CN107303508B - Modified alumina carrier and preparation method thereof, dehydrogenation catalyst and application thereof - Google Patents
Modified alumina carrier and preparation method thereof, dehydrogenation catalyst and application thereof Download PDFInfo
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- CN107303508B CN107303508B CN201610246862.1A CN201610246862A CN107303508B CN 107303508 B CN107303508 B CN 107303508B CN 201610246862 A CN201610246862 A CN 201610246862A CN 107303508 B CN107303508 B CN 107303508B
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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 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000012265 solid product Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 54
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 28
- 239000001294 propane Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 2
- 239000011707 mineral Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 27
- 239000002184 metal Substances 0.000 abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 6
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 31
- 239000011148 porous material Substances 0.000 description 19
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 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
- 239000011780 sodium chloride Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- B01J23/38—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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a modified alumina carrier and a preparation method thereof, a dehydrogenation catalyst and application thereof, wherein the preparation method comprises the following steps: the preparation method comprises the following steps of carrying out contact reaction on an alumina carrier and an inorganic acid aqueous solution, separating a reaction product, and then washing, drying and roasting a solid product obtained by separation. According to the method, other metal or nonmetal elements are not added into the carrier, so that the original chemical components of the carrier can be better kept, and the performance change of the carrier caused by the introduction of other elements is effectively avoided; in addition, the method can effectively improve the acid-base property of the surface of the alumina carrier, is more favorable for the dispersion of active metal components, reduces the risk of carbon deposition and improves the selectivity of a target product.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for modifying an alumina carrier, the modified alumina carrier prepared by the method, a dehydrogenation catalyst containing the modified alumina carrier, and application of the dehydrogenation catalyst in preparation of propylene by propane dehydrogenation.
Background
The present invention relates to a method for producing propylene, and more particularly, to a method for producing propylene, which comprises the steps of using propylene as a basic raw material of organic petrochemical industry, wherein propylene is an important organic petrochemical raw material second only to ethylene, and is widely used for producing chemical products such as polypropylene, acrolein, acrylic acid, glycerol, isopropanol, polyacrylonitrile, butanol, octanol and the like.
Researchers find that the catalyst carrier structure (including physical structures such as specific surface area, pore volume and pore size distribution, and chemical structures such as surface acid sites and electronic properties) not only has an important influence on the dispersion degree of the loaded active components, but also directly influences mass transfer and diffusion in the reaction process. Thus, the catalytic properties of heterogeneous catalysts, such as activity, selectivity, and stability, depend both on the catalytic characteristics of the active components and on the structure of the catalyst support. In order to reduce the noble metal content of the Pt-based catalyst as much as possible and to improve the activity and stability of the catalyst, it is important to use an appropriate alumina carrier. If the mechanical strength, pore structure and acid-base property of the carrier of the existing alumina carrier do not meet the requirements of catalyst preparation, a proper method can be adopted for modification to obtain a proper carrier structure, so that a catalyst with excellent performance is obtained. In recent years, alumina carriers are widely applied in the fields of chemical catalysis and the like, and the requirements of people on the physical and chemical properties of the alumina carriers are higher and higher. Therefore, a great deal of alumina modification experience has been accumulated in academia, for example: the pore size of the alumina carrier can be adjusted by a steam treatment method or a pore-expanding agent addition method (Journal of Molecular Catalysts A: Chemical, 2002, 181 (1-2): 33-39; industrial catalysis, 2006, 14 (11): 56-59; inorganic chemistry bulletin, 2005, 21 (2): 212-; the acid-base property of the surface of the alumina can be adjusted by adding metal elements, metal oxides and nonmetal elements (advanced chemical bulletin 2002, 23 (10): 1952-; rare earth metals, alkaline earth metals, metalloids and their oxides may be added to improve the hydrothermal stability of the alumina support (US 4722920, CN 1958456, US 4677095).
Disclosure of Invention
The invention aims to overcome the defect of excessive acid sites on the surface of the existing alumina carrier, and provides a modified alumina carrier, a preparation method thereof, a dehydrogenation catalyst and application thereof.
