CN114225848B - Device and method for preparing butene-2-acid through high-yield continuous oxidation - Google Patents
Device and method for preparing butene-2-acid through high-yield continuous oxidation Download PDFInfo
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- CN114225848B CN114225848B CN202210168491.5A CN202210168491A CN114225848B CN 114225848 B CN114225848 B CN 114225848B CN 202210168491 A CN202210168491 A CN 202210168491A CN 114225848 B CN114225848 B CN 114225848B
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/001—Controlling catalytic processes
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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- 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
- B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
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- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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Abstract
The invention relates to the technical field of preparation of butenoic acid, and provides a device and a method for preparing butene-2-oic acid through high-yield continuous oxidation. The device provided by the invention comprises a butene-2-aldehyde raw material kettle (V-101), a solvent raw material kettle (V-102), a static mixer (M-101), a raw material preheater (E-101), a feeding gas-liquid mixer (M-102), a multi-stage tubular reactor, an interstage gas-liquid mixer and a gas-liquid separator (V-103). The device provided by the invention can be used for continuously catalyzing, oxidizing and synthesizing the butene-2-acid, so that the continuous production of the butene-2-acid is realized, the operation is simpler and more convenient, the environment is protected, the energy is saved, the heat supply and heat transfer of the reaction are easier, the safety is higher, the production efficiency is high, and the conversion rate of the butene-2-aldehyde is high; in addition, the device of the invention adopts a continuous tubular reactor to carry out catalytic oxidation reaction, and the regeneration operation of the catalyst is simple and convenient.
Description
Technical Field
The invention relates to the technical field of preparation of butenoic acid, in particular to a device and a method for preparing butene-2-acid through high-yield continuous oxidation.
Background
Butene-2-acid (the structural formula is shown as follows) is unsaturated fatty acid, contains double bond and carboxyl in the molecule, has strong reactivity, has wide application in industry, is mainly used for preparing various resins, bactericides, surface coatings and plasticizers, and is also an important medical intermediate and pesticide intermediate.
At present, butene-2-acid is generally obtained by oxidation of butene-2-aldehyde, and the basic principle is as follows:
patent CN1415594A discloses a method for preparing butene-2-acid by oxidizing butene-2-aldehyde in an oxidation tower, which takes metal silver powder as a catalyst and prepares the butene-2-acid by air oxidation in the oxidation tower.
Patent CN100494151A discloses a method for synthesizing butene-2-acid by selectively oxidizing butene-2-aldehyde in an autoclave, which takes butene-2-aldehyde as raw material and acetone, acetic acid, benzene or tolueneTaking phosphomolybdic acid as a main catalyst and vanadium pentoxide as an auxiliary catalyst as a solvent, and introducing oxygen to react and synthesize the butene-2-acid under the conditions of reaction temperature of 30-100 ℃ and pressure of 0.3-0.9 MPa. Phosphomolybdic acid can also be loaded onto catalyst supports (activated carbon, SiO)2、γ-Al2O3Molecular sieves, etc.).
The above patents carry out the reaction in an oxidation tower or an autoclave, which are all batch reactions, and the efficiency is low.
Disclosure of Invention
The invention aims to provide a device and a method for preparing butene-2-acid by high-yield continuous oxidation. The invention can realize the continuous production of the butene-2-acid, and has high production efficiency and low energy consumption.
In order to achieve the above object, the present invention provides the following technical solutions:
an apparatus for producing butene-2-oic acid by high-yield continuous oxidation, comprising:
the butene-2-aldehyde raw material kettle V-101 is provided with a feeding hole and a discharging hole;
the solvent raw material kettle V-102 is provided with a feeding hole and a discharging hole;
a feed inlet of the static mixer M-101 is respectively communicated with a discharge outlet of the butene-2-aldehyde raw material kettle V-101 and a discharge outlet of the solvent raw material kettle V-102;
the feed inlet of the raw material preheater E-101 is communicated with the discharge outlet of the static mixer M-101;
the feed gas-liquid mixer M-102 is communicated with a discharge port of the raw material preheater E-101, and the feed gas-liquid mixer M-102 is also provided with a gas inlet;
the multistage tubular reactor comprises a plurality of tubular reactors which are communicated in series, and a feed inlet of the multistage tubular reactor is communicated with a discharge outlet of the feed gas-liquid mixer M-102;
an interstage gas-liquid mixer is arranged between stages of the multistage tubular reactor;
and a gas-liquid separator V-103, wherein the feed inlet of the gas separator V-103 is communicated with the discharge outlet of the multistage tubular reactor.
The height of the gas separator V-103 is higher than that of the multi-stage tubular reactor.
Preferably, the number of stages of the multistage tubular reactor is at least 3.
