CN116943647A - PtSn catalyst with load type modified carrier, preparation method and application thereof in propane dehydrogenation coupling reverse water gas - Google Patents
PtSn catalyst with load type modified carrier, preparation method and application thereof in propane dehydrogenation coupling reverse water gas Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000001294 propane Substances 0.000 title claims abstract description 83
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 230000002441 reversible effect Effects 0.000 title claims abstract description 56
- 229910002847 PtSn Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000008878 coupling Effects 0.000 title claims abstract description 16
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 115
- 239000007789 gas Substances 0.000 claims abstract description 74
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 34
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract 3
- 238000010438 heat treatment Methods 0.000 claims description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 23
- 230000036961 partial effect Effects 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 16
- 239000012495 reaction gas Substances 0.000 claims description 13
- 230000010355 oscillation Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 150000004687 hexahydrates Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 abstract description 3
- 239000005431 greenhouse gas Substances 0.000 abstract description 2
- 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 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 abstract 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- -1 ethylene, propylene, butylene, butadiene Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a PtSn catalyst of a load type modified carrier, a preparation method and application thereof in propane dehydrogenation coupling reverse water gas, wherein the modified carrier is selected, sn is taken as an auxiliary agent, and load Pt is taken as an active component; the preparation method comprises soaking the carrier in aqueous solution of cerium nitrate, standing, drying, calcining at high temperature, and reducing at high temperature to obtain CeO with high defect site 2 Modifying carrier, immersing the carrier in the mixed aqueous solution of hexahydrated chloroplatinic acid or tetramine platinum nitrate and stannous chloride dihydrate,the PtSn/CA catalyst is obtained through standing, drying, high-temperature roasting, high-temperature reduction and the like, has high propane dehydrogenation and reverse water gas conversion capacity, can realize reaction process coupling through CO-feeding, and is used for preparing greenhouse gas CO 2 The purpose of propylene production is realized while the resource utilization is realized.
Description
Technical Field
The invention relates to a supported catalyst, in particular to CeO 2 Modified Al 2 O 3 (or SiO) 2 、SBA-15、ZrO 2 ) The PtSn catalyst loaded by the carrier and the preparation method thereof and the application of the catalyst in the process of preparing olefin by dehydrogenation of light alkane (taking propane dehydrogenation as an example) and preparing propylene by reverse water gas reaction and reverse water gas coupling propane dehydrogenation.
Background
Low-carbon olefins (such as ethylene, propylene, butylene, butadiene, etc.) are important chemical base materials, and can be used for producing various high-added-value chemicals, such as propylene, acetone, acrylonitrile, propylene oxide, etc. With the increasing demand for high additional products downstream, the demand for propylene is becoming more urgent. Traditional propylene is mainly derived from naphtha steam cracking, but with the development of shale gas technology, steam cracked feedstocks are shifted from petroleum-based naphtha to shale gas-based ethane, resulting in a great gap between worldwide limited propylene supply and increasing demand. Therefore, there is a need to develop efficient technology to meet the growing global demand for propylene.
The direct dehydrogenation processes of propane for the purpose of propylene production are currently mainly five, namely Catofin (Lummus), oleflex (UOP), STAR (UHDE), FBD (Snamprogetti and Yarsintez) and Linde-BASF PDH, all of which are carried out on a fixed bed with Pt-or Cr-based catalysts, and although the direct dehydrogenation processes have been studied for a long time and are used in industrial production, due to the strong endothermic reactions of the direct dehydrogenation processes, the thermodynamic limitations often require higher reaction temperatures (usually. Gtoreq.650℃) to obtain sufficiently high propylene yields. In addition, severe reaction conditions inevitably cause serious catalyst deactivation and thermal decomposition of propylene, limiting the application of the process.
Meanwhile, along with the increasing approach of 'double carbon' targets in China, CO serving as main greenhouse gas 2 If it can be used as resource, it can effectively promote the carbon peak and carbon neutralization. CO 2 Hydrogenation to CO and H 2 O(CO 2 +H 2 ＝CO+H 2 The reaction of O) is known as the reverse water gas reaction, which consists of CO 2 Starting from CO, it is an important step in the carbon cycle that high additional products can be further produced by the fischer-tropsch synthesis process. With CO 2 The reverse water gas reaction is considered to be the most reliable current technology route compared to sequestration. To sum up, if propane dehydrogenation can be coupled with reverse water gas reaction, the equilibrium of propane dehydrogenation reaction is pulled to right through reverse water gas reaction, and CO is consumed 2 Meanwhile, the aim of producing more propylene is achieved, and the synergistic effect is expected to be produced in various aspects such as environment, energy, economy and the like.
Disclosure of Invention
The invention aims to solve the technical problems of the existing Pt-based catalyst in a propane dehydrogenation and co-feeding carbon dioxide coupling reverse water gas reaction process, and provides a PtSn catalyst with a load type modified carrier, a preparation method and application thereof in propane dehydrogenation coupling reverse water gas.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a PtSn catalyst with a load type modified carrier and a preparation method thereof are prepared according to the following steps:
step 1, using Al 2 O 3 、SiO 2 SBA-15 or ZrO 2 Is taken as a carrier and takes the carrier as 100 percent, ceO 2 The mass percentage of the catalyst is 5-55 percent, ceO is used 2 Mass calculations corresponding to Ce (NO 3 ) 2 ·6H 2 O is dissolved in deionized water, the carrier is immersed in the deionized water, and the carrier is kept stand and dried after ultrasonic oscillation;
in step 1, ceO 2 The mass percentage of (2) is 10-20%.
