CN114835147A - 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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- CN114835147A CN114835147A CN202210334095.5A CN202210334095A CN114835147A CN 114835147 A CN114835147 A CN 114835147A CN 202210334095 A CN202210334095 A CN 202210334095A CN 114835147 A CN114835147 A CN 114835147A
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- hydrotalcite
- flake
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- microsphere
- slurry
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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 60
- 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 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000000395 magnesium oxide Substances 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 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 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
- 239000007921 spray Substances 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
- 238000001354 calcination Methods 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
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 23
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 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
- 238000002161 passivation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000007654 immersion Methods 0.000 description 9
- 238000009718 spray deposition Methods 0.000 description 9
- 238000002791 soaking Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000006078 metal deactivator Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel 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
- 239000003502 gasoline Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- -1 magnesium aluminate Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture 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
- 239000003795 chemical substances by application Substances 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
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002060 nanoflake Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement 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
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 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
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming 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
- 238000001694 spray drying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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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
- 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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- 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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- 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
- B01J37/08—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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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 particle size 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 flake structure; treating the precursor of the hydrotalcite microsphere with the flake structure by water vapor at 100-180 ℃, filtering and drying to obtain the hydrotalcite microsphere with the flake structure; the method has good nickel and vanadium passivation effect, prolongs the service life of the catalyst, improves the conversion rate, reduces the oil slurry yield, and improves the total liquid yield.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a hydrotalcite microsphere with a flake structure and a preparation method and application thereof.
Background
The layered double hydroxide is a layered double mixed hydroxide, which is a general name of hydrotalcite and hydrotalcite-like compounds, and can be used as a basic catalyst, a redox catalyst and a catalyst carrier due to the unique structural characteristics of the layered double hydroxide, such as a catalyst for reactions such as hydrogenation, reforming, cracking, polycondensation, polymerization and the like.
CN201010221354.0 introduces hydrotalcite which is helpful for reducing sulfur transfer in flue gas, CN200480039856.4 introduces hydrotalcite compounds to reduce gasoline sulfur, and CN201510109946.6 introduces hydrotalcite which can be used for reducing NO in catalytic cracking regeneration flue gas x And the emission and the combustion-supporting function of CO are realized. CN201710338271.1 describes a combined catalytic cracking process for treating residual oil and extra heavy oil, hydrotalcite helps to reduce coke production in the cracked product, and hydrotalcite is added into the FCC catalyst to form a whole. Patent CN201510109947.0 discloses a sulfur transfer auxiliary agent for catalytic cracking regeneration flue gas and a preparation method thereof, and magnesium aluminate spinel (MgAl) is prepared by adopting a coprecipitation method 2 O 4 ) Combined with Mn and rare earthAnd FCC regenerated flue gas sulfur transfer agent obtained from copper.
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, stirring the mixed solution after dripping is finished to react for nucleation and crystallization to obtain magnesium aluminate spinel, and the magnesium aluminate spinel is dried and roasted to obtain the catalytic cracking regenerated flue gas desulfurization catalyst.
CN201510108402.8 discloses an assistant for removing catalytic cracking regenerated flue gas pollutants and a preparation method thereof, which is prepared by modifying magnesia-alumina spinel, layered double hydroxide and pseudo-boehmite with rare earth elements, adding a binder to form slurry with high solid content, preparing an assistant carrier with high hydrothermal stability by spray forming, drying and roasting, then immersing noble metals by an isovolumetric immersion method, and roasting again.
Magnesium oxide has also been used to passivate heavy metals in catalytic cracking processes, and CN201080050059.1 discloses the use of kaolin, magnesium oxide or mixtures of magnesium hydroxide and calcium carbonate to improve metal passivation during FCC cracking.
The existing hydrotalcite series vanadium-resistant and nickel-resistant auxiliary agent has the advantages of high abrasion index, low exposed MgO content, small specific surface area, insufficient performance of passivating vanadium and nickel and small specific surface area of a magnesium oxide passivating agent.
Disclosure of Invention
Aiming at the problems of the existing magnesium oxide passivator and hydrotalcite passivator, the invention provides a preparation method of a hydrotalcite microsphere with a flake structure, which comprises the following steps:
adding 0.75-0.82 weight part of alumina into the acidic solution to mix 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 flake structure;
treating a precursor of the hydrotalcite microsphere with the flake structure by water vapor at 100-180 ℃, filtering and drying to obtain the hydrotalcite microsphere with the flake structure;
the hydrotalcite microspheres with the flake structures have hydrotalcite crystal structures, the average particle size of the hydrotalcite microspheres with the flake structures is 65-85 microns, the primary structures of the hydrotalcite microspheres with the flake structures are hydrotalcite flakes, and the thicknesses of the hydrotalcite flakes are 20-50 nm.