Preferably, a pipeline for communicating the discharge port of the butene-2-aldehyde raw material kettle V-101 with the feed port of the static mixer M-101 is provided with a butene-2-aldehyde raw material pump P-101, and a pipeline for communicating the discharge port of the solvent raw material kettle V-101 with the feed port of the static mixer M-101 is provided with a solvent raw material pump P-102.
The invention also provides a method for preparing butene-2-acid by using the device in the scheme, which comprises the following steps:
the butene-2-aldehyde and the solvent respectively flow out of a butene-2-aldehyde raw material kettle V-101 and a solvent raw material kettle V-102 and enter a static mixer M-101 to be mixed to obtain mixed feed liquid;
preheating the mixed material liquid in a raw material preheater E-101 to obtain preheated mixed material liquid;
the preheated mixed feed liquid enters a feed gas-liquid mixer M-102, nitrogen-oxygen mixed gas is introduced into the feed gas-liquid mixer M-102 at the same time, the preheated mixed feed liquid and the nitrogen-oxygen mixed gas are mixed, the obtained gas-liquid mixture enters a multistage tubular reactor for catalytic oxidation reaction, an interstage gas-liquid mixer supplies oxygen to the interstage of the multistage tubular reactor, and the reacted feed liquid enters a gas-liquid separator V-103 for gas-liquid separation to obtain butene-2-acid; the multistage tubular reactor is filled with a supported silver catalyst.
Preferably, the solvent is an acetate solvent; the mass ratio of the butene-2-aldehyde to the solvent is 1: 1-5.
Preferably, the preheating temperature is 20-50 ℃; the space velocity of the butene-2-aldehyde is 0.1-20 h-1The molar ratio of oxygen in the mixed gas of the butene-2-aldehyde and the nitrogen and oxygen is 1: 5-80; the temperature of the catalytic oxidation reaction is 20-80 ℃.
Preferably, when the number of stages of the multistage tubular reactor is three, the temperature of the catalytic oxidation reaction in the first stage tubular reactor is 20-50 ℃, the temperature of the catalytic oxidation reaction in the second stage tubular reactor is 35-65 ℃, and the temperature of the catalytic oxidation reaction in the third stage tubular reactor is 50-80 ℃; the amount of the interstage supplemental oxygen is such that the molar ratio of the butene-2-aldehyde to the oxygen in the first-stage tubular reactor is 1: 5-80, the molar ratio of the butene-2-aldehyde to the oxygen in the second-stage tubular reactor is 1: 15-90, and the molar ratio of the butene-2-aldehyde to the oxygen in the third-stage tubular reactor is 1: 20-100.
Preferably, the supported silver catalyst comprises a carrier and silver supported on the carrier; the carrier is ZrO2And/or TiO2。
The preparation method of the supported silver catalyst comprises the following steps:
mixing the carrier after the first roasting with the adhesive for granulation to obtain carrier particles;
carrying out second roasting on the carrier particles, and then soaking the carrier particles in a soluble silver salt solution to obtain a soaked product;
and sequentially drying and roasting the obtained impregnated product for the third time to obtain the supported silver catalyst.
Preferably, the temperature of the first roasting is 400-900 ℃, and the time is 1-6 h; the temperature of the second roasting is 400-900 ℃, and the time is 1-6 h; the dipping time is 1-5 h; the temperature of the third roasting is 400-500 ℃, and the time is 3-6 h.
Preferably, after the activity of the catalyst is reduced to be below 80% of the initial activity, the mixed gas of the butene-2-aldehyde and the nitrogen and the oxygen is stopped, only the solvent is introduced, and hydrogen is introduced to reduce the catalyst.
The invention provides a device for preparing butene-2-acid by high-yield continuous oxidation, which comprises a butene-2-aldehyde raw material kettle V-101, a solvent raw material kettle V-102, a static mixer M-101, a raw material preheater E-101, a feeding gas-liquid mixer M-102, a multistage tubular reactor, an interstage gas-liquid mixer and a gas-liquid separator V-103. The device provided by the invention can be used for synthesizing the butene-2-acid by continuous catalytic oxidation, realizes the continuous production of the butene-2-acid, is simpler and more convenient to operate, is environment-friendly and energy-saving, is easier to heat supply and heat transfer of reaction, and is higher in safety.
