CN118162121A - Toothed spherical alumina carrier and preparation method and application thereof - Google Patents
Toothed spherical alumina carrier and preparation method and application thereof Download PDFInfo
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- CN118162121A CN118162121A CN202311318233.1A CN202311318233A CN118162121A CN 118162121 A CN118162121 A CN 118162121A CN 202311318233 A CN202311318233 A CN 202311318233A CN 118162121 A CN118162121 A CN 118162121A
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- alumina carrier
- spherical alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims description 26
- 239000000843 powder Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 24
- 238000004898 kneading Methods 0.000 claims abstract description 21
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 17
- 239000011029 spinel Substances 0.000 claims abstract description 17
- 239000003292 glue Substances 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 235000010981 methylcellulose Nutrition 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 244000215068 Acacia senegal Species 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000205 acacia gum Substances 0.000 claims description 3
- 235000010489 acacia gum Nutrition 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 229910001960 metal nitrate Inorganic materials 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract description 6
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 241000219782 Sesbania Species 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007602 hot air drying Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a tooth-ball alumina carrier and its preparing process and application, wherein the tooth-ball alumina carrier is prepared from aluminum hydroxide dry glue powder, water, processing aid, etc. through kneading, shaping, drying, low-temperature roasting, immersing the alumina precursor in metal nitrate solution, drying, high-temperature roasting, solid phase reacting the metal oxide produced by high-temperature decomposition with alumina to form spinel structure, which imparts excellent structural stability and higher compressive strength to the carrier.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a toothed spherical alumina carrier, a preparation method and application thereof.
Background
Currently, most hydrotreating catalysts used in oil refining and petrochemical industry are supported solid catalysts. It mainly consists of active component, cocatalyst and carrier. Wherein, the carrier is used as a framework of the catalyst, and plays roles of improving the utilization rate of active components, endowing the catalyst with higher mechanical strength, improving the stability of the catalyst and prolonging the service life of the catalyst.
The common Ni, co, mo, W metal active components of the hydrotreating catalyst can be used as the catalyst which has a certain shape, particle size, mechanical strength and the like and meets the hydrotreating process requirements after being loaded on carriers such as alumina, aluminum silicate, molecular sieves and the like.
The carrier has interaction with the catalyst to provide partial active center, and has been known in the fields of raising catalyst antitoxic performance, preventing coking, raising catalyst selectivity, etc. Therefore, recent innovations in hydrotreating catalyst supports have become one of the most important and active areas of research for improving catalyst performance.
The hydrotreating catalyst carrier with the largest industrial usage amount is prepared by taking aluminum hydroxide as a main raw material, adding a processing aid, kneading, forming, drying and roasting to prepare spherical, cylindrical, clover-shaped and other particles with different specific surface areas and mechanical strength.
Because the spherical, cylindrical, clover-shaped and other carriers have the defects of small outer surface area, large fluid resistance, difficult improvement of reaction efficiency and the like, the special-shaped and tooth-shaped spherical catalyst carriers are developed by some patent technologies from the perspective of improving the outer surface area of the carriers. Particularly, the tooth-shaped spherical carrier has spherical appearance, and the surface is processed into tooth shape, so that the outer surface area of the carrier can be obviously improved, the bed layer is uniform during filling, the void ratio is large, the reaction pressure difference is small, the coking resistance and the scale holding capacity are strong, and the hot spot of the catalyst bed layer can be avoided. Therefore, the toothed sphere carrier is widely used in the production of hydrotreating catalysts.
The patent CN1204230A discloses a special-shaped hydrofining catalyst and a preparation method thereof, aluminum hydroxide produced by a nitric acid method or a carbonization method is used as a main raw material, processing aids such as sesbania powder, citric acid, nitric acid and the like and deionized water are added, the mixture is kneaded into soft block-shaped plastic bodies by a kneading machine, then the soft block-shaped plastic bodies are added into a trough of an extruder, a tooth-spherical carrier precursor is obtained after extrusion and granulation by a tooth-spherical pore plate, and a carrier finished product is obtained after hot air drying and high-temperature roasting, so that the catalyst can be used for manufacturing heavy oil hydrotreating catalysts.
