CN112774579A - Intelligent micro-interface reaction system and method for hydrofining of crude terephthalic acid - Google Patents
Intelligent micro-interface reaction system and method for hydrofining of crude terephthalic acid Download PDFInfo
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- CN112774579A CN112774579A CN202011574804.4A CN202011574804A CN112774579A CN 112774579 A CN112774579 A CN 112774579A CN 202011574804 A CN202011574804 A CN 202011574804A CN 112774579 A CN112774579 A CN 112774579A
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 131
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 119
- 239000001257 hydrogen Substances 0.000 claims abstract description 119
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 92
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 62
- 238000009826 distribution Methods 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 42
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 28
- 230000005587 bubbling Effects 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 18
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 13
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- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/29—Mixing systems, i.e. flow charts or diagrams
- B01F23/291—Mixing systems, i.e. flow charts or diagrams for obtaining foams or aerosols
-
- 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
-
- 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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Abstract
An intelligent micro-interface reaction system for hydrofining of crude terephthalic acid, comprising: the device comprises a hydrogenation reactor, a hydrogen micro-interface generator for dispersing and crushing hydrogen is arranged in the hydrogenation reactor, a bubble tower type reactor is arranged in the hydrogenation reactor in parallel, products obtained after the reaction of the hydrogenation reactor and the bubble tower type reactor are connected in parallel and then sequentially enter a crystallization tower, a centrifugal separator and a dryer, and finally solid refined terephthalic acid is formed and enters a collection tank; the intelligent control system comprises a detection module, a feedback module and an intelligent operation module. The intelligent micro-interface reaction system reduces the temperature and pressure of the hydrogenation reaction.
Description
Technical Field
The invention relates to the field of refining of crude terephthalic acid, in particular to an intelligent micro-interface reaction system and method for hydrofining of crude terephthalic acid.
Background
The main stream terephthalic acid (PTA) production process, which is a purified terephthalic acid production process, generally includes an oxidation process and a hydrotreating process, and the production process is as follows: crude Terephthalic Acid (CTA) obtained by oxidizing paraxylene serving as a raw material is conveyed to a hydrogenation reactor through a raw material preparation unit, is distributed through a distribution header pipe and is fully contacted with compressed hydrogen conveyed into the hydrogenation reactor in a space above a liquid layer in the hydrogenation reactor to achieve the dissolving balance, then flows through the reaction liquid layer and a catalyst bed layer, and is subjected to hydrogenation reaction in the catalyst bed layer, the catalyst bed layer is usually formed by stacking palladium-carbon catalysts, the crude terephthalic acid (mainly comprises Terephthalic Acid (TA), P-carboxybenzaldehyde (4-CBA) and P-toluic acid (P-T acid), main impurities of P-carboxybenzaldehyde (4-CBA) are subjected to hydrogenation reaction to generate P-toluic acid (P-T acid), and the content of the P-carboxybenzaldehyde (4-CBA) in a reaction product after hydrogenation treatment under the same process conditions is usually used as an index for measuring the effect of the hydrogenation treatment, that is, the lower the content of p-carboxybenzaldehyde (4-CBA) in the reaction product, the better the hydrotreatment effect.
Through the research on the reaction process, the speed of the gas-phase and liquid-phase main bodies in the reactants (4-CBA, hydrogen and p-toluic acid) diffusing inside and outside the surface of the catalyst is the control step of the hydrogenation reaction process of the p-carboxybenzaldehyde (4-CBA), and how to increase the gas-liquid phase interfacial area and improve or strengthen the gas-phase and liquid-phase main bodies in the reactants diffusing inside and outside the surface of the catalyst is very important for improving the hydrogenation treatment effect.
At present, the hydrogenation process of crude terephthalic acid is mainly a trickle bed hydrogenation process. The following problems are common in the conventional hydrogenation process:
(1) small gas-liquid phase interface area and low mass transfer rate. And the hydrogen is distributed unevenly in the solution, the hydrogenation effect is poor, and the catalyst loss is large.
(2) The trickle bed hydrogenation process has high reaction pressure (about 8MPa), high investment cost and operation cost of the device and reduced safety.
