CN114029047A - Preparation method of array carbon nanotube supported catalyst - Google Patents
Preparation method of array carbon nanotube supported catalyst Download PDFInfo
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- CN114029047A CN114029047A CN202111584587.1A CN202111584587A CN114029047A CN 114029047 A CN114029047 A CN 114029047A CN 202111584587 A CN202111584587 A CN 202111584587A CN 114029047 A CN114029047 A CN 114029047A
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- 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
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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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
- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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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
- B01J37/0201—Impregnation
Abstract
The invention discloses a preparation method of an array carbon nanotube supported catalyst, which comprises the steps of impregnating a carrier material and a catalytic active metal salt solution at high temperature and high pressure to obtain a supported catalyst precursor; calcining the supported catalyst precursor in an oxygen-containing atmosphere to obtain a supported catalyst; and generating the array carbon nano tube on the carrier catalyst through CVD deposition to obtain the array carbon nano tube supported catalyst. The method adopts a high-temperature high-pressure impregnation mode, and utilizes the pressure of high-temperature water vapor to perform pressurized impregnation, so that the diffusion rate of the catalytic active component elements is accelerated, the driving force of the catalytic active component elements entering the pore channels of the layered carrier material is increased, the adsorption capacity of the catalytic active elements on the carrier and the ion exchange capacity of the catalytic active elements and the carrier are improved, the loading effect of the catalyst is improved, the production cost and the production period of the carbon nano tube are reduced, and the wastewater discharge is reduced.
Description
Technical Field
The invention relates to a preparation method of an array carbon nanotube supported catalyst, in particular to a method for preparing the array carbon nanotube supported catalyst based on a high-temperature high-pressure impregnation mode, and belongs to the technical field of preparation of catalytic materials.
Background
The carbon nanotube is a novel carbon material with a complete molecular structure, and is a seamless hollow nano-scale tube body formed by curling graphite sheets formed by carbon atoms according to a certain angle. Since the discovery, the material has the advantages of large specific surface area, high conductivity, super-strong mechanical property, extremely high chemical stability and thermal stability, and the like, and is widely applied to a plurality of fields of new energy automobiles, 3C digital, semiconductors, aerospace, national defense war industry and the like as a conductive agent, a heat conducting agent, a reinforcing material, a hydrogen storage material, an electromagnetic wave absorbing material and the like.
The carbon nanotubes can be classified into disordered carbon nanotubes that grow freely and aligned carbon nanotubes that are arrayed in an aligned manner, depending on their growth orientation. The disordered carbon nano-tube which grows freely is in an agglomerated state, disorderly oriented and uneven in distribution of length and tube diameter, which seriously affects the performance of the carbon nano-tube and limits the practical application of the carbon nano-tube. The carbon nano tubes in the array in the directional arrangement are piled in a beam shape, the tube diameter length and the orientation are basically consistent, and the excellent axial charge transmission performance and the heat conduction performance of the carbon nano tubes can be fully exerted, so that the carbon nano tubes have wider application fields. For example, the native array can be directly used as a field emission device, an electrode material of a lithium ion battery and a super capacitor, a sensor and other functional materials; partial arrays can be subjected to filament drawing and film drawing to obtain carbon nanotube fibers or films with extremely excellent performance; even if the arrangement of the carbon nano tubes in the array is damaged, the carbon nano tubes are applied to the fields of lithium ion battery conductive agents and conductive plastics after being monodispersed, and still have more excellent performance than agglomerated carbon nano tubes.
At present, the batch production of the array carbon nano tube is mainly to grow the carbon nano tube on the inner surface of a catalyst-loaded lamellar material through intercalation by a chemical vapor deposition method, and then remove a stripped lamellar material and catalyst particles through hydrofluoric acid and hydrochloric acid treatment. The supersaturated solution impregnation method is the main method for preparing the array carbon nanotube supported catalyst. The basic principle is that the carrier material is put into liquid containing active substances for impregnation, the active substances are gradually adsorbed on the surface of the carrier through diffusion, after the impregnation is balanced, the remaining liquid is removed, and then the steps of drying, roasting, activating and the like are carried out to obtain the carrier material. For example, chinese patents (publication nos. CN101073934A), (CN 101665249A), (CN 101665248A), and the like disclose that the growth of the arrayed carbon nanotubes is realized by impregnating a supported catalyst with an active material solution by using a layered inorganic substance such as lamellar alumina, silica, vermiculite, mica, graphite flake, and lamellar dihydroxy metal oxide as a carrier; and chinese patent publication No. CN111247094A discloses the use of carbon nanotube arrays immersed in exfoliated layered minerals to grow controlled heights. In the above works, the loading mode is natural exchange type impregnation, and the loading time is long, the uniformity is poor, the level is low (the loading is insufficient), so that the prepared array carbon nanotube has low multiplying power, long production period and high cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of an array carbon nanotube supported catalyst, which accelerates the diffusion speed of an active catalytic component and promotes the active catalytic component to permeate into the internal pores of a layered carrier material by a high-temperature pressurizing mode, shortens the loading time, and improves the loading capacity and the loading uniformity, thereby being more beneficial to the generation of array carbon nanotubes, improving the production rate of the carbon nanotubes and reducing the production period and the cost.
