CN115382541B - Method for regulating existence form of Rh species in rhodium-based catalyst - Google Patents
Method for regulating existence form of Rh species in rhodium-based catalyst Download PDFInfo
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- CN115382541B CN115382541B CN202211000625.9A CN202211000625A CN115382541B CN 115382541 B CN115382541 B CN 115382541B CN 202211000625 A CN202211000625 A CN 202211000625A CN 115382541 B CN115382541 B CN 115382541B
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- catalyst
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- rhodium
- formaldehyde
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- 239000010948 rhodium Substances 0.000 title claims abstract description 305
- 239000003054 catalyst Substances 0.000 title claims abstract description 159
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 50
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 156
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 238000011068 loading method Methods 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 230000002776 aggregation Effects 0.000 claims abstract description 4
- 238000004220 aggregation Methods 0.000 claims abstract description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 125000004429 atom Chemical group 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000002161 passivation Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000008247 solid mixture Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OHGGMGNYWFOMBC-UHFFFAOYSA-M Cl[Rh].[Na] Chemical compound Cl[Rh].[Na] OHGGMGNYWFOMBC-UHFFFAOYSA-M 0.000 claims description 2
- LGZVIFDFEQVAKL-UHFFFAOYSA-N azane cerium(3+) trinitrate Chemical compound N.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LGZVIFDFEQVAKL-UHFFFAOYSA-N 0.000 claims description 2
- 229960001759 cerium oxalate Drugs 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 230000001276 controlling effect Effects 0.000 abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 53
- 230000000694 effects Effects 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000007210 heterogeneous catalysis Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000012695 Ce precursor Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LVGLLYVYRZMJIN-UHFFFAOYSA-N carbon monoxide;rhodium Chemical group [Rh].[Rh].[Rh].[Rh].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] LVGLLYVYRZMJIN-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- -1 glycol compound Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Classifications
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Composite Materials (AREA)
- Thermal Sciences (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for regulating and controlling the existence form of Rh species in a rhodium-based catalyst, wherein the rhodium-based catalyst is Rh/CeO 2 The catalyst is characterized in that the carrier of the catalyst is cerium oxide, the active component is an Rh species, and the Rh species exists in one or more forms of Rh single atoms, rh atom clusters formed by a plurality of Rh single atoms or Rh nano particles formed by the aggregation of the Rh atom clusters; based on Rh/CeO 2 Is supported in an amount of 0.05 to 2.0wt% based on the total mass of the Rh species. The invention adopts the method of electrostatic adsorption, high-temperature roasting and reduction to prepare Rh/CeO 2 The catalyst can control the existence form of the Rh species by regulating the loading of the Rh species. Further, rh/CeO of the present invention 2 When Rh species in the catalyst exist in a form of Rh atom clusters, the Rh atom clusters are used for formaldehyde hydroformylation reaction, so that the Rh atom clusters have high catalytic activity, glycolaldehyde selectivity and stability, and industrial application is easy to realize.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for regulating and controlling the existence form of Rh species in a rhodium-based catalyst and application of the prepared catalyst in formaldehyde hydroformylation heterogeneous catalytic reaction.
Background
Ethylene glycol is an important organic chemical basic raw material, is the simplest glycol compound, has chemical properties similar to ethanol, has wide application, and can be used for synthesizing various high-added-value chemicals, such as polyester fibers, polyester resin, antifreezing agent, coolant and the like, wherein the production of the polyester fibers accounts for more than 90% of the apparent demand of the ethylene glycol. In recent years, the polyester industry in China is rapidly developed, the ethylene glycol demand is kept to be increased, the apparent ethylene glycol demand in China is expected to reach 2560 ten thousand tons by the end of 2022 year, however, the domestic productivity is limited, and most of the ethylene glycol demand still depends on import. Therefore, the improvement of the industrial synthesis process route of the glycol is expected to improve the production capacity of the glycol in China and reduce the production cost of downstream products.
The direct synthesis of synthesis gas, proposed by DuPont in 1948 (patent US 2534018A), is considered to be the simplest and most efficient method for synthesizing ethylene glycol. The route accords with the principle of atom economy, has the advantages of short process flow, less equipment investment, wide raw material sources, low production cost and the like, and receives wide attention. At present, catalysts for directly synthesizing glycol from synthesis gas are mainly homogeneous Rh-based, ru-based and Co-based catalysts, and particularly rhodium-phosphine complex homogeneous catalysts. Patent US 3833634A in 1974 reports a rhodium carbonyl complex catalyst for directly synthesizing glycol from synthesis gas under high temperature and high pressure (230 ℃ and 172 MPa) conditionAnd propose the generation of glycol and H x Rh(CO) y (L) z (x=0-1, y=1-3, z=1-3, x+y+z=3-5) species are closely related. In 1980, research by Keim et al, german, university of Industrial science (J.Catal.1980, 61 (2), 359-365.) found that Rh (CO) was found to be effective at 230℃and 200MPa 2 The acac catalyst shows better catalytic performance in a polar solvent N-methyl pyrrolidone, the selectivity of ethylene glycol in a liquid phase product is 44.4%, but in a nonpolar solvent toluene, methanol as a byproduct is mainly generated. Keim et al believe that Rh has excellent hydrogenation activity in polar solvents, and is capable of catalyzing the hydrogenation of formyl species to hydroxymethyl species, thereby promoting the insertion of carbonyl groups to form glycolaldehyde key intermediates, followed by hydrogenation to form ethylene glycol. Although the direct process enables the one-step conversion of synthesis gas to ethylene glycol, the reaction conditions required are extremely demanding and the selectivity of ethylene glycol in the product is low, so achieving direct synthesis of ethylene glycol from synthesis gas under mild conditions is a significant challenge.