In addition, with the development of informatization becoming faster and faster, the application of an intelligent system becomes wider and wider, and moreover, by adopting a manual control mode, errors are easy to occur, and the labor cost is higher.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide an intelligent micro-interface reaction system for hydrofining crude terephthalic acid, which is based on a micro-interface reaction strengthening technology, takes a crude terephthalic acid solvent as a continuous phase, efficiently crushes hydrogen into micron-sized bubbles through a micro-interface generator, disperses the micron-sized bubbles into the solution to form a micro-interface system, improves the gas-liquid phase interface area in a hydrogenation reactor by tens of times, greatly improves the mass transfer rate from a gas phase to a reaction liquid and the macroscopic hydrogenation rate, further can reduce the original reaction pressure, reaction temperature and catalyst usage amount, and improves the reaction efficiency;
meanwhile, the intelligent reaction system can detect the internal pressure and temperature of the hydrogenation reactor and the bubble tower reactor, carry out operation analysis through the intelligent system, directly feed back the operation analysis to the reaction system, and adjust the temperature and pressure during reaction, does not need manual control, reduces the error rate, reduces the labor cost, and is widely popularized and implemented.
The second purpose of the invention is to provide a reaction method for hydrofining terephthalic acid by adopting the reaction system, the refined terephthalic acid obtained by the reaction has high purity, low impurity content and wide application, the application range of the refined terephthalic acid is improved, and the method is worthy of wide popularization and application.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides an intelligent micro-interface reaction system for hydrofining crude terephthalic acid, which comprises: the device comprises a hydrogenation reactor, wherein a hydrogen micro-interface generator for dispersing and crushing hydrogen is arranged inside the hydrogenation reactor;
the side wall of the hydrogenation reactor is communicated with a crude terephthalic acid pipeline and a hydrogen inlet pipeline, and the hydrogen inlet pipeline passes through the side wall of the hydrogenation reactor and is introduced into the hydrogen micro-interface generator;
the hydrogenation reactor is provided with a bubble tower reactor in parallel, the bubble tower reactor is connected with an external micro-interface unit, and the crude terephthalic acid pipeline and the hydrogen inlet pipeline are introduced into the external micro-interface unit;
and products obtained after the reaction of the hydrogenation reactor and the bubble tower reactor are connected in parallel and sequentially enter a crystallization tower, a centrifugal separator and a dryer, and finally solid refined terephthalic acid is formed and enters a collecting tank.
The system comprises a hydrogenation reactor, a bubble tower reactor, a detection device, an intelligent operation module and a feedback module, wherein the detection device can detect the pressure and the temperature in the hydrogenation reactor and the bubble tower reactor and send data to the intelligent operation module;
preferably, the intelligent control system further comprises a wireless signal sending module, and the wireless signal sending module is connected with the intelligent operation module and used for feeding back parameters in the intelligent operation module to experimenters.
In the prior art, the reaction for hydrorefining terephthalic acid has the following defects of small gas-liquid phase interface area and low mass transfer rate. And the hydrogen is distributed unevenly in the solution, the hydrogenation effect is poor, and the catalyst loss is large. Secondly, the existing hydrogenation process has higher reaction pressure, high investment cost and operation cost of the device and reduced safety. The invention uses the hydrogen micro-interface generator arranged in the hydrogenation reactor to crush and disperse the hydrogen into hydrogen micro-bubbles, thereby improving the mass transfer effect, enhancing the reaction efficiency, and reducing the pressure, temperature and catalyst consumption during the reaction. The invention also breaks and disperses the hydrogen gas entering into hydrogen gas micro bubbles through an external micro interface unit arranged outside the bubble tower type reactor, and the hydrogen gas is mixed with the crude terephthalic acid in advance and enters the bubble tower type reactor, thereby improving the mass transfer effect, enhancing the reaction efficiency and further reducing the pressure, the temperature and the using amount of the catalyst during the reaction. And (3) feeding products generated by the reaction of the hydrogenation reactor and the bubble column reactor into a crystallization tower to remove p-toluic acid, then feeding the products into a centrifugal separator to obtain solid refined terephthalic acid, then feeding the solid refined terephthalic acid into a dryer to remove excessive moisture, and finally feeding the solid refined terephthalic acid into a collection tank for packaging and storage.
The intelligent reaction system can realize the detection of the internal pressure and temperature of the hydrogenation reactor and the bubble tower reactor, and the intelligent system carries out operation analysis and directly feeds back to the reaction system to adjust the temperature and pressure during reaction.
