CN114452966A - Preparation method of macroporous alumina - Google Patents

Preparation method of macroporous alumina Download PDF

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Publication number
CN114452966A
CN114452966A CN202011135395.8A CN202011135395A CN114452966A CN 114452966 A CN114452966 A CN 114452966A CN 202011135395 A CN202011135395 A CN 202011135395A CN 114452966 A CN114452966 A CN 114452966A
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alumina
pseudo
boehmite
roasting
hours
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CN114452966B (en
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翁延博
季洪海
袁胜华
隋宝宽
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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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Abstract

The invention discloses a preparation method of macroporous alumina. The preparation method of the macroporous alumina comprises the following steps: (1) dipping and treating an alumina precursor by using ammonium chloride aqueous solution with proper concentration; (2) roasting the material obtained in the step (1) to prepare macroporous alumina; wherein the alumina precursor is pseudo-boehmite with the peptization index lower than 85 percent. The method disclosed by the invention is simple in operation process and obvious in pore-expanding effect, the content of 10-30nm pore channels in the alumina can be effectively improved, and the obtained macroporous alumina can be applied to the fields of macromolecule catalysis, macromolecule adsorption and the like.

Description

Preparation method of macroporous alumina
Technical Field
The invention relates to the field of inorganic material preparation, in particular to a preparation method of macroporous alumina.
Background
Activated alumina is a porous material with excellent physical and chemical properties and is widely used as a catalyst or a carrier. The pore structure of the alumina carrier not only influences the dispersion degree of the loaded active components, but also is closely related to the activity, selectivity, service life and the like of the catalyst. With the increasing weight of crude oil, the traditional small-pore alumina can not meet the production requirements, and the research and development and production of mesoporous and macroporous active alumina are increasingly important.
CN104340997A discloses a method for preparing large-aperture alumina, which comprises dissolving boehmite, pseudo-boehmite or a mixture of boehmite and pseudo-boehmite in an arbitrary proportion in deionized water to form an aluminum hydroxide suspension; heating treatment in sections; carrying out hydrothermal aging on the treated aluminum hydroxide suspension; and drying and roasting after aging to finally obtain the alumina product with large pore diameter.
CN105600810A discloses a preparation method of a macroporous alumina material, which comprises the steps of mixing and stirring carbon black and alkali liquor, preparing an aluminum salt solution, mixing and stirring the carbon black obtained by filtering and drying and the aluminum salt solution, carrying out ultrasonic treatment, adding ammonium salt, drying the mixture, and finally sequentially placing the mixture in nitrogen, oxygen and nitrogen atmospheres for treatment to obtain alumina.
CN102795647A discloses a macroporous alumina and a preparation method thereof, the alumina is prepared by a two-stage aging method, the first stage aging is carried out after adding an alkaline compound or an acidic compound into an aluminum hydroxide suspension to adjust the pH value of the suspension, the second stage aging is carried out after adding fatty alcohol, after aging is finished, the fatty alcohol is separated out, and the slurry without the fatty alcohol is dried and roasted to obtain the macroporous alumina.
Dumingxian et al (Dumingxian, Dianxianzhen, Li Yuan, Li Lindong, Zhuhua Qing, Tan Changyu, influence of precipitation conditions, preparation of alumina with high specific surface area and narrow pore distribution I, catalytic academy 2002, 23(5): 465 and 468.) adopt a pH swing method to prepare alumina with higher specific surface area and higher macroporous content.
Researches find that the alumina with higher macroporous content can be prepared by adopting the technology, but the preparation process is complex and the industrial production is not easy to realize.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of macroporous alumina. The method adopts a simple hole expanding technology, can effectively improve the pore channel content of 10-30nm in the alumina, and simultaneously reduces the pore channel content below 10nm, and the obtained macroporous alumina can be applied to the fields of macromolecule catalysis, macromolecule adsorption and the like.
The preparation method of the macroporous alumina comprises the following steps:
(1) soaking an alumina precursor by using ammonium chloride aqueous solution with proper concentration, carrying out solid-liquid separation, and drying;
(2) and (2) roasting the solid-phase material obtained in the step (1) to obtain macroporous alumina powder or a macroporous alumina molded carrier.
In the method of the present invention, the alumina precursor in step (1) is pseudoboehmite powder with a peptization index of less than 85% or a molded product prepared from the powder, and preferably, the peptization index is less than 80%.