The reaction principle of directly synthesizing glycol from synthesis gas comprises three continuous steps of CO hydrogenation to formaldehyde, formaldehyde hydroformylation to glycolaldehyde and glycolaldehyde hydrogenation to glycol, wherein the formaldehyde hydroformylation to glycolaldehyde step is a key for influencing glycol production. Compared with the whole reaction, the intermediate step of formaldehyde hydroformylation is easy to occur in thermodynamics, so researchers pay more attention to the formaldehyde hydroformylation process, and the aim is to reduce the temperature and pressure required by a direct synthesis route and improve the selectivity and yield of ethylene glycol through catalyst design and reaction mechanism research. At present, the reported catalyst systems are similar to those of the direct process, mainly Rh-based, ru-based and Co-based homogeneous catalysts, wherein the activity of the Rh-based catalyst is optimal. In 1977 patent EP 0002908A, rhodium carbonyl complexes were reported to be capable of formylating formaldehyde under milder conditions. Patent US 4405814a in 1983 reports on RhCl (CO) (PPh 3 ) 2 And N, N-dibutyl formamide, a small amount of triethylamine (110 ℃ and 28.5MPa of synthetic gas pressure) is added into a homogeneous system formed by the N, N-dibutyl formamide, so that the conversion rate of formaldehyde and the selectivity of glycolaldehyde can be respectively improved to 86% and 91%. Although rhodium complexes are capable of effecting formaldehyde hydroformylation processes, the reactionThe generation still needs higher synthesis gas pressure, and the noble metal Rh catalyst dosage is larger (more than or equal to 4 multiplied by 10) -3 mol/L), separation and recovery are difficult after the reaction.
In the prior art, rh-based catalysts are generally prepared by an impregnation method, that is, rh active components are loaded on the surface of a carrier by an impregnation method, and the preparation method has the following problems: 1. the prepared active component Rh on the surface of the Rh-based catalyst carrier has poor dispersity, rh exists in the form of agglomerated nano particles, and the nano particles of Rh with the surface copper species of Rh single atoms or Rh atomic clusters composed of a plurality of Rh single atoms can not be obtained at all, so that the size of the Rh atomic clusters and the existence form of Rh species can be freely regulated and controlled. 2. Because the noble metal Rh has higher cost, if the loading of Rh is used for reducing the cost, the catalytic activity of the Rh-based catalyst is low, the loading is large, the cost is high, the active components of Rh are seriously agglomerated, and Rh exists in the form of nano particles, so that the preparation of the Rh-based catalyst by an impregnation method has the difficult problem of ensuring that the loading is less, the Rh dispersibility is good and the catalytic activity is high.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling Rh/CeO 2 The method for existence form of Rh species in the catalyst can obtain Rh/CeO in which the Rh species exist in one or more forms of Rh nano particles formed by Rh single atoms, rh atom clusters formed by Rh single atoms or Rh atom clusters agglomerated by Rh atoms 2 A catalyst. Furthermore, rh/CeO of the invention 2 When Rh species in the catalyst exist in the form of Rh atom clusters, the catalyst is used for formaldehyde hydroformylation heterogeneous catalytic reaction, has the characteristics of mild reaction conditions, high reaction activity, high glycolaldehyde selectivity, high stability, easy separation and recovery and the like, and is a potential industrialized catalyst
In addition, the method can obtain the noble metal-based solid catalyst with atomically dispersed, thereby realizing that a plurality of reactions are catalyzed from homogeneous phase to heterogeneous phaseThe atomic-level dispersed noble metal-based solid catalyst retains the high activity of the homogeneous catalyst on one hand and has the high stability and the recyclability of the heterogeneous catalyst on the other hand. Rh/CeO in the invention 2 The catalyst has the advantages of simple preparation method, high catalytic activity, glycolaldehyde selectivity and stability, and easy realization of industrial application.
The invention aims to provide Rh/CeO for heterogeneous catalysis of formaldehyde hydroformylation 2 The preparation scheme of the catalyst has the characteristics of simple operation, high repeatability and the like.
