CN111375394A - Alumina carrier and preparation method and application thereof - Google Patents
Alumina carrier and preparation method and application thereof Download PDFInfo
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- CN111375394A CN111375394A CN201811634399.3A CN201811634399A CN111375394A CN 111375394 A CN111375394 A CN 111375394A CN 201811634399 A CN201811634399 A CN 201811634399A CN 111375394 A CN111375394 A CN 111375394A
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- containing compound
- weight
- carrier
- lanthanum
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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 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 238000001035 drying Methods 0.000 claims abstract description 44
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 38
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- 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
- B01J35/651—50-500 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalyst carrier preparation, and discloses a preparation method of an alumina carrier. The method comprises the steps of sequentially forming, first drying and first roasting a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide and optional lanthanum or a lanthanum-containing compound. The preparation method of the alumina carrier has the advantages of simple process, stable carrier performance, high selective hydrogenation conversion rate and good selectivity of the obtained carbon dioxide three-fraction selective hydrogenation catalyst.
Description
Technical Field
The invention relates to the field of catalyst carrier preparation, in particular to an alumina carrier and a preparation method and application thereof.
Background
The cracked gas generated by cracking the liquid hydrocarbon steam contains 0.2-0.7 mol% of acetylene and 0.2-0.9 mol% of propyne and propadiene (MAPD). In order to obtain polymerization grade ethylene and propylene, acetylene and MAPD must be removed to required indexes. The catalytic hydrogenation method is the most commonly used method, and refers to that acetylene is hydrogenated to generate ethylene and propyne is hydrogenated to generate propylene under certain process operation conditions in the presence of a hydrogenation catalyst, so that the purpose of purification is achieved.
The selective hydrogenation of carbon-two-fraction generally adopts a multi-metal supported catalyst mainly comprising palladium, and the catalyst performance is mainly improved by a carrier and an added cocatalyst component, so that the purposes of improving the ethylene selectivity, reducing the green oil generation amount and prolonging the catalyst operation period are achieved. The carbon dioxide three-fraction selective hydrogenation catalyst carrier is generally a tooth ball or spherical particle, and the component is mainlyTo be α -Al2O3The preparation process mainly comprises the steps of powder mixing, kneading, strip extruding, grain cutting, drying, roasting and the like. The performance of the carrier directly determines the performance of the catalyst, so that the carrier with excellent performance is obtained in a crucial way.
Although the preparation of a catalyst support having excellent physical properties is an important approach to improving the catalyst performance, it is difficult to further improve the support performance today with the development of catalyst preparation technology. In the field of preparation of carbon two three-fraction selective hydrogenation catalyst carriers, no research aiming at carrying out technical improvement on the carbon two three-fraction selective hydrogenation catalyst carriers is seen at present.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the alumina carrier, the preparation method and the application thereof.
In order to achieve the above object, an aspect of the present invention provides a method for preparing an alumina carrier, which comprises subjecting a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide, and optionally lanthanum or a lanthanum-containing compound to molding, first drying, and first firing in this order.
Preferably, the aluminum-containing compound is aluminum hydroxide and/or pseudo-boehmite.
Preferably, the binder is one or more of sesbania powder, starch and hydroxypropyl methylcellulose.
Preferably, the acid is one or more of nitric acid, citric acid and acetic acid.
Preferably, the acid is used in an amount of 1 to 8% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
Preferably, in the mixture, the weight ratio of the aluminum-containing compound, the binder and the acid is 1: 0.03-0.1: 0.015-0.08.
Preferably, the binder is used in an amount of 5 to 15% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
Preferably, the lanthanum or lanthanum-containing compound is used in an amount of 0.35 to 1% by weight in terms of lanthanum element, relative to the weight of the aluminum-containing compound in terms of alumina.
Preferably, the polyethylene oxide has a molecular weight of 200 to 500 ten thousand.
Preferably, the polyethylene oxide is used in an amount of 0.5 to 8% by weight, preferably 1 to 5% by weight, relative to the weight of the aluminum-containing compound, calculated as alumina.
Preferably, the method comprises mixing an aluminum-containing compound, a binder, and polyethylene oxide, followed by adding an acid and optionally lanthanum or a lanthanum-containing compound to the mixture.
Preferably, the temperature of the mixing is 5-45 ℃ and the time of the mixing is 15-60 minutes.
Preferably, the conditions of the first drying include: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours.
Preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours.
Preferably, the method further comprises impregnating the first calcined support with a potassium hydroxide solution, followed by second drying and second calcination.
Preferably, the concentration of the potassium hydroxide solution is 0.01-0.1 mol/L.