The invention relates to a preparation method of a Pt-based propane dehydrogenation catalyst, which is characterized in that an acid site on the surface of an alumina carrier is an active center for catalytic reaction and a carbon deposition center for reaction, hydrocarbon is easy to crack and condense on a L acid center on the surface of the carrier to generate carbon deposition, and the stronger the acidity of the acid center, the greater the carbon deposition is.
The inventor of the invention finds in research that the acid-base property of the surface of the alumina can be effectively improved by carrying out contact reaction on the commercial alumina and an inorganic acid aqueous solution, so that the alumina is more beneficial to the dispersion of active metal components and the risk of carbon deposition is reduced.
Therefore, the invention provides a method for modifying an alumina carrier, wherein the method comprises the following steps: the preparation method comprises the following steps of carrying out contact reaction on an alumina carrier and an inorganic acid aqueous solution, separating a reaction product, and then washing, drying and roasting a solid product obtained by separation.
The invention also provides the modified alumina carrier prepared by the method.
The invention also provides a dehydrogenation catalyst, wherein the carrier in the dehydrogenation catalyst is the modified alumina carrier.
In addition, the invention also provides application of the dehydrogenation catalyst in preparation of propylene by propane dehydrogenation.
The modification method of the alumina carrier and the modified alumina carrier prepared by the method have the following advantages:
(1) compared with the prior art, other metal or nonmetal elements are not added into the carrier, so that the original chemical components of the carrier can be better kept, and the property change of the carrier caused by the introduction of other elements is effectively avoided;
(2) the method can effectively improve the acidity and alkalinity of the surface of the alumina carrier, is more favorable for the dispersion of active metal components, reduces the risk of carbon deposition and improves the selectivity of a target product;
(3) the method has the advantages of simple process, easily controlled conditions and good product repeatability;
(4) the dehydrogenation catalyst prepared by adopting the modified alumina carrier prepared by the method as the carrier has lower mass percentage content of the main active component of noble metal Pt, thereby effectively reducing the preparation cost of the dehydrogenation catalyst;
(5) the dehydrogenation catalyst prepared by using the modified alumina carrier prepared by the method as the carrier shows good catalytic performance when used for preparing propylene by propane dehydrogenation, and has the advantages of high propane conversion rate, high propylene selectivity, good catalyst stability and low carbon deposition amount.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph comparing the catalytic performance of dehydrogenation catalyst A prepared in example 1 with that of dehydrogenation catalyst D1 prepared in comparative example 1 in the reaction of propane dehydrogenation to propylene.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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 invention provides a method for modifying an alumina carrier, which comprises the following steps: the preparation method comprises the following steps of carrying out contact reaction on an alumina carrier and an inorganic acid aqueous solution, separating a reaction product, and then washing, drying and roasting a solid product obtained by separation.
In the present invention, the amount of the alumina support and the amount of the aqueous solution of the inorganic acid are not particularly limited, but in order to sufficiently improve the acid-base property of the surface of the alumina support, the weight ratio of the amount of the alumina support to the amount of the aqueous solution of the inorganic acid is preferably 1: 3-30, preferably 1: 5-20, more preferably 1: 10-15.
In the present invention, the selection of the alumina carrier is not particularly limited, and for example, a commercially available alumina carrier may be used, or an alumina carrier prepared by a conventional method may be used.
In the present invention, the concentration of the aqueous solution of the inorganic acid is not particularly limited, and may be a concentration which is conventional in the art, and preferably, the molar concentration of the aqueous solution of the inorganic acid is 2 to 10 mol/L, and preferably 3 to 8 mol/L.
In the present invention, the selection of the inorganic acid is not particularly limited, and may be a selection conventionally used in the art. Preferably, the inorganic acid is one or more of nitric acid, hydrochloric acid and sulfuric acid, more preferably nitric acid and/or hydrochloric acid, and still more preferably nitric acid.
In the present invention, the conditions for the contact reaction are not particularly limited, and may be those conventional in the art. Preferably, the conditions of the contact reaction include: the temperature is 90-120 ℃, preferably 95-110 ℃; the time is 4-16h, preferably 8-12 h.
According to a preferred embodiment of the present invention, the method of the present invention may further comprise: the contact reaction was carried out under stirring. In the present invention, the stirring conditions are not particularly limited, and may be those conventional in the art.
