CN112047843A - Method for improving stability of m-xylylenediamine fixed bed hydrogenation catalyst - Google Patents
Method for improving stability of m-xylylenediamine fixed bed hydrogenation catalyst Download PDFInfo
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- CN112047843A CN112047843A CN202010919722.2A CN202010919722A CN112047843A CN 112047843 A CN112047843 A CN 112047843A CN 202010919722 A CN202010919722 A CN 202010919722A CN 112047843 A CN112047843 A CN 112047843A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/03—Precipitation; Co-precipitation
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- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
A method for improving the stability of a m-xylylenediamine fixed bed hydrogenation catalyst adopts a fixed bed reactor, and 1, 3-cyclohexyldimethylamine is prepared by m-xylylenediamine hydrogenation reaction under the condition of ammonia, wherein a protective agent, barium modified magnesium oxide and a hydrogenation catalyst are sequentially filled in a single reaction tube of the fixed bed along the material flow direction; the protective agent is a cobalt catalyst loaded by barium-modified magnesium oxide. In order to solve the problem of short service life of a hydrogenation catalyst in a fixed bed, according to the method provided by the invention, a protective agent is arranged in a single fixed bed reaction tube before the hydrogenation catalyst is contacted with a raw material of m-xylylenediamine, and the protective agent is contacted with the raw material firstly, so that nitrile-based substances in the raw material are effectively removed, and the service life of the hydrogenation catalyst is prolonged. The method is simple and easy to implement, and can be used in industrial production.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a method for improving the stability of a fixed bed catalyst for preparing 1, 3-cyclohexyldimethylamine by hydrogenation of m-xylylenediamine under the condition of ammonia, so that the hydrogenation catalyst can stably and efficiently hydrogenate m-xylylenediamine in the fixed bed to prepare the 1, 3-cyclohexyldimethylamine.
Background
1, 3-cyclohexyldimethylamine, 1, 3-BAC for short, is a colorless and slightly ammonia-flavored transparent liquid, can be dissolved in water, alcohol, ether, benzene, cyclohexane and other organic solvents, and is mainly applied to epoxy resin curing agents, polyurethane intermediates and anticorrosive antirust agents.
The method for producing 1, 3-cyclohexyldimethylamine is classified into an isophthalonitrile hydrogenation method and an m-xylylenediamine hydrogenation method according to the difference in the raw materials. Patent US 5371293 uses isophthalonitrile as raw material, dioxane as solvent, liquid ammonia as auxiliary agent, and hydrogenation reaction is carried out on ruthenium catalyst, and the molar yield of the obtained product 1, 3-cyclohexyldimethylamine is only 87.8%; therefore, the product selectivity of the isophthalonitrile hydrogenation method is not high, and the product yield is low. In addition, in the hydrogenation process of m-xylylene nitrile, the intermediate imine is very active and is very easy to condense with a reaction intermediate and a product, and the generated condensation polymer can reduce the selectivity of 1, 3-cyclohexyldimethylamine and easily deactivate a hydrogenation catalyst, so that the application is limited, and the method is not as wide as a m-xylylene diamine hydrogenation method. At the same time, the xylylenediamine can also be used as an epoxy resin curing agent, a polyurethane intermediate and an anticorrosive antirust agent, so that foreign manufacturers often choose to simultaneously produce two special amine products in an industrial chain manner so as to reduce the production cost.
The hydrogenation method of m-xylylenediamine is the most reported method in the current patent, is also a production method adopted industrially, and can be divided into a batch kettle type process and a fixed bed continuous process according to the difference of reactors. In the patent CN 102909035B, a Cu, Co and Ce modified Ru/C catalyst can be continuously used for 80 times in a batch still, and the product selectivity is more than 97 percent; in the patent CN 109772312A, tetrahydrofuran is used as a reaction solvent in an autoclave, a ruthenium catalyst is adopted to react for 4 hours at the temperature of 130 ℃ and the pressure of 5MPa, the conversion rate of m-xylylenediamine is 100 percent, and the selectivity of 1, 3-cyclohexyldimethylamine is 96.1 percent. The 1, 3-cyclohexyldimethylamine is produced by adopting an intermittent kettle type process, so that the industrial realization is convenient, the selectivity and the stability of the catalyst can easily meet the requirements, but the intermittent kettle has the defects of complicated operation, high labor consumption, increased equipment fatigue caused by frequent pressure charging and discharging, and simplicity and stability in the aspect of reactor control compared with a fixed bed reactor. The patents CN 110105223a and CN 110090641a both use fixed bed reactors, Co, Mn, or Mg modified ruthenium catalyst is used, isopropanol is used as solvent, nitrate and nitrite are used as auxiliary agents, the conversion rate of m-xylylenediamine is greater than 99%, and the selectivity of 1, 3-cyclohexyldimethylamine is greater than 96% at 120-150 ℃ and 5-7 MPa, although the fixed bed reactor can also achieve the conversion rate and selectivity of a batch reactor, the difficulty of the fixed bed continuous process lies in the stability of the catalyst and the service life of the catalyst. How to efficiently and stably produce 1, 3-cyclohexyldimethylamine in a fixed bed reactor is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the problems of insufficient stability and high inactivation speed of a catalyst in the conventional fixed bed continuous process, and provides a method for prolonging the service life of a hydrogenation catalyst in a m-xylylenediamine fixed bed reactor under the ammonia-contacting condition. According to the method, a protective agent and a hydrogenation catalyst are sequentially filled in a single reaction tube of a fixed bed reactor along the material flow direction, the protective agent and the hydrogenation catalyst are separated by barium-modified magnesium oxide, the barium-modified magnesium oxide is prepared from a soluble magnesium salt and a soluble barium salt through a coprecipitation method, and the protective agent is selected from a supported catalyst which takes Co as a main active component and barium-modified magnesium oxide as a carrier. The method can realize the long-period stable and high-efficiency operation of the hydrogenation catalyst in the fixed bed.
