CN113198468B - Modified mesoporous material and preparation method and application thereof - Google Patents
Modified mesoporous material and preparation method and application thereof Download PDFInfo
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 18
- 239000002210 silicon-based material Substances 0.000 claims abstract description 16
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 11
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 11
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 1
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229910052758 niobium Inorganic materials 0.000 abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 229910052741 iridium Inorganic materials 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 7
- 239000010955 niobium Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 3
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 polytrimethylene terephthalate Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 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
- 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
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
Abstract
The invention provides a modified mesoporous material which is a silicon-based material doped with hetero atoms, and comprises hetero atoms, silicon dioxide and active metals; the heteroatom is one or more selected from Nb, la, W and Ce; the active metal is one or more selected from Pt, rh and Ir. The modified mesoporous material provided by the invention has a stable structure, hetero atoms exist in a catalyst in a single atom form, acid sites necessary for the hydrogenolysis of glycerol are provided, the specific surface area of the mesoporous silicon-based material is large, metals are loaded on the mesoporous silicon-based material, the number of active sites is increased, and the catalytic activity of the catalyst is further improved; therefore, the catalyst has excellent performance and good repeatability in preparing the 1, 3-propanediol by catalyzing the hydrogenolysis of the glycerol.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a silicon-based catalyst doped with hetero atoms, a preparation method and application thereof.
Background
Glycerol, is the most predominant byproduct of biodiesel production, producing approximately 1kg of glycerol per 9kg of biodiesel produced. In recent years, with rapid development of biodiesel industry, glycerol productivity has been severely exceeded. Therefore, effective conversion and utilization of glycerol is becoming increasingly popular. And selective hydrogenolysis of glycerol is one of the ways to make efficient use of glycerol. Among them, the preparation of 1,2-PDO, 1,3-PDO, etc. by catalytic hydrogenolysis of glycerol is one of the most promising routes. In terms of economic value, the research significance of preparing 1,3-PDO by hydrogenolysis of glycerol is more remarkable. The 1,3-PDO has wide application, can be used as a solvent and a lubricant, and has the most economic value of synthesizing an important monomer of degradable polytrimethylene terephthalate (PTT). The PTT has excellent performance, integrates the advantages of the prior polyester (terylene, nylon and acrylon), and has the advantages of easy processing, rebound resilience, stain resistance, biodegradability and the like.
The current industrial production methods of 1,3-PDO mainly comprise an acrolein method, an ethylene oxide method and a microbial fermentation method. The acrolein method uses highly toxic, inflammable and explosive acrolein as a raw material, and is hydrated under the acid catalysis condition to obtain 3-hydroxy propanal, and further hydrogenation is carried out to obtain 1,3-PDO, so that the production cost is high, and the product performance is unstable. The ethylene oxide method is that 3-hydroxy propanal is first carbonylated and then hydrogenated to 1,3-PDO, and the production process is complex and the reaction condition is harsh. The microbial fermentation method has mild conditions, but the concentration of the product is too low, the product is difficult to separate, and the production efficiency is low. Therefore, the production of 1,3-PDO from glycerol, which is inexpensive and readily available and renewable, has become a hotspot in current research. From a thermodynamic point of view, however, the primary hydroxyl group of glycerol molecules has a C-O bond-breaking activation energy of 296.4kJ/mol which is 9.6kJ/mol lower than that of the secondary hydroxyl group C-O. In addition, glycerol molecules have only one secondary hydroxyl group and two primary hydroxyl groups, so that the difficulty of selectively catalyzing the hydrogenolysis of the secondary hydroxyl groups in the glycerol molecules to obtain the 1, 3-propanediol is great.
Therefore, there is a need to develop a catalyst for preparing 1, 3-propanediol by hydrogenolysis of glycerol with high catalytic activity, high selectivity and good stability.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a modified mesoporous material, and a preparation method and an application thereof, which are used for solving the problems of low activity, unsatisfactory selectivity and instability of a catalyst for preparing 1, 3-propanediol by hydrogenolysis of glycerol in the prior art.
To achieve the above and other related objects, the present invention is achieved by including the following technical means.