The invention also provides a method for preparing butene-2-acid by using the device in the scheme, and the method provided by the invention has the advantages of high production efficiency, low energy consumption and high conversion rate of butene-2-aldehyde.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for producing butene-2-oic acid by high-yield continuous oxidation according to the present invention, wherein the number of stages of a multistage tubular reactor is 3; in fig. 1: v-101-butene-2-aldehyde raw material kettle, V-102-solvent raw material kettle, M-101-static mixer, E-101-raw material preheater, M-102-feeding gas-liquid mixer, R-101-first stage tubular reactor, R-102-second stage tubular reactor, R-103-third stage tubular reactor, M-103-interstage gas-liquid mixer arranged between first stage and second stage tubular reactor, M-104-interstage gas-liquid mixer arranged between second stage and third stage tubular reactor, and V-103-gas-liquid separator.
Detailed Description
The invention provides a device for preparing butene-2-acid by high-yield continuous oxidation, which comprises a butene-2-aldehyde raw material kettle V-101, wherein the butene-2-aldehyde raw material kettle V-101 is provided with a feeding hole and a discharging hole;
the solvent raw material kettle V-102 is provided with a feeding hole and a discharging hole;
a feed inlet of the static mixer M-101 is respectively communicated with discharge outlets of the butene-2-aldehyde raw material kettle V-101 and the solvent raw material kettle V-102;
the feed inlet of the raw material preheater E-101 is communicated with the discharge outlet of the static mixer M-101;
the feed gas-liquid mixer M-102 is communicated with a discharge port of the raw material preheater E-101, and the feed gas-liquid mixer M-102 is provided with a gas inlet;
the multistage tubular reactor comprises a plurality of tubular reactors which are communicated in series, and a feed inlet of the multistage tubular reactor is communicated with a discharge outlet of the gas-liquid mixer M-102;
an interstage gas-liquid mixer is arranged between stages of the multistage tubular reactor;
and a gas-liquid separator V-103, wherein the feed inlet of the gas separator V-103 is communicated with the discharge outlet of the multistage tubular reactor.
The height of the gas separator V-103 is higher than that of the multi-stage tubular reactor.
As a specific embodiment of the invention, a pipeline for communicating the discharge port of the butene-2-aldehyde raw material kettle V-101 with the feed port of the static mixer M-101 is also preferably provided with a butene-2-aldehyde raw material pump P-101, and a pipeline for communicating the discharge port of the solvent raw material kettle V-101 with the feed port of the static mixer M-101 is also preferably provided with a solvent raw material pump P-102.
In the invention, the number of stages of the multistage tubular reactor is at least 3, preferably 3-5, each reactor in the multistage tubular reactor is sequentially connected in series, a feed inlet of the multistage tubular reactor is specifically a feed inlet of a first-stage tubular reactor, and a discharge outlet of the multistage tubular reactor is specifically a discharge outlet of a last-stage tubular reactor; and each tubular reactor is preferably provided with a jacket, and cooling liquid is introduced into the jacket. In the present invention, the interstage of the multistage tubular reactor is provided with an interstage gas-liquid mixer, and in the specific embodiment of the present invention, it is preferable to provide an interstage gas-liquid mixer between adjacent two stages of tubular reactors, for example, when the multistage tubular reactor has 3 stages (first stage tubular reactor R-101, second stage tubular reactor R-102 and third stage tubular reactor R-103, respectively, see FIG. 1), an interstage gas-liquid mixer M-103 is provided between the first stage tubular reactor R-101 and the second stage tubular reactor R-102, and an interstage gas-liquid mixer M-104 is provided between the second stage tubular reactor R-102 and the third stage tubular reactor R-103. That is, a plurality of the interstage gas-liquid mixers are provided, and if the number of stages of the multistage tubular reactor is denoted by n, the number of the interstage gas-liquid mixers is n-1.
In the invention, the height of the gas separator V-103 is higher than that of the multistage tubular reactor, in particular, the topmost end of the gas-liquid separator is higher than that of the multistage tubular reactor; according to the invention, the gas separator V-103 is arranged at a position higher than the multistage tubular reactor, so that the reactor can be filled with reaction liquid, the reaction liquid is fully contacted with the catalyst, and the high-efficiency reaction is facilitated.
FIG. 1 is a schematic structural view of the apparatus for producing butene-2-oic acid by high-yield continuous oxidation, wherein CWS represents a cooling feed liquid and CWR represents a cooling return liquid in FIG. 1, when the number of stages of the multistage tubular reactor is 3.