In the present invention, the separation is not particularly limited, and may be performed in a manner conventional in the art, for example, by filtration or centrifugation.
In the present invention, the washing is performed to remove residual acid ions from the solid product, and the washing may be performed according to conventional methods in the art without any particular limitation. Preferably, the washing process comprises: adding distilled water into the solid product, stirring for 0.5-2h, and performing suction filtration.
In the present invention, the amount of the distilled water and the amount of the solid product are not particularly limited as long as acid ions remaining in the solid product can be removed. Preferably, the volume ratio of the amount of the distilled water to the amount of the solid product is 5 to 30: 1, more preferably 15 to 20: 1.
preferably, the washing process is repeated 3 to 10 times, more preferably 5 to 8 times.
According to a preferred embodiment of the present invention, the method of the present invention may further comprise: refluxing is carried out simultaneously with the contact reaction. Preferably, the temperature of the reflux is the same as the temperature of the contact reaction.
In the present invention, the drying conditions are not particularly limited, and may be those conventional in the art. Preferably, the drying conditions include: the temperature is 90-180 ℃, and the temperature is preferably 110-150 ℃; the time is 1-20h, preferably 3-10 h.
In the present invention, the conditions for the calcination are not particularly limited, and may be those conventionally used in the art. Preferably, the roasting conditions include: the temperature is 550-750 ℃, preferably 600-700 ℃; the time is 2-15h, preferably 3-10 h.
The invention also provides a modified alumina carrier prepared by the method. The modified alumina carrier prepared by the method has fewer acid sites, thereby being more beneficial to the dispersion and loading of metal components.
The invention also provides a dehydrogenation catalyst, which is characterized in that a carrier in the dehydrogenation catalyst is the modified alumina carrier. In the dehydrogenation catalyst, the dispersion of the metal component is good, thereby exhibiting excellent catalytic performance.
The preparation method of the dehydrogenation catalyst of the present invention may comprise: loading main active metal components and metal additives on the modified alumina carrier by adopting an impregnation method, then removing solvent water, drying and roasting.
In the present invention, the selection of the impregnation method is not particularly limited, and may be a conventional one in the art, and for example, a co-impregnation method or a stepwise impregnation method may be used.
In the present invention, the main active metal component and the metal additive are not particularly limited and may be conventionally selected in the art, and preferably, the main active metal component is Pt, and the metal additive may include a first metal additive and a second metal additive, and preferably, the first metal additive is Sn, and the second metal additive is one or more of Na, K, L a, L i, Ca, Fe, Zn, Co, Mn, and Sr.
In the present invention, the amounts of the main active metal component and the metal auxiliary are not particularly limited and may be conventionally selected in the art. Preferably, the primary active metal component is present in an amount of from 0.2 to 0.6 wt.%, preferably from 0.3 to 0.4 wt.%, calculated as the metal element, based on the total weight of the dehydrogenation catalyst; the dosage of the first metal auxiliary agent calculated by the metal element is 0.2-1.5 wt%, preferably 0.4-1.2 wt%; the second metal additive is used in an amount of 0 to 2 wt%, preferably 0.3 to 0.8 wt%, based on the metal element.
In the present invention, the solvent water removal method is not particularly limited, and may be a method conventionally used in the art, for example, a rotary evaporator may be used.
In the present invention, the drying conditions in the method for producing the dehydrogenation catalyst are not particularly limited, and may be conventional conditions in the art. Preferably, the drying conditions include: the temperature is 90-160 ℃, and preferably 100-130 ℃; the time is 1-20h, preferably 2-5 h.
In the present invention, the conditions for the calcination in the method for producing the dehydrogenation catalyst are not particularly limited, and may be those conventional in the art. Preferably, the roasting conditions include: the temperature is 500-700 ℃, preferably 550-650 ℃; the time is 2-15h, preferably 3-10 h.