In order to achieve the aim of the invention, the specific technical scheme of the invention is as follows:
the first aspect of the present invention provides a method for controlling the form of presence of Rh species in a rhodium-based catalyst, wherein the rhodium-based catalyst is Rh/CeO 2 The catalyst comprises a carrier and an active component, wherein the carrier is cerium oxide, the active component is an Rh species, and the Rh species exists in one or more forms of Rh single atoms, rh atom clusters formed by a plurality of Rh single atoms or Rh nano particles formed by the aggregation of the Rh atom clusters; based on the Rh/CeO 2 The loading of the Rh species is 0.05-2.0wt%;
the Rh/CeO 2 The preparation method of the (C) comprises the following steps:
1) And (3) preparing a carrier: ceO is weighed 2 Grinding, crushing and screening to below 300 meshes to obtain CeO 2 A carrier;
2) Preparation of an active component precursor: weighing rhodium precursor, dissolving in a solvent, and performing ultrasonic treatment until the rhodium precursor is completely dissolved to obtain rhodium precursor solution;
3) Mixing: dropwise adding the rhodium precursor solution in the step 2) to the CeO of the step 1) 2 Magnetic stirring is kept on the carrier to obtain suspension, and the suspension is sealed;
4) Electrostatic adsorption: continuously stirring the suspension in the step 3) to perform electrostatic adsorption to obtain a suspension subjected to electrostatic adsorption;
5) Removing the solvent: evaporating the suspension subjected to electrostatic adsorption obtained in the step 4) to dryness, and removing the solvent to obtain a solid mixture;
6) Drying and crushing: drying, grinding and crushing the solid mixture obtained in the step 5) to obtain catalyst precursor powder;
7) Roasting: placing the catalyst precursor powder obtained in the step 6) in a muffle furnace for high-temperature roasting to obtain roasted catalyst powder;
8) And (3) reduction: placing the calcined catalyst powder obtained in the step 7) in a tube furnace, and reducing in a reducing atmosphere to obtain reduced catalyst powder;
9) Passivation: passivating the reduced catalyst powder obtained in the step 8) in an inert atmosphere (the reducing atmosphere in a tube furnace can be directly changed into the inert atmosphere), and obtaining the Rh/CeO after passivation 2 A catalyst;
wherein, when the Rh loading is 0.05-0.2wt%, including 0.05wt% and excluding 0.2wt%, rh/CeO 2 Rh species are present on the catalyst in monoatomic form;
when the Rh-carrying amount is 0.2 to 0.7wt%, 0.2wt% is included and 0.7wt% is excluded, rh/CeO 2 Rh species on the catalyst exist in the form of monoatomic Rh and clustered Rh;
when the Rh-carrying amount is 0.7 to 1.0wt%, it is 0.7wt% and 1.0wt% is included, rh/CeO 2 The Rh species on the catalyst exist in the form of Rh atom clusters;
when the Rh-carrying amount is 1.0 to 2.0wt%, 1.0wt% is excluded and 2.0wt% is included, rh/CeO 2 The Rh species on the catalyst exist in the form of Rh clusters and Rh nanoparticles.
When the Rh loading is higher than 2.0wt%, rh/CeO 2 The Rh species on the catalyst are present in the form of Rh nanoparticles.
Preferably, ceO as described in step 1) 2 Can be commercially available CeO 2 Or CeO synthesized by a laboratory using various cerium sources 2 The cerium source is selected from one or more of cerium carbonate, cerium oxalate, cerium chloride, cerium nitrate and cerium ammonia nitrate. More preferably, the carrier in step 1) is commercially available CeO 2 Grinding, crushing and sieving to below 300 mesh.
Preferably, in the step 2), the rhodium precursor is selected from one or more of tetrarhodium dodecacarbonyl, hexarhodium dodecacarbonyl, rhodium acetylacetonate dicarbonyl, rhodium chloride, rhodium iodide, rhodium nitrate and sodium chlororhodium; in the step 2), the solvent is one or more selected from deionized water, absolute methanol, absolute ethanol, acetone and toluene. More preferably, in step 2), rhodium dicarbonyl acetylacetonate is used as the Rh precursor, and acetone is used as the solvent.
Preferably, in step 3), the stirring temperature is 20-60 ℃ and the dropping speed is 1-10mL/min. More preferably, the Rh precursor solution is added dropwise at 30-50deg.C in step 3) at a drop rate of 2mL/min.
Preferably, in the step 4), the electrostatic adsorption temperature is 20-60 ℃ and the electrostatic adsorption time is 12-72h. More preferably, the electrostatic adsorption is performed in step 4) at 30-50 ℃ for a period of 12-36 hours.
Preferably, in step 5), the evaporation to dryness is carried out at a temperature of 30-80 ℃ and the evaporation to dryness method is selected from normal pressure drying or reduced pressure rotary evaporation. More preferably, in step 5) the rotary evaporation is carried out at a reduced pressure of 30-50 ℃ and the solvent is pumped off to a solid.
Preferably, in step 6), drying is carried out in air at a drying temperature of 50-110 ℃ for 6-12 hours; crushing and sieving to 100-300 mesh. More preferably, the drying temperature in step 6) is 80-100℃for a period of 8-12 hours. More preferably, the screen is sized to 300 mesh or less.
Preferably, in the step 7), the roasting temperature is 200-900 ℃, the heating rate is 1-10 ℃/min, and the roasting time is 2-12h. More preferably, the calcination temperature in step 7) is 600-800℃for a period of 5-10 hours.
Preferably, in the step 8), the reducing atmosphere is hydrogen, or a mixture of hydrogen and nitrogen, or a mixture of hydrogen and argon, the flow rate of the reducing gas is 20-100mL/min, the reducing temperature is 300-700 ℃, the heating rate is 1-10 ℃/min, and the reducing time is 1-5h; more preferably, in the step 8), the reducing atmosphere is hydrogen or a hydrogen-containing mixed gas, the hydrogen content in the mixed gas is 10% -50%, the other gases except hydrogen are nitrogen, argon or helium, the gas flow rate is 50-80mL/min, the reducing temperature is 400-600 ℃, and the time is 2-4h.
Preferably, in the step 9), the passivation atmosphere is nitrogen, argon or an oxygen-containing mixed gas, wherein the oxygen content in the mixed gas is 1-5%, and the passivation time is 1-5h. More preferably, the passivation gas in the step 9) is nitrogen, argon or an oxygen-containing mixed gas, wherein the oxygen content in the mixed gas is 1% -5%, and the passivation time is 1-3h.
