CN117225400B - Modified alumina carrier, preparation method and application - Google Patents
Modified alumina carrier, preparation method and application Download PDFInfo
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- CN117225400B CN117225400B CN202311524431.3A CN202311524431A CN117225400B CN 117225400 B CN117225400 B CN 117225400B CN 202311524431 A CN202311524431 A CN 202311524431A CN 117225400 B CN117225400 B CN 117225400B
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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 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 31
- 239000001294 propane Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 50
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 229910001868 water Inorganic materials 0.000 claims description 38
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 17
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 16
- 239000000600 sorbitol Substances 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 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 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- -1 zirconium nitrate-chromium nitrate Chemical compound 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- LBPYPRXFFYUUSI-UHFFFAOYSA-N furan-2-carbaldehyde;hydrate Chemical compound O.O=CC1=CC=CO1 LBPYPRXFFYUUSI-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 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
- 238000003775 Density Functional Theory Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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 alumina carrier, a preparation method and application thereof, and relates to the field of catalysts; the BET specific surface area of the modified alumina carrier is 300-400m 2 Per gram, pore volume of 0.5-1.2cm 3 And/g, the average pore diameter is 8-10nm. The preparation method of the modified alumina carrier is simple and efficient, can promote mesoporous generation, obtain the mesoporous carrier, further effectively inhibit carbon deposition of the catalyst by matching with active sites and surface groups when preparing the catalyst, and improve the service life of the catalyst, and finally the prepared catalyst can effectively improve the conversion rate of propane and the selectivity of propylene in the process of preparing propylene by dehydrogenating propane.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a modified alumina carrier, a preparation method and application.
Background
Propylene is one of the basic raw materials of three synthetic materials, and is widely applied to the processing of products such as polypropylene, phenol, acrylic acid and the like. At present, the propylene obtaining mode mainly comprises catalytic cracking of petroleum, cracking of diesel oil and naphtha, and the like, but along with the shortage of petroleum resources, oxidative dehydrogenation of propane to prepare propylene has become one of the important methods for preparing propylene.
Literature: du Kaimin, fan Jie research progress for the oxidative dehydrogenation of propane to propylene [ J]Chemical advances 2019, 38 (6): 2697-3706. The propane oxidative dehydrogenation catalyst systems reported in the literature in recent years (V-, cr-, co-, ni-, mo-, pt-, ce-and nonmetallic-based catalysts) have been reviewed and shown to be the major problems facing this field in terms of propylene selectivity and yield. Academic paper: zhou Hao propaneResearch on preparation of propylene by catalytic dehydrogenation [ D]The catalyst with different chromium loadings is prepared by an isovolumetric impregnation method by taking a chromium-based catalyst for preparing propylene by oxygen-free dehydrogenation of propane as a base and taking active alumina as a carrier and chromium-containing compounds such as chromium nitrate, chromium trioxide and the like as precursors, and the result shows that the introduction of rare earth elements can improve the conversion rate of propane and the selectivity of propylene in the reaction process, but the phenomenon that carbide blocks a catalyst hole and covers an active center in the use process can cause the activity of the catalyst to be reduced and further deactivated is also found. In addition, literature: guo Qiushuang, yang Yuwang, li Xiaoyun, etc. propane dehydrogenation to propylene Cr 2 O 3 /Al 2 O 3 Deactivation study of the catalyst [ J]Inorganic salt industry, 2019, 4 (4): 86-89. Cr is prepared by impregnation method using alumina as carrier 2 O 3 /Al 2 O 3 The catalyst is applied to the reaction of preparing propylene by dehydrogenating propane, and the result also shows that along with Cr 2 O 3 /Al 2 O 3 The catalyst is used for a long time, the trivalent chromium ions of the active components and the crystal phase of the alumina are changed, and the trivalent chromium ions of the active components on the surface of the catalyst gradually enter the crystal phase of the catalyst from the surface of the catalyst, so that the crystal form is changed, and the activity of the catalyst is reduced.
