CN114426300A - Preparation method of macroporous alumina carrier - Google Patents

Preparation method of macroporous alumina carrier Download PDF

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Publication number
CN114426300A
CN114426300A CN202011099229.7A CN202011099229A CN114426300A CN 114426300 A CN114426300 A CN 114426300A CN 202011099229 A CN202011099229 A CN 202011099229A CN 114426300 A CN114426300 A CN 114426300A
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pseudo
alumina
powder
boehmite
pseudoboehmite
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CN114426300B (en
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季洪海
王少军
凌凤香
袁胜华
谷明镝
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
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Abstract

The invention discloses a preparation method of a macroporous alumina carrier, which comprises the following steps: (1) uniformly mixing a proper amount of pseudo-boehmite powder A and pseudo-boehmite powder B; (2) adding a proper amount of ammonium chloride into the mixed material obtained in the step (1), uniformly mixing, and then roasting to obtain alumina powder C; (3) uniformly mixing a proper amount of pseudo-boehmite D and the alumina powder C obtained in the step (2), adding a peptizing agent and an extrusion aid, uniformly kneading, extruding and forming; (4) and (4) drying and roasting the strip-shaped material obtained in the step (3) to obtain the macroporous alumina carrier. The method has simple process and easy industrial production, and the prepared alumina carrier has higher pore volume and higher pore contents of 10-20nm and 20-60 nm.