The second aspect of the invention provides an application of the rhodium-based catalyst prepared by the method of the first aspect of the invention, wherein the rhodium-based catalyst is Rh/CeO 2 Catalyst, said Rh/CeO 2 The catalyst is applied to formaldehyde hydroformylation heterogeneous catalytic reaction;
specifically, the Rh/CeO 2 The catalyst is applied to the formaldehyde hydroformylation reaction of the liquid-solid batch kettle, and the reaction conditions are as follows: the reaction raw materials are formaldehyde, CO and H 2 Mixture of gas, CO and H 2 The molar ratio is 1:1, the ligand is an organic phosphine ligand, the molar ratio of the ligand to Rh is 10-35, the reaction temperature is 50-200 ℃, the pressure is 1-10MPa, and the reaction time is 1-24h.
More preferably, the Rh/CeO 2 The reaction conditions of the catalyst for the heterogeneous formaldehyde hydroformylation reaction are as follows: rh concentration of 1×10 -3 mol/L, the reaction system contains formaldehyde, CO and H 2 The mole ratio of formaldehyde to Rh is 500-1500, CO and H 2 The molar ratio is 1:1, the ligand is an organic phosphine ligand, the molar ratio of the ligand to Rh is 10-35, the solvent is N-methylpyrrolidone, the reaction temperature is 70-130 ℃, the pressure is 3-10MPa, and the reaction time is 1-12h.
In a third aspect, the present invention provides a method for improving formaldehyde conversion, glycolaldehyde selectivity, and catalyst stability in formaldehyde hydroformylation reactions, wherein Rh/CeO is controlled by the method of the first aspect of the present invention 2 The active component Rh species in the catalyst exists in the form of Rh atom clusters consisting of several Rh single atoms; based on the Rh/CeO 2 The loading of the Rh species is 0.7-1.0wt%, including 0.7wt% and including 1.0wt% of the total mass of the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the method of electrostatic adsorption, high-temperature roasting and reduction to prepare Rh/CeO 2 The catalyst can control the existence of the Rh species in one or more forms of Rh nano particles formed by Rh single atoms, rh atom clusters formed by several Rh single atoms or Rh atom clusters agglomeration by regulating the load of the Rh species. Further, rh/CeO of the present invention 2 When Rh species in the catalyst exist in the form of Rh atom clusters, the Rh atoms are used for formaldehyde hydroformylation reaction, so that the formaldehyde conversion rate, the glycolaldehyde selectivity and the stability of the formaldehyde hydroformylation reaction catalyst can be obviously improved, and compared with Rh/CeO prepared by an impregnation method 2 The catalyst really realizes the effects of reducing the load and guaranteeing the catalytic activity. The invention utilizes the unique geometrical structure and electronic effect of Rh active components, and Rh clusters can promote formaldehyde hydroformylation reaction to generate glycolaldehyde with high selectivity.
2. The reagent used in the method only comprises cerium precursor, rhodium precursor and solvent, and the solvent is less in dosage, does not need washing, and does not produce waste liquid to pollute the environment.
3. The formaldehyde hydroformylation heterogeneous catalysis Rh/CeO provided by the invention 2 The preparation method of the catalyst is simple and reliable, easy to operate, high in repeatability and suitable for large-scale production.
4. The formaldehyde hydroformylation heterogeneous catalysis Rh/CeO provided by the invention 2 The catalyst is a solid catalyst, and after the liquid-solid formaldehyde hydroformylation reaction, separation and recovery of the noble metal catalyst can be realized through centrifugation or filtration, so that the reaction cost is greatly reduced.
5. The formaldehyde hydroformylation heterogeneous catalysis Rh/CeO provided by the invention 2 CeO is adopted as catalyst 2 As a carrier, rh can be well dispersed, and the high-temperature roasting and reduction strengthen Rh and CeO 2 The interaction between carriers simultaneously modulates the electronic state of Rh active species, promotes the generation of high-efficiency stable active Rh cluster species, remarkably improves the hydroformylation reaction performance of formaldehyde, and under the conditions of shorter reaction time, mild reaction temperature and pressure, wherein Rh is in atomic clusters0.7% Rh/CeO in the form 2 The catalyst exhibited relatively excellent catalytic activity, the formaldehyde conversion was 15.1%, and the glycolaldehyde selectivity was 81.7%.
6. The formaldehyde hydroformylation heterogeneous catalysis Rh/CeO provided by the invention 2 Compared with the traditional Rh-based homogeneous catalyst, the catalyst reduces the use amount of Rh, has excellent circulating stability, is easy to realize separation and recovery, has higher economic value and market prospect, and is a potential industrial catalyst.
Drawings
FIG. 1 is a graph of Rh/CeO for different Rh loadings 2 XRD patterns of the catalyst;
FIG. 2 is a graph of Rh/CeO at different Rh loadings 2 HRTEM images of the catalyst;
FIG. 3 is a graph of Rh/CeO for different Rh loadings 2 CO adsorption infrared spectrum of the catalyst;
FIG. 4 is a graph of Rh/CeO for different Rh loadings 2 Formaldehyde hydroformylation performance of the catalyst is compared with a graph;
FIG. 5 shows 0.7% Rh/CeO 2 A formaldehyde hydroformylation performance cycle test performance comparison chart of the catalyst;
FIG. 6 shows the reduced concentration of 0.7% Rh/CeO at 500 ℃ 2 0.7% Rh/CeO reduced at 300℃and 700℃compared with the control sample 2 Formaldehyde hydroformylation performance of the catalyst is compared with a graph;
FIG. 7 is a graph comparing formaldehyde hydroformylation performance of Rh-based catalysts of different supports;
FIG. 8 shows 0.7% Rh/CeO prepared by various methods 2 Comparative graph of catalyst formaldehyde hydroformylation performance.
