CN106866380B - Method and equipment for preparing 2, 6-di-tert-butyl-p-cresol by using micro-reaction rectifying plate - Google Patents

Method and equipment for preparing 2, 6-di-tert-butyl-p-cresol by using micro-reaction rectifying plate Download PDF

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CN106866380B
CN106866380B CN201710088202.XA CN201710088202A CN106866380B CN 106866380 B CN106866380 B CN 106866380B CN 201710088202 A CN201710088202 A CN 201710088202A CN 106866380 B CN106866380 B CN 106866380B
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plate
cresol
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reaction
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CN106866380A (en
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吕建华
葛珊珊
李品
刘继东
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Hebei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
    • 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
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • 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
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/141—Fractional distillation or use of a fractionation or rectification column where at least one distillation column contains at least one dividing wall
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/685—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
    • 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
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    • Y02P20/10—Process efficiency

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Abstract

The invention relates to a process method for preparing 2, 6-di-tert-butyl-p-cresol by using a micro-reaction rectifying plate. The method comprises the following steps: preheating p-cresol to 70-90 ℃ by a first preheater, feeding the p-cresol into a micro-reaction rectifying plate from an upper central channel, simultaneously preheating isobutene to 70-90 ℃ by a second preheater, feeding the isobutene into the micro-reaction rectifying plate from a lower central channel, reacting the p-cresol and the isobutene in the micro-reaction rectifying plate to generate a liquid-phase product, extracting the liquid-phase product from a side channel below the micro-reaction rectifying plate, rectifying and separating the liquid-phase reaction product to obtain 2, 6-di-tert-butyl-p-cresol, and recrystallizing and drying the liquid-phase product to obtain a finished product; and (3) discharging excessive isobutene and low-boiling-point products from a side channel above the micro-reaction rectifying plate. The invention has high p-cresol conversion rate, high 2, 6-di-tert-butyl-p-cresol yield, low reaction temperature and no temperature runaway.

Description

Method and equipment for preparing 2, 6-di-tert-butyl-p-cresol by using micro-reaction rectifying plate
Technical Field
The invention relates to a process method for preparing 2, 6-di-tert-butyl-p-cresol and equipment thereof, in particular to a process method for preparing 2, 6-di-tert-butyl-p-cresol by using a micro-reaction rectifying plate and equipment thereof.
Background
2, 6-di-tert-butyl-p-cresol is an excellent general phenol antioxidant, can inhibit or delay the oxidative degradation of plastics and rubber, is widely used in various lubricating oils, gasoline and paraffin, and can also be used as a food antioxidant. The prior production process mainly comprises alkylation reaction, wherein an alkylating agent such as isobutene, tert-butyl alcohol or methyl tert-butyl ether and the like is adopted, concentrated sulfuric acid, arylsulfonic acid and the like are used as catalysts, and the preparation is carried out under normal pressure or high pressure. However, the traditional liquid acid has strong corrosivity to equipment, so that the equipment investment is increased, alkali washing and water washing are needed to remove residual acid after alkylation, a large amount of waste water is generated, and the production cost is high. And the catalyst can not be recycled, the side reaction is not easy to control, and the product is difficult to separate.
Chinese patent CN 1313270 a discloses a new process for preparing 2, 6-di-tert-butyl-p-cresol, which adopts ion exchange resin as catalyst, and isobutene is introduced into two serially connected reaction kettles for alkylation reaction until the reaction reaches the end point. However, the traditional reaction kettle has small gas-liquid contact area, the reaction rate is limited by gas-liquid mass transfer, the reaction needs long time, the reaction temperature is high, the isobutylene polymerization reaction is easily aggravated, and the byproducts are increased.
Chinese patent CN 103212438B discloses a catalyst for alkylation separation of m-cresol and p-cresol and a separation method thereof, wherein methyl tert-butyl ether is used as an alkylating agent, ionic liquid is used as a catalyst, which can effectively inhibit side reactions and has little corrosion to equipment. However, the ionic liquid is used as a catalyst, which has the problems of high cost, large difficulty in industrial production and the like.
