Hollow spherical catalyst for fixed bed with internal fluidization of particles, and method for preparing same

Abstract

A hollow spherical catalyst for a fixed bed with internal fluidization of particles and a method for preparing the same. The preparation method includes: fully mixing precious metal nanopowder with an organic oil phase to form an internal oil phase; preparing a gel ball of an oil-in-water structure by taking an aluminum oxide molding solution as an outer aqueous phase using an independently researched and developed coaxial dual-dropper forming apparatus; and then preparing a hollow aluminum oxide catalyst containing precious metal powder from the gel ball through processes of aging, calcination, and reduction. The resulting catalyst is expressed as X@Al.sub.2O.sub.3, where the precious metal nanopowder X is wrapped inside hollow Al.sub.2O.sub.3, and the catalyst has an outer diameter of 1.5-5.0 mm, a shell pore diameter (aluminum oxide) of 10-50 nm, and the precious metal nanopowder sized 200-500 nm.

Claims

1. A method for preparing a hollow spherical catalyst for a fixed bed with internal fluidization of particles, comprising: A. preparing an aluminum oxide molding solution fully mixing an aluminum sol and a hexamethylenetetramine aqueous solution at a mass ratio of 2.0-6.0:1 in an ice water bath to get aluminum oxide molding solution; preparing the aluminum sol: weighing aluminum powder with a purity greater than 99.6%, dissolving the aluminum powder in dilute hydrochloric acid at a concentration of 5-20% or an aluminum chloride crystal solution at a concentration of 10-25% at 95-105 C. to obtain the transparent and stable aluminum sol, wherein the aluminum content is 6-20%, and the Al/Cl mass ratio is 0.3-3.0; and preparing the hexamethylenetetramine solution: adding hexamethylenetetramine into deionized water to prepare the hexamethylenetetramine aqueous solution at a concentration of 20-40%, and then adding a viscosity regulator therein to obtain the hexamethylenetetramine solution; wherein the viscosity regulator is 10-30% acrylamide and/or hydroxymethylacrylamide, and the amount added is 1-10% of a mass of the hexamethylenetetramine aqueous solution; B. preparing an internal oil phase suspension fully dispersing powder of precious metal X in an oily substance at a mass fraction of 0.1-5.0% to obtain a suspension, i.e., the internal oil phase suspension; wherein the powder of the precious metal X is one of Pd, Pt, Au, or Ag nanopowder with a size of 200-500 nm; and the oily substance is one of liquid paraffin, white oil No. 2, white oil No. 3, or white oil No. 7; C. preparing oil-in-water alumina gel balls preparation using a coaxial dual-dropper forming apparatus comprising steps of: transferring the aluminum oxide molding solution in a material tank 2, switching on the delivery pump; adding the internal oil phase suspension into the material tank for pumping into an inner tube 6 of the coaxial dropper through the delivery pump at a flow rate of 6-20 mL/h; simultaneously loading the aluminum oxide molding solution into another material tank for pumping into an outer tube of the coaxial dropper through another delivery pump at a flow rate of 8-25 mL/h, and controlling the flow rate in the outer tube to be 2-5 mL/h faster than that in the inner tube; oil-in-water sol balls will be formed at the outlet of the dropper; dropwise adding the sol balls into a hot oil column at 70-95 C., then adding the sol balls into forming oil at 70-95 C. present in an aging reactor, heating the forming oil to 130-160 C. for aging for 4-6 h, cooling the mixture to room temperature, taking out the mixture, washing and drying. In this way, oil-in-water alumina gel balls with a diameter of 1.5-5.0 mm can be obtained; wherein the forming oil is one of vacuum pump oil, dimethicone, or white oil No. 15; and a mass fraction of the precious metal X in each catalyst particle is controlled by regulating the feed liquid flow rates in the outer tube and the inner tube; and D. preparing an X@ Al.sub.2O.sub.3 catalyst heating dry alumina gel balls in a muffle furnace to 400-500 C. at a rate of 1-5 C./min, and keeping the gel balls at the temperature for 2-4 h, to remove oily substances in the internal oil phase suspension; then heating the mixture to 550-1,000 C. at a rate of 5-10 C./min for calcination for 2-4 h, to obtain different crystal forms of aluminum oxide; air cooling the aluminum oxide to room temperature, transferring the aluminum oxide to an atmosphere furnace, and heating the aluminum oxide in a reduction atmosphere to 200-450 C. at a rate of 2-10 C./min for reduction for 1-4 h, to obtain the X@Al.sub.2O.sub.3 catalyst; wherein the reduction atmosphere is one of 5-40% H.sub.2/N.sub.2 or 5-40% CO/N.sub.2 at a gas flow rate of 20-100 mL/min.