At present, the research of preparing the catalyst by taking alumina as a carrier and introducing other elements so as to improve the propylene selectivity or the service life of the catalyst is more, for example, the academic paper: shi Junjun the synthesis of mesoporous alumina carrier and its application in propane dehydrogenation catalysis [ D ] southeast university, 2013. Mesoporous alumina is used as propane dehydrogenation catalyst carrier, and rare earth element and alkaline earth element are used to modify the carrier so as to raise its heat stability and regulate its surface acidity, so that a series of catalysts are prepared, and its catalytic activity and selectivity are raised to a certain extent, and at the same time, the mesoporous channel catalyst has good carbon-holding capacity.
As further patent CN106944088A discloses a method for preparing a propylene catalyst by oxidative dehydrogenation of propane, the catalyst comprises a first active component, a second active component, a first auxiliary agent, a second auxiliary agent and a carrier; the preparation method of the catalyst comprises the following steps: firstly preparing a catalyst precursor B, then carrying out reduction treatment on the catalyst precursor B, dissolving an auxiliary precursor in water, uniformly mixing with a furfural water solution, then adding the mixture and the catalyst precursor B into a high-pressure reaction kettle, adding a solution D, carrying out reaction, treating and separating an obtained solid-liquid mixture, filtering the obtained solid sample, and then drying and roasting the solid sample to obtain the catalyst. The prepared catalyst has high reaction activity, low metal consumption and high propylene selectivity which can reach more than 50.3 percent. However, the invention uses a large amount of furfural water when preparing the catalyst, which is easy to cause the problems of safety and pollution, and the invention does not further explore the problems of service life of the related catalyst, etc.
Aiming at the problems of poor propylene selectivity, low conversion rate and easy deactivation of related catalysts in long-term use in the prior art, the invention provides a modified alumina carrier which has long service life and can effectively improve propylene selectivity and conversion rate, and a preparation method and application thereof.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a modified alumina carrier, a preparation method and application thereof, wherein the preparation method of the modified alumina carrier is simple and efficient, and can promote mesoporous generation, further inhibit carbon deposition of the alumina carrier, prolong the service life of the alumina carrier, and finally the prepared product can effectively improve the conversion rate of propane and the selectivity of propylene in the process of preparing propylene by dehydrogenating propane.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a modified alumina carrier, which comprises alumina, sodium, tungsten, zirconium and chromium; the BET specific surface area of the modified alumina carrier is 300-400m 2 Per gram, pore volume of 0.5-1.2cm 3 And/g, the average pore diameter is 8-10nm.
Further, the BET specific surface area of the modified alumina carrier is 307-400m 2 Per gram, pore volume of 0.58-1.19cm 3 And/g, the average pore diameter is 8.2-9.8nm.
Preferably, the modified alumina supportHas a BET specific surface area of 400m 2 Per gram, pore volume of 0.58-1.19cm 3 And/g, average pore diameter of 9.8nm.
Further, the raw materials of the modified alumina carrier comprise alumina, disodium hydrogen phosphate, tungstate, zirconium nitrate, chromium nitrate, sorbitol, glycerol and ethanol.
Further, the tungstate comprises ammonium tungstate and/or ammonium metatungstate; ammonium tungstate is preferred.
Further, the invention also provides a preparation method of the modified alumina carrier, which comprises the following steps:
(1) Mixing disodium hydrogen phosphate, tungstate and water, adding aluminum oxide, dipping, drying and roasting to obtain a precursor A;
(2) The precursor A is mixed with the solution A after being reduced, and the precursor B is obtained after the reaction; the solution A is a mixed solution of sorbitol, glycerol, ethanol and water;
(3) Mixing zirconium nitrate, chromium nitrate and water, adding the precursor B, dipping, drying and roasting to obtain the zirconium nitrate-chromium nitrate composite material.
Further, the time of the soaking in the step (1) is 5-6 hours, the temperature of the roasting is 400-500 ℃ and the time is 0.5-1 hour.
Further, the reduction in the step (2) is performed in a mixed gas of hydrogen and nitrogen, the temperature is 400-500 ℃, the time is 3-4h, and the pressure is 0.1-0.2MPa (absolute pressure).