Preferably, the hydrogen micro-interface generator is arranged at the bottom of the hydrogenation reactor. The hydrogen micro-interface generator is arranged at the bottom of the hydrogenation reactor because the density of hydrogen is small and the rising speed in liquid is high, and the hydrogen micro-interface generator is arranged at the bottom of the hydrogenation reactor, so that the rising distance of hydrogen can be prolonged, and hydrogen can be subjected to hydrogenation reaction with crude terephthalic acid more fully. And through setting up hydrogen micro-interface generator at the bottommost, can let the raw materials liquid phase that gets into and hydrogen contact each other more abundant, after hydrogen micro-interface generator smashed the dispersion gas, the microbubble part that comes out can stop in the liquid surface motionless, has also given abundant detention space for this part microbubble that stops like this to more effective mass transfer effect between the improvement gas-liquid two-phase.
Preferably, a gas distribution pipeline is arranged inside the hydrogenation reactor, gas distribution holes are uniformly distributed on the gas distribution pipeline, the gas distribution pipeline is vertically arranged on the upper surface of the hydrogen micro-interface generator and communicated with the upper surface of the hydrogen micro-interface generator, and a gas outlet of the hydrogen micro-interface generator is connected with the gas distribution pipeline so as to uniformly disperse the hydrogen micro-bubbles crushed and dispersed by the hydrogen micro-interface generator into the hydrogenation reactor. The gas distribution pipeline is vertically arranged on the upper surface of the hydrogen micro-interface generator and communicated with the upper surface, a gas outlet of the hydrogen micro-interface generator is connected with the gas distribution pipeline, and hydrogen micro-bubbles from the hydrogen micro-interface generator are discharged from the gas distribution holes through the vertically arranged gas distribution pipeline and are uniformly dispersed in the hydrogenation reactor.
Preferably, a palladium-carbon catalyst bed layer is arranged inside the hydrogenation reactor, and the palladium-carbon catalyst bed layer is coated on the outer side of the gas distribution pipeline. The palladium-carbon catalyst bed layer is coated on the outer side of the gas distribution pipeline, the crude terephthalic acid enters the palladium-carbon catalyst bed layer, the broken and dispersed micro bubbles are uniformly dispersed into the palladium-carbon catalyst bed layer from the gas distribution pipeline to carry out hydrogenation reaction with the crude terephthalic acid, the utilization rate of the palladium-carbon catalyst is enhanced, and the reaction efficiency is improved.
In the structure, through carrying out the combined use with gas distribution pipeline and hydrogen micro-interface generator, hydrogen micro-interface generator's dispersion crushing effect has been improved more, wherein gas distribution pipeline's design can be understood as the micro-interface generator of auxiliary type, because utilize the gas distribution hole on the gas distribution pipeline also can reach the broken effect of redispersing gas to a certain extent, and the bubble itself that comes out from hydrogen micro-interface generator is disorderly, can lay the bubble orientation direction of setting for through the gas distribution effect that utilizes gas distribution pipeline, in order to guarantee to pass catalyst bed and bed abundant contact and with raw materials liquid phase abundant contact from the equidirectional. Therefore, the mode of arranging the palladium-carbon catalyst bed layer at the outer side of the gas distribution pipeline is specially designed for improving the catalytic mass transfer effect.
Preferably, the hydrogen micro-interface generator, the gas distribution pipeline and the palladium-carbon catalyst bed layer are all arranged on the central axis of the hydrogenation reactor. The hydrogen micro-interface generator, the gas distribution pipeline and the palladium-carbon catalyst bed layer have the same central axis, the gas outlet of the hydrogen micro-interface generator is arranged on the central axis of the hydrogen micro-interface generator, the gas distribution pipeline is connected with the gas outlet of the hydrogen micro-interface generator, the gas distribution pipeline is also arranged on the central axis of the hydrogen micro-interface generator, the palladium-carbon catalyst bed layer is coated on the outer side of the gas distribution pipeline, and the central axis of the palladium-carbon catalyst bed layer is also identical to that of the hydrogen micro-interface generator. The central axes of the hydrogen micro-interface generator, the gas distribution pipeline and the palladium-carbon catalyst bed layer are arranged on the central axis of the hydrogenation reactor, so that the distances between hydrogen micro-bubbles coming out of the gas distribution pipeline and the inner wall of the hydrogenation reactor are equal, and the reaction range can be enlarged to the maximum extent.