Description

Preparation method of macroporous alumina carrier
Technical Field
The invention relates to the field of inorganic material preparation, in particular to a preparation method of a macroporous alumina carrier.
Background
With the increase of the heavy and inferior degree of crude oil and the change of the light oil demand structure in the market, the processing technology of inferior heavy oil (including various heavy oil, residue oil and the like) has become the research focus direction of various large oil companies and oil research institutions. The residual oil fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil, the residual oil contains a large amount of impurity components which mainly exist in the form of macromolecular micelles such as colloid, asphaltene and the like, and the residual oil has a complex structure, a large molecular size and difficult diffusion. The traditional microporous alumina can not meet the production requirements, and a carrier material which has reasonable pore channel distribution and can effectively improve the mass transfer diffusion and reaction of macromolecular reactants needs to be developed.
CN104556164A discloses a macroporous alumina and a preparation method thereof, the method comprises the following steps: (1) preparing a solution containing ester and organic acid, an acidic aluminum salt solution and an alkaline aluminate solution which are respectively marked as a solution A, a solution B and a solution C; (2) performing a gelling reaction on the solution B and the solution C in a parallel flow manner, controlling the pH value to be 9.0-11.0, preferably 9.5-10.5, controlling the reaction temperature to be 60-95 ℃, preferably 75-85 ℃, and after the gelling reaction is finished, aging, filtering, washing and drying; adding the solution A before or during gelling, preferably carrying out the gelling reaction by parallel flow of the solution A, the solution B and the solution C; (3) and (3) forming the material obtained in the step (2), and drying and roasting to obtain the macroporous alumina carrier. The process for preparing the alumina carrier is complex and is not easy to realize industrial production, and in addition, the lipid, the organic acid and other substances are used in the preparation process of the carrier, so that the preparation cost of the carrier is increased.
CN1120971A discloses a method for preparing an alumina carrier with a bimodal pore structure, which is to uniformly mix dry glue powder of pseudo-boehmite prepared by two or more different raw material routes, and then carry out peptization, molding, drying and roasting treatment to prepare the alumina carrier. The alumina carrier prepared by the method has double-hole distribution, two pore channel structures are respectively provided by pseudo-boehmite prepared by two or more different raw material routes, a pore-expanding agent is not used in the preparation process, the pore channel structure of the carrier is controlled by the property of the pseudo-boehmite, and the pore-expanding effect is not obvious.
CN107913691A discloses an alumina carrier containing macropores and a preparation method thereof, wherein the method uses styrene-butadiene rubber emulsion as a pore-enlarging agent to adjust the pore structure of the alumina carrier, and the method is complex in the process of preparing the styrene-butadiene rubber emulsion and high in cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a macroporous alumina carrier. The prepared alumina carrier has high pore volume, high pore contents of 10-20nm and 20-60nm, simple process and easy industrial production.
The preparation method of the macroporous alumina carrier comprises the following steps:
(1) uniformly mixing a proper amount of pseudo-boehmite powder A and pseudo-boehmite powder B;
(2) adding a proper amount of ammonium chloride into the mixed material obtained in the step (1), uniformly mixing, and then roasting to obtain alumina powder C;
(3) uniformly mixing a proper amount of pseudo-boehmite D and the alumina powder C obtained in the step (2), adding a peptizing agent and an extrusion aid, uniformly kneading, extruding and forming;
(4) and (4) drying and roasting the strip-shaped material obtained in the step (3) to obtain the macroporous alumina carrier.
In the method of the invention, the pseudoboehmite A in the step (1) can be prepared by any method such as acid precipitation, alkali precipitation, aluminum alkoxide hydrolysis and the like, the pore volume of the pseudoboehmite is 0.5-1.0mL/g, and the specific surface area is 150-300m2A few pores of 9-17.5nm in diameter/g.
In the method of the invention, the pseudoboehmite B in the step (1) can be prepared by any method such as acid precipitation, alkali precipitation, aluminum alkoxide hydrolysis and the likeThe pore volume of the pseudo-boehmite is 0.8-1.5mL/g, and the specific surface area is 200-350m2A few pores of 20-40nm in diameter/g.
In the method, the molar ratio of the pseudoboehmite A and the pseudoboehmite B in the step (1) is 1: 1-1: 3, preferably 1: 2-1: 3.
in the method, the ammonium chloride in the step (2) is solid powder, and the molar ratio of the added amount of the ammonium chloride calculated by ammonium radicals to the mixed material calculated by aluminum elements is 1: 18-1: 4.5, preferably 1: 10-1: 5.
in the method, the roasting conditions in the step (2) are as follows: the roasting temperature is 500-850 ℃, preferably 650-800 ℃, and the roasting time is 1-10 hours, preferably 4-8 hours; the roasting can be carried out in an inert atmosphere or an oxygen-containing atmosphere, the oxygen content in the oxygen-containing atmosphere has no special requirement and can be an oxygen atmosphere, an air atmosphere or a mixed atmosphere of oxygen and inert gas. The roasting can be carried out in equipment such as a high-temperature box furnace, a high-temperature tube furnace, a high-temperature atmosphere furnace, a high-temperature pit furnace and the like.
In the method, the pseudoboehmite D in the step (3) is pseudoboehmite with the peptization index of more than 75%, and preferably pseudoboehmite with the peptization index of more than 85%. The molar ratio of the pseudo-boehmite D to the alumina powder C is 1: 4-1: 6, preferably 1: 5-1: 6.
in the method, the peptizing agent in the step (3) is one or a mixture of several of nitric acid, hydrochloric acid, citric acid, acetic acid and oxalic acid, the mass percentage concentration of the solution is 1-3%, and the adding amount is determined according to the forming effect.
In the method, the extrusion aid in the step (3) is one or a mixture of sesbania powder, methylcellulose, graphite and the like, and the addition amount of the extrusion aid is 1-3% of the weight of the alumina.
In the method, the drying temperature in the step (4) is 80-160 ℃, the drying time is 4-10 hours, the roasting temperature is 500-800 ℃, and the roasting time is 4-10 hours.
The macroporous alumina carrier prepared by the method can be widely applied to macromolecular reaction processes such as catalysis, adsorption and the like.
Compared with the prior art, the invention has the following advantages:
(1) the invention firstly mixes the two kinds of pseudo-boehmite with different pore channel structures evenly, and the final alumina carrier has higher 10-20nm and 20-60nm pore channel contents due to the difference of the properties of the two kinds of pseudo-boehmite. Meanwhile, ammonium chloride is added into the mixture, and is decomposed to generate ammonia gas and hydrogen chloride gas when being heated, and the generated gas can play a role in punching; on the other hand, because the alumina is amphoteric oxide, the generated gas can react with the alumina crystal grains to change the size and the accumulation form of the crystal grains, so that the pore structure of the alumina powder is improved, the pore structure of the powder is integrally improved, particularly, the pore which is less than 10nm and is not beneficial to macromolecular diffusion is partially improved to be more than 10nm after hole expansion, and the macroporous content of the carrier is further improved.
(2) The pseudoboehmite powder is roasted to form alumina powder, and then the pseudoboehmite with high peptization index is used as a binder to extrude and form the alumina powder, and the pseudoboehmite is roasted to be transformed into alumina, so that the strength of the powder is enhanced, the damage to the pore channel structure of the powder caused by extrusion can be reduced during extrusion and formation, and the content of macropores of a final carrier is improved; in addition, the peptizing agent and the alumina powder have weaker action, so that the hole killing effect of the peptizing agent is reduced, and the content of macropores of the carrier is further improved.
Detailed Description
The technical solutions and effects of the present invention are further described below with reference to the following examples, but the present invention is not limited to the following examples.
The BET method: application N2Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N2And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 100nm is obtained according to a BJH model.
The properties of the pseudoboehmite A1 used in the method of the invention are as follows: the pore volume is 0.73mL/g, the specific surface area is 215m2Per g, a minor pore diameter of 12.5 nm.
The properties of the pseudoboehmite A2 used in the method of the invention are as follows: the pore volume is 0.81mL/g, the specific surface area is 246m2A few pore diameters of 15nm per g.
The properties of the pseudoboehmite B used in the method of the invention are as follows: the pore volume is 1.3mL/g, the specific surface area is 320m2A few pores of 30nm in diameter/g.
The peptization index of the pseudoboehmite D used in the method is 87%, and the measurement method of the peptization index is as follows: weighing 5g of pseudo-boehmite (dry basis) screened by a sieve with a size less than 200 meshes, placing the pseudo-boehmite into a 250mL conical flask, adding an appropriate amount of distilled water, starting electromagnetic stirring, adding an appropriate amount of hydrochloric acid, continuously stirring for a certain time, standing and settling for 24 hours, pouring out upper suspension, drying, roasting, weighing the residual sample mass as w, and the peptization index = (5-w)/5 × 100%.
Example 1
Weighing a proper amount of pseudoboehmite A1 and pseudoboehmite B, and controlling the molar ratio of the pseudoboehmite A1 to the pseudoboehmite B to be 1: 1.5, uniformly mixing the materials, adding a proper amount of ammonium chloride into the mixed material, and controlling the molar ratio of ammonium ions to aluminum elements to be 1: 12, uniformly mixing the materials, and then placing the mixture into a high-temperature furnace to bake for 6 hours at 750 ℃ to obtain the alumina powder C1.
Weighing a proper amount of alumina powder C1 and pseudo-boehmite D, and controlling the molar ratio of the pseudo-boehmite D to the alumina powder C1 to be 1: and 5, adding a proper amount of sesbania powder into the materials, uniformly mixing, adding a proper amount of 1.5 mass percent nitric acid aqueous solution into the mixture, uniformly kneading, extruding into strips, drying the formed product at 120 ℃ for 4 hours, and roasting at 600 for 4 hours to obtain the alumina carrier S1, wherein the properties of the carrier are shown in Table 1.
Example 2
As in example 1, except that the molar ratio of pseudoboehmite a1 to pseudoboehmite B was 1: 2.5, the molar ratio of ammonium ions to aluminum elements is 1: 8, the powder roasting temperature is 700 ℃, and the molar ratio of the pseudo-boehmite D to the alumina powder is 1: 5.5, preparing an alumina carrier S2, the properties of which are shown in Table 1.
Example 3
As in example 1, except that the molar ratio of pseudoboehmite a1 to pseudoboehmite B was 1: 2, the molar ratio of ammonium ions to aluminum elements is 1: 16, the powder roasting temperature is 800 ℃, and the molar ratio of the pseudo-boehmite D to the alumina powder is 1: 4.5, preparing an alumina carrier S3, the properties of which are shown in Table 1.
Example 4
Similar to example 1 except that pseudoboehmite A1 was changed to A2, the molar ratio of pseudoboehmite A2 to pseudoboehmite B was 1: 2.75, the molar ratio of ammonium ions to aluminum elements is 1: 5, the powder roasting temperature is 600 ℃, and the molar ratio of the pseudo-boehmite D to the alumina powder is 1: 6, an alumina carrier S4 was prepared, the properties of which are shown in Table 1.
Comparative example 1
Comparative alumina S5 was prepared as in example 1 except that the mixed pseudoboehmite was not added with ammonium chloride, and the support properties are shown in Table 1.
Comparative example 2
Comparative alumina S6 was prepared as in example 4 except that the mixed pseudoboehmite was not added with ammonium chloride, and the support properties are shown in Table 1.
Comparative example 3
Similar to example 1, only pseudoboehmite A1 was used alone as the raw material, and no ammonium chloride was added to the material to prepare a comparative alumina support S7, the properties of which are shown in Table 1.
Comparative example 4
Similar to example 1, only pseudoboehmite A1 was used alone as a raw material, and the same amount of ammonium chloride was added to the material to prepare a comparative alumina support S8, the properties of which are shown in Table 1.
Comparative example 5
Similar to example 1, except that pseudo-boehmite B was used alone as a raw material and ammonium chloride was not added to the material, comparative alumina support S9 was prepared, and the support properties are shown in Table 1.
Comparative example 6
Similar to example 1, only pseudoboehmite B was used alone as a raw material, and the same amount of ammonium chloride was added to the material to prepare a comparative alumina support S10, the properties of which are shown in Table 1.
TABLE 1 Properties of the alumina Supports
Figure 859493DEST_PATH_IMAGE001
As can be seen from Table 1, the alumina carrier prepared by the method of the present invention can simultaneously give consideration to the pore contents of 10-20nm and 20-60nm, i.e., the content of 10-20nm pore is ensured to be higher while the content of 20-60nm pore is also relatively higher. In contrast, in comparative examples 1 and 2, when ammonium chloride was not added, no pore-enlarging substance was present in the carrier, and therefore, the content of pores of 10 to 20nm and 20 to 60nm in the carrier was lower than that of the carrier of examples. When a single pseudoboehmite is used as a raw material, no matter ammonium chloride is added or not added (although the pore diameter of the carrier can be improved by adding the ammonium chloride), for example, in comparative examples 3 to 6, the prepared carrier can not simultaneously take account of the pore contents of 10-20nm and 20-60 nm.