Detailed Description
The present invention will be described with reference to specific examples, but embodiments of the present invention are not limited thereto. The experimental methods, which do not specify specific conditions in the examples, are generally commercially available according to conventional conditions and conditions described in handbooks, or according to conditions suggested by manufacturers, using general-purpose equipment, materials, reagents, etc., unless otherwise specified. The starting materials required for the catalyst synthesis in the following examples and comparative examples are commercially available.
Examples 1-5 are Rh/CeO with different Rh loadings 2 Preparation of the catalyst:
example 1
0.9930g of CeO was weighed 2 Putting into a 50mL eggplant-shaped bottle, weighing 0.0177g of rhodium dicarbonyl acetylacetonate, weighing 10mL of acetone, adding into a 10mL centrifuge tube, performing ultrasonic dissolution to obtain rhodium precursor solution, and dripping the solution into CeO at a speed of 2mL/min 2 Sealing with glass plug after dripping, stirring at 30deg.C for 24 hr to complete electrostatic adsorption, rotary evaporating at 40deg.C, evaporating solvent to solid, drying at 80deg.C in blast drying oven for 12 hr to obtain dry solid, grinding and crushing to below 300 mesh, transferring to muffle furnace, heating to 800deg.C at a rate of 5deg.C/min and maintaining for 10 hr, and cooling to room temperature to obtain baked Rh/CeO 2 Transferring the catalyst into a tube furnace, reducing for 4 hours in a hydrogen atmosphere of 80mL/min at 500 ℃, cooling to room temperature, and then switching the gas into argon for passivation for 3 hours to obtain 0.7 percent Rh/CeO 2 And (5) performing vacuum sealing and preservation on the catalyst.
Example 2
0.9995g of CeO was removed 2 And 0.0013g rhodium dicarbonyl acetylacetonate, the other preparation methods were exactly the same as in example 1, giving 0.05% Rh/CeO 2 A catalyst.
Example 3
0.9980g of CeO was weighed out 2 And 0.0051g rhodium dicarbonyl acetylacetonate, the other preparation methods are exactly the same as in example 1, giving 0.2% Rh/CeO 2 A catalyst.
Example 4
0.9910g of CeO was removed 2 And 0.0253g rhodium dicarbonyl acetylacetonate, the other preparation methods were exactly the same as in example 1, giving 1.0% Rh/CeO 2 A catalyst.
Example 5
0.9800g of CeO was removed 2 And 0.0507g rhodium dicarbonyl acetylacetonate, the other preparation methods were the same as in example 1, giving 2.0% Rh/CeO 2 A catalyst.
Implementation of the embodimentsExamples 6-8 are comparative samples of unreduced, reduced 0.7% Rh/CeO at 300℃and 700 ℃ 2 Preparation of the catalyst
Example 6
Rh/CeO obtained after calcination 2 The catalyst was not subjected to reduction and passivation treatment, and the rest of the preparation method was exactly the same as in example 1, to obtain unreduced 0.7% Rh/CeO 2 A catalyst.
Example 7
The preparation process was exactly the same as in example 1 except that the reduction temperature was 300℃to obtain 0.7% Rh/CeO reduced at 300 ℃ 2 A catalyst.
Example 8
The preparation process was exactly the same as in example 1 except that the reduction temperature was 700℃to obtain 0.7% Rh/CeO reduced at 700 ℃ 2 A catalyst.
Examples 9-13 are comparative samples of 0.7% Rh/ZnO and 0.7% Rh/TiO 2 Preparation of the catalyst
Example 9
The preparation method was exactly the same as in example 1 except that the carrier was changed to ZnO, to obtain a 0.7% Rh/ZnO catalyst.
Example 10
The carrier is ZrO 2 The other preparation processes were exactly the same as in example 1, giving 0.7% Rh/ZrO 2 A catalyst.
Example 11
The carrier is Al 2 O 3 The remainder of the preparation was identical to that of example 1, giving 0.7% Rh/Al 2 O 3 A catalyst.
Example 12
The preparation method was exactly the same as in example 1 except that the carrier was changed to MgO, to obtain a catalyst of 0.7% Rh/MgO.
Example 13
The carrier is removed and replaced by TiO 2 The rest of the preparation method is exactly the same as in example 1, obtaining 0.7% Rh/TiO 2 A catalyst.
Example 14 comparative sample 0.7% Rh/CeO 2 The catalyst is prepared by an isovolumetric impregnation method
Example 14
0.0724g of RhCl was weighed out 3 ·xH 2 O was dissolved in 2mL of deionized water and added dropwise to 4.000g of CeO 2 The preparation method comprises the steps of carrying out ultrasonic drying for 6 hours after uniformly stirring by using a glass rod to remove redundant moisture, drying for 12 hours in a blast drying box at 80 ℃ to obtain a dry solid, grinding and crushing the dry solid to be less than 300 meshes, then placing the dry solid in a muffle furnace, heating to 800 ℃ at a speed of 5 ℃/min, keeping the temperature for 10 hours, cooling to room temperature to obtain a catalyst precursor, transferring the catalyst precursor into a tubular furnace, reducing for 4 hours at 500 ℃ in 80mL/min hydrogen atmosphere, cooling to room temperature, switching the gas into argon for passivation for 3 hours, and obtaining the impregnation method of 0.7% Rh/CeO 2 And (5) vacuumizing, sealing and preserving the catalyst.