Preferably, the external micro-interface unit is composed of a plurality of external micro-interface generators, the crude terephthalic acid pipeline is communicated with the external micro-interface generator at the top of the external micro-interface unit, and the hydrogen gas inlet pipeline is communicated with the external micro-interface generator at the bottom of the external micro-interface unit.
Preferably, the number of the external micro-interface generators is 3, and a connecting channel is arranged between every two adjacent external micro-interface generators.
Preferably, the external micro-interface generators are sequentially arranged from top to bottom along the vertical direction.
The number of the external micro-interface generators is three, the external micro-interface generators are sequentially arranged from top to bottom in the vertical direction, and the hydrogen gas inlet pipeline is connected with the external micro-interface generators at the bottom of the external micro-interface unit. The reason that the crude terephthalic acid pipeline is connected with the external micro-interface generator at the top of the external micro-interface unit is that the crude terephthalic acid solution is liquid and flows from the top of the external micro-interface unit to the bottom of the external micro-interface unit under the influence of gravity, so that the circulation of hydrogen in the micro-interface unit is driven. A connecting channel is arranged between the external micro-interface generators, so that the crude terephthalic acid solution and the hydrogen between the three external micro-interface generators can be communicated. An extraction pump is arranged outside the external micro-interface unit and is used for conveying the crude terephthalic acid solution and the hydrogen microbubbles in the external micro-interface unit to the bubbling tower reactor. The external micro-interface unit has the advantages that the hydrogen is crushed and dispersed in advance before reaction and is mixed with the crude terephthalic acid solution, so that the phase boundary mass transfer area between the hydrogen and the crude terephthalic acid solution is increased, and the reaction efficiency is improved.
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.
In addition, the invention also provides a reaction method for hydrofining the crude terephthalic acid, which comprises the following steps:
the crude terephthalic acid and hydrogen are mixed with a micro interface under the catalytic action of a palladium-carbon catalyst, dispersed and crushed, then subjected to hydrogenation reaction, crystallized, centrifugally separated and dried to obtain the purified terephthalic acid.
Preferably, the temperature of the hydrogenation reaction is 260-290 ℃, and the pressure of the hydrogenation reaction is 5-8 MPa.
Specifically, the reaction method comprises the steps of smashing hydrogen into micro-bubbles with a micron scale through a hydrogen micro-interface generator, and releasing the micro-bubbles into a hydrogenation reactor to increase the mass transfer area of a phase boundary between the hydrogen and crude terephthalic acid in the hydrogenation process of the crude terephthalic acid, so that the hydrogen is in full contact with a crude terephthalic acid solution in a micro-bubble state. The formed hydrogen microbubbles enter the palladium-carbon catalyst bed layer and carry out hydrogenation reaction with the crude terephthalic acid. The reaction method also comprises the step of crushing and dispersing hydrogen in advance into hydrogen microbubbles by arranging an external micro-interface unit, mixing the hydrogen microbubbles with the crude terephthalic acid, and then sending the mixture into the bubble tower reactor, so that the phase boundary mass transfer area of the hydrogen and the crude terephthalic acid is increased, and the reaction efficiency is improved.
The product obtained by the hydrofining reaction of the crude terephthalic acid has good quality and high yield. Greatly reduces the pressure and temperature of the hydrogenation reaction of the crude terephthalic acid and the dosage of the palladium-carbon catalyst, has high product purity and equivalently improves the productivity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the micro-interface reaction system for crude terephthalic acid hydrofining is characterized in that a hydrogen micro-interface generator connected with a hydrogen inlet pipeline is arranged in a hydrogenation reactor, the hydrogen micro-interface generator breaks hydrogen into micro bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, the hydrogen is contacted with crude terephthalic acid particles in a micro bubble state to increase the phase boundary mass transfer area between the hydrogen and the crude terephthalic acid in the process of crude terephthalic acid hydrofining reaction, the hydrogen and the crude terephthalic acid are subjected to hydrofining reaction after being fully mixed, an external micro-interface unit is arranged on the outer side of a bubble tower type reactor, the hydrogen is broken and dispersed into hydrogen micro bubbles in advance to be mixed with the crude terephthalic acid, and then the hydrogen is sent into the bubble tower type reactor to perform a hydrogenation catalytic reaction, so that the reaction efficiency is improved.