The purpose of the invention can be realized by the following technical scheme:
a method for improving the stability of a m-xylylenediamine fixed bed hydrogenation catalyst adopts a fixed bed reactor, and 1, 3-cyclohexyldimethylamine is prepared by m-xylylenediamine hydrogenation reaction under the condition of ammonia, wherein a protective agent, barium modified magnesium oxide and a hydrogenation catalyst are sequentially filled in a single reaction tube of the fixed bed along the material flow direction;
the protective agent is a barium-modified magnesium oxide-loaded cobalt catalyst, and the cobalt content is preferably 1-30 wt%, and more preferably 10-15 wt% based on the total mass of the cobalt catalyst.
In the invention, the volume ratio of the protective agent to the hydrogenation catalyst is 1: 8-30, preferably 1: 10 to 20.
In the invention, the volume ratio of the barium-modified magnesium oxide to the protective agent is 1: 0.25 to 4, preferably 1: 0.5 to 2, most preferably 1: 1.
in some examples, the protective agent, the barium-modified magnesium oxide and the hydrogenation catalyst are filled in the middle part of the reaction tube, namely 1/4-3/4, and the barium-modified magnesium oxide and the protective agent are positioned in the part between the reaction tubes 1/4-1/2; the hydrogenation catalyst is positioned between the reaction tubes 1/2-3/4; the filling height is directly determined by the volume of the barium modified magnesium oxide and the protective agent, and as the volume of the hydrogenation catalyst is fixed, if the barium modified magnesium oxide is filled too much, the protective agent is particularly close to the upper part of the reaction tube, and the heat preservation effect of the middle part of the reaction tube is good, so that the protective agent can be as close to the middle part of the reaction tube as possible to obtain good effect; however, if the protective agent is too close to the middle part of the reaction tube, the filling amount of the barium-modified magnesium oxide is reduced, the heat dissipation of the reaction liquid after contacting with the protective agent is weakened, and the temperature when entering the hydrogenation catalyst bed layer is higher, so that the hydrogenation catalyst, the barium-modified magnesium oxide and the hydrogenation catalyst are also selected to be in proper positions by proper filling proportions.
In the invention, the particle sizes of the protective agent, the barium-modified magnesium oxide and the hydrogenation catalyst are 20-40 meshes, and the particle sizes of the protective agent, the barium-modified magnesium oxide and the hydrogenation catalyst can be the same or different, and preferably the same particle size is adopted; the particles of the protective agent, the barium-modified magnesium oxide and the hydrogenation catalyst need to be selected with proper sizes, if the particle size is too small, the stacking density in the reaction tube is large, the pressure difference between the inlet and the outlet of the reaction tube is large, otherwise, if the particle size is too large, the channeling of the reaction liquid is serious when the reaction liquid flows through the catalyst, and the reaction effect is also poor.
In the invention, the barium content of the barium-modified magnesium oxide is 10-40 wt%, preferably 27-32 wt%, based on the total mass of the barium-modified magnesium oxide.
In the invention, the barium-modified magnesium oxide can be prepared by a coprecipitation method from a soluble magnesium salt and a soluble barium salt, wherein the soluble magnesium salt is selected from one or more of magnesium nitrate, magnesium sulfate and magnesium chloride, and the soluble barium salt is selected from one or more of barium nitrate and barium chloride; preferably, the soluble barium salt and the soluble magnesium salt are respectively in a molar ratio of 1: 5-10, preferably 1: 8-10;
in some examples, the preparation method of the barium-modified magnesium oxide comprises the following specific steps: the molar ratio of barium to magnesium elements is 1: dissolving 8-10 parts of soluble barium salt and magnesium salt in deionized water (the concentration is not specifically required, and the soluble barium salt and the magnesium salt are dissolved in the deionized water in proportion), then adding 1-2 mol/L ammonia water, carrying out ultrasonic mixing uniformly, adjusting the pH value of a precipitation solution to 11-12 after the ultrasonic treatment is finished, standing at room temperature, aging for 36-48 h, removing a supernatant, drying the obtained precipitate at 120 ℃ for 12-24 h, roasting at 550 ℃ in an air atmosphere for 10-15 h to obtain barium-modified magnesium oxide, and crushing into particles of 20-40 meshes for later use.
In the invention, the protective agent is preferably prepared by adopting an impregnation method, and is prepared by impregnating a barium modified magnesium oxide carrier into a cobalt source solution, wherein the cobalt source is selected from cobalt nitrate or cobalt chloride;
in some preferred examples, the preparation method that can be used is: adding a cobalt source into deionized water to prepare a solution, then dipping the solution on a 20-40-mesh barium modified magnesium oxide carrier, drying the dipped carrier at 120 ℃ for 12-18 h, and roasting the carrier at 550 ℃ in an air atmosphere for 8-15 h to obtain the protective agent with the Co content of 10-15 wt%.
