CN113527113A - Equipment and process for preparing michelil by catalytic oxidation - Google Patents
Equipment and process for preparing michelil by catalytic oxidation Download PDFInfo
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- CN113527113A CN113527113A CN202010303887.7A CN202010303887A CN113527113A CN 113527113 A CN113527113 A CN 113527113A CN 202010303887 A CN202010303887 A CN 202010303887A CN 113527113 A CN113527113 A CN 113527113A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 38
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000001301 oxygen Substances 0.000 claims abstract description 77
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 77
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 239000010963 304 stainless steel Substances 0.000 claims description 3
- 241000218378 Magnolia Species 0.000 claims description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000004804 winding Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000003252 repetitive effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960001110 miglitol Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AUOKSPBBOCQYIX-UHFFFAOYSA-N n,n-dimethyl-1,1-diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N(C)C)C1=CC=CC=C1 AUOKSPBBOCQYIX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- -1 tetramethyl miglitol Chemical compound 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses equipment and a process for preparing Michler's alcohol by catalytic oxidation, which relate to the technical field of chemical industry and comprise a shell, wherein a catalyst is filled in the shell, the shell is connected with a feeding one-way valve, a feeding electromagnetic valve, a safety valve, a temperature sensor, an oxygen one-way valve and an oxygen concentration meter, a heating belt is wound outside the shell, the outlet end of the shell is sequentially connected with a condenser, a gas-liquid separator, a reduced pressure distiller and a cooling crystallization tank through pipelines, and a temperature controller and a master controller are arranged outside the shell. The invention avoids frequent loading and unloading, has a plurality of repetitive operations, can realize continuous production, can stably run for a long time, has higher efficiency and better energy saving performance compared with the intermittent kettle type reactor, can realize continuous and stable automatic production by applying an accurate sensing and control system, ensures the conversion rate and the product purity, does not generate a large amount of three wastes, and is suitable for popularization and use.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to equipment and a process for preparing michelian alcohol by catalytic oxidation.
Background
Nowadays, the chemical industry is developed more and more, for example, the michelil is an important intermediate of medicine and dye, and has wide application. The michelia alcohol is used as a main raw material of dye Crystal Violet Lactone (CVL), and the market demand is large. Methane bis (4, 4' -bis dimethylamino diphenylmethane) and oxygen are usually used as raw materials to prepare the michelian alcohol through a catalytic oxidation process.
The published data show that the oxidation method is commonly used for producing the michaelis alcohol in China and the batch production of the reaction kettle is generally adopted. The reaction is simulated in a laboratory, supported multi-element metal oxide catalyst is used, oxygen is supplied by an air bubbling method, the reaction time is 120min in a spherical reaction device, and the product yield and the purity are both satisfactory. However, the batch reactor type reaction has many repetitive operations such as frequent material loading and unloading, repeated temperature rise and drop and the like, and the production capacity is restricted. In order to improve the production efficiency, I designed and manufactured a small tubular reactor to produce the michaelis alcohol.
Disclosure of Invention
The invention aims to provide equipment and a process for preparing michelian alcohol by catalytic oxidation, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: the device for preparing the michelia alcohol through catalytic oxidation comprises a shell, wherein a catalyst is filled in the shell, the inlet end of the shell is sequentially connected with a feeding one-way valve and a feeding electromagnetic valve through a pipeline, a safety valve is arranged at the upper end of the shell, a heating belt is wound outside the shell, a temperature sensor (a plurality of temperature measuring points) is arranged in the shell, an oxygen interface is arranged on the shell, an oxygen one-way valve (preventing suck-back and backflushing) is arranged on the interface, the oxygen one-way valve is connected with the oxygen electromagnetic valve through a pipeline, a pressure gauge is arranged on the pipeline between the oxygen one-way valve and the oxygen electromagnetic valve, an oxygen concentration meter (having the function of adjusting the supply amount of downstream oxygen according to the data of the oxygen sensor to ensure complete oxidation and prevent excessive oxidation) is arranged beside the oxygen interface on the shell, the outlet end of the shell is sequentially connected with a condenser and a condenser through a pipeline, The device comprises a gas-liquid separator, a reduced pressure distiller and a cooling crystallization tank, wherein a heating belt and a temperature sensor are connected onto a temperature controller through leads, and a feeding electromagnetic valve, an oxygen electromagnetic valve, a pressure gauge, an oxygen concentration meter and the temperature controller are respectively connected onto a master controller through leads.
