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 PDFInfo
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 61
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 55
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 55
- 239000004005 microsphere Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 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 17
- 238000011282 treatment Methods 0.000 claims abstract description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007921 spray Substances 0.000 claims abstract description 9
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 25
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 239000006078 metal deactivator Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
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- 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
- 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
-
- 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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
- 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
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- 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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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
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
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
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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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
WO2008129034A1 (en) * | 2007-04-20 | 2008-10-30 | Euro Support Catalyst Group Bv | Hydrotalcite-like layered double hydroxide (ldh) composition and process of making same |
CN104226235A (en) * | 2013-06-14 | 2014-12-24 | 中国石油化工股份有限公司 | Metal trapping agent and catalytic cracking method |
CN107115853A (en) * | 2017-05-15 | 2017-09-01 | 中国海洋石油总公司 | Mg Al houghite catalyst for handling residual oil and extra heavy oil raw material and preparation method thereof |
CN113233481A (en) * | 2021-06-24 | 2021-08-10 | 潍坊正轩稀土催化材料有限公司 | Petal-shaped macroporous hydrotalcite material, preparation method and application thereof, mixed metal oxide and preparation method thereof |
-
2022
- 2022-03-30 CN CN202210334095.5A patent/CN114835147B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101049953A (en) * | 2007-01-12 | 2007-10-10 | 北京化工大学 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
WO2008129034A1 (en) * | 2007-04-20 | 2008-10-30 | Euro Support Catalyst Group Bv | Hydrotalcite-like layered double hydroxide (ldh) composition and process of making same |
CN104226235A (en) * | 2013-06-14 | 2014-12-24 | 中国石油化工股份有限公司 | Metal trapping agent and catalytic cracking method |
CN107115853A (en) * | 2017-05-15 | 2017-09-01 | 中国海洋石油总公司 | Mg Al houghite catalyst for handling residual oil and extra heavy oil raw material and preparation method thereof |
CN113233481A (en) * | 2021-06-24 | 2021-08-10 | 潍坊正轩稀土催化材料有限公司 | Petal-shaped macroporous hydrotalcite material, preparation method and application thereof, mixed metal oxide and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
花球状镁铝复合氧化物负载Ni⁃Co催化剂的合成 及正十二烷水蒸气重整制氢;肖周荣;《无机化学学报》;第37卷(第4期);第629-637页 * |
镁铝水滑石衍生复合氧化物的 COS 水解性能;魏征;《环境科学》;第40卷(第10期);第4423-4430页 * |
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