In the method, the forming object preparation in the step (1) is a material prepared by taking pseudo-boehmite powder with the peptization index lower than 85% as a raw material and performing mixing kneading, forming and drying. The kneading and forming process is that a proper amount of pseudo-boehmite and a proper amount of sesbania powder are uniformly mixed, then a proper amount of peptizing agent aqueous solution with a proper concentration is added, the peptizing agent aqueous solution is one or a mixture of nitric acid, hydrochloric acid, citric acid, acetic acid and oxalic acid, the mass concentration of the solution is 1-3%, and the adding amount is determined according to the forming effect. The drying temperature is 80-160 ℃, and the drying time is 1-10 hours.
In the method, the concentration of the ammonium chloride solution in the step (1) is 2-7.5mol/L, preferably 3-6mol/L, the solution is used in an amount that the pseudo-boehmite powder or the pseudo-boehmite forming product is completely immersed, and the immersion time is 0.5-3 hours, preferably 2-3 hours.
In the method of the invention, the solid-liquid separation in the step (1) generally adopts filtration, centrifugation and other modes, and the separated liquid phase can be recycled after concentration adjustment.
In the method of the invention, the drying conditions in the step (1) are as follows: the drying temperature is 80-200 ℃, preferably 100-160 ℃, and the drying time is 1-10 hours, preferably 4-8 hours.
In the method, the roasting conditions in the step (2) are as follows: the calcination temperature is 500-850 ℃, preferably 650-800 ℃, and the calcination time is 1-10 hours, preferably 4-8 hours. The roasting process has no special requirement on roasting atmosphere, and the roasting is generally carried out in the air atmosphere, and can also be carried out in the inert atmosphere and/or the oxygen atmosphere.
The invention also provides a hydrogenation catalyst, which comprises the macroporous alumina forming carrier prepared by the method or the alumina carrier prepared by the macroporous alumina powder.
The hydrogenation catalyst is applied to the hydrogenation process of heavy oil, and is particularly suitable for hydrogenation processes of hydrodemetallization, desulfurization, denitrification and the like of the heavy oil.
Compared with the prior art, the invention has the following advantages:
(1) the invention uses ammonium chloride aqueous solution to dip pseudo-boehmite, and the dipped pseudo-boehmite is dried and roasted to prepare alumina. During dipping, substances such as chloride ions, ammonium ions, water molecules and the like are uniformly distributed on the surface of the pseudo-boehmite crystal grain and in the lamellar structure. When the impregnated pseudo-boehmite is roasted at a high temperature, the ammonium chloride solution is heated and decomposed to generate ammonia gas, hydrogen chloride and water vapor, and the generated gas can play a role in punching on one hand; on the other hand, as the alumina is amphoteric oxide, the generated ammonia gas and hydrogen chloride gas can react with the alumina crystal grains to change the size and the accumulation form of the crystal grains, thereby improving the pore channel structure of the alumina material and increasing the content of macropores in the carrier.
(2) The method has simple process, easily obtained raw materials, and easy industrialized production.
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 peptization index DI of the pseudo-boehmite is determined according to the following method: 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, and weighing the residual sample mass as w, DI = (5-w)/5 × 100%.
The peptization index DI of the pseudoboehmite A1 used in the process of the invention was 82%, and the peptization index DI of the pseudoboehmite A2 was 78%.
Example 1
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 4.5mol/L to completely immerse the pseudo-boehmite, immersing the immersed material for 2 hours, carrying out liquid-solid separation, drying the solid material for 6 hours at 120 ℃, placing the dried material in a muffle furnace for roasting at 700 ℃ for 6 hours in an air atmosphere, and obtaining the alumina S1, wherein the properties of the carrier are shown in Table 1.
Example 2
Weighing a proper amount of pseudo-boehmite A2, adding a proper amount of ammonium chloride solution with the molar concentration of 3.5mol/L to completely immerse the pseudo-boehmite, immersing the immersed material for 2 hours, carrying out liquid-solid separation, drying the solid material for 5 hours at 140 ℃, placing the dried material in a muffle furnace for roasting at 750 ℃ for 4 hours under the nitrogen atmosphere, and obtaining the alumina S2, wherein the properties of the carrier are shown in Table 1.
Example 3
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 2.5mol/L to completely immerse the pseudo-boehmite, immersing the immersed material for 2 hours, carrying out liquid-solid separation, drying the solid material for 4 hours at 160 ℃, placing the dried material in a muffle furnace at 800 ℃, and roasting for 6 hours under the oxygen atmosphere to obtain the alumina S3, wherein the properties of the carrier are shown in Table 1.
Example 4
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 5.5mol/L to completely immerse the pseudo-boehmite, immersing the immersed material for 2 hours, carrying out liquid-solid separation, drying the solid material for 7 hours at 100 ℃, placing the dried material in a muffle furnace at 650 ℃, and roasting for 7 hours in an air atmosphere to obtain the alumina S4, wherein the properties of the carrier are shown in Table 1.
Example 5