The invention also provides the application of the dehydrogenation catalyst in the preparation of propylene by propane dehydrogenation. The dehydrogenation catalyst shows good catalytic performance when applied to the reaction of preparing propylene by propane dehydrogenation, and has the advantages of high propane conversion rate, high propylene selectivity, good catalyst stability and low carbon deposition amount.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the reagents used were all commercially available analytical reagents;
the alumina sample A is a commercial product of industrial grade high specific surface area active alumina sold by Qingdao sea wave silica gel desiccant company, and the specific surface area of the commercial product is 286m2Per g, pore volume 0.78cm3(ii)/g, average pore diameter 7.6 nm;
the alumina sample B is a commercial product of Qingdao Seawa silica gel desiccant company, which is an industrial grade activated alumina with a specific surface area of 162m2Per g, pore volume 0.82cm3(ii)/g, average pore diameter 15.5 nm;
the alumina sample C was a calcined product of SB from Sasol, Germany, and had a specific surface area of 229m2Per g, pore volume 0.87cm3(ii)/g, average pore diameter 9.5 nm;
the rotary evaporator is produced by German IKA company, and the model is RV10 digital;
the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A;
the muffle furnace is manufactured by CARBO L ITE company, model CWF 1100;
the N2 adsorption-desorption experiment of the sample is carried out on an ASAP2020-M + C type adsorption apparatus produced by Micromeritics in America, and the BET method is adopted for calculating the specific surface area and the pore volume of the sample;
the content of each metal component in the prepared dehydrogenation catalyst is determined by calculating raw material feeding during preparation;
the propane conversion was calculated as follows:
the propane conversion was × 100% based on the amount of propane consumed by the reaction/initial amount of propane;
the propylene selectivity was calculated as follows:
propylene selectivity is × 100% of the amount of propane consumed to form propylene/total propane consumption;
the propylene yield was calculated as follows:
the propylene yield was × 100% based on the actual yield of propylene/theoretical yield of propylene.
Example 1
(1) Modification of alumina carrier
30g of alumina sample A was mixed with 300ml of HNO having a concentration of 5.0 mol/L3Mixing the aqueous solutions, refluxing for 10 hours at 100 ℃ under the condition of continuous stirring, and filtering to obtain a solid product. The solid product was washed with 2000ml of distilled water, sufficiently stirred, centrifuged, and washed repeatedly 6 times according to the washing method. The resulting product was placed in a drying oven at 130 ℃ and dried for 5 hours. Then the mixture is roasted in a muffle furnace for 6 hours at the temperature of 650 ℃ to obtain the modified alumina carrier A. The specific surface area of the modified alumina carrier A was 301m2Per g, pore volume 0.77cm3In terms of/g, the mean pore diameter is 8.1 nm.
(2) Preparation of dehydrogenation catalyst
0.080g H2PtCl6·6H2O、0.207g SnCl4·5H2O and 0.185g NaNO3Dissolving in 100ml deionized water, mixing with 10g of modified alumina carrier A prepared in the step (1), and continuously stirring and reacting for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 120 ℃ for 3 hours. Then, the catalyst was calcined in a muffle furnace at 600 ℃ for 6 hours to obtain a dehydrogenation catalyst A.
The dehydrogenation catalyst A comprises the following components in percentage by weight: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance being alumina carrier.
Comparative example 1
A dehydrogenation catalyst D1 was prepared according to the procedure of example 1 except that step (1) was eliminated and the dehydrogenation catalyst was prepared in step (2) directly on unmodified alumina sample A as the support.
The dehydrogenation catalyst D1 comprises the following components in percentage by weight: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance being alumina carrier.
Example 2
(1) Modification of alumina carrier
30g of alumina sample B was mixed with 600ml of HNO having a concentration of 3.0 mol/L3Mixing the aqueous solutions, refluxing for 12 hours at 95 ℃ under the condition of continuous stirring, and filtering to obtain a solid product. The solid product was washed with 2000ml of distilled water, sufficiently stirred, centrifuged, and washed repeatedly 8 times according to the washing method. The obtained product was dried in a drying oven at 110 ℃ for 10 hours. Then roasting the mixture in a muffle furnace at the temperature of 600 ℃ for 10 hours to obtain a modified alumina carrier B. The specific surface area of the modified alumina carrier B is 183m2Per g, pore volume 0.80cm3In terms of/g, the mean pore diameter is 15.7 nm.