Further, the acidic solution is one or a combination of several of nitric acid, formic acid and acetic acid.
Further limited, the weight part of the solute in the acidic solution is 0.25-0.35 parts.
Further limiting, wherein the roasting temperature in the roasting process is 550-650 ℃.
Further limited, the roasting temperature in the roasting process is 600 ℃.
Further defined, the weight parts of the aluminum oxide and the magnesium oxide are 0.8 and 0.65 respectively.
Further defined, the alumina is derived from pseudoboehmite and/or aluminum carbonate.
Further defined, the water vapor has a temperature of 120 ℃.
The invention has the beneficial effects that: according to the invention, through carrying out water vapor treatment on the hydrotalcite microsphere precursor with the flake structure, more MgO can be exposed, the specific surface area is large, a plurality of gaps are formed on the surface, more nickel and vanadium can be accommodated, and the vanadium resistance and the nickel resistance are good.
The wear index of the hydrotalcite microspheres with the flake structures prepared by the method is less than or equal to 3, the hydrotalcite microspheres have hydrotalcite structures, the average particle size (D50) is within the range of 65-85 mu m, the primary structures of the hydrotalcite microspheres with the flake structures are hydrotalcite flakes, the thickness of the hydrotalcite flakes is 20-50nm, and a large number of secondary pore passages smaller than 10nm are enriched on the surfaces of the flakes, so that the performance requirements of a catalytic cracking auxiliary agent are met, the auxiliary agent is ensured to be remained in a catalytic cracking device for a long time, and when the hydrotalcite microspheres are used in a catalytic cracking process, the conversion rate and the total liquid yield of residual oil can be obviously improved.
Drawings
FIG. 1 is an XRD pattern of the products prepared in examples 1-6 and comparative examples 1-2;
FIG. 2 is an SEM picture (100K) of the product prepared in comparative example 1;
FIG. 3 is an SEM photograph (10K) of the product prepared in comparative example 1;
FIG. 4 is an SEM photograph (1K) of the product prepared in comparative example 1;
FIG. 5 is an SEM photograph (100K) of the product prepared in comparative example 2;
FIG. 6 is an SEM photograph (10K) of the product prepared in comparative example 2;
FIG. 7 is an SEM photograph (1K) of the product prepared in comparative example 2;
FIG. 8 is an SEM picture (100K) of the product prepared in example 1;
FIG. 9 is an SEM photograph (50K) of the product prepared in example 1;
FIG. 10 is an SEM photograph (1K) of the product prepared in example 1;
FIG. 11 is an SEM picture (100K) of the product prepared in example 2;
FIG. 12 is an SEM photograph (10K) of the product obtained by the preparation of 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 below by way of specific examples, comparative examples, and with reference to the accompanying drawings.
In each example, the BET low-temperature nitrogen adsorption method measures the specific surface area of a sample, the X-ray fluorescence spectrometer measures the elemental composition (normalization result) of the sample, and the wear index analyzer measures the wear index of the sample.
The catalytic cracking reactions of the samples in the examples and comparative examples were evaluated on a micro fluidized bed reactor (ACE) and a matched gas chromatograph, and the Research Octane Number (RON) was analyzed using a gas chromatograph 7980A from Agilent. The samples in the examples and the comparative examples are subjected to 6000ppm Ni and 4000ppm V impregnation by an equal-volume impregnation method, then aged for 10 hours by 100 percent water vapor at 810 ℃, and then subjected to catalytic cracking performance evaluation on an ACE device. 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-oil ratio is 5. The feed is hydrogenated vacuum residue.
Other tests are described in (national Standard of test methods for Petroleum and Petroleum products, published in 1989 by the Chinese Standard Press).
Comparative example 1:
pseudo-boehmite (containing 0.8kg of alumina) was added to 6kg of water, and 0.3kg of nitric acid was added with stirring, and labeled as slurry A1.
0.65kg of MgO was dispersed in 0.9kg of water and labeled as slurry B1.