The micro chemical technology is a leading technology of chemical science and technology which is rapidly developed since the 90 s of the 20 th century, and the micro chemical equipment shows good performance in the aspects of mass transfer, heat transfer, reaction and the like, so the micro chemical technology gradually becomes a hot point of research. However, the existing research on the micro chemical engineering equipment has a simpler form, mainly focuses on a single micro-channel, or a cross-shaped or Y-shaped cross micro-channel, and the like, has a simple structure, and cannot meet the actual chemical production requirements of complexity, diversity and various varieties; on the other hand, researchers separately and not together research the reaction and separation of micro chemical engineering equipment, and therefore, the structure, unit coupling mode, material flow mode, hydraulic characteristics, and the like of micro reaction and micro rectification devices are in need of research.
Based on the current preparation situation of 2, 6-di-tert-butyl-p-cresol and the advantages of a micro-processing device, the invention provides a process method and equipment for preparing 2, 6-di-tert-butyl-p-cresol by using a micro-reaction rectifying plate.
Disclosure of Invention
The invention aims to provide a method and equipment for preparing 2, 6-di-tert-butyl-p-cresol by using a micro-reaction rectifying plate, aiming at the defects in the prior art. The method adopts a micro-reaction rectifying plate as a reaction device, obtains reaction parameters suitable for the device according to a large amount of research and experiments, ensures that gas and liquid in the reaction rectifying device are fully contacted, realizes high-efficiency mass and heat transfer, improves the conversion rate, and removes reaction heat in time.
The technical scheme of the invention is as follows:
a method for preparing 2, 6-di-tert-butyl-p-cresol by using a micro-reaction rectifying plate comprises the following steps:
preheating p-cresol to 70-90 ℃ by a first preheater, and feeding the p-cresol into a micro-reaction rectifying plate from an upper central channel under the feeding pressure of 0.3-1.0 MPa; simultaneously, preheating isobutene to 70-90 ℃ by a second preheater, feeding the isobutene into a micro-reaction rectifying plate from a lower central channel under the feeding pressure of 0.3-1.0 MPa, reacting paracresol and isobutene in the micro-reaction rectifying plate to generate a liquid-phase product, extracting the liquid-phase product from a side channel below the micro-reaction rectifying plate, rectifying and separating the liquid-phase reaction product to obtain 2, 6-di-tert-butyl-paracresol, and recrystallizing and drying the 2, 6-di-tert-butyl-paracresol to obtain a finished product; discharging excessive isobutene and low-boiling-point products from a side channel above the micro-reaction rectifying plate;
an acid catalyst is arranged in the micro-reaction rectifying plate; the acidic catalyst is specifically a metal catalyst, specifically V2O5/ZrO2(ii) a Wherein, V2O5The mass fraction of the metal catalyst is 0.1-0.5%;
the molar ratio of the p-cresol to the isobutene feeding amount is 1: 3-4; the space velocity of p-cresol is 0.2-1.0 h-1；
The micro-reaction rectifying plate comprises a base plate, a cover plate and a plate clamp; the substrate is a Polydimethylsiloxane (PDMS) thin plate engraved with a micro-chamber, the cover plate is a glass sheet, and the substrate and the cover plate are bonded through a plate clamp; the micro-cavity comprises two side channels positioned above the micro-reaction rectifying plate, an upper central channel, two side channels positioned below the micro-reaction rectifying plate, a lower central channel and a central cavity;
the central cavity is square, and the side length is 1300-2200 mu m; the depth of the central cavity is 80-100 mu m;
the widths of the upper and lower channels of the micro-chamber are the same and are all 80-100 mu m;
the widths of an upper central channel and a lower central channel of the micro-chamber are the same and are both 160-200 mu m;
an unetched pi-shaped partition plate is symmetrically distributed in the central cavity and comprises a top plate and two support legs, wherein the length of the top plate is 400-500 mu m, the width of the top plate is 50-100 mu m, and the width of the support legs is 50-100 mu m;
both ends of the top plate are provided with lower edges, the length of each lower edge is 40-50 mu m, and the lower edges are parallel to the adjacent supporting legs;
the two supporting legs and the top plate form a 75-90-degree angle, and the distance between the uppermost ends of the two supporting legs and the top plate is 200-300 mu m;
the distance between the bottommost ends of the two support legs and the lower inner wall of the central cavity is 80-100 micrometers;
four horizontal micro-channels are etched on the upper part of each supporting leg, and the width of each micro-channel is 40-60 mu m; the top end of the uppermost micro-channel is flush with the height of the lower edge of the top plate, and the micro-channel interval is 40-60 mu m;
the height of the Pi-shaped partition plate is 1000-1500 mu m;
the outer sides of two support legs of the Pi-shaped partition plate are respectively reserved with four vertical rectangular partition plates, the length of each rectangular partition plate is 400-600 microns, and the width of each rectangular partition plate is 50-100 microns; the distance between the adjacent rectangular partition plates is 50-100 mu m; the distance between the rectangular partition plate at the leftmost side and the similar inner wall is 50-100 mu m; the distance between the rectangular partition plate on the rightmost side and the adjacent inner wall is 50-100 mu m; the distance between the bottom end of the rectangular partition board and the inner wall of the central cavity is 160-200 mu m;
the periphery of the side wall of the rectangular partition plate is coated with an acid catalyst, and the coating thickness of the acid catalyst is 2-5 microns.