Preferably, the potassium hydroxide solution is used in an amount of 30 to 100% by weight of the support after the first calcination.
Preferably, the conditions of the second drying include: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours.
Preferably, the conditions of the second firing include: the roasting temperature is 1050 ℃ and 1300 ℃, and the drying time is 8-25 hours.
In a second aspect, the present invention provides an alumina carrier prepared by the above-described method of the present invention.
The third aspect of the invention provides the application of the alumina carrier in the preparation of a carbon dioxide three-fraction selective hydrogenation catalyst.
The fourth aspect of the present invention provides a selective hydrogenation catalyst for carbon-two three-fraction, which comprises the carrier of the present invention as described above, and an active metal component supported on the carrier.
The inventor of the invention unexpectedly finds in the research process that by treating the alumina carrier with polyethylene oxide as a modifier in the preparation process of the carrier, the prepared alumina carrier is very suitable for being used as a carrier of a carbon-two three-fraction selective hydrogenation catalyst, and can simultaneously improve the conversion rate and the selectivity of the carbon-two three-fraction selective hydrogenation catalyst prepared by the alumina carrier. The preparation method has the advantages of simple process, stable carrier performance, no need of adding operation steps, high selective hydrogenation conversion rate and good selectivity of the obtained carbon dioxide three-fraction selective hydrogenation catalyst.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The method for preparing the alumina carrier comprises the steps of sequentially forming a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide and optional lanthanum or a lanthanum-containing compound, and performing first drying and first roasting to obtain the alumina carrier.
In the present invention, the aluminum-containing compound may be any of various aluminum-containing compounds conventionally used for preparing an alumina carrier, and may be, for example, aluminum hydroxide and/or pseudo-boehmite.
In the present invention, the binder may use various binders that are currently used to prepare the alumina carrier, and may be, for example, one or more of sesbania powder, starch, and hydroxypropylmethylcellulose. Preferably, the binder is used in an amount of 5 to 15 wt.%, preferably 8 to 12 wt.%, more preferably 8 to 10 wt.%, relative to the weight of the aluminum-containing compound, calculated as alumina. According to one embodiment of the present invention, sesbania powder, starch and hydroxypropyl methylcellulose are preferably used together, and more preferably in a weight ratio of 1: 0.5-0.7: 0.1-0.3.
In the present invention, the acid may be one or more of nitric acid, citric acid and acetic acid. Preferably, the acid is used in an amount of 1 to 8 wt.%, preferably 4 to 6 wt.%, relative to the weight of the aluminium-containing compound, calculated as aluminium oxide. As the nitric acid, a commercially available concentrated nitric acid having a mass fraction of about 68%; as the above citric acid, commercially available solid citric acid (e.g., chemically pure or analytically pure citric acid) is preferably used; glacial acetic acid (e.g., 98% by mass) is preferably used as the acetic acid. According to one embodiment of the present invention, nitric acid, citric acid and acetic acid are preferably used as the acid at the same time, and more preferably in a weight ratio of 1: 0.9-1.1: 0.1-0.3.
According to a preferred embodiment of the present invention, in the mixture, the weight ratio of the aluminum-containing compound, the binder and the acid is 1: 0.03-0.1: 0.015 to 0.08, more preferably 1: 0.08-0.1: 0.04-0.06. More preferably, the binder and the lanthanum or lanthanum-containing compound are used in an amount of 2 to 15 wt.%, preferably 8 to 12 wt.%, relative to the weight of the aluminum-containing compound, calculated as alumina.
The inventors of the present invention have unexpectedly found that by using polyethylene oxide in combination with lanthanum or a lanthanum-containing compound in the process of preparing an alumina carrier, the prepared alumina carrier can simultaneously improve the conversion rate and selectivity of the catalyst in the selective hydrogenation reaction of carbon-two three-fraction.
According to the present invention, the lanthanum or lanthanum-containing compound may be a simple lanthanum or any lanthanum-containing compound capable of being calcined to obtain lanthanum oxide, and from the viewpoint of operability, it is preferable to use simple lanthanum. More preferably, the lanthanum or lanthanum-containing compound is used in an amount of 0.35 to 1 wt.%, preferably 0.4 to 0.6 wt.%, more preferably 0.4 to 0.5 wt.%, calculated as lanthanum element, relative to the weight of the aluminum-containing compound, calculated as alumina.
