CN113880124A - Method for preparing magnesium aluminate spinel by impregnation - Google Patents
Method for preparing magnesium aluminate spinel by impregnation Download PDFInfo
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- CN113880124A CN113880124A CN202010623032.2A CN202010623032A CN113880124A CN 113880124 A CN113880124 A CN 113880124A CN 202010623032 A CN202010623032 A CN 202010623032A CN 113880124 A CN113880124 A CN 113880124A
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- magnesium aluminate
- aluminate spinel
- impregnation
- dipping
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 37
- 239000011029 spinel Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 31
- 239000011777 magnesium Substances 0.000 title claims abstract description 31
- -1 magnesium aluminate Chemical class 0.000 title claims abstract description 31
- 238000005470 impregnation Methods 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 54
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007598 dipping method Methods 0.000 claims abstract description 25
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000005086 pumping Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000010298 pulverizing process Methods 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 13
- 239000012982 microporous membrane Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/162—Magnesium aluminates
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B01J35/61—
-
- B01J35/63—
Abstract
The invention discloses a method for preparing magnesium aluminate spinel by impregnation, which comprises the following steps: pumping the sodium metaaluminate solution and the aluminum sulfate solution into the microreactor to form a mixed solution; adjusting the pumping amount of the sodium metaaluminate solution and the aluminum sulfate solution to control the pH value of the mixed solution to be stable within the range of 5.0-9.0; collecting the mixed solution, carrying out pretreatment, and then carrying out shower washing until the conductivity is less than or equal to 500 mu S; drying, pulverizing, sieving, and heating in muffle furnace to obtain gamma-Al2O3(ii) a Mixing gamma-Al2O3Adding magnesium nitrate dipping solution for dipping, and carrying out product post-treatment to obtain the magnesium aluminate spinel. The method of the invention improves the conversion rate of the magnesia-alumina spinel product, increases the pore volume of the catalyst carrier,The specific surface area is large, the method realizes continuous reaction, the preparation period is short, and the production cost is greatly reduced.
Description
Technical Field
The invention relates to the technical field of magnesium aluminate spinel, in particular to a method for preparing magnesium aluminate spinel by dipping.
Background
With the improvement of the deep processing requirement of raw materials in the world, the main energy structure gradually develops towards macromolecules and high carbon, especially for China with the general heavy crude oil. In order to effectively solve the problems of catalyst activity reduction or inactivation and the like caused by overlarge diffusion resistance of heavy oil components in catalyst pore channels and heavy metal impurity deposition and coking, the gamma-Al widely used in the industries of petrochemical industry and the like is urgently required2O3The carrier has the characteristics of large pore volume and high specific surface. The large pore volume is beneficial to the diffusion of macromolecular compounds to the interior of catalyst particles, and the high specific surface area is beneficial to the dispersion of active metals, so that the reaction performance of the catalyst is improved. For example, heavy oil hydrodenitrogenation catalysts require γ -Al2O3Pore volume is more than 0.6cm3·g-1And a specific surface area higher than 250m2·g-1The pores with the pore radius of 2-5nm account for more than 60% of the total pore size distribution; heavy oil demetallization catalyst requires gamma-Al2O3Has the advantages of<100nm and>100nm bimodal pore distribution, whereas residue hydrodesulphurization and demetallization catalysts require gamma-Al2O3Has a bimodal pore distribution of 17.5 to 27.5nm and>300 nm. In addition, the adsorption field also needs to develop gamma-Al with large pore volume2O3。
The acid method and the alkali method (the alkali method is more commonly used) are commonly used for synthesizing the pseudo-boehmite in China, acid-base neutralization reaction is inevitably generated, harmful gas is released during acid-base decomposition, harm is caused to human bodies and the environment, the whole process flow of the two methods is more, the preparation period is longer, the pore volume of the obtained catalyst carrier is too low, the carbon precipitation and coking of the catalyst are easily caused in the catalysis process, the subsequent catalysis efficiency is low, and the requirements of macromolecular hydrogenation experiments cannot be met.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the technical defects and provide a preparation method of magnesium aluminate spinel, which has the advantages of continuous production, high pore volume, high specific surface area and high production efficiency.