Patent CN1209359a discloses a special-shaped catalyst carrier, which is prepared by taking pseudo-boehmite dry powder produced by carbonization method as raw material, adding dilute nitric acid, kneading to prepare a plastic body, then sending the plastic body to an extruder, extruding and granulating through a special pore plate to prepare a special-shaped carrier precursor, and then drying and roasting at high temperature to prepare the catalyst carrier, which is suitable for preparing the catalyst for hydrodesulfurization, hydrodenitrogenation and hydrodemetallization.
Patent CN1513600a discloses a catalyst active carrier and its preparation, which uses alumina, silicon oxide, synthetic zeolite and the like as main raw materials, adds deionized water, acid and auxiliary agent to knead, puts the knead into a container with a hole template to squeeze and shape, then makes into tooth sphere carrier precursor through dicing, then makes into tooth sphere catalyst carrier through oven drying and high temperature roasting, and can increase the outer surface area of the carrier.
Patent CN1160602a discloses a large-aperture alumina carrier and its preparation method, in which activated carbon or chemical pore-enlarging agent is added in the process of mixing and kneading pseudo-boehmite and water or aqueous solution, and the mixture is kneaded to prepare a plastic body, and then extruded and formed on an extruder. Baking at 800-1000 deg.C to obtain the final product.
The said technology features that aluminium hydroxide dry powder is used as main material, and through adding various kinds of processing assistant, kneading, forming, drying, roasting and other steps, catalyst carrier with different shapes, specific surface area and mechanical strength is produced. The physical properties of the carrier thus obtained are often closely related to the properties of the raw meal used. Such as aluminum hydroxide powder produced by carbonization, has inferior molding properties to aluminum hydroxide dry powder produced by nitric acid. In order to improve the physical properties of the carrier, a plurality of processing aids are often added during kneading to obtain the required properties; and has the defects of poor mechanical strength, dispersed pore distribution, unstable physical properties and the like of the carrier.
Disclosure of Invention
The invention provides a tooth spherical alumina carrier with large specific surface area and high mechanical strength and a preparation method of the alumina carrier. The preparation method of the alumina carrier provided by the invention comprises two steps, wherein the first step is to prepare a precursor of the tooth spherical alumina carrier, and the second step is to impregnate the precursor of the carrier with a metal nitrate solution, and then the precursor is dried and baked at high temperature to generate a spinel structure. The alumina carrier provided by the invention is tooth-shaped, the specific surface area of the carrier is obviously improved compared with that of a spherical carrier with the same diameter, and the crystal form of the alumina comprises theta-Al 2O3 and alpha-Al 2O3.
One of the purposes of the invention is to provide a tooth-sphere alumina carrier, the appearance of the carrier is tooth sphere, the inside of the carrier contains a spinel structure, the chemical formula of the spinel is AB 2O4, wherein A is at least one of Ni 2+、Mn2+、Co2+、Cu2+、Fe2+; b is Al 3+; preferably, the spinel has the chemical formula AB 2O4, wherein a is at least one of Ni 2+、Co2+; b is Al 3+; in the alumina carrier, alumina contains a theta-Al 2O3 crystal phase and an alpha-Al 2O3 crystal phase.
In the toothed spherical alumina carrier provided by the invention, the content of the metal A is 0.3-2 wt%, preferably 0.3-1 wt%.
The tooth spherical alumina carrier provided by the invention has the specific surface area and pore volume which are the same as or similar to those of the prior art. For example, the specific surface area of the tooth-spherical alumina carrier is 20 to 80m 2/g, preferably 20 to 50m 2/g; the pore volume is 0.4 to 0.8ml/g, preferably 0.4 to 0.6ml/g.