Mixing A1 and B1 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was added with 20 times the weight of water, stirred at 60 ℃ for 1 hour, filtered and dried. To obtain 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 the XRD diffraction pattern is shown in FIG. 1.
Respectively mixing 6% D1 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then performing catalytic cracking performance evaluation. The evaluation results are shown in Table 2.
Comparative example 2:
pseudo-boehmite (containing 0.8kg of alumina added to 6kg of water and 0.3kg of nitric acid added with stirring, labeled as slurry A2.
0.65kg of MgO was dispersed in 0.9kg of water and labeled as slurry B2.
Mixing A2 and B2 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was treated with steam at 60 ℃ for 12 hours. To obtain 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 the XRD diffraction pattern is shown in figure 1.
Respectively mixing 6% D2 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then performing catalytic cracking performance evaluation. The evaluation results are shown in Table 2.
Comparative example 3:
5% alumina (named D2) was mixed in an FCC catalyst, and after 6000ppm Ni and 4000ppm V were impregnated by an isovolumetric impregnation method, the catalytic cracking performance was evaluated after aging at 810 ℃ for 10 hours with 100% steam. The evaluation results are shown in Table 2.
Comparative example 4:
2% magnesium oxide (named D3) is mixed into FCC catalyst, 6000ppm Ni and 4000ppm V are impregnated by an isovolumetric impregnation method, and then catalytic cracking performance evaluation is carried out after aging is carried out for 10 hours by 100% steam at 810 ℃. 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 with stirring, and labeled as slurry A3.
0.65kg of MgO was dispersed in 0.9kg of water and labeled as slurry B3.
Mixing A3 and B3 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was treated with 100 ℃ steam for 12 hours, filtered and dried. The metal deactivator MV1 was obtained.
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.
Respectively mixing 6% MV1 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then carrying out catalytic cracking performance evaluation. 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 with stirring, and labeled as slurry A4.
0.65kg of MgO was dispersed in 0.9kg of water and labeled as slurry B4.
Mixing A4 and B4 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was treated with 120 ℃ steam for 12 hours, filtered and dried. The metal deactivator MV2 was obtained.
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.
Respectively mixing 6% MV2 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then carrying out catalytic cracking performance evaluation. 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 with stirring, and labeled as slurry A5.
0.65kg of MgO was dispersed in 0.9kg of water and labeled as slurry B5.
Mixing A5 and B5 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was treated with 150 ℃ steam for 6 hours, filtered and dried. The metal deactivator MV3 was obtained.
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.
Respectively mixing 6% MV3 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then carrying out catalytic cracking performance evaluation. 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 with stirring, and labeled as slurry A6.
0.65kg of MgO was dispersed in 0.9kg of water and labeled as slurry B6.
Mixing A6 and B6 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was treated with steam at 180 ℃ for 2 hours, filtered and dried. The metal deactivator MV4 was obtained.
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.
Respectively mixing 6% MV4 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then carrying out catalytic cracking performance evaluation. The evaluation results are shown in Table 2.
Example 5:
pseudo-boehmite (0.8kg alumina) was added to 6kg water and 0.3kg nitric acid, labeled as slurry A7, with stirring.
0.45kg of MgO was dispersed in 0.9kg of water and labeled as slurry B7.
Mixing A7 and B7 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was treated with 120 ℃ steam for 12 hours, filtered and dried. The metal deactivator MV5 was obtained.
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.
Respectively mixing 6% MV5 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then carrying out catalytic cracking performance evaluation. 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 with stirring, and labeled as slurry A8.
1.2kg of MgO was dispersed in 0.9kg of water and labeled as slurry B8.
Mixing A8 and B8 under stirring, homogenizing for 2 hr, spray forming, and calcining at 600 deg.C for 2 hr.
The calcined sample was treated with 120 ℃ steam for 12 hours, filtered and dried. The metal deactivator MV6 was obtained.
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.
Respectively mixing 6% MV6 into FCC catalyst, soaking 6000ppm Ni and 4000ppm V by an isovolumetric immersion method, aging for 10 hours at 810 ℃ by 100% steam, and then carrying out catalytic cracking performance evaluation. The evaluation results are shown in Table 2.