In order to achieve the above object, the present invention discloses a method for preparing magnesium aluminate spinel by impregnation, comprising the steps of:
1) pumping the sodium metaaluminate solution and the aluminum sulfate solution into the microreactor to form a mixed solution;
2) adjusting the pumping amount of the sodium metaaluminate solution and the aluminum sulfate solution to control the pH value of the mixed solution to be stable within the range of 5.0-9.0;
3) collecting the mixed solution obtained in the step 2), carrying out pretreatment, and then carrying out shower washing until the conductivity is less than or equal to 500 mu S;
4) drying, pulverizing, sieving, and heating in muffle furnace to obtain gamma-Al2O3；
5) gamma-Al obtained in the step 4)2O3Adding magnesium nitrate dipping solution for dipping, and carrying out product post-treatment to obtain the magnesium aluminate spinel.
In one embodiment, the concentration of the sodium metaaluminate solution is 0.02 mol/L-10 mol/L, the concentration of the aluminum sulfate solution is 0.01 mol/L-10 mol/L, and the solution is pumped into the microreactor by using a advection pump.
In one embodiment, in the step 3), the pretreatment includes heat preservation, stirring and aging, wherein the heat preservation temperature is 30-100 ℃, the stirring speed is 150-300 r/min, and the aging time is 30-120 min.
Preferably, the stirring speed is 200r/min, and the aging time is 30 min.
In one embodiment, in step 5), the product post-processing is drying, pulverizing and sieving, and muffle furnace heating.
In one embodiment, the drying temperature is 80-120 ℃, the drying time is 2-6 h, and the number of the sieving meshes is 100-300.
Preferably, the drying temperature is 120 ℃, the drying time is 4h, and the number of the sieving meshes is 200.
In one embodiment, in the step 4), the heating temperature of the muffle furnace is 30-800 ℃, and the heating time is 60-300 min.
Preferably, the muffle furnace heating temperature is 200-800 ℃.
In one embodiment, in step 5), the magnesium nitrate dipping solution has a concentration of 0.01 to 1.00mol/L, γ -Al2O3The amount of (A) is 10-100 g.
In one embodiment, the dipping condition is a constant temperature water bath of 20-100 ℃, the stirring speed is 150-300 r/min, and the dipping time is 30-240 min.
Preferably, the stirring speed is 200r/min, and the dipping time is 60 min.
In one embodiment, the temperature of the sodium metaaluminate solution and the aluminum sulfate solution is 30-100 ℃, and the solution is pumped into the microreactor for suction filtration.
In one embodiment, the micro-porous membrane of the micro-reactor has a pore size of 2 μm to 125 μm.
The method for preparing the magnesium aluminate spinel by dipping has the advantages that:
1. the method takes sodium metaaluminate solution and aluminum sulfate solution as reaction raw materials in a microreactor, and controls reaction conditions to prepare the gamma-Al2O3The magnesium aluminate spinel obtained by dipping the magnesium nitrate solution as dipping solution has higher conversion rate and gamma-Al2O3The carrier has larger pore volume and specific surface area.
2. The preparation method of the invention can not release harmful gas, and avoids the harm to human body and environment in the preparation process.
3. The preparation method provided by the invention is a continuous reaction and has the characteristics of short preparation period, high production efficiency and low production cost.
Drawings
FIG. 1 is a schematic view of an apparatus for carrying out the method of the present invention.
Detailed Description
Referring to fig. 1, the method for preparing magnesium aluminate spinel by impregnation in the present invention specifically includes the following steps:
1) weighing sodium metaaluminate solid and aluminum sulfate solid, and respectively dissolving the solid and the aluminum sulfate solid in hot water at 85 ℃ to obtain sodium metaaluminate aqueous solution with the concentration of 0.02-10 mol/L and aluminum sulfate aqueous solution with the concentration of 0.01-10 mol/L; weighing sodium hydroxide solid, dissolving in deionized water to obtain sodium hydroxide solution with concentration of 1mol/L for later use;
2) quickly filtering the sodium metaaluminate aqueous solution and the aluminum sulfate aqueous solution through medium-speed filter paper to obtain clear sodium metaaluminate aqueous solution and aluminum sulfate aqueous solution at the temperature of 30-100 ℃, sealing, and reserving in water bath at the temperature of 85 ℃ for later use;
