CN106902815B - A kind of preparation method of carried palladium-aluminium oxide catalyst - Google Patents
A kind of preparation method of carried palladium-aluminium oxide catalyst Download PDFInfo
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- CN106902815B CN106902815B CN201710177187.6A CN201710177187A CN106902815B CN 106902815 B CN106902815 B CN 106902815B CN 201710177187 A CN201710177187 A CN 201710177187A CN 106902815 B CN106902815 B CN 106902815B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000012266 salt solution Substances 0.000 claims abstract description 31
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 30
- 239000004411 aluminium Substances 0.000 claims abstract description 29
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000012696 Pd precursors Substances 0.000 claims abstract description 20
- 239000003292 glue Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 99
- 229910052763 palladium Inorganic materials 0.000 claims description 49
- 239000003921 oil Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 239000002199 base oil Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 239000010721 machine oil Substances 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 27
- 230000037396 body weight Effects 0.000 description 25
- 239000011148 porous material Substances 0.000 description 24
- 239000012752 auxiliary agent Substances 0.000 description 21
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 14
- 150000004056 anthraquinones Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 238000002386 leaching Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229960004011 methenamine Drugs 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000012224 working solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000002940 palladium Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ILXDAXZQNSOSAE-UHFFFAOYSA-N [AlH3].[Cl] Chemical compound [AlH3].[Cl] ILXDAXZQNSOSAE-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000012360 testing method 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of carried palladium-aluminium oxide catalyst, comprising: premixed liquid is made in the precursor salt solution of alkaline earth oxide, hexamethylenetetramine solution and Aluminum sol mixture；Premixed liquid is granulated to obtain aluminium glue ball by oil-drop method；After the aging of aluminium glue ball warp, washing, dried in 100~120 DEG C 4 hours, 200~300 DEG C are handled 2~3 hours, and 550 DEG C are handled 3~4 hours, and 960~1000 DEG C are handled 3~4 hours, obtain alumina support；It is dried after the precursor salt solution of alumina support alkali metal oxide is impregnated；Washing, drying, roast 3~5 hours in 450~550 DEG C, air atmosphere, obtain carried palladium-aluminium oxide catalyst after alumina support after drying is impregnated with Metal Palladium precursor solution.Carried palladium-aluminium oxide catalyst produced by the present invention can have higher catalytic activity and selectivity under the premise of guaranteeing preferable catalytic life.
Description
Technical field
The present invention relates to a kind of preparation methods of metallic catalyst, more particularly to one kind to be used for the anthraquinone peroxidating of fixed bed
Palladium-aluminium oxide catalyst preparation method of hydrogen production.
Background technique
Anthraquinone is that H is mass produced in the world at present2O2Most widely used method.And carrying alumina palladium or other
Platinum metal catalysts are then the most common hydrogenation catalysts of the technique.In order to constantly improve the performance of catalyst, more rationally make
With expensive platinum group metal, people are in the impregnation technology of platinum group metal (such as palladium) and the structure and catalyst performance of carrier for a long time
A lot of research work can be done in terms of relationship, carry out a large amount of beneficial spies to improve the activity, selectivity and service life of catalyst
It begs for.
Anthraquinone hydrogenation reaction is a kind of catalysis reaction for being related to gas, liquid, solid three-phase complex system.It is catalyzed as anthraquinone hydrogenation
Agent, especially fixed bed catalyst, are carried palladium metal catalyst mostly, and particle diameter is generally 2~6mm, it is ensured that urges
Agent has high activity and selectivity, in addition to making Metal Palladium particle have reasonable distribution and high score on carrier in preparation process
Outside divergence, also to guarantee that reactant and reaction product can quickly be spread in catalyst reaction channel.Catalyst contains palladium layers thickness
Moderate, palladium particle dispersion degree height and the relatively large catalyst of carrier aperture are spent, is conducive to improve working solution in catalyst pores
Diffusion velocity and diffusion flux, greatly improve the utilization rate of catalyst inner surface and Metal Palladium, thus catalyst can be improved
Activity and selectivity.