The invention also provides a method for preparing butene-2-acid by using the device in the scheme, which comprises the following steps:
the butene-2-aldehyde and the solvent respectively flow out of a butene-2-aldehyde raw material kettle V-101 and a solvent raw material kettle V-102 and enter a static mixer M-101 to be mixed to obtain mixed feed liquid;
preheating the mixed feed liquid in a raw material preheater E-101 to obtain a preheated mixed feed liquid;
the preheated mixed feed liquid enters a feed gas-liquid mixer M-102, nitrogen-oxygen mixed gas is introduced into the feed gas-liquid mixer M-102 at the same time, the preheated mixed feed liquid and the nitrogen-oxygen mixed gas are mixed, the obtained gas-liquid mixture enters a multistage tubular reactor for catalytic oxidation reaction, the feed liquid obtained after the interstage gas-liquid mixer supplies oxygen to the interstage of the multistage tubular reactor for reaction enters a gas-liquid separator V-103 for gas-liquid separation, and butene-2-acid is obtained; the multistage tubular reactor is filled with a supported silver catalyst, and the supported silver catalyst comprises a carrier and silver loaded on the carrier; the carrier is ZrO2And/or TiO2。
In the invention, butene-2-aldehyde and a solvent respectively flow out of a butene-2-aldehyde raw material kettle V-101 and a solvent raw material kettle V-102 and enter a static mixer M-101 for mixing to obtain a mixed feed liquid. In the invention, the solvent is preferably an acetate solvent, more preferably one or more of ethyl acetate, methyl acetate, butyl acetate and amyl acetate, and more preferably ethyl acetate; the mass ratio of the butene-2-aldehyde to the solvent is preferably 1: 1-5, and more preferably 1: 2-4; in the specific embodiment of the present invention, it is preferable to control the mass ratio of butene-2-aldehyde and the solvent according to the flow rates of the two.
And after the mixed material liquid is obtained, preheating the mixed material liquid in a raw material preheater E-101 to obtain the preheated mixed material liquid. In the invention, the preheating temperature is preferably 20-50 ℃, and more preferably 30-40 ℃.
And after the preheated mixed material liquid is obtained, the preheated mixed material liquid enters a feeding gas-liquid mixer M-102, nitrogen-oxygen mixed gas is introduced into the feeding gas-liquid mixer M-102, and the preheated mixed material liquid and the nitrogen-oxygen mixed gas are mixed to obtain a gas-liquid mixture. In the invention, the molar ratio of oxygen in the mixed gas of butene-2-aldehyde and nitrogen and oxygen is preferably 1: 5-80, and more preferably 1: 10-60; the volume ratio of oxygen to nitrogen in the nitrogen-oxygen mixed gas is preferably 1: 2.
And after a gas-liquid mixture is obtained, the gas-liquid mixture enters a multistage tubular reactor for catalytic oxidation reaction, a gas-liquid mixer is arranged between stages, and oxygen is supplemented between stages to obtain reaction liquid. In the invention, the multistage tubular reactor is filled with a supported silver catalyst, and the supported silver catalyst comprises a carrier and silver supported on the carrier; the carrier is ZrO2And/or TiO2(ii) a The TiO is2Preferably anatase type TiO2Said TiO being2The specific surface area of (A) is preferably 50 to 90 m2A/g, more preferably 80 m2(iv)/g, the ZrO2Preferably monoclinic crystal form, and the specific surface area is preferably 40-90 m2A/g, more preferably 50 m2(ii)/g; the preparation method of the supported silver catalyst comprises the following steps:
mixing a carrier and an adhesive for granulation to obtain carrier particles;
carrying out first roasting on the carrier particles, and then soaking the carrier particles in a soluble silver salt solution to obtain a soaked product;
and sequentially drying and roasting the obtained impregnated product for the second time to obtain the supported silver catalyst.
In the invention, the first roasting temperature is preferably 400-900 ℃, more preferably 600 ℃, and the first roasting time is preferably 1-6 h, more preferably 5 h; the binder is preferably polyvinyl alcohol; the dosage of the adhesive is preferably 2-5% of the weight of the carrier, and more preferably 3-4%; the carrier particles are preferably spherical particles having a diameter of 2 mm; the second roasting temperature is preferably 400-900 ℃, more preferably 500-800 ℃, and the second roasting time is preferably 1-6 hours, more preferably 2-5 hours; after the second calcination is completed, the present invention preferably cools the calcined carrier particles before impregnation.
In the present invention, the soluble silver salt is preferably silver nitrate; the concentration of the soluble silver salt solution is preferably 0.1-0.2 g/L, and more preferably 0.11 g/L; the invention has no special requirement on the dosage ratio of the roasted carrier and the soluble silver salt solution, and in the specific embodiment of the invention, the impregnation is carried out according to the equivalent volume impregnation method according to the silver loading capacity in the target catalyst; the dipping temperature is preferably room temperature, and the time is preferably 1-5 h, and more preferably 2 h. During impregnation, the soluble silver salt is adsorbed into the support.
