CN114835147B - Hydrotalcite microsphere with flake structure, and preparation method and application thereof - Google Patents

Hydrotalcite microsphere with flake structure, and preparation method and application thereof Download PDF

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CN114835147B
CN114835147B CN202210334095.5A CN202210334095A CN114835147B CN 114835147 B CN114835147 B CN 114835147B CN 202210334095 A CN202210334095 A CN 202210334095A CN 114835147 B CN114835147 B CN 114835147B
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hydrotalcite
microsphere
flake
slurry
flake structure
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CN114835147A (en
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施宗波
张青
卓润生
刘新生
钟嘉兴
李邵洪
彭飞
胡泽松
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Shanghai Runhe Kehua Engineering Design Co ltd
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Runhe Kehua Catalyst Shanghai Co ltd
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract

The invention discloses a hydrotalcite microsphere with a flake structure and a preparation method thereof, wherein the hydrotalcite microsphere with the flake structure has a hydrotalcite crystal structure, the average granularity of the hydrotalcite microsphere with the flake structure is 65-85 mu m, the primary structure of the hydrotalcite microsphere with the flake structure is a hydrotalcite flake, and the thickness of the hydrotalcite flake is 20-50nm, and the method comprises the following steps: adding 0.75-0.82 weight part of alumina into an acidic solution, and mixing to form slurry A; adding 0.45-1.2 parts by weight of magnesium oxide into water to form slurry B; mixing the slurry A and the slurry B, and then sequentially carrying out spray granulation and roasting to obtain a hydrotalcite microsphere precursor with a sheet structure; carrying out steam treatment, filtration and drying on the hydrotalcite microsphere precursor with the flake structure at the temperature of 100-180 ℃ to obtain hydrotalcite microsphere with the flake structure; has good effect of passivating nickel and vanadium, prolongs the service life of the catalyst, improves the conversion rate, reduces the yield of slurry oil and improves the total liquid yield.

Description

Hydrotalcite microsphere with flake structure, and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysis, in particular to hydrotalcite microspheres with a sheet structure, and a preparation method and application thereof.
Background
The layered double hydroxide is a layered double mixed hydroxide, which is a generic term of hydrotalcite and hydrotalcite-like compounds, and can be used as an alkaline catalyst, an oxidation-reduction catalyst and a catalyst carrier, such as a catalyst for hydrogenation, reforming, cracking, polycondensation, polymerization and other reactions, because the layered double hydroxide has unique structural characteristics.
CN201010221354.0 describes hydrotalcite to help reduce sulfur transfer in flue gas, CN200480039856.4 uses hydrotalcite-like compounds to reduce gasoline sulfur, CN201510109946.6 describes hydrotalcite to reduce NO in catalytic cracking regeneration flue gas x The emission and CO combustion-supporting function. CN201710338271.1 describes a combined catalytic cracking process for treating resid and extra heavy oil, hydrotalcite helps to reduce coke production in the cracked product, and hydrotalcite is added to the FCC catalyst to form an integral body. Patent CN201510109947.0 discloses a catalytic cracking regenerated flue gas sulfur transfer auxiliary agent and a preparation method thereof, and magnesia-alumina spinel (MgAl) is prepared by adopting a coprecipitation method 2 O 4 ) And combining Mn, rare earth and copper to obtain the FCC regenerated flue gas sulfur transfer agent.
CN201811425042.4 discloses a catalytic cracking regenerated flue gas desulfurization catalyst and a preparation method thereof, wherein a mixed solution prepared from magnesium salt and aluminum salt is slowly dripped into a mixed solution prepared from sodium hydroxide and sodium carbonate, after dripping is completed, stirring reaction is performed to nucleate and crystallize, magnesia-alumina spinel is obtained, and after drying, roasting is performed to obtain the catalytic cracking regenerated flue gas desulfurization catalyst.
CN201510108402.8 discloses an auxiliary agent for removing catalytic cracking regenerated flue gas pollutant and its preparation method, which is prepared by modifying magnesia-alumina spinel, layered double metal hydroxide and pseudo-boehmite with rare earth element, adding binder to form slurry with high solid content, spray forming, drying, roasting to obtain auxiliary agent carrier with high hydrothermal stability, immersing noble metal by isovolumetric impregnation method, and roasting again.
Magnesium oxide is also used to deactivate heavy metals in catalytic cracking processes, CN201080050059.1 discloses the use of kaolin, magnesium oxide or mixtures of magnesium hydroxide and calcium carbonate to improve metal deactivation during FCC cracking.