Preferably: the shell is made of 304 stainless steel, the pipe diameter D is phi 16-50mm, the wall thickness of the pipe is 2-6mm, the length L is 800-2500mm, end sockets are arranged on two sides and connected through flanges, the length-diameter ratio L/D is not less than 50, and the inner wall of the shell 1 is provided with flow deflectors and forms an included angle of 90-145 degrees with the pipe wall.
Preferably: the catalyst is Co-Mn-Ce multi-element metal oxide, and the carrier is active gamma-Al2O3The diameter d of the microspheres is 3-5mm, and the length of the flow deflector 101 is 0.5d-0.86 d; the catalyst filling mode adopts a radial layered composite accumulation mode, and the filling volume value is half of the effective length value of the shell.
Preferably: the oxygen interfaces on the shell are distributed linearly or spirally.
Preferably: and the heating belt is externally wound with a heat insulation material.
The specific process steps are as follows:
1) methane bass is dissolved by hot ethanol, the content of the hot ethanol is 20 percent, the solution enters tubular reaction equipment from a pipeline, and the flow is controlled by controlling a feeding electromagnetic valve;
2) the oxygen comes from an oxygen generator or a gas bottle group, the pressure of the oxygen is reduced by a pressure reducing valve, the oxygen enters the reaction equipment from an oxygen interface after being regulated to about 350 kPa, and the oxygen supply amount is controlled by controlling an oxygen solenoid valve;
3) opening the heating belt to start heating and start reaction when the reaction temperature is reached, controlling the reaction temperature to be 70 +/-2 ℃, setting the temperature and the heating time by the temperature controller, and carrying out catalytic oxidation on methane bass in the advancing process in the shell to generate tetramethyl miglitol;
4) the outlet end of the shell is connected with a condenser and a gas-liquid separator, the gas phase of the gas-liquid separator is discharged through the condenser at normal pressure, and the discharge pressure is about 101.3 kPa;
5) the separated liquid phase product enters a reduced pressure distiller, the solvent is evaporated for recycling, the mother liquor is cooled in a cooling crystallization tank and then crystallized and separated out, and a crude product is obtained after suction filtration;
6) the crude product is dissolved by ethanol and then recrystallized to obtain a product with the purity of more than or equal to 99.5 percent, and the mother liquor can be used as a solvent for recycling, but can influence the purity and the color of the product after being repeatedly used, and can be selected according to the requirement;
one advantage of using the tubular reactor for catalytic oxidation reaction to prepare the michaelis alcohol is that the oxygen supply can be dynamically adjusted at multiple points to completely carry out the oxidation reaction and avoid excessive oxidation reaction as much as possible. When the detection result of the oxygen sensor at the front end of the oxygen interface shows that the content of free oxygen is less than or equal to 0.1mol/L, oxygen supplementation is needed, and when the detection result of the oxygen sensor at the front end of the discharge port is more than or equal to 0.1mol/L, the oxygen supply amount of the oxygen interface at the previous stage needs to be reduced.
The tubular reactor is a unit structure with complete functions and can work independently. According to actual needs, a plurality of tubular reactors form a reactor array. A plurality of reactors can be connected in series to form a reactor with longer effective length, and the contact time of materials and the catalyst in the reactor is increased. Or a plurality of reactors can be connected in parallel to form a reactor with larger effective section flux. And can be used in series and parallel according to the requirements of specific processes and productivity.