In the invention, the drying temperature is preferably 115 ℃, and the drying time is preferably 2 hours; the temperature of the third roasting is 400-500 ℃, and more preferably 430-450 ℃; the third roasting time is preferably 3-6 h, and more preferably 4-5 h; the atmosphere of the third roasting is preferably nitrogen or argon; in the third roasting process, the silver salt loaded on the carrier is converted into the silver simple substance. In the invention, the loading amount of the silver in the supported silver catalyst is preferably 2-15 wt%, and preferably 5-10 wt%; the loading amount of the silver is the percentage of the mass of the silver in the catalyst in the total mass of the catalyst.
In the invention, the space velocity of the butene-2-aldehyde is 0.1-20 h-1More preferably 1 to 15 hours-1The temperature of the catalytic oxidation reaction is preferably 20-80 ℃, and more preferably 30-60 ℃; in the invention, the catalytic oxidation reaction is carried out in a plurality of tubular reactors of the multistage tubular reactor, wherein the catalytic oxidation reaction temperature in each stage of tubular reactor can be independently controlled, namely the catalytic oxidation reaction temperature of each stage of tubular reactor can be the same or can be the sameThe temperature of each stage of tubular reactor is adjusted according to actual conditions in different ranges of 20-80 ℃. In the invention, in the process of carrying out catalytic oxidation reaction, fresh oxygen is supplemented into the tubular reactors of each stage by utilizing an interstage gas-liquid mixer, and the supplement amount of the fresh oxygen is preferably controlled according to reaction conditions; in the specific embodiment of the invention, when the number of stages of the tubular reactor is 3, the reaction temperature in the tubular reactor is preferably gradually increased from the first stage to the third stage, and the oxygen proportion is gradually increased, specifically, in the first stage tubular reactor, the temperature of the catalytic oxidation reaction is preferably 20-50 ℃, the temperature of the catalytic oxidation reaction in the second stage tubular reactor is preferably 35-65 ℃, and the temperature of the catalytic oxidation reaction in the third stage tubular reactor is preferably 50-80 ℃; the interstage oxygen supplementation amount enables the molar ratio of the butene-2-aldehyde to the oxygen in the first-stage tubular reactor to be 1: 5-80, the molar ratio of the butene-2-aldehyde to the oxygen in the second-stage tubular reactor to be 1: 15-90, and the molar ratio of the butene-2-aldehyde to the oxygen in the third-stage tubular reactor to be 1: 20-100; in a specific embodiment of the present invention, it is preferred to test the remaining amount of butene-2-carbaldehyde and the remaining amount of oxygen in each stage of the reactor after the first stage and then determine the amount of oxygen to be supplemented.
After the catalytic oxidation reaction is finished, the obtained reaction liquid enters a gas-liquid separator V-103 for gas-liquid separation to obtain the butene-2-acid. In the invention, the liquid obtained after gas-liquid separation is the crude feed liquid of the butene-2-acid, and the butene-2-acid with higher purity can be obtained after purification by a method well known by the technical personnel in the field.
In the invention, when the activity of the continuous catalyst is reduced to be below 80 percent of the initial activity, the mixed gas of the butene-2-aldehyde and the nitrogen and the oxygen is stopped to be introduced, only the solvent is introduced, the catalyst is reduced by introducing the hydrogen, and after the activity of the catalyst is recovered, the solvent and the butene-2-aldehyde are continuously introduced for catalytic oxidation reaction.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
The structure of the apparatus used in the examples is shown in FIG. 1, and the number of stages of the multistage tubular reactor is 3.
Example 1
Preparing a catalyst:
adding TiO into the mixture2The powder is roasted at 600 ℃ for 5 h (anatase type, specific surface area about 80 m)2/g) mixing with 2% polyethylene glycol, granulating to obtain 2mm spherical particles, and calcining at 700 deg.C for 5 hr to obtain particles with pore diameter of 5-15 nm and specific surface area of 60 m2Cooling carrier ball, mixing with silver nitrate solution, soaking for 2 hr, drying at 115 deg.c in a stoving oven for 2 hr, roasting at 450 deg.c for 4 hr to obtain Ag/TiO carrier with 5% loading2A silver catalyst is supported.