XRD patterns of the catalysts obtained in comparative examples 1 to 5, as shown in FIG. 1a, showed the removal of CeO 2 Outside the diffraction peaks, no Rh species (Rh, rhO) was observed 2 、Rh 2 O 3 RhCe alloy), whereas in XRD slow-scan pattern 1b in the interval 39 ° -45 °, a distinct characteristic diffraction peak of the metal Rh (111) appears at about 41.1 ° 2θ after an increase in Rh loading to 2%. This indicates that Rh/CeO at Rh loadings of no more than 1.0% 2 The Rh species on the catalyst are highly dispersed, exist as single atom Rh or cluster Rh, do not form nanoparticles, and at Rh loadings of 2.0%, the Rh species agglomerate significantly, forming metallic Rh particles.
HRTEM images of the catalysts obtained in comparative examples 1 to 5, as shown in FIG. 2, at Rh loadings of 0.05% -1.0% Rh/CeO 2 On the catalyst, only CeO is observed in the high-resolution HRTEM spectrogram 2 Is not observed with any Rh species (Rh, rhO) 2 、Rh 2 O 3 RhCe alloy) and a distinct difference from CeO was observed when Rh loading was increased to 2.0% 2 The lattice fringes of the crystal, the measured distance was about 0.22nm, which was assigned to the metal Rh (111) plane, and the measurement revealed that the Rh nanoparticles were uniformly distributed at 1.9.+ -. 0.2nm.
The infrared spectra of CO adsorption of the catalysts obtained in comparative examples 1 to 5, as shown in FIG. 3, with Rh loadingThe CO adsorption configuration and the adsorption strength are obviously changed. From the adsorption strength, 0.05% Rh/CeO 2 The intensity of the infrared vibration peak of the CO in the chemical adsorption state on the catalyst is extremely low, and the intensity of the infrared vibration peak of the CO in the chemical adsorption state is obviously increased along with the increase of Rh loading. This result demonstrates that the increased loading of Rh enhances the adsorption capacity of the catalyst for CO molecules. From the adsorption configuration, 0.05% and 0.2% Rh/CeO 2 The catalyst had only 2085cm -1 And 2012cm -1 Is respectively attributed to Rh (CO) formed by adsorbing CO molecules by single-atom Rh 2 Symmetrical telescopic vibration and asymmetrical telescopic vibration of CO on the species. 0.7%, 1.0% and 2.0% RhCeO 2 Four infrared vibration peaks were observed at 2100, 2070, 2033 and 1861cm-1 on the catalyst, with 2100cm -1 And 2033cm -1 The nearby peaks are respectively assigned to Rh (CO) 2 Symmetrical telescopic vibration and asymmetrical telescopic vibration of CO on species, and 0.05% and 2.0% Rh/CeO 2 Compared with the catalyst, the two peak positions have a certain blue shift, and the reason is that the electronic states of Rh species on the three catalysts are changed, so that CO adsorption is more stable. 2070cm -1 The peak around the adsorption column is linear adsorption of CO molecules on 0-valence Rh, 1861cm -1 The peaks belonging to (1) are bridge adsorption of CO on Rh-Rh, and the simultaneous occurrence of CO linear adsorption and bridge adsorption indicate 0.7% and 1.0% Rh/CeO 2 Rh on these two catalysts was not present as a single atom, and combined with XRD in FIG. 1 and TEM results in FIG. 2, it can be shown that 0.7% and 1.0% Rh/CeO 2 Rh exists in the form of clusters on the catalyst, and Rh/CeO is 2.0% 2 Rh exists in the form of nano particles on the catalyst. CO adsorption infrared result shows that Rh/CeO is regulated and controlled 2 The loading capacity of Rh on the catalyst can effectively regulate the existence form of Rh species, change the electronic property of Rh species, further influence the adsorption behavior of Rh species on CO, and 0.7% Rh/CeO 2 Rh species on the catalyst exist in a cluster form, have relatively strong CO adsorption capacity, and are beneficial to promoting CO insertion steps in the hydroformylation reaction process of formaldehyde and improving catalytic activity.
The catalysts obtained in examples 1-14 were used in formaldehyde hydroformylation reactions and their catalytic activities were compared, and specific catalytic reaction methods were:
1) The catalyst was weighed. Weighing Rh/CeO containing 0.02mmol of Rh in an argon-protected glove box 2 The catalyst is filled into a centrifuge tube and sealed for standby.
2) The reactor was installed. Weighing paraformaldehyde as formaldehyde donor (molar ratio of formaldehyde to Rh is 1000-1500), organic phosphine ligand (molar ratio of ligand to Rh is 10-30), weighing 20mL of organic solvent, adding into 100mL quartz lining, and adding Rh/CeO weighed in step 1) 2 The catalyst is added quickly, and the quartz lining is sealed in the stainless steel high-pressure reaction kettle body immediately.
3) And (5) inflating and pressurizing. Introducing CO with the molar ratio of 3MPa to 1:1 into a high-pressure reaction kettle 2 /H 2 The mixed gas is discharged, the pressure is then discharged, the filling and the discharging are repeated for 3 times, the air in the kettle is discharged, the pressure is increased to 5-10MPa, the leakage is detected, and the pressure is relieved to be less than 1/2 of the pressure to be reacted after no gas leakage is confirmed.
4) Catalyst performance test. And (3) starting programmed heating, wherein the heating rate is 10 ℃/min, after the temperature is raised to the reaction temperature of 70-130 ℃, supplementing pressure to the reaction pressure, starting stirring, timing at the same time, stopping heating and stirring after reacting for 1-5h, taking out the reaction kettle, and naturally cooling to the room temperature.