It is known that increasing the cross-sectional area of the catalyst bed increases the flux of reactants per unit time and that increasing the length of the tubular reactor increases the residence time of reactants in the catalyst bed. Thus, a better way to increase the capacity is to design and manufacture a tubular reactor with a larger diameter and a longer length.
Assuming that the tubular reactor made by us is a standard unit and the productivity is E, n identical tubular reactors are connected in parallel, and the operating conditions are not changed, the total productivity is nE. If a tubular reactor with the capacity of nE is manufactured, the tubular reactor can be produced according to the formula Rnew = n ^ n（1/2）R, to calculate the new tubular reactor catalyst bed section radius. While the radius of the reactor Rnew is increased, the length of the reactor Lnew is also increased to meet the requirement of a proper length-diameter ratio, and the actual production capacity is larger than nE.
Compared with the prior art, the invention has the beneficial effects that:
1. the tubular reactor replaces a reaction kettle for intermittent reaction, and avoids a plurality of repeated operations such as frequent material loading and unloading, repeated temperature rise and drop and the like. The tubular reactor can be used for continuous production, and can stably run for a long time after parameters such as temperature, pressure, flow and the like are immobilized. The tubular reactor is adopted for catalytic oxidation reaction, and compared with an intermittent kettle type reactor, the efficiency is higher, and the energy saving performance is better. Under the control of accurate sensing and PLC embedded control system, continuous and stable automatic production can be realized, and the conversion rate and the product purity can be ensured.
2. The process adopts ethanol as solvent, the product is easy to separate, and the solvent can be recycled after low-temperature reduced pressure distillation. The method does not need acid-base neutralization process, does not corrode equipment, and does not produce a large amount of three wastes.
3. The tubular reactor of the invention has the function of adjusting the reaction balance. The reaction depth can be controlled by adjusting the oxygen supply amount, and the side reaction caused by over-oxidation can be prevented.
4. The unique design of the flow deflector avoids the adverse effect of the wall effect on the fluid mass transfer and heat transfer to the maximum extent.
5. The catalyst adopts a radial layered composite stacking structure, and is the most effective stacking mode.
6. The tubular reactor is a multipurpose reactor and can be used for various catalytic oxidation reactions.
7. The physical parameters of the tubular reactor and the performance of the catalyst determine the oxidation efficiency of the reactor. The method can increase the treatment capacity per unit time and realize the purpose of improving the productivity by increasing the sectional area of the reactor, prolonging the length of the catalyst bed and increasing the airspeed. When designing a new tubular reactor, the formula Rnew = n ^ n（1/2）R has certain guiding significance.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic view of the inner wall structure of the housing;
FIG. 3 is a reaction equation;
figure 4 is a plot of space velocity versus conversion.
In the figure: 1. the device comprises a shell, 2, a catalyst, 3, a feeding one-way valve, 4, a feeding electromagnetic valve, 5, a safety valve, 6, a heating belt, 7, a temperature sensor, 8, an oxygen one-way valve, 9, a pressure gauge, 10, an oxygen electromagnetic valve, 11, an oxygen concentration meter, 12, a temperature controller, 13, a master controller, 14, a condenser, 15, a gas-liquid separator, 16, a reduced pressure distiller, 17, a cooling crystallization tank, 101 and a flow deflector.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Referring to fig. 1-4, the present invention provides a technical solution, which includes a housing 1, a catalyst 2 is filled in the housing 1, an inlet end of the housing 1 is sequentially connected with a feeding check valve 3 and a feeding electromagnetic valve 4 through a pipeline, an upper end of the housing 1 is provided with a safety valve 5, the housing 1 is externally wound with a heating belt 6, the housing 1 is internally provided with a temperature sensor 7 (a plurality of temperature measuring points), the housing 1 is provided with an oxygen port and an oxygen check valve 8 (preventing suck-back and recoil) are mounted on the port, the oxygen check valve 8 is connected with an oxygen electromagnetic valve 10 through a pipeline and a pressure gauge 9 is mounted on the pipeline between the oxygen solenoid valve and the oxygen solenoid valve, an oxygen concentration meter 11 is mounted beside the oxygen port on the housing 1 (for adjusting the downstream oxygen supply amount according to the data of the oxygen sensor, ensuring complete oxidation without over-oxidation), the outlet end of the shell 1 is sequentially connected with a condenser 14, a gas-liquid separator 15, a reduced pressure distiller 16 and a cooling crystallization tank 17 through pipelines, the heating belt 6 and the temperature sensor 7 are connected onto a temperature controller 12 through leads, and the feeding electromagnetic valve 4, the oxygen electromagnetic valve 10, the pressure gauge 9, the oxygen concentration meter 11 and the temperature controller 12 are respectively connected onto a master controller 13 through leads.