In the invention, the barium-modified magnesium oxide adopted by the protective agent carrier is any one of the barium-modified magnesium oxides prepared by the method;
the barium-modified magnesium oxide adopted by the protective agent carrier and the barium-modified magnesium oxide filled between the protective agent and the hydrogenation catalyst can be the same or different, and preferably the same.
In the invention, the active component of the hydrogenation catalyst is selected from one or more of ruthenium, rhodium and palladium, preferably ruthenium, the source of the hydrogenation catalyst is not particularly required, and the hydrogenation catalyst is common commercial catalysts, such as ruthenium/carbon, ruthenium/alumina catalyst, ruthenium/carbon and ruthenium/alumina catalyst of new Xian Keli material.
The method for improving the stability of the m-xylylenediamine fixed bed hydrogenation catalyst is suitable for the following preparation method of 1, 3-cyclohexyldimethylamine, and comprises the following steps of mixing m-xylylenediamine, a reaction solvent and liquid ammonia, pumping the mixture into a reaction tube of a fixed bed reactor, and carrying out hydrogenation reaction under the following hydrogenation reaction conditions: the reaction temperature is 100-130 ℃, and the reaction pressure is 8-20 MPaG. The volume airspeed is 0.5-3 h-1The molar ratio of the hydrogen to the m-xylylenediamine is 10-50: 1.
in the method for producing 1, 3-cyclohexyldimethylamine according to the invention, the purity of the starting material m-xylylenediamine is required to be more than 99.0 wt%, preferably more than 99.9 wt%; wherein the 3-cyanobenzylamine content is preferably less than 0.1% by weight, more preferably less than 0.05% by weight; the isophthalonitrile content is preferably less than 0.1% by weight, more preferably less than 0.05% by weight.
In the method for preparing 1, 3-cyclohexyldimethylamine according to the invention, the reaction solvent can be selected from one or more of lower alcohols, aromatic hydrocarbons, ethers and cyclohexane, preferably one or more of ethers and lower alcohols, further preferably the lower alcohols are ethanol and isopropanol, and the ethers are tetrahydrofuran and dioxane.
In the preparation method of 1, 3-cyclohexyldimethylamine, the mass ratio of m-xylylenediamine to a reaction solvent to liquid ammonia is (1-5): 1-10: 1-10, preferably 1-2: 1-8: 5 to 8.
Further, the fixed bed reactor is preferably a down-flow reactor; the hydrogenation reaction conditions are preferably as follows: the reaction temperature is 100-120 ℃, the reaction pressure is 10-15 MPaG, and the volume space velocity is 0.5-2 h-1The molar ratio of hydrogen to m-xylylenediamine is 10-20: 1.
the method can obviously improve the stability of the hydrogenation catalyst, always keep the conversion rate of m-xylylenediamine to be more than 98.5 percent and the selectivity of 1, 3-cyclohexyldimethylamine to be more than 95.0 percent during the operation of the catalyst, obviously inhibit the side reaction of deamination condensation, and reduce the selectivity of deamination condensation products (mainly comprising di- (3-aminomethyl benzyl) amine CAS: 34235-31-9, 3-azabicyclo [3.3.1] nonane CAS: 280-70-6 and dimers generated by the intermolecular deamination condensation of 1, 3-cyclohexyldimethylamine) to be less than 2.8 percent.
The preparation of the 1, 3-cyclohexyldimethylamine is mostly from the deep hydrogenation of m-xylylenediamine, and in the hydrogenation process of the m-xylylenediamine, side reactions such as deamination condensation, hydrogenolysis deamination, hydrogen desorption methylamine and the like are accompanied, the hydrogenolysis side reaction is influenced more obviously by the reaction temperature, and the deamination condensation side reaction is influenced more obviously by the ammonia concentration in a receptor system and the acidity of a catalyst carrier. The hydrogenolysis side reaction has little influence on the service life of the catalyst, and only the selectivity of the product is reduced; the deamination condensation side reaction not only affects the selectivity of the product, but also can cause the inactivation of the catalyst and needs to be strictly controlled. The reaction temperature is strictly controlled to inhibit the hydrogenolysis side reaction, and the ammonia concentration in the system is required to be increased to inhibit the deamination side reaction, and the acidity of the catalyst carrier is weakened as much as possible, so that the liquid ammonia is particularly suitable to be used as an auxiliary agent, and the suitable catalyst carrier is selected. However, in order to solve the problem of catalyst deactivation, in addition to the inhibition of the deamination condensation side reaction, special attention is paid to that in the raw material m-xylylenediamine, the residual trace nitrile substances can also cause the deactivation of the hydrogenation catalyst, and the reaction conversion rate and selectivity are reduced, but the problem cannot be solved only by optimizing the process conditions, and the nitrile substances mainly comprise m-phthalonitrile and 3-cyanobenzylamine, and because the boiling points of the nitrile substances and the m-xylylenediamine are close, the nitrile substances are difficult to be completely separated by a rectification separation method.