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of ammonium chloride solution with the molar concentration of 2.5mol/L to completely immerse the pseudo-boehmite, immersing the immersed material for 2 hours, carrying out liquid-solid separation, drying the solid material for 3 hours at 180 ℃, placing the dried material in a muffle furnace for roasting at 700 ℃ for 6 hours in an air atmosphere, and obtaining the alumina S5, wherein the properties of the carrier are shown in Table 1.
Example 6
Weighing a proper amount of pseudo-boehmite A1, adding a proper amount of sesbania powder, controlling the mass of the sesbania powder to be 1% of the mass of the pseudo-boehmite A1, uniformly mixing the materials, adding a proper amount of nitric acid aqueous solution with the mass concentration of 1%, uniformly mixing and kneading, extruding into strips, and drying the formed strip-shaped materials at 120 ℃ for 6 hours to obtain the pseudo-boehmite forming product.
Weighing a proper amount of the pseudo-boehmite forming matter, then adding a proper amount of ammonium chloride solution with the molar concentration of 4.5mol/L to completely immerse the pseudo-boehmite forming matter, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material for 6 hours at 120 ℃, placing the dried material in a muffle furnace, roasting at 700 ℃ for 6 hours in air atmosphere, and obtaining the alumina carrier S6, wherein the carrier property is shown in Table 1.
Example 7
Weighing a proper amount of pseudo-boehmite A2, adding a proper amount of sesbania powder, controlling the mass of the sesbania powder to be 1% of the mass of the pseudo-boehmite A1, uniformly mixing the materials, adding a proper amount of nitric acid aqueous solution with the mass concentration of 1%, uniformly mixing and kneading, extruding into strips, and drying the formed strip-shaped materials at 120 ℃ for 6 hours to obtain the pseudo-boehmite forming product.
Weighing a proper amount of the pseudo-boehmite forming matter, then adding a proper amount of ammonium chloride solution with the molar concentration of 4.5mol/L to completely immerse the pseudo-boehmite forming matter, immersing the immersed material for 2 hours, then carrying out liquid-solid separation, drying the solid material for 6 hours at 120 ℃, placing the dried material in a muffle furnace, roasting at 700 ℃ for 6 hours in air atmosphere, and obtaining the alumina carrier S7, wherein the carrier property is shown in Table 1.
Comparative example 1
Similar to example 1, except that ammonium chloride was not added to pseudo-boehmite A1, the pseudo-boehmite was directly calcined to prepare comparative alumina S8, and the properties of the support are shown in Table 1.
Comparative example 2
Similar to example 1, except that ammonium chloride was not added to pseudo-boehmite A2, the pseudo-boehmite was directly calcined to prepare comparative alumina S9, and the properties of the support are shown in Table 1.
Comparative example 3
Comparative alumina S10 was prepared as in example 1 except that ammonium chloride was replaced with ammonium fluoride at the same molar concentration and the support properties are shown in Table 1.
Comparative example 4
Comparative alumina S11 was prepared as in example 1 except that ammonium chloride was replaced with ammonium citrate at the same molar concentration and the support properties are shown in Table 1.
Comparative example 5
In the same way as example 6, except that the pseudo-boehmite forming product is not impregnated with ammonium chloride solution, the pseudo-boehmite forming product is prepared and calcined to prepare a comparative alumina carrier S12, and the carrier properties are shown in Table 1.
Comparative example 6
Comparative alumina support S13 was prepared as in example 6 except that ammonium chloride was replaced with ammonium fluoride at the same molar concentration and the support properties are shown in Table 1.
Comparative example 7
In the same way as example 7, except that the pseudo-boehmite formed product was not subjected to impregnation treatment with ammonium chloride solution, the pseudo-boehmite formed product was prepared and calcined to prepare a comparative alumina support S14, and the properties of the support are shown in Table 1.
Table 1 alumina properties.
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
Alumina carrier S1 S2 S3 S4 S5 S6 S7
Specific surface area, m2/g 212 230 204 221 213 181 209
Pore volume, mL/g 0.80 0.86 0.79 0.79 0.81 0.73 0.83
Pore distribution, v%
<10nm，% 34.8 32.4 36.2 35.7 38.5 41.1 37.8
10-30nm，% 56.4 62.8 55.7 55.3 53.6 54.6 58.6
>30nm，% 8.8 4.8 8.1 8.0 7.9 4.3 3.6
Table 1 (continuous) alumina properties.
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7
Alumina carrier S8 S9 S10 S11 S12 S13 S14
Specific surface area, m2/g 217 241 146 228 183 151 215
Pore volume, mL/g 0.81 0.86 0.61 0.81 0.72 0.60 0.82
Pore distribution, v%
<10nm，% 45.7 41.2 39.6 50.1 48.3 44.2 45.8
10-30nm，% 48.6 55.6 52.5 45.8 47.6 50.1 51.6
>30nm，% 5.7 3.2 7.9 4.1 4.1 5.7 2.6
As can be seen from Table 1, the alumina prepared by the method of the present invention after the pseudo-boehmite is impregnated with the ammonium chloride solution has a reduced pore channel content of less than 10nm compared with the untreated alumina, and the pore channel contents of 10-30nm and more than 30nm are increased, which shows that the treatment method has the effect of increasing the pore diameter of the alumina. When ammonium fluoride solution is added, the pore volume and specific surface area of the carrier are seriously damaged. The pore size of the support was reduced after addition of ammonium citrate solution.