The shell 1 is made of 304 stainless steel, the pipe diameter D is phi 16-50mm, the pipe wall thickness is 2-6mm, the length L is 800-2500mm, end sockets are arranged on two sides and connected through flanges, the length-diameter ratio L/D is not less than 50, and the inner wall of the shell 1 is provided with a flow deflector 101 which forms an included angle of 90-145 degrees with the pipe wall.
The catalyst 2 is Co-Mn-Ce multi-element metal oxide, and the carrier is active gamma-Al2O3The diameter d of the microspheres is 3-5mm, and the length of the flow deflector 101 is 0.5d-0.86 d; the filling mode of the catalyst 2 adopts a radial layered composite accumulation mode, and the filling volume value is half of the effective length value of the shell 1.
The oxygen interface on the housing 1 is distributed linearly or spirally.
And the heating belt 6 is externally wound with a heat insulation material.
The method comprises the following specific steps:
1) methane bass is dissolved by hot ethanol, the content of the hot ethanol is 20 percent, the solution enters a tubular reaction device from a pipeline, and the flow is controlled by controlling a feeding electromagnetic valve 4;
2) the oxygen comes from an oxygen generator or a gas cylinder group, the pressure of the oxygen is reduced by a pressure reducing valve, the pressure is adjusted to about 350 kPa, the oxygen enters the reaction equipment from an oxygen interface, and the oxygen supply amount is controlled by controlling an oxygen solenoid valve 10;
3) starting the heating belt 6 to heat and start reaction when the reaction temperature is reached, controlling the reaction temperature at 70 +/-2 ℃, setting the temperature and the heating time by the temperature controller 12, and carrying out catalytic oxidation on methane bass in the advancing process in the shell 1 to generate tetramethylMil alcohol;
4) the outlet end of the shell 1 is connected with a condenser 14 and a gas-liquid separator 15, the gas phase of the gas-liquid separator 15 is discharged through the condenser at normal pressure, and the discharge pressure is about 101.3 kPa;
5) the separated liquid phase product enters a reduced pressure distiller 16, the distilled solvent is recycled, the mother liquor is cooled in a cooling crystallization tank 17 and then crystallized and separated out, and a crude product is obtained after suction filtration;
6) the crude product is dissolved by ethanol and then recrystallized to obtain a product with the purity of more than or equal to 99.5 percent, and the mother liquor can be used as a solvent for recycling, but can influence the purity and the color of the product after being repeatedly used, and can be selected according to the requirement;
in using the present invention, it is first necessary to know the relationship between space velocity, which reflects the throughput of the apparatus, and the conversion, and the volumetric space velocity andmass space velocity two expression forms. In the examples we mark the catalytic oxidation capacity of this tubular reactor with the space velocity in volume. Volumetric space velocity = raw material volumetric flow (temperature 20 ℃, unit m)3In terms of catalyst volume (m) (/ h)3) The final unit of space velocity is h-1。
We have tested the oxidation reaction of the tubular reactor for preparing tetramethylMilkol from methane Bess under different airspeeds (same other conditions, the pipe diameter D is phi 50mm, the pipe wall thickness is 6mm, the length L is 2500mm, the flow deflector 101 and the pipe wall form an included angle of 145 degrees, the diameter D of the carrier microsphere is 5mm, and the length of the flow deflector 101 is 4.3 mm). In order to examine the catalytic oxidation performance of the tubular reactor and eliminate the positive effect of dynamic oxygen supply on the oxidation reaction, the oxygen supply mode of the experiment adopts the fixed flow and enough oxygen supply from the first oxygen interface. Experimental implementation data are shown below:
example 1: the flow rate of the methane bass ethanol solution is 50ml/min, and the airspeed is 6h-1(ii) a The conversion was 92.2%.