In order to achieve the technical purpose, the invention provides a preparation method of an array carbon nanotube supported catalyst, which comprises the following steps:
1) impregnating a carrier material and a catalytic active metal salt solution at high temperature and high pressure to obtain a supported catalyst precursor;
2) calcining the supported catalyst precursor in an oxygen-containing atmosphere to obtain a supported catalyst;
3) and generating the array carbon nano tube on the carrier catalyst through CVD deposition to obtain the array carbon nano tube supported catalyst.
The key point of the technical scheme of the invention is that the impregnation process of the carrier material is realized by adopting a high-temperature high-pressure impregnation mode, under the conditions of high temperature and high pressure, the diffusion speed of the active catalytic component in the carrier material can be accelerated, the active catalytic component can be promoted to permeate into the internal pores of the layered carrier material, the load time is shortened, and the load capacity and the load uniformity are improved, so that the generation of the array carbon nanotube is facilitated, the production rate of the carbon nanotube is improved, and the production period and the cost are reduced.
As a preferred embodiment, the carrier material comprises at least one of alumina, silica, magnesia, vermiculite, mica, hydrotalcite, graphite, expanded graphite. The preferable carrier material is a layered carrier material which is common in the prior art, is mainly used for loading transition metal catalysts and is used for catalyzing the generation of the array carbon nano-tubes in the CVD deposition process.
As a preferred embodiment, the catalytically active metal salt solution comprises a metal salt of the catalytic component and a metal salt of the promoter component. As a more preferable scheme, the metal salt of the catalytic component is a metal salt including at least one of iron, cobalt and nickel. As a more preferred embodiment, the metal salt of the promoter component is a metal salt including molybdenum. The catalytic activity generated by the catalytic array carbon nano tube can be improved by matching the catalytic component and the cocatalyst component. The metal salt is common water-soluble salt, for example, the metal salt of the catalytic component can be nitrate, sulfate, chloride and the like. The metal salt of the co-catalyst component may be ammonium tetramolybdate, ammonium molybdate tetrahydrate, ammonium dimolybdate, ammonium heptamolybdate, or ammonium octamolybdate, among others.
As a preferable scheme, the metal salt solution with catalytic activity is obtained by mixing a metal salt solution of a catalytic component and a metal salt solution of a cocatalyst component according to a volume ratio of 1-5: 1; the concentration of the metal salt solution of the catalytic component is 0.1-3 mol/L; the concentration of the metal salt solution of the catalysis-assisting component is 0.001-0.1 mol/L. By controlling the catalytic component and the co-catalytic component within a suitable range, a catalyst having higher catalytic activity can be obtained.
As a preferable scheme, the solid-liquid mass ratio of the carrier material to the catalytically active metal salt solution is 1:1 to 1: 5.
As a preferred scheme, the conditions of the high-temperature high-pressure impregnation are as follows: the pressure is 0.2-0.5 MPa, the temperature is 200-500 ℃, and the time is 30-180 min. The impregnation method is that when a carrier material with a porous structure is impregnated in a solution containing a catalytic active component, the solution is absorbed into pores of the carrier from the surface under the action of capillary force, and the catalytic active component permeates and diffuses towards the inner wall of the pores and is adsorbed by active points on the surface of the carrier, or is deposited, is subjected to ion exchange, or even reacts, so that the catalytic active component is loaded on the carrier. The impregnation process depends on capillary penetration, diffusion and adsorption, which are closely related to temperature and pressure. The invention improves the dipping effect by controlling the pressure and the temperature, accelerates the thermal motion of active molecules in the solution by increasing the temperature, increases the probability of the active molecules entering the carrier material, but changes the crystal structure of the carrier when the temperature is too high, damages the pore channel, reduces the specific surface area and reduces the adsorption quantity. Under the sealing condition of the dipping reaction kettle, the pressure of the dipping reaction kettle is increased due to high temperature, the driving force of active molecules entering the pore channels of the carrier is improved, the permeation rate of the active molecules is accelerated, the permeation depth and the permeation quantity are improved, but the pressure is too high, the pore channels are compacted, and the permeation rate is reduced. Therefore, the impregnation speed is increased and the active component adsorption amount is increased by properly increasing the temperature and the pressure, so that the exchange or the reaction of the carrier material and active ions and the like are facilitated, and the loading level of the carrier material is increased. In actual production, the pressure is improved under the limitation of various factors of comprehensive equipment, the production requirement can be met under the pressure of 0.2-0.5 MPa generally, the temperature is also suitable to be controlled within the range of 200-500 ℃, and a better effect can be obtained.