3) the constant-current pump is connected with the micro-reactor, and the aperture of the micro-porous membrane of the micro-reactor is between 2 and 125 mu m. Setting flow parameters of an advection pump, starting a dispersed phase advection pump, pumping aluminum sulfate into a microreactor, starting a mobile phase advection pump after liquid flows out of an outlet of the microreactor, pumping sodium metaaluminate into the microreactor, receiving a sample material after a transparent gel-like solid is produced at the outlet of the microreactor, measuring the pH value of the sample material, and adjusting the flow of the dispersed phase according to the measured pH value to stabilize the pH value of the sample material at the outlet of the microreactor within the range of 5.0-9.0;
4) starting material collection, and simultaneously putting a material collecting beaker in a constant-temperature water bath at 30-100 ℃, starting electric stirring, wherein the stirring speed is 150-300 r/min;
5) and (5) after the material receiving is finished, washing the equipment, and measuring the pH value of the received material. If the pH value is changed, slowly dropwise adding 1mol/L sodium hydroxide solution, and adjusting the pH value to 5.0-9.0;
6) collecting the material in a constant-temperature water bath at 75 ℃, wherein the stirring speed is 150-300 r/min, and the aging time is 30-120 min;
7) taking out the aging material, performing suction filtration by using medium-speed filter paper, and continuously leaching by using deionized water until the conductivity of filtrate is less than or equal to 500 mu S;
8) drying in an oven at the temperature of 80-120 ℃ for 2-6 h;
9) grinding and crushing, and sieving by a 100-mesh and 300-mesh sieve;
10) heating in a muffle furnace at the temperature of 30-800 ℃ for 60-300 min; preferably, the heating temperature is 200-;
11) weighing magnesium nitrate hexahydrate solid, adding deionized water, and fixing the volume to 250mL to obtain 250 mL0.01-1.00 mol/L magnesium nitrate impregnation solution;
12) balanceTaking 10g to 100g of gamma-Al2O3Adding the magnesium nitrate into the magnesium nitrate dipping solution, carrying out constant-temperature water bath at 20-100 ℃, stirring at the rotating speed of 150-300 r/min, and dipping for 30-240 min;
13) the blast drying temperature of the impregnation liquid is 80-120 ℃, and the drying time is 2-6 h;
14) grinding and crushing, and sieving by a 100-mesh and 300-mesh sieve;
15) heating in a muffle furnace at the temperature of 30-800 ℃ for 60-300 min; preferably, the heating temperature is 200-800 ℃, and the magnesium aluminate spinel prepared by the method is obtained.
To further illustrate the method of the present invention, the following preferred embodiments are described below, it being noted that these embodiments are merely illustrative and not restrictive.
Example 1
Pumping 0.02mol/L sodium metaaluminate solution and 0.01mol/L aluminum sulfate solution at the temperature of 30 ℃ into a microreactor through a constant flow pump, wherein the aperture of a microporous membrane of the microreactor is 2 mu m; adjusting the flow rates of the sodium metaaluminate solution and the aluminum sulfate solution to control the pH value of the mixed solution in the microreactor to be 5.0; collecting materials, namely, simultaneously collecting the materials in a beaker in a constant-temperature water bath at 30 ℃, starting electric stirring, wherein the stirring speed is 150 r/min; collecting material in 75 deg.C constant temperature water bath, stirring at 200r/min, and aging for 30 min; taking out the aging material, performing suction filtration by using medium-speed filter paper, and continuously leaching by using deionized water until the conductivity of filtrate is 500 mu S; drying in an oven at 80 ℃ for 6 h; grinding and crushing, and sieving by a 100-mesh sieve; heating in a muffle furnace at 200 ℃ for 300min to obtain gamma-Al2O3Carrier, detected the gamma-Al2O3The pore volume is 1.1mL/g, the specific surface area is 380m2(ii)/g; weighing magnesium nitrate hexahydrate solid, adding deionized water, and fixing the volume to 250mL to obtain 0.01mol/L magnesium nitrate impregnation solution; weighing 10g of alumina, adding the alumina into the magnesium nitrate dipping solution, carrying out constant-temperature water bath at 20 ℃, stirring at the rotating speed of 200r/min, and dipping for 60 min; drying the maceration extract at 120 deg.C for 2 h; grinding and crushing, and sieving by a 100-mesh sieve; heating the magnesium aluminate spinel in a muffle furnace for 300min at 200 ℃ to obtain the magnesium aluminate spinel prepared by the method, wherein the conversion rate of the magnesium aluminate spinel product is 99.0%.