Example 2: the flow rate of the methane bass ethanol solution is 100ml/min, and the space velocity is 12 h-1(ii) a The conversion was 93.0%.
Example 3: the flow rate of the methane bass ethanol solution is 200ml/min, and the airspeed is 24h-1(ii) a The conversion rate is 94.1 percent
Example 4: the flow rate of the methane bass ethanol solution is 300ml/min, and the airspeed is 36h-1(ii) a The conversion was 94.2%.
Example 5: the flow rate of the methane bass ethanol solution is 500ml/min, and the space velocity is 60 h-1(ii) a The conversion was 92.5%.
Example 6: the flow rate of the methane bass ethanol solution is 750ml/min, and the space velocity is 90h-1(ii) a The conversion was 72.2%.
Example 7: the flow rate of the methane bass ethanol solution is 1000ml/min, and the space velocity is 120 h-1(ii) a The conversion was 45.3%.
Example 8: the flow rate of the methane bass ethanol solution is 1500ml/min, and the airspeed is 180 h-1(ii) a The conversion was 22.6%.
Example 9: the flow rate of the methane bass ethanol solution is 2000ml/min, and the space velocity is 240h-1(ii) a The conversion was 5.1%。
As shown in graph 4, the space velocity vs. conversion rate tends to increase and decrease with increasing space velocity. This is because, operating at a lower space velocity, the material remains in the tubular reactor for too long a time and is oxidized excessively to cause side reactions, which leads to a reduction in the conversion. As the space velocity increases, the residence time of the raw materials entering the reactor is shortened, the side reactions are less and less, and the conversion rate tends to gradually increase until the highest point. As the space velocity continues to increase, the amount of feed passing through the catalyst bed per unit time increases, the residence time of the reactants in the reactor decreases, the reaction does not complete and leaves, and this is a reasonable explanation for the sharp drop in conversion as the space velocity increases. Within the proper operating window, higher conversion and higher throughput can be achieved. A certain balance point in this interval is the sought suitable operating condition.
In production, the requirements for the chemical process are stability and simple operation. Higher conversion rate is pursued, raw material consumption can be reduced, and the difficulty of product separation is also reduced. On the premise of ensuring that the conversion rate meets the requirement, the yield per unit time is improved.
Deducted from FIG. 4, at an airspeed of 36h-1The best operation condition of the tubular reactor is to carry out methane Beth catalytic oxidation reaction.
The experimental data in FIG. 4 show that the air speed is 36-72 h-1Within the range, the catalytic oxidation efficiency of the tubular reactor can be further improved by starting the dynamic adjustment of the oxygen supply, and a larger capacity can be realized on the basis of ensuring a higher conversion rate, as shown in the following examples:
example 11: the flow rate of the methane bass ethanol solution is 300ml/min, and the airspeed is 36h-1(ii) a The conversion rate is 94.2%; the actual production capacity is 3.2 Kg/h.
Example 12: the flow rate of the methane bass ethanol solution is 400ml/min, and the space velocity is 48 h-1(ii) a The conversion rate is 94.1%; the actual production capacity is 4.4 Kg/h.