Further, in the step (2), the reduction is specifically carried out by placing the precursor A in a nitrogen atmosphere, heating and introducing hydrogen for reduction; wherein the volume ratio of hydrogen to nitrogen is 1:1.
Further, the mass-to-volume ratio of the precursor A and the solution A is 1g (15-25) mL; preferably 1g:20mL.
Further, the temperature of the reaction in the step (2) is 600-700 ℃, the time is 1.5-2.5h, and the pressure is 2-4MPa.
Further, the weight ratio of the disodium hydrogen phosphate to the tungstate to the alumina in the step (1) is (4-5), the weight ratio of the disodium hydrogen phosphate to the tungstate to the alumina in the step (1) is (0.8-1), the weight ratio of the sorbitol to the glycerol to the ethanol to the water in the step (2) is (15-20), the weight ratio of the sorbitol to the glycerol to the ethanol to the water in the step (2) is (10-15), the weight ratio of the zirconium nitrate to the chromium nitrate to the precursor B in the step (3) is (0.5-1.5), the weight ratio of the sorbitol to the ethanol to the water in the step (10-15) is (3-5), and the weight ratio of the zirconium nitrate to the chromium nitrate to the precursor B in the step (3) is (1-2).
Preferably, the weight ratio of the disodium hydrogen phosphate, the tungstate and the alumina in the step (1) is 5:0.9:25, the weight ratio of the sorbitol, the glycerol, the ethanol and the water in the step (2) is 18:12:5:65, and the weight ratio of the zirconium nitrate, the chromium nitrate and the precursor B in the step (3) is 1:1:18.
Further, the firing in step (3) includes a secondary firing stage: the first stage roasting temperature is 400-500 deg.c for 0.5-1 hr, and the second stage roasting temperature is 700-800 deg.c for 1-2 hr.
Further, the firing includes a secondary firing stage: the temperature of the first stage roasting is 450 ℃, the time is 0.5h, the temperature of the second stage roasting is 800 ℃, and the time is 1.5h.
Further, the invention also provides a catalyst, which comprises the modified alumina carrier or the modified alumina carrier prepared by the preparation method.
Further, the catalyst includes a Cr-based catalyst.
Further, the modified alumina carrier prepared by the preparation method or the catalyst provided by the invention can be applied to propylene preparation by propane dehydrogenation.
The invention has the technical effects that:
1. according to the invention, alumina is used as a carrier, a plurality of elements are introduced to load the alumina to the surface, safer and more environment-friendly sorbitol, glycerol and ethanol are used in a water phase hydrogenation system, the diffusion of metal elements in a precursor is inhibited, the uniform dispersion of the metal elements on the carrier surface is promoted, and the BET specific surface area of the finally prepared modified alumina carrier can reach 300-400m 2 Per gram, pore volume of 0.5-1.2cm 3 And/g, the average pore diameter is 8-10nm. The prepared modified alumina carrier is further introduced with active ingredients to prepare the catalyst with high catalytic efficiency, so that the adsorption and desorption process is quickened, and the production is avoidedAnd the oxidation of the material effectively improves the conversion rate of propane and the selectivity of propylene.
2. According to the invention, through adjusting roasting parameters, roasting step by step, reasonably controlling temperature and time, and promoting micropore collapse, the multi-mesoporous carrier material is obtained, and the multi-mesoporous property of the carrier material is matched with surface groups and loaded active sites, so that the carbon deposit trend in long-term use can be effectively inhibited after the catalyst is prepared, and the service life is further prolonged.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
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.
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.
It should be noted that the raw materials used in the present invention are all common commercial products, and therefore the sources thereof are not particularly limited.