Example 2
Pumping 10mol/L sodium metaaluminate solution and 10mol/L aluminum sulfate solution at the temperature of 100 ℃ into a microreactor through an advection pump, wherein the aperture of a microporous membrane of the microreactor is 125 mu m; adjusting the flow rates of the sodium metaaluminate solution and the aluminum sulfate solution to control the pH value of the mixed solution in the microreactor to be 9.0; collecting materials, namely, simultaneously collecting the materials in a beaker in a constant-temperature water bath at 100 ℃, and starting electric stirring at the stirring speed of 300 r/min; collecting material in 75 deg.C constant temperature water bath, stirring at 300r/min, and aging for 120 min; taking out the aging material, performing suction filtration by using medium-speed filter paper, and continuously leaching by using deionized water until the conductivity of filtrate is 500 mu S; drying in an oven at 120 ℃ for 2 h; grinding and crushing, and sieving by a 300-mesh sieve; heating in a muffle furnace at 800 ℃ for 600min to obtain gamma-Al2O3Carrier, detected the gamma-Al2O3The pore volume is 1.1mL/g, the specific surface area is 370m2(ii)/g; weighing magnesium nitrate hexahydrate solid, adding deionized water, and fixing the volume to 250mL to obtain 1.0mol/L magnesium nitrate impregnation solution; weighing 100g of alumina, adding the alumina into the magnesium nitrate dipping solution, carrying out constant-temperature water bath at 100 ℃, stirring at the rotating speed of 300r/min, and dipping for 240 min; drying the maceration extract at 80 deg.C for 6 h; grinding and crushing, and sieving by a 300-mesh sieve; heating the magnesium aluminate spinel in a muffle furnace for 60min at 800 ℃ to obtain the magnesium aluminate spinel prepared by the method, wherein the conversion rate of the magnesium aluminate spinel product is 98.6%.
Example 3
Pumping 5.0mol/L sodium metaaluminate solution and 5.0mol/L aluminum sulfate solution at the temperature of 80 ℃ into a micro-reactor through a constant flow pump, wherein the aperture of a microporous membrane of the micro-reactor is 50 mu m; adjusting the flow rates of the sodium metaaluminate solution and the aluminum sulfate solution to control the pH value of the mixed solution in the microreactor to be 7.0; collecting materials, namely, simultaneously collecting the materials in a beaker in a constant-temperature water bath at 70 ℃, starting electric stirring, wherein the stirring speed is 200 r/min; collecting material in 75 deg.C constant temperature water bath, stirring at 200r/min, and aging for 60 min; taking out the aging material, performing suction filtration by using medium-speed filter paper, and continuously leaching by using deionized water until the conductivity of filtrate is 500 mu S; drying in an oven at 100 ℃ for 4 h; grinding, crushing and sieving by a 200-mesh sieve; heating in a muffle furnace at 550 ℃ for 180min to obtain gamma-Al2O3Carrier, detected by gamma-Al2O3The pore volume is 1.2mL/g, the specific surface area is 390m2(ii)/g; weighing magnesium nitrate hexahydrate solid, adding deionized water, and fixing the volume to 250mL to obtain 0.6mol/L magnesium nitrate impregnation solution; weighing 50g of alumina, adding the alumina into the magnesium nitrate dipping solution, carrying out constant-temperature water bath at 70 ℃, stirring at the rotating speed of 200r/min, and dipping for 180 min; drying the maceration extract at a blast temperature of 100 deg.C for 4 h; grinding, crushing and sieving by a 200-mesh sieve; the magnesia-alumina spinel prepared by the method is obtained by heating the magnesia-alumina spinel in a muffle furnace for 180min at 550 ℃, and the conversion rate of the magnesia-alumina spinel product is 99.7%.
Gamma-Al prepared by the method of the above example2O3The properties of the support and the magnesium aluminate spinel are shown in table 1:
TABLE 1
As can be seen from the experimental data in Table 1, the conversion rate of the magnesia-alumina spinel product prepared by the method of the invention is greatly improved, and the carrier has higher pore volume and specific surface area.
Claims (11)
1. A process for the preparation of magnesium aluminate spinel by impregnation, comprising the steps of:
1) pumping the sodium metaaluminate solution and the aluminum sulfate solution into the microreactor to form a mixed solution;
2) adjusting the pumping amount of the sodium metaaluminate solution and the aluminum sulfate solution to control the pH value of the mixed solution to be stable within the range of 5.0-9.0;
3) collecting the mixed solution obtained in the step 2), carrying out pretreatment, and then carrying out shower washing until the conductivity is less than or equal to 500 mu S;
4) drying, pulverizing, sieving, and heating in muffle furnace to obtain gamma-Al2O3；
5) gamma-Al obtained in the step 4)2O3Adding magnesium nitrate dipping solution for dipping, and carrying out product post-treatment to obtain the magnesium aluminate spinel.