Through known to retrieval: Chinese invention patent ZL 03115503.0 describes a kind of alumina support through rare earth metal oxygen
The modified carried palladium-aluminium oxide catalyst for anthraquinone hydrogenation reaction of compound.Rare-earth substance used be La, Ce, Pr,
The oxide of Nd, Sm, aluminium oxide are the δ through high-temperature roasting, θ crystal phase, specific surface area about 60~130m2/ g, average pore radius is about
For 10~14nm, Na2O content < 0.05%.The catalyst can reduce the use of Metal Palladium under the premise of keeping high activity
Amount.But only used single auxiliary agent here, the co-catalysis effect to catalyst is simultaneously not up to best.Practice is it is also shown that make
For the anthraquinone hydrogenation catalyst for gas, liquid, solid three-phase complex reaction, 10~14nm average pore radius is unfavorable in catalyst
Surface makes full use of, to influence the raising of catalyst activity and selectivity.
Chinese patent ZL200410061031.4 discloses a kind of for the carried palladium-oxidation of process for prepairng hydrogen peroxide by anthraquinone
Al catalysts and preparation method thereof, it is related to one kind to coat appropriate amount alkaline earth oxide in advance, and through high-temperature roasting
δ, θ-Al2O3For carrier, the specific surface area of the aluminium oxide about 60~130m2/ g, average pore radius are 10~14nm, Kong Rong
Product >=0.5ml/g, Na2O content < 0.05%, the alkaline earth oxide are the oxide of Mg, Ca, Sr, Ba, activity at
The loading for dividing palladium is 0.15~0.24wt%, is prepared using dipping method.The catalyst can keep reasonable metal palladium layers
Precious metals pd is reduced to 0.2% or so under the premise of thickness (30~90 μm) and higher catalytic activity.The patent and previous example
Son has equally used single auxiliary agent, and the co-catalysis effect to catalyst is simultaneously not up to best, 10~14nm average pore radius
It is unfavorable for making full use of for catalyst inner surface for airwater mist cooling catalysis reaction, and influences catalyst activity and choosing
The raising of selecting property.
Summary of the invention
In order to overcome the defects of the prior art described above, technical problem to be solved by the invention is to provide one kind guarantee compared with
Under the premise of good catalytic life, the preparation of carried palladium-aluminium oxide catalyst with higher catalytic activity and selectivity
Method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A kind of preparation method of carried palladium-aluminium oxide catalyst, comprising:
Prepare the Aluminum sol that Al/Cl mass ratio is 1.0~1.5, Al content is 9~16wt%；
Premixed liquid is made in the precursor salt solution of alkaline earth oxide, hexamethylenetetramine solution and Aluminum sol mixture,
The temperature for keeping premixed liquid is 5~10 DEG C；
Premixed liquid is granulated by oil-drop method, obtains aluminium glue ball；
After the aging of aluminium glue ball warp, washing, successively dried in 100~120 DEG C 4 hours, 200~300 DEG C of processing 2~3 are small
When, 550 DEG C are handled 3~4 hours, and 960~1000 DEG C are handled 3~4 hours, and cooling obtains alumina support；
It is dried after the precursor salt solution of alumina support alkali metal oxide is impregnated；
Washing, drying after alumina support after drying is impregnated with Metal Palladium precursor solution, in 450~550 DEG C, air
It is roasted 3~5 hours in atmosphere, obtains carried palladium-aluminium oxide catalyst；
Wherein, the precursor salt solution of alkaline earth oxide be selected from one of magnesium, calcium, the acetate of barium or nitrate or
A variety of, the precursor salt solution of alkali metal oxide is selected from Na2CO3、NaHCO3、K2CO3And KHCO3One of or a variety of, metal
Palladium precursor solution is H2PdCl4Aqueous solution or Na2PdCl4Aqueous solution.
