CN110975875B - Preparation method and application of coated skeleton Ni catalyst - Google Patents
Preparation method and application of coated skeleton Ni catalyst Download PDFInfo
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- CN110975875B CN110975875B CN201911313393.0A CN201911313393A CN110975875B CN 110975875 B CN110975875 B CN 110975875B CN 201911313393 A CN201911313393 A CN 201911313393A CN 110975875 B CN110975875 B CN 110975875B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- 239000000843 powder Substances 0.000 claims abstract description 41
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 21
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- PQPVPZTVJLXQAS-UHFFFAOYSA-N hydroxy-methyl-phenylsilicon Chemical compound C[Si](O)C1=CC=CC=C1 PQPVPZTVJLXQAS-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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Abstract
The invention discloses a preparation method of a coated skeleton Ni catalyst, which comprises the following steps: firstly, adding Si, Ni and a metal auxiliary agent into a medium-frequency induction furnace to be smelted into alloy, then crushing the alloy into 50-250 mu m powder, coating the powder on ZnO pellets to obtain a catalyst precursor, and then drying and activating in situ to obtain the catalyst. The catalyst is applied to the chemical process of preparing m-xylylenediamine by hydrogenating m-phthalonitrile, the yield of the m-xylylenediamine is more than 96.2 percent, and the catalyst has good industrialization prospect.
Description
The technical field is as follows:
the invention relates to a preparation method of a coated skeleton Ni catalyst, a prepared catalyst and application thereof, in particular to a preparation method of a coated skeleton Ni catalyst and application of the catalyst prepared by the method as a catalyst for preparing m-xylylenediamine by hydrogenation of m-phthalonitrile.
Background art:
meta-xylylenediamine is an epoxy resin curing agent with excellent performance, and is also a synthetic polyurethane, xylene nylon resin (MXD) 6 ) Isocyanate (XDI, H) 6 XDI) and aromatic polyamides. The main production method is that the isophthalonitrile is hydrogenated under the action of a catalyst. Common hydrogenation catalysts are Raney-Co/Ni and deposit-formed Co/Ni catalysts.
Raney-Co/Ni catalysts are a class of commercial catalysts. For example, U.S. patent publication nos. US6087296A and US7569513 disclose the preparation method thereof as follows: taking metal Co and Al as an alloy main body, adding transition metals such as Ni, Mo, Ti and the like as auxiliaries, smelting the alloy into Co-Al alloy at high temperature, and crushing the Co-Al alloy into alloy particles which are called as catalyst precursors; and (3) extracting the surface layer Al in the catalyst precursor by using a NaOH solution with a certain concentration (the step is called activation) to prepare the Raney-Co catalyst. The disadvantages of preparing this type of catalyst are: only the surface layer can be activated (if the activation depth is too deep, the activation layer is not firmly combined with the alloy core), the activation depth is about 100 mu m, and a large amount of alloy cannot be effectively utilized.
Mitsubishi gas patents JP2001215006, JP2002245222, JP20030061258, US2005004399, US2007270613 and the like disclose a catalyst for preparing xylylenediamine by continuous hydrogenation of isophthalonitrile, which is prepared by preparing a NiO/CoO (with a loading of about 50 wt%) supported catalyst precursor by using diatomite as a carrier through an impregnation precipitation method and then performing molding and reactivation. The disadvantages of this type of catalyst are: the carrier has acidity, so that an imine intermediate and a product m-xylylenediamine are easy to deaminate and condense in the hydrogenation process of m-phthalonitrile to generate a heavy component, the heavy component is easy to attach to the surface of the catalyst, an active center is covered, the catalyst is inactivated, and the stability of the catalyst is poor; the yield of the intermediate xylylenediamine disclosed by the company is 85-92%, and the yield is low; and liquid ammonia or alkali is required to be added as a secondary amine or heavy component inhibitor when the two catalysts are applied to the nitrile hydrogenation reaction process, so that the difficulty of product separation and device operation stability is increased.
Based on the defects of the catalyst, the catalyst which has high utilization rate of active components, stable performance of the catalyst, high yield of m-xylylenediamine and no need of adding an inhibitor in the reaction process is urgently needed to be developed.
The invention content is as follows:
the invention aims to provide a preparation method of a coated skeleton Ni catalyst, and the obtained catalyst has the advantages of high utilization rate of active components and stable performance.