In the step 1, ultrasonic oscillation is carried out for 15min-30min, standing is carried out for 5-12h at the room temperature of 20-30 ℃, and then drying is carried out for 5-12h in an oven at the temperature of 80-120 ℃.
Step 2, grinding the dried solid sample obtained in the step 1, heating to 450-650 ℃ in an air atmosphere from the room temperature of 20-30 ℃ at a programmed heating rate of 2-10 ℃/min, preserving heat and roasting for 1-5 h, and then cooling to the room temperature;
in step 2, the firing is performed using a muffle furnace.
In the step 2, the temperature is raised to 500-600 ℃ at a programmed temperature raising rate of 5-10 ℃ per minute from 20-30 ℃ in the air atmosphere, the temperature is kept for 2-4 hours, and then the air cooling is carried out to the room temperature.
Step 3, grinding the roasted sample obtained in the step 2, heating to 550-850 ℃ at a programmed heating rate of 2-10 ℃ per minute from the room temperature of 20-30 ℃ and preserving heat for 1-5 hours to reduce, and cooling to the room temperature along with a furnace to obtain CeO 2 Modifying the carrier; the reducing atmosphere is a mixed atmosphere of hydrogen and argon, and the volume percentage of the hydrogen is 5-20%;
in step 3, the temperature is raised to 650-750 ℃ from the room temperature of 20-30 ℃ at a temperature programming rate of 5-10 ℃ per minute, and the temperature is kept for 3-4 hours for reduction.
In step 3, the reduction is performed using a tube furnace.
In step 3, the volume percentage of hydrogen is 10% -20%.
Step 4, the CeO obtained in the step 3 is processed 2 Modifying the carrier, taking the carrier as 100%, taking the Pt as 0.1% -3% by mass and taking the Sn as 0.15% -5% by mass, calculating the corresponding chloroplatinic acid hexahydrate or platinum tetrammine nitrate, stannous chloride dihydrate as well as dissolving the corresponding chloroplatinic acid hexahydrate or the platinum tetrammine nitrate in deionized water or 0.1-0.5 mol/L hydrochloric acid aqueous solution, and adding CeO 2 Immersing the modified carrier therein, standing after ultrasonic oscillation, and drying;
in the step 4, the mass percentage of Pt is 0.5% -1%, and the mass percentage of Sn is 2.1% -2.5%.
In the step 4, the ultrasonic oscillation is carried out for 15min-30min, the standing is carried out for 5-12h at the room temperature of 20-30 ℃, and then the drying is carried out for 5-12h in an oven at the temperature of 80-120 ℃.
Step 5, grinding the dried solid sample obtained in the step 4, heating to 450-650 ℃ at a programmed heating rate of 2-10 ℃/min from the room temperature of 20-30 ℃ in an air atmosphere, preserving heat and roasting for 1-5 h, and then cooling to the room temperature;
in step 5, the firing is performed using a muffle furnace.
In the step 5, the temperature is raised to 500-600 ℃ at a programmed temperature raising rate of 5-10 ℃ per minute from 20-30 ℃ in the air atmosphere, the temperature is kept for 2-4 hours, and then the air cooling is carried out to the room temperature.
Step 6, grinding the roasted sample obtained in the step 5, heating to 500-600 ℃ from the room temperature of 20-30 ℃ at a programmed heating rate of 2-10 ℃/min, and preserving heat for 30-60 min to reduce, and cooling to the room temperature along with a furnace, wherein the reducing atmosphere is a mixed atmosphere of hydrogen and argon, and the volume percentage of the hydrogen is 5-20%;
in step 6, the reduction is performed using a tube furnace.
In step 6, the volume percentage of hydrogen is 10% -20%.
In step 6, the temperature is raised to 550-600 ℃ at a programmed temperature raising rate of 5-10 ℃ per minute from 20-30 ℃ at room temperature, and the temperature is kept for 40-60 min for reduction, and then the temperature is cooled to room temperature along with a furnace.
In the prepared catalyst, ceO is used as 2 As modifier, ceO is used 2 Modified Al 2 O 3 、SiO 2 SBA-15 or ZrO 2 Is carrier, pt is active component, sn is auxiliary agent, al is used 2 O 3 、SiO 2 SBA-15 or ZrO 2 Is calculated by 100 percent of the mass of CeO 2 The mass percentage of (2) is 5% -55%; with CeO 2 Modified Al 2 O 3 、SiO 2 SBA-15 or ZrO 2 The mass percentage of Pt is calculated as 100 percent0.1 to 3 percent and 0.15 to 5 percent of Sn.
Of these, ceO is preferable 2 As a carrier modifier, al 2 O 3 As carrier, ceO 2 The mass percentage of the alloy is 10-20%, the mass percentage of Pt is 0.5-1%, and the mass percentage of Sn is 2.1-2.5%.
The catalyst of the invention is applied to the preparation of propylene by propane dehydrogenation, reverse water gas reaction or the preparation of propylene by reverse water gas coupling propane dehydrogenation.