The micro-cavity on the substrate is processed on a PDMS substrate by adopting a photoetching technology, and the wall thicknesses of the substrate and the micro-cavity are both 2 cm;
the invention has the beneficial effects that:
in the invention, the conversion rate of p-cresol can be improved by excessive isobutene, and the excessive isobutene can take away reaction heat, thereby preventing the temperature runaway of the device and ensuring the normal reaction; the reaction temperature is low, the self-polymerization reaction of the isobutene hardly occurs, and the product refining process is simplified; the active component of the acid catalyst is loaded in the reaction channel, so that the corrosion to equipment is low, alkali washing and water washing are not needed, no waste water is generated, and the equipment investment is saved; compared with the traditional reactive distillation equipment, the micro-reactive distillation plate has the micron-sized size, the mass transfer and heat transfer gradient in the gas-liquid contact process is large, the specific surface area of the micro-equipment is large, and the mass transfer and heat transfer area provided for gas-liquid two phases is large, so that the mass transfer and heat transfer efficiency is high, and the rapid reaction and rapid reaction heat transfer are promoted; compared with the traditional micro-reaction rectifying equipment, the micro-reaction rectifying plate has a simple amplification process, can realize the increase and decrease of the treatment capacity through the parallel connection of the micro-equipment, and has no amplification effect.
Drawings
FIG. 1 is a diagram of a process for preparing 2, 6-di-tert-butyl-p-cresol by using a micro-reaction rectification plate according to an embodiment of the invention;
FIG. 2 is a front view of a bottom plate of a micro reactive distillation panel of the present invention;
wherein, 1, a first preheater; 2, a second preheater; 3, a micro-reaction rectifying plate; 4, an upper side channel; 5, an upper central channel; 6, a lower side channel; 7, a lower central channel; 8, a central chamber; 9, pi-shaped partition boards; 10, a top plate; 11, a support leg; 12, micro-vias; 13, rectangular partition.
Detailed Description
As shown in figure 1, the process method for preparing 2, 6-di-tert-butyl-p-cresol by using the micro-reaction rectification plate comprises the following steps:
subjecting p-cresol to first pre-treatmentPreheating a heater 1 to 70-90 ℃, feeding the heated isobutylene into a micro-reaction rectifying plate 3 from an upper central channel 5, simultaneously preheating the isobutylene to 70-90 ℃ by a second preheater 2, feeding the preheated isobutylene into the micro-reaction rectifying plate from a lower central channel 7, reacting the p-cresol and the isobutylene in the micro-reaction rectifying plate 3 to generate a liquid phase product, extracting the liquid phase product from a side channel 6 below the micro-reaction rectifying plate, rectifying and separating the liquid phase reaction product to obtain 2, 6-di-tert-butyl-p-cresol, and recrystallizing and drying the liquid phase product to obtain a finished product; excess isobutene and low-boiling-point products are discharged from a side channel 4 above the micro-reaction rectifying plate (can be collected and recycled after treatment); the feeding pressure of the paracresol and isobutene raw materials is 0.3-1.0 MPa; an acid catalyst is arranged in the micro-reaction rectifying plate; the acidic catalyst is a metal catalyst, is a known material, and is V2O5/ZrO2(ii) a Wherein, V2O5The mass fraction of the metal catalyst is 0.1-0.5%; the molar ratio of the p-cresol to the isobutene feeding amount is 1: 3-4; the space velocity of p-cresol is 0.2-1.0 h-1。
As shown in FIG. 2, the device for preparing 2, 6-di-tert-butyl-p-cresol by using the micro-reaction rectifying plate is a micro-reaction rectifying plate and comprises a base plate, a cover plate and a plate clamp; the substrate is a Polydimethylsiloxane (PDMS) monolithic thin plate engraved with a micro-chamber, the cover plate is a glass sheet, and the substrate and the cover plate are bonded through a plate clamp;