The second object of the present invention is to provide a method for preparing the above toothed spherical alumina carrier, comprising: immersing the precursor of the dentiform spherical alumina in a nitrate solution of the metal A, taking out, drying, and roasting at high temperature to enable part of the alumina and metal oxide generated by decomposing the nitrate of the metal A to generate a spinel structure, and simultaneously, enabling part of the alumina to generate a phase transition to generate a theta-Al 2O3 crystal phase and an alpha-Al 2O3 crystal phase. Preferably, a proper amount of dispersing agent is also added into the metal A nitrate solution, so that the dispersibility of the alumina precursor in the nitrate solution is improved, and the migration of metal salt to the surface of the carrier during drying is prevented.
The preparation method of the tooth spherical alumina carrier provided by the invention specifically comprises the following steps:
(1) Uniformly mixing aluminum hydroxide dry glue powder, water, an acid compound and a forming auxiliary agent, kneading, extruding, forming a tooth-shaped template, granulating, drying and roasting at a low temperature to obtain a tooth-shaped spherical alumina precursor;
(2) Immersing the precursor of the dentiform spherical alumina obtained in the step (1) in a metal A nitrate solution containing a dispersing agent, taking out, drying and roasting at high temperature to obtain the dentiform spherical alumina carrier.
The preparation method of the tooth spherical alumina carrier comprises the following steps:
The aluminum hydroxide dry rubber powder can be aluminum hydroxide dry rubber powder commonly used in the field, for example, the aluminum hydroxide dry rubber powder is produced by a carbonization method, a nitric acid method or an aluminum sulfate method;
the water is preferably deionized water;
The forming auxiliary agent is at least one selected from sesbania powder, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, gum arabic powder, polyvinyl alcohol, epoxy resin and acrylic resin;
The acid compound is selected from organic acid and/or inorganic acid, preferably at least one of citric acid, nitric acid, acetic acid, propionic acid and tartaric acid;
the dispersing agent is at least one of fatty alcohol polyoxyethylene ether and fatty acid polyethylene oxide ester;
the metal A nitrate is at least one selected from nickel nitrate, cobalt nitrate, manganese nitrate, ferrous nitrate and copper nitrate, preferably at least one selected from nickel nitrate and cobalt nitrate.
The preparation method of the tooth spherical alumina carrier comprises the following steps:
the aluminum hydroxide dry rubber powder is taken as 100 parts by weight, the water consumption is 60-120 parts, the acid compound consumption is 1-5 parts, and the molding auxiliary agent consumption is 3-8 parts;
the dosage of the dispersing agent is 0.05 to 0.1 percent of the weight of the alumina carrier, and is preferably 0.07 to 0.09 percent;
The water absorption rate of the tooth spherical alumina precursor is 50-70%;
the volume of the metal A nitrate solution is 2-4 times of the water absorption rate of the tooth-spherical alumina precursor.
The preparation method of the tooth spherical alumina carrier comprises the following steps of:
The kneading may be carried out using usual kneading conditions on kneading equipment commonly used in the art, for example, kneading for 40 to 80 minutes;
The drying may be performed on drying equipment commonly used in the art using commonly used drying conditions, for example, the drying conditions are: the temperature is 120-150 ℃ and the time is 2-5 h;
the low temperature calcination may be performed using conventional calcination conditions on calcination equipment commonly used in the art, for example, the conditions of low temperature calcination are: the temperature is 300-400 ℃ and the time is 5-8 h.
The preparation method of the tooth spherical alumina carrier comprises the following steps of:
The impregnation is not particularly limited, and for example, the impregnation time is 30 to 60 minutes;
The drying may be performed on drying equipment commonly used in the art using commonly used drying conditions, for example, the drying conditions are: the temperature is 120-150 ℃ and the time is 2-5 h;
the high temperature calcination may be performed using conventional calcination conditions on calcination equipment commonly used in the art, for example, the conditions of the high temperature calcination are: the temperature is 800-1100 ℃ and the time is 6-10 h.