Tabletting and sieving the catalyst, selecting the catalyst with the mesh number of 20-40 mesh, loading the catalyst into a reactor, and introducing N 2 Purging, and introducing mixed gas of hydrogen and nitrogen to carry out H 2 Pretreating, cooling to a reaction temperature, and introducing a reaction gas to react, wherein in the mixed gas of hydrogen and nitrogen, the volume percentage of the hydrogen is 10% -30%, heating to 500 ℃ -600 ℃ from the room temperature of 20-30 ℃ at a programmed heating rate of 2 ℃/min-10 ℃/min, and maintaining for 30min-60min for hydrogen pretreatment;
dehydrogenating propane to prepare propylene: the reaction temperature is 500-600 ℃, preferably 500-550 ℃; c (C) 3 H 8 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system is maintained at 100kPa, and the partial pressure based on propane is 8 to 20kPa, preferably 14 to 18kPa.
Reverse water gas reaction: the reaction temperature is 500-600 ℃, preferably 500-550 ℃; CO 2 And H 2 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system was maintained at 100kPa, based on CO 2 Is 15kPa to 20kPa, based on H 2 Is preferably based on CO and has a partial pressure of 2kPa to 15kPa 2 Is 15kPa to 17kPa, based on H 2 The partial pressure of (2) is 14kPa to 15kPa.
Preparing propylene by reverse water gas coupling propane dehydrogenation: the reaction temperature is 500-600 ℃, preferably 500-550 ℃; CO 2 And C 3 H 8 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system was maintained at 100kPa, based on CO 2 Is 0kPa to 10kPa, based on C 3 H 8 Is 2kPa-15kPa, preferably based on CO 2 Is 8kPa to 10kPa, based on C 3 H 8 The partial pressure of (2) is 14kPa to 15kPa.
The invention adopts PtSn/Al with wide industrial application 2 O 3 Propane dehydrogenation catalyst is taken as an outlet point, and CO can be carried out by introducing 2 Activated reaction sites, coupling the two processes, ceO 2 Is a kind of catalyst with CO 2 Activating capacity metal oxide, ceO 2 Supported Pt-based catalysts have been reported in the reverse water gas reaction, but by reaction to PtSn/Al 2 O 3 CeO is introduced into the catalyst 2 No report was made. Dehydrogenation reaction occurs at Pt metal sites by modifying a propane dehydrogenation catalyst support, and CO occurs at the catalyst support 2 Activation reaction, CO-feeding propane and CO 2 Is used for coupling the reverse water gas reaction with the propane dehydrogenation reaction, and is applied to the coupling of the propane dehydrogenation reaction and the reverse water gas reaction-CO consumption 2 Meanwhile, the technical problem of propylene production is realized, and the application of the catalyst in propane dehydrogenation, reverse water gas and reverse water gas coupling propane dehydrogenation reactions is realized. The catalyst of the invention has high activity, high selectivity, low noble metal loading and high CO 2 Conversion, either for propane dehydrogenation or reverse water gas only, or for co-feed C 3 H 8 And CO 2 The propane dehydrogenation and the reverse water gas process are coupled when the reaction gas is generated.
The catalyst of the invention is prepared by using CeO 2 Modified Al 2 O 3 (or SiO) 2 、SBA-15、ZrO 2 ) The PtSn catalyst supported by the carrier has high specific surface area, is beneficial to the dispersion of active components, reduces the particle size of the active components, and is beneficial to inhibiting side reactions of structural sensitivity (the larger the particle size of the active components is, the more beneficial to the occurrence of side reactions) such as hydrogenolysis, isomerization, carbon deposition and the like which are accompanied in the dehydrogenation process of low-carbon alkane; secondly, the catalyst can be applied to propane dehydrogenation reaction, has higher propylene selectivity, can also be applied to reverse water gas reaction, and can be used for reducing H 2 Partial pressure and higher H 2 Maintaining proper CO within partial pressure range 2 Conversion capability withThe catalyst has excellent stability and can be applied to C 3 H 8 And CO 2 The CO-feed reaction system is characterized in that reverse water gas and propane dehydrogenation reaction are coupled to maintain a certain CO 2 While at the same time achieving conversion capability, higher propylene yields are achieved compared to the dehydrogenation of propane alone. The catalyst of the invention is prepared by a step-by-step impregnation method, and firstly, the modified carrier is prepared by the impregnation method, so that CO is improved 2 Activation capacity, and then loading propane dehydrogenation active component by impregnation method. The method has the advantages of easily available raw materials, easy learning of operation technology and high repeatability. The catalyst of the invention takes a Pt-based catalyst applied in propane dehydrogenation industry as a starting point, has excellent reverse water gas reaction activity after being subjected to carrier modification, and has certain industrial application significance.
Drawings
FIG. 1 shows the CeO obtained in example 1 2 Modified Al 2 O 3 Carrier, ptSn/CA catalyst and comparative PtSn/Al sample without modified carrier 2 O 3 Is a XRD pattern of (C).
FIG. 2 is a TEM photograph of the PtSn/CA catalyst prepared in example 1.
FIG. 3 is a graph showing the propane dehydrogenation activity at 550℃of the PtSn/CA catalyst prepared in example 1, wherein the upper curve corresponds to C 3 H 6 Selectivity, lower curve corresponds to C 3 H 8 Conversion rate.
FIG. 4 is a graph showing the reverse water gas activity at 550℃of the PtSn/CA catalyst prepared in example 2, wherein the curve corresponds to CO 2 Conversion rate.
FIG. 5 is a graph (1) showing the reverse water gas coupled propane dehydrogenation activity at 550℃of the PtSn/CA catalyst prepared in example 3, where the curve corresponds to CO 2 Conversion rate.