Butene-2-acid Synthesis:
the prepared catalyst is filled into a continuous multistage tubular reactor with the pipe diameter of about 32 mm. The butene-2-aldehyde and the ethyl acetate respectively flow out of a butene-2-aldehyde raw material kettle V-101 and a solvent raw material kettle V-102 and enter a static mixer M-101 to be mixed, and the mass ratio of the butene-2-aldehyde to the ethyl acetate is 1: 2; the obtained mixed liquid enters a raw material preheater E-101 to be preheated to 40 ℃, and then enters a feeding gas-liquid mixer M-102 and O2/N2Mixed gas (1: 2) is mixed and injected into a multistage tubular reactor filled with a catalyst, and interstage gas-liquid mixers are respectively arranged at the first-stage tubular reactor, the second-stage tubular reactor and the third-stage tubular reactor and used for supplementing fresh oxygen into the tubular reactor; the temperature of the first-stage, second-stage and third-stage tubular reactors is controlled at 40 ℃, 50 ℃ and 60 ℃ respectively. The mass space velocity of the butene-2-aldehyde is 1.2 h-1The molar ratio of the butene-2-aldehyde to the oxygen at the inlet is 1:10, the secondary tubular reactor is supplemented with fresh oxygen so that the molar ratio of the butene-2-aldehyde to the oxygen in the reactor is 1:30, and the tertiary tubular reactor is supplemented with fresh oxygen so that the molar ratio of the butene-2-aldehyde to the oxygen in the reactor is 1: 50. The material from the tubular reactor was subjected to gas-liquid separation by a gas-liquid separator V-103 to obtain a butene-2-oic acid solution with a yield of 76.57% and a butene-2-carbaldehyde conversion of 82.33%. In the reaction process, the temperature difference of the reaction liquid is about 3 ℃ (namely the temperature fluctuation range of the reaction liquid in the reaction process, the smaller the temperature difference is, the more the heat supply and the heat transfer of the reaction are representedEasy, higher safety).
Example 2
Preparing a catalyst:
ZrO 2 is mixed with2The powder is roasted at 600 ℃ for 5 h (monoclinic type, specific surface area is about 50 m2/g) mixing with 2% polyethylene glycol, granulating to obtain 2mm spherical particles, and calcining at 700 deg.C for 5 hr to obtain particles with aperture of 5-15 nm and specific surface area of 40 m2Cooling carrier ball, mixing with silver nitrate solution, soaking for 2 hr, drying at 115 deg.c in a stoving oven for 2 hr, roasting at 450 deg.c for 4 hr to obtain Ag/ZrO with 5% load2A silver catalyst is supported.
Butene-2-acid Synthesis:
the prepared catalyst is filled into a continuous three-stage tubular reactor with the pipe diameter of about 32 mm. The butene-2-aldehyde and the ethyl acetate respectively flow out of a butene-2-aldehyde raw material kettle V-101 and a solvent raw material kettle V-102 and enter a static mixer M-101 to be mixed, and the mass ratio of the butene-2-aldehyde to the ethyl acetate is 1: 2; the obtained mixed liquid enters a raw material preheater E-101 to be preheated to 40 ℃, and then enters a feeding gas-liquid mixer M-102 and O2/N2Mixed gas (1: 2) is mixed and injected into a multistage tubular reactor filled with a catalyst, interstage gas-liquid mixers are respectively arranged at the first-stage tubular reactor, the second-stage tubular reactor and at the third-stage tubular reactor and used for supplementing fresh oxygen into the tubular reactors, and the temperatures of the first-stage tubular reactor, the second-stage tubular reactor and the third-stage tubular reactor are respectively controlled at 40 ℃, 50 ℃ and 60 ℃. The mass space velocity of the butene-2-aldehyde is 1.2 h-1The molar ratio of the butene-2-aldehyde to the oxygen at the inlet is 1:30, the secondary tubular reactor is supplemented with fresh oxygen so that the molar ratio of the butene-2-aldehyde to the oxygen in the reactor is 1:50, and the tertiary tubular reactor is supplemented with fresh oxygen so that the molar ratio of the butene-2-aldehyde to the oxygen in the reactor is 1: 70. The material from the tubular reactor was subjected to gas-liquid separation by a gas-liquid separator V-103 to obtain a butene-2-oic acid solution with a yield of 76.48% and a conversion of butene-2-carbaldehyde of 81.92%. During the reaction, the temperature difference of the reaction solution was about 3 ℃.
Example 3
Preparing a catalyst:
ZrO 2 is mixed with2The powder is roasted at 600 ℃ for 5 h (monoclinic type, specific surface area is about 50 m2/g) mixing with 2% polyethylene glycol, granulating to obtain 2mm spherical particles, and calcining at 700 deg.C for 5 hr to obtain particles with aperture of 5-15 nm and specific surface area of 40 m2Cooling carrier ball, mixing with silver nitrate solution, soaking for 2 hr, drying in oven at 115 deg.c for 2 hr, roasting at 450 deg.c for 4 hr to obtain Ag/ZrO with solid content of 5%2A silver catalyst is supported.