The invention provides a modified mesoporous material, which is a heteroatom doped silicon-based material loaded with active metal; the heteroatom is one or more selected from Nb, la, W and Ce; the active metal is one or more selected from Pt, rh and Ir.
According to the modified mesoporous material, the hetero atoms are embedded in the skeleton of the modified mesoporous material in a monodisperse form and replace Si atoms.
The modified mesoporous material according to the above, wherein the content of the hetero atoms is not more than 5wt% based on the total mass of the modified mesoporous material. Preferably, the content of the hetero atom is 0.5 to 5wt%.
According to the modified mesoporous material, the content of the active metal is not more than 5wt% based on the total mass of the modified mesoporous material. Preferably, the content of the active metal is 0.5 to 5wt%.
According to the modified mesoporous material, the pore diameter of the modified mesoporous material is 25-40 nm.
The invention provides a preparation method of the modified mesoporous material, which at least comprises the following steps:
1) Carrying out hydrothermal reaction on a silicon source precursor, a template agent, a heteroatom precursor and an expanding agent under an acidic condition to obtain a silicon-based material;
2) Calcining the silicon-based material in an air atmosphere at the calcining temperature of 300-1000 ℃ to obtain a carrier;
3) And mixing the carrier with a precursor solution of the active metal, heating and impregnating, and roasting in a reducing atmosphere to obtain the modified mesoporous material.
According to the preparation method, the silicon source precursor is ethyl orthosilicate.
According to the above preparation method, the acidic condition in the step 1) means a condition of pH 4.5 to 6.5. Preferably, the acidic conditions are provided by aqueous nitric acid or aqueous hydrochloric acid. More preferably, the concentration of the aqueous nitric acid solution is 0.5 to 5mol/L.
According to the preparation method, in the step 1), the template agent is one or two selected from P123 and F127, and more preferably P123.
In this application, P123 is a triblock copolymer, which is collectively referred to as a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, having the molecular formula PEO-PPO-PEO.
In the present application, F127 refers to a copolymer of polypropylene glycol and ethylene oxide.
According to the preparation method, the expanding agent in the step 1) is one or more of mesitylene, n-octane and n-heptane, and more preferably, the expanding agent is mesitylene.
The preparation method according to the above, wherein in the step 1), the heteroatom is one or more selected from Nb, la, W and Ce, and preferably, the heteroatom is one or two selected from Nb and W.
According to the preparation method, in the step 1), the mass ratio of the silicon source precursor, the template agent and the expanding agent is (0.9-5): (0.05-0.5): (0.2-8).
According to the preparation method, in the step 1), the heat treatment temperature is 65-125 ℃.
According to the preparation method, in the step 2), the calcination time is 2-6 h.
Further, in the step 3), the precursor solution of the active metal is one or more of salt solutions of Pt, rh and Ir.
Further, in the step 3), the impregnation temperature is 40 to 100 ℃. Preferably, the impregnation time is 2 to 10 hours.
Further, in step 3), the baking temperature is 200 to 600 ℃.
Further, in the step 3), the roasting time is 1 to 5 hours.
Further, the reducing atmosphere refers to a mixed gas of hydrogen and argon.
In another aspect, the invention also provides the use of the modified mesoporous material as described above as a catalyst in glycerol hydrogenolysis reactions.
Preferably, the modified mesoporous material is used as a catalyst in the reaction of preparing 1, 3-propanediol by hydrogenolysis of glycerol.
The modified mesoporous material provided by the invention has a stable structure, hetero atoms exist in a catalyst in a single atom form, acid sites necessary for the hydrogenolysis of glycerol are provided, the specific surface area of the mesoporous silicon-based material is large, metals are loaded on the mesoporous silicon-based material, the number of active sites is increased, and the catalytic activity of the catalyst is further improved; the preparation method has the advantages that the performance of preparing the 1, 3-propanediol by catalyzing the hydrogenolysis of the glycerol is excellent, and the repeatability is good; in addition, the preparation method has simple process, low cost and good controllability.
Drawings
FIG. 1 shows a transmission electron micrograph of the catalyst prepared according to example 3 of the present invention.
