CN109331811A - Mesoporous chromium aluminium composite oxide catalyst and the preparation method and application thereof - Google Patents
Mesoporous chromium aluminium composite oxide catalyst and the preparation method and application thereof Download PDFInfo
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- CN109331811A CN109331811A CN201811315601.6A CN201811315601A CN109331811A CN 109331811 A CN109331811 A CN 109331811A CN 201811315601 A CN201811315601 A CN 201811315601A CN 109331811 A CN109331811 A CN 109331811A
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- Prior art keywords
- chromium
- composite oxide
- oxide catalyst
- mesoporous
- aluminium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011651 chromium Substances 0.000 claims abstract description 34
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 26
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 239000010953 base metal Substances 0.000 claims abstract description 8
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 6
- 239000013384 organic framework Substances 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 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 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 abstract description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001282 iso-butane Substances 0.000 abstract description 6
- 235000013847 iso-butane Nutrition 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 239000001294 propane Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 9
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 7
- 229910001950 potassium oxide Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 alkanes Hydrocarbon Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B01J35/615—
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B01J35/647—
-
- 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
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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 discloses a kind of preparation methods of mesoporous chromium aluminium composite oxide catalyst, comprising: aluminium salt and auxiliary agent are dissolved in solvent, vacuum-treated presoma containing chromium is added, stirring to solvent is volatilized, and the first presoma is obtained；By the first presoma dry roasting, mesoporous chromium aluminium composite oxide catalyst is made.The present invention is with the presoma containing chromium of bigger serface, mesoporous chromium aluminium composite oxide catalyst is prepared if chromium Base Metal organic framework material is cell reservoirs and chromium presoma, active component and carrier interaction is stronger, inhibit the aggregation and loss of active component in reaction process, mesoporous chromium aluminium composite oxide catalyst has meso-hole structure, big specific surface area and relatively narrow mesopore orbit distribution, corresponding alkene is generated particularly suitable for the reaction of C3-C4 dehydrating alkanes, propane or iso-butane conversion ratio and propylene or selective isobutene are respectively up to 37-55% and 85-97%, selectivity and regenerating stability with higher.
Description
Technical field
The invention belongs to catalysis technical fields, and in particular to a kind of mesoporous chromium aluminium composite oxide catalyst and its preparation side
Method and its application in low-carbon alkanes (C3-C4) dehydrogenation reaction.
Background technique
It is a kind of important industrial processes that dehydrogenating low-carbon alkane, which prepares low-carbon alkene, which is the endothermic reaction, because
This needs relatively high reaction temperature, but high temperature frequently can lead to a variety of side reactions such as cracking, addition and carbon distribution, reactant
System and product are complicated, and olefine selective is poor.Therefore how to develop with high activity, highly selective and high stability catalyst
It is the key that dehydrating alkanes technology.Alkane dehydrogenating catalyst mainly divides two major classes at present: precious metals pt catalyst and base metal
Cr catalyst.In contrast, Cr series catalysts production cost is low.Up to the present, related Cr series catalysts are anti-in dehydrating alkanes
There are more document report and patent application in answering.The catalyst usually does carrier and alkali gold by active component, aluminium oxide of chromium
Belong to modification to be prepared.The breaths such as the specific form and carrier, chromium load capacity and preparation condition of catalyst surface chromium species breath
Correlation, while its property determines catalytic activity and selectivity.Current preparation method reported in the literature has infusion process, co-precipitation
Method, sol-gal process and volatilization self-assembly method etc..
For example, CN1668555A disclose it is a kind of prepared by infusion process containing aluminium oxide, chromium oxide, lithia and sodium oxide molybdena
Dehydrogenation.
In another example CN101940922B discloses one kind using chromium as active component, using alkali metal as auxiliary agent, with chromium aluminium oxide
For the catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof of carrier.The preparation process of the catalyst is to load part chromic salts in advance
Onto expanding agent, extruded moulding then is mixed with aluminium hydroxide etc., carrier containing chromium is made through drying and roasting etc., it finally will be remaining
Chromic salts and auxiliary agent are loaded to by infusion process is made dehydrogenation on carrier.With the method prepare catalyst intensity compared with
Low, wear-resisting property is bad.