The invention also provides a coated skeleton Ni catalyst prepared by the method, which is applied to the chemical process of preparing m-xylylenediamine by hydrogenation of m-phthalonitrile, the yield of the m-xylylenediamine is high and is more than 96.2%, and inhibitors (such as NaOH and KOH) are not required to be added in the reaction process, so that the coated skeleton Ni catalyst has a good industrial prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a coated skeleton Ni catalyst comprises the steps of firstly adding Si, Ni and a metal auxiliary agent into a medium-frequency induction furnace to be smelted into an alloy, then crushing the alloy into powder of 50-250 mu m, coating the powder on the surface of a ZnO pellet to obtain a catalyst precursor, and then drying and activating in situ to obtain the catalyst.
As an embodiment, a method for preparing a Ni catalyst with a coated skeleton, comprises the steps of:
(1) adding Si, Ni and a metal auxiliary agent into a medium-frequency induction furnace to be smelted into an alloy;
(2) crushing the alloy obtained by smelting in the step (1) into powder of 50-250 microns;
(3) coating the alloy powder obtained in the step (2) on the surface of the ZnO pellet;
(4) drying the coating formed product obtained in the step (3) to obtain a catalyst precursor;
(5) and (4) activating the catalyst precursor obtained in the step (4) in situ in a reactor to obtain the catalyst.
In the invention, the purity of Si in the step (1) is more than 99%; purity of Ni > 99.5%; the purity of the promoter metal is > 99.5%. If the raw materials used have low purity, the performance of the catalyst may not meet the requirements. The smelting of alloy in a medium frequency induction furnace is a common practice in the industry, and will not be described in detail herein. For example, Ni and Si can be weighed according to a certain proportion, the Si is firstly added into a medium-frequency induction furnace for smelting, the Ni and other metal additives are added after the Si is molten, and the molten Ni and metal additives are poured into a cooling crucible after being molten.
In the invention, the metal of the auxiliary agent in the step (1) is one or more of Ti, Cr, Fe and Co, and the addition amount of the metal auxiliary agent is 1-4 wt% based on the total weight of Si and Ni. The addition of the metal auxiliary agent effectively improves the activity and selectivity of the catalyst, and particularly, the addition of Cr can improve the adsorption capacity of the catalyst on-CN in the reaction process and can effectively improve the selectivity of the catalyst.
In the invention, based on the total amount of Si and Ni, the amount of Si is 40-50 wt%, and the amount of Ni is 50-60 wt%.
In the invention, the alloy is crushed into 50-250 μm powder in the step (2), which is beneficial to coating the surface of the ZnO pellet uniformly.
In the invention, a certain amount of urea and Na also needs to be sprayed when the ZnO pellets in the step (3) and the powder obtained in the step (2) are coated and molded 3 PO 4 +ZnCl 2 Mixing the aqueous solution with urea and Na 3 PO 4 +ZnCl 2 The concentration of the mixed aqueous solution is 30-50 wt%, and the mixed aqueous solution contains urea and Na 3 PO 4 And ZnCl 2 The mass ratio of (1: 1) - (3: 3) - (5), the specific spraying amount is determined according to the requirement of the coating forming process, and is usually 25% -40% of the total mass of the coated alloy powder and the ZnO pellets. The diameter of the ZnO globule is 1-3 mm, and the purity>99 percent. ZnO is used as a catalyst support body, and meanwhile, ZnO has alkalinity, can inhibit an imine intermediate or a product m-xylylenediamine from deaminating and condensing to form a component (heavy component) with a two-condensation or higher molecular weight in the reaction process, effectively improves the selectivity of m-xylylenediamine, avoids catalyst deactivation caused by covering the active center of the catalyst by the heavy component, and improves the stability of the catalyst. Adding urea and Na in the process of coating and forming 3 PO 4 +ZnCl 2 The mixed aqueous solution is used as a forming agent, urea and Na 3 PO 4 +ZnCl 2 The phosphoric acid and chloride double salt which reacts with the carrier ZnO to generate zinc can be adhered with the carrier ZnO, and can be used as an adhesive of alloy powder and ZnO spheres to adhere the alloy powder on the surfaces of the ZnO spheres. Therefore, the invention does not need to newly introduce other binders, and avoids influencing the performance of the catalyst. In the microwave drying stage of step (3), urea is decomposed into NH 3 And CO 2 ，NH 3 The drying atmosphere is in an alkaline environment, the bonding strength of the alloy powder layer and the carrier can be provided, and the urea is decomposed into NH 3 And CO 2 Can be on the alloy powder layerA certain pore channel structure is formed, and the porous structure can be used as a transmission channel of raw materials and products, so that the specific surface area of the catalyst can be improved; but also is beneficial to activating more alloy powder, forming more active centers and improving the activity of the catalyst.