2. The method for preparing a hollow spherical catalyst for a fixed bed with internal fluidization of particles according to claim 1, wherein in the aluminum sol in step A, the aluminum content is 10-15%, and the Al/Cl mass ratio is 1-2.

3. The method for preparing a hollow spherical catalyst for a fixed bed with internal fluidization of particles according to claim 1, wherein the catalyst is expressed as X@Al.sub.2O.sub.3; X represents precious metal nanopowder, and is one of Pd, Pt, Au, or Ag; Al.sub.2O.sub.3 is a hollow spherical particle; the catalyst has an outer diameter of 1.5-5.0 mm, a shell thicknesses of 0.5-3.0 mm, a shell pore diameter (aluminum oxide) of 10-50 nm, and a crushing strength of 15-40 N; and X is wrapped inside Al.sub.2O.sub.3, has a size of 200-500 nm, and has a mass fraction of 0.05-10% in the catalyst.

4. The method for preparing a hollow spherical catalyst for a fixed bed with internal fluidization of particles according to claim 3, wherein the catalyst has the outer diameter of 2.5-4.1 mm, the shell thickness of 0.6-2 mm, the shell pore diameter of 10-50 nm, and the crushing strength of 20-30 N, and the mass fraction of 1-5.0% of X in the spherical catalyst.

5. An apparatus for preparing the hollow spherical catalyst for a fixed bed with internal fluidization of particles according to claim 3, wherein the apparatus comprises two material tanks, two delivery pumps, a coaxial dropper, a hot oil column, and an aging reactor; wherein the coaxial dropper comprises an inner tube and an outer tube with different diameters; and a connection mode of the apparatus is as follows: one of the material tanks is connected to an inlet end of the inner tube of the coaxial dropper through one of the delivery pumps, and the other material tank is connected to an inlet end of the outer tube of the coaxial dropper through the other delivery pump, the hot oil column is located under the coaxial dropper, an outlet of the hot oil column is connected to a feed inlet of the aging reactor located under the hot oil column; and an inner diameter of the inner tube is 0.3-2.5 mm, an inner diameter of the outer tube is 0.9-5.0 mm, an outlet end of the inner tube protrudes 0.3-0.8 mm from an outlet end of the outer tube; the hot oil column is provided with a heating jacket, and is provided with a discharge valve at a lower end; and the aging reactor is a reactor with a heating apparatus.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a diagram of a forming apparatus for making a gel ball of a water-oil structure, where (1) and (2) are material tanks, (3) and (4) are delivery pumps, (5) is a coaxial dropper, (6) is an inner tube of the coaxial dropper, (7) is an outer tube of the coaxial dropper, (8) is a hot oil column, and (9) is an aging reactor.

(2) FIG. 2 is a picture (a), a particle size picture (b), and a cross-section view (c) of a millimeter-level spherical catalyst prepared in Example 1.

(3) FIG. 3 is a low-temperature nitrogen adsorption/desorption curve (a) and a pore size distribution diagram (b) of the catalyst obtained in Example 1.

(4) FIG. 4 is a picture (a), a particle size picture (b), and a cross-section view (c) of a millimeter-level spherical catalyst prepared in Example 2.

(5) FIG. 5 is a low-temperature nitrogen adsorption/desorption curve (a) and a pore size distribution diagram (b) of the catalyst obtained in Example 2.