The invention discovers in the research process that a Co catalyst taking barium-modified magnesium oxide as a carrier has weaker hydrogenation catalytic activity in the reaction of preparing 1, 3-cyclohexyldimethylamine by hydrogenating m-xylylenediamine, but has extremely high hydrogenation conversion selectivity on nitrile-based impurities contained in the catalyst and good catalyst stability, so that trace residual nitrile groups in m-xylylenediamine can be completely hydrogenated and converted by adding a supported catalyst taking Co as a main active component and taking barium-modified magnesium oxide as a carrier into a fixed bed reactor, the raw material m-xylylenediamine is firstly contacted with a protective agent before the hydrogenation catalyst, the hydrogenation catalyst is prevented from being poisoned by trace nitrile groups in the m-xylylenediamine raw material, and simultaneously, because of the ultrahigh selectivity of the active component Co, the alkalinity of the barium-modified magnesium oxide carrier and the action of high ammonia concentration in a system, the deamination condensation side reaction of m-xylylenediamine is effectively inhibited, not only reduces the loss of the raw material of the m-xylylenediamine, but also is beneficial to improving the stability of the m-xylylenediamine hydrogenation catalyst. Meanwhile, after the barium element is introduced into the magnesium oxide carrier for modification, the adsorption capacity of the magnesium oxide carrier to hydrogen can be enhanced, the nitrile group hydrogenation reaction on the protective agent is easier to perform, and the stability of the m-xylylenediamine hydrogenation catalyst is further improved.
The barium modified magnesium oxide with the same volume and particle size as the protective agent is filled between the protective agent and the hydrogenation catalyst, so that the deamination condensation reaction of m-xylylenediamine is inhibited, the heat dissipation effect is realized, the obvious temperature rise of m-xylylenediamine before entering a hydrogenation catalyst bed is avoided, and the occurrence of side reactions such as hydrogenolysis at high temperature is further reduced.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw materials except the protective agent in the examples or the comparative examples are all commercial raw materials, and specific information of part of the raw materials is described below (see table 1):
TABLE 1 manufacturer and model information of part of raw materials
Preparing barium modified magnesium oxide:
barium-modified magnesium oxide with a barium content of 27 wt% (27 wt% Ba-MgO): calculating the mass of 1mol of magnesium nitrate hexahydrate and 0.1mol of barium nitrate, weighing, dissolving the magnesium nitrate hexahydrate and the barium nitrate in a proper amount of deionized water, adding 1.1L of 2mol/L ammonia water, performing ultrasonic treatment for 120min, continuously dropwise adding the ammonia water after the ultrasonic treatment to adjust the pH value of a precipitation solution to 11, standing, aging for 48h, removing a supernatant, placing the obtained precipitate at 120 ℃ for drying for 12h, roasting at 550 ℃ in an air atmosphere for 10h to obtain a solid, namely barium modified magnesium oxide (27 wt% of Ba-MgO), and crushing the solid into 20-40-mesh particles for later use.
By the same method, the raw material ratio is adjusted according to the product composition, and barium-modified magnesium oxide (30 wt% Ba-MgO) with the content of 30 wt% and barium-modified magnesium oxide (32 wt% Ba-MgO) with the content of 32 wt% are respectively prepared.
Preparing a Co series protective agent:
firstly, taking 24.7g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare a cobalt nitrate solution, then soaking the cobalt nitrate solution on 45g of 20-40-mesh modified magnesium oxide carrier (27 wt% Ba-MgO), placing the soaked carrier at 120 ℃ for drying for 12h, and roasting at 550 ℃ in an air atmosphere for 8h to obtain a Co series protective agent 1 named 10 wt% Co/27 wt% Ba-MgO.
② taking 37.0g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare cobalt nitrate solution, then dipping the cobalt nitrate solution on 42.5g of 20-40 mesh modified magnesium oxide carrier (27 wt% Ba-MgO), placing the dipped carrier at 120 ℃ for drying for 15h, and then roasting at 550 ℃ in air atmosphere for 12h to obtain Co series protective agent 2, named 15 wt% Co/27 wt% Ba-MgO.
③ taking 24.7g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare a cobalt nitrate solution, then dipping the cobalt nitrate solution on 45g of 20-40 mesh modified magnesium oxide carrier (30 wt% of Ba-MgO), placing the dipped carrier at 120 ℃ for drying for 18h, and then roasting at 550 ℃ in an air atmosphere for 15h to obtain the Co series protective agent 3, wherein the name is 10 wt% Co/30 wt% of Ba-MgO.
And fourthly, taking 24.7g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare a cobalt nitrate solution, then dipping the cobalt nitrate solution on 45g of 20-40-mesh modified magnesium oxide carrier (32 wt% Ba-MgO), placing the dipped carrier at 120 ℃ for drying for 12h, and roasting at 550 ℃ in an air atmosphere for 8h to obtain the Co series protective agent 4 named 10 wt% Co/32 wt% Ba-MgO.
Fifthly, taking 37.0g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare a cobalt nitrate solution, then dipping the cobalt nitrate solution on 42.5g of 20-40-mesh modified magnesium oxide carrier (32 wt% Ba-MgO), placing the dipped carrier at 120 ℃ for drying for 12h, and roasting at 550 ℃ in an air atmosphere for 15h to obtain the Co series protective agent 5 named 15 wt% Co/32 wt% Ba-MgO.
Sixthly, taking 24.7g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare a cobalt nitrate solution, then soaking the cobalt nitrate solution on 45g of a 20-40-mesh magnesium oxide carrier (MgO), drying the soaked carrier at 120 ℃ for 12h, and roasting the dried carrier at 550 ℃ in an air atmosphere for 8h to obtain the Co series protective agent 6, wherein the name of the Co series protective agent is 10 wt% of Co/MgO.