In the invention, the coating process in the step (3) comprises the following steps: putting a certain amount of ZnO pellets into a coating machine, wherein the mass of the ZnO pellets is 3-5 times of that of the alloy powder; the coating machine rotates at a certain rotating speed, and alloy powder accounting for 30-50% of the total consumption is added; then a certain amount of urea and Na are sprayed 3 PO 4 +ZnCl 2 Mixing the aqueous solution, adding a certain amount of alloy powder for coating, and spraying a certain amount of urea and Na 3 PO 4 +ZnCl 2 And mixing the aqueous solution, and repeating the steps until a certain amount of alloy powder is coated on the surface of the ZnO pellet. In the invention, the drying in the step (3) is microwave drying, and the drying temperature is controlled to be 160-250 ℃. The drying time is 1-2.5 h; experiments show that the microwave drying can improve the bonding strength of the active component layer and the ZnO spheres.
In the invention, the in-situ activation in the step (4) is carried out in NaOH solution, the concentration of the NaOH solution is 2-7 wt%, and the volume space velocity of the feeding of the NaOH solution is 20-40 hr -1 The activation temperature is 50-80 ℃, and the activation time is 180-360 min. The activation process comprises the following steps: loading the precursor dried by microwave into a fixed bed reactor, heating to a set temperature, pumping NaOH solution into the reactor by a pump according to a certain flow rate, and controlling the temperature of a bed layer to be below 80 ℃; high activation temperatures can cause sintering of the active component grains, affecting catalyst activity.
The reaction conditions of the catalyst prepared by the invention for preparing m-xylylenediamine by hydrogenation of m-phthalonitrile can be, for example: a fixed bed reactor, wherein the loading of the catalyst is 50g, and the isophthalonitrile is dissolved in an organic solvent to obtain an isophthalonitrile solution (the concentration is 5 wt% -15 wt%), and the organic solvent can be one or more of tetrahydrofuran, methanol or toluene; the mass airspeed of liquid feeding is 2-4 h -1 ，H 2 The feeding amount of the catalyst is 50-200L/hr, the reaction temperature is 70-130 ℃, and the reaction pressure is 5-18 Mpa.
The pressures referred to in the present invention are gauge pressures.
The invention has the following positive effects:
(1) the coated framework Ni catalyst is similar to an eggshell type catalyst, the utilization rate of catalyst components is high, the catalyst cost is reduced, the catalytic efficiency is higher, and the unit consumption of the catalyst per ton of products is only 14% of Raney-Ni; (2) the alloy powder is only subjected to microwave drying after being coated on the carrier, high-temperature roasting is not needed, and energy consumption is reduced; (3) the catalyst has stable performance, and the performance does not decline when the small scale test runs continuously for 2000 hours; (4) the selectivity of the target product m-xylylenediamine is high and can reach more than 96 percent; (5) in the reaction process of preparing m-xylylenediamine by hydrogenation of m-phthalonitrile, liquid ammonia or alkali inhibitor is not required to be added, and the difficulty in product separation is reduced.
Description of the drawings:
fig. 1 is a schematic view of a process flow of an activation and evaluation device for a Ni catalyst with a coated skeleton, wherein P001: and a NaOH solution feeding pump is used for catalyst activation, a phthalonitrile and tetrahydrofuran raw material feeding pump is used for catalyst evaluation time, and MC001 is a hydrogen mass flow meter for catalyst evaluation.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples further illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
The intermediate frequency induction furnace adopted in the embodiment of the invention is produced by Xian Lanhui electromechanical equipment Limited company, and has the model of KGPS-300 KW/0.25T; the smelting process of the alloy in the embodiment is as follows: firstly adding Si into a hearth, smelting for 5min under 40KW, then adding Ni and other metal additives into the hearth, then increasing the smelting power to 110KW, and pouring alloy liquid into a crucible for cooling after smelting for 25 min.