(2) The intelligent micro-interface reaction system provided by the invention has the advantages that the intelligent system is arranged, the feeding amount, the temperature and the pressure during reaction are automatically adjusted, and the reaction process is more efficiently and safely controlled, so that the reaction efficiency is improved.
(3) Compared with the traditional hydrogenation reaction, the whole reaction system of the invention greatly reduces the reaction pressure and temperature and improves the product purity.
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 micro-interface reaction system for hydrorefining crude terephthalic acid according to an embodiment of the present invention;
wherein:
11-crude terephthalic acid storage tank; 12-a hydrogen gas inlet line;
13-a raw material preheater; 14-a hydrogen pressurizer;
15-a crude terephthalic acid conduit; 20-a hydrogenation reactor;
201-hydrogen micro-interface generator; 202-gas distribution pipeline;
2021-air distribution holes; 203-palladium-carbon catalyst bed;
21-a bubble column reactor; 211-external micro-interface generator;
213-connecting the channels; 214-external micro interface unit;
215-bubble column reactor feed inlet; 212-catalyst bed in bubble column;
30-a crystallization tower; 40-a centrifugal separator;
50-a dryer; 60-a collection tank;
70-Intelligent control system.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Examples
Referring to fig. 1, a micro-interface reaction system for hydrorefining crude terephthalic acid according to an embodiment of the present invention mainly includes a crude terephthalic acid storage tank 11, a hydrogen gas inlet pipe 12, a hydrogenation reactor 20, a bubble column reactor 21, a crystallization tower 30, a centrifugal separator 40, a dryer 50, and a collection tank 60. The crude terephthalic acid storage tank 11 is connected with the hydrogenation reactor 20 and the bubble column reactor 21 through a crude terephthalic acid pipeline 15, and a raw material preheater 13 is further arranged on the crude terephthalic acid pipeline 15 and can preheat the crude terephthalic acid to the reaction temperature. The hydrogen inlet pipe 12 is directly connected to the hydrogen micro-interface generator 201 inside the hydrogenation reactor 20 and the external micro-interface generator 211 at the bottom of the external micro-interface unit 214, and the hydrogen inlet pipe 12 is further provided with a hydrogen pressurizer 14, which can pressurize the hydrogen and increase the flow rate of the hydrogen in the liquid.
The crude terephthalic acid pipeline 15 on one side of the parallel reaction is introduced into the hydrogenation reactor 20 to provide the crude terephthalic acid raw material to the inside of the hydrogenation reactor 20, and the hydrogen inlet pipeline 12 is introduced into the hydrogen micro-interface generator 201 to break and disperse the hydrogen into hydrogen micro-bubbles in advance. The hydrogenation reactor 20 is also provided with a gas distribution pipe 202 and a palladium-carbon catalyst bed 203 inside. The hydrogen micro-interface generator 201 is arranged at the bottom of the hydrogenation reactor 20, because the density of hydrogen is small and the rising speed in the solution is high, the arrangement of the hydrogen micro-interface generator 201 at the bottom of the hydrogenation reactor 20 can prolong the distance from the hydrogen to the hydrogenation reactor 20 after the hydrogen comes out of the hydrogen micro-interface generator 201, thereby increasing the reaction time of the hydrogen and the crude terephthalic acid and improving the reaction efficiency.
The gas outlet of the hydrogen micro-interface generator 201 faces upwards and is connected with the gas distribution pipeline 202, the gas distribution pipeline 202 is vertically arranged on the hydrogen micro-interface generator 201, and gas distribution holes 2021 are uniformly distributed on the gas distribution pipeline 202. So that the microbubbles of hydrogen gas from the hydrogen gas micro-interface generator 201 can be uniformly dispersed into the hydrogenation reactor 20. The outer side of the gas distribution pipeline 202 is coated by a palladium-carbon catalyst bed layer 203, and hydrogen gas micro bubbles from the gas distribution holes 2021 enter the palladium-carbon catalyst bed layer 203 to perform hydrogenation reaction with crude terephthalic acid under the catalytic action of a palladium-carbon catalyst, so that the P-carboxybenzaldehyde (4-CBA) is converted into P-toluic acid (P-T acid).