As a preferred scheme, the high-temperature high-pressure impregnation process is realized by a high-temperature pressure impregnation device; the high-temperature pressure impregnation device comprises an impregnation reaction kettle (10); the top of the impregnation reaction kettle is provided with a feed inlet (2), a dosing port (6) and an exhaust device (4), the bottom of the impregnation reaction kettle is provided with a discharge port (9), and a stirring device is arranged inside the impregnation reaction kettle; a heating furnace (12) is arranged outside the dipping reaction kettle; the high-temperature pressure impregnation device realizes the high-temperature high-pressure impregnation of the carrier material and the catalytic active metal salt solution by the following steps: adding a carrier material into the impregnation reaction kettle from a feeding port, dropwise adding a catalytic activity metal salt solution into the impregnation reaction kettle from a dosing port under the condition of starting a stirring device, fully mixing the carrier material and the catalytic activity metal salt solution, stopping the stirring device, controlling a heating furnace to heat to an impregnation temperature, discharging gas from an automatic pressure relief exhaust device after the gas is not discharged, cooling, and discharging from a discharge port. The high-temperature pressure impregnation device provided by the invention can be used for carrying out pressurized impregnation by utilizing the pressure of high-temperature water vapor, so that the diffusion rate of catalytic active component elements is accelerated at high temperature, and the driving force of the active component elements entering the pore channels of the flaky carrier material is increased in a high-pressure environment. Particularly, the high-temperature pressure impregnation device has an automatic pressure relief function, when the gas pressure in the impregnation reaction kettle body is higher than the set rated gas pressure, the gas medium of the impregnation reaction kettle body acts on a safety valve in the automatic pressure relief device to push the valve core to rise, and then the gas is discharged out of the reaction kettle body through the air leakage port, so that the gas pressure in the impregnation reaction kettle is restored to the rated pressure, and the impregnation reaction kettle is prevented from causing danger due to overhigh gas pressure; the stability of the pressure in the dipping reaction kettle is ensured, and the structural uniformity and the performance stability of the catalyst product are improved.
As a preferred embodiment, the calcination conditions are: the temperature is 400-600 ℃, and the time is 1-6 h. The catalytically active metal ions impregnated in the support material are converted to metal oxides by a calcination process.
As a preferred scheme, the CVD deposition conditions are: the deposition temperature is 600-1100 ℃, the deposition time is 40-80min, and the flow ratio of the carbon source gas to the carrier gas is 0.3-2.
Preferably, the carbon source gas is at least one of methane, ethane, ethylene, propane, propylene, propyne, cyclohexane, benzene and toluene; the carrier gas is at least one of argon, nitrogen and hydrogen.
The preparation method of the array carbon nanotube supported catalyst comprises the following steps:
(1) and (3) selecting a carrier: the layered support material is washed and dried.
(2) Preparing an impregnation salt solution: the impregnation salt solution comprises a catalytic component salt solution and a cocatalyst component salt solution. Catalytic component salt solution: weighing and metering Fe-containing2+、Co2+、Ni2+Dissolving metal salt of an active component in deionized water, and magnetically stirring at room temperature for 10-30 min to form a catalytic component salt solution, wherein the concentration of the catalytic component is 0.1-3 mol/L. Salt solution of the catalytic promoter component: weighing a metered metal molybdate compound, dissolving the metal molybdate compound in deionized water, and magnetically stirring for 10-30 min at room temperature to form an auxiliary component salt solution, wherein the concentration of the auxiliary catalytic component salt solution is 0.001-0.1 mol/L. The volume ratio of the catalytic component salt solution to the cocatalyst component salt solution is 1-5: 1.
(3) Preparing a supported catalyst precursor: loading the catalytic active component elements on the inner surface of the layered carrier by adopting a high-temperature pressurized impregnation method to obtain a loaded catalyst precursor. The specific implementation process is as follows:
s1: and (3) feeding the layered carrier material prepared in the step (1) into the bottom of the reaction kettle (10) of the impregnation device from the feeding port (2) through pneumatic transmission.
S2: and (3) starting a motor 3 for stirring, dropwise adding the catalytic component salt solution and the cocatalyst component salt solution prepared in the step (2) into the reaction kettle from a reagent adding port 6 in sequence through a rotor pump while stirring, and continuously stirring for 5-10 min after dropwise adding is finished at a stirring speed of 50-200 r/min, so that the layered carrier material is fully contacted with the impregnated salt solution. The mass ratio of the layered carrier material to the impregnated salt solution is 1: 1-1: 5.
And S3, stopping stirring, heating the heating furnace to 200-500 ℃ at the pressure of 0.2-0.5 MPa for 30-180 min, cooling after no gas is discharged from the pressure relief port 4, taking the impregnation reaction kettle out of the heating furnace 12, and taking the material from a bottom discharge port 9 to obtain the supported catalyst precursor.
(4) Preparing a supported catalyst: placing the catalyst precursor prepared in the step (3) in a muffle furnace, calcining in an oxygen-containing environment, cooling, and sieving to obtain a supported catalyst; wherein the calcining temperature is 400-600 ℃, the calcining time is 1-6 h, and the sieving mesh number is 80-100 meshes. The mass fraction of active components of iron, nickel and cobalt in the obtained supported catalyst is 5-30%.
(5) Preparing the array carbon nano tube: and (3) placing the supported catalyst prepared in the step (4) in a CVD reactor, introducing a carbon source gas and a carrier gas, wherein the flow ratio of the carbon source gas to the carrier gas in the CVD reaction is 0.3-2, the CVD reaction temperature is 600-1100 ℃, and the CVD reaction time is 40-80min, so that the array carbon nanotube is obtained on the carrier. Wherein, the CVD reaction adopts one or a combination bed of a fixed bed, a moving bed and a fluidized bed; the carbon source gas adopted by the CVD reaction is one or more of methane, ethane, ethylene, propane, propylene, propyne, cyclohexane, benzene, toluene and the like; the carrier gas used in the CVD reaction is one or more of argon, nitrogen and hydrogen.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
compared with the normal pressure impregnation mode adopted in the preparation process of the array carbon nanotube supported catalyst in the prior art, the high temperature pressurization impregnation mode adopted by the technical scheme of the invention has the following advantages:
(1) the pressure impregnation is carried out by utilizing the pressure of high-temperature water vapor, so that the diffusion rate of the catalytic active component elements is accelerated at high temperature, and the driving force of the active component elements entering the pore channels of the flaky carrier material is increased in a high-pressure environment.