the micro-cavity comprises two side channels 4 positioned above the micro-reaction rectifying plate, an upper central channel 5, two side channels 6 positioned below the micro-reaction rectifying plate, a lower central channel 7 and a central cavity 8; the central cavity 8 is square, and the side length is 1300-2200 mu m; the depth of the central cavity is 80-100 mu m; the widths of the upper and lower four side channels 4(6) of the micro-chamber are the same and are all 80-100 mu m; the widths of the upper central channel 5(7) and the lower central channel of the micro-chamber are the same and are both 160-200 mu m;
an unetched pi-shaped partition plate 9 is symmetrically distributed in the central cavity 8, the pi-shaped partition plate comprises a top plate 10 and two support legs 11, the length of the top plate is 400-500 mu m, the two ends of the top plate are provided with lower edges, the length of the lower edges is 40-50 mu m, and the lower edges are parallel to the adjacent support legs; the two support legs and the top plate form an acute angle of 75-90 degrees, and the distance between the uppermost ends of the two support legs and the top plate is 200-300 mu m; the distance between the bottommost ends of the two support legs and the lower inner wall of the central cavity is 80-100 micrometers; four horizontal micro-channels are etched on the upper part of each support leg of the support leg, and the width of each micro-channel is 40-60 mu m; the top end of the uppermost micro-channel is flush with the height of the lower edge of the top plate, and the micro-channel interval is 40-60 mu m; the height of the pi-shaped partition plate is 1000-1500 mu m (the height of the pi-shaped partition plate refers to the size from the top of the top plate to the bottom end of the supporting leg); two sides of two support legs of the Pi-shaped partition plate are respectively reserved with four vertical rectangular partition plates 13, the length of each rectangular partition plate 13 is 400-600 mu m, and the width of each rectangular partition plate 13 is 50-100 mu m; the distance between the rectangular partition plates 13 is 50-100 mu m; the distance between the rectangular partition plate at the leftmost side and the adjacent inner wall is 50-100 mu m; the distance between the rectangular partition plate on the rightmost side and the adjacent inner wall is 50-100 mu m; the distance between the bottommost end of the rectangular partition board and the inner wall of the central cavity is 160-200 mu m; the periphery of the side wall of the rectangular partition plate is coated with an acid catalyst, and the coating thickness of the acid catalyst is 2-5 microns. (the shapes described for the Pi-shaped partition 9 and the rectangular partition 13 in the microcavity refer to their projected shapes at the bottom of the central chamber and are the result of remaining unetched, i.e., the thickness of the unetched portion is the same as the depth of the central chamber)
As shown in figure 2, the flow and reactive distillation process of the paracresol and the isobutene in the micro-reactive distillation plate comprises the steps that the paracresol flows into a central chamber 8 of the micro-reactive distillation plate from an upper central channel 5, enters gaps of rectangular partition plates 13 under the action of a top plate 10, the paracresol reacts under the action of an acid catalyst on the surfaces of the rectangular partition plates 13, part of liquid generated by the reaction enters the pi-shaped partition plates 9 from gaps at the bottoms of supporting legs, and the other part of liquid flows out from a lower side channel 6. The liquid entering the pi-shaped partition plate 9 is contacted with the isobutene coming from the central channel below, the liquid enters the pi-shaped partition plate 9, the fresh isobutene and the liquid phase are mixed and subjected to mass transfer, the isobutene exhaust gas is vaporized and coalesced with a low-boiling-point byproduct generated by the reaction, a gas-liquid mixture is sprayed out from the micro through holes 12, the paracresol wrapped with the fresh isobutene enters the gaps of the rectangular partition plate to react, and the excessive isobutene exhaust gas and the low-boiling-point reaction product are discharged from the side channel 4 above.