Although very big effort has been made for the exploitation of the catalyst system in researcher, there are also much rooms to mention
The selectivity of high catalytic activity and alkene.
Metal-organic framework materials (MOFs) be used as a kind of novel porous material, have Modulatory character, bigger serface,
The features such as high porosity, orderly duct and higher stability.These features allow to other porous as preferably preparing
The cell reservoirs of material.Had been reported that in document use MOFs as cell reservoirs prepare nano material, such as nanoporous Carbon Materials,
Metal nanometre cluster, metal hydride and metal oxide nanoparticles etc., these materials are in gas absorption, electrochemistry and catalysis etc.
Field shows excellent performance.Therefore, how the catalytic activity of catalyst and the selectivity of alkene are improved using MOFs,
Become the problem of should focusing on research.
Summary of the invention
The main purpose of the present invention is to provide a kind of mesoporous chromium aluminium composite oxide catalyst and preparation method thereof with answer
With to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of preparation methods of mesoporous chromium aluminium composite oxide catalyst, comprising:
Aluminium salt and auxiliary agent are dissolved in solvent, vacuum-treated presoma containing chromium is added, stirring to solvent is volatilized, obtained
To the first presoma；
By the first presoma dry roasting, mesoporous chromium aluminium composite oxide catalyst is made.
The embodiment of the invention also provides a kind of mesoporous chromium aluminium composite oxide catalyst prepared by preceding method.
The embodiment of the invention also provides mesoporous chromium aluminium composite oxide catalyst above-mentioned in low-carbon alkanes catalytic dehydrogenation
Prepare the application in corresponding alkene.
Compared with prior art, the beneficial effect comprise that
(1) preparation method of mesoporous chromium aluminium composite oxide catalyst provided in an embodiment of the present invention, with common dipping
Method is compared, with the presoma containing chromium of bigger serface, as chromium Base Metal organic framework material Cr-MIL-101 be cell reservoirs and
Chromium presoma prepares mesoporous chromium aluminium composite oxide catalyst, and active component and carrier interaction is stronger, to inhibit
The aggregation and loss of active component in reaction process, mesoporous chromium aluminium composite oxide catalyst have meso-hole structure, big ratio table
Area and the distribution of relatively narrow mesopore orbit, are to have highly selective and high stability catalyst for dehydrogenation of low-carbon paraffin.
(2) the mesoporous chromium aluminium composite oxide catalyst generates corresponding alkene particularly suitable for the reaction of C3-C4 dehydrating alkanes
Hydrocarbon.Propane or iso-butane conversion ratio and propylene or selective isobutene are respectively up to 37-55% and 85-97%, catalyst tool
There are higher selectivity and regenerating stability.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
Chromium Base Metal organic framework material, as Cr-MIL-101 has big specific surface area, up to 4100m2·g-1.The bone
There are two types of mesoporous pore sizes, respectively 2.9nm and 3.4nm for frame tool, and corresponding hatch bore diameter is respectively 1.2nm and 1.6nm.Therefore
There is Cr-MIL-101 sufficiently large duct metal ion to be allowed to diffuse into its skeleton, be ideal cell reservoirs and forerunner
Body, while it is good chromium source presoma again.
The preparation method of mesoporous chromium aluminium composite oxide catalyst provided in an embodiment of the present invention, comprising:
Aluminium salt and auxiliary agent are dissolved in solvent, vacuum-treated presoma containing chromium is added, stirring to solvent is volatilized, obtained
To the first presoma；
By the first presoma dry roasting, mesoporous chromium aluminium composite oxide catalyst is made.
In some embodiments, stirring is included in stirring to solvent under 40-90 DEG C of constant temperature and volatilizees.
In some embodiments, the presoma containing chromium includes chromium Base Metal organic framework material.
Further, the chromium Base Metal organic framework material is Cr-MIL-101.