(2) The high-temperature pressure impregnation device adopted by the invention has an automatic pressure relief function, so that the stability of the pressure in the impregnation reaction kettle is ensured, and the structural uniformity and the performance stability of a catalyst product are improved.
(3) The invention can enable the active catalytic component salt solution to be easily and fully infiltrated into the carrier by adopting a high-temperature pressurization impregnation mode, the impregnation time is shortened from tens of hours to several hours, the supersaturated salt solution remained in the impregnation reaction kettle can be gasified and discharged at high pressure, the drying link is reduced, and the production cost and the production period of the carbon nano tube are reduced.
(4) The method adopts a high-temperature pressurized impregnation mode, so that the removal of residual saturated liquid after impregnation balance in the conventional impregnation process is omitted, the discharge of waste water is reduced, and the method is green and environment-friendly.
Drawings
FIG. 1 is a schematic structural diagram of a high-temperature pressure impregnation apparatus according to the present invention;
wherein, 1 is a temperature measuring device, 2 is a feeding port, 3 is a motor, 4 is an exhaust device, 5 is a pressure gauge, 6 is a dosing port, 7 is a transmission shaft, 8 is a stirring paddle, 9 is a discharge port, 10 is an impregnation reaction kettle, 11 is a support lug, 12 is a heating furnace, and 13 is a support.
Fig. 2 is a scanning electron micrograph of the vermiculite-supported catalyst prepared in example 1.
Fig. 3 is a scanning electron micrograph of the arrayed carbon nanotubes prepared in example 1.
Fig. 4 is a scanning electron micrograph of the arrayed carbon nanotubes prepared in example 1.
Fig. 5 is a scanning electron micrograph of the vermiculite-supported catalyst prepared in example 2.
Fig. 6 is a scanning electron micrograph of the vermiculite-supported catalyst prepared in example 3.
Fig. 7 is a scanning electron micrograph of the vermiculite-supported catalyst prepared in example 4.
Fig. 8 is a scanning electron micrograph of the vermiculite-supported catalyst prepared in comparative example 1.
Fig. 9 is a scanning electron micrograph of the arrayed carbon nanotubes prepared in comparative example 1.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the drawings and specific examples, and the following examples do not further limit the scope of the claims.
The structure of the high-temperature pressure impregnation device referred to in the following examples is schematically shown in fig. 1. The main structure of the high-temperature pressure impregnation device is an impregnation reaction kettle 10; the top of dipping reaction kettle is equipped with dog-house 2 that is used for the solid to feed in raw material, is used for the reinforced agent mouth 6 that adds of liquid, exhaust apparatus 4 for automatic pressure release, temperature measurement device 1 for temperature in the monitoring dipping reaction kettle and manometer 5 that is used for monitoring dipping reaction kettle internal pressure, and temperature measurement device is the bar-shaped, and it inserts and stretches into the lower part from dipping reaction kettle top. And a discharge hole 9 is formed in the bottom of the impregnation reaction kettle. The inside agitating unit that is equipped with of illustrated impregnation reaction cauldron, agitating unit include transmission shaft 7 and stirring rake 8, and transmission shaft one end is connected with the stirring rake, and one end links to each other with the motor that the impregnation reaction cauldron top set up outside the impregnation reaction cauldron in addition. The outside of the dipping reaction kettle is provided with a heating furnace 12 which is of a cylindrical structure and can heat the bottom and the periphery of the dipping reaction kettle. The outer upper portion of the dipping reaction kettle is provided with a supporting hanging lug 11 for arranging the dipping reaction kettle supporting frame on the heating furnace, and the bottom of the heating furnace is provided with a support 13 for supporting and fixing the heating furnace.
Example 1
The preparation method comprises the steps of preparing an Fe-supported vermiculite catalyst by taking laminated vermiculite as a catalyst carrier, Fe as an active component and Mo as an auxiliary component through high-temperature pressurized impregnation and preparing an array carbon nanotube by using a fixed bed. Wherein the mass ratio of the catalytic component Fe salt to the cocatalyst component Mo salt to the vermiculite is 50:2: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: selecting 80-100 meshes of vermiculite as a carrier, removing oil contamination impurities in the vermiculite by using a water flotation method, and then drying the vermiculite in an air-blast drying oven for 24 hours at 120 ℃; 100g of washed vermiculite is put into 1mol/L hydrochloric acid, pretreated for 2 hours at 90 ℃, filtered and washed until the filtrate is neutral, the vermiculite suspension subjected to acid washing pretreatment is centrifugally dewatered by a centrifugal machine at 1500rpm, and is put into an air-blowing drying oven to be dried for 24 hours at 120 ℃.
(2) Preparing an impregnation salt solution: weighing 50g of ferric nitrate nonahydrate, adding into 300mL of deionized water, and magnetically stirring at room temperature for 30min to obtain a homogeneous catalysis component salt solution; 2g of ammonium molybdate tetrahydrate is weighed and added into 100mL of deionized water, and the mixture is magnetically stirred for 30min at room temperature to obtain a homogeneous catalysis-assisting component salt solution.