FIG. 6 is a graph (2) showing the reverse water gas coupled propane dehydrogenation activity at 550℃of the PtSn/CA catalyst prepared in example 3, wherein the upper curve corresponds to C 3 H 6 Selectivity, lower curve corresponds to C 3 H 8 Conversion rate.
FIG. 7 shows the different COs in example 4 2 And H is 2 Partial pressure ratio to inverseCO in a water gas reaction 2 Effect of conversion test results graphs.
FIG. 8 is a graph showing the effect of different reaction temperatures on propane dehydrogenation and reverse water gas coupled propane dehydrogenation reaction propane conversion in example 5.
FIG. 9 is a graph of the results of the test of the effect of different reaction temperatures on propane dehydrogenation and reverse water gas coupled propane dehydrogenated propylene selectivity in example 5.
FIG. 10 is a graph of the dehydrogenation of propane with the dehydrogenation of CO with reverse water gas coupled with propane at different reaction temperatures in example 5 2 Effect of conversion test results graphs.
FIG. 11 is a graph of different Sn to Pt molar ratios versus CO for example 6 2 Effect of conversion test results graphs.
FIG. 12 shows the molar ratio of Sn to Pt versus the CO derived from CO in example 6 2 The effect of the amount on the test result graph.
Detailed Description
The present invention is described in further detail below by way of specific examples, which will enable those skilled in the art to more fully understand the invention, but are not limited in any way.
In all of the examples below, the catalyst activity was measured as propane conversion, CO 2 Conversion and propylene selectivity and propylene yield are expressed and calculated by the following formula:
selectivity (S):
the flow rates of propane at the inlet and the outlet of the reactor are respectively represented in ml/min;
respectively representing the propylene flow rate at the outlet of the reactor, wherein the unit is ml/min;
conversion (X):
the flow rates of propane at the inlet and the outlet of the reactor are respectively represented in ml/min;respectively represents CO at the inlet and outlet of the reactor 2 Flow rate in ml/min;
yield (Y):
respectively representing the conversion rate of propane and the selectivity of propylene, wherein the units are as follows;
the source of CO in the product may represent the extent of side-reaction dry reforming, represented by the following formula:
respectively represents CO at the inlet and outlet of the reactor 2 Flow rate in ml/min;
represented by CO 2 CO produced in ml/min.
The reaction product was analyzed on line using a gas chromatograph.
Example 1
(1) Taking 1 part by mass of Al 2 O 3 As a carrier, and taking the carrier as 100 percent, ceO 2 The mass percentage is 10 percent, and CeO is used 2 Mass calculations corresponding to Ce (NO 3 ) 2 ·6H 2 O is dissolved in 3ml of deionized water;
(2) 1.000 parts by mass of Al 2 O 3 Soaking the mixture in the solution obtained in the step (1), fully stirring, oscillating, performing ultrasonic treatment for 30min, standing for 10h at the room temperature of 20-30 ℃, and then drying for 12h in a baking oven at the temperature of 120 ℃;
(3) Grinding the dried solid sample obtained in the step (2), heating to 500 ℃ at a programmed heating rate of 10 ℃/min in the air atmosphere of a muffle furnace from the room temperature of 20-30 ℃ and roasting for 4 hours, and then air-cooling to the room temperature;
(4) Grinding the roasted sample obtained in the step (3), heating to 750 ℃ in a tube furnace at a programmed heating rate of 10 ℃/min from 20-30 ℃ at room temperature, preserving heat for 4 hours for reduction, and cooling to room temperature along with the furnace to obtain CeO 2 Modified Al 2 O 3 A carrier; the atmosphere in the tube furnace is a mixed atmosphere of hydrogen and argon, and the volume percent of the hydrogen is 10 percent (the volume of the hydrogen is the sum of the volumes of the hydrogen and the argon);
(5) CeO obtained in the step (4) is subjected to 2 Modified Al 2 O 3 The carrier is taken as 100%, the mass percent of Pt is 0.5%, the mass percent of Sn is 2.1%, and corresponding chloroplatinic acid hexahydrate and stannous chloride dihydrate are calculated and dissolved in 3ml deionized water;
(6) CeO obtained in the step (4) is subjected to 2 Modified Al 2 O 3 Soaking the carrier in the solution obtained in the step (5), fully stirring, oscillating, performing ultrasonic treatment for 30min, standing for 10h at the room temperature of 20-25 ℃, and then drying for 12h in a baking oven at the temperature of 120 ℃;
(7) Grinding the dried solid sample obtained in the step (6), heating to 600 ℃ at a programmed heating rate of 10 ℃/min in the air atmosphere of a muffle furnace from 20-30 ℃ at room temperature, roasting for 4 hours, and then air-cooling to room temperature;
(8) Grinding the roasted sample obtained in the step (7), heating to 600 ℃ in a tube furnace at a programmed heating rate of 10 ℃/min from the room temperature of 20-30 ℃ and preserving the temperature for 60min for reduction, and then cooling to the room temperature along with the furnace to obtain the loaded CeO 2 Modified Al 2 O 3 PtSn catalyst (PtSn/CA) having carrier, in which catalyst CeO 2 10 mass percent of Pt, 0.5 mass percent of Sn and 2.1 mass percent of Sn; the atmosphere in the tube furnace is a mixed atmosphere of hydrogen and argon, and the volume percentage of the hydrogen is 10%;
(9) Tabletting and sieving the prepared PtSn/CA catalyst, wherein the mesh size is 20-40 meshes;
(10) Weighing 0.15g of the pressed granular catalyst obtained in the step (9), loading the catalyst into a quartz reaction tube of a fixed bed reactor, and introducing N 2 Purging for 10min;
(11) Introducing 30% H into the reaction system purged in the step (10) 2 /N 2 The mixture (volume percent of hydrogen: volume of hydrogen/total volume of hydrogen and nitrogen) was subjected to H 2 Pretreating, namely heating the mixture to 600 ℃ at a programmed heating rate of 10 ℃/min from the room temperature of 20-25 ℃ and keeping the mixture at the corresponding temperature for 60min;
(12) Naturally cooling the pretreated catalyst to 550 ℃;
(13) Introducing the pretreated catalyst into reaction gas to react, wherein for propane dehydrogenation reaction: c (C) 3 H 8 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system was kept at 100kPa, and the partial pressure based on propane was kept at 14kPa.