The beneficial effects of the present invention are: it is different from the prior art, the present invention can efficiently and safely prepare impurity and contain
The alumina balls as anthraquinone hydrogenation palladium catalyst carrier that amount is less, specific surface is moderate, pore size is controllable, BET surface area
For 60~100m2/ g, 32~45nm of average pore size (are the 1.50 of current 20~28nm of common carrying alumina body aperture on the market
~2.25 times), Na2O content < 0.05wt%, crystal phase δ, θ-Al2O3, crush strength >=35N/, biggish aperture is advantageous
In diffusion of the anthraquinone working solution in catalyst pores, improve catalyst utilization rate of inner surface, thus improve catalyst activity and
Selectivity.Also, alkaline earth oxide and alkali metal oxide is used in combination as co-catalyst, alkaline-earth metal oxygen in the present invention
Compound can avoid alumina grain in catalyst preparation process and grow up, and promote the dispersion of Metal Palladium particle, in use process and energy
The intensity of fortifying catalytic agent, and alkali metal oxide can quickly change alumina carrier surface and palladium leaching in catalyst preparation process
The pH value of stain liquid promotes the reasonable layout of palladium particle, increases the activated centre number of catalyst, to further increase catalysis
The activity of agent.
In conclusion the preparation method of carried palladium-aluminium oxide catalyst provided by the invention, can be prepared and protect
Under the premise of demonstrate,proving preferable catalytic life, carried palladium-aluminium oxide catalyst with higher catalytic activity and selectivity, and
And production process is safe and efficient, high financial profit.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
The most critical design of the present invention is: done from large pore spherical alumina support, and be added alkali metal oxide and
The two different auxiliary agents of alkaline earth oxide, with soak law by auxiliary agent and Metal Palladium precursor appendix to alumina support, from
And be prepared a kind of palladium content be suitable for and have high activity, it is highly selective, the long-life be suitable for it is industrial at present anthraquinone
Carried palladium-aluminium oxide catalyst of hydrogen peroxide manufacture technique.
Specifically, the preparation method of carried palladium-aluminium oxide catalyst provided by the invention, comprising:
Prepare the Aluminum sol that Al/Cl mass ratio is 1.0~1.5, Al content is 9~16wt%；
Premixed liquid is made in the precursor salt solution of alkaline earth oxide, hexamethylenetetramine solution and Aluminum sol mixture,
The temperature for keeping premixed liquid is 5~10 DEG C；
Premixed liquid is granulated by oil-drop method, obtains aluminium glue ball；
After the aging of aluminium glue ball warp, washing, successively dried in 100~120 DEG C 4 hours, 200~300 DEG C of processing 2~3 are small
When, 550 DEG C are handled 3~4 hours, and 960~1000 DEG C are handled 3~4 hours, and cooling obtains alumina support；
It is dried after the precursor salt solution of alumina support alkali metal oxide is impregnated；
Washing, drying after alumina support after drying is impregnated with Metal Palladium precursor solution, in 450~550 DEG C, air
It is roasted 3~5 hours in atmosphere, obtains carried palladium-aluminium oxide catalyst；
Wherein, the precursor salt solution of alkaline earth oxide be selected from one of magnesium, calcium, the acetate of barium or nitrate or
A variety of, the precursor salt solution of alkali metal oxide is selected from Na2CO3、NaHCO3、K2CO3And KHCO3One of or a variety of, metal
Palladium precursor solution is H2PdCl4Aqueous solution or Na2PdCl4Aqueous solution.
In the above preparation method, Aluminum sol (AlCl3Glue) Al/Cl mass ratio be 1.0~1.5, Al content be 9~
16wt%, the Aluminum sol can be obtained by prior art preparation.Preferably, the Aluminum sol by metallic aluminium powder, deionized water with it is dilute
Hydrochloric acid is obtained in the at a temperature of reaction not higher than 110 DEG C, purity >=99.0wt% of metallic aluminium powder.Control aluminium, the chlorine of Aluminum sol
It is to control the suitable pH value and liquid-solid ratio of Aluminum sol than the purpose with aluminium content, to guarantee prepared alumina balls
(i.e. chlorination alumina supporter) has the physical and chemical performances such as suitable micro-structure, mechanical strength and density.