Example 1: the 2, 6-di-tert-butyl-p-cresol is prepared by using the equipment and the process method, wherein:
the preheating temperature of the paracresol preheater and the isobutene preheater is 70 ℃;
the feeding pressure of the raw materials is 0.5 MPa;
in catalyst V2O5The mass fraction of (B) is 0.1%
The catalyst coating thickness is 2 μm;
the space velocity of p-cresol is 1.0h-1；
The molar ratio of the p-cresol to the isobutylene is 1: 3.
The side length of the central cavity is 2200 μm;
the depth of the central cavity is 100 μm;
the width of the upper and lower channels of the micro-chamber is 100 μm;
the widths of the upper central channel and the lower central channel of the micro-chamber are 200 mu m;
the height of the Pi-shaped partition board is 1500 mu m;
two supporting legs of the Pi-shaped partition board form an angle of 80 degrees with a top plate of the Pi-shaped partition board;
the length of the top plate is 400 μm;
the width of the top plate is 50 μm, and the width of the support leg is 50 μm;
the length of the lower edges of the two ends of the top plate of the Pi-shaped partition plate is 40 mu m;
the spacing size of the uppermost ends of the two supporting legs of the Pi-shaped partition board is 200 mu m;
the widths of four micro-channels above two supporting legs of the Pi-shaped partition plate are 50 mu m;
the space between the four micro-channels above the two supporting legs of the Pi-shaped partition plate is 50 mu m;
the distance between the bottommost end of the Pi-shaped partition board and the inner wall of the central cavity is 100 mu m;
the length of the rectangular partition board is 600 mu m;
the width of the rectangular partition board is 100 mu m;
the spacing of the rectangular partition plates is 100 mu m;
the distance between the rectangular clapboard at the leftmost side and the similar inner wall is 100 mu m;
the distance between the rectangular partition board at the rightmost side and the similar inner wall is 100 mu m;
the distance between the bottommost end of the rectangular partition board and the inner wall of the central cavity is 200 mu m;
the temperature of the micro-reaction rectifying plate is stabilized at 76 ℃;
the mass fraction of 2, 6-di-tert-butyl-p-cresol in the liquid phase reaction product extracted by the micro-reaction rectification plate is as follows: 82%; p-cresol conversion: 90 percent of
Example 2: the 2, 6-di-tert-butyl-p-cresol is prepared by using the equipment and the process method, wherein:
the preheating temperature of the paracresol preheater and the isobutene preheater is 70 ℃;
the feeding pressure of the raw materials is 0.5 MPa;
in catalyst V2O5The mass fraction of (B) is 0.1%
The catalyst coating thickness is 2 μm;
the space velocity of p-cresol is 1.0h-1；
The molar ratio of the p-cresol to the isobutylene is 1: 4.
The side length of the central cavity is 2200 μm;
the depth of the central cavity is 100 μm;
the width of the upper and lower channels of the micro-chamber is 100 μm;
the widths of the upper central channel and the lower central channel of the micro-chamber are 200 mu m;
the height of the Pi-shaped partition board is 1500 mu m;
two supporting legs of the Pi-shaped partition board form an angle of 80 degrees with a top plate of the Pi-shaped partition board;
the length of the top plate is 400 μm;
the width of the top plate is 50 μm, and the width of the support leg is 50 μm;
the length of the lower edges of the two ends of the top plate of the Pi-shaped partition plate is 40 mu m;
the spacing size of the uppermost ends of the two supporting legs of the Pi-shaped partition board is 200 mu m;
the widths of four micro-channels above two supporting legs of the Pi-shaped partition plate are 50 mu m;
the space between the four micro-channels above the two supporting legs of the Pi-shaped partition plate is 50 mu m;
the distance between the bottommost end of the Pi-shaped partition board and the inner wall of the central cavity is 100 mu m;
the length of the rectangular partition board is 600 mu m;
the width of the rectangular partition board is 100 mu m;
the spacing of the rectangular partition plates is 100 mu m;
the distance between the rectangular clapboard at the leftmost side and the similar inner wall is 100 mu m;
the distance between the rectangular partition board at the rightmost side and the similar inner wall is 100 mu m;
the distance between the bottommost end of the rectangular partition board and the inner wall of the central cavity is 200 mu m;
the temperature of the micro-reaction rectifying plate is stabilized at 75 ℃;
the mass fraction of 2, 6-di-tert-butyl-p-cresol in the liquid phase reaction product extracted by the micro-reaction rectification plate is as follows: 85 percent; p-cresol conversion: 93 percent
Example 3: the 2, 6-di-tert-butyl-p-cresol is prepared by using the equipment and the process method, wherein:
the preheating temperature of the paracresol preheater and the isobutene preheater is 70 ℃;
the feeding pressure of the raw materials is 0.5 MPa;
in catalyst V2O5The mass fraction of (B) is 0.1%
The catalyst coating thickness is 2 μm;
the space velocity of p-cresol is 0.5h-1；
The molar ratio of the p-cresol to the isobutylene is 1: 4.