According to the preparation method and the technological parameters, al is directly used 2 O 3 Preparation of control PtSn/Al as Carrier 2 O 3 . As can be seen from FIG. 1, the XRD pattern reflects cubic fluorite CeO well 2 And gamma-Al 2 O 3 This suggests that we succeeded in the mixing phase of Al 2 O 3 The carrier is modified. However, no diffraction peaks related to Pt and Sn occur, which may be due to the fact that we prepared Pt and Sn species having smaller particle sizes and being highly dispersed on the surface of the support. As shown in FIG. 2, the supported PtSn catalyst with the prepared CeO2 modified Al2O3 carrier is characterized in that Pt is highly dispersed on the surface of the modified carrier, and the particle size is about 2nm.
For the propane dehydrogenation reaction, the propane conversion and propylene selectivity are plotted against time as shown in FIG. 3. It can be seen that the initial propane conversion was 40.6% with a selectivity of 95.3% and that the propylene selectivity remained high (95%) with a slight decrease in propane conversion over the reaction time.
Example 2
Catalyst preparation and reaction were carried out as in example 1, with the difference that in step (13), for the reverse water gas reaction: CO 2 And H 2 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system was maintained at 100kPa, based on CO 2 Is 17kPa, based on H 2 The partial pressure of (2) was 14kPa.
In the case of the reverse water gas reaction, carbon dioxide and hydrogen are used as reaction gases, and the target product is carbon monoxide, the selectivity of carbon monoxide is temporarily not considered in the invention, and only the conversion rate of raw material carbon dioxide is considered. As can be seen from FIG. 4, CO at a reaction temperature of 550 ℃ 2 And H is 2 The ratio of partial pressures is 17:14, the catalyst obtained has excellent CO 2 Conversion capability (> 63%), which indicates that the catalyst produced has reverse water gas reaction properties under the appropriate reaction conditions.
Example 3
Catalyst preparation and reaction were carried out as in example 1, except that in step (13) for the reverse water gas coupled propane dehydrogenation reaction: CO 2 And C 3 H 8 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system was maintained at 100kPa, based on CO 2 Is 8.6kPa, based on C 3 H 8 The partial pressure of (2) was 14kPa.
For the reverse water gas coupling propane dehydrogenation reaction, the raw material gas is carbon dioxide and propane, the reaction products are propylene, carbon monoxide, hydrogen and the like, and the propane conversion rate and CO are obtained 2 The conversion and propylene selectivity are shown in FIGS. 5 and 6 as a function of time. As can be seen from fig. 5 and 6, the initial propane conversion rate reaches 44.2%, which is approximately 45% higher than that of pure propane dehydrogenation, and the selectivity under the reverse water gas coupled propane dehydrogenation reaction condition is lower than that of pure propane dehydrogenation, the selectivity is generally about 90% and is maintained for a quite long time, but the total propylene yield is improved, especially the initial reaction period (within half an hour) is obviously higher than that of pure propane dehydrogenation; under the reaction condition, has a certain CO at the same time 2 Conversion capacity (-40%).
According to the data of example 1 and example 2 and the data of example 3, the prepared catalyst can couple propane dehydrogenation reaction and reverse water gas reaction, and has good CO while improving propylene yield 2 Conversion ability.
EXAMPLE 4 different COs 2 And H is 2 Influence of partial pressure ratio on reverse water gas reactivity
Catalyst preparation was carried out using the procedure of example 1 and performance evaluation reaction was carried out in example 2, differing only in the CO in step (13) 2 And H is 2 The ratio of partial pressures is 17:4.
for different COs in the above embodiments 2 And H is 2 CO in reverse water gas reactions at partial pressure ratios 2 The conversion was tested as shown in figure 7. When different COs are 2 And H is 2 When the partial pressure ratio increases, CO 2 Conversion increases and at different H 2 Under the partial pressure condition, the prepared catalyst is quite stable. This demonstrates that the catalyst produced has superior reverse water gas reactivity and stability.
Example 5 influence of different reaction temperatures on the Performance of propane dehydrogenation and reverse water gas coupled propane dehydrogenation reactions
(1) The catalyst preparation performance evaluation reaction was conducted using the method of example 1, except that the reaction temperature in step (12) was 500 ℃.
(2) The catalyst preparation was carried out using the method of example 1 and the performance evaluation reaction was carried out in example 3, except that the reaction temperature in step (12) was 500 ℃.