Claims (10)

1. The preparation method of the macroporous alumina is characterized by comprising the following steps: (1) soaking an alumina precursor by using ammonium chloride aqueous solution with proper concentration, carrying out solid-liquid separation, and drying; (2) roasting the solid-phase material obtained in the step (1) to obtain macroporous alumina powder or a macroporous alumina molded carrier; the alumina precursor is pseudo-boehmite powder with the peptization index lower than 85 percent or a forming object prepared from the powder.
2. The method of claim 1, wherein: the alumina precursor is pseudo-boehmite powder with the peptization index lower than 80 percent or a forming object prepared from the powder.
3. The method of claim 1, wherein: the forming object preparation in the step (1) is a material prepared by taking pseudo-boehmite powder with a peptization index lower than 85% as a raw material, and performing mixing kneading, forming and drying.
4. The method of claim 1, wherein: the concentration of the ammonium chloride solution in the step (1) is 2-7.5mol/L, the dosage of the solution is to completely immerse the pseudo-boehmite powder or the pseudo-boehmite forming matter, and the immersion time is 0.5-3 hours.
5. The method of claim 1, wherein: the concentration of the ammonium chloride solution in the step (1) is 3-6 mol/L.
6. The method of claim 1, wherein: the drying conditions in the step (1) are as follows: the drying temperature is 80-200 deg.C, and the drying time is 1-10 hr.
7. The method of claim 1, wherein: the roasting conditions in the step (2) are as follows: the roasting temperature is 500-850 ℃, and the roasting time is 1-10 hours.
8. The method of claim 1, wherein: the roasting conditions in the step (2) are as follows: the roasting temperature is 650-800 ℃, and the roasting time is 4-8 hours.
9. A hydrogenation catalyst characterized by: the catalyst comprises a macroporous alumina molded carrier or macroporous alumina powder prepared by the method of any one of claims 1 to 7.
10. Use of a hydrogenation catalyst according to claim 9 in a heavy oil hydrogenation process.
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