Example 1
The preparation method of the modified alumina carrier comprises the following steps:
(1) Uniformly mixing 4 parts of disodium hydrogen phosphate, 0.8 part of ammonium tungstate and a proper amount of water, adding 20 parts of aluminum oxide into the mixture, soaking the mixture for 5 hours, drying the mixture, and roasting the mixture at 400 ℃ for 1 hour to obtain a precursor A;
(2) Placing the precursor A in a nitrogen atmosphere, heating to 400 ℃, introducing hydrogen, reducing the mixture for 4 hours under the conditions of the volume ratio of nitrogen to hydrogen being 1:1 and 0.1MPa (absolute pressure), mixing the mixture with the solution A, adding the mixture into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, introducing hydrogen for replacement for 3 times, reacting for 2.5 hours under the conditions of the temperature being 600 ℃ and the pressure being 4MPa, filtering, discarding the filtrate, and drying to obtain a precursor B; wherein, the solution A is prepared by mixing 15 parts of sorbitol, 10 parts of glycerol, 3 parts of ethanol and 60 parts of water; 15mL of solution A is correspondingly added to each 1g of precursor A;
(3) Uniformly mixing 0.5 part of zirconium nitrate, 1 part of chromium nitrate and a proper amount of water, adding 15 parts of precursor B prepared by the method, immersing, drying, performing primary roasting at 400 ℃ for 1h, performing secondary roasting at 700 ℃ for 2h, and obtaining the modified alumina carrier.
The finally prepared modified alumina carrier contains alumina, sodium, tungsten, zirconium and chromium.
Example 2
The preparation method of the modified alumina carrier comprises the following steps:
(1) Uniformly mixing 5 parts of disodium hydrogen phosphate, 1 part of ammonium metatungstate and a proper amount of water, adding 30 parts of aluminum oxide into the mixture, immersing the mixture for 6 hours, drying the mixture, and roasting the mixture at 500 ℃ for 0.5 hour to obtain a precursor A;
(2) Placing the precursor A in a nitrogen atmosphere, heating to 500 ℃, introducing hydrogen, reducing the mixture for 3 hours under the conditions of the volume ratio of nitrogen to hydrogen being 1:1 and 0.2MPa (absolute pressure), mixing the mixture with the solution A, adding the mixture into a high-pressure reaction kettle together, sealing the high-pressure reaction kettle, introducing hydrogen for replacement for 3 times, reacting for 1.5 hours under the conditions of the temperature being 700 ℃ and the pressure being 2MPa, filtering, discarding the filtrate, and drying to obtain a precursor B; wherein, the solution A is prepared by mixing 20 parts of sorbitol, 15 parts of glycerol, 5 parts of ethanol and 70 parts of water; 25mL of solution A is correspondingly added to each 1g of precursor A;
(3) Uniformly mixing 1.5 parts of zirconium nitrate, 2 parts of chromium nitrate and a proper amount of water, adding 20 parts of precursor B prepared by the method, immersing, drying, performing primary roasting at 500 ℃ for 0.5h, performing secondary roasting at 800 ℃ for 1h, and obtaining the modified alumina carrier.
The finally prepared modified alumina carrier contains alumina, sodium, tungsten, zirconium and chromium.
Example 3
The preparation method of the modified alumina carrier comprises the following steps:
(1) Uniformly mixing 5 parts of disodium hydrogen phosphate, 0.9 part of ammonium tungstate and a proper amount of water, adding 25 parts of aluminum oxide into the mixture, soaking the mixture for 5 hours, drying the mixture, and roasting the mixture at 450 ℃ for 1 hour to obtain a precursor A;
(2) Placing the precursor A in a nitrogen atmosphere, heating to 350 ℃, introducing hydrogen, reducing the mixture for 4 hours under the conditions of nitrogen and hydrogen in a volume ratio of 1:1 and 0.1MPa (absolute pressure), mixing the mixture with the solution A, adding the mixture into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, introducing hydrogen for replacement for 3 times, reacting for 2 hours under the conditions of 650 ℃ and 3MPa, filtering, discarding the filtrate, and drying to obtain a precursor B; wherein, the solution A is prepared by mixing 18 parts of sorbitol, 12 parts of glycerol, 5 parts of ethanol and 65 parts of water; 20mL of solution A is correspondingly added to each 1g of precursor A;
(3) Mixing 1 part of zirconium nitrate, 1 part of chromium nitrate and a proper amount of water uniformly, adding 18 parts of precursor B prepared by the method, immersing, drying, performing primary roasting at 450 ℃ for 0.5h, and performing secondary roasting at 800 ℃ for 1.5h to obtain the modified alumina carrier.