In the above preparation method, hexamethylenetetramine (methenamine UTP) is added when preparing premixed liquid, six methines
For tetramine during forming oil column, with the whereabouts of glueballs, can decompose to give off ammonia makes aluminium glue ball be gelled rapidly, determines to play
Type and cured effect.The dosage of hexamethylenetetramine changes according to the variation of the chlorinity in Aluminum sol, practice have shown that, six times
The molar ratio of tetramine and chlorine is (UTP): Cl=1.10~1.28: 4 is more appropriate, this value is too small to Aluminum sol above-mentioned
Al/Cl ratio requires big, that is, needs to prepare the bigger Aluminum sol of Al/Cl mass ratio, otherwise not easily molded；This value then wastes greatly very much medicine
Product.
In the above preparation method, the shaping work of aluminium glue ball is divided into aluminium glue and is granulated and two processes of spherolite aging.Into
When row aluminium glue oil bath is granulated, the temperature range for shaping oil is preferably controlled in 85~98 DEG C, and higher oil temperature is conducive to consolidating for micelle
Change.In micelle aging process, oil temperature is preferably controlled in 120~150 DEG C, and pressure is preferably controlled in 0.35~0.40MPa, when aging
Between preferably 10~20 hours.
In the above preparation method, molding can be selected from diesel oil, lubricating oil, machine oil, transformer oil, bobbin oil, mineral with oil
Base oil or synthetic base oil will lead to substance such as sulphur, phosphorus, copper, iron of catalyst poisoning etc. wherein to select not containing
Oil product, being preferably selected the kinematic viscosity at 100 DEG C is 10~12mm2The oil product of/s.
The step of present invention is before cooling obtains alumina support, it is believed that be the preparation process of alumina balls.It should
Technique is different from existing alumina balls preparation process, and being advantageous in that can efficiently and safely prepare that impurity content is few, compares table
The alumina balls for the anthraquinone hydrogenation palladium catalyst carrier that face is moderate, pore size is controllable, BET surface area are 60~100m2/ g,
32~45nm of average pore size (being 1.50~2.25 times of current 20~28nm of common carrying alumina body aperture on the market), Na2O
Content < 0.05wt%, crystal phase δ, θ-Al2O3, crush strength >=35N/.Biggish aperture is conducive to anthraquinone working solution
Diffusion in catalyst pores improves catalyst utilization rate of inner surface, to improve the activity and selectivity of catalyst.Therefore,
The present invention is done from large pore spherical alumina support, is suitable for and has high activity, Gao Xuan for a kind of palladium content is finally prepared
Selecting property, the carried palladium-aluminium oxide catalyst for being suitable for industrial hydrogen peroxide obtained by anthraquinone process production technology at present of long-life, beat
Solid foundation is descended.
In addition, the present invention, which is different from the prior art, only uses single auxiliary agent, but alkali metal oxide is used in combination
With the two different auxiliary agents of alkaline earth oxide, both auxiliary agents are impregnated into oxygen in the form of soluble precursor salting liquid respectively
Change on alumina supporter, becomes alkali metal oxide and alkaline earth oxide after being fired.The good of both auxiliary agents is used in combination
It is in structural promoter of the alkaline earth oxide as catalyst, can avoid alumina grain in catalyst preparation process
Grow up, promote Metal Palladium particle dispersion, use process again can fortifying catalytic agent intensity.And alkali metal oxide is being catalyzed
The pH value of carrier surface and palladium maceration extract (i.e. Metal Palladium precursor solution) can quickly be changed in agent preparation process, promote palladium particle
Reasonable layout, increase the activated centre number of catalyst, further increase the activity of catalyst.