In order to improve the conversion rate and selectivity of the selective hydrogenation catalyst for the carbon-two three-fraction, the molecular weight of the polyethylene oxide is preferably 200-500 ten thousand, and more preferably 300-400 ten thousand. And the polyoxyethylene is used in an amount of 0.5 to 8% by weight, preferably 1 to 5% by weight, more preferably 3 to 5% by weight, relative to the weight of the aluminum-containing compound in terms of alumina, in order to further improve the conversion and selectivity of the selective hydrogenation reaction.
As a production process of the above-mentioned mixture containing the aluminum-containing compound, the binder, the acid, the polyethylene oxide, and optionally lanthanum or the lanthanum-containing compound, for example, the aluminum-containing compound, the binder, and the polyethylene oxide may be mixed, followed by adding the acid and optionally lanthanum or the lanthanum-containing compound to the mixture and mixing. Preferably, the aluminum-containing compound, the binder and the polyethylene oxide are mixed using a powder, and then the mixture is mixed with an aqueous solution in which an acid and optionally lanthanum or a lanthanum-containing compound are dissolved. When hydroxypropylmethylcellulose is used as the binder, it is preferably mixed in the form of an aqueous solution.
In order to achieve good mixing effect, the weight ratio of water to the aluminum-containing compound (based on the dry weight of the aluminum hydroxide) added during mixing is preferably 1-4: 1, preferably 1.8 to 2.2: 1.
the mixing can achieve the effect of uniformly mixing the materials, preferably, the mixing temperature can be 5-45 ℃, and the mixing time can be 15-60 minutes.
In the present invention, the molding is used to form the mixed materials into the desired shape of the catalyst, and the molding method is not particularly limited, and may be specifically selected according to the use requirements of the catalyst. The shape of the molding may be, for example, a pellet shape, a clover shape, a cylinder shape, a spherical shape, a porous shape, or the like. From the viewpoint of producing the selective hydrogenation catalyst for the three-carbon fraction, preferred are denticular or spherical particles, generally 1 to 10mm in diameter.
In the present invention, the method of the first drying is not particularly limited, and any conventional method for producing an alumina support may be used. Preferably, the conditions of the first drying include: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours; more preferably, the drying temperature is 80-100 ℃ and the drying time is 3-5 hours. The first drying may be performed using a drying belt heater.
In the present invention, the method of the first calcination is not particularly limited, and any conventional method for producing an alumina support may be used. Preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours; more preferably, the calcination temperature is 450-550 ℃ and the calcination time is 8-12 hours. The first firing may be performed using, for example, a mesh belt kiln calciner.
In order to further improve the conversion rate and selectivity of the obtained carbo-two three-fraction selective hydrogenation catalyst, more preferably, the method further comprises the steps of impregnating the first calcined carrier with a potassium hydroxide solution, and then carrying out second drying and second calcination.
The potassium hydroxide solution used for impregnation has a concentration of preferably 0.01 to 0.1mol/L, more preferably 0.02 to 0.05mol/L, and is used in an amount of 30 to 100% by weight, more preferably 50 to 80% by weight, of the support after the first calcination.
As the conditions of the second drying, for example, there may be included: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours; preferably, the drying temperature is 110-. The second drying may be performed using a drying belt heater.
As the conditions of the second firing, for example, there may be included: the roasting temperature is 1050 ℃ and 1300 ℃, and the drying time is 8-25 hours; more preferably, the calcination temperature is 1100-. The second calcination may be performed, for example, using a mesh belt kiln calciner.
By immersing the potassium hydroxide solution under the above conditions, and performing the second drying and the second calcination, the conversion rate and the selectivity of the obtained carbo-dioxide three-fraction selective hydrogenation catalyst can be further improved.
In a second aspect, the present invention provides an alumina carrier prepared by the above-described method of the present invention.
The carrier of the invention has the following physical properties: the bulk density is 0.6-0.9g/mL, the pore volume is 0.3-0.6mL/g, and the specific surface area is 10-70m2Per g, the average pore diameter is 40-300 nm. Preferably, the bulk density of the alumina carrier is 0.65-0.8 g/mL; the pore volume is 0.3-0.6 mL/g; the specific surface area is 35-70m2A/g, more preferably 40 to 60m2(ii)/g; the average pore diameter is 100-300nm, more preferably 150-300 nm. And can provide high conversion rate and selectivity simultaneously when preparing the carbon two-cut selective hydrogenation catalyst.
The third aspect of the invention provides the application of the alumina carrier in the preparation of a carbon dioxide three-fraction selective hydrogenation catalyst.
In the invention, the alumina carrier can be used for preparing the two-carbon three-fraction selective hydrogenation catalyst by loading an active metal component suitable for the two-carbon three-fraction selective hydrogenation catalyst.