The first step of the invention is to add deionized water, acid compound and forming assistant into aluminum hydroxide dry glue powder as main raw materials, uniformly mix, make plastic by a kneader, extrude by an extruder, form tooth form template, cut into particles, dry at 120-150 ℃ and bake at 300-400 ℃ to obtain tooth spherical alumina precursor.
The second step of the invention is to prepare metal A nitrate solution with proper concentration according to the water absorption rate of the alumina precursor, to impregnate the prepared dentiform alumina precursor with the metal A nitrate solution, to dry the dentiform alumina precursor at 120-150 ℃ and to bake the dentiform alumina precursor at high temperature of 800-1100 ℃ so that part of alumina in the carrier and metal oxide generated by decomposing the metal A nitrate react with each other to generate spinel structure, and at the same time, part of alumina generates phase change in the high temperature roasting process to generate theta-Al 2O3 and alpha-Al 2O3.
The invention also aims to provide the toothed spherical alumina carrier or the toothed spherical alumina carrier obtained by the preparation method, which is applied to the preparation of catalysts for oil refining and petrochemical industry, in particular to the preparation of hydrofining catalysts and hydrocracking catalysts.
Compared with spherical, clover-shaped and tooth-spherical alumina carrier prepared by using aluminium hydroxide dry rubber powder as raw material and adopting similar processes of kneading, forming, drying and roasting, the alumina carrier prepared by using the method of the invention contains spinel structure, so that it has better structural stability and higher mechanical strength. The trace amount of Ni, co and other metals contained in the carrier can also provide active centers for the catalyst.
The above characteristics of the toothed spherical alumina carrier provided by the invention make the carrier more suitable for being used as a carrier of a hydrotreating catalyst with severe reaction conditions.
Detailed Description
The tooth-spherical alumina carrier provided by the invention has the appearance of tooth-spherical, the inside of the carrier contains a spinel structure, and the alumina crystal phase contains theta-Al 2O3 and alpha-Al 2O3 and has specific surface area and pore volume which are the same as or similar to those of the prior art. For example, the specific surface area is 20 to 80m 2/g, preferably 20 to 50m 2/g; the pore volume is 0.4 to 0.8ml/g, preferably 0.4 to 0.6ml/g.
According to the preparation method provided by the invention, the raw materials can be aluminum hydroxide dry rubber powder produced by a carbonization method or a nitric acid method, and also can be aluminum hydroxide dry rubber powder produced by an aluminum sulfate method.
According to the preparation method provided by the invention, raw material powder is weighed and then added with quantitative deionized water and processing aid. The auxiliary agent includes acid compound and molding auxiliary agent, such as sesbania powder, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, gum arabic powder, polyvinyl alcohol, epoxy resin, acrylic resin, citric acid, nitric acid, acetic acid, propionic acid, tartaric acid, etc. When the raw material powders are different, the varieties and the amounts of the added auxiliary agents are also different. When the aluminium hydroxide dry glue powder produced by carbonization is used as raw material, the additives added are sesbania powder, methylcellulose, acetic acid, epoxy resin and the like.
The mixing of the aluminum hydroxide dry powder and the processing aid is carried out in a kneader for a kneading time of 40 to 80 minutes, preferably 60 minutes. And after kneading, sending the obtained plastic dough into a strip extruder, and forming, granulating, hot air drying and roasting the extrudate through a tooth-shaped template to obtain a precursor of the catalyst carrier. The drying may be performed by a forced air oven or a mesh belt dryer. The drying temperature is 120-150 ℃ and the drying time is 2-5 hours. The calcination is carried out in a mesh belt type high-temperature kiln, and the calcination temperature is 300-400 ℃, preferably 320-350 ℃. The calcination time is 5-8 hours, preferably 5-6 hours, and the product obtained by calcination is the precursor of the alumina carrier.