The existing hydrotalcite series vanadium-resistant and nickel-resistant auxiliary agent has high abrasion index, low exposed MgO content, small specific surface area, insufficient performance of passivating vanadium and nickel and small specific surface area of magnesium oxide passivating agent.
Disclosure of Invention
Aiming at the problems of the existing magnesium oxide passivating agent and hydrotalcite passivating agent, the invention provides a preparation method of hydrotalcite microspheres with a flake structure, which comprises the following steps:
adding 0.75-0.82 weight part of alumina into an acidic solution, and mixing to form slurry A;
adding 0.45-1.2 parts by weight of magnesium oxide into water to form slurry B;
mixing the slurry A and the slurry B, and then sequentially carrying out spray granulation and roasting to obtain a hydrotalcite microsphere precursor with a sheet structure;
carrying out steam treatment, filtration and drying on the hydrotalcite microsphere precursor with the flake structure at the temperature of 100-180 ℃ to obtain the hydrotalcite microsphere with the flake structure;
the hydrotalcite microsphere with the flake structure has a hydrotalcite crystal structure, the average granularity of the hydrotalcite microsphere with the flake structure is 65-85 mu m, the primary structure of the hydrotalcite microsphere with the flake structure is hydrotalcite flakes, and the thickness of the hydrotalcite flakes is 20-50 nm.
Further defined, the acidic solution is one or a combination of several of nitric acid, formic acid or acetic acid.
Further defined, the acidic solution comprises 0.25 to 0.35 parts by weight of solute.
Further defined, the firing temperature in the firing process is 550 to 650 ℃.
Further defined, the firing temperature during the firing is 600 ℃.
Further defined, the parts by weight of alumina and magnesia are 0.8 and 0.65, respectively.
Further defined, the alumina is derived from pseudo-boehmite and/or aluminum carbonate.
Further defined, the temperature of the water vapor is 120 ℃.
The beneficial effects of the invention are as follows: according to the invention, the hydrotalcite microsphere precursor with a sheet structure is subjected to steam treatment, so that more MgO is exposed, the specific surface area is large, a plurality of gaps are formed on the surface, more nickel and vanadium are contained, and the vanadium resistance and nickel resistance are good.
The hydrotalcite microsphere with the flake structure prepared by the invention has the advantages that the index of the micro ball milling loss of the hydrotalcite microsphere is less than or equal to 3, the hydrotalcite microsphere has a hydrotalcite structure, the average granularity (D50) is in the range of 65-85 mu m, the primary structure of the hydrotalcite microsphere with the flake structure is hydrotalcite flakes, the thickness of the hydrotalcite flakes is 20-50nm, the surface of the flakes is rich in a large number of secondary pore channels smaller than 10nm, the performance requirement of a catalytic cracking auxiliary agent is met, the auxiliary agent is ensured to stay in the catalytic cracking device for a long time, and the conversion rate of residual oil and the total liquid yield can be obviously improved when the auxiliary agent is used in the catalytic cracking process.
Drawings
FIG. 1 is an XRD pattern of the products prepared in examples 1-6 and comparative examples 1-2;
FIG. 2 is a SEM photograph (100K) of the product prepared in comparative example 1;
FIG. 3 is an SEM photograph (10K) of the product prepared according to comparative example 1;
FIG. 4 is an SEM photograph (1K) of the product prepared in comparative example 1;
FIG. 5 is a SEM photograph (100K) of the product prepared in comparative example 2;
FIG. 6 is an SEM photograph (10K) of the product prepared according to comparative example 2;
FIG. 7 is an SEM photograph (1K) of the product prepared in comparative example 2;
FIG. 8 is a SEM photograph (100K) of the product prepared according to example 1;
FIG. 9 is a SEM photograph (50K) of the product prepared according to example 1;
FIG. 10 is an SEM photograph (1K) of the product prepared in example 1;
FIG. 11 is a SEM photograph (100K) of the product prepared according to example 2;
FIG. 12 is an SEM photograph (10K) of the product prepared according to example 2;
fig. 13 is an SEM picture (1K) of the product prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, comparative examples, and accompanying drawings.
In each example, the BET low temperature nitrogen adsorption method was used to measure the specific surface area of the sample, the X-ray fluorescence spectrometer was used to measure the elemental composition (normalization result) of the sample, and the wear index analyzer was used to measure the wear index of the sample.
