material inlet is provided with a second micro-interface generator for dispersing and crushing materials into micro-bubbles;
a product outlet is formed in the bottom of the carbonylation reaction kettle and connected with a flash tank to be used for carrying out flash evaporation on the carbonylation reaction product; the top of the flash tank is provided with a gas phase outlet, and the gas phase outlet is connected with a light component rectifying tower and is used for separating and rectifying a gas phase product obtained by flash evaporation; a side extraction port is arranged at the side part of the light component rectifying tower, the side extraction port is connected with a dehydrating tower to be used for dehydrating the product, and the dehydrated product enters the heavy component rectifying tower to be continuously separated and rectified; the side part of the heavy component rectifying tower is provided with an acetic acid outlet, the bottom part of the heavy component rectifying tower is provided with a heavy component outlet, and the heavy component outlet is connected with a waste acid stripping tower and used for carrying out superheated steam stripping on heavy components.
2. The external micro-interface enhancement system for preparing acetic acid by carbonylation of methanol according to claim 1, wherein the side wall of the first micro-interface generator is provided with a first gas phase inlet for introducing carbon monoxide, and the top of the first micro-interface generator is provided with a first liquid phase inlet for introducing raw material methanol; the side wall of the second micro-interface generator is provided with a second gas phase inlet for introducing carbon monoxide, and the bottom of the second micro-interface generator is provided with a second liquid phase inlet for introducing raw material methanol.
3. The external micro-interface enhancement system for the production of acetic acid by the carbonylation of methanol according to claim 1 further comprising a first conduit and a second conduit, wherein the first conduit and the second conduit both extend through a side wall of the first micro-interface generator and a side wall of the second micro-interface generator, and wherein the material flow in the first conduit and the material flow in the second conduit are in a counter-current direction.
4. The external micro-interface enhancement system for the carbonylation of methanol to acetic acid as defined in claim 2 further comprising a first methanol preheater and a second methanol preheater for preheating the methanol feedstock, wherein the first methanol preheater is connected to the first liquid phase inlet and the second methanol preheater is connected to the second liquid phase inlet.
5. The external micro-interface enhancement system for preparing acetic acid by carbonylation of methanol according to claim 1, wherein the bottom of the flash tank is provided with a catalyst outlet, and the catalyst outlet is connected with the bottom of the carbonylation reaction kettle for recycling of the catalyst.
6. The external micro-interface enhancement system for preparing acetic acid by carbonylation of methanol according to claim 5, wherein the catalyst outlet is connected with a catalyst filter, and the bottom of the catalyst filter is connected with the bottom of the carbonylation reaction kettle so as to filter the catalyst and return the filtered catalyst for reuse.
7. The external micro-interface enhancement system for preparing acetic acid by carbonylation of methanol according to claim 1, wherein a return line is provided at the bottom of the light fraction rectification column, and the return line is connected with the bottom of the flash tank for continuing returning part of the reflux material to flash separation.
8. The external micro-interface enhancement system for preparing acetic acid by carbonylation of methanol as claimed in claim 1, wherein the top of the waste acid stripping tower is provided with a stripping outlet, and the stripping outlet is connected with the side wall of the heavy component rectifying tower for re-returning and purifying the steam containing acetic acid.
9. A process for the carbonylation of methanol to produce acetic acid using the external micro-interface enhancement system of any one of claims 1-8, comprising the steps of:
dispersing and crushing carbon monoxide into micro bubbles, and fully emulsifying the micro bubbles and methanol to form an emulsion;
carrying out carbonylation reaction on the emulsion to obtain a reaction product;
the reaction product is flashed and separated to obtain the acetic acid.
10. The process as claimed in claim 9, wherein the carbonylation reaction temperature is 168-171 ℃; the reaction pressure is 2.2-3.9 MPa.
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