(3) Preparing a supported catalyst by high-temperature pressure impregnation: putting 100g of acid-washed vermiculite carrier into a dipping kettle from a feeding port of a dipping device shown in figure 1, sequentially dropwise adding the prepared 300ml of catalytic component salt solution and 100ml of cocatalyst component salt solution into the dipping kettle from a dosing port while stirring, wherein the dropping speed is 5ml/min, the stirring speed is 200r/min, stopping stirring after 8min of dropping, heating the heating furnace to 200 ℃, and carrying out pressure-maintaining dipping for 2h under 0.2MPa to prepare the Fe-loaded vermiculite catalyst precursor.
(4) Preparing a supported catalyst: and placing the prepared Fe-supported vermiculite catalyst precursor in a muffle furnace, calcining for 2h at 500 ℃, cooling, and sieving by using a 80-100-mesh sieve to obtain the Fe-supported vermiculite catalyst. FIG. 2 is a scanning photograph of the obtained supported catalyst, and it can be seen that after pressure impregnation, the vermiculite surface and interlayer are supported with a plurality of particle coatings, and the particle size of the particles is basically 20-30 nm.
(5) Preparing the array carbon nano tube by CVD: weighing 0.5g of Fe-supported vermiculite catalyst, paving the Fe-supported vermiculite catalyst in a porcelain boat, placing the porcelain boat in a middle position of a quartz tube type CVD furnace with the diameter of phi 100mm, introducing nitrogen at the flow rate of 300mL/min, heating to 650 ℃ at the heating rate of 10 ℃/min, then introducing hydrogen at the flow rate of 100mL/min, stopping introducing the hydrogen after 10min, simultaneously introducing propylene gas at the flow rate of 200mL/min, stopping introducing the propylene gas after reacting for 60min, and continuously reducing the temperature to the normal temperature under the protection of nitrogen to obtain 4.9g of carbon nano tubes, wherein the yield of the carbon nano tubes is 9.8 times. Fig. 3 and 4 are SEM photographs of the resulting arrayed carbon nanotubes, and it can be seen that the vermiculite sheets are spread apart and the carbon nanotubes are 20 μm in length.
Example 2
The preparation method comprises the steps of preparing an Fe-supported vermiculite catalyst by using laminated vermiculite as a catalyst carrier, Fe as a catalytic component and Mo as a cocatalyst component through high-temperature pressure impregnation, and preparing the array carbon nanotube by using a fixed bed. Wherein the mass ratio of the catalytic component Fe salt to the cocatalyst component Mo salt to the vermiculite is 50:2: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: the carrier selection and pretreatment procedures as in example 1.
(2) Preparing an impregnation salt solution: the same configuration as in example 1 was used for the salt solution impregnation process.
(3) Preparing a supported catalyst by high-temperature pressure impregnation: the preparation process of the supported vermiculite catalyst precursor of the example 1 is the same. The difference is that the heating furnace in the step is heated to 200 ℃ and is soaked for 60min under the pressure of 0.5MPa to prepare the precursor of the Fe-supported vermiculite catalyst.
(4) Preparing a supported catalyst: the same procedure as in example 1 was used to prepare the supported catalyst. Fig. 5 is a scanning photograph of the obtained supported catalyst, and it can be seen that after pressure impregnation under the condition, the pressure is increased, the coating of the supported particles on the surface of vermiculite and among layers is thin, the particle size is small, and excessive infiltration particle agglomeration and accumulation are generated among stripping layers.
(5) Preparing the array carbon nano tube by CVD: the yield of the carbon nanotubes obtained by the above method was 10.6 times, which is 5.3g of the carbon nanotubes prepared by the CVD method of example 1.
Example 3
The preparation method comprises the steps of preparing an Fe-supported vermiculite catalyst by using laminated vermiculite as a catalyst carrier, Fe as a catalytic component and Mo as a cocatalyst component through high-temperature pressure impregnation, and preparing the array carbon nanotube by using a fixed bed. Wherein the mass ratio of the catalytic component Fe salt to the cocatalyst component Mo salt to the vermiculite is 50:2: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: the carrier selection and pretreatment procedures as in example 1.
(2) Preparing an impregnation salt solution: the same configuration as in example 1 was used for the salt solution impregnation process.
(3) Preparing a supported catalyst by high-temperature pressure impregnation: the preparation process of the supported vermiculite catalyst precursor of the example 1 is the same. The difference is that the heating furnace in the step is heated to 500 ℃ and is soaked for 50min under the pressure of 0.2MPa to prepare the precursor of the Fe-supported vermiculite catalyst. FIG. 6 is a scanning photograph of the obtained supported catalyst, and it can be seen that after pressure impregnation, the vermiculite surface and interlayer supported particle coatings are uniformly dispersed, and the particles are fine and have the particle size of basically 15-25 nm.
(4) Preparing a supported catalyst: the same procedure as in example 1 was used to prepare the supported catalyst.
(5) Preparing the array carbon nano tube by CVD: in the same manner as in the CVD process of example 1, 5.8g of the carbon nanotubes were obtained in an array with a yield of 11.6 times.
Example 4
The preparation method comprises the steps of preparing an Fe-supported vermiculite catalyst by using laminated vermiculite as a catalyst carrier, Fe as a catalytic component and Mo as a cocatalyst component through high-temperature pressure impregnation, and preparing the array carbon nanotube by using a fixed bed. Wherein the mass ratio of the catalytic component Fe salt to the cocatalyst component Mo salt to the vermiculite is 50:2: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: the carrier selection and pretreatment procedures as in example 1.