The catalytic cracking reactions of the samples in examples and comparative examples were evaluated on a micro-fluidized bed reactor (ACE) and a mating gas chromatograph, and the Research Octane Number (RON) was analyzed using a gas chromatograph 7980A from Agilent corporation. Samples of the examples and comparative examples were impregnated 6000ppm Ni,4000ppm V by the isovolumetric impregnation method, aged for 10 hours at 810℃with 100% steam, and then subjected to catalytic cracking performance evaluation on an ACE apparatus. The catalytic cracking reaction temperature is 540 ℃, the oil inlet speed is 1.2g/min, the oil inlet time is 1.5min, and the catalyst-to-oil ratio is 5. The feed is hydrogenated vacuum residuum.
For other tests, see (national Standard for Petroleum and Petroleum products testing methods, chinese Standard Press publication 1989).
Comparative example 1:
pseudo-boehmite (containing 0.8kg of alumina) was added to 6kg of water, and 0.3kg of nitric acid was added under stirring, and marked as slurry A1.
0.65kg MgO is dispersed in 0.9kg water and marked as slurry B1.
A1 and B1 are mixed and homogenized for 2 hours under stirring, then spray-formed and baked for 2 hours at 600 ℃.
The calcined sample was added with 20 times the weight of water, stirred at 60 ℃ for 1 hour, filtered and dried. Obtaining the metal passivator D1.
The Mg/Al (atomic number) ratio, specific surface area, abrasion index and particle size distribution of D1 are shown in Table 2, and XRD diffraction pattern is shown in FIG. 1.
After mixing 6% d1 into the FCC catalyst, 6000ppm Ni,4000ppm V was impregnated by the isovolumetric impregnation method, and further aged by 100% steam at 810 ℃ for 10 hours, and then the catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
Comparative example 2:
pseudo-boehmite (containing 0.8kg of alumina in 6kg of water, 0.3kg of nitric acid with stirring, marked as slurry A2.
0.65kg MgO was dispersed in 0.9kg water and labeled as slurry B2.
A2 and B2 are mixed and homogenized for 2 hours under the stirring condition, then spray-formed and baked for 2 hours at 600 ℃.
The calcined sample was subjected to steam treatment at 60℃for 12 hours. Obtaining the metal passivator D2.
The Mg/Al ratio, specific surface area, abrasion index and particle size distribution of D2 are shown in Table 2, and XRD diffraction pattern is shown in figure 1.
After mixing 6% d2 into the FCC catalyst, 6000ppm Ni,4000ppm V was impregnated by an isovolumetric impregnation method, and further aged by 100% steam at 810 ℃ for 10 hours, and then catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
Comparative example 3:
5% alumina (designated D2) was mixed into the FCC catalyst, impregnated 6000ppm Ni,4000ppm V by the isovolumetric impregnation method, aged with 100% steam at 810℃for 10 hours, and then evaluated for catalytic cracking performance. The evaluation results are shown in Table 2.
Comparative example 4:
2% magnesium oxide (designated D3) was mixed into the FCC catalyst, impregnated 6000ppm Ni,4000ppm V by the isovolumetric impregnation method, aged with 100% steam at 810℃for 10 hours, and then evaluated for catalytic cracking performance. The evaluation results are shown in Table 2.
Example 1
Pseudo-boehmite (containing 0.8kg of alumina) was added to 6kg of water, and 0.3kg of nitric acid was added under stirring, and marked as slurry A3.
0.65kg MgO is dispersed in 0.9kg water and marked as slurry B3.
Mixing A3 and B3 under stirring, homogenizing for 2 hr, spray shaping, and calcining at 600deg.C for 2 hr.
The calcined sample was subjected to steam treatment at 100℃for 12 hours, filtered and dried. Obtaining the metal deactivator MV1.
The Mg/Al ratio, specific surface area, abrasion index and particle size distribution of MV1 are shown in Table 2, and the XRD diffraction pattern is shown in FIG. 1.
After mixing 6% MV1 into FCC catalyst and impregnating 6000ppm Ni,4000ppm V by an isovolumetric impregnation method, the catalyst was aged with 100% steam at 810℃for 10 hours, and then the catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
Example 2:
pseudo-boehmite (containing 0.8kg of alumina) was added to 6kg of water, and 0.3kg of nitric acid was added under stirring, and marked as slurry A4.
0.65kg MgO is dispersed in 0.9kg water and marked as slurry B4.
Mixing A4 and B4 under stirring, homogenizing for 2 hr, spray shaping, and calcining at 600deg.C for 2 hr.
The calcined sample was subjected to water vapor treatment at 120℃for 12 hours, filtered and dried. Obtaining the metal deactivator MV2.