Example 13: the flow rate of the methane bass ethanol solution is 500ml/min, and the space velocity is 60 h-1(ii) a The conversion rate is 93.9%; actual capacity5.3Kg/h。
Example 14: the flow rate of the methane Beth ethanol solution is 600ml/min, and the space velocity is 72h-1(ii) a The conversion rate is 90.2%; the actual production capacity is 6.1 Kg/h.
Example 15: the flow rate of the methane bass ethanol solution is 750ml/min, and the space velocity is 90h-1(ii) a The conversion rate is 82.6 percent; the actual production capacity is 6.5 Kg/h.
The experiment proves that the airspeed is 36h-1Under these conditions, about 3.2kg of tetramethylMil alcohol per hour can be produced, which is in substantial agreement with the theoretical data.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The equipment for preparing the michelia alcohol by catalytic oxidation is characterized in that: including casing (1), casing (1) inside is filled with catalyst (2), casing (1) entry end has connected gradually pan feeding check valve (3) and pan feeding solenoid valve (4) through the pipeline, casing (1) upper end is equipped with relief valve (5), casing (1) outside winding has heating tape (6), casing (1) internally mounted has temperature sensor (7), be equipped with the oxygen interface on casing (1) and install oxygen check valve (8) on the interface, oxygen check valve (8) have oxygen solenoid valve (10) and install manometer (9) on the pipeline between through the pipe connection, other oxygen concentration meter (11) of installing of oxygen interface on casing (1), casing (1) exit end has connected gradually condenser (14), vapour and liquid separator (15) through the pipeline, Decompression distiller (16) and cooling crystallization pond (17), heating band (6) and temperature sensor (7) pass through the wire and connect on temperature controller (12), pan feeding solenoid valve (4), oxygen solenoid valve (10), manometer (9), oxygen concentration meter (11) and temperature controller (12) are connected through the wire respectively and are total controller (13).
2. The apparatus for preparing michaelis alcohol by catalytic oxidation according to claim 1, wherein: the shell (1) is made of 304 stainless steel, the pipe diameter D is phi 16-50mm, the pipe wall thickness is 2-6mm, the length L is 800-.
3. The apparatus for preparing michaelis alcohol by catalytic oxidation according to claim 1, wherein: the catalyst (2) is Co-Mn-Ce multi-element metal oxide, and the carrier is active gamma-Al2O3The diameter d of the microspheres is 3-5mm, and the length of the flow deflector (101) is 0.5d-0.86 d; the filling mode of the catalyst (2) adopts a radial layered composite accumulation mode, and the filling volume value is half of the effective length value of the shell (1).
4. The apparatus for preparing michaelis alcohol by catalytic oxidation according to claim 1, wherein: the oxygen interfaces on the shell (1) are distributed linearly or spirally.
5. The apparatus for preparing michaelis alcohol by catalytic oxidation according to claim 1, wherein: and the heating belt (6) is externally wound with a heat insulation material.
6. The process for preparing the michelian alcohol by adopting the catalytic oxidation as claimed in any one of claims 1 to 5, which is characterized by comprising the following specific steps:
1) methane bass is dissolved by hot ethanol, the solution enters a tubular reaction device from a pipeline, and the input flow is controlled by controlling a feeding electromagnetic valve (4);
2) the oxygen comes from an oxygen generator or a gas bottle group, the oxygen enters the reaction equipment from an oxygen interface after being decompressed by a decompression valve, and the oxygen supply amount is controlled by controlling an oxygen solenoid valve (10);
3) starting heating by opening the heating belt (6) and starting reaction when the reaction temperature is reached, setting the temperature and the heating time by the temperature controller (12), and carrying out catalytic oxidation on methane Beth in the advancing process in the shell (1) to generate tetramethyl micheli alcohol;
4) the outlet end of the shell (1) is connected with a condenser (14) and a gas-liquid separator (15), and the gas phase of the gas-liquid separator (15) is discharged through the condenser under normal pressure;
5) the separated liquid phase product enters a reduced pressure distiller (16), the solvent is evaporated for recycling, the mother liquor is cooled in a cooling crystallization tank (17) and then crystallized and separated out, and a crude product is obtained after suction filtration;
6) and (3) dissolving the crude product by using ethanol, and then recrystallizing to obtain a product with the purity of more than or equal to 99.5 percent, wherein the mother liquor can be used as a solvent for recycling, but can influence the purity and color of the product after being repeatedly used, and can be selected according to the requirement.