(2) Preparing an impregnation salt solution: the same configuration as in example 1 was used for the salt solution impregnation process.
(3) Preparing a supported catalyst by high-temperature pressure impregnation: the preparation process of the supported vermiculite catalyst precursor of the example 1 is the same. The difference is that the heating furnace in the step is heated to 500 ℃ and is soaked for 30min under the pressure of 0.5MPa to prepare the precursor of the Fe-supported vermiculite catalyst.
(4) Preparing a supported catalyst: the same procedure as in example 1 was used to prepare the supported catalyst. Fig. 7 is a scanning photograph of the resulting supported catalyst, and it can be seen that the amount of supported particles on the surface and between layers of vermiculite increases, the particles are larger, and many excessive particles are agglomerated and piled up between layers peeled apart due to the increase of pressure and temperature.
(5) Preparing the array carbon nano tube by CVD: the yield of the carbon nanotubes obtained by the above method was 12.4 times that of 6.2g of the carbon nanotubes prepared by CVD method in example 1.
The above examples 1, 2, 3 and 4 and the comparative example 1 test the performance of the method under the conditions of different impregnation temperatures (200-500 ℃) and different impregnation pressures (0.2-0.5 MPa), and the test results show that the method has more stable performance (yield: 8-11.6 times) within the above impregnation temperature and impregnation pressure ranges, the performance is obviously higher than that of the comparative example 1 (yield: 3.6 times), and the performance of the method has an increasing trend along with the increase of the temperature and the pressure. The experimental comparison results described above show that the preferred embodiment of the process with respect to impregnation temperature and impregnation pressure is reasonable.
Example 5
The preparation method comprises the steps of preparing a Fe + Co loaded vermiculite catalyst by taking laminated vermiculite as a catalyst carrier, Fe and Co as catalytic components and Mo as a cocatalyst component through high-temperature pressure impregnation and preparing an array carbon nanotube by using a fixed bed. Wherein the mass ratio of the catalytic component Fe salt to the catalytic component Co salt to the cocatalyst component Mo salt to the vermiculite is 45:5:3: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: the carrier selection and pretreatment procedures as in example 1.
(2) Preparing an impregnation salt solution: weighing 45g of ferric nitrate nonahydrate and 5g of cobalt nitrate hexahydrate, adding into 300mL of deionized water, and magnetically stirring at room temperature for 30min to obtain a homogeneous active component salt solution; 3g of ammonium molybdate tetrahydrate is weighed and added into 100mL of deionized water, and the mixture is magnetically stirred for 30min at room temperature to obtain a homogeneous auxiliary component salt solution.
(3) Preparing a supported catalyst by high-temperature pressure impregnation: the preparation process of the supported vermiculite catalyst precursor of the example 1 is the same.
(4) Preparing a supported catalyst: the same procedure as in example 1 was used to prepare the supported catalyst.
(5) Preparing the array carbon nano tube by CVD: the yield of the carbon nanotubes obtained by the above method for preparing the carbon nanotubes array was 14.3 times, which is the same as that of the CVD method of example 1, and is 7.15 g.
Example 6
The preparation method comprises the steps of preparing a Fe + Co loaded vermiculite catalyst by taking laminated vermiculite as a catalyst carrier, Fe and Co as catalytic components and Mo as a cocatalyst component through high-temperature pressure impregnation and preparing an array carbon nanotube by using a fixed bed. Wherein the mass ratio of the catalytic component Fe salt, the catalytic component Co salt, the cocatalyst component Mo salt and the vermiculite is 35:15:3: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: the carrier selection and pretreatment procedures as in example 1.
(2) Preparing an impregnation salt solution: weighing 35g of ferric nitrate nonahydrate and 15g of cobalt nitrate hexahydrate, adding into 300mL of deionized water, and magnetically stirring at room temperature for 30min to obtain a homogeneous catalytic component salt solution; 3g of ammonium molybdate tetrahydrate is weighed and added into 100mL of deionized water, and the mixture is magnetically stirred for 30min at room temperature to obtain a homogeneous catalysis-assisting component salt solution.
(3) Preparing a supported catalyst by high-temperature pressure impregnation: the preparation process of the supported vermiculite catalyst precursor of the example 1 is the same.
(4) Preparing a supported catalyst: and placing the prepared Fe-loaded vermiculite catalyst precursor in a muffle furnace, calcining for 2h at 600 ℃, cooling, and sieving by using a 80-100-mesh sieve to obtain the loaded vermiculite catalyst. .
(5) Preparing the array carbon nano tube by CVD: the yield of the carbon nanotubes obtained by the above method was 19.6 times that of 9.8g of the carbon nanotubes prepared by CVD method in example 1.
Example 7
The preparation method comprises the steps of preparing a Fe + Co + Ni loaded vermiculite catalyst by using laminated vermiculite as a catalyst carrier, Fe, Co and Ni as catalytic components and Mo as a cocatalyst through high-temperature pressurized impregnation and preparing an array carbon nanotube by using a fluidized bed. Wherein the mass ratio of the catalytic component Fe salt, the catalytic component Co salt, the catalytic component Ni salt, the cocatalyst component Mo salt and the vermiculite is 35:10:10:1.5: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: the carrier selection and pretreatment procedures as in example 1. Except that the hydrochloric acid concentration in said step 1 is 2 mol/L.
