CN111569788B - External micro-interface oxidation system and method for preparing terephthalic acid from p-xylene - Google Patents
External micro-interface oxidation system and method for preparing terephthalic acid from p-xylene Download PDFInfo
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- CN111569788B CN111569788B CN202010243410.4A CN202010243410A CN111569788B CN 111569788 B CN111569788 B CN 111569788B CN 202010243410 A CN202010243410 A CN 202010243410A CN 111569788 B CN111569788 B CN 111569788B
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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 56
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 63
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 23
- 239000007791 liquid phase Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 69
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 12
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000013067 intermediate product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000002912 waste gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
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- 230000005501 phase interface Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
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- 239000011552 falling film Substances 0.000 description 1
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- 238000009434 installation Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 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
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- 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
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides an external micro-interface oxidation system for preparing terephthalic acid from paraxylene. The oxidation system comprises: the device comprises a first reactor, a rectifying tower and a second reactor which are sequentially connected, wherein a first outlet is formed in the side wall of the first reactor, a first inlet is formed in the side wall of the second reactor, a material inlet is formed in the side wall of the rectifying tower, and a material outlet is formed in the bottom of the rectifying tower; the first outlet is connected with the material inlet of the rectifying tower, and the first inlet is connected with the material outlet of the rectifying tower; a first micro-interface generator is arranged outside the first reactor, and a second micro-interface generator is arranged outside the second reactor; the side wall of the first micro-interface generator is connected with a first air inlet, the bottom of the first micro-interface generator is connected with a raw material inlet, and the bottom of the second micro-interface generator is connected with a second air inlet. The invention solves the problem of low reaction efficiency in the traditional process by arranging the micro-interface generator outside the reactor and adopting a sectional process, thereby saving the cost for enterprises.
Description
Technical Field
The invention relates to the field of oxidation reaction for preparing terephthalic acid from paraxylene, in particular to an external micro-interface oxidation system and method for preparing terephthalic acid from paraxylene.
Background
Terephthalic acid is an important chemical raw material, which is generally prepared by oxidizing p-xylene and an oxygen-containing gas, and mainly comprises 4 steps, namely p-xylene (PX) → p-Tolualdehyde (TALD) → p-toluic acid (p-TA) → p-carboxybenzaldehyde (4-CBA) → Terephthalic Acid (TA), wherein the 4 steps are very complicated in reaction process and involve gas-liquid heat and mass transfer, a reaction device in the prior art is generally low in mass transfer efficiency, reaction mixed raw materials and air cannot be sufficiently mixed, and the phase interface area is limited, so that the raw material conversion rate is low, and the yield of the terephthalic acid is reduced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an external micro-interface oxidation system for preparing terephthalic acid from p-xylene. The external micro-interface oxidation system is provided with the micro-interface generator outside the reactor, and after the micro-interface generator is arranged, the phase interface area between air and liquid-phase materials can be increased, so that the air and the liquid-phase materials are fully crushed and mixed before entering the reactor, the mass transfer space is fully satisfied, and the retention time of the air in the liquid phase is increased, thereby greatly improving the reaction speed, effectively controlling side reactions and improving the product yield, remarkably reducing the energy consumption in the reaction process, simultaneously reducing the operation temperature and the pressure, improving the safety of the reaction, and adopting the sectional process, solving the contradiction that the acetic acid solvent cannot bear the high-temperature oxidation condition, and improving the reaction efficiency.
The second purpose of the invention is to provide a method for preparing terephthalic acid by adopting the paraxylene of the external micro-interface oxidation 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 oxidation system for preparing terephthalic acid from paraxylene, which comprises: the device comprises a first reactor, a rectifying tower and a second reactor which are sequentially connected, wherein a first outlet is formed in the side wall of the first reactor, a first inlet is formed in the side wall of the second reactor, a material inlet is formed in the side wall of the rectifying tower, and a material outlet is formed in the bottom of the rectifying tower;
the first outlet is connected with the material inlet of the rectifying tower, and the first inlet is connected with the material outlet of the rectifying tower;
a first micro-interface generator is arranged outside the first reactor, and a second micro-interface generator is arranged outside the second reactor;
the side wall of the first micro-interface generator is connected with a first air inlet, and the bottom of the first micro-interface generator is connected with a raw material inlet; the bottom of the second micro-interface generator is connected with a second air inlet;
the outer side of the first reactor is provided with a first circulating pipeline, one end of the first circulating pipeline is connected with the side wall of the first micro-interface generator, and the other end of the first circulating pipeline is connected with the side wall of the first reactor.