Fig. 2 shows a nitrogen adsorption/desorption isotherm plot of the catalyst prepared in example 3 of the present invention.
FIG. 3 shows a small angle X-ray diffraction pattern of the catalyst prepared in example 3 of the present invention.
FIG. 4 shows a Pt 4f X ray photoelectron spectrum of the catalyst prepared in inventive example 3.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.
The applicant carries out heteroatom doping modification on the silicon-based mesoporous material, then loads active metal, and experiments find that the heteroatoms in the modified mesoporous material exist in a single atom form, and are used for replacing a part of Si atoms to form in a framework of the silicon-based material. Due to the presence of these heteroatoms, the acid sites necessary for glycerol hydrogenolysis are provided; and the silicon-based material has a regular mesoporous structure and a large specific surface area, and then the number of active sites is increased by loading metal, so that the catalytic performance of the catalyst is further improved.
Specifically, the modified mesoporous material is a heteroatom doped silicon-based material loaded with active metal; the heteroatom is one or more selected from Nb, la, W and Ce; the active metal is one or more selected from Pt, rh and Ir.
Specifically, the heteroatoms are embedded in the backbone of the modified mesoporous material in a monodisperse form and replace Si atoms.
Specifically, the content of the hetero atom is not more than 5wt% based on the total mass of the modified mesoporous material. More specifically, the content of the hetero atom is 0.5 to 5wt%.
Specifically, the content of the active metal is not more than 5wt% based on the total mass of the modified mesoporous material. More specifically, the content of the active metal is 0.5 to 5wt%.
Preferably, the pore diameter of the modified mesoporous material is 25-40nm
Specifically, the modified silicon-based mesoporous material can firstly form a heteroatom-doped silicon-based mesoporous material through hydrothermal reaction, and then obtain the heteroatom-doped silicon-based mesoporous material loaded with active metal through impregnation.
Specifically, the following steps may be employed:
1) Carrying out hydrothermal reaction on a silicon source precursor, a template agent, a heteroatom precursor and an expanding agent under an acidic condition to obtain a silicon-based material;
2) Calcining the silicon-based material in an air atmosphere at the calcining temperature of 300-1000 ℃ to obtain a carrier;
3) And mixing the carrier with a precursor solution of the active metal, heating and impregnating, and roasting in a reducing atmosphere to obtain the modified mesoporous material.
Specifically, the silicon source precursor is ethyl orthosilicate.
Specifically, the acidic condition in the step 1) means that the pH is 4.5-6.5. Preferably, the acidic conditions are provided by aqueous nitric acid or aqueous hydrochloric acid. More preferably, the concentration of the aqueous nitric acid solution is 0.5 to 5mol/L.
Specifically, in step 1), the template agent is one or two selected from P123 and F127.
Specifically, the expanding agent in the step 1) is one or more of mesitylene, n-octane and n-heptane.
Specifically, the heteroatom is one or more selected from Nb, la, W and Ce, wherein preferably, the heteroatom is one or two selected from Nb and W.
Specifically, the mass ratio of the silicon source precursor, the template agent and the expanding agent is (0.9-5): (0.05-0.5): (0.2-8).
Specifically, the heat treatment temperature is 65-125 ℃.
Specifically, the impregnation temperature is 40 to 100 ℃.
Specifically, the baking temperature is 200-600 ℃.
Specifically, the reducing atmosphere refers to a mixed gas of hydrogen and argon.
The modified silicon-based mesoporous material has stable structure, good catalytic performance when being used for preparing 1, 3-propanediol by hydrogenolysis of glycerol, and good repeatability.
To further illustrate and confirm the above schemes and effects, the following examples are specifically employed as supplements.