Gas chromatographic analysis: performing sample analysis by Agilent GC-7820, and using HP-5 capillary chromatographic column and FID detector; the sample injector and the detector are both at 300 ℃, and the column temperature is controlled by adopting a programmed temperature rise: the column temperature is initially maintained at 120 ℃ for 3 minutes, and the temperature is raised to 300 ℃ at 10 ℃/min for 10 minutes. Sample introduction amount: 0.2. mu.L. Conversion and selectivity were calculated using area normalization.
The conversion and selectivity involved in the examples or comparative examples were calculated as follows:
the definition of the stable running time is based on the simultaneous satisfaction of the conversion of m-xylylenediamine > 98.5% and the selectivity of 1, 3-cyclohexyldimethylamine > 95.0%.
The temperature rise test method comprises the following steps: and measuring the temperature at the top of the hydrogenation catalyst bed by using a thermocouple, and subtracting the furnace temperature before the raw material of the m-xylylenediamine enters the hydrogenation catalyst bed from the measured value to obtain the temperature rise.
Example 1
5mL of Co protective agent 1, 5mL of barium-modified magnesium oxide (27 wt% Ba-MgO) and 50mL of commercially available Ru/C (i.e., hydrogenation catalyst) were sequentially loaded in the middle section of a 100mL fixed bed reaction tube along the material flow direction, and after the catalyst reduction was performed in a hydrogen atmosphere, the reaction temperature was set to 120 ℃, the reaction pressure was set to 15MPaG, and the molar ratio of hydrogen to m-xylylenediamine was 20: 1, the raw materials are as follows: tetrahydrofuran: the mass ratio of liquid ammonia is 1: 4: 4 mixing at a volume space velocity of 1.0h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 2
3mL of Co-based protective agent 1, 3mL of modified magnesium oxide (30 wt% Ba-MgO) and 50mL of commercial magnesium oxide were sequentially filled in the middle section of a 100mL fixed bed reaction tube along the material flow directionCommercial Ru/Al2O3A catalyst (hydrogenation catalyst) which is reduced in a hydrogen atmosphere, wherein the reaction temperature is set to 110 ℃, the reaction pressure is set to 13MPaG, and the molar ratio of hydrogen to m-xylylenediamine is 15: 1, the raw materials are as follows: tetrahydrofuran: the mass ratio of liquid ammonia is 1: 8: 8 after mixing, the volume space velocity is 1.5h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 3
3mL of Co protective agent 2, 3mL of modified magnesium oxide (32 wt% Ba-MgO) and 50mL of commercially available Ru/C (titanium carbide) catalyst (hydrogenation catalyst) are sequentially filled in the middle section of a 100mL fixed bed reaction tube along the material flow direction, after the catalyst reduction is carried out in the hydrogen atmosphere, the reaction temperature is set to be 100 ℃, the reaction pressure is set to be 10MPaG, and the molar ratio of hydrogen to m-xylylenediamine is 10: 1, the raw materials are as follows: dioxane: the mass ratio of liquid ammonia is 1: 1: 5 mixing at a volume space velocity of 2.0h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 4
6mL of Co-based protective agent 2, 6mL of modified magnesium oxide (32 wt% Ba-MgO) and 50mL of commercially available Ru/Al were sequentially filled in the middle section of a 100mL fixed bed reaction tube along the material flow direction2O3Secondly, after the catalyst (hydrogenation catalyst) is reduced in a hydrogen atmosphere, the reaction temperature is set to be 100 ℃, the reaction pressure is set to be 8MPaG, and the molar ratio of hydrogen to m-xylylenediamine is 50: 1, the raw materials are as follows: isopropyl alcohol: the mass ratio of liquid ammonia is 1: 2: 2 mixing at a volume space velocity of 0.5h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 5
Sequentially filling 4mL of Co protective agent 3, 4mL of modified magnesium oxide (30 wt% Ba-MgO) and 50mL of commercially available Ru/C (hydrochloric acid) catalyst (hydrogenation catalyst) in the middle section of a 100mL fixed bed reaction tube along the material flow direction, and after the catalyst reduction is carried out in the hydrogen atmosphere, setting the reaction temperature to be 130 ℃, the reaction pressure to be 20MPaG, and setting the molar ratio of hydrogen to m-xylylenediamine to be 30: 1, the raw materials are as follows: ethanol: the mass ratio of liquid ammonia is 1: 10: 1 after mixingAt a volume space velocity of 3.0h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 6
In the middle of a 100mL fixed bed reaction tube, 4mL of Co-based protective agent 3, 4mL of modified magnesium oxide (27 wt% Ba-MgO), and 50mL of commercially available Ru/Al were sequentially charged in the flow direction2O3② a catalyst (hydrogenation catalyst), after the catalyst reduction is carried out in hydrogen atmosphere, the reaction temperature is set to 105 ℃, the reaction pressure is set to 14MPaG, and the molar ratio of hydrogen to m-xylylenediamine is 40: 1, the raw materials are as follows: dioxane: the mass ratio of liquid ammonia is 1: 5: 5 mixing and then using the volume space velocity of 1.5h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 7