The fourth aspect of the present invention provides a selective hydrogenation catalyst for carbon-two three-fraction, which comprises the carrier of the present invention as described above, and an active metal component supported on the carrier.
As the above active metal component, the active metal component of the existing carbo-two three-cut selective hydrogenation catalyst may be used, preferably comprising palladium and optionally a promoter component. As the promoter component, Ga, Ag, Mn, W, Cu, etc. may be mentioned, and among them, Ag and Mn are preferable. The palladium may be used in an amount of 0.01 to 0.4 wt%, preferably 0.02 to 0.1 wt%, relative to the alumina support; the promoter component may be used in an amount of 0.02 to 0.2 wt%, preferably 0.04 to 0.1 wt%, relative to the alumina support. The loading method can adopt any method which can be used for preparing the supported catalyst, and the active metal component can be loaded on the carrier by adopting the known existing methods such as dipping, spraying and the like, and the loading can be carried out in a step-by-step mode or a synchronous mode. For example, the support may be impregnated with a solution of a salt of the active metal dissolved therein, and then dried and calcined.
The present invention will be described in detail below by way of examples. In the following examples, polyethylene oxide (molecular weight 400 ten thousand) was purchased from ZiboKai far Chemicals, Inc.
Example 1
Aluminum hydroxide powder (20000 g calculated by alumina), sesbania powder 1000g, starch 600g and polyethylene oxide 375g modifier are sequentially added into a kneader and uniformly mixed, and then 41000g deionized water dissolved with concentrated nitric acid 400g, citric acid 400g, glacial acetic acid 200g, lanthanum rare earth element 92g and hydroxypropyl methyl cellulose 200g (molecular weight 20 ten thousand) is added into the kneader by a spraying mode, and the kneading time is 25 min. And adding the kneaded material into a bin of a granulator, and starting the granulator to granulate to prepare the toothed sphere particles with the outer diameter of 5 mm.
The drying belt heater, mesh belt kiln roaster and exhaust fan were started, the drying curve was checked, and the carrier particles were poured into the drying belt using the loading hopper. The temperature range of the drying belt is controlled to be 90 ℃, and the drying time is controlled to be 4 hours.
And roasting the dried carrier for 10 hours at 500 ℃ by a mesh belt kiln roasting furnace to obtain the carrier. 20000g of the carrier is immersed in 12000g of potassium hydroxide solution with the concentration of 0.04mol/L, dried at 120 ℃ for 8 hours and then calcined at 1150 ℃ for 15 hours to obtain the catalyst carrier 1.
Example 2
Carrier production was carried out in the same manner as in example 1 except that the amount of polyethylene oxide added was 630g, to obtain carrier 2.
Example 3
The carrier preparation process was the same as in example 1 except that the amount of polyoxyethylene added was 960g, to prepare a carrier 3.
Example 4
Carrier production was conducted in the same manner as in example 1 except that the amount of polyethylene oxide added was 100g, to produce a carrier 4.
Example 5
Carrier preparation the same as in example 1 except that the amount of polyoxyethylene added was 1550g, carrier 5 was prepared.
Example 6
The carrier preparation process was the same as in example 1 except that the rare earth element lanthanum was changed from 92g to 110g, to prepare a carrier 6.
Example 7
The procedure of preparing the carrier was the same as in example 1 except that the calcination temperature of the carrier was changed from 1150 ℃ to 1200 ℃ to prepare a carrier 7.
Comparative example 1
An alumina carrier was prepared by the same procedure as in example 1, except that no polyethylene oxide was added, to prepare a carrier D1.
Test example 1
The vehicle performance results are listed in table 1.
TABLE 1
As shown in Table 1, compared with the prior art, the catalyst of the present invention has physical properties such as bulk density, pore volume, specific surface area and average pore diameter superior to those of the catalyst without addition of polyethylene oxide due to the addition of polyethylene oxide as a modifier during the preparation of the catalyst carrier.
Test example 2
Preparation of the catalyst:
and taking 30mL of palladium nitrate solution with the concentration of 12mgPd/mL, adding 180mL of deionized water for dilution, spraying the solution on 1000g of the prepared catalyst carrier, drying the solution at 120 ℃ for 7 hours, and roasting the solution at 450 ℃ for 8 hours to obtain the catalyst.
Evaluation of catalyst Performance:
the prepared catalyst is used for the reaction of removing acetylene by selective hydrogenation of carbon-containing fraction.