The central axes of the hydrogen micro-interface generator 201, the gas distribution pipeline 202 and the palladium-carbon catalyst bed layer 203 are all arranged on the central axis of the hydrogenation reactor 20. Because the reaction area can be enlarged to the maximum, if the central axes of the hydrogen micro-interface generator 201, the gas distribution pipeline 202 and the palladium-carbon catalyst bed 203 are arranged at one side of the hydrogenation reactor 20, the reaction effect at the other side is affected, thereby reducing the reaction efficiency. The central axes of the hydrogen micro-interface generator 201, the gas distribution pipeline 202 and the palladium-carbon catalyst bed layer 203 are arranged on the central axis of the hydrogenation reactor 20, and the distances from the hydrogen micro-bubbles crushed and dispersed in all directions to the inner wall of the hydrogenation reactor 20 are equal, so that the reaction range is more uniform, the utilization rate of the crude terephthalic acid is improved, and the reaction efficiency is enhanced.
On the other hand, the crude terephthalic acid pipeline 15 is introduced into an external micro-interface generator 211 at the top of the external micro-interface unit 214, the hydrogen gas inlet pipeline 12 is introduced into the external micro-interface generator 211 at the bottom of the external micro-interface unit 214, the external micro-interface unit 214 is sequentially arranged from top to bottom by 3 external micro-interface generators 211, and the 3 external micro-interface generators 211 are connected through a connecting channel 213. The hydrogen inlet pipe 12 is connected with the external micro-interface generator 211 at the bottom of the external micro-interface unit 214, because hydrogen is gas which enters the three external micro-interface generators 211 from bottom to top in sequence, which is equivalent to a primary micro-interface system formed in each micro-interface generator, so as to realize that the gas phase is sufficiently crushed and dispersed in the micro-interface generator on the premise that the liquid phase is the medium. The reason why the crude terephthalic acid pipe 15 is connected with the external micro-interface generator 211 at the top of the external micro-interface unit 214 is that the crude terephthalic acid solution is liquid and flows from the top of the external micro-interface unit 214 to the bottom of the external micro-interface unit 214 under the influence of gravity, thereby driving the circulation of hydrogen in the micro-interface unit. The external micro-interface generators 211 are provided with a connecting channel 213 therebetween, so that the crude terephthalic acid solution and the hydrogen gas can be communicated with each other among the three external micro-interface generators 211. An extraction pump is also arranged outside the external micro-interface unit 214 and is used for conveying the crude terephthalic acid solution and the hydrogen microbubbles in the external micro-interface unit 214 to the bubble column reactor 21. The advantage of the external micro-interface unit 214 is that the hydrogen is crushed and dispersed in advance before the reaction and mixed with the crude terephthalic acid solution, and the mass transfer area of the phase boundary between the hydrogen and the crude terephthalic acid solution is increased. The mixed hydrogen microbubbles and the crude terephthalic acid enter the bubble column reactor 21 through a feeding hole 215 of the bubble column reactor to perform catalytic hydrogenation reaction with the palladium-carbon catalyst in the catalyst bed layer 212 in the bubble column, so that the P-carboxybenzaldehyde (4-CBA) is converted into P-toluic acid (P-T acid).
The products after the reaction in the hydrogenation reactor 20 and the bubble column reactor 21 are connected in parallel and then enter the crystallization tower 30, and because the solubility of the P-toluic acid (P-T acid) in water is much higher than that of the terephthalic acid, the terephthalic acid is crystallized in the crystallization tower 30, and the P-toluic acid (P-T acid) is removed as an impurity.
The purified terephthalic acid precipitated from the crystallization tower 30 is sent to a centrifugal separator 40 to be centrifugally separated, whereby solid purified terephthalic acid is obtained. Then the solid purified terephthalic acid is sent into a dryer 50 for drying, the excess moisture is removed, the product solid purified terephthalic acid is obtained, and finally the solid purified terephthalic acid is put into a collecting tank 60 for packaging and storage.
The intelligent control system 70 comprises a detection module, a feedback module and an intelligent operation module, wherein the detection device can detect the pressure and the temperature inside the hydrogenation reactor 20 and the bubbling tower reactor 21 and send data to the intelligent operation module, the intelligent operation module operates through an internal algorithm to send parameters needing to be adjusted to the feedback module, and the feedback module controls the pressure and the temperature inside the hydrogenation reactor 20 and the bubbling tower reactor 21 by adjusting the crude terephthalic acid pipeline 15, the raw material preheater 13, the hydrogen pressurizer 14 and the hydrogen inlet pipeline 12.