The side length of the central cavity is 2200 μm;
the depth of the central cavity is 100 μm;
the width of the upper and lower channels of the micro-chamber is 100 μm;
the widths of the upper central channel and the lower central channel of the micro-chamber are 200 mu m;
the height of the Pi-shaped partition board is 1500 mu m;
two supporting legs of the Pi-shaped partition board form an angle of 80 degrees with a top plate of the Pi-shaped partition board;
the length of the top plate is 400 μm;
the width of the top plate is 50 μm, and the width of the support leg is 50 μm;
the length of the lower edges of the two ends of the top plate of the Pi-shaped partition plate is 40 mu m;
the spacing size of the uppermost ends of the two supporting legs of the Pi-shaped partition board is 200 mu m;
the widths of four micro-channels above two supporting legs of the Pi-shaped partition plate are 50 mu m;
the space between the four micro-channels above the two supporting legs of the Pi-shaped partition plate is 50 mu m;
the distance between the bottommost end of the Pi-shaped partition board and the inner wall of the central cavity is 100 mu m;
the length of the rectangular partition board is 600 mu m;
the width of the rectangular partition board is 100 mu m;
the spacing of the rectangular partition plates is 100 mu m;
the distance between the rectangular clapboard at the leftmost side and the similar inner wall is 100 mu m;
the distance between the rectangular partition board at the rightmost side and the similar inner wall is 100 mu m;
the distance between the bottommost end of the rectangular partition board and the inner wall of the central cavity is 200 mu m;
the temperature of the micro-reaction rectifying plate is stabilized at 73 ℃;
the mass fraction of 2, 6-di-tert-butyl-p-cresol in the liquid phase reaction product extracted by the micro-reaction rectification plate is as follows: 92 percent; p-cresol conversion: 97 percent
Example 4: the 2, 6-di-tert-butyl-p-cresol is prepared by using the equipment and the process method, wherein:
the preheating temperature of the paracresol preheater and the isobutene preheater is 80 ℃;
the feeding pressure of the raw materials is 0.5 MPa;
in catalyst V2O5The mass fraction of (B) is 0.1%
The catalyst coating thickness is 2 μm;
the space velocity of p-cresol is 0.3h-1；
The molar ratio of the p-cresol to the isobutylene is 1: 4.
The side length of the central cavity is 2200 μm;
the depth of the central cavity is 100 μm;
the width of the upper and lower channels of the micro-chamber is 100 μm;
the widths of the upper central channel and the lower central channel of the micro-chamber are 200 mu m;
the height of the Pi-shaped partition board is 1500 mu m;
two supporting legs of the Pi-shaped partition board form an angle of 80 degrees with a top plate of the Pi-shaped partition board;
the length of the top plate is 400 μm;
the width of the top plate is 50 μm, and the width of the support leg is 50 μm;
the length of the lower edges of the two ends of the top plate of the Pi-shaped partition plate is 40 mu m;
the spacing size of the uppermost ends of the two supporting legs of the Pi-shaped partition board is 200 mu m;
the widths of four micro-channels above two supporting legs of the Pi-shaped partition plate are 50 mu m;
the space between the four micro-channels above the two supporting legs of the Pi-shaped partition plate is 50 mu m;
the distance between the bottommost end of the Pi-shaped partition board and the inner wall of the central cavity is 100 mu m;
the length of the rectangular partition board is 600 mu m;
the width of the rectangular partition board is 100 mu m;
the spacing of the rectangular partition plates is 100 mu m;
the distance between the rectangular clapboard at the leftmost side and the similar inner wall is 100 mu m;
the distance between the rectangular partition board at the rightmost side and the similar inner wall is 100 mu m;
the distance between the bottommost end of the rectangular partition board and the inner wall of the central cavity is 200 mu m;
the temperature of the micro-reaction rectifying plate is stabilized at 82 ℃;
the mass fraction of 2, 6-di-tert-butyl-p-cresol in the liquid phase reaction product extracted by the micro-reaction rectification plate is as follows: 92 percent;
p-cresol conversion: 99 percent
Therefore, the 2, 6-di-tert-butyl-p-cresol is prepared by adopting the micro-reaction rectifying plate, although the alkylation reaction is an exothermic reaction, the isobutene is excessive, the heat transfer rate of the device is high, the device is only slightly heated in the reaction process, the temperature is stable, and the temperature runaway phenomenon cannot occur; analysis of the reaction product shows that the conversion rate of p-cresol is high, and the yield of 2, 6-di-tert-butyl-p-cresol is high.