Specifically, the precursor salt solution of alkaline earth oxide is selected from one of magnesium, calcium, the acetate of barium or nitrate
Or it is a variety of, the precursor salt solution of alkali metal oxide is selected from Na2CO3、NaHCO3、K2CO3And KHCO3One of or it is a variety of.Its
In, the soluble precursor salting liquid of alkaline earth oxide can be added in Aluminum sol in Aluminum sol ball, later with made
At aluminium glue ball enter subsequent step, or with equi-volume impregnating the precursor salt solution of alkaline earth oxide is loaded to
On finished product alumina support, become corresponding alkaline earth oxide using drying, calcining.It is with dry carrying alumina body weight
Benchmark, the coated weight of alkaline earth oxide are 0.05~2wt%.And the isometric leaching of the precursor salt solution of alkali metal oxide
Stain method is added, and on the basis of dry carrying alumina body weight, the additional amount of alkali metal oxide is 0.02~1wt%, aluminium oxide
After carrier has soaked the precursor salt solution of alkali metal oxide, dried 2~4 hours in 100~150 DEG C.
The present invention, for main active ingredient, is loaded to palladium on alumina support with soak law, the use of the Metal Palladium with palladium
It measures on the basis of dry carrying alumina body weight, the loading of palladium is 0.15~0.32wt%.
Catalyst of the present invention can with above-mentioned impregnate containing the alumina support of alkaline earth oxide and alkali metal oxide
Dissolubility palladium salt aqueous solution (i.e. Metal Palladium precursor solution), the palladium salt solution impregnation sequence are that carrier is added in palladium salt solution
In, or carrier is added in palladium salt solution, restored after through reducing agent aqueous solution or without reduction, then uses pure water
Washing catalyst is until wash water can't check Cl-It afterwards, is finished product through drying, calcination process, wherein made without reduction treatment
Standby catalyst can be in catalyst use site hydrogen reducing.
The Metal Palladium precursor solution is H2PdCl4Or Na2PdCl4Aqueous solution.
The present invention alumina support soak palladium after to products obtained therefrom carry out washing dechlorination, 100~120 DEG C drying and
450~550 DEG C are calcined and/or are restored with reducing agent.
The reducing agent is hydrazine hydrate or formaldehyde, and dosage is 0.5~3.5: 1 for the molar ratio of reducing agent and palladium
(mol/mol), reduction temperature is room temperature~60 DEG C.
The dry water removal of carried palladium-aluminium oxide catalyst produced by the present invention can use any conventional method, but dry
Dry temperature is preferably not more than 200 DEG C.
As can be seen from the above description, the beneficial effects of the present invention are: carried palladium-aluminium oxide catalyst provided by the invention
Preparation method, can be prepared under the premise of guaranteeing preferable catalytic life, have higher catalytic activity and selection
Carried palladium-aluminium oxide catalyst of property, and production process is safe and efficient, high financial profit.
Embodiment 1
It weighs 60g purity >=99.0wt% metallic aluminium powder and 240g deionized water is added with glassed agitator, temperature
It counts, in the 1000ml three-necked flask of reflux condensing tube, by aluminium chlorine weight ratio Al/Cl=1.4/1, the ratio of (w/w) is burnt to three mouthfuls
The hydrochloric acid that concentration is 15wt% is added in bottle, and at 1000 revs/min, the hydrogen that reaction process generates passes through condensation for mixing speed control
Manage export suitable for reading.Metallic aluminium powder and hydrochloric acid initial reaction stage stop heating, thereafter after so that temperature is rapidly increased to 50 DEG C by outside heating
Reaction system temperature is maintained into 95~100 DEG C of ranges by the hydrolysis heat release of aluminium.Phase reaction heat cannot maintain after the reaction
When the temperature, system temperature is maintained by above range by outside heating.Aluminium powder be completely dissolved and solution become clear after followed by
Continuous stirring 2 hours, discharging, filtering, weighing, obtains the Aluminum sol of aluminium content about 10wt%.