And a second circulating pipeline is arranged on the outer side of the second reactor, one end of the second circulating pipeline is connected with the side wall of the second micro-interface generator, and the other end of the second circulating pipeline is connected with the side wall of the second reactor.
In the prior art, the reaction steps for preparing terephthalic acid from paraxylene are as follows:
namely, p-xylene (PX) → p-Tolualdehyde (TALD) → p-toluic acid (p-TA) → p-carboxybenzaldehyde (4-CBA) → Terephthalic Acid (TA)
The oxidation reaction process is very complex, and relates to gas-liquid heat and mass transfer, the reaction device in the prior art generally has low mass transfer efficiency, and reaction mixed raw materials and air cannot be fully mixed, so that the reaction efficiency and the raw material conversion rate are influenced. According to the external micro-interface oxidation system, after the micro-interface generator is arranged outside the reactor, air and raw materials are introduced into the micro-interface generator, the internal strengthening mass transfer and the dispersing crushing are realized, micro bubbles are formed by crushing and then enter the reactor, so that the mass transfer space is fully satisfied, the air consumption is reduced, and the high reaction efficiency of the reaction can be ensured even if the temperature and the pressure are not required to be too high. In addition, the invention adopts a sectional type process, solves the contradiction that the acetic acid solvent can not bear the high-temperature oxidation condition, and improves the reaction efficiency.
Furthermore, the first micro-interface generator and the second micro-interface generator are not limited in arrangement mode, arrangement position and quantity; the first micro-interface generator and the second micro-interface generator can be connected with the inlet of the reactor in a welding or flange mode; furthermore, it is preferable that each of the first reactor and the second reactor is provided with a plurality of micro-interfacial generators in series or in parallel, and each of the micro-interfacial generators is connected to the inlet of the reactor.
Further, the number of the first micro-interface generators is at least 1; the number of the second micro-interface generators is at least 1.
It can be understood by those skilled in the art that the micro-interface generator used in the present invention is embodied in the previous patent of the present inventor, such as the patent with the publication number 106215730A, the core of the micro-interface generator is bubble breaking, and the principle of the bubble breaking is that the gas carried by the high-speed jet flow collides with each other to perform energy transfer, so that the bubbles are broken. The connection between the micro-interface generator and the first and second reactors and other devices, including the connection structure and the connection position, is not limited according to the structure of the micro-interface generator. The reaction mechanism and control method of the micro-interface generator are disclosed in the prior patent CN 10756051B of the inventor, and are not described in detail.
Further, the first circulating pipeline passes through circulating material flow (including p-tolualdehyde, acetic acid, water, a small amount of unreacted p-xylene, intermediate products and the like obtained by reaction), the circulating material flow, the reaction mixed raw materials and air are introduced into the first micro-interface generator together for dispersion and crushing, and micro-bubbles are formed after crushing and then enter the first reactor for oxidation reaction.
Further, the second circulating pipeline passes through circulating material flow (including p-carboxybenzaldehyde, water, an intermediate product and the like obtained by reaction), the circulating material flow and air are introduced into the second micro-interface generator together for dispersing and crushing, micro-bubbles formed after crushing enter the second reactor, and the micro-bubbles are mixed with materials (including p-toluic acid, hydrobromic acid and the like) entering from the first inlet and then continue the secondary oxidation reaction.
In addition, the first circulating pipeline and the second circulating pipeline are both provided with circulating pumps for providing power, the inner wall of a pump shell of each circulating pump is provided with a metal sensing probe, the outer wall of the pump shell on one side of the metal sensing probe is provided with a temperature sensor, and the metal sensing probe and the temperature sensor are connected through a lead and can monitor the temperature of liquid-phase materials in the circulating pumps at any time. More preferably, first circulating line and second circulating line all are provided with the heat exchanger for the temperature of control cycle material to make inside the first reactor and the second reactor keep the constant temperature, preferred plate heat exchanger compares other heat exchangers, and plate heat exchanger has the heat exchange efficiency height, and the heat loss is little, and is energy-efficient, washs characteristics such as easy dismouting convenient easily.
A first outlet of the first reactor is arranged at the middle upper part of the side wall, and through an overflow pipeline, produced intermediate products (mainly comprising p-toluic acid, acetic acid, water, a small amount of unreacted p-xylene, the intermediate products and the like) enter the middle part of the rectifying tower and are purified and separated in the rectifying tower.