DETAILED DESCRIPTION

Example 1

(6) Target catalyst: Pd@Al.sub.2O.sub.3 with an average particle diameter of 2.6 mm, a shell thickness of 0.85 mm, and a Pd (active component) loading of 2.0%.

Preparation of an Aluminum Oxide Molding Solution

(7) The aluminum oxide molding solution was formed by mixing an aluminum sol with an aluminum content of 17% and a 40% hexamethylenetetramine solution. The aluminum sol and the hexamethylenetetramine solution were prepared as follows:

(8) 25 g of aluminum powder with a purity of 99.8% was weighed, and added into 120 g of dilute hydrochloric acid at a concentration of 10%. The aluminum powder was dissolved at 102 C. to obtain the transparent and stable aluminum sol. The aluminum sol has an aluminum content of 17%, and an Al/Cl mass ratio of 2.1.

(9) 49.5 g of the aluminum sol prepared in the above steps was weighed, and placed in an ice water bath. 6.2 g of hexamethylenetetramine was added into another beaker, and 9.3 g of deionized water was added to form the hexamethylenetetramine solution at a concentration of 40%. Then, 1.0 g of an acrylamide solution was added, and the mixture was stirred until the mixture was transparent and stable. In an ice water bath, the two solutions were fully mixed and fully stirred.

B. Preparation of a Pd-containing Oil Phase Suspension

(10) 40 g of liquid paraffin was mixed with 0.3 g of Pd powder to obtain the internal oil phase suspension with an average particle size of Pd powder of 200 nm.

C. Preparation of an Oil-in-water Gel Ball

(11) The internal oil phase suspension was transferred to a material tank 1, the aluminum oxide molding solution was transferred to a material tank 2, a delivery pump was switched on, and the material liquid in the material tank 1 was pumped into an inner tube 6 through a delivery pump 3 at a flow rate of 7 mL/h. Simultaneously, the material liquid in the material tank 2 was pumped into an outer tube 7 of a dropper through a delivery pump 4 at a flow rate of 10 mL/h. The two liquids dropped out from a coaxial dropper to form an oil-in-water emulsion droplet, which fell into a hot oil column at 88 C., and then dropped into dimethicone present in an aging reactor through the hot oil column to form a gel ball of a water-oil structure. There was dimethicone at 88 C. in the aging reactor. Dimethicone was heated to 150 C. for aging for 4 h, cooled to room temperature, taken out, washed, and dried, to obtain a water-oil alumina gel ball with a diameter of 2.6 mm.

(12) An inner tube of the coaxial dropper has a diameter of 0.5 mm, an outer tube of the coaxial dropper has a diameter of 1.5 mm, and the inner tube protrudes 0.5 mm from the outer tube.

D. Preparation of a Pd@Al.SUB.2.O.SUB.3 .Catalyst

(13) The dried alumina gel ball was heated in a muffle furnace to 400 C. at a heating rate of 2 C./min, kept at this temperature for 2 h, then heated to 960 C. at a heating rate of 6 C./min, kept at this temperature for 3 h, and then naturally cooled to room temperature.

(14) The resulting spherical aluminum oxide was transferred to an atmosphere furnace, and heated to 350 C. in the presence of 10% H.sub.2/N.sub.2 reducing gas at a gas flow rate of 50 mL/min at a heating rate of 2 C./min for reduction for 2 h, to obtain the Pd@Al.sub.2O.sub.3 catalyst. The performance test results are shown in Table 1.

Example 2

(15) Target catalyst: Pt@Al.sub.2O.sub.3 with an average particle diameter of 2.6 mm, a shell thickness of 0.75 mm, and a Pt (active component) loading of 2.0%.

A. Preparation of an Aluminum Oxide Molding Solution

(16) The aluminum oxide molding solution was formed by mixing an aluminum sol with an aluminum content of 17% and a 40% hexamethylenetetramine solution. The aluminum sol and the hexamethylenetetramine solution were prepared as follows:

(17) 25 g of aluminum powder with a purity of 99.7% was weighed, and added into 120 g of an aluminum chloride crystal solution at a concentration of 10%. The aluminum powder was dissolved at 102 C. to obtain the transparent and stable aluminum sol. The aluminum sol has an aluminum content of 17%, and an Al/Cl mass ratio of 2.1.