20mL of catalyst is loaded into a fixed bed reactor, hydrogen is introduced for reduction, then feed gas is switched, the feed gas from the top of the deethanizing tower is introduced into the reactor after being matched with hydrogen, the hydrogen-acetylene ratio is 1.4, the concentration of acetylene at the inlet is 0.45 mol%, and the gas phase volume space velocity is 10000h-1. The composition of the tail gas of the reaction was monitored by gas chromatography, and the acetylene conversion and selectivity of the catalyst were determined and are shown in table 2.
TABLE 2
| Catalyst and process for preparing same | 1 | 2 | 3 | 4 | 5 | 6 | 7 | D1 |
| Conversion rate% | 96 | 99 | 98 | 92 | 93 | 96 | 96 | 88 |
| Selectively, according to | 75 | 80 | 77 | 72 | 75 | 68 | 72 | 65 |
As shown in Table 2, compared with the catalyst in the prior art, the catalyst carrier of the invention has higher conversion rate and selectivity when applied to the selective hydrogenation process of carbon-two three-fraction due to the addition of polyethylene oxide as a modifier in the preparation process.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The preparation method of the alumina carrier is characterized by comprising the steps of sequentially forming a mixture containing an aluminum-containing compound, a binder, an acid, polyethylene oxide and optional lanthanum or a lanthanum-containing compound, and performing first drying and first roasting to obtain the alumina carrier.
2. The method of claim 1, wherein the aluminum-containing compound is aluminum hydroxide and/or pseudo-boehmite;
preferably, the binder is one or more of sesbania powder, starch and hydroxypropyl methyl cellulose;
preferably, the acid is one or more of nitric acid, citric acid and acetic acid;
preferably, the acid is used in an amount of 1 to 8% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
3. The process according to claim 1 or 2, wherein the binder is used in an amount of 5 to 15% by weight relative to the weight of the aluminium-containing compound calculated as alumina;
preferably, the lanthanum or lanthanum-containing compound is used in an amount of 0.35 to 1% by weight in terms of lanthanum element, relative to the weight of the aluminum-containing compound in terms of alumina.
4. A process according to any one of claims 1 to 3, wherein the polyethylene oxide has a molecular weight of from 200 to 500 ten thousand;
preferably, the polyethylene oxide is used in an amount of 0.5 to 8% by weight, preferably 1 to 5% by weight, relative to the weight of the aluminum-containing compound, calculated as alumina.
5. A process according to any one of claims 1 to 3, wherein the process comprises mixing an aluminium-containing compound, a binder and polyethylene oxide, followed by the addition of an acid and optionally lanthanum or a lanthanum-containing compound;
preferably, the temperature of the mixing is 5-45 ℃ and the time of the mixing is 15-60 minutes.
6. The method of any of claims 1-3, wherein the conditions of the first drying comprise: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours;
preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours.
7. The method of claim 6, further comprising impregnating the first calcined support with a potassium hydroxide solution, followed by a second drying and a second calcination;
preferably, the concentration of the potassium hydroxide solution is 0.01-0.1 mol/L;
preferably, the amount of the potassium hydroxide solution is 30-100% of the weight of the first calcined carrier;
preferably, the conditions of the second drying include: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours;
preferably, the conditions of the second firing include: the roasting temperature is 1050 ℃ and 1300 ℃, and the drying time is 8-25 hours.
8. An alumina support prepared by the method of any one of claims 1 to 7.
9. Use of the alumina support of claim 8 in the preparation of a carbon-dioxide three-fraction selective hydrogenation catalyst.
10. A selective hydrogenation catalyst for carbon-two three-cut, characterized by comprising the carrier of claim 8 and an active metal component supported on the carrier.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250017A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | Method for selective hydrogenation of carbon three-fraction |
| CN108855094A (en) * | 2017-05-16 | 2018-11-23 | 中国石油化工股份有限公司 | The method of loaded catalyst and preparation method thereof and methane dry reforming preparing synthetic gas |
| CN108855237A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | Porous alumina carrier and preparation method thereof and silver catalyst and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108250017A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | Method for selective hydrogenation of carbon three-fraction |
| CN108855237A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | Porous alumina carrier and preparation method thereof and silver catalyst and application |
| CN108855094A (en) * | 2017-05-16 | 2018-11-23 | 中国石油化工股份有限公司 | The method of loaded catalyst and preparation method thereof and methane dry reforming preparing synthetic gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797855A (en) * | 2021-01-29 | 2022-07-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst and catalyst carrier, and preparation method and application thereof |
| CN114797855B (en) * | 2021-01-29 | 2023-12-22 | 中国石油化工股份有限公司 | Hydrogenation catalyst and catalyst carrier, and preparation method and application thereof |
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