(2) Preparing an impregnation salt solution: weighing 35g of ferric nitrate nonahydrate, 10g of cobalt nitrate hexahydrate and 10g of nickel nitrate nonahydrate, adding into 500mL of deionized water, and magnetically stirring at room temperature for 30min to obtain a homogeneous catalysis component salt solution; 1.5g of ammonium molybdate tetrahydrate is weighed and added into 200mL of deionized water, and the mixture is magnetically stirred for 30min at room temperature to obtain a homogeneous catalysis-assisting component salt solution.
(3) Preparing a supported catalyst by high-temperature pressure impregnation: putting 100g of acid-washed vermiculite carrier into a dipping kettle from a feeding port of a dipping device shown in figure 1, sequentially dropwise adding 500ml of prepared catalytic component salt solution and 200ml of prepared cocatalyst component salt solution into the dipping kettle from a dosing port while stirring, wherein the dropping speed is 10ml/min, the stirring speed is 300r/min, stopping stirring after 8min of dropping is finished, heating a heating furnace to 400 ℃, and carrying out pressure-maintaining dipping for 1h under 0.2MPa to prepare the Fe-loaded vermiculite catalyst precursor.
(4) Preparing a supported catalyst: the same procedure as in example 1 was used to prepare the supported catalyst.
(5) Preparing the array carbon nano tube by CVD: weighing 3g of Fe + Co + Ni loaded vermiculite catalyst, placing the catalyst in a fluidized bed reactor with the diameter of 200mm, introducing nitrogen at the flow rate of 1000mL/min, heating to 650 ℃ at the heating rate of 10 ℃/min, introducing hydrogen at the flow rate of 1000mL/min, stopping introducing hydrogen after 10min, adjusting the flow rate of nitrogen to 3000L/min, simultaneously introducing propylene gas at the flow rate of 3000mL/min, stopping introducing the propylene gas after reacting for 60min, and continuously reducing the temperature to the normal temperature under the protection of nitrogen to obtain 47g of carbon nano tubes, wherein the yield of the carbon nano tubes is 15.6 times.
Comparative example 1
The preparation method comprises the steps of preparing an Fe-supported vermiculite catalyst by ordinary normal-pressure impregnation by using laminated vermiculite as a catalyst carrier, Fe as a catalytic component and Mo as a cocatalyst component, and preparing the array carbon nanotube by using a fixed bed. Wherein the mass ratio of the catalytic component Fe salt to the cocatalyst component Mo salt to the vermiculite is 50:2: 100. The preparation method comprises the following steps:
(1) selecting and pretreating a carrier: the same carrier selection and pretreatment procedure as in example 1.
(2) Preparing an impregnation salt solution: the salt impregnation step was performed as in the configuration of example 1.
(3) Preparing a supported catalyst by ordinary normal-pressure impregnation: putting 100g of acid-washed vermiculite carrier into a normal-pressure glass reaction kettle, sequentially dropwise adding 300ml of prepared catalytic component salt solution and 100ml of prepared cocatalyst component salt solution into a dipping kettle while stirring, heating in an oil bath, stirring and dipping for 12 hours at 160 ℃, then cooling, centrifuging at 1500rpm of a centrifuge to remove redundant saturated liquid, and obtaining Fe-loaded vermiculite catalyst precursor centrifugate.
(4) Preparing a supported catalyst: and (3) putting the Fe-supported vermiculite catalyst precursor centrifugate prepared in the step into an air-blowing drying oven, drying for 24h at 120 ℃, cooling, then putting into a muffle furnace, calcining for 2h at 500 ℃, cooling, and then sieving by using an 80-100-mesh sieve to obtain the Fe-supported vermiculite catalyst. Fig. 8 is a scanning photograph of the resulting supported catalyst, and it can be seen that after 12 hours of atmospheric impregnation, adequate impregnation of the vermiculite surface and interlamination was not achieved. Compared with the example 1 and the figure 2, the high-temperature pressurizing impregnation preparation method provided by the application has the advantages of high impregnation efficiency and good uniformity.
(5) Preparing the array carbon nano tube by CVD: the yield of the carbon nanotubes obtained by the above method was 3.6 times that of 1.8g of the carbon nanotubes prepared by CVD method in example 1. FIG. 9 is an SEM photograph of the obtained carbon nanotube array, and it can be seen that the active component can not be dispersed between the vermiculite sheets, and most of the vermiculite sheets have no carbon nanotube grown between them, and the grown carbon nanotube has low density and 5-10 μm length. Compared with the example 1 and the figure 3, the supported catalyst prepared by the method has higher carbon yield, good orientation and density uniformity of the grown array carbon nano-tube and large length-diameter ratio.
Claims (10)
1. A preparation method of an array carbon nanotube supported catalyst is characterized by comprising the following steps: the method comprises the following steps:
1) impregnating a carrier material and a catalytic active metal salt solution at high temperature and high pressure to obtain a supported catalyst precursor;
2) calcining the supported catalyst precursor in an oxygen-containing atmosphere to obtain a supported catalyst;
3) and generating the array carbon nano tube on the carrier catalyst through CVD deposition to obtain the array carbon nano tube supported catalyst.
2. The method for preparing the array carbon nanotube supported catalyst according to claim 1, wherein the method comprises the following steps: the carrier material comprises at least one of aluminum oxide, silicon dioxide, magnesium oxide, vermiculite, mica, hydrotalcite, graphite and expanded graphite.