(18) 62.3 g of the aluminum sol prepared in the above step A was weighed, and placed in an ice water bath. 7.8 g of hexamethylenetetramine was added into another beaker, and 11.7 g of deionized water was added to form the hexamethylenetetramine solution at a concentration of 40%. Then, 0.8 g of a hydroxymethyl acrylamide solution was added, and the mixture was fully stirred until the mixture was transparent and stable. In an ice water bath, the two solutions were fully mixed and fully stirred.

B. Preparation of a Pt-containing Oil Phase Suspension

(19) 45 g of liquid paraffin was mixed with 0.4 g of Pt powder to obtain the internal oil phase suspension with an average particle size of Pt powder of 250 nm.

C. Preparation of an Oil-in-water Gel Ball

(20) The preparation processes are the same as those in Example 1, where an inner tube of a dropper has a diameter 0.6 mm, an outer tube of the dropper has a diameter of 1.5 mm, and the inner tube protrudes 0.6 mm from the outer tube; a flow rate of the aluminum oxide molding solution is 12 mL/h, and a flow rate of the internal oil phase suspension is 8 mL/h; a falling oil-in-water emulsion droplet fell into a hot oil column at 90 C., and then dropped into dimethicone present in an aging reactor through the hot oil column to form a gel ball of a water-oil structure. There was dimethicone at 90 C. in the aging reactor. Dimethicone was heated to 155 C. for aging for 4 h, cooled to room temperature, taken out, washed, and dried, to obtain a water-oil alumina gel ball with a diameter of 2.6 mm.

D. Preparation of a Pt@Al.SUB.2.O.SUB.3 .Catalyst

(21) The dried alumina gel ball was heated in a muffle furnace to 400 C. at a heating rate of 2 C./min, kept at this temperature for 2.5 h, then heated to 960 C. at a heating rate of 6 C./min, kept at this temperature for 3 h, and then naturally cooled to room temperature.

(22) The resulting spherical aluminum oxide was transferred to an atmosphere furnace, and heated to 400 C. in the presence of 15% H.sub.2/N.sub.2 reducing gas at a gas flow rate of 50 mL/min at a heating rate of 2 C./min for reduction for 2 h, to obtain the Pt@Al.sub.2O.sub.3 catalyst. The performance test results are shown in Table 1.

Example 3

(23) Target catalyst: Ru@Al.sub.2O.sub.3 with an average particle diameter of 3.1 mm, a shell thickness of 1.0 mm, and a Ru (active component) loading of 4.0%.

A. Preparation of an Aluminum Oxide Molding Solution

(24) The aluminum oxide molding solution was formed by mixing an aluminum sol with an aluminum content of 12% and a 40% hexamethylenetetramine solution. The aluminum sol and the hexamethylenetetramine solution were prepared as follows:

(25) 17 g of aluminum powder with a purity of 99.8% was weighed, and added into 120 g of dilute hydrochloric acid at a concentration of 10%. The aluminum powder was dissolved at 102 C. to obtain the transparent and stable aluminum sol. The aluminum sol has an aluminum content of 12%, and an Al/Cl mass ratio of 1.4.

(26) 75 g of the aluminum sol prepared in the above step A was weighed, and placed in an ice water bath. 9.4 g of hexamethylenetetramine was added into another beaker, and 14.1 g of deionized water was added to form the hexamethylenetetramine solution at a concentration of 40%. Then, 1.1 g of a hydroxymethyl acrylamide solution was added, and the mixture was fully stirred until the mixture was transparent and stable. In an ice water bath, the two solutions were fully mixed and fully stirred.

B. Preparation of a Ru-containing Internal Oil Phase Suspension

(27) 40 g of liquid paraffin was mixed with 0.7 g of Ru powder to obtain the internal oil phase suspension with an average particle size of Ru powder of 320 nm.