The conversion of propane at 500℃and 550℃for examples 1, 3 and (1) and (2) of example 5 and the conversion of CO at 500℃and 550℃for example 3 and (2) of example 5 2 Conversion was tested as shown in FIG. 8, 1 is the Propane Dehydrogenation (PDH) of example 1, 2 is the reverse water gas coupled propane dehydrogenation reaction (CO) of example 3 2 PDH), 3 is (1) in example 5, and 4 is (2) in example 5. As can be seen from the graph, the propane conversion rate of the propane dehydrogenation and the reverse water gas coupled propane dehydrogenation increases when the reaction temperature increases from 500 ℃ to 550 ℃, but the catalyst deactivation is accelerated due to the increase of the reaction temperature, and the temperature is selected to be 500-550 ℃ under the condition of comprehensively considering the activity and the conversion rate. At any temperature, the initial conversion rate of the reverse water gas coupled propane dehydrogenation is higher than that of pure propane dehydrogenation, which proves that the prepared catalyst can effectively perform reaction coupling and produce more propylene to a certain extent.
In FIG. 9, 1 is the Propane Dehydrogenation (PDH) of example 1, 2 is the reverse water gas coupled propane dehydrogenation reaction (CO) of example 3 2 PDH), 3 is (1) in example 5, and 4 is (2) in example 5. It can be seen from fig. 9 that the higher the reaction temperature, the closer the propylene selectivity for the propane dehydrogenation reaction, but the greater the difference in selectivity for the reverse water gas coupled propane dehydrogenation reaction, indicating that the high temperature reaction is detrimental to the reverse water gas coupled propane dehydrogenation reaction.
In FIG. 10, 1 is the reverse water gas coupled propane dehydrogenation reaction (CO) of example 3 2 PDH), 2 is the reverse water gas coupled propane dehydrogenation reaction (CO) of example 5 (2) 2 PDH), it can be seen from FIG. 10 that the higher the reaction temperature, the higher the CO 2 The higher conversion, in combination with the selectivity data in fig. 9, demonstrates that high temperatures can lead to side reactions, and therefore, suitable reaction temperatures are required for the reverse water gas coupled propane dehydrogenation reaction.
EXAMPLE 6 Effect of different mole ratios of Sn to Pt on reactivity
(1) The catalyst preparation was carried out by the method of example 1 and the performance evaluation reaction was carried out in example 3, except that the Sn mass percentage in step (5) was 0.3%, and the catalyst in this example was represented as Pt1Sn1/CA for convenience of representation, and correspondingly, the catalyst in example 1 was represented as Pt1Sn7/CA (atomic molar ratio of PtSn)
(2) The catalyst preparation was carried out by the method of example 1 and the performance evaluation reaction was carried out by the method of example 3, except that the Sn in step (5) was 0.9 mass%, and the catalyst was represented as Pt1Sn3/CA
(3) The catalyst preparation was carried out by the method of example 1 and the performance evaluation reaction was carried out by the method of example 3, except that the Sn in step (5) was 1.5% by mass, and the catalyst was represented as Pt1Sn5/CA
(4) The catalyst preparation was carried out by the method of example 1 and the performance evaluation reaction was carried out by the method of example 3, except that the Sn in step (5) was 3% by mass, and the catalyst was represented as Pt1Sn10/CA
(5) The catalyst preparation was carried out by the method of example 1 and the performance evaluation reaction was carried out in example 3, except that the Sn in step (5) was 4.5% by mass, and the catalyst was represented as Pt1Sn15/CA
For PtSn/CA catalysts of the same Pt content and different Sn content in the above examples, initial activity tests were performed using the same reaction conditions, using CO 2 Conversion rate andcatalyst performance is shown, see fig. 11 and 12. As can be seen from FIG. 11, when the molar ratio of Sn to Pt is increased from 1 to 3, CO 2 The conversion rate is slightly reduced, and CO is increased when the mole ratio of Sn to Pt is increased 2 The conversion remains substantially unchanged; as can be seen from fig. 12, when the molar ratio of Sn to Pt is increased from 1 to 15, it is derived from CO 2 CO from CO increases and decreases, when the molar ratio of Sn to Pt is 7 2 At a molar ratio of Sn to Pt of 7, the catalyst resists the dry weight of side reactionsThe whole capacity is the strongest.