The gas chromatography conditions used in the examples of the invention were: shimadzu GC-2010 gas chromatograph (hydrogen flame detector, nitrogen as carrier gas) equipped with a DB-5 capillary column (fixative 5% Phenyl Methyl Siloxane, 30m x 0.32mm x 0.25 μm) and a hydrogen flame detector (FID). The sample injector and detector temperatures were both 280 ℃; column temperature is controlled by adopting programmed temperature rise: the column temperature is initially maintained at 100 ℃ for 2 minutes, and the temperature is raised to 250 ℃ at 15 ℃/min and maintained for 5 minutes. Column pressure 8.5868psi (about 59.2KPa), flow 1.5 mL/min. Sample introduction amount: 0.2. mu.L. Conversion and selectivity were calculated using external standard methods.
An inductively coupled plasma emission spectrometer (ICP-OES) used in the embodiment of the invention is produced by Agilent Technologies and is 720ICP-OES in model number;
the ZnO pellets used in the examples had an average diameter of 2mm and a purity of >99.5% and were obtained from Zibo Zifeng aluminium magnesium Co.
The process conditions of the catalyst used for preparing m-xylylenediamine by hydrogenation of m-phthalonitrile in the examples and comparative examples are as follows: a fixed bed reactor with an inner diameter of 24mm, and the loading amount of the catalyst is 50 g; the liquid feeding mass space velocity is 2h -1 ，H 2 The feed amount of (3) was 50L/hr, the reaction temperature: the reaction pressure is 10MPa at 75 ℃.
Example 1
Weighing 150g of Ni, 150g of Si, 1.5g of Ti and 1.5g of Cr, adding the materials into a medium-frequency induction furnace to be smelted into a Ni-Si-Ti-Cr alloy, crushing the alloy into alloy powder of 50-250 mu m, and weighing 16g of alloy powder. According to the ratio of urea to Na 3 PO 4 :ZnCl 2 Preparing 30 wt% of urea and Na according to the mass ratio of 1:1:3 3 PO 4 +ZnCl 2 Mixing 16.5g of aqueous solution, weighing 50g of ZnO pellets and 6g of alloy powder, putting the ZnO pellets and the alloy powder into a coating machine, and spraying and preparing 30 wt% of urea and Na 3 PO 4 +ZnCl 2 And adding the residual alloy powder into the mixed aqueous solution for coating. And (3) drying the coated catalyst precursor in a microwave oven, wherein the drying temperature is controlled to be 160 ℃, and the drying time is 1.5 h. As the device in figure 1, 50g of dried catalyst precursor is weighed and added into a reactor for activation, the concentration of NaOH is 2 percent, and the volume space velocity of NaOH solution feeding is 20h -1 The activation temperature is 80 ℃, and the activation time is 360 min. After the activation, the catalyst was washed with distilled water to a pH of about 9 and 300ml/min H 2 After the reaction system was purged for 1 hour, evaluation of the performance of the catalyst for producing m-xylylenediamine by hydrogenation of m-phthalonitrile was started. ContinuousRunning for 1000hr, sampling, GC analysis, and conversion rate of m-phthalonitrile>99.9 percent, the highest selectivity of the m-xylylenediamine reaches 96 percent, and the average selectivity reaches 95.6 percent. The product is collected for ICP-OES analysis, no catalyst components of Ni, Cr and Ti are found, and the catalyst stability is good.
Example 2
Weighing 165g of Ni, 135g of Si, 3g of Fe and 3g of Cr, adding the materials into a medium-frequency induction furnace to be smelted into Ni-Si-Fe-Cr alloy, crushing the alloy into alloy powder of 50-250 mu m, and weighing 12.5g of alloy powder. According to the ratio of urea to Na 3 PO 4 :ZnCl 2 Preparing 35 wt% of urea and Na by taking the ratio as 1:2:4 3 PO 4 +ZnCl 2 Mixing water solution 18.7g, weighing 50g ZnO globule and 5g alloy powder, putting into coating machine, spraying prepared 35 wt% urea + Na 3 PO 4 +ZnCl 2 And adding the residual alloy powder into the mixed aqueous solution for coating. And (3) drying the coated catalyst precursor in a microwave oven, wherein the drying temperature is controlled to be 200 ℃, and the drying time is 1 h. 50g of dried catalyst precursor is weighed and added into a reactor for activation, the concentration of NaOH is 3 percent, and the volume space velocity of NaOH solution feeding is 30h -1 The activation temperature is 60 ℃, and the activation time is 240 min. After the activation, the catalyst was washed with distilled water to a pH of about 9 and 300ml/min H 2 After the reaction system was purged for 1 hour, evaluation of the performance of the catalyst for producing m-xylylenediamine by hydrogenation of m-phthalonitrile was started. Continuously running for 1200hr, sampling, performing GC analysis, and converting isophthalonitrile>99.99 percent, the highest selectivity of the m-xylylenediamine reaches 96.2 percent, and the average selectivity reaches 95.9 percent. Products are collected and subjected to ICP-OES analysis, catalyst components of Ni, Cr and Fe are not found, and the catalyst stability is good.