Example 1
The embodiment discloses a specific preparation method of a modified mesoporous material, which comprises the following steps:
1) 5.0g F127 and 28g deionized water are added into 150mL 1.6mol/L hydrochloric acid solution, after stirring for 3h, 8g tetraethoxysilane, 7g mesitylene and 5mL cerium nitrate solution with the concentration of 0.20mol/L are added, the mixed solution is transferred into a 200mL hydrothermal kettle with a tetrafluoroethylene liner, the hydrothermal reaction is carried out, and the mixture is put into an oven with the temperature of 80 ℃ for reaction for 30h. Cooling to room temperature after the reaction is finished, washing the product by a large amount of deionized water, and drying;
2) Grinding the white solid obtained in the step 1), roasting in a muffle furnace at 500 ℃ in an air atmosphere, and heating at a rate of 3 ℃/min. Obtaining white powder;
3) Taking 0.5g of the white powder obtained in the step 2), adding a certain amount of tetramine platinum nitrate solution and 20ml of deionized water, mixing, and performing 400W ultrasonic dispersion for 0.5h. Heating and soaking for 2H after ultrasonic treatment, drying, and then adding into H 2 The catalyst obtained by calcination in Ar reducing atmosphere at 200℃for 2 hours was designated as C1, and the theoretical loading of Pt on the catalyst was 1wt%.
Example 2
The embodiment discloses a specific preparation method of a modified mesoporous material, which comprises the following steps:
1) 3.0g of P123 and 20g of deionized water are added into 150mL of 2.0mol/L hydrochloric acid solution, after stirring for 4 hours, 8g of tetraethoxysilane, 6g of mesitylene and a certain amount of 0.20mol/L niobium nitrate solution are added, the mixed solution is transferred into a 200mL hydrothermal kettle with a tetrafluoroethylene liner, the hydrothermal reaction is carried out, and the mixture is put into an oven with the temperature of 100 ℃ for 48 hours for reaction. Cooling to room temperature after the reaction is finished, washing the product by a large amount of deionized water, and drying;
2) Grinding the white solid obtained in the step 1), roasting in a muffle furnace at 600 ℃ in an air atmosphere, and heating at a rate of 5 ℃/min. Obtaining white powder, wherein the theoretical molar ratio of Si/Nb is 200;
3) Taking 0.5g of the white powder obtained in the step 2), adding a certain amount of tetramine platinum nitrate and rhodium nitrate solution, mixing with 20ml of deionized water, and performing 600W ultrasonic dispersion for 0.5h. Heating and soaking for 2H after ultrasonic treatment, drying, and then adding into H 2 Roasting for 2 hours at 300 ℃ in Ar reducing atmosphere, and the obtained catalyst is named asAnd C2, the theoretical loading of Pt and Rh on the catalyst is 1wt%.
Example 3
The embodiment discloses a specific preparation method of a modified mesoporous material, which comprises the following steps:
1) 3.0g of P123 and 20g of deionized water are added into 120mL of 2.0mol/L hydrochloric acid solution, after stirring for 3 hours, 6g of tetraethoxysilane, 6g of n-heptane and a certain amount of 0.20mol/L ammonium tungstate aqueous solution are added, the mixed solution is transferred into a 200mL hydrothermal kettle with a tetrafluoroethylene liner, the hydrothermal reaction is carried out, and the mixture is put into an oven with the temperature of 100 ℃ for 48 hours for reaction. Cooling to room temperature after the reaction is finished, washing the product by a large amount of deionized water, and drying;
2) Grinding the white solid obtained in the step 1), roasting in a muffle furnace at 600 ℃ in an air atmosphere, and heating at a rate of 5 ℃/min. Obtaining white powder, wherein the theoretical Si/W molar ratio is 100;
3) Taking 0.5g of the white powder obtained in the step 2), adding a certain amount of tetramine platinum nitrate solution and 20ml of deionized water, mixing, and performing 600W ultrasonic dispersion for 1h. Heating and soaking for 3H after ultrasonic treatment, drying, and then adding into H 2 Roasting for 3 hours at 400 ℃ in Ar reducing atmosphere to obtain a catalyst C3, wherein the theoretical loading of Pt on the catalyst is 2wt%.
FIG. 1 is a transmission electron micrograph of the catalyst prepared in example 3 of the present invention. As can be seen from fig. 1, the catalyst is capable of maintaining a characteristic honeycomb morphology comprising a plurality of uniformly distributed cavities, the size of which is between 25 and 40nm.