2. The process for preparing magnesia-alumina spinel by impregnation according to claim 1, wherein in step 1), the concentration of the sodium metaaluminate solution is 0.02mol/L to 10mol/L and the concentration of the aluminum sulfate solution is 0.01mol/L to 10mol/L, and the solution is pumped into the microreactor by using an advection pump.
3. The method for preparing magnesium aluminate spinel by impregnation according to claim 1, wherein in the step 3), the pretreatment comprises heat preservation, stirring and aging, the heat preservation temperature is 30-100 ℃, the stirring speed is 150-300 r/min, and the aging time is 30-120 min.
4. The process for preparing magnesium aluminate spinel by impregnation according to claim 1, wherein in step 5), the product post-treatments are drying, pulverizing and sieving and muffle furnace heating.
5. The method for preparing magnesium aluminate spinel by impregnation according to claim 1 or 4, wherein the drying temperature is 80-120 ℃, the drying time is 2-6 h, and the sieve mesh number is 100-300.
6. The method for preparing magnesium aluminate spinel by impregnation according to claim 1 or 4, wherein in the step 4), the muffle furnace is heated at 30-800 ℃ for 60-300 min.
7. The method for preparing magnesium aluminate spinel by impregnation as claimed in claim 6, wherein the muffle furnace heating temperature is 200-800 ℃.
8. The method for preparing magnesium aluminate spinel by impregnation according to claim 1, wherein in the step 5), the magnesium nitrate impregnation solution has a concentration of 0.01 to 1.00mol/L of said gamma-Al2O3The amount of (A) is 10-100 g.
9. The method for preparing the magnesium aluminate spinel by dipping according to claim 1, wherein the dipping condition is constant temperature water bath at 20-100 ℃, stirring speed at 150-300 r/min, and dipping time at 30-240 min.
10. The process for the preparation of magnesium aluminate spinel by impregnation according to claim 1, wherein the sodium metaaluminate solution and the aluminum sulfate solution are at a temperature of 30 ℃ to 100 ℃ and are pumped into the microreactor before suction filtration.
11. The method for preparing magnesium aluminate spinel by impregnation according to claim 1, wherein the micro-porous membrane pore size of the micro-reactor is 2 μm to 125 μm.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2202850A1 (en) * | 1972-10-12 | 1974-05-10 | Laporte Industries Ltd | Pseudoboehmite alumina prodn - by controlled reaction of aluminium sulphate and sodium aluminate solns |
| US4019978A (en) * | 1972-08-29 | 1977-04-26 | Laporte Industries Limited | Process for the production of alumina |
| CN1184078A (en) * | 1997-12-19 | 1998-06-10 | 中国石油化工总公司 | Preparation process of alumina |
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| CN102219245A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Pseudoboehmite and aluminium oxide prepared from same |
| CN103787393A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of alumina |
| CN106348325A (en) * | 2016-11-11 | 2017-01-25 | 清华大学 | Gamma-alumina and preparation method thereof |
| CN110314675A (en) * | 2018-03-28 | 2019-10-11 | 国家能源投资集团有限责任公司 | TiO2Modified alumina base magnesium aluminate spinel and preparation method thereof and sulfur-resistant transformation catalyst |
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2020
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| US4019978A (en) * | 1972-08-29 | 1977-04-26 | Laporte Industries Limited | Process for the production of alumina |
| FR2202850A1 (en) * | 1972-10-12 | 1974-05-10 | Laporte Industries Ltd | Pseudoboehmite alumina prodn - by controlled reaction of aluminium sulphate and sodium aluminate solns |
| CN1184078A (en) * | 1997-12-19 | 1998-06-10 | 中国石油化工总公司 | Preparation process of alumina |
| CN101757941A (en) * | 2009-12-30 | 2010-06-30 | 山东齐鲁科力化工研究院有限公司 | Novel Co-Mo sulfur-tolerant shift catalyst and preparation method thereof |
| CN102219245A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Pseudoboehmite and aluminium oxide prepared from same |
| CN103787393A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of alumina |
| CN106348325A (en) * | 2016-11-11 | 2017-01-25 | 清华大学 | Gamma-alumina and preparation method thereof |
| CN110314675A (en) * | 2018-03-28 | 2019-10-11 | 国家能源投资集团有限责任公司 | TiO2Modified alumina base magnesium aluminate spinel and preparation method thereof and sulfur-resistant transformation catalyst |
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