The invention is not the best and the technology is not known.

Claims (4)

1. A method for preparing 2, 6-di-tert-butyl-p-cresol by using a micro-reaction rectifying plate is characterized by comprising the following steps:
preheating p-cresol to 70-90 ℃ by a first preheater, and feeding the p-cresol into a micro-reaction rectifying plate from an upper central channel under the feeding pressure of 0.3-1.0 MPa; simultaneously, preheating isobutene to 70-90 ℃ by a second preheater, feeding the isobutene into a micro-reaction rectifying plate from a lower central channel under the feeding pressure of 0.3-1.0 MPa, reacting paracresol and isobutene in the micro-reaction rectifying plate to generate a liquid-phase product, extracting the liquid-phase product from a side channel below the micro-reaction rectifying plate, rectifying and separating the liquid-phase reaction product to obtain 2, 6-di-tert-butyl-paracresol, and recrystallizing and drying the 2, 6-di-tert-butyl-paracresol to obtain a finished product; discharging excessive isobutene and low-boiling-point products from a side channel above the micro-reaction rectifying plate;
an acidic catalyst is arranged in the micro-reaction rectifying plate, and the acidic catalyst is specifically a metal catalyst;
the molar ratio of the p-cresol to the isobutene feeding amount is 1: 3-4; the space velocity of p-cresol is 0.2-1.0 h-1；
The micro-reaction rectifying plate comprises a base plate, a cover plate and a plate clamp; the substrate is a Polydimethylsiloxane (PDMS) thin plate engraved with a micro-chamber, the cover plate is a glass sheet, and the substrate and the cover plate are bonded through a plate clamp; the micro-cavity comprises two side channels positioned above the micro-reaction rectifying plate, an upper central channel, two side channels positioned below the micro-reaction rectifying plate, a lower central channel and a central cavity;
the central cavity is square, and the side length is 1300-2200 mu m; the depth of the central cavity is 80-100 mu m;
the widths of the upper and lower channels of the micro-chamber are the same and are all 80-100 mu m;
the widths of an upper central channel and a lower central channel of the micro-chamber are the same and are both 160-200 mu m;
an unetched Pi-shaped partition board is symmetrically distributed in the central cavity and comprises a top board and two support legs, the length of the top board is 400-500 mu m, the two ends of the top board are provided with lower edges, the length of the lower edges is 40-50 mu m, and the lower edges are parallel to the adjacent support legs;
the two supporting legs and the top plate form a 75-90-degree angle, and the distance between the uppermost ends of the two supporting legs and the top plate is 200-300 mu m;
the distance between the bottommost ends of the two support legs and the lower inner wall of the central cavity is 80-100 micrometers;
four horizontal micro-channels are etched on the upper part of each supporting leg, and the width of each micro-channel is 40-60 mu m; the top end of the uppermost micro-channel is flush with the height of the lower edge of the top plate, and the micro-channel interval is 40-60 mu m;
the height of the Pi-shaped partition plate is 1000-1500 mu m;
four vertical rectangular partition plates are reserved on the outer sides of two support legs of the Pi-shaped partition plate respectively, the length of each rectangular partition plate is 400-600 mu m, and the width of each rectangular partition plate is 50-100 mu m; the distance between the adjacent rectangular partition plates is 50-100 mu m; the distance between the rectangular partition plate at the leftmost side and the similar inner wall is 50-100 mu m; the distance between the rectangular partition plate on the rightmost side and the adjacent inner wall is 50-100 mu m; the distance between the bottom end of the rectangular partition board and the inner wall of the central cavity is 160-200 mu m;
the periphery of the side wall of the rectangular partition plate is coated with an acid catalyst, and the coating thickness of the acid catalyst is 2-5 microns.