The Mg/Al ratio, specific surface area, abrasion index and particle size distribution of MV2 are shown in Table 2, and the XRD diffraction pattern is shown in FIG. 1.
After mixing 6% MV2 into FCC catalyst and impregnating 6000ppm Ni,4000ppm V by an isovolumetric impregnation method, the catalyst was aged with 100% steam at 810℃for 10 hours, and then the catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
Example 3:
pseudo-boehmite (containing 0.8kg of alumina) was added to 6kg of water, and 0.3kg of nitric acid was added under stirring, and marked as slurry A5.
0.65kg MgO is dispersed in 0.9kg water and marked as slurry B5.
Mixing A5 and B5 under stirring, homogenizing for 2 hr, spray shaping, and calcining at 600deg.C for 2 hr.
The calcined sample was subjected to steam treatment at 150℃for 6 hours, filtered and dried. Obtaining the metal deactivator MV3.
The Mg/Al ratio, specific surface area, abrasion index and particle size distribution of MV3 are shown in Table 2, and the XRD diffraction pattern is shown in FIG. 1.
After mixing 6% MV3 into FCC catalyst and impregnating 6000ppm Ni,4000ppm V by an isovolumetric impregnation method, the catalyst was aged with 100% steam at 810℃for 10 hours, and then the catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
Example 4:
pseudo-boehmite (containing 0.8kg of alumina) was added to 6kg of water, and 0.3kg of nitric acid was added under stirring, and marked as slurry A6.
0.65kg MgO was dispersed in 0.9kg water and labeled as slurry B6.
Mixing A6 and B6 under stirring, homogenizing for 2 hr, spray shaping, and calcining at 600deg.C for 2 hr.
The calcined sample was subjected to steam treatment at 180℃for 2 hours, filtered and dried. Obtaining the metal deactivator MV4.
The Mg/Al ratio, specific surface area, abrasion index and particle size distribution of MV4 are shown in Table 2, and the XRD diffraction pattern is shown in FIG. 1.
After mixing 6% MV4 into FCC catalyst and impregnating 6000ppm Ni,4000ppm V by an isovolumetric impregnation method, the catalyst was aged with 100% steam at 810℃for 10 hours, and then the catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
Example 5:
pseudo-boehmite (0.8 kg alumina) was added to 6kg water and 0.3kg nitric acid was added with stirring and marked as slurry A7.
0.45kg MgO was dispersed in 0.9kg water and labeled as slurry B7.
Mixing A7 and B7 under stirring, homogenizing for 2 hr, spray shaping, and calcining at 600deg.C for 2 hr.
The calcined sample was subjected to water vapor treatment at 120℃for 12 hours, filtered and dried. Obtaining the metal deactivator MV5.
The Mg/Al ratio, specific surface area, abrasion index and particle size distribution of MV5 are shown in Table 2, and the XRD diffraction pattern is shown in FIG. 1.
After mixing 6% MV5 into FCC catalyst and impregnating 6000ppm Ni,4000ppm V by an isovolumetric impregnation method, the catalyst was aged with 100% steam at 810℃for 10 hours, and then the catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
Example 6:
pseudo-boehmite (containing 0.8kg of alumina) was added to 6kg of water, and 0.3kg of nitric acid was added under stirring, and marked as slurry A8.
1.2kg MgO was dispersed in 0.9kg water and labeled as slurry B8.
Mixing A8 and B8 under stirring, homogenizing for 2 hr, spray shaping, and calcining at 600deg.C for 2 hr.
The calcined sample was subjected to water vapor treatment at 120℃for 12 hours, filtered and dried. Obtaining the metal deactivator MV6.
The Mg/Al ratio, specific surface area, abrasion index and particle size distribution of MV6 are shown in Table 2, and the XRD diffraction pattern is shown in FIG. 1.
After mixing 6% MV6 into FCC catalyst and impregnating 6000ppm Ni,4000ppm V by an isovolumetric impregnation method, the catalyst was aged with 100% steam at 810℃for 10 hours, and then the catalytic cracking performance was evaluated. The evaluation results are shown in Table 2.
TABLE 1 elemental composition, specific surface area, wear index, particle size distribution for examples and comparative examples
Figure BDA0003573940720000091
Figure BDA0003573940720000101
As shown in Table 1, compared with water or steam at 60 ℃ (D1, D2), after the samples are subjected to water treatment at not less than 100 ℃ (MV 1, MV2, MV3, MV 4), the specific surface area is obviously increased, the abrasion indexes of the samples MV1 to MV6 obtained in the examples can be basically controlled within the range of not more than 3, the average particle size (D50) can be controlled within the range of 65-85 mu m, the performance requirements of the FCC auxiliary agent are met, and the auxiliary agent can be basically ensured to remain in the FCC device for a long time.