In the middle section of a 100mL fixed bed reaction tube, 4mL of a Co-based protective agent 4, 5mL of modified magnesium oxide (27 wt% Ba-MgO) and 50mL of a commercially available Ru/C (r) catalyst (hydrogenation catalyst) were sequentially loaded in the material flow direction, and after the catalyst reduction was performed in a hydrogen atmosphere, the reaction temperature was set to 120 ℃, the reaction pressure was set to 15MPaG, and the molar ratio of hydrogen to m-xylylenediamine was 10: 1, the raw materials are as follows: dioxane: the mass ratio of liquid ammonia is 1: 8: 5 mixing and then using the volume space velocity of 0.5h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 8
3mL of Co-based protective agent 4, 2mL of modified magnesium oxide (30 wt% Ba-MgO) and 50mL of commercially available Ru/Al were sequentially filled in the middle section of a 100mL fixed bed reaction tube along the material flow direction2O3A catalyst (hydrogenation catalyst) which is reduced in a hydrogen atmosphere, wherein the reaction temperature is set to 100 ℃, the reaction pressure is set to 13MPaG, and the molar ratio of hydrogen to m-xylylenediamine is 20: 1, the raw materials are as follows: tetrahydrofuran: the mass ratio of liquid ammonia is 1: 10: 10 are mixed and then the volume space velocity is 2.0h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 9
3mL of Co series protection are sequentially filled in the middle section of a 100mL fixed bed reaction tube along the material flow direction5mL of modified magnesium oxide (32 wt% of Ba-MgO) and 50mL of commercially available Ru/C (titanium carbide) catalyst (hydrogenation catalyst), and after the catalyst reduction is carried out in a hydrogen atmosphere, the reaction temperature is set to 120 ℃, the reaction pressure is set to 12MPaG, and the molar ratio of hydrogen to m-xylylenediamine is 20: 1, the raw materials are as follows: tetrahydrofuran: the mass ratio of liquid ammonia is 1: 5: 5 mixing and then using the volume space velocity of 1.5h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Example 10
2mL of Co-based protective agent 5, 2mL of modified magnesium oxide (32 wt% Ba-MgO) and 50mL of commercially available Ru/Al were sequentially filled in the middle section of a 100mL fixed bed reaction tube along the material flow direction2O3② a catalyst (hydrogenation catalyst), after the catalyst reduction is carried out in hydrogen atmosphere, the reaction temperature is set to 110 ℃, the reaction pressure is set to 12MPaG, and the molar ratio of hydrogen to m-xylylenediamine is 30: 1, the raw materials are as follows: isopropyl alcohol: the mass ratio of liquid ammonia is 2: 1: 5 mixing and then using the volume space velocity of 1.5h-1Pumping into a reaction tube for hydrogenation reaction. The reaction results are shown in tables 2 and 3.
Comparative example 1
50mL of a commercially available Ru/C (hydrogenation catalyst) was placed in the middle of a 100mL fixed bed reaction tube, and after the catalyst reduction was carried out in a hydrogen atmosphere, the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
Comparative example 2
50mL of commercially available Ru/Al were placed in the middle of a 100mL fixed bed reaction tube2O3The catalyst (hydrogenation catalyst) was reduced in a hydrogen atmosphere, and then the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
Comparative example 3
Calcium-modified magnesium oxide (Ca — MgO): calculating the mass of 1mol of magnesium nitrate hexahydrate and 0.1mol of calcium chloride, weighing, dissolving the magnesium nitrate hexahydrate and the calcium chloride in a proper amount of deionized water, adding 1.1L of 2mol/L ammonia water, performing ultrasonic treatment for 120min, adjusting the pH value of a precipitation solution to 11 after the ultrasonic treatment is finished, standing, aging for 48h, removing a supernatant, drying the obtained precipitate at 120 ℃ for 12h, roasting at 550 ℃ in an air atmosphere for 10h to obtain a solid, namely calcium modified magnesium oxide (Ca-MgO), and crushing the solid into 20-40-mesh particles for later use.
Preparing a Co series protective agent: taking 24.7g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare a cobalt nitrate solution, then soaking the cobalt nitrate solution on 45g of 20-40-mesh calcium modified magnesium oxide carrier (Ca-MgO), drying the soaked carrier at 120 ℃ for 12h, and roasting the dried carrier at 550 ℃ in an air atmosphere for 8h to obtain a Co series protective agent 7, wherein the name of the Co series protective agent is 10 wt% of Co/Ca-MgO.
3mL of Co-based protective agent 7, 3mL of calcium-modified magnesium oxide (Ca-MgO), and 50mL of commercially available Ru/C (titanium carbide) catalyst (hydrogenation catalyst) were sequentially loaded in the direction of flow in the middle section of a 100mL fixed bed reaction tube, and after the catalyst reduction in a hydrogen atmosphere, the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
Comparative example 4
Barium-modified calcium oxide (Ba — CaO): calculating the mass of 1mol of calcium chloride and 0.1mol of barium nitrate, weighing, dissolving the calcium chloride and the barium nitrate in a proper amount of deionized water, adding 1.1L of 2mol/L ammonia water, performing ultrasonic treatment for 120min, adjusting the pH value of a precipitation solution to 11 after the ultrasonic treatment is finished, standing, aging for 48h, removing a supernatant, placing the obtained precipitate at 120 ℃, drying for 12h, roasting for 10h at 550 ℃ in an air atmosphere, and crushing the obtained solid, namely barium-modified calcium oxide (Ba-CaO), into 20-40-mesh particles for later use.