7. The process for preparing michaelis alcohol by catalytic oxidation according to claim 6, wherein: in the step 1), the hot ethanol content is 20%.
8. The process for preparing michaelis alcohol by catalytic oxidation according to claim 6, wherein: the oxygen supply pressure in step 2) was adjusted to about 350 kPa.
9. The process for preparing michaelis alcohol by catalytic oxidation according to claim 6, wherein: the reaction temperature of the step 3) is controlled to be 70 +/-2 ℃.
10. The process for preparing michaelis alcohol by catalytic oxidation according to claim 6, wherein: the emptying pressure of the gas-liquid separator in the step 4) is about 101.3 kPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010303887.7A CN113527113A (en) | 2020-04-17 | 2020-04-17 | Equipment and process for preparing michelil by catalytic oxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010303887.7A CN113527113A (en) | 2020-04-17 | 2020-04-17 | Equipment and process for preparing michelil by catalytic oxidation |
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| CN113527113A true CN113527113A (en) | 2021-10-22 |
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| CN202010303887.7A Pending CN113527113A (en) | 2020-04-17 | 2020-04-17 | Equipment and process for preparing michelil by catalytic oxidation |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2478626A1 (en) * | 1980-03-20 | 1981-09-25 | Union Carbide Corp | CONTINUOUS CATALYTIC PROCESS FOR LIQUID PHASE OXIDATION OF ACETIC ACID BUTANE |
| RU2233831C2 (en) * | 2002-06-28 | 2004-08-10 | Юнусов Рауф Раисович | Method of production of methanol and plant for realization of this method |
| CN104529902A (en) * | 2015-01-07 | 2015-04-22 | 江苏沿江化工资源开发研究院有限公司 | Method for preparing imidazole through coiled tubing gas phase catalytic reaction |
| CN106588605A (en) * | 2016-11-07 | 2017-04-26 | 常州大学 | Method for preparing benzaldehyde by continuously oxidizing methylbenzene through tubular reactor |
| CN212174842U (en) * | 2020-04-17 | 2020-12-18 | 大连第一有机化工有限公司 | Equipment for preparing michelil by catalytic oxidation |
-
2020
- 2020-04-17 CN CN202010303887.7A patent/CN113527113A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2478626A1 (en) * | 1980-03-20 | 1981-09-25 | Union Carbide Corp | CONTINUOUS CATALYTIC PROCESS FOR LIQUID PHASE OXIDATION OF ACETIC ACID BUTANE |
| RU2233831C2 (en) * | 2002-06-28 | 2004-08-10 | Юнусов Рауф Раисович | Method of production of methanol and plant for realization of this method |
| CN104529902A (en) * | 2015-01-07 | 2015-04-22 | 江苏沿江化工资源开发研究院有限公司 | Method for preparing imidazole through coiled tubing gas phase catalytic reaction |
| CN106588605A (en) * | 2016-11-07 | 2017-04-26 | 常州大学 | Method for preparing benzaldehyde by continuously oxidizing methylbenzene through tubular reactor |
| CN212174842U (en) * | 2020-04-17 | 2020-12-18 | 大连第一有机化工有限公司 | Equipment for preparing michelil by catalytic oxidation |
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