Above-mentioned Aluminum sol is placed in 2000ml beaker, it is molten that the calcium acetate that 10ml molar concentration is 0.6086mol/L is added
Liquid (calculating in the ratio of alumina catalyst support 0.3wt% containing calcium oxide) and 121.8ml weight concentration are the hexa-methylene of 40wt%
Four amine aqueous solutions (molar ratio of the chlorine in hexa and Aluminum sol is (UTP): Cl=1.15: 4), mix well be made into it is pre-
Mixed liquid and the temperature for keeping premixed liquid are 5~10 DEG C.
Above-mentioned premixed liquid is fitted into 100ml glass syringe, in the oil column in drop-wise injection 1.5m high, with glueballs
It falls, hexa, which decomposes to give off ammonia, makes aluminium glue ball be gelled rapidly.Oil temperature in oil column is 95~98 DEG C, and molding is with oil
500# base oil, repetitive operation to all premixed liquids granulation finish.
By aluminium glue ball obtained together with molding with it is oily be transferred to high 60mm, volume 2L, can temperature-pressure tubulose
In stainless steel closed container.Container pressure resistance 0.8MPa, 1000 watts of heating power, band automatic temperature-adjusting control instrument, temperature and pressure
Power shows that container top is equipped with charge valve, exhaust valve by the thermometer inside insertion container and the pressure gauge being connected with container
It originates with safety valve for burnin operation with nitrogen displacement tainer air, and provides necessary operation pressure for container with nitrogen,
It can be also used for regulating and controlling the pressure in container in time in aging simultaneously.The temperature of burnin operation controls are as follows: reaches in system temperature
It can be heated at full speed before to 90 DEG C, heating voltage can be adjusted to the 50~60% of total voltage after system temperature reaches 90 DEG C, when
Start recording ageing time when temperature reaches 120 DEG C, final aging temperature are 150 DEG C, and aging pressure is 0.58MPa, when aging
Between 15 hours.
After burnin operation, aluminium glue ball is separated with molding with oil and is placed in 1000ml beaker, is washed with deionized water
Only oil and floating glue on aluminium glue ball are attached, aluminium glue ball is then transferred to porcelain crucible and is placed in Muffle furnace at 100~120 DEG C
Drying 4 hours, 200~300 DEG C are handled 2~3 hours, and 550 DEG C are handled 3~4 hours, and 960~1000 DEG C are handled 3~4 hours, it
Cooling, which is taken out, afterwards obtains about 113g large pore spherical alumina support, and sealing is stand-by.After tested, the crystal phase of the alumina support is δ,
θ-Al2O3, particle diameter is 2.5~3.2mm, specific surface area 72.2m2/ g, specific pore volume product are 0.42cm3/g。
It weighs 30g large pore spherical alumina support obtained above to be placed in 1000ml beaker, molar concentration, which is added, is
The Na of 0.006975mol/L2CO3Solution 28ml (is calculated) in the ratio of alumina catalyst support 0.04wt% containing sodium oxide molybdena, and it is equal to mix suction
It is even, in dislocation porcelain crucible, dried 4 hours in baking oven in 120 DEG C.
The 30g alumina support containing double auxiliary agents after above-mentioned drying is placed in 250ml beaker, pouring into 70ml concentration is
0.00958mol/L, the Na that temperature is room temperature2PdCl4(on the basis of carrying alumina body weight, metal palladium content is solution
0.232wt%), under stiring, it impregnates about 60 minutes, after filtering out alumina support and draining, is washed till with the deionized water of flowing
(usable concentration is the AgNO of 2wt% until can't check chloride ion3Solution is detected).Then by alumina support through 80~
After 150 DEG C dry 2 hours and roast about 4 hours in 450~550 DEG C, air atmosphere in high temperature furnace, it is cooled to room temperature, obtains
To carried palladium-aluminium oxide catalyst.