FIG. 2 is a diagram showing the isothermal line of adsorption and desorption of nitrogen in the catalyst prepared in example 3 of the present invention. As can be seen from FIG. 2, N of the catalyst 2 The adsorption and desorption isotherms all belong to the IV-type adsorption and desorption isotherms and have H1-type hysteresis loops, which indicate the existence of a mesoporous structure.
FIG. 3 is a small angle X-ray diffraction pattern of the catalyst prepared in example 3 of the present invention. As can be seen from fig. 3, the catalyst has three diffraction peaks (10), (11) and (20) of the mesoporous molecular sieve, which indicate that the heteroatom doped mesoporous material is successfully synthesized, and the mesoporous structure is not destroyed by the metal load.
FIG. 4 is a graph showing the Pt 4f X ray photoelectron spectrum of the catalyst prepared in example 3 of the present invention. As can be seen from FIG. 4, some Pt still exists on the reduced catalyst 2+ Species derived from the strong interactions between highly dispersed Pt particles and heteroatom doped mesoporous silica-based supports 2+ The species may be formed by Pt atoms bonding to the oxide support surface.
Example 4
The embodiment discloses a specific preparation method of a modified mesoporous material, which comprises the following steps:
1) 4.0g F123 and 20g deionized water are added into 150mL of 2.0mol/L hydrochloric acid solution, after stirring for 4 hours, 8g of ethyl orthosilicate, 6g of n-octane and a certain amount of cerium nitrate solution with the concentration of 0.20mol/L are added, the mixed solution is transferred into a 200mL hydrothermal kettle with a tetrafluoroethylene liner, the hydrothermal reaction is carried out, and the mixture is put into an oven with the temperature of 100 ℃ for 48 hours for reaction. Cooling to room temperature after the reaction is finished, washing the product by a large amount of deionized water, and drying;
2) Grinding the white solid obtained in the step 1), roasting in a muffle furnace at 600 ℃ in an air atmosphere, and heating at a rate of 5 ℃/min. Obtaining white powder, wherein the theoretical molar ratio of Si/Ce is 200;
3) Taking 0.5g of the white powder obtained in the step 2), adding a certain amount of rhodium nitrate solution, mixing with 20ml of deionized water, and performing 600W ultrasonic dispersion for 0.5h. Heating and soaking for 2H after ultrasonic treatment, drying, and then adding into H 2 The catalyst obtained by roasting in Ar reducing atmosphere at 300 ℃ for 2 hours is named as C4, and the theoretical loading of Pt and Rh on the catalyst is 2wt%.
Example 5
The embodiment discloses a specific preparation method of a modified mesoporous material, which comprises the following steps:
1) 3.0g of P123 and 50g of deionized water are added into 150mL of 2.0mol/L hydrochloric acid solution, after stirring for 4 hours, 3g of tetraethoxysilane, 6g of mesitylene and a certain amount of lanthanum nitrate solution with the concentration of 0.20mol/L are added, the mixed solution is transferred into a 200mL hydrothermal kettle with a tetrafluoroethylene liner, the hydrothermal reaction is carried out, and the mixture is put into an oven with the temperature of 120 ℃ for 60 hours for reaction. Cooling to room temperature after the reaction is finished, washing the product by a large amount of deionized water, and drying;
2) Grinding the white solid obtained in the step 1), roasting in a muffle furnace at 800 ℃ in an air atmosphere, and heating at a rate of 5 ℃/min. Obtaining white powder, wherein the theoretical molar ratio of Si/La is 200;
3) Taking 0.5g of the white powder obtained in the step 2), adding a certain amount of chloroplatinic acid and ruthenium nitrate solution, mixing with 20ml of deionized water, and performing 400W ultrasonic dispersion for 0.5h. Heating and soaking for 2H after ultrasonic treatment, drying, and then adding into H 2 The catalyst obtained by roasting the catalyst in Ar reducing atmosphere at 400 ℃ for 3 hours is named as C6, and the theoretical loading of Pt and Ru on the catalyst is 3 weight percent and 1 weight percent respectively.