Example 3
Weighing 174g of Ni, 126g of Si, 3g of Co and 3g of Cr, adding the materials into a medium-frequency induction furnace to be smelted into Ni-Si-Co-Cr alloy, crushing the alloy into alloy powder of 50-250 mu m, and weighing 10g of alloy powder. According to the ratio of urea to Na 3 PO 4 :ZnCl 2 Preparing 40 wt% of urea and Na by taking the formula as 1:3:4 3 PO 4 +ZnCl 2 21g of the mixed aqueous solution is prepared by weighing 50g of ZnO pellets and 5g of alloy powderSpraying 40 wt% of urea and Na in a coating machine 3 PO 4 +ZnCl 2 And adding the residual alloy powder into the mixed aqueous solution for coating. And (3) drying the coated catalyst precursor in a microwave oven, wherein the drying temperature is controlled to be 200 ℃, and the drying time is 2 hours. 50g of dried catalyst precursor is weighed and added into a reactor for activation, the concentration of NaOH is 5 percent, and the volume space velocity of NaOH solution feeding is 35h -1 The activation temperature is 60 ℃, and the activation time is 200 min. After the activation, the catalyst was washed with distilled water to a pH of about 9 and 300ml/min H 2 After the reaction system was purged for 1 hour, evaluation of the performance of the catalyst for producing m-xylylenediamine by hydrogenation of m-phthalonitrile was started. Continuously running for 2000hr, sampling for GC analysis, and converting m-phthalonitrile>99.99 percent, the highest selectivity of the m-xylylenediamine reaches 96.9 percent, and the average selectivity reaches 96.2 percent. Products are collected and subjected to ICP-OES analysis, no catalyst components such as Ni, Cr and Co are found, and the catalyst stability is good.
Example 4
Weighing 180g of Ni, 120g of Si and 12g of Cr, adding the materials into a medium-frequency induction furnace to be smelted into Ni-Si-Cr alloy, crushing the alloy into alloy powder with the diameter of 50-250 mu m, and weighing 10g of alloy powder. According to the ratio of urea to Na 3 PO 4 :ZnCl 2 Preparing 50wt% of urea and Na by taking the ratio as 1:3:5 3 PO 4 +ZnCl 2 Mixing 24g of aqueous solution, weighing 50g of ZnO pellets and 5g of alloy powder, putting the ZnO pellets and the alloy powder into a coating machine, and spraying and preparing 50wt% of urea and Na 3 PO 4 +ZnCl 2 And adding the residual alloy powder into the mixed aqueous solution for coating. And (3) drying the coated catalyst precursor in a microwave oven, wherein the drying temperature is controlled to be 250 ℃, and the drying time is 2.5 h. 50g of dried catalyst precursor is weighed and added into a reactor for activation, the concentration of NaOH is 7 percent, and the volume space velocity of NaOH solution feeding is 40h -1 The activation temperature is 50 ℃, and the activation time is 180 min. After the activation, the catalyst was washed with distilled water to a pH of about 9 and 300ml/min H 2 After the reaction system was purged for 1 hour, evaluation of the performance of the catalyst for producing m-xylylenediamine by hydrogenation of phthalonitrile was started. Continuously running for 1000hr, sampling, performing GC analysis, and collecting m-benzeneConversion of dinitrile>99.9 percent, the highest selectivity of the m-xylylenediamine reaches 96.1 percent, and the average selectivity reaches 95.5 percent. Products are collected and subjected to ICP-OES analysis, no catalyst components Ni and Cr are found, and the catalyst stability is good.