The activity of catalyst is evaluated using micro fixed-bed reactor (is detailed in " University of Fuzhou's journal (natural science
Version) " 2000 years the 4th phase P70-73 1000-2243 of volume 28, " micro fixed-bed reactor evaluates Pd-Al2O3Catalyst is living
Property ").50 DEG C of reaction temperature, pressure is normal pressure, mixing speed 1400r/min, hydrogen source use H-N ratio for 3: 1 hydrogen nitrogen
Gaseous mixture, catalyst loading are 40ml (about 20g), and active testing procatalyst uses hydrogen nitrogen mixed gas 60~80 in the reactor
DEG C normal pressure in situ reductase 12 0 hour.The working solution composition that this experiment uses are as follows: 2- ethyl hydrazine (EAQ) content 130g/L, solvent
Using the mixture of trioctyl phosphate (TOP) and heavy aromatics, ratio 25/75, working solution dosage is 240ml.Due to this experiment
The H that reaction generates in first 2 hours2O2It is linear with the reaction time, therefore can describe to urge with zero-order reaction kinetic model
Change anti-speed degree, the activity height of catalyst is compared with the size of zero-order reaction velocity constant.
The Activity evaluation of catalyst is shown in Table 1.
Embodiment 2
The process of embodiment 1 is repeated, difference is:
The precursor salt of alkaline earth oxide is changed to Mg (NO3)2.That is, adding alkaline earth oxide into Aluminum sol
When precursor salt solution, it is changed to the Mg (NO for being 3.7486mol/L 15ml concentration3)2Aqueous solution is added in Aluminum sol and stirs equal
It is even.On the basis of carrying alumina body weight, the MgO appendix amount on carrier is about 2wt%.
The precursor salt of alkali metal oxide is changed to NaHCO3.That is, the NaHCO for being 0.05163mol/L with 30ml concentration3Water
Solution impregnates 30g large pore spherical alumina support obtained above.Na on the basis of carrying alumina body weight, on carrier2O is attached
Carrying capacity is about 0.16wt%.
Metal Palladium precursor solution is changed to H2PdCl4Solution.That is, pouring into, 70ml concentration is 0.00958mol/L, temperature is room
The H of temperature2PdCl4Solution is impregnated.On the basis of dry carrying alumina body weight, Metal Palladium weight content is about
0.231wt%.
The activity rating device of the catalyst of the present embodiment 2, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Embodiment 3
The process of embodiment 1 is repeated, difference is:
The precursor salt of alkaline earth oxide is changed to Ba (NO3)2.That is, adding alkaline earth oxide into Aluminum sol
When precursor salt solution, it is changed to the Ba (NO for being 0.307887mol/L 12ml concentration3)2Aqueous solution is added in Aluminum sol and stirs equal
It is even.On the basis of dry carrying alumina body weight, the BaO appendix amount on carrier is about 0.5wt%.
The precursor salt of alkali metal oxide is changed to K2CO3.That is, the potassium carbonate for being 0.0042463mol/L with 30ml concentration
Aqueous solution impregnates 30g large pore spherical alumina support obtained above.On the basis of dry carrying alumina body weight, on carrier
K2O appendix amount is about 0.04wt%.
The activity rating device of the catalyst of the present embodiment 3, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Embodiment 4
The process of embodiment 1 is repeated, difference is:
When preparing premixed liquid, it is added without the precursor salt solution of alkaline earth oxide, prepares the pure oxygen without auxiliary agent
Change alumina supporter.The particle diameter for measuring the alumina support is 2.5~3.2mm, specific surface area 68.6m2/ g, specific pore volume product are
0.40cm3/ g, average pore radius 45nm.
It after pure alumina carrier is made, weighs the above-mentioned pure alumina carrier of 30g and is placed in 1000