The wireless signal transmission module in the intelligent control system 70 is connected with an intelligent operation module for feeding back the parameters in the intelligent operation module to the experimenter.
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 intelligent micro-interface reaction system for hydrofining of crude terephthalic acid is characterized by comprising: the device comprises a hydrogenation reactor, wherein a hydrogen micro-interface generator for dispersing and crushing hydrogen is arranged inside the hydrogenation reactor;
the side wall of the hydrogenation reactor is communicated with a crude terephthalic acid pipeline and a hydrogen inlet pipeline, and the hydrogen inlet pipeline passes through the side wall of the hydrogenation reactor and is introduced into the hydrogen micro-interface generator;
the hydrogenation reactor is provided with a bubble tower reactor in parallel, the bubble tower reactor is connected with an external micro-interface unit, and the crude terephthalic acid pipeline and the hydrogen inlet pipeline are introduced into the external micro-interface unit;
products after the hydrogenation reactor and the bubbling tower reactor are reacted are connected in parallel and then sequentially enter a crystallization tower, a centrifugal separator and a dryer, and finally solid refined terephthalic acid is formed and enters a collecting tank;
the system comprises a hydrogenation reactor, a bubble tower reactor, a detection device, an intelligent operation module and a feedback module, wherein the detection device can detect the pressure and the temperature in the hydrogenation reactor and the bubble tower reactor and send data to the intelligent operation module;
preferably, the intelligent control system further comprises a wireless signal sending module, and the wireless signal sending module is connected with the intelligent operation module and used for feeding back parameters in the intelligent operation module to experimenters.
2. The reaction system of claim 1 wherein the hydrogen micro-interface generator is disposed at the bottom of the hydrogenation reactor.
3. The reaction system of claim 2, wherein a gas distribution pipeline is arranged inside the hydrogenation reactor, gas distribution holes are uniformly distributed on the gas distribution pipeline, the gas distribution pipeline is vertically arranged on the upper surface of the hydrogen micro-interface generator and is communicated with the upper surface of the hydrogen micro-interface generator, and a gas outlet of the hydrogen micro-interface generator is connected with the gas distribution pipeline so as to uniformly disperse the hydrogen micro-bubbles crushed and dispersed by the hydrogen micro-interface generator into the hydrogenation reactor.
4. The reaction system of claim 3, wherein a palladium-carbon catalyst bed is arranged inside the hydrogenation reactor, and the palladium-carbon catalyst bed is coated outside the gas distribution pipeline.
5. The reaction system of claims 1-4, wherein the hydrogen micro-interface generator, the gas distribution pipeline, and the palladium-carbon catalyst bed have central axes disposed on the central axis of the hydrogenation reactor.
6. The reaction system of claim 1, wherein the external micro-interface unit is composed of a plurality of external micro-interface generators, the crude terephthalic acid pipeline is communicated with the external micro-interface generator at the top of the external micro-interface unit, and the hydrogen gas inlet pipeline is communicated with the external micro-interface generator at the bottom of the external micro-interface unit.
7. The reaction system of claim 6, wherein the number of the external micro-interface generators is 3, and a connecting channel is arranged between adjacent external micro-interface generators.
8. The reaction system of claim 7, wherein the external micro-interface generators are arranged in a vertical direction from top to bottom.
9. The reaction method using the reaction system for hydrorefining of crude terephthalic acid according to any one of claims 1 to 8, characterized by comprising the steps of:
the crude terephthalic acid and hydrogen are mixed with a micro interface under the catalytic action of a palladium-carbon catalyst, dispersed and crushed, then subjected to hydrogenation reaction, crystallized, centrifugally separated and dried to obtain the purified terephthalic acid.
10. The reaction process as claimed in claim 9, wherein the temperature of the hydrogenation reaction is 260 ℃ to 290 ℃, and the pressure of the hydrogenation reaction is 5 to 8 MPa.
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| WO2022142326A1 (en) * | 2020-12-28 | 2022-07-07 | 南京延长反应技术研究院有限公司 | Reaction system and method for refining crude terephthalic acid by hydrogenation |
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