5) And (5) product analysis. Adding an internal standard into the solution after the reaction, analyzing by using a Shimadzu 2014C GC system chromatograph, wherein a detector is a TCD and FID double detector, helium is used as carrier gas, a TCD chromatographic column is a Porapak-T (1.0m3.2mm) packed column, a FID detector is a WondaCap FFAP (30 m0.53m1 μm) capillary column, and data processing is performed by using Labsolutions software, so that the contents of reactants and products are obtained according to an internal standard curve.
Rh/CeO for different Rh loadings 2 The catalytic performance of the catalysts was compared and the test results are shown in figure 4.0.05% Rh/CeO 2 The catalyst has low catalytic activity, and glycolaldehyde is not detected in the reaction product. With increasing Rh loading, 0.7% Rh/CeO 2 Exhibits relatively excellent catalytic activity, formaldehyde conversion rate reaches 15.1%, and glycolaldehyde selectivity reaches 81.7%. Continuously increasing the loading of Rh, 2.0% Rh/CeO 2 The catalyst activity is greatly reduced, and the glycolaldehyde selectivity is lower than 60.0%. The activity test result shows that the existence form of Rh species can be regulated and controlled through regulating and controlling Rh loading, and when Rh exists in a single atom form, rh/CeO 2 The catalyst has hydrogenation activity, when Rh exists in the form of atomic clusters, rh/CeO 2 The catalyst has higher formaldehyde hydroformylation activity, and when Rh exists in a nano particle form, the formaldehyde hydroformylation activity is greatly reduced.
To investigate Rh/CeO 2 Stability of catalyst in heterogeneous catalytic reaction of formylating, the invention is about 0.7% Rh/CeO after reaction 2 After the catalyst was subjected to centrifugal washing to separate out a solid catalyst, a cycle stability test was performed. The other steps are the same as the above catalytic method except that the catalyst is a catalyst recovered by separation after the reaction. The results of the cycle stability test are shown in figure 5.0.7% Rh/CeO 2 The catalyst undergoes four-time cyclic reaction, and the selectivity of glycolaldehyde in the product is kept above 73.0%. This result indicates that the 0.7% Rh/CeO 2 The catalyst has better stability.
To investigate the reduction temperature for Rh/CeO 2 The effect of the catalyst on the hydroformylation reaction performance of formaldehyde was compared with that of example 1 with 0.7% Rh/CeO reduced at 300℃and 700℃without reduction 2 The catalytic performance of the catalyst was compared with that of the sample, and the test results are shown in FIG. 6. With the increase of the reduction temperature, the formaldehyde conversion rate and the selectivity of glycolaldehyde in the product all show the trend of increasing and then reducing, and the optimal catalytic effect is obtained at 500 ℃. The unreduced and 700 ℃ reduced catalysts have the lowest glycolaldehyde selectivity and the lowest formaldehyde conversion, respectively. This result indicates that reduced 0.7% Rh/CeO at 500℃ 2 The catalyst can form a more efficient Rh cluster active site and promote formaldehyde hydroformylation reaction.
In order to explore the influence of the carrier on the performance of the Rh-based catalyst in catalyzing formaldehyde hydroformylation reaction, the invention compares the catalytic performance (Rh loading of 0.7%) of Rh-based catalysts loaded by different carriers, and tests the resultsSee fig. 7. Under the same reaction conditions, the activity sequence of the catalyst is as follows: rh/CeO 2 >Rh/ZnO>Rh/Al 2 O 3 >Rh/ZrO 2 >Rh/TiO 2 >Rh/MgO. The selective sequence of glycolaldehyde in the product is as follows: rh/CeO 2 >Rh/ZnO>Rh/ZrO 2 >Rh/Al 2 O 3 >Rh/MgO>Rh/TiO 2 . The results show that the type of the carrier has important influence on the catalytic performance, al 2 O 3 MgO and TiO 2 Rh species formed as a carrier is mainly hydrogenation active sites, promotes side reaction of methanol generated by hydrogenation of formaldehyde, and CeO 2 As a carrier, the catalyst is favorable for forming more Rh species with hydroformylation catalytic activity, and promotes formaldehyde hydroformylation to generate glycolaldehyde.