TABLE 1 elemental composition, specific surface area, abrasion index, particle size distribution of examples and comparative examples
As shown in Table 1, compared with water or steam at 60 ℃ (D1 and D2), the specific surface area of the sample is obviously increased after the sample is treated by water at more than or equal to 100 ℃ (MV1, MV2, MV3 and MV4), the abrasion index of the sample MV1 to MV6 obtained in the embodiment can be basically controlled within a range of less than or equal to 3, the average particle size (D50) can be controlled within a range of 65 to 85 mu m, the performance requirement of the FCC auxiliary agent is met, and the auxiliary agent can be basically ensured to be remained in the FCC device for a longer time.
Table 2 shows the catalytic cracking performance of the samples of examples and comparative examples
Total liquid yield is gasoline yield, diesel oil yield and liquefied gas yield
The reaction raw material is hydrogenation vacuum residue, the reaction temperature is 540 ℃, and the catalyst-oil ratio is 5.
As shown in Table 2, after the metal passivator of the examples is added, the conversion rate of the sample is improved, the yield of liquefied gas and gasoline is improved, the yield of slurry oil is reduced, and the total liquid yield of the sample is improved. The water vapor treatment temperatures of the D2, MV1, MV2 and MV3 samples were 60 ℃, 100 ℃, 120 ℃ and 150 ℃, respectively, and the conversion rate of the samples gradually increased with the increase in the water vapor treatment temperature from 60 ℃ to 150 ℃, and the total liquid yield also gradually increased.
As can be seen from fig. 1, samples D1 and D2 did not have significant hydrotalcite structures after comparative example 1(D1) and comparative example 2(D2) were treated with water at 60 ℃ or water vapor at 60 ℃; in the examples 1-4, after the treatment of water vapor at 180 ℃ under 100-; the Mg/Al (atomic number) ratios of examples 5 and 6 are different from those of example 2, and examples 5 and 6 have a significant hydrotalcite structure after steam treatment.
As can be seen from FIGS. 2 to 13, the product obtained in comparative example 1, which is a directly spray-molded magnesium-aluminum mixed oxide, is formed into amorphous particles of 10 to 60nm after being treated with water at 60 ℃ for 1 hour; after the sample is treated by the steam at 100 ℃ for 12 hours, a small amount of nano-flake structures appear on the surface of the sample, after the sample is treated by the steam at 120 ℃ for 12 hours, the surface of the sample is wrapped by a layer of nano-flake structures, the thickness of the flake is 20-50nm, the surface of the flake is rich in a large amount of secondary pore channels smaller than 10nm, the adsorption of more nickel and vanadium is facilitated, and the passivation effect is good.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement 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 microspheres with the flake structures is characterized by comprising the following steps of:
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 flake structure;
treating a precursor of the hydrotalcite microsphere with the flake structure by water vapor at 100-180 ℃, filtering and drying to obtain the hydrotalcite microsphere with the flake structure;
the hydrotalcite microspheres with the flake structures have hydrotalcite crystal structures, the average particle size of the hydrotalcite microspheres with the flake structures is 65-85 microns, the primary structures of the hydrotalcite microspheres with the flake structures are hydrotalcite flakes, and the thicknesses of the hydrotalcite flakes are 20-50 nm.
2. The method for preparing hydrotalcite microspheres with a flake structure according to claim 1, wherein the acidic solution is one or a combination of nitric acid, formic acid or acetic acid.
3. The method for preparing hydrotalcite microspheres with a flake structure according to claim 1 or 2, wherein the weight part of the solute in the acidic solution is 0.25-0.35 parts.
4. The method for preparing hydrotalcite microspheres with a flake structure according to claim 1, wherein the roasting temperature is 550-650 ℃ in the roasting process.
5. The method for preparing hydrotalcite microspheres with a flake structure according to claim 4, wherein the calcination temperature during the calcination process is 600 ℃.
6. The method for preparing hydrotalcite microspheres with a lamellar structure according to claim 1, wherein the parts by weight of alumina and magnesia are 0.8 and 0.65, respectively.
7. The process for producing flake-structured hydrotalcite microspheres according to any one of claims 1 to 6, wherein the temperature of the water vapor is 120 ℃.
8. The method for preparing hydrotalcite microspheres with a flake structure according to claim 1, wherein the alumina is derived from pseudo-boehmite and/or aluminum carbonate.
9. A hydrotalcite microsphere having a lamellar structure prepared by the method according to any one of claims 1 to 8.
10. Use of the platelet-structured hydrotalcite microspheres according to claim 9 in catalytic cracking.
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