The precursor of the alumina carrier is immersed in a metal nitrate solution, the metal nitrate solution is prepared by dissolving metal nitrate such as nickel nitrate, cobalt nitrate, manganese nitrate, ferrous nitrate, copper nitrate and the like in deionized water, wherein the nickel nitrate and the cobalt nitrate are preferably adopted, the concentration of the solution is controlled to be 0.3-2%, and the metal content of the carrier is preferably 0.3-1%. In order to uniformly impregnate the carrier and prevent the migration of metal salts to the surface of the carrier during drying, a small amount of dispersant fatty alcohol-polyoxyethylene ether is added, preferably 0.05 to 0.1%, more preferably 0.07 to 0.09%, more preferably 0.08% by weight of the carrier, when preparing the impregnation liquid.
When the alumina precursor is impregnated, the water absorption is accurately measured. The volume of the impregnating solution is 2 to 4 times, preferably 3 times, the water absorption so that the carrier is immersed in the solution entirely. The impregnation time is 30 to 60 minutes, preferably 40 minutes. After the completion of the impregnation, the excess solution was filtered off. And (3) drying in an oven or a drying belt at 120-150 ℃. Finally, delivering the mixture to a high-temperature kiln (for example, a roller-type high-temperature kiln) for roasting at 800-1100 ℃, preferably 900-950 ℃; the calcination time is 6 to 10 hours, preferably 6 to 8 hours.
According to the preparation method, in the roasting process, metal oxide generated by decomposing metal nitrate and Al 2O3 are subjected to solid-phase reaction to generate a spinel structure, for example, niO generated by decomposing nickel nitrate is reacted with Al 2O3 to generate nickel spinel NiAl 2O4. Meanwhile, phase transformation of alumina is generated in the high-temperature roasting process, and theta-Al 2O3 and alpha-Al 2O3 are generated, so that a stable carrier structure is obtained. The specific surface area is controlled to be 20-80 m 2/g, and the pore volume is controlled to be 0.4-0.8 mL/g.
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention. The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Example 1
1) Taking 400g of aluminum hydroxide dry adhesive powder produced by a carbonization method, mixing and kneading 20g of sesbania powder, 16g of citric acid, 4g of acetic acid, 3g of methyl cellulose, 4g of epoxy resin and 460g of deionized water in a kneader, feeding the mixture into a strip extruder for extrusion, and forming and granulating through a tooth form template to prepare the catalyst carrier formed product. Followed by hot air drying at 120℃for 2h. And delivering the dried material into a high-temperature furnace for roasting at the temperature of 300 ℃ for 5 hours. And taking out the alumina carrier after roasting, namely the precursor of the alumina carrier, and measuring the water absorption rate to be 60 percent.
2) 3G of nickel nitrate is taken and dissolved in 60g of deionized water, and 0.35g of fatty alcohol-polyoxyethylene ether is added, and the mixture is fully stirred to prepare the metal nitrate impregnating solution.
3) The precursor prepared in 1) is immersed in 2) a metal nitrate immersion liquid, and after immersion for 40 minutes, the excess solution is removed and filtered off.
4) And 3) sending the metal salt-containing precursor prepared in the step 3) into a blast oven for drying for 4 hours, wherein the drying temperature is 120 ℃. And (3) drying, transferring into a high-temperature furnace, roasting for 6 hours at 900 ℃, and cooling to obtain the toothed spherical alumina carrier.
Example 2
1) Taking 400g of aluminum hydroxide dry adhesive powder produced by a nitric acid method, 20g of sesbania powder, 10g of dilute nitric acid (the mass percentage concentration is 2%), 3g of acrylic resin, 5g of citric acid and 480g of deionized water, kneading by a kneader, feeding into a strip extruder for extrusion, and forming and granulating by a tooth form template to prepare the alumina carrier formed product. Followed by hot air drying at 120℃for 2h. And (5) delivering the dried material into a high-temperature furnace for roasting at the temperature of 300 ℃ for 5 hours. And taking out the alumina carrier after roasting, namely the precursor of the alumina carrier, and measuring the water absorption rate of the alumina carrier to be 62%.