Table 2 shows the catalytic cracking performance of the samples of the examples and comparative examples
Figure BDA0003573940720000102
Total liquid yield = gasoline yield + diesel yield + liquefied gas yield
The reaction raw material is hydrogenated vacuum residuum, the reaction temperature is 540 ℃, and the catalyst-to-oil ratio is 5.
As shown in table 2, after the metal deactivator of example was added, the conversion rate of the sample was increased, the yields of liquefied gas and gasoline were increased, the slurry yield was decreased, and the total liquid yield of the sample was increased. The water vapor treatment temperatures of the D2, MV1, MV2 and MV3 samples are 60 ℃, 100 ℃, 120 ℃ and 150 ℃ respectively, and the conversion rate of the samples is gradually increased and the total liquid yield is also gradually increased along with the increase of the water vapor treatment temperature from 60 ℃ to 150 ℃.
As can be seen from fig. 1, after comparative example 1 (D1) and comparative example 2 (D2) were treated with water at 60 ℃ or water vapor at 60 ℃, samples D1 and D2 had no significant hydrotalcite structure; examples 1-4 had significant hydrotalcite structure in the samples after treatment with 100-180 ℃ water vapor, which demonstrates that water vapor helps to convert the magnesium aluminum mixed oxide to a hydrotalcite structure; examples 5 and 6 have different Mg/Al (atomic number) ratios from example 2, and the hydrotalcite structures are apparent after the steam treatment of examples 5 and 6.
As can be seen from FIGS. 2 to 13, the product obtained in comparative example 1, which is a directly spray-formed magnesium-aluminum mixed oxide, after being subjected to water treatment at 60℃for 1 hour, has an amorphous particle composition of 10 to 60 nm; after the sample is treated by steam at the temperature of 100 ℃ for 12 hours, a small amount of nano-sheet structures appear on the surface of the sample, after the sample is treated by steam at the temperature of 120 ℃ for 12 hours, the surface of the sample is wrapped with a layer of nano-sheet structures, the thickness of the sheet is 20-50nm, the surface of the sheet is rich in a large number of secondary pore channels smaller than 10nm, which is favorable for adsorbing more nickel and vanadium, and the passivation effect is good.
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the hydrotalcite microsphere with the flake structure is characterized by comprising the following steps of:
adding 0.75-0.82 parts by weight of aluminum oxide into an acidic solution, and mixing to form slurry A;
adding 0.45-1.2 parts by weight of magnesium oxide into water to form slurry B;
mixing the slurry A and the slurry B, and then sequentially carrying out spray granulation and roasting to obtain a hydrotalcite microsphere precursor with a sheet structure;
carrying out steam treatment, filtration and drying on the hydrotalcite microsphere precursor with the flake structure at 100-180 ℃ to obtain the hydrotalcite microsphere with the flake structure;
the hydrotalcite microsphere with the flake structure has a hydrotalcite crystal structure, the average granularity of the hydrotalcite microsphere with the flake structure is 65-85 mu m, the primary structure of the hydrotalcite microsphere with the flake structure is a hydrotalcite flake, and the thickness of the hydrotalcite flake is 20-50 nm.
2. The method for preparing hydrotalcite microsphere according to claim 1, wherein the acidic solution is one or a combination of several of nitric acid, formic acid and acetic acid.
3. The method for preparing the hydrotalcite microsphere according to claim 1, wherein the weight part of the solute in the acidic solution is 0.25 to 0.35.
4. The method for preparing the hydrotalcite microsphere with a flake structure according to claim 1, wherein the roasting temperature in the roasting process is 550-650 ℃.
5. The method for preparing hydrotalcite microsphere according to claim 4, wherein the baking temperature during said baking is 600 ℃.
6. The method for preparing hydrotalcite microsphere according to claim 1, wherein the parts by weight of the aluminum oxide and the magnesium oxide are 0.8 and 0.65, respectively.
7. The method for preparing hydrotalcite microsphere according to any one of claims 1 to 6, wherein the temperature of said water vapor is 120 ℃.
8. The method for preparing hydrotalcite microsphere according to claim 1, wherein said alumina is derived from pseudo-boehmite and/or aluminum carbonate.
9. A hydrotalcite microsphere of lamellar structure prepared by the method according to any one of claims 1 to 8.
10. Use of the hydrotalcite microsphere according to claim 9 in catalytic cracking.
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