Further, the preparation method of the Cr-MIL-101 may include:
By Cr (NO3)3·9H2O, hydrofluoric acid solution is added into water in terephthalic acid (TPA) stirring and dissolving, continues to stir 1-4h,
In 180-220 DEG C of crystallization 12-24h, it is down to room temperature, filtering is placed on 80-120 DEG C of dry 6-12h, later in 80-120 DEG C of vacuum
Dry 4-24h, obtains Cr-MIL-101.
In some more preferred embodiments, the Cr (NO3)3·9H2O, terephthalic acid (TPA), water and hydrofluoric acid are molten
The molar ratio of liquid is 0.5-2:0.5-1.75:150-280:0.25-1.
In some embodiments, the aluminium salt includes any one in aluminum nitrate, aluminium chloride, aluminium isopropoxide and aluminium butoxide
Kind or two or more combinations.
In some embodiments, the auxiliary agent include sodium nitrate, sodium hydroxide, sodium chloride, potassium nitrate, potassium hydroxide,
Any one in potassium chloride, magnesium nitrate and calcium nitrate or two or more combinations.
In some embodiments, the solvent includes water and/or dehydrated alcohol.
In some embodiments, the drying temperature of first presoma is 80-150 DEG C, drying time 4-12h.
In some embodiments, the maturing temperature of first presoma is 400-900 DEG C, calcining time 4-24h.
The presoma after baking, is down to room temperature naturally, so that mesoporous chromium aluminium composite oxide catalyst be made.
The embodiment of the invention also provides a kind of mesoporous chromium aluminium composite oxide catalyst prepared by the method.
In some embodiments, chromium oxide, auxiliary agent and oxidation are contained in the mesoporous chromium aluminium composite oxide catalyst
Aluminium, wherein the mass percent of chromium oxide, auxiliary agent and aluminium oxide is 5-20: 0.5-2: 79.5-93.
In some embodiments, the aperture of the mesoporous chromium aluminium composite oxide catalyst is 5-20nm, specific surface area
For 60-400m2·g-1。
The embodiment of the invention also provides the mesoporous chromium aluminium composite oxide catalyst in low-carbon alkanes catalytic dehydrogenation system
Application in standby corresponding alkene.
The ranges such as mole value, temperature and time given by the above present invention include endpoint value.
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, further detailed by the following examples
Illustrate technical solution of the present invention.However, selected embodiment is merely to illustrate the present invention, and do not limit the scope of the invention.
Embodiment 1:
By 6.13g Al (i-OC3H7)3It is dissolved in 100mL dehydrated alcohol, is added at 0.56g vacuum with 0.038g KOH
After the Cr-MIL-101 of reason, 40 DEG C of constant temperature stirrings are volatilized completely to dehydrated alcohol, after 120 DEG C of dry 12h, 700 DEG C of roasting 6h,
Naturally it is down to room temperature, obtains the mesoporous chromium aluminium that chromium oxide, potassium oxide and quality of alumina percentage are respectively 10%, 2% and 88%
Composite oxide catalysts.The specific surface area of the catalyst is 197.6m2·g-1, average pore size 16.9nm.
Embodiment 2
By 11.25gAl (NO3)3·9H2O and 0.01 g KOH are dissolved in 100mL water, and 1.21gCr-MIL-101 is added
Afterwards, 90 DEG C of constant temperature stirrings are volatilized completely to water, after 150 DEG C of dry 4h, in 700 DEG C of roasting 4h, are down to room temperature naturally, must be aoxidized
Chromium, potassium oxide and quality of alumina percentage are respectively 20%, 0.5% and 79.5% mesoporous chromium aluminium composite oxide catalysis
Agent.The specific surface area of the catalyst is 66.0m2·g-1, average pore size 5.6nm.
Embodiment 3
By 7.24gAlCl3·6H2O and 0.07g KNO3It is dissolved in 100mL water, after 0.37g Cr-MIL-101 is added,
60 DEG C of constant temperature stirrings are volatilized completely to solution, after 100 DEG C of dry 6h, in 800 DEG C of roasting 6h, are down to room temperature naturally, must be aoxidized
Chromium, potassium oxide and quality of alumina percentage are respectively 7%, 2% and 91% mesoporous chromium aluminium composite oxide catalyst.This is urged
The specific surface area of agent is 102.0m2·g-1, average pore size 12.3nm.