The finally prepared modified alumina carrier contains alumina, sodium, tungsten, zirconium and chromium.
Comparative example 1
The preparation method of the modified alumina carrier comprises the following steps:
(1) Uniformly mixing 5 parts of disodium hydrogen phosphate, 0.9 part of ammonium tungstate and a proper amount of water, adding 25 parts of aluminum oxide into the mixture, soaking the mixture for 5 hours, drying the mixture, and roasting the mixture at 450 ℃ for 1 hour to obtain a precursor A;
(2) Placing the precursor A in a nitrogen atmosphere, heating to 350 ℃, introducing hydrogen, reducing the mixture for 4 hours under the conditions of nitrogen and hydrogen in a volume ratio of 1:1 and 0.1MPa (absolute pressure), mixing the mixture with the solution A, adding the mixture into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, introducing hydrogen for replacement for 3 times, reacting for 2 hours under the conditions of 650 ℃ and 3MPa, filtering, discarding the filtrate, and drying to obtain a precursor B; wherein, the solution A is prepared by mixing 35 parts of sorbitol and 65 parts of water; 20mL of solution A is correspondingly added to each 1g of precursor A;
(3) Mixing 1 part of zirconium nitrate, 1 part of chromium nitrate and a proper amount of water uniformly, adding 18 parts of precursor B prepared by the method, immersing, drying, performing primary roasting at 450 ℃ for 0.5h, and performing secondary roasting at 800 ℃ for 1.5h to obtain the modified alumina carrier.
Comparative example 2
The preparation method of the modified alumina carrier comprises the following steps:
(1) Uniformly mixing 5 parts of disodium hydrogen phosphate, 0.9 part of ammonium tungstate and a proper amount of water, adding 25 parts of aluminum oxide into the mixture, soaking the mixture for 5 hours, drying the mixture, and roasting the mixture at 450 ℃ for 1 hour to obtain a precursor A;
(2) Placing the precursor A in a nitrogen atmosphere, heating to 350 ℃, introducing hydrogen, reducing the mixture for 4 hours under the conditions of nitrogen and hydrogen in a volume ratio of 1:1 and 0.1MPa (absolute pressure), mixing the mixture with the solution A, adding the mixture into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, introducing hydrogen for replacement for 3 times, reacting for 2 hours under the conditions of 650 ℃ and 3MPa, filtering, discarding the filtrate, and drying to obtain a precursor B; wherein, the solution A is prepared by mixing 35 parts of glycerol and 65 parts of water; 20mL of solution A is correspondingly added to each 1g of precursor A;
(3) Mixing 1 part of zirconium nitrate, 1 part of chromium nitrate and a proper amount of water uniformly, adding 18 parts of precursor B prepared by the method, immersing, drying, performing primary roasting at 450 ℃ for 0.5h, and performing secondary roasting at 800 ℃ for 1.5h to obtain the modified alumina carrier.
Comparative example 3
The preparation method of the modified alumina carrier comprises the following steps:
(1) Uniformly mixing 5 parts of disodium hydrogen phosphate, 0.9 part of ammonium tungstate and a proper amount of water, adding 25 parts of aluminum oxide into the mixture, soaking the mixture for 5 hours, drying the mixture, and roasting the mixture at 450 ℃ for 1 hour to obtain a precursor A;
(2) Placing the precursor A in a nitrogen atmosphere, heating to 350 ℃, introducing hydrogen, reducing the mixture for 4 hours under the conditions of nitrogen and hydrogen in a volume ratio of 1:1 and 0.1MPa (absolute pressure), mixing the mixture with the solution A, adding the mixture into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, introducing hydrogen for replacement for 3 times, reacting for 2 hours under the conditions of 650 ℃ and 3MPa, filtering, discarding the filtrate, and drying to obtain a precursor B; wherein the solution A is prepared by mixing 35 parts of ethanol and 65 parts of water; 20mL of solution A is correspondingly added to each 1g of precursor A;
(3) Mixing 1 part of zirconium nitrate, 1 part of chromium nitrate and a proper amount of water uniformly, adding 18 parts of precursor B prepared by the method, immersing, drying, performing primary roasting at 450 ℃ for 0.5h, and performing secondary roasting at 800 ℃ for 1.5h to obtain the modified alumina carrier.