The preparation of the catalyst can be achieved by adjusting the process parameters according to the present disclosure, and the test shows that the catalyst has properties substantially consistent with the present disclosure. The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. A PtSn catalyst with a load type modified carrier is characterized in that CeO is used for preparing 2 As modifier, ceO is used 2 Modified Al 2 O 3 、SiO 2 SBA-15 or ZrO 2 Is carrier, pt is active component, sn is auxiliary agent, al is used 2 O 3 、SiO 2 SBA-15 or ZrO 2 Is calculated by 100 percent of the mass of CeO 2 The mass percentage of (2) is 5% -55%; with CeO 2 Modified Al 2 O 3 、SiO 2 SBA-15 or ZrO 2 The alloy is prepared by the following steps of:
step 1, using Al 2 O 3 、SiO 2 SBA-15 or ZrO 2 Is taken as a carrier and takes the carrier as 100 percent, ceO 2 The mass percentage of the catalyst is 5-55 percent, ceO is used 2 Mass calculations corresponding to Ce (NO 3 ) 2 ·6H 2 O is dissolved in deionized water, the carrier is immersed in the deionized water, and the carrier is kept stand and dried after ultrasonic oscillation;
step 2, grinding the dried solid sample obtained in the step 1, heating to 450-650 ℃ in an air atmosphere from the room temperature of 20-30 ℃ at a programmed heating rate of 2-10 ℃/min, preserving heat and roasting for 1-5 h, and then cooling to the room temperature;
step 3, grinding the roasted sample obtained in the step 2, heating to 550-850 ℃ at a programmed heating rate of 2-10 ℃ per minute from the room temperature of 20-30 ℃ and preserving heat for 1-5 hours to reduce, and then cooling to the room temperature along with a furnaceObtaining CeO 2 Modifying the carrier; the reducing atmosphere is a mixed atmosphere of hydrogen and argon, and the volume percentage of the hydrogen is 5-20%;
step 4, the CeO obtained in the step 3 is processed 2 Modifying the carrier, taking the carrier as 100%, taking the Pt as 0.1% -3% by mass and taking the Sn as 0.15% -5% by mass, calculating the corresponding chloroplatinic acid hexahydrate or platinum tetrammine nitrate, stannous chloride dihydrate as well as dissolving the corresponding chloroplatinic acid hexahydrate or the platinum tetrammine nitrate in deionized water or 0.1-0.5 mol/L hydrochloric acid aqueous solution, and adding CeO 2 Immersing the modified carrier therein, standing after ultrasonic oscillation, and drying;
step 5, grinding the dried solid sample obtained in the step 4, heating to 450-650 ℃ at a programmed heating rate of 2-10 ℃/min from the room temperature of 20-30 ℃ in an air atmosphere, preserving heat and roasting for 1-5 h, and then cooling to the room temperature;
and 6, grinding the roasted sample obtained in the step 5, heating to 500-600 ℃ from the room temperature of 20-30 ℃ at a programmed heating rate of 2-10 ℃/min, and preserving the temperature for 30-60 min to reduce, and cooling to the room temperature along with a furnace, wherein the reducing atmosphere is a mixed atmosphere of hydrogen and argon, and the volume percentage of the hydrogen is 5-20%.
2. The PtSn catalyst having a modified supported carrier according to claim 1, wherein CeO is used as a catalyst 2 As a carrier modifier, al 2 O 3 As carrier, ceO 2 The mass percentage of the alloy is 10-20%, the mass percentage of Pt is 0.5-1%, and the mass percentage of Sn is 2.1-2.5%.
3. The supported modified-carrier PtSn catalyst according to claim 1, wherein in step 1, ceO 2 The mass percentage of the material is 10-20%, ultrasonic oscillation is carried out for 15-30 min, standing is carried out for 5-12h at the room temperature of 20-30 ℃, and then drying is carried out for 5-12h in an oven at the temperature of 80-120 ℃; in the step 4, the mass percentage of Pt is 0.5% -1%, the mass percentage of Sn is 2.1% -2.5%, the ultrasonic oscillation is carried out for 15min-30min, and the mixture is in a roomStanding for 5-12h at 20-30 ℃, and then drying in an oven at 80-120 ℃ for 5-12h.
4. The PtSn catalyst of claim 1, wherein in step 2, the catalyst is calcined using a muffle furnace, and is heated to 500-600 ℃ at a programmed heating rate of 5-10 ℃/min from 20-30 ℃ in an air atmosphere, and is calcined at a temperature for 2-4 hours, and then air-cooled to room temperature; in the step 5, roasting is carried out by using a muffle furnace, heating to 500-600 ℃ at a programmed heating rate of 5-10 ℃ per minute from 20-30 ℃ in an air atmosphere, preserving heat and roasting for 2-4 hours, and then cooling to the room temperature.
5. The PtSn catalyst of claim 1, wherein in step 3, the temperature is raised to 650-750 ℃ from 20-30 ℃ at a programmed rate of 5-10 ℃/min and maintained for 3-4 hours, the reduction is performed by a tube furnace, and the volume percentage of hydrogen is 10-20%; in the step 6, a tube furnace is used for reduction, the volume percentage of hydrogen is 10% -20%, the temperature is raised to 550 ℃ -600 ℃ from the room temperature of 20-30 ℃ at a programmed temperature raising rate of 5 ℃/min-10 ℃/min, the temperature is kept for 40-60 min, the reduction is carried out, and then the furnace is cooled to the room temperature.