Embodiment 4
By 11.25g Al (NO3)3·9H2O and 0.06g Ca (NO3)2·4H2O is dissolved in 50mL water and 50mL dehydrated alcohol
In the mixed solvent, be added 0.86g Cr-MIL-101 after, 50 DEG C of constant temperature stirrings are volatilized completely to solvent, in 80 DEG C of dry 12h
Afterwards, in 600 DEG C of roasting 8h, it is down to room temperature naturally, obtaining chromium oxide, potassium oxide and quality of alumina percentage is respectively 15%, 1%
With 84% mesoporous chromium aluminium composite oxide catalyst.The specific surface area of the catalyst is 86.9m2·g-1, average pore size is
6.8nm。
Embodiment 5
By 7.15g Al (i-OC3H7)3With 0.090g NaNO3It is dissolved in 100mL dehydrated alcohol, 0.56g Cr- is added
After MIL-101,60 DEG C of constant temperature stirrings are volatilized completely to solution, after 100 DEG C of dry 10h, in 900 DEG C of roasting 4h, are down to naturally
Room temperature obtains the mesoporous chromium aluminium composite oxygen that chromium oxide, potassium oxide and quality of alumina percentage are respectively 9%, 1.5% and 89.5%
Compound catalyst.The specific surface area of the catalyst is 149.4m2·g-1, average pore size 17.2nm.
Embodiment 6
By 5.90g Al (i-OC3H7)3With 0.204g Mg (NO3)2·6H2O is dissolved in 100mL dehydrated alcohol, is added
After 0.70gCr-MIL-101,60 DEG C of constant temperature stirrings are volatilized completely to solution, after 120 DEG C of dry 6h, for 24 hours in 400 DEG C of roastings,
Naturally it is down to room temperature, obtains the mesoporous chromium aluminium that chromium oxide, potassium oxide and quality of alumina percentage are respectively 13%, 2% and 85%
Composite oxide catalysts.The specific surface area of the catalyst is 337.2m2·g-1, average pore size 9.5nm.
Comparative example 1
By 0.90g Cr (NO3)3·9H2O and 0.050g KCl is dissolved in 100mL dehydrated alcohol and forms solution, is added
1.53g Al2O3Then the mixture is stirred in 40 DEG C of constant temperature to solution and is volatilized completely by powder, after 120 DEG C of dry 12h, in
700 DEG C of roasting 6h, are down to room temperature naturally, and obtaining chromium oxide, potassium oxide and quality of alumina percentage is respectively 10%, 2% and
88% chromium aluminium composite oxide catalyst.The specific surface area of the catalyst is 234.3m2·g-1, average pore size 3.4nm.
By the mesoporous chromium Al catalysts of the preparation of method described in embodiment 1 to embodiment 6 and comparative example 1 for propane or
The specific reaction condition of dehydrogenation of isobutane reaction are as follows: 1.0g catalyst is in N2After being heated to 600 DEG C under atmosphere, start to be passed through propane
Or isobutane gas, air speed 1200h-1, on-line analysis product.Reaction product passes through gas chromatograph (north point 3420, Beijing North
Divide Rayleigh analysis instrument company) twin columns dual detector on-line analysis.CO fills post separation, TCD detection by TDX.Hydrocarbon product by
γ-Al2O3(30m × 0.53mm × 10.0 μm) hydrogen hydrocarbon post separation, FID detection.Catalyst performance test result is as follows table 1:
Table 1.
As it can be seen from table 1 being had using mesoporous chromium aluminium composite oxide catalyst prepared by the method for the present invention good
Olefine selective.Embodiment 1-6 and comparative example 1 are compared, although they have common chemical composition, taken same
Catalysis test mode, but the mesoporous chromium aluminium composite oxide catalyst alkene relatively with higher of 1-6 of the embodiment of the present invention
Selectivity.Such as embodiment 1, compared with comparative example 1, Propylene Selectivity improves 1.6%, and selective isobutene improves
1.9%.