Comparative example 4
The preparation method of the modified alumina carrier comprises the following steps:
(1) Uniformly mixing 5 parts of disodium hydrogen phosphate, 0.9 part of ammonium tungstate and a proper amount of water, adding 25 parts of aluminum oxide into the mixture, soaking the mixture for 5 hours, drying the mixture, and roasting the mixture at 450 ℃ for 1 hour to obtain a precursor A;
(2) Mixing 1 part of zirconium nitrate, 1 part of chromium nitrate and a proper amount of water uniformly, adding 18 parts of precursor A prepared by the method, immersing, drying, performing primary roasting at 450 ℃ for 0.5h, and performing secondary roasting at 800 ℃ for 1.5h to obtain the modified alumina carrier.
1. Surface Performance parameter analysis of modified alumina Carrier in the present invention
Analysis of surface performance parameters: the modified alumina carrier in each example was degassed under vacuum at 300℃for 4 hours using an ASAP2020 specific surface area analyzer from America microphone instruments, and measured under 77K, the specific surface area was calculated using the BET equation, the pore volume was calculated using the BJH model, and the pore size distribution was analyzed using the DFT method to give Table 1.
TABLE 1 specific surface area results for modified alumina supports
2. Analysis of carbon deposition of catalyst prepared from modified alumina Carrier in the invention
Preparation of Cr-based catalyst: dissolving chromium nitrate in water to prepare a solution with the mass fraction of 10%, respectively soaking the modified alumina carriers in each example in the solution for 5 hours, drying in a drying box for 12 hours, and roasting in a muffle furnace for 4 hours at 600 ℃ to obtain the catalyst.
And (3) carbon deposition analysis: the temperature-programmed oxidation (TPO test) method is adopted, specifically, the method is carried out on a thermal analyzer, 30mg of the catalyst prepared by the modified alumina carrier in each example is taken as a sample, after the reaction time of 10 minutes, the temperature is increased from room temperature to 800 ℃ according to the temperature-increasing rate of 10 ℃/min under the air atmosphere of 50mL/min, and the carbon deposit amount is counted to Table 2.
TABLE 2 results of carbon deposit amount of modified alumina Carrier
3. Application of catalyst prepared from modified alumina carrier in propane dehydrogenation propylene preparation test
The preparation method of the Cr-series catalyst is the same as that of the second test; the prepared catalyst is used for a propylene preparation test of propane dehydrogenation;
the oxidative dehydrogenation of propane is carried out in a fixed window tubular reactor, and the specific parameters are as follows:
TABLE 3 reaction parameters
The conversion of propane and the selectivity of propylene are counted, and the calculation formula is as follows:
conversion of propane =×100%；
Propylene selectivity =×100%；
The results were counted in the following table:
TABLE 4 propane conversion and propylene selectivity results
As shown by combining the analysis of the results, the modified alumina prepared by the invention is a mesoporous carrier, and the specific surface area of the modified alumina can reach 300-400m 2 Per gram, pore volume of 0.5-1.2cm 3 And/g, the average pore diameter is 8-10nm, the alumina carrier can be used for preparing Cr catalysts, the carbon deposition amount of the finally prepared Cr catalysts is lower and is less than 3%, and meanwhile, the alumina carrier can realize improvement of propane conversion rate and propylene selectivity when the catalyst is applied to experimental verification of propylene preparation by propane dehydrogenation. In contrast, the surface pores of the carriers prepared in each comparative example are blocked by metal elements, so that the specific surface area is reduced, meanwhile, the surface mesopores of the carriers are relatively less, the problem of carbon deposition of the finally prepared catalyst is outstanding, and meanwhile, the propane conversion rate and the propylene selectivity are relatively low.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A modified alumina carrier, characterized in that: comprising alumina, sodium, tungsten, zirconium and chromium;