The subsequent steps are the same as those of examples 1, 2), 3) and 4).
Example 3
1) Taking 400g of aluminum hydroxide dry powder produced by an aluminum sulfate method, adding 10g of dilute nitric acid (2%), 5g of acetic acid, 5g of polyvinyl alcohol, 3g of hydroxypropyl cellulose, 15g of sesbania powder and 400g of deionized water, uniformly kneading on a kneader, feeding into a strip extruder for extrusion, and forming and granulating by a tooth form template to prepare the alumina carrier formed product. Followed by hot air drying at 120℃for 2h. And delivering the dried material into a high-temperature furnace for roasting at the temperature of 300 ℃ for 5 hours. And taking out the alumina carrier after roasting, namely the precursor of the alumina carrier, and measuring the water absorption rate of the alumina carrier to be 58%.
The subsequent steps are the same as those of examples 1, 2), 3) and 4).
Comparative example 1
According to the method provided by CN1209359A, 400g of aluminum hydroxide dry rubber powder produced by carbonization method is taken, put into a kneader, added with 352mL of 2% dilute nitric acid, continuously kneaded for 35 minutes, extruded by a strip extruder to prepare a special-shaped carrier, dried for 5 hours at 120 ℃, and then put into a high-temperature kiln to be roasted for 3 hours at 900 ℃ to prepare the spherical alumina carrier.
Comparative example 2
According to the method provided by CN1513600A, 400g of aluminum hydroxide dry gel powder produced by a nitric acid method is taken and put into a kneader, and 12g of dilute nitric acid (2%), 5g of methylcellulose, 16g of sesbania powder, 5g of citric acid and 460g of deionized water are added. After 30 minutes of continuous kneading, extruding, pressing and granulating the plastic material by a strip extruder to prepare a tooth spherical shaped material, and then drying and roasting to prepare the tooth spherical carrier.
The physical properties of the alumina carriers prepared in the above examples and comparative examples are shown in the following table 1:
TABLE 1 physical Property measurement results of alumina supports of different preparations
From the above results, it is seen that since the alumina carriers of examples 1 to 3 of the present invention have tooth-shaped external appearance, the specific surface area is increased somewhat as compared with other carriers of the same size of comparative examples 1 to 2. Moreover, the alumina carrier in the embodiments 1 to 3 of the present invention has the greatest characteristic that the compressive strength of the alumina carrier is greatly increased compared with the carrier without spinel in the comparative examples 1 to 2 due to the spinel structure in the carrier, thereby remarkably improving the fluid impact resistance and prolonging the service life of the catalyst.
Claims (10)
1. The tooth-sphere alumina carrier is characterized in that the appearance of the carrier is tooth-sphere, the inside of the carrier contains spinel structure, the chemical formula of the spinel is AB 2O4, wherein A is at least one of Ni 2+、Mn2+、Co2+、Cu2+、Fe2+; b is Al 3+.
2. The toothed spherical alumina carrier of claim 1, wherein the toothed spherical alumina carrier comprises a toothed spherical alumina carrier,
The chemical formula of the spinel is AB 2O4, wherein A is at least one of Ni 2+、Co2+; b is Al 3+; and/or the number of the groups of groups,
In the alumina carrier, alumina contains a theta-Al 2O3 crystal phase and an alpha-Al 2O3 crystal phase.
3. The toothed spherical alumina carrier of claim 1, wherein the toothed spherical alumina carrier comprises a toothed spherical alumina carrier,
The content of the metal A in the alumina carrier is 0.3-2 wt%, preferably 0.3-1 wt%; and/or the number of the groups of groups,
The specific surface area of the alumina carrier is 20-80 m 2/g, preferably 20-50 m 2/g; the pore volume is 0.4 to 0.8ml/g, preferably 0.4 to 0.6ml/g.