Butene-2-acid synthesis:
the prepared catalyst is filled into a continuous three-stage tubular reactor with the pipe diameter of about 32 mm. The butene-2-aldehyde and the ethyl acetate respectively flow out of a butene-2-aldehyde raw material kettle V-101 and a solvent raw material kettle V-102 and enter a static mixer M-101 to be mixed, and the mass ratio of the butene-2-aldehyde to the ethyl acetate is 1: 2; the obtained mixed liquid enters a raw material preheater E-101 to be preheated to 40 ℃, and then enters a feeding gas-liquid mixer M-102 and O2/N2Mixed gas (1: 2) is mixed and injected into a multistage tubular reactor filled with a catalyst, an interstage gas-liquid mixer is respectively arranged between the first-stage tubular reactor and the second-stage tubular reactor and between the stages of the second-stage tubular reactor and the third-stage tubular reactor and used for supplementing fresh oxygen into the tubular reactors, and the temperatures of the first-stage tubular reactor, the second-stage tubular reactor and the third-stage tubular reactor are respectively controlled at 30 ℃, 50 ℃ and 70 ℃. The mass space velocity of the butene-2-aldehyde is 3h-1The molar ratio of the butene-2-aldehyde to the oxygen at the inlet is 1:8, the secondary tubular reactor is supplemented with fresh oxygen so that the molar ratio of the butene-2-aldehyde to the oxygen in the reactor is 1:30, and the tertiary tubular reactor is supplemented with fresh oxygen so that the molar ratio of the butene-2-aldehyde to the oxygen in the reactor is 1: 50. The material from the tubular reactor is subjected to gas-liquid separation by a gas-liquid separator V-103 to obtain a butene-2-acid solution with the yield of 74.06 percent, and the conversion rate of the butene-2-aldehyde is 79.64 percent. During the reaction, the temperature difference of the reaction solution was about 3 ℃.
Comparative example 1
70 g of butene-2-aldehyde, 140 g of ethyl acetate, 1.726 g of Ag/TiO2The catalyst (prepared in example 1) was placed in an autoclave and reacted at 40 ℃ with oxygen at a reaction pressure of 1 MPa. During the reaction process, the temperature difference of the reaction liquid is aboutIt was 15 ℃.
Comparative example 2
The three-stage tubular reactor in the device used in example 1 is replaced by a single-stage tubular reactor (correspondingly, an interstage gas-liquid mixer is omitted), other components are the same as those in example 1, and the specific steps are as follows:
preparing a catalyst:
ZrO 2 is mixed with2The powder is roasted at 600 ℃ for 5 h (monoclinic type, specific surface area is about 50 m2/g) mixing with 2% polyethylene glycol, granulating to obtain 2mm spherical particles, and calcining at 700 deg.C for 5 hr to obtain particles with aperture of 5-15 nm and specific surface area of 40 m2Cooling carrier ball, mixing with silver nitrate solution, soaking for 2 hr, drying at 115 deg.c in a stoving oven for 2 hr, roasting at 450 deg.c for 4 hr to obtain Ag/ZrO with 5% load2A silver catalyst is supported.
Butene-2-acid Synthesis:
the prepared catalyst is filled into a single-stage tubular reactor with the pipe diameter of about 32 mm. The butene-2-aldehyde and the ethyl acetate respectively flow out of a butene-2-aldehyde raw material kettle V-101 and a solvent raw material kettle V-102 and enter a static mixer M-101 to be mixed, and the mass ratio of the butene-2-aldehyde to the ethyl acetate is 1: 2; the obtained mixed liquid enters a raw material preheater E-101 to be preheated to 40 ℃, and then enters a feeding gas-liquid mixer M-102 and O2/N2The mixed gas (1: 2) is injected into a single-stage tubular reactor filled with catalyst after being mixed, and the system materials are controlled to react at 40 ℃. The mass space velocity of the butene-2-aldehyde is 1.2 h-1The molar ratio of butene-2-aldehyde to oxygen was 1: 50. The material from the tubular reactor was subjected to gas-liquid separation by a gas-liquid separator V-103 to obtain a butene-2-oic acid solution with a yield of 54.02% and a conversion of butene-2-carbaldehyde of 55.56%. During the reaction, the temperature difference of the reaction solution was about 5 ℃.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for preparing butene-2-acid by high-yield continuous oxidation is characterized in that the adopted device comprises:
the system comprises a butene-2-aldehyde raw material kettle (V-101), wherein the butene-2-aldehyde raw material kettle (V-101) is provided with a feeding hole and a discharging hole;
the solvent raw material kettle (V-102) is provided with a feeding hole and a discharging hole;
the feed inlet of the static mixer (M-101) is respectively communicated with the discharge outlets of the butene-2-aldehyde raw material kettle (V-101) and the solvent raw material kettle (V-102);
the feed inlet of the raw material preheater (E-101) is communicated with the discharge outlet of the static mixer (M-101);
a feed gas-liquid mixer (M-102), wherein the feed gas-liquid mixer (M-102) is communicated with a discharge port of the raw material preheater (E-101), and the feed gas-liquid mixer (M-102) is also provided with a gas inlet;
the multistage tubular reactor comprises a plurality of tubular reactors which are communicated in series, and a feed inlet of the multistage tubular reactor is communicated with a discharge outlet of the feed gas-liquid mixer (M-102); the number of stages of the multistage tubular reactor is at least 3; the multistage tubular reactor is filled with a supported silver catalyst; the supported silver catalyst comprises a carrier and silver supported on the carrier; the carrier is ZrO2And/or TiO2；
An interstage gas-liquid mixer is arranged between stages of the multistage tubular reactor;
the feed inlet of the gas-liquid separator (V-103) is communicated with the discharge outlet of the multistage tubular reactor;
the height of the gas-liquid separator (V-103) is higher than that of the multi-stage tubular reactor.