Claims (10)

1. The preparation method of the macroporous alumina carrier is characterized by comprising the following steps: (1) uniformly mixing a proper amount of pseudo-boehmite powder A and pseudo-boehmite powder B; (2) adding a proper amount of ammonium chloride into the mixed material obtained in the step (1), uniformly mixing, and then roasting to obtain alumina powder C; (3) uniformly mixing a proper amount of pseudo-boehmite D and the alumina powder C obtained in the step (2), adding a peptizing agent and an extrusion aid, uniformly kneading, extruding and forming; (4) and (4) drying and roasting the strip-shaped material obtained in the step (3) to obtain the macroporous alumina carrier.
2. The method of claim 1, wherein: the pore volume of the pseudoboehmite A in the step (1) is 0.5-1.0mL/g, and the specific surface area is 150-300m2A few pores of 9-17.5nm in diameter/g.
3. The method of claim 1, wherein: the pore volume of the pseudoboehmite B in the step (1) is 0.8-1.5mL/g, and the specific surface area is 200-350m2A few pores of 20-40nm in diameter/g.
4. The method of claim 1, wherein: the molar ratio of the pseudo-boehmite A to the pseudo-boehmite B in the step (1) calculated by aluminum elements is 1: 1-1: 3.
5. the method of claim 1, wherein: the ammonium chloride in the step (2) is solid powder, and the molar ratio of the added amount of the ammonium chloride calculated by ammonium ions to the mixed material calculated by aluminum elements is 1: 18-1: 4.5, preferably 1: 10-1: 5.
6. the method of claim 1, wherein: the roasting conditions in the step (2) are as follows: the calcination temperature is 500-850 deg.C, preferably 650-800 deg.C, and the calcination time is 1-10 hr, preferably 4-8 hr.
7. The method of claim 1, wherein: the pseudoboehmite D in the step (3) is pseudoboehmite with the peptization index of more than 75 percent, and preferably pseudoboehmite with the peptization index of more than 85 percent.
8. The method of claim 1, wherein: the molar ratio of the pseudo-boehmite D to the alumina powder C in the step (3) is 1: 4-1: 6, both in terms of alumina.
9. The method of claim 1, wherein: the peptizing agent in the step (3) is a mixed aqueous solution of one or more of nitric acid, hydrochloric acid, citric acid, acetic acid or oxalic acid, and the mass percentage concentration of the solution is 1-3 wt%; the extrusion aid is one or more of sesbania powder, methyl cellulose and graphite; the adding amount is 1-3% of the weight of the alumina.
10. The method of claim 1, wherein: the drying temperature in the step (4) is 80-160 ℃, and the drying time is 4-10 hours; the roasting temperature is 500-800 ℃, and the roasting time is 4-10 hours.
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