3. The method for preparing the array carbon nanotube supported catalyst according to claim 1, wherein the method comprises the following steps:
the catalytically active metal salt solution comprises metal salts of the catalytic component and metal salts of the promoter component;
the metal salt of the catalytic component is metal salt containing at least one of iron, cobalt and nickel;
the metal salt of the catalytic promoter component is a metal salt comprising molybdenum.
4. The method for preparing the array carbon nanotube supported catalyst according to claim 1 or 3, wherein:
the catalytic activity metal salt solution is obtained by mixing a metal salt solution of a catalytic component and a metal salt solution of a cocatalyst component according to the volume ratio of 1-5: 1;
the concentration of the metal salt solution of the catalytic component is 0.1-3 mol/L;
the concentration of the metal salt solution of the catalysis-assisting component is 0.001-0.1 mol/L.
5. The method for preparing the array carbon nanotube supported catalyst according to claim 1, wherein the method comprises the following steps: the solid-liquid mass ratio of the carrier material to the catalytically active metal salt solution is 1: 1-1: 5.
6. The method for preparing the array carbon nanotube supported catalyst according to claim 1, wherein the method comprises the following steps: the high-temperature high-pressure impregnation conditions are as follows: the pressure is 0.2-0.5 MPa, the temperature is 200-500 ℃, and the time is 30-180 min.
7. The method for preparing the array carbon nanotube supported catalyst according to claim 1 or 6, wherein:
the high-temperature high-pressure impregnation process is realized by a high-temperature pressure impregnation device;
the high-temperature pressure impregnation device comprises an impregnation reaction kettle (10); the top of the impregnation reaction kettle is provided with a feed inlet (2), a dosing port (6) and an exhaust device (4), the bottom of the impregnation reaction kettle is provided with a discharge port (9), and a stirring device is arranged inside the impregnation reaction kettle; a heating furnace (12) is arranged outside the dipping reaction kettle;
the high-temperature pressure impregnation device realizes the high-temperature high-pressure impregnation of the carrier material by the catalytic active metal salt solution, and comprises the following steps: adding a carrier material into the impregnation reaction kettle from a feeding port, dropwise adding a catalytic activity metal salt solution into the impregnation reaction kettle from a dosing port under the condition of starting a stirring device, fully mixing the carrier material and the catalytic activity metal salt solution, stopping the stirring device, controlling a heating furnace to heat to an impregnation temperature, discharging gas from an automatic pressure relief exhaust device after the gas is not discharged, cooling, and discharging from a discharge port.
8. The method for preparing the array carbon nanotube supported catalyst according to claim 1, wherein the method comprises the following steps: the calcining conditions are as follows: the temperature is 400-600 ℃, and the time is 1-6 h.
9. The method for preparing the array carbon nanotube supported catalyst according to claim 1, wherein the method comprises the following steps: the CVD deposition conditions are as follows: the deposition temperature is 600-1100 ℃, the deposition time is 40-80min, and the flow ratio of the carbon source gas to the carrier gas is 0.3-2.
10. The method for preparing the array carbon nanotube supported catalyst according to claim 9, wherein:
the carbon source gas is at least one of methane, ethane, ethylene, propane, propylene, propyne, cyclohexane, benzene and toluene;
the carrier gas is at least one of argon, nitrogen and hydrogen.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618544A (en) * | 2022-03-17 | 2022-06-14 | 无锡东恒新能源科技有限公司 | Synthetic method of lamellar structure catalyst |
| CN114632521A (en) * | 2022-04-08 | 2022-06-17 | 湖北冠毓新材料科技有限公司 | Preparation method of vermiculite-based catalyst and preparation method of carbon nanotube, and catalyst and carbon nanotube prepared thereby |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077464A (en) * | 1996-12-19 | 2000-06-20 | Alliedsignal Inc. | Process of making carbon-carbon composite material made from densified carbon foam |
| CN101073934A (en) * | 2007-06-15 | 2007-11-21 | 清华大学 | Carbon nano-pipe array/laminated composite and its production |
| CN109382145A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Catalyst impregnating equipment and its application method |
-
2021
- 2021-12-22 CN CN202111584587.1A patent/CN114029047A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077464A (en) * | 1996-12-19 | 2000-06-20 | Alliedsignal Inc. | Process of making carbon-carbon composite material made from densified carbon foam |
| CN101073934A (en) * | 2007-06-15 | 2007-11-21 | 清华大学 | Carbon nano-pipe array/laminated composite and its production |
| CN109382145A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Catalyst impregnating equipment and its application method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618544A (en) * | 2022-03-17 | 2022-06-14 | 无锡东恒新能源科技有限公司 | Synthetic method of lamellar structure catalyst |
| CN114618544B (en) * | 2022-03-17 | 2023-10-03 | 无锡东恒新能源科技有限公司 | Method for synthesizing catalyst with lamellar structure |
| CN114632521A (en) * | 2022-04-08 | 2022-06-17 | 湖北冠毓新材料科技有限公司 | Preparation method of vermiculite-based catalyst and preparation method of carbon nanotube, and catalyst and carbon nanotube prepared thereby |
| CN114632521B (en) * | 2022-04-08 | 2023-09-08 | 湖北冠毓新材料科技有限公司 | Preparation method of catalyst based on vermiculite and preparation method of carbon nanotube, and catalyst and carbon nanotube prepared by using preparation method |
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