Preparing a Co series protective agent: taking 24.7g of cobalt nitrate hexahydrate, adding 50mL of deionized water to prepare a cobalt nitrate solution, then dipping the cobalt nitrate solution on 45g of 20-40-mesh barium modified calcium oxide carrier (Ba-CaO), drying the dipped carrier at 120 ℃ for 12h, and roasting the dried carrier at 550 ℃ in an air atmosphere for 8h to obtain a Co series protective agent 8, wherein the Co/Ba-CaO is named 10 wt%.
3mL of Co-based protective agent 8, 3mL of barium-modified calcium oxide (Ba-CaO), and 50mL of commercially available Ru/C (titanium carbide) catalyst (hydrogenation catalyst) were sequentially loaded in the middle section of a 100mL fixed bed reaction tube along the flow direction, and after the catalyst reduction was carried out in a hydrogen atmosphere, the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
Comparative example 5
5mL of Co-based protective agent 6, 5mL of barium-modified magnesium oxide (27 wt% Ba-MgO), and 50mL of a commercially available Ru/C (r) catalyst (hydrogenation catalyst) were sequentially loaded in the middle of a 100mL fixed bed reaction tube along the flow direction, and after the catalyst reduction in a hydrogen atmosphere, the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
Comparative example 6
5mL of Co-based protective agent 1, 5mL of silica (SiO2) and 50mL of a commercially available Ru/C (r) catalyst (hydrogenation catalyst) were sequentially charged in the middle of a 100mL fixed bed reaction tube in the flow direction, and after the catalyst reduction was carried out in a hydrogen atmosphere, the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
Comparative example 7
5mL of Co-based protective agent 1 and 50mL of a commercially available Ru/C (hydrogenation catalyst) were sequentially charged in the middle of a 100mL fixed bed reaction tube in the flow direction, and after the catalyst reduction in a hydrogen atmosphere, the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
Comparative example 8
After 5mL of barium-modified magnesium oxide (27 wt% Ba-MgO) and 50mL of a commercially available Ru/C (r) catalyst (hydrogenation catalyst) were sequentially loaded in the direction of flow in the middle of a 100mL fixed bed reaction tube and subjected to catalyst reduction in a hydrogen atmosphere, the hydrogenation reaction conditions were the same as in example 9, and the reaction results are shown in tables 2 and 3.
TABLE 2 comparison of the results of hydrogenation of m-xylylenediamine
TABLE 3 comparison of results of running 1608h m-xylylenediamine hydrogenation reaction
As can be seen from the results in tables 2 and 3, the comparative examples 1, 2 and 8 without adding the protective agent have the worst effect, and because the nitrile-based substance is not eliminated before the hydrogenation reaction, the nitrile-based substance participates in the hydrogenation reaction process and is influenced by the nitrile-based substance, the conversion rate is lowest, the number of deamination condensation byproducts is the most, and the stable operation time is the shortest; comparative example 7, although nitrile group substances were eliminated by the protective agent before hydrogenation, since barium-modified magnesium oxide was not added, temperature rise was large, reaction activity was relatively high, but selectivity was poor, and deamination condensation products were also numerous; comparative example 6 the barium modified magnesium oxide is replaced by non-alkaline silicon dioxide, which has temperature control effect but reduces selectivity; comparative examples 3, 4 and 5 have inferior effects to those of the present invention when the protecting agent and the basic filler component are replaced. The comparison of the hydrogenation reaction results shows that the method has obvious effects on improving the stability of the catalyst, prolonging the operation time of the device and improving the operation stability of the device by arranging the protective agent which takes Co as a main active component and takes modified magnesium oxide as a carrier in the process of preparing the 1, 3-cyclohexyldimethylamine by the fixed bed hydrogenation of the m-xylylenediamine under the ammonia reaction condition.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A method for improving the stability of a m-xylylenediamine fixed bed hydrogenation catalyst is characterized in that a fixed bed reactor is adopted in the method, 1, 3-cyclohexyldimethylamine is prepared by m-xylylenediamine hydrogenation reaction under the condition of ammonia, and a protective agent, barium modified magnesium oxide and the hydrogenation catalyst are sequentially filled in a single reaction tube of the fixed bed along the material flow direction;
the protective agent is a barium-modified magnesium oxide-loaded cobalt catalyst, and the cobalt content is 1-30 wt%, preferably 10-15 wt%, based on the total mass of the cobalt catalyst.
2. The method of claim 1, wherein the volume ratio of the protecting agent to the hydrogenation catalyst is 1: 8-30, preferably 1: 10-20;
the volume ratio of the barium-modified magnesium oxide to the protective agent is 1: 0.25 to 4, preferably 1: 0.5 to 2, most preferably 1: 1.
3. the method according to claim 1 or 2, wherein the particle size of the protecting agent, the barium-modified magnesium oxide and the hydrogenation catalyst is 20-40 meshes, and the particle size of the protecting agent, the barium-modified magnesium oxide and the particle size of the hydrogenation catalyst can be the same or different, and the same particle size is preferably adopted.
4. A process according to any one of claims 1 to 3, wherein the barium-modified magnesium oxide has a barium content of 10 to 40 wt.%, preferably 27 to 32 wt.%, based on the total mass of the barium-modified magnesium oxide.
5. The method according to any one of claims 1 to 4, wherein the barium-modified magnesium oxide is prepared by a coprecipitation method from a soluble magnesium salt and a soluble barium salt, wherein the soluble magnesium salt is selected from one or more of magnesium nitrate, magnesium sulfate and magnesium chloride, and the soluble barium salt is selected from one or more of barium nitrate and barium chloride;
preferably, the soluble barium salt and the soluble magnesium salt are respectively in a molar ratio of 1: 5-10, preferably 1: 8 to 10.