(2) Preparation of dehydrogenation catalyst
(a) 0.059g of SnCl4·5H2Dissolving O in 100ml of deionized water, mixing with 10g of the modified alumina carrier B prepared in the step (1), and continuously stirring and reacting for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then calcined in a muffle furnace at 650 ℃ for 3 hours. (b) 0.106g H2PtCl6·6H2O and 0.153g KCl were dissolved in 100ml deionized water, mixed with the above calcined product, and reacted at room temperature with continuous stirring for 5 hours. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then calcined in a muffle furnace at 650 ℃ for 3 hours. To obtain dehydrogenation catalyst B.
The dehydrogenation catalyst B comprises the following components in percentage by weight: 0.4 wt% of platinum component calculated by platinum element, 0.2 wt% of tin component calculated by tin element, 0.8 wt% of sodium component calculated by sodium element, and the balance being alumina carrier.
Comparative example 2
Dehydrogenation catalyst D2 was prepared according to the procedure of example 2, except that step (1) was eliminated and the dehydrogenation catalyst was prepared directly in step (2) on unmodified alumina sample B as the support.
The dehydrogenation catalyst D2 comprises the following components in percentage by weight: 0.4 wt% of platinum component calculated by platinum element, 0.2 wt% of tin component calculated by tin element, 0.8 wt% of sodium component calculated by sodium element, and the balance being alumina carrier.
Example 3
(1) Modification of alumina carrier
30g of alumina sample C was mixed with 150ml of HNO having a concentration of 8.0 mol/L3The aqueous solutions are mixed, refluxed at 110 ℃ for 8 hours under the condition of continuous stirring, and filtered to obtain a solid product. The solid product was washed with 2000ml of distilled water, sufficiently stirred, centrifuged, and washed repeatedly 5 times according to the washing method. The resulting product was dried in a drying oven at 150 ℃ for 3 hours. Then the mixture is roasted in a muffle furnace for 3 hours at the temperature of 700 ℃ to obtain a modified alumina carrier C. The specific surface area of the modified alumina carrier C was 234m2Per g, pore volume 0.85cm3In terms of/g, the mean pore diameter was 9.9 nm.
(2) Preparation of dehydrogenation catalyst
0.080g H2PtCl6·6H2O、0.207g SnCl4·5H2O, 0.076g NaCl and 0.156g L a (NO)3)3·6H2Dissolving O in 100ml of deionized water, mixing with 10g of the modified alumina carrier C prepared in the step (1), and continuously stirring and reacting for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 130 ℃ and dried for 2 hours. Then, the catalyst was calcined in a muffle furnace at 550 ℃ for 10 hours to obtain a dehydrogenation catalyst C.
The dehydrogenation catalyst C comprises the following components in percentage by weight: 0.3 wt% of a platinum component calculated as platinum element, 1.2 wt% of a tin component calculated as tin element, 0.3 wt% of a sodium component calculated as sodium element, 0.5 wt% of a lanthanum component calculated as lanthanum element, and the balance being an alumina carrier.
Comparative example 3
Dehydrogenation catalyst D3 was prepared according to the procedure of example 3, except that step (1) was eliminated and the dehydrogenation catalyst was prepared in step (2) directly on unmodified alumina sample C as the support.
The dehydrogenation catalyst D3 comprises the following components in percentage by weight: 0.3 wt% of a platinum component calculated as platinum element, 1.2 wt% of a tin component calculated as tin element, 0.3 wt% of a sodium component calculated as sodium element, 0.5 wt% of a lanthanum component calculated as lanthanum element, and the balance being an alumina carrier.
Example 4
A dehydrogenation catalyst A' was prepared according to the method of example 1, except that the alumina sample A was contacted with HNO3The weight ratio of the using amount of the aqueous solution is 1: 3.
the specific surface area of the obtained modified alumina carrier A' is 264m2Per g, pore volume 0.76cm3In terms of/g, the mean pore diameter is 7.8 nm.
The specific gravity of each component of the obtained dehydrogenation catalyst A' is as follows: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance being alumina carrier.