Example 6
The above examples 1 to 5 were tested as catalysts to evaluate the catalytic performance of the hydrogenolysis of glycerol to 1, 3-propanediol. Adding 0.1g of the catalyst prepared in the above example and 2g of 30wt% glycerol aqueous solution into a high-pressure reaction kettle, and using H 2 Displacing for 6 times to exhaust the air in the kettle, and filling H with a certain pressure 2 And heated. After heating to the reaction temperature, H is filled in 2 To the pressure required for the reaction, electromagnetic stirring was turned on to bring the rotation to 500rpm and the timing was started. After the reaction is finished for 20 hours, cooling the reaction kettle to room temperature, collecting a gas phase product by using a gas bag, opening the reaction kettle, taking out a reaction liquid, centrifugally separating, taking a supernatant, and adding n-butanol and 1, 4-butanediol as internal standards. After mixing well, 0.6. Mu.L was taken for chromatography. The catalytic performance of the same catalyst is repeatedly examined at least twice, and the error of the reaction result is within 2%.
The results are shown in Table 1, and show that the catalyst No. 3 has the best catalytic performance, and the catalytic performance is obviously higher than that of most catalysts reported in the literature for preparing 1, 3-propanediol by hydrogenolysis of glycerol.
Table 1 catalytic results of glycerol hydrogenolysis to produce 1, 3-propanediol using the catalysts of the present invention prepared in example 1, example 2, example 3, example 4, and example 5.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (7)
1. The application of the modified mesoporous material as a catalyst in the reaction of preparing 1, 3-propanediol by glycerol hydrogenolysis is characterized in that the modified mesoporous material is a heteroatom doped silicon-based material loaded with active metal; the heteroatom is Ce; the active metal is one or more selected from Pt and Rh; the hetero atoms are embedded in the skeleton of the modified mesoporous material in a monodisperse form and replace Si atoms;
the modified mesoporous material is prepared by a method comprising the following steps:
1) Carrying out hydrothermal reaction on a silicon source precursor, a template agent, a heteroatom precursor and an expanding agent under an acidic condition to obtain a silicon-based material; the expanding agent is one or more of mesitylene, n-octane and n-heptane;
2) Calcining the silicon-based material in an air atmosphere at the calcining temperature of 300-1000 ℃ to obtain a carrier;
3) And mixing the carrier with a precursor solution of the active metal, heating and impregnating, and roasting in a reducing atmosphere to obtain the modified mesoporous material.
2. Use according to claim 1, characterized in that the content of heteroatoms is not more than 5% by weight, based on the total mass of the modified mesoporous material.
3. Use according to claim 1, characterized in that the active metal content is not more than 5% by weight, based on the total mass of the modified mesoporous material.
4. Use according to claim 1, characterized by comprising one or more of the following features:
the silicon source precursor is ethyl orthosilicate;
the template agent is one or two selected from P123 and F127.
5. The use according to claim 1, wherein the mass ratio of the silicon source precursor, the template agent and the expanding agent is (0.9-5): (0.05-0.5): (0.2-8).
6. Use according to claim 1, characterized by comprising one or more of the following features:
the hydrothermal treatment temperature is 65-125 ℃;
the dipping temperature is 40-100 ℃;
the roasting temperature is 200-600 ℃.
7. Use according to claim 1, characterized in that the reducing atmosphere is a mixture of hydrogen and argon.
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| CN105344357A (en) * | 2015-09-30 | 2016-02-24 | 东南大学 | Catalyst for preparing 1,3-propanediol through glycerine hydrogenolysis |
| WO2016098013A1 (en) * | 2014-12-17 | 2016-06-23 | Consejo Nacional De Investigaciones Científicas Y Técnicas (Conicet) | Catalytic process for the production of propylene glycol from glycerol, cerium and copper catalyst, and method for the production of said catalyst |
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| US9464015B2 (en) * | 2013-03-07 | 2016-10-11 | University Of Saskatchewan | Process for hydrogenolysis of glycerol |
| CN107096564B (en) * | 2017-06-05 | 2019-11-01 | 扬州大学 | A kind of SAPO-34 supporting Pt and the catalyst of WOx and preparation method thereof |
| CN109665939A (en) * | 2017-10-17 | 2019-04-23 | 中国科学院上海高等研究院 | A kind of method that propyl alcohol prepares 1,3-PD |
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