4. A process for preparing a toothed spherical alumina carrier as claimed in any one of claims 1 to 3, comprising: immersing the precursor of the dentiform spherical alumina in a nitrate solution of the metal A, taking out, drying, and roasting at high temperature to enable part of the alumina and metal oxide generated by the decomposition of the nitrate of the metal A to generate a spinel structure, and simultaneously, enabling part of the alumina to generate a theta-Al 2O3 crystal phase and an alpha-Al 2O3 crystal phase by phase transformation.
5. The preparation method according to claim 4, wherein the preparation method specifically comprises the following steps:
(1) Uniformly mixing aluminum hydroxide dry glue powder, water, an acid compound and a forming auxiliary agent, kneading, extruding, forming a tooth-shaped template, granulating, drying and roasting at a low temperature to obtain a tooth-shaped spherical alumina precursor;
(2) Immersing the precursor of the dentiform spherical alumina obtained in the step (1) in a metal A nitrate solution containing a dispersing agent, taking out, drying and roasting at high temperature to obtain the dentiform spherical alumina carrier.
6. The method according to claim 5, wherein,
The aluminum hydroxide dry rubber powder is produced by a carbonization method, a nitric acid method or an aluminum sulfate method; and/or the number of the groups of groups,
The forming auxiliary agent is at least one selected from sesbania powder, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, gum arabic powder, polyvinyl alcohol, epoxy resin and acrylic resin; and/or the number of the groups of groups,
The acid compound is selected from organic acid and/or inorganic acid, preferably at least one of citric acid, nitric acid, acetic acid, propionic acid and tartaric acid; and/or the number of the groups of groups,
The dispersing agent is at least one of fatty alcohol polyoxyethylene ether and fatty acid polyethylene oxide ester; and/or the number of the groups of groups,
The metal A nitrate is at least one selected from nickel nitrate, cobalt nitrate, manganese nitrate, ferrous nitrate and copper nitrate, preferably at least one selected from nickel nitrate and cobalt nitrate.
7. The method according to claim 5, wherein,
The aluminum hydroxide dry rubber powder is taken as 100 parts by weight, the water consumption is 60-120 parts, the acid compound consumption is 1-5 parts, and the molding auxiliary agent consumption is 3-8 parts; and/or the number of the groups of groups,
The dosage of the dispersing agent is 0.05 to 0.1 percent of the weight of the alumina carrier, and is preferably 0.07 to 0.09 percent; and/or the number of the groups of groups,
The water absorption rate of the tooth spherical alumina precursor is 50-70%; and/or the number of the groups of groups,
The volume of the metal A nitrate solution is 2-4 times of the water absorption rate of the tooth-spherical alumina precursor.
8. The method according to claim 5, wherein in the step (1):
kneading for 40-80 min; and/or the number of the groups of groups,
The drying conditions are as follows: the temperature is 120-150 ℃ and the time is 2-5 h; and/or the number of the groups of groups,
The conditions of low-temperature roasting are as follows: the temperature is 300-400 ℃ and the time is 5-8 h.
9. The method according to claim 5, wherein in the step (2):
The soaking time is 30-60 min; and/or the number of the groups of groups,
The drying conditions are as follows: the temperature is 120-150 ℃ and the time is 2-5 h; and/or the number of the groups of groups,
The conditions of high-temperature roasting are as follows: the temperature is 800-1100 ℃ and the time is 6-10 h.
10. A toothed spherical alumina carrier according to any one of claims 1 to 3 or a toothed spherical alumina carrier obtained by the preparation method according to any one of claims 4 to 9, which is applied to the preparation of catalysts for oil refining and petrochemical industry, in particular to the preparation of hydrofining catalysts and hydrocracking catalysts.
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