To explore the preparation method for Rh/CeO 2 The invention compares the influence of the catalyst on the hydroformylation reaction performance of formaldehyde with the influence of 0.7 percent of Rh/CeO prepared by an electrostatic adsorption method and an isovolumetric impregnation method 2 The catalytic performance of the catalyst is shown in figure 8. The catalyst prepared by the electrostatic adsorption method has the catalysis performance obviously superior to that of the catalyst prepared by the isovolumetric impregnation method, the glycolaldehyde selectivity of the former is about 1.3 times that of the latter, and the formaldehyde conversion rate is about 1.8 times. This result shows that the electrostatic adsorption method is more suitable for preparing Rh/CeO with high activity 2 The catalyst can improve the formaldehyde hydroformylation reaction performance.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A method for regulating existence form of Rh species in rhodium-based catalyst is characterized in that the rhodium-based catalyst is Rh/CeO 2 A catalyst comprising a carrier andthe active component is cerium oxide, and the active component is an Rh species which exists in one or more forms of Rh single atoms, rh atom clusters formed by a plurality of Rh single atoms or Rh nano particles formed by the aggregation of the Rh atom clusters; based on the Rh/CeO 2 The loading of the Rh species is 0.05-2.0wt% of the total mass of the catalyst;
the Rh/CeO 2 The preparation method of the catalyst comprises the following steps:
1) And (3) preparing a carrier: ceO is weighed 2 Grinding, crushing and screening to below 300 meshes to obtain CeO 2 A carrier;
2) Preparation of an active component precursor: weighing rhodium precursor, dissolving in a solvent, and performing ultrasonic dissolution to obtain rhodium precursor solution;
3) Mixing: dropwise adding the rhodium precursor solution in the step 2) to the CeO of the step 1) 2 Stirring on the carrier to obtain suspension, and sealing;
4) Electrostatic adsorption: continuously stirring the suspension in the step 3) to perform electrostatic adsorption to obtain a suspension subjected to electrostatic adsorption;
5) Removing the solvent: evaporating the suspension subjected to electrostatic adsorption obtained in the step 4) to dryness, and removing the solvent to obtain a solid mixture;
6) Drying and crushing: drying, grinding and crushing the solid mixture obtained in the step 5) to obtain catalyst precursor powder;
7) Roasting: roasting the catalyst precursor powder obtained in the step 6) to obtain roasted catalyst powder;
8) And (3) reduction: placing the calcined catalyst powder obtained in the step 7) in a reducing atmosphere for reduction to obtain reduced catalyst powder;
9) Passivation: passivating the reduced catalyst powder obtained in the step 8) in an inert atmosphere to obtain the Rh/CeO 2 A catalyst;
wherein, when the Rh loading is 0.05-0.2wt%, including 0.05wt% and excluding 0.2wt%, rh/CeO 2 Rh species are present on the catalyst in monoatomic form;
when the Rh loading is 0.2-0.7wt%Includes 0.2wt% and does not include 0.7wt% Rh/CeO 2 Rh species on the catalyst exist in the form of monoatomic Rh and clustered Rh;
when the Rh-carrying amount is 0.7 to 1.0wt%, it is 0.7wt% and 1.0wt% is included, rh/CeO 2 The Rh species on the catalyst exist in the form of Rh atom clusters;
when the Rh-carrying amount is 1.0 to 2.0wt%, 1.0wt% is excluded and 2.0wt% is included, rh/CeO 2 The Rh species on the catalyst exist in the form of Rh atom clusters and Rh nano-particles;
when the Rh loading is higher than 2.0wt%, rh/CeO 2 The Rh species on the catalyst are present in the form of Rh nanoparticles.
2. The method according to claim 1, wherein the CeO in step 1) 2 Can be commercially available CeO 2 Or CeO synthesized by a laboratory using various cerium sources 2 The cerium source is selected from one or more of cerium carbonate, cerium oxalate, cerium chloride, cerium nitrate and cerium ammonia nitrate; in the step 2), rhodium precursors are selected from one or more of tetrarhodium laurcarbonyl, hexarhodium laurcarbonyl, rhodium acetylacetonate dicarbonyl, rhodium chloride, rhodium iodide, rhodium nitrate and sodium chlororhodium; in the step 2), the solvent is one or more selected from deionized water, absolute methanol, absolute ethanol, acetone and toluene.
3. The method according to claim 1, wherein in step 3), the stirring temperature is 20-60 ℃ and the dropping speed is 1-10mL/min.
4. The method according to claim 1, wherein in step 4), the electrostatic adsorption temperature is 20 to 60 ℃ and the electrostatic adsorption time is 12 to 72 hours.
5. The method according to claim 1, wherein in step 5), the evaporating is performed at a temperature of 30-80 ℃, the evaporating method being selected from the group consisting of normal pressure drying and reduced pressure rotary evaporation; in the step 6), drying is carried out in air at the drying temperature of 50-110 ℃ for 6-12h; crushing and sieving to 100-300 mesh.
6. The method according to claim 1, wherein in step 7), the firing temperature is 200 to 900 ℃, the heating rate is 1 to 10 ℃/min, and the firing time is 2 to 12 hours.
7. The method according to claim 1, wherein in the step 8), the reducing atmosphere is hydrogen, or a mixture of hydrogen and nitrogen, or a mixture of hydrogen and argon, the flow rate of the reducing gas is 20-100mL/min, the reducing temperature is 300-700 ℃, the heating rate is 1-10 ℃/min, and the reducing time is 1-5h.
8. The method according to claim 1, wherein in the step 9), the passivation atmosphere is nitrogen, argon or a mixed gas containing oxygen, the oxygen content in the mixed gas is 1% -5%, and the passivation time is 1-5h.
9. The use of a rhodium-based catalyst prepared by the method of any one of claims 1-8, wherein the rhodium-based catalyst is Rh/CeO 2 Catalyst, said Rh/CeO 2 The catalyst is applied to formaldehyde hydroformylation heterogeneous catalytic reaction;
specifically, the Rh/CeO 2 The catalyst is applied to the formaldehyde hydroformylation reaction of the liquid-solid batch kettle, and the reaction conditions are as follows: the reaction raw materials are formaldehyde, CO and H 2 Mixture of gas, CO and H 2 The molar ratio is 1:1, the ligand is an organic phosphine ligand, the molar ratio of the ligand to Rh is 1-50, the reaction temperature is 50-200 ℃, the pressure is 1-10MPa, and the reaction time is 1-24h.
10. A method for improving formaldehyde conversion, glycolaldehyde selectivity, and catalyst stability in formaldehyde hydroformylation reactions, wherein the Rh/CeO is controlled using the method of any one of claims 1-8 2 The active component Rh species in the catalyst exists in the form of Rh atom clusters composed of a plurality of Rh single atoms; based on the Rh/CeO 2 The loading of the Rh species is 0.7-1.0wt%, including 0.7wt% and including 1.0wt% of the total mass of the catalyst.
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