The first inlet of the second reactor is arranged at the middle lower part of the side wall, materials (p-toluic acid and water), supplemented catalyst (hydrobromic acid) and water separated from the acid water separator, which are produced at the bottom of the rectifying tower, enter the second reactor from the first inlet to continue to react, air enters from the second air inlet, circulating material flow enters from the side wall of the second micro-interface generator, the air and the circulating material flow enter the second reactor after being dispersed and crushed in the second micro-interface generator, the air and the circulating material flow are mixed with liquid-phase materials entering from the first inlet to perform secondary oxidation reaction, and the generated terephthalic acid solution is extracted from a third outlet at the upper part of the side wall of the second reactor.
Furthermore, wave-proof grids are arranged above the inner parts of the first reactor and the second reactor, the wave-proof grids mainly play a role in filtering foams and removing foams carried in air flow so as to ensure mass transfer efficiency and reduce valuable material loss, and the wave-proof grids can be made of high-quality materials imported in China, such as: q235, 304L, 321, 316L, F46, NS-80, nickel wire, titanium wire and alloy.
Further, the inside top of first reactor and second reactor all is provided with except that the filter screen, and impurity such as a large amount of intermediate products have been gathered to the top of reactor, sets up and removes the filter screen and can filter these impurity, improves the purity that generates the result, remove the filter screen material and can adopt metal or plastics, preferred stainless steel and nylon material.
Furthermore, a second outlet is arranged at the top of the first reactor and connected with an acid water separator. Part of acetic acid and water extracted from the top of the rectifying tower and tail gas extracted from the top of the first reactor are jointly converged and then enter an acid water separator, the separated acetic acid returns to the inside of the first reactor again for recycling, part of the separated water is discharged, and part of the separated water enters the inside of the second reactor for recycling.
Furthermore, a rectifying tower adopted by the invention mainly comprises a light component separation section and a heavy component separation section, wherein a tower section between the light component separation section and the heavy component separation section is provided with a material inlet for introducing oxidation products in a first reactor into the rectifying tower, materials entering from the material inlet of the rectifying tower mainly comprise p-toluic acid, acetic acid, water, a small amount of unreacted p-xylene, intermediate products and the like, the p-toluic acid and the small amount of water are rectified and separated to the tower bottom through the heavy component separation section positioned below the material inlet, the acetic acid and the large amount of water pass through the light component separation section and then are rectified and separated towards the tower top direction, the acetic acid and the water vapor led out from a distillate outlet pass through a condenser, one part of the acetic acid and the water vapor return to the rectifying tower from the tower top as reflux liquid, the rest of the acetic acid and the tail gas in the first reactor are mixed through a pipeline and then enter an acid water separator, and the other part of liquid phase materials such as p-toluic acid and the small amount of water enter a second reactor after being extracted from a reboiler of a tower bottom, and then continue to return to the heavy component separation section through a reboiler, and then enter a second reactor for reaction.
The light component separation section and the heavy component separation section in the rectifying tower can be formed by randomly combining a plurality of tower plates and fillers, preferably, the tower plate structure is adopted at the position close to the tower kettle, and the filler structure is adopted at the position close to the tower top, because the pressure drop of the tower plates is larger and the pressure drop of the fillers is smaller.
Further, the top of the rectifying tower is provided with a tower top condenser, the tower kettle is provided with a tower kettle reboiler, the type of the tower kettle reboiler is a falling film type reboiler, compared with the common reboiler type, the reboiler of the type forms a film on the pipe wall, the heat exchange efficiency is very high, the residence time is short, coking is not easy, and the generation of byproducts due to polymerization of materials in the tower kettle is avoided.
In addition, the invention also provides a method for preparing terephthalic acid by adopting the paraxylene of the external micro-interface oxidation system, which is characterized by comprising the following steps:
dispersing and crushing air and mixed raw materials through a micro-interface generator arranged outside the first reactor, and then allowing the air and the mixed raw materials to enter the first reactor for oxidation reaction;
the liquid phase material obtained by oxidation reaction enters a rectifying tower for separation;
the liquid-phase material separated by the rectifying tower enters a second reactor;
and (3) dispersing and crushing the air through a micro-interface generator arranged outside the second reactor, then feeding the air into the second reactor, mixing the air with the liquid-phase material separated from the rectifying tower, and then carrying out secondary oxidation reaction to obtain the terephthalic acid.