6. The preparation method of the PtSn catalyst with the load type modified carrier is characterized by comprising the following steps:
step 1, using Al 2 O 3 、SiO 2 SBA-15 or ZrO 2 Is taken as a carrier and takes the carrier as 100 percent, ceO 2 The mass percentage of the catalyst is 5-55 percent, ceO is used 2 Mass calculations corresponding to Ce (NO 3 ) 2 ·6H 2 O is dissolved in deionized water, the carrier is immersed in the deionized water, and the carrier is kept stand and dried after ultrasonic oscillation;
step 2, grinding the dried solid sample obtained in the step 1, heating to 450-650 ℃ in an air atmosphere from the room temperature of 20-30 ℃ at a programmed heating rate of 2-10 ℃/min, preserving heat and roasting for 1-5 h, and then cooling to the room temperature;
step 3, grinding the roasted sample obtained in the step 2, heating to 550-850 ℃ at a programmed heating rate of 2-10 ℃ per minute from the room temperature of 20-30 ℃ and preserving heat for 1-5 hours to reduce, and cooling to the room temperature along with a furnace to obtain CeO 2 Modifying the carrier; the reducing atmosphere is a mixed atmosphere of hydrogen and argon, and the volume percentage of the hydrogen is 5-20%;
step 4, the CeO obtained in the step 3 is processed 2 Modifying the carrier, taking the carrier as 100%, taking the Pt as 0.1% -3% by mass and taking the Sn as 0.15% -5% by mass, calculating the corresponding chloroplatinic acid hexahydrate or platinum tetrammine nitrate, stannous chloride dihydrate as well as dissolving the corresponding chloroplatinic acid hexahydrate or the platinum tetrammine nitrate in deionized water or 0.1-0.5 mol/L hydrochloric acid aqueous solution, and adding CeO 2 Immersing the modified carrier therein, standing after ultrasonic oscillation, and drying;
step 5, grinding the dried solid sample obtained in the step 4, heating to 450-650 ℃ at a programmed heating rate of 2-10 ℃/min from the room temperature of 20-30 ℃ in an air atmosphere, preserving heat and roasting for 1-5 h, and then cooling to the room temperature;
and 6, grinding the roasted sample obtained in the step 5, heating to 500-600 ℃ from the room temperature of 20-30 ℃ at a programmed heating rate of 2-10 ℃/min, and preserving the temperature for 30-60 min to reduce, and cooling to the room temperature along with a furnace, wherein the reducing atmosphere is a mixed atmosphere of hydrogen and argon, and the volume percentage of the hydrogen is 5-20%.
7. The method for producing a PtSn catalyst on a modified carrier according to claim 6, wherein in step 1, ceO 2 The mass percentage of the material is 10-20%, ultrasonic oscillation is carried out for 15-30 min, standing is carried out for 5-12h at the room temperature of 20-30 ℃, and then drying is carried out for 5-12h in an oven at the temperature of 80-120 ℃; in the step 4, the mass percentage of Pt is 0.5% -1%, the mass percentage of Sn is 2.1% -2.5%, the ultrasonic oscillation is carried out for 15min-30min, and the mixture is kept stand for 5-12h at the room temperature of 20-30 DEG CThen drying in an oven at 80-120 ℃ for 5-12h.
8. The method for producing a PtSn catalyst on a modified support according to claim 6, wherein in step 2, a muffle furnace is used for calcination, and the temperature is raised to 500-600 ℃ at a programmed temperature rise rate of 5 ℃/min-10 ℃/min from 20-30 ℃ in an air atmosphere, and the temperature is kept for calcination for 2-4 hours, and then air-cooled to room temperature; in the step 5, roasting is carried out by using a muffle furnace, heating to 500-600 ℃ at a programmed heating rate of 5-10 ℃ per minute from 20-30 ℃ in an air atmosphere, preserving heat and roasting for 2-4 hours, and then cooling to the room temperature.
9. The method for preparing a PtSn catalyst of a modified carrier according to claim 6, wherein in step 3, the temperature is raised to 650-750 ℃ from 20-30 ℃ at a programmed temperature rise rate of 5-10 ℃/min and maintained for 3-4 hours for reduction, a tube furnace is used for reduction, and the volume percentage of hydrogen is 10% -20%; in the step 6, a tube furnace is used for reduction, the volume percentage of hydrogen is 10% -20%, the temperature is raised to 550 ℃ -600 ℃ from the room temperature of 20-30 ℃ at a programmed temperature raising rate of 5 ℃/min-10 ℃/min, the temperature is kept for 40-60 min, the reduction is carried out, and then the furnace is cooled to the room temperature.
10. The use of a PtSn catalyst on a modified carrier as claimed in any one of claims 1 to 5 in the dehydrogenation of propane to propylene, the reverse water gas reaction or the reverse water gas coupled propane dehydrogenation to propylene, wherein the catalyst is tableted, sieved, of a mesh size of 20 to 40 mesh, loaded into a reactor and introduced with N 2 Purging, and introducing mixed gas of hydrogen and nitrogen to carry out H 2 Pretreating, cooling to the reaction temperature, introducing a reaction gas to react, wherein in the mixed gas of hydrogen and nitrogen, the volume percentage of the hydrogen is 10% -30%, heating to 500 ℃ -600 ℃ from the room temperature of 20-30 ℃ at a programmed heating rate of 2 ℃/min-10 ℃/min, andmaintaining for 30-60 min for hydrogen pretreatment;
dehydrogenating propane to prepare propylene: the reaction temperature is 500-600 ℃, preferably 500-550 ℃; c (C) 3 H 8 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system is maintained at 100kPa, and the partial pressure based on propane is 8 to 20kPa, preferably 14 to 18kPa;
reverse water gas reaction: the reaction temperature is 500-600 ℃, preferably 500-550 ℃; CO 2 And H 2 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system was maintained at 100kPa, based on CO 2 Is 15kPa to 20kPa, based on H 2 Is preferably based on CO and has a partial pressure of 2kPa to 15kPa 2 Is 15kPa to 17kPa, based on H 2 The partial pressure of (2) is 14kPa to 15kPa.
Preparing propylene by reverse water gas coupling propane dehydrogenation: the reaction temperature is 500-600 ℃, preferably 500-550 ℃; CO 2 And C 3 H 8 As reaction gas, N 2 To balance the gas, the total pressure of the reaction system was maintained at 100kPa, based on CO 2 Is 0kPa to 10kPa, based on C 3 H 8 Is preferably based on CO and has a partial pressure of 2kPa to 15kPa 2 Is 8kPa to 10kPa, based on C 3 H 8 The partial pressure of (2) is 14kPa to 15kPa.
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