C. Preparation of an Oil-in-water Gel Ball

(28) The preparation processes are the same as those in Example 1, where an inner tube of a dropper has a diameter 0.6 mm, an outer tube of the dropper has a diameter of 2.5 mm, and the inner tube protrudes 0.5 mm from the outer tube; a flow rate of the aluminum oxide molding solution is 15 mL/h, and a flow rate of the internal oil phase suspension is 11 mL/h; a falling oil-in-water emulsion droplet fell into a hot oil column at 94 C., and then dropped into dimethicone present in an aging reactor through the hot oil column to form a gel ball of a water-oil structure. There was dimethicone at 94 C. in the aging reactor. Dimethicone was heated to 150 C. for aging for 4.5 h, cooled to room temperature, taken out, washed, and dried, to obtain a water-oil alumina gel ball with a diameter of 3.1 mm.

D. Preparation of Ru @Al.SUB.2.O.SUB.3 .Catalyst

(29) The dried alumina gel ball was heated in a muffle furnace to 400 C. at a heating rate of 3 C./min, kept at this temperature for 2 h, then heated to 800 C. at a heating rate of 8 C./min, kept at this temperature for 3 h, and then naturally cooled to room temperature.

(30) The resulting spherical aluminum oxide was placed in an atmosphere furnace, and heated to 400 C. in the presence of 7% H.sub.2/N.sub.2 reducing gas at a gas flow rate of 50 mL/min at a heating rate of 4 C./min for reduction for 2 h, to obtain the Ru@Al.sub.2O.sub.3 catalyst. The performance test results are shown in Table 1.

Example 4

(31) Target catalyst: Ag@Al.sub.2O.sub.3 with an average particle diameter of 3.1 mm, a shell thickness of 0.9 mm, and an Ag (active component) loading of 3.9%.

A. Preparation of an Aluminum Oxide Molding Solution

(32) The aluminum oxide molding solution was formed by mixing an aluminum sol with an aluminum content of 14% and a 40% hexamethylenetetramine solution. The aluminum sol and the hexamethylenetetramine solution were prepared as follows:

(33) 20 g of aluminum powder with a purity of 99.7% was weighed, and added into 120 g of dilute hydrochloric acid at a concentration of 10%. The aluminum powder was dissolved at 102 C. to obtain the transparent and stable aluminum sol. The aluminum sol has an aluminum content of 14%, and an Al/Cl mass ratio of 1.7.

(34) 87 g of the aluminum sol prepared in the above step A was weighed, and placed in an ice water bath. 10.9 g of hexamethylenetetramine was added into another beaker, and 16.4 g of deionized water was added to form the hexamethylenetetramine solution at a concentration of 40%. Then, 1.0 g of a hydroxymethyl acrylamide solution was added, and the mixture was fully stirred until the mixture was transparent and stable. In an ice water bath, the two solutions were fully mixed and fully stirred.

B. Preparation of an Ag-containing Internal Oil Phase Suspension

(35) 40 g of liquid paraffin was mixed with 0.9 g of Ag powder to obtain the internal oil phase suspension with an average particle size of Ag powder of 360 nm.

C. Preparation of an Oil-in-water Gel Ball

(36) The preparation processes are the same as those in Example 1, where an inner tube of a dropper has a diameter 0.8 mm, an outer tube of the dropper has a diameter of 2.5 mm, and the inner tube protrudes 0.6 mm from the outer tube; a flow rate of the aluminum oxide molding solution is 14 mL/h, and a flow rate of the internal oil phase suspension is 11 mL/h; a falling oil-in-water emulsion droplet dropped into a hot oil column at 92 C., and then dropped into dimethicone present in an aging reactor through the hot oil column to form a gel ball of a water-oil structure. There was dimethicone at 92 C. in the aging reactor. Dimethicone was heated to 155 C. for aging for 5 h, cooled to room temperature, taken out, washed, and dried, to obtain a water-oil alumina gel ball with a diameter of 3.1 mm.