2. The method of claim 1, wherein the metal catalyst is V2O5/ZrO2(ii) a Wherein, V2O5The mass fraction of the metal catalyst is 0.1-0.5%.
3. A micro-reaction rectifying plate is characterized in that the rectifying plate comprises a base plate, a cover plate and a plate clamp; the substrate is a Polydimethylsiloxane (PDMS) thin plate engraved with a micro-chamber, the cover plate is a glass sheet, and the substrate and the cover plate are bonded through a plate clamp; the micro-cavity comprises two side channels positioned above the micro-reaction rectifying plate, an upper central channel, two side channels positioned below the micro-reaction rectifying plate, a lower central channel and a central cavity;
the central cavity is square, and the side length is 1300-2200 mu m; the depth of the central cavity is 80-100 mu m;
the widths of the upper and lower channels of the micro-chamber are the same and are all 80-100 mu m;
the widths of an upper central channel and a lower central channel of the micro-chamber are the same and are both 160-200 mu m;
an unetched Pi-shaped partition board is symmetrically distributed in the central cavity and comprises a top board and two support legs, the length of the top board is 400-500 mu m, the two ends of the top board are provided with lower edges, the length of the lower edges is 40-50 mu m, and the lower edges are parallel to the adjacent support legs;
the two supporting legs and the top plate form a 75-90-degree angle, and the distance between the uppermost ends of the two supporting legs and the top plate is 200-300 mu m;
the distance between the bottommost ends of the two support legs and the lower inner wall of the central cavity is 80-100 micrometers;
four horizontal micro-channels are etched on the upper part of each supporting leg, and the width of each micro-channel is 40-60 mu m; the top end of the uppermost micro-channel is flush with the height of the lower edge of the top plate, and the micro-channel interval is 40-60 mu m;
the height of the Pi-shaped partition plate is 1000-1500 mu m;
four vertical rectangular partition plates are reserved on the outer sides of two support legs of the Pi-shaped partition plate respectively, the length of each rectangular partition plate is 400-600 mu m, and the width of each rectangular partition plate is 50-100 mu m; the distance between the adjacent rectangular partition plates is 50-100 mu m; the distance between the rectangular partition plate at the leftmost side and the similar inner wall is 50-100 mu m; the distance between the rectangular partition plate on the rightmost side and the adjacent inner wall is 50-100 mu m; the distance between the bottom end of the rectangular partition board and the inner wall of the central cavity is 160-200 mu m;
the periphery of the side wall of the rectangular partition plate is coated with an acid catalyst, and the coating thickness of the acid catalyst is 2-5 microns.
4. The rectification plate of claim 3 wherein the top plate has a width of 50 to 100 μm and the legs have a width of 50 to 100 μm in the central chamber.
CN201710088202.XA 2017-02-20 2017-02-20 Method and equipment for preparing 2, 6-di-tert-butyl-p-cresol by using micro-reaction rectifying plate Expired - Fee Related CN106866380B (en)

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CN111099966B (en) * 2018-10-27 2022-08-12 中国石油化工股份有限公司 Method for preparing tert-butyl phenol
CN111302904A (en) * 2020-02-21 2020-06-19 江苏迈达新材料股份有限公司 Alkylation continuous reaction device for BHT production
CN111943816B (en) * 2020-07-23 2021-04-23 安徽海华科技集团有限公司 Preparation method of 2, 6-di-tert-butyl-p-cresol
CN112843765B (en) * 2020-12-03 2022-04-01 天津大学 Micro-scale efficient rectification separation process strengthening device and process
CN113248349A (en) * 2021-06-16 2021-08-13 南京元素科技有限公司 Device for alkylation continuous reaction of m-cresol and/or p-cresol
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