the BET specific surface area of the modified alumina carrier is 300-400m 2 Per gram, pore volume of 0.5-1.2cm 3 /g, average pore size of 8-10nm;
the raw materials of the modified alumina carrier comprise alumina, disodium hydrogen phosphate, tungstate, zirconium nitrate, chromium nitrate, sorbitol, glycerol and ethanol;
the preparation method of the modified alumina carrier comprises the following steps:
(1) Mixing disodium hydrogen phosphate, tungstate and water, adding aluminum oxide, dipping, drying and roasting to obtain a precursor A;
(2) The precursor A is reduced and then mixed with the solution A, the mixture is added into a high-pressure reaction kettle together, the high-pressure reaction kettle is sealed and then is filled with hydrogen for replacement for 3 times, and the precursor B is obtained after reaction; the solution A is a mixed solution of sorbitol, glycerol, ethanol and water;
(3) Mixing zirconium nitrate, chromium nitrate and water, adding a precursor B for dipping, drying and roasting to obtain the zirconium nitrate-chromium nitrate composite material;
the temperature of the reaction in the step (2) is 600-700 ℃, the time is 1.5-2.5h, and the pressure is 2-4MPa; the weight ratio of the disodium hydrogen phosphate to the tungstate to the alumina in the step (1) is (4-5) (0.8-1) (20-30), the weight ratio of the sorbitol to the glycerol to the ethanol to the water in the step (2) is (15-20) (10-15) (3-5) (60-70), and the weight ratio of the zirconium nitrate to the chromium nitrate to the precursor B in the step (3) is (0.5-1.5) (1-2) (15-20); the firing in step (3) includes a secondary firing stage: the first stage roasting temperature is 400-500 deg.c for 0.5-1 hr, and the second stage roasting temperature is 700-800 deg.c for 1-2 hr.
2. The modified-alumina support of claim 1, wherein: the tungstate comprises ammonium tungstate and/or ammonium metatungstate.
3. The method for producing a modified alumina carrier according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) Mixing disodium hydrogen phosphate, tungstate and water, adding aluminum oxide, dipping, drying and roasting to obtain a precursor A;
(2) The precursor A is reduced and then mixed with the solution A, the mixture is added into a high-pressure reaction kettle together, the high-pressure reaction kettle is sealed and then is filled with hydrogen for replacement for 3 times, and the precursor B is obtained after reaction; the solution A is a mixed solution of sorbitol, glycerol, ethanol and water;
(3) Mixing zirconium nitrate, chromium nitrate and water, adding a precursor B for dipping, drying and roasting to obtain the zirconium nitrate-chromium nitrate composite material;
the temperature of the reaction in the step (2) is 600-700 ℃, the time is 1.5-2.5h, and the pressure is 2-4MPa; the weight ratio of the disodium hydrogen phosphate to the tungstate to the alumina in the step (1) is (4-5) (0.8-1) (20-30), the weight ratio of the sorbitol to the glycerol to the ethanol to the water in the step (2) is (15-20) (10-15) (3-5) (60-70), and the weight ratio of the zirconium nitrate to the chromium nitrate to the precursor B in the step (3) is (0.5-1.5) (1-2) (15-20); the firing in step (3) includes a secondary firing stage: the first stage roasting temperature is 400-500 deg.c for 0.5-1 hr, and the second stage roasting temperature is 700-800 deg.c for 1-2 hr.
4. A method of preparation according to claim 3, characterized in that: the time of the soaking in the step (1) is 5-6h, the roasting temperature is 400-500 ℃ and the time is 0.5-1h.
5. A method of preparation according to claim 3, characterized in that: the reduction in the step (2) is carried out in a mixed gas of hydrogen and nitrogen, the temperature is 400-500 ℃, and the time is 3-4h.
6. A catalyst, characterized in that: a modified alumina carrier comprising the modified alumina carrier according to any one of claims 1 to 2 or the modified alumina carrier produced by the production method according to any one of claims 3 to 5.
7. Use of the modified alumina carrier according to any one of claims 1-2, the modified alumina carrier produced by the production process according to any one of claims 3-5 or the catalyst according to claim 6 in the dehydrogenation of propane to propylene.
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