D. Preparation of an Ag@Al.SUB.2.O.SUB.3 .Catalyst

(37) The dried alumina gel ball was heated in a muffle furnace to 500 C. at a heating rate of 3 C./min, kept at this temperature for 3 h, then heated to 900 C. at a heating rate of 7 C./min, kept at this temperature for 3 h, and then naturally cooled to room temperature.

(38) The resulting spherical aluminum oxide was placed in an atmosphere furnace, and heated to 350 C. in the presence of 20% H.sub.2/N.sub.2 reducing gas at a flow rate of 50 mL/min at a heating rate of 3 C./min for reduction for 3 h, to obtain the Ag@Al.sub.2O.sub.3 catalyst. The performance test results are shown in Table 1.

Example 5

(39) Target catalyst: Pt@Al.sub.2O.sub.3 with an average particle diameter of 4.1 mm, a shell thickness of 1.4 mm, and a Pt (active component) loading of 2.5%.

A. Preparation of an Aluminum Oxide Molding Solution

(40) The aluminum oxide molding solution was formed by mixing an aluminum sol with an aluminum content of 17% and a 40% hexamethylenetetramine solution. The aluminum sol and the hexamethylenetetramine solution were prepared as follows:

(41) 25 g of aluminum powder with a purity of 99.7% was weighed, and added into 120 g of an aluminum chloride crystal solution at a concentration of 10%. The aluminum powder was dissolved at 102 C. to obtain the transparent and stable aluminum sol. The aluminum sol has an aluminum content of 17%, and an Al/Cl mass ratio of 2.1.

(42) 62.3 g of the aluminum sol prepared in the above step A was weighed, and placed in an ice water bath. 7.8 g of hexamethylenetetramine was added into another beaker, and 11.7 g of deionized water was added to form the hexamethylenetetramine solution at a concentration of 40%. Then, 1.1 g of an acrylamide solution was added, and the mixture was fully stirred until the mixture was transparent and stable. In an ice water bath, the two solutions were fully mixed and fully stirred.

B. Preparation of a Pt-containing Oil Phase Suspension

(43) 40 g of liquid paraffin was mixed with 0.5 g of Pt powder to obtain the internal oil phase suspension with an average particle size of Pt powder of 400 nm.

C. Preparation of an Oil-in-water Gel Ball

(44) The preparation processes are the same as those in Example 1, where an inner tube of a dropper has a diameter 0.8 mm, an outer tube of the dropper has a diameter of 3.5 mm, and the inner tube protrudes 0.5 mm from the outer tube; a flow rate of the aluminum oxide molding solution is 14 mL/h, and a flow rate of the internal oil phase suspension is 10 mL/h; a falling oil-in-water emulsion droplet dropped into a hot oil column at 94 C., and then dropped into dimethicone present in an aging reactor through the hot oil column to form a gel ball of a water-oil structure. There was dimethicone at 94 C. in the aging reactor. Dimethicone was heated to 150 C. for aging for 4 h, cooled to room temperature, taken out, washed, and dried, to obtain a water-oil alumina gel ball with a diameter of 4.1 mm.

D. Preparation of a Pt@Al.SUB.2.O.SUB.3 .Catalyst

(45) The dried alumina gel ball was heated in a muffle furnace to 500 C. at a heating rate of 4 C./min, kept at this temperature for 2 h, then heated to 960 C. at a heating rate of 8 C./min, kept at this temperature for 3 h, and then naturally cooled to room temperature.

(46) The resulting spherical aluminum oxide was transferred to an atmosphere furnace, and heated to 450 C. in the presence of 10% H.sub.2N.sub.2 reducing gas at a flow rate of 50 mL/min at a heating rate of 4 C./min for reduction for 2 h, to obtain the Pt@Al.sub.2O.sub.3 catalyst. The performance test results are shown in Table 1.

(47) TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Outer 2.6 2.6 3.1 3.1 4.1 diameter (mm) Shell 0.8 0.7 1.0 0.9 1.4 thickness (mm) Catalyst 2.0% 2.0% 4.0% 3.9% 2.5% content Bulk 0.37 0.34 0.32 0.27 0.25 density (g/m.sup.3) Crushing 26 23 28 26 30 strength (N)