The used catalyst of embodiment 1 is regenerated, regenerative process are as follows: by the catalyst after reaction in N2In atmosphere
0.5h is purged, atmosphere temperature rising is then switched to 650 DEG C and carries out roasting 0.5h, then be passed through N2After purging 0.5h, it is passed through iso-butane
Gas the reaction was continued carry out catalytically active assessment, so circulation carry out 10 secondary responses.Urge agent the performance test results such as the following table 2:
Table 2.
From table 2 it can be seen that using the catalyst of the method for the present invention preparation after being recycled 10 times, iso-butane conversion ratio
With selective isobutene without the mesoporous chromium aluminium composite oxide catalyst tool for being decreased obviously, therefore being prepared using the method for the present invention
There is good regenerability.
In addition, inventor also utilize it is corresponding in the alternate embodiments 1-6 such as above listed other process conditions
Process conditions have carried out corresponding test, the content of required verifying and close with embodiment 1-6 product.So herein not to each
The verifying content of a embodiment is explained one by one, and only illustrates the excellent place of the present patent application using Examples 1 to 6 as representative.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from concept of the invention, other modification and improvement can also be made, these are all
It belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of mesoporous chromium aluminium composite oxide catalyst, characterized by comprising:
Aluminium salt and auxiliary agent are dissolved in solvent, are added vacuum-treated presoma containing chromium, stirring to solvent volatilization obtains the
One presoma；
By the first presoma dry roasting, mesoporous chromium aluminium composite oxide catalyst is made.
2. preparation method according to claim 1, it is characterised in that: stirring, which is included under 40-90 DEG C of constant temperature, stirs to molten
Agent volatilization.
3. preparation method according to claim 1, which is characterized in that the presoma containing chromium includes the organic bone of chromium Base Metal
Frame material；Preferably, the chromium Base Metal organic framework material is Cr-MIL-101.
4. preparation method according to claim 3, which is characterized in that the preparation method of the Cr-MIL-101 includes:
By Cr (NO3)3·9H2O, hydrofluoric acid solution is added into water in terephthalic acid (TPA) stirring and dissolving, continues to stir 1-4h, in
180-220 DEG C of crystallization 12-24h is down to room temperature, and filtering is placed on 80-120 DEG C of dry 6-12h, dry in 80-120 DEG C of vacuum later
Dry 4-24h, obtains Cr-MIL-101.
5. the preparation method according to claim 4, it is characterised in that: the Cr (NO3)3·9H2O, terephthalic acid (TPA), water
And the molar ratio of hydrofluoric acid solution is 0.5-2: 0.5-1.75: 150-280: 0.25-1.
6. preparation method according to claim 1, it is characterised in that: the aluminium salt includes aluminum nitrate, aluminium chloride, isopropanol
Any one in aluminium and aluminium butoxide or two or more combinations；And/or the auxiliary agent includes sodium nitrate, sodium hydroxide, chlorination
Any one in sodium, potassium nitrate, potassium hydroxide, potassium chloride, magnesium nitrate and calcium nitrate or two or more combinations；And/or institute
Stating solvent includes water and/or dehydrated alcohol.
7. preparation method according to claim 1, it is characterised in that: the drying temperature of first presoma is 80-150
DEG C, drying time 4-12h；And/or the maturing temperature of first presoma is 400-900 DEG C, calcining time 4-24h.
8. the mesoporous chromium aluminium composite oxide catalyst prepared by any one of claim 1-7 the method.
9. mesoporous chromium aluminium composite oxide catalyst according to claim 8, it is characterised in that: the mesoporous chromium aluminium is compound
Contain chromium oxide, auxiliary agent and aluminium oxide in oxide catalyst, wherein the mass percent of chromium oxide, auxiliary agent and aluminium oxide is 5-
20:0.5-2:79.5-93；And/or the aperture of the mesoporous chromium aluminium composite oxide catalyst is 5-20nm, specific surface area is
60-400m2·g-1。
10. mesoporous chromium aluminium composite oxide catalyst according to any one of claims 8 prepares corresponding alkene in low-carbon alkanes catalytic dehydrogenation
In application.
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