2. The method according to claim 1, wherein a butene-2-aldehyde raw material pump (P-101) is arranged on a pipeline communicating the discharge port of the butene-2-aldehyde raw material kettle (V-101) with the feed port of the static mixer (M-101), and a solvent raw material pump (P-102) is arranged on a pipeline communicating the discharge port of the solvent raw material kettle (V-101) with the feed port of the static mixer (M-101).
3. The method according to any one of claims 1 to 2, comprising the steps of:
the butene-2-aldehyde and the solvent respectively flow out of a butene-2-aldehyde raw material kettle (V-101) and a solvent raw material kettle (V-102) and enter a static mixer (M-101) for mixing to obtain mixed feed liquid;
the mixed material liquid enters a raw material preheater (E-101) for preheating to obtain preheated mixed material liquid;
the preheated mixed feed liquid enters a feed gas-liquid mixer (M-102), nitrogen-oxygen mixed gas is introduced into the feed gas-liquid mixer (M-102) at the same time, the preheated mixed feed liquid and the nitrogen-oxygen mixed gas are mixed, the obtained gas-liquid mixture enters a multistage tubular reactor for catalytic oxidation reaction, the interstage gas-liquid mixer supplies oxygen to the stages of the multistage tubular reactor, and the reacted feed liquid enters a gas-liquid separator (V-103) for gas-liquid separation to obtain butene-2-acid; the multistage tubular reactor is filled with a supported silver catalyst.
4. The method according to claim 3, wherein the solvent is an acetate-based solvent; the mass ratio of the butene-2-aldehyde to the solvent is 1: 1-5.
5. The method according to claim 3 or 4, wherein the temperature of the preheating is 20-50 ℃; the space velocity of the butene-2-aldehyde is 0.1-20 h-1The molar ratio of oxygen in the mixed gas of the butene-2-aldehyde and the nitrogen and oxygen is 1: 5-80; the temperature of the catalytic oxidation reaction is 20-80 ℃.
6. The method according to claim 5, wherein when the number of stages of the multistage tubular reactor is three, the temperature of the catalytic oxidation reaction in the first stage tubular reactor is 20 to 50 ℃, the temperature of the catalytic oxidation reaction in the second stage tubular reactor is 35 to 65 ℃, and the temperature of the catalytic oxidation reaction in the third stage tubular reactor is 50 to 80 ℃; the amount of the interstage supplemental oxygen is such that the molar ratio of the butene-2-aldehyde to the oxygen in the first-stage tubular reactor is 1: 5-80, the molar ratio of the butene-2-aldehyde to the oxygen in the second-stage tubular reactor is 1: 15-90, and the molar ratio of the butene-2-aldehyde to the oxygen in the third-stage tubular reactor is 1: 20-100.
7. The method according to claim 3 or 6, wherein the preparation method of the supported silver catalyst comprises the steps of:
mixing the carrier after the first roasting with the adhesive for granulation to obtain carrier particles;
carrying out second roasting on the carrier particles, and then soaking the carrier particles in a soluble silver salt solution to obtain a soaked product;
drying and roasting the obtained impregnated product in sequence to obtain a supported silver catalyst;
the temperature of the first roasting is 400-900 ℃, and the time is 1-6 h; the temperature of the second roasting is 400-900 ℃, and the time is 1-6 h; the dipping time is 1-5 h; the temperature of the third roasting is 400-500 ℃, and the time is 3-6 h.
8. The method of claim 3, wherein after the activity of the catalyst is reduced to less than 80% of the initial activity, the introduction of the mixed gas of butene-2-aldehyde and nitrogen and oxygen is stopped, only the solvent is introduced, and the catalyst is reduced by introducing hydrogen.
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