Comparative example 1
50g of a commercial Raney-Ni (available from Renyi technologies, Inc., Jiangsu, Inc., modified with Fe and Cr) catalyst was used to evaluate the performance of a catalyst for producing m-xylylenediamine by hydrogenation of m-phthalonitrile with reference to example 1. The operation is continuously carried out for 80 hours, samples are taken for GC analysis, the conversion rate of the m-phthalonitrile is more than 98.5 percent, the selectivity of the m-xylylenediamine is up to 85.1 percent at most, and the average is 84 percent. After 500ppm of NaOH is added into the raw materials of the m-phthalonitrile and the tetrahydrofuran, the evaluation is carried out again, the operation is continuously carried out for 60 hours, and the sampling is carried out for gas chromatographic analysis, so that the conversion rate of the m-xylylenediamine is more than 98.5 percent, the selectivity of the m-xylylenediamine reaches 94.1 percent at most, and the average reaches 93.7 percent. It can be seen that the existing catalysts, even when added with an alkaline promoter, still have inferior effects to the present invention.
Claims (8)
1. A preparation method of a coated skeleton Ni catalyst comprises the following steps:
(1) adding Si, Ni and a metal auxiliary agent into a medium-frequency induction furnace to be smelted into alloy;
(2) crushing the alloy obtained by smelting in the step (1) into powder of 50-250 microns;
(3) coating the alloy powder obtained in the step (2) on the surface of the ZnO pellet;
(4) drying the coating formed product obtained in the step (3) to obtain a catalyst precursor;
activating the catalyst precursor obtained in the step (4) in situ in a reactor to obtain a catalyst; spraying a certain amount of urea and Na when the ZnO pellets in the step (3) and the powder obtained in the step (2) are coated and molded 3 PO 4 +ZnCl 2 Mixing the aqueous solution with urea and Na 3 PO 4 +ZnCl 2 The amount of the mixed aqueous solution is 25-40% of the total weight of the alloy powder and the ZnO spheres, and the urea and the Na are added 3 PO 4 +ZnCl 2 The concentration of the mixed aqueous solution is 30-50 wt%, and the urine isElement, Na 3 PO 4 And ZnCl 2 The mass ratio of (A) to (B) is 1: 1-3: 3-5.
2. The method according to claim 1, wherein the purity of Si in step (1) is > 99%; purity of Ni > 99.5%; the purity of the promoter metal is > 99.5%.
3. The method according to claim 1, wherein the promoter metal in step (1) is one or more of Ti, Cr, Fe and Co, and the metal promoter is added in an amount of 1-4 wt% based on the total weight of Si and Ni.
4. The method according to any one of claims 1 to 3, wherein Si is used in an amount of 40 to 50wt% and Ni is used in an amount of 50 to 60wt%, based on the total amount of Si and Ni.
5. The method as claimed in any one of claims 1 to 3, wherein the ZnO pellets have a diameter of 1 to 3mm and a purity of >99% and are used in an amount of 3 to 5 times the mass of the alloy powder.
6. The method according to any one of claims 1 to 3, wherein the microwave drying is adopted in the step (3), and the drying temperature is controlled to be 160-250 ℃ for 1-2.5 h.
7. The method according to any one of claims 1 to 3, wherein the in-situ activation in step (4) is carried out in NaOH solution, the concentration of the NaOH solution is 2 to 7wt%, and the volume space velocity of the NaOH solution feeding is 20 to 40hr -1 The activation temperature is 50-80 ℃, and the activation time is 180-360 min.
8. Use of the coated skeletal Ni catalyst prepared according to the method of any one of claims 1 to 7 for the catalytic hydrogenation of isophthalonitrile to m-xylylenediamine.
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| CN106423185A (en) * | 2016-08-19 | 2017-02-22 | 万华化学集团股份有限公司 | Preparation method and application of coated skeleton Co catalyst |
| CN109529861A (en) * | 2018-12-12 | 2019-03-29 | 万华化学集团股份有限公司 | A kind of skeletal Co catalysts and its preparation method and application |
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| US3150011A (en) * | 1958-03-05 | 1964-09-22 | Varta Ag And Siemens Schuckert | Shaped metal parts having a superficial double skeleton catalyst structure |
| US5536694A (en) * | 1993-10-16 | 1996-07-16 | Degussa Aktiengesellschaft | Catalyst precursor for an activated raney metal fixed-bed catalyst, an activated raney metal fixed-bed catalyst and a process for its preparation and use, and a method of hydrogenating organic compounds using said catalyst |
| WO2008062725A1 (en) * | 2006-11-21 | 2008-05-29 | Gojo Inc. | Small catalyst ball for modification and device employing the same for modifying object to be modified |
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