Test example 1
0.5g of dehydrogenation catalyst A was charged into a fixed bed quartz reactor, the reaction temperature was controlled at 600 ℃, the reaction pressure was 0.1MPa, and the molar ratio of propane: the molar ratio of hydrogen is 1: 1, the mass space velocity of propane is 3.0h-1The reaction time is 24 h. By Al2O3The reaction product separated by the S molecular sieve column was directly subjected TO on-line analysis by Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID). The determination of the carbon deposit amount of the dehydrogenation catalyst was carried out on a TGA/DSC1 thermogravimetric analyzer of the company METT L ER-TO L EDO. the results are shown in Table 1. the propane conversion and propylene selectivity of the dehydrogenation catalyst A are shown in FIG. 1.
Test example 2
The process of test example 1 was followed except that the dehydrogenation catalyst D1 was used in place of the catalyst A to conduct the dehydrogenation of propane to propylene. The results are shown in Table 1. The propane conversion and propylene selectivity of dehydrogenation catalyst D1 are shown in figure 1.
Test examples 3 to 7
According to the method of test example 1, except that the dehydrogenation catalyst a was replaced with the dehydrogenation catalyst B, the dehydrogenation catalyst D2, the dehydrogenation catalyst C, the dehydrogenation catalyst D3 and the dehydrogenation catalyst a', respectively, the reaction for producing propylene by dehydrogenation of propane was carried out. The results are shown in Table 1.
TABLE 1
By comparing the results of test example 1 and test example 2, it can be found that the propylene selectivity of dehydrogenation catalyst a is greatly improved (from 80.0% to 91.1%) while the deposition of coke species on the catalyst surface is greatly suppressed (from 10.58% to 4.77%) compared to dehydrogenation catalyst D1; also, as can be seen from fig. 1, the stability of propane conversion is significantly improved. Apparently with aqueous solutions of strong acids (e.g. HNO)3Aqueous solution) to modify the alumina carrier, and the propane dehydrogenation catalyst prepared by using the modified alumina as the carrier can effectively improve the catalytic performance. If a catalyst support suitable for propane dehydrogenation is to be obtained, a treatment with a strong acid is effective.
It can be seen from table 1 that when the dehydrogenation catalyst A, B, C, A' prepared by the method of the present invention is used in the reaction of propane dehydrogenation to produce propylene, the catalytic performance is significantly better than that of dehydrogenation catalysts D1, D2 and D3 prepared by using commercially available alumina as a carrier, the average conversion rate of propane, the average selectivity of propylene and the average yield of propylene are significantly improved, and the amount of carbon deposition is significantly reduced. The method for modifying the alumina carrier can realize the effect of improving the catalytic performance of the dehydrogenation catalyst.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A method for modifying an alumina carrier, comprising: carrying out contact reaction on an alumina carrier and an inorganic acid aqueous solution, separating a reaction product, and then washing, drying and roasting a solid product obtained by separation;
the weight ratio of the using amount of the alumina carrier to the using amount of the inorganic acid aqueous solution is 1: 5-20 parts of;
the conditions of the contact reaction include: the temperature is 95-110 ℃; the time is 8-12 h;
the inorganic acid is nitric acid;
refluxing is carried out simultaneously with the contact reaction.
2. The method as claimed in claim 1, wherein the weight ratio of the amount of the alumina carrier to the amount of the aqueous solution of the inorganic acid is 1: 10-15.
3. The process according to claim 1 or 2, wherein the aqueous solution of mineral acid has a molar concentration of 2-10 mol/L.
4. The process according to claim 3, wherein the aqueous solution of mineral acid has a molar concentration of 3-8 mol/L.
5. The method of claim 1, wherein the washing comprises: adding distilled water into the solid product, stirring for 0.5-2h, and performing suction filtration.
6. The method of claim 5, wherein the volume ratio of the amount of distilled water to the amount of solid product is 5-30: 1.
7. the method of claim 6, wherein the volume ratio of the amount of distilled water to the amount of solid product is 15-20: 1.
8. the method of claim 5, wherein the washing process is repeated 3-10 times.
9. The method of claim 8, wherein the washing process is repeated 5-8 times.
10. A modified alumina support prepared by the method of any one of claims 1 to 9.
11. A dehydrogenation catalyst wherein the carrier is the modified alumina carrier of claim 10.
12. Use of the dehydrogenation catalyst of claim 11 in the dehydrogenation of propane to propylene.
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