6. The method according to any one of claims 1 to 5, wherein the protective agent is prepared by impregnating a barium-modified magnesia support into an aqueous solution of a cobalt source selected from the group consisting of cobalt nitrate or cobalt chloride;
the barium-modified magnesium oxide carrier adopted by the protective agent and the barium-modified magnesium oxide filled between the protective agent and the hydrogenation catalyst can be the same or different, and preferably the same.
7. Process according to any one of claims 1 to 6, characterized in that the hydrogenation catalyst active component is selected from one or more of ruthenium, rhodium, palladium, preferably ruthenium, more preferably ruthenium/carbon catalyst, ruthenium/alumina catalyst.
8. The method according to any one of claims 1 to 7, characterized by comprising the step of pumping m-xylylenediamine, a reaction solvent and liquid ammonia mixed together into a reaction tube of a fixed bed reactor to carry out a hydrogenation reaction under the following conditions: the reaction temperature is 100-130 ℃, the reaction pressure is 8-20 MPaG, and the volume space velocity is 0.5-3 h-1The molar ratio of the hydrogen to the m-xylylenediamine is 10-50: 1.
9. the process according to any one of claims 1 to 8, wherein the reaction solvent is selected from one or more of lower alcohols, aromatic hydrocarbons, ethers, cyclohexane, preferably one or more of ethers, lower alcohols;
the lower alcohol is preferably ethanol or isopropanol;
the ethers are preferably tetrahydrofuran and dioxane.
10. The method according to any one of claims 1 to 9, wherein the mass ratio of m-xylylenediamine to the reaction solvent and the liquid ammonia is from 1 to 5: 1-10: 1-10, preferably 1-2: 1-8: 5-8;
the hydrogenation reaction conditions are as follows: the reaction temperature is 100-120 ℃, the reaction pressure is 10-15 MPaG, and the volume space velocity is 0.5-2 h-1The molar ratio of hydrogen to m-xylylenediamine is 10-20: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890903A (en) * | 2022-06-07 | 2022-08-12 | 万华化学集团股份有限公司 | Preparation method of 1, 3-cyclohexanedimethanamine with high cis-isomer content |
| CN116589363A (en) * | 2023-05-17 | 2023-08-15 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690203A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-cyclohexanebis(methylamine) |
| CN102688766A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing 1,3-cyclohexanebis(methylamine) by m-xylylenediamine hydrogenation under ammonia reaction conditions |
| CN110090641A (en) * | 2019-05-21 | 2019-08-06 | 常州大学 | A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine |
| CN110105223A (en) * | 2019-05-15 | 2019-08-09 | 常州大学 | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine |
| CN110433823A (en) * | 2019-07-30 | 2019-11-12 | 万华化学集团股份有限公司 | It is a kind of for synthesizing the catalyst and its preparation method and application of diaminomethyl hexamethylene |
| CN110947389A (en) * | 2019-11-29 | 2020-04-03 | 万华化学集团股份有限公司 | In-situ treatment method for preparing m-xylylenediamine catalyst by hydrogenation of m-phthalonitrile |
| CN111330629A (en) * | 2020-04-08 | 2020-06-26 | 万华化学集团股份有限公司 | M-xylylenediamine hydrogenation catalyst, and preparation method and application thereof |
-
2020
- 2020-09-04 CN CN202010919722.2A patent/CN112047843B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690203A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-cyclohexanebis(methylamine) |
| CN102688766A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Catalyst for preparing 1,3-cyclohexanebis(methylamine) by m-xylylenediamine hydrogenation under ammonia reaction conditions |
| CN110105223A (en) * | 2019-05-15 | 2019-08-09 | 常州大学 | A kind of method that continuity method prepares 1,3- hexamethylene dimethylamine |
| CN110090641A (en) * | 2019-05-21 | 2019-08-06 | 常州大学 | A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine |
| CN110433823A (en) * | 2019-07-30 | 2019-11-12 | 万华化学集团股份有限公司 | It is a kind of for synthesizing the catalyst and its preparation method and application of diaminomethyl hexamethylene |
| CN110947389A (en) * | 2019-11-29 | 2020-04-03 | 万华化学集团股份有限公司 | In-situ treatment method for preparing m-xylylenediamine catalyst by hydrogenation of m-phthalonitrile |
| CN111330629A (en) * | 2020-04-08 | 2020-06-26 | 万华化学集团股份有限公司 | M-xylylenediamine hydrogenation catalyst, and preparation method and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890903A (en) * | 2022-06-07 | 2022-08-12 | 万华化学集团股份有限公司 | Preparation method of 1, 3-cyclohexanedimethanamine with high cis-isomer content |
| CN114890903B (en) * | 2022-06-07 | 2023-07-14 | 万华化学集团股份有限公司 | Preparation method of 1, 3-cyclohexanedimethylamine with high cis-form content |
| CN116589363A (en) * | 2023-05-17 | 2023-08-15 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
| CN116589363B (en) * | 2023-05-17 | 2024-05-03 | 河南省君恒实业集团生物科技有限公司 | Preparation method of catalyst for preparing 1, 3-cyclohexanediamine by hydrogenating m-xylylenediamine in micro-packed bed |
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