Furthermore, the temperature in the first reactor is 120-155 ℃, and the pressure is 0.20-0.66MPa.
Furthermore, the temperature in the second reactor is 135-180 ℃, and the pressure is 0.56-0.82MPa.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the micro-interface generator is arranged outside the reactor, so that the phase interface area between air and the liquid-phase material can be increased, the air and the liquid-phase material are fully crushed and mixed before entering the reactor, the mass transfer space is fully satisfied, and the retention time of the air in the liquid phase is increased, thereby greatly improving the reaction speed, effectively controlling the side reaction, improving the product yield, remarkably reducing the energy consumption in the reaction process, simultaneously reducing the operation temperature and pressure, and improving the reaction safety.
(2) The invention solves the contradiction that acetic acid as a solvent can not bear high-temperature oxidation conditions in the process of preparing the terephthalic acid by the p-xylene through a sectional process and giving different reaction conditions aiming at different reactions, and can take out products in time, and the sectional oxidation is favorable for reducing investment and consumption and achieves better reaction effect than the prior process.
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 oxidation system for preparing terephthalic acid from paraxylene according to an embodiment of the present invention.
Description of the drawings:
10-a first reactor; 11-a first outlet;
12-a second inlet; 13-a second outlet;
14-a first circulation conduit;
20-a rectifying tower; 21-material inlet;
22-material outlet; 23-a distillate outlet;
24-a light fraction separation section; 25-a heavy ends separation section;
26-a condenser;
30-a second reactor; 31-a first inlet;
32-a third outlet; 33-a third inlet;
34-a second recycle conduit; 35-an exhaust gas outlet;
40-a first micro-interface generator; 41-a first air inlet;
42-raw material inlet;
50-a second micro-interface generator; 51-a second air inlet;
60-acid water separator; 70-wave-resisting grating;
80-removing a filter screen; 90-circulating pump;
100-a heat exchanger; 110-column reboiler.
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 simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific 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 and may be, for example, fixedly connected, detachably connected, or integrally connected; 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 explain 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 oxidation system for preparing terephthalic acid from paraxylene comprises a first reactor 10, a rectifying tower 20, a second reactor 30, a first micro-interface generator 40 and a second micro-interface generator 50, wherein the micro-interface generators are used for dispersing broken air and/or a mixture into bubbles.
Wherein, the lateral wall of first reactor 10 is provided with first export 11, and the relative lateral wall leans on the position to be provided with second import 12, and second import 12 is connected with the lateral wall of first little interfacial generator 40, and first circulating line 14 is connected to another lateral wall of first little interfacial generator 40, be provided with circulating pump 90 on the first circulating line 14, the top of first reactor 10 is provided with second export 13, and the material that second export 13 came out mainly has acetic acid and vapor.
The side wall of the rectifying tower 20 is provided with a material inlet 21, the bottom of the rectifying tower is provided with a material outlet 22, the side wall of the second reactor 30 is provided with a first inlet 31 at the lower position, the other side of the second reactor is provided with a third inlet 33, the third inlet 33 is connected with the side wall of the second micro-interface generator 50, the other side wall of the second micro-interface generator 50 is connected with a second circulating pipeline 34, the second circulating pipeline 34 is provided with a circulating pump 90, the first outlet 11 is connected with the material inlet 21, the first inlet 31 is connected with the material outlet 22, circulating material flow and mixed raw material in the first circulating pipeline 14 and air enter the first reactor 10 for primary oxidation reaction after the circulating material flow and the mixed raw material and the air disperse and break bubbles in the first micro-interface generator 40, products (main components of which are p-toluic acid, acetic acid, water, a small amount of unreacted p-xylene, intermediate products and the like) after the oxidation reaction enter the rectifying tower 20 through the first outlet 11 for separation, products (p-toluic acid, water and the like) separated from the tower bottom enter the second reactor 30 from the first inlet 31 through the material outlet 22, air and circulating material flow in the second circulating pipeline 34 enter the second reactor 30 after dispersing broken bubbles in the second micro-interface generator, are mixed with liquid-phase materials entering from the first inlet 31 for secondary oxidation reaction, and terephthalic acid as a reaction product is collected from the third outlet 32 on the side wall of the second reactor 30. The recycle streams in the first recycle pipeline 14 and the second recycle pipeline 34 are respectively subjected to heat exchange by a heat exchanger 100 and then enter the micro-interface generator, so that the temperature in the reactor is kept constant all the time.
In addition, the tail gas of the first reactor 10 is discharged through the second outlet 13 at the top, the product enters the rectifying tower 20 through the first outlet 11 for separation, the rectifying tower 20 mainly comprises a light component separation section 24 and a heavy component separation section 25, a part of the separated light component acetic acid and water returns to the rectifying tower from the top of the tower as reflux liquid through a condenser 26, the other part of the acetic acid and water enters the acid water separator 60 after being mixed with the tail gas discharged from the second outlet 13 through a distillate outlet 23 of the rectifying tower, the separated water enters the second reactor 30, and the acetic acid returns to the first reactor 10 for recycling. One part of heavy component products (p-methyl benzoic acid, water and the like) at the material outlet 22 at the bottom of the rectifying tower passes through the tower kettle reboiler 110 and returns to the heavy component separation section 25 as reflux liquid to be continuously rectified, and the other part enters the second reactor 30 through the first inlet 31 to carry out secondary oxidation reaction.
The reaction product terephthalic acid is extracted from a third outlet 32 on the side wall above the second reactor 30, a waste gas outlet 35 is also arranged at the top of the second reactor 30, and the waste gas enters a subsequent treatment stage from the outlet and is discharged to the atmosphere after reaching the standard.
In the above embodiment, the first reactor 10 is provided with the first raffinate outlet, the second reactor 30 is provided with the second raffinate outlet, and the collected raffinate enters the subsequent recycling process, so that the discharge is reduced, and the environmental pollution is reduced.
In the above embodiment, the temperature in the first reactor 10 is 120-155 deg.C, and the pressure is 0.20-0.66MPa; the temperature in the second reactor 30 is 135-180 deg.C, and the pressure is 0.56-0.82MPa.
In the above embodiment, the number of the pump bodies is not specifically required, and the pump bodies may be arranged at corresponding positions as required. In addition, the height, diameter, number of plates, and division of the column section of the rectifying column 20 can be adjusted according to actual needs.
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.
In the above embodiment, the breakwaters 70 are disposed above the liquid level of the first reactor 10 and the second reactor 30, so as to filter out the entrainment entrained in the gas flow and ensure the mass transfer efficiency.
In the above embodiment, a filter screen 80 is disposed above the liquid level in each of the first reactor 10 and the second reactor 30 to separate air and a part of the gaseous substances.
The operation and principle of the external micro-interface oxidation system for preparing terephthalic acid from paraxylene according to the present invention will be briefly described.
The mixture of paraxylene, acetic acid and catalyst (cobalt acetate, manganese acetate) enters the first micro-interface generator 40 from the raw material inlet 42, air enters the first micro-interface generator 40 from the first air inlet 41, the circulating material flow of the first reactor 10 enters the first micro-interface generator 40 through the first circulating pipeline 14, and the three gas-liquid phase materials are dispersed and broken into micro-bubbles and then enter the first reactor 10 for oxidation reaction.
Products (main components are p-methylbenzoic acid, and the main components also comprise acetic acid, water, a small amount of unreacted p-xylene, intermediate products and the like) obtained after full reaction enter a rectifying tower 20 through a first outlet 11, wherein the acetic acid and the water are rectified and separated towards the top direction after passing through a light component separation section 24, a part of the acetic acid and the water vapor led out from a distillate outlet 23 flow back to the rectifying tower 20 again through a condenser 26, the other part of the acetic acid and the water are mixed with tail gas discharged from a second outlet 13 through a pipeline and then enter an acid water separator 60, the water separated from the acid water separator 60 enters a second reactor 30, the acetic acid returns to the first reactor 10 for recycling, a part of heavy component products (p-methylbenzoic acid, water and the like) produced from a bottom material outlet 22 of the rectifying tower 20 are boiled again through a tower kettle reboiler 110 and then return to the rectifying tower 20, and the other part of the heavy component products enter the second reactor 30 through a first inlet 31.
The circulating material flow of the second reactor 30 enters the second micro interface generator 50 through the second circulating pipeline 34, the air enters the second micro interface generator 50 through the second air inlet 51, the air and the micro air are dispersed and broken into micro bubbles in the second micro interface generator 50 and then enter the second reactor 30 to perform secondary oxidation reaction with the liquid phase material (p-toluic acid, water and the like) entering from the first inlet 31, the resultant terephthalic acid solution is produced through the third outlet 32 and enters the post-treatment refining and separating section, the waste gas is extracted from the waste gas outlet 35 of the second reactor 30 and then is subjected to the post-treatment stage, and the waste gas reaches the standard and is discharged to the atmosphere.
The above steps are repeated circularly to make the whole treatment system run smoothly.
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 (7)
1. An external micro-interface oxidation system for preparing terephthalic acid from p-xylene, which is characterized by comprising: the device comprises a first reactor, a rectifying tower and a second reactor which are sequentially connected, wherein a first outlet and a second inlet are formed in the side wall of the first reactor, a first inlet and a third inlet are formed in the side wall of the second reactor, a material inlet is formed in the side wall of the rectifying tower, and a material outlet is formed in the bottom of the rectifying tower;
the first outlet is connected with the material inlet of the rectifying tower, and the first inlet is connected with the material outlet of the rectifying tower;
a first micro-interface generator is arranged outside the first reactor, the second inlet is connected with the side wall of the first micro-interface generator, a second micro-interface generator is arranged outside the second reactor, and the third inlet is connected with the side wall of the second micro-interface generator;
the side wall of the first micro-interface generator is connected with a first air inlet, the bottom of the first micro-interface generator is connected with a raw material inlet, and the bottom of the second micro-interface generator is connected with a second air inlet;
the outer side of the first reactor is provided with a first circulating pipeline, one end of the first circulating pipeline is connected with the side wall of the first micro-interface generator, and the other end of the first circulating pipeline is connected with the side wall of the first reactor.
A second circulating pipeline is arranged on the outer side of the second reactor, one end of the second circulating pipeline is connected with the side wall of the second micro-interface generator, and the other end of the second circulating pipeline is connected with the side wall of the second reactor;
the number of the first micro-interface generators is at least one;
the number of the second micro-interface generators is at least one;
the rectifying tower comprises a light component separation section and a heavy component separation section, and the material inlet is arranged on a tower section between the light component separation section and the heavy component separation section.
2. The external micro-interface oxidation system as set forth in claim 1, wherein a wave-proof grating is disposed above the inside of each of the first reactor and the second reactor.
3. The external micro-interface oxidation system as set forth in claim 1, wherein a filter screen is disposed above the inside of each of the first reactor and the second reactor.
4. The external micro-interface oxidation system as set forth in claim 1, wherein a second outlet is further provided at the top of the first reactor, and the second outlet is connected to an acid water separator.
5. A process for producing terephthalic acid from paraxylene using the external micro-interfacial oxidation system of claim 1, comprising the steps of:
dispersing and crushing air and mixed raw materials through a micro-interface generator arranged outside the first reactor, and then allowing the air and the mixed raw materials to enter the first reactor for oxidation reaction;
the liquid phase material obtained by oxidation reaction enters a rectifying tower for separation;
the liquid-phase material separated from the rectifying tower enters a second reactor;
and (3) dispersing and crushing the air through a micro-interface generator arranged outside the second reactor, then feeding the air into the second reactor, mixing the air with the liquid-phase material separated from the rectifying tower, and then carrying out secondary oxidation reaction to obtain the terephthalic acid.
6. The method of claim 5, wherein the temperature in the first reactor is 120-155 ℃ and the pressure is 0.20-0.66MPa.
7. The method of claim 6, wherein the temperature in the second reactor is 135-180 ℃ and the pressure is 0.56-0.82MPa.
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| PCT/CN2020/092772 WO2021196388A1 (en) | 2020-03-31 | 2020-05-28 | External micro-interface oxidation system and method for preparing terephthalic acid from p-xylene |
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| US4151738A (en) * | 1977-11-03 | 1979-05-01 | General Electric Company | Toxic gas monitor having automatic calibration |
| US7196215B2 (en) * | 2001-06-04 | 2007-03-27 | Eastman Chemical Company | Process for the production of purified terephthalic acid |
| MX2007002503A (en) * | 2004-09-02 | 2007-05-04 | Eastman Chem Co | Optimized production of aromatic dicarboxylic acids. |
| US7572936B2 (en) * | 2004-09-02 | 2009-08-11 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| CN101531588B (en) * | 2008-03-13 | 2016-02-24 | 周向进 | The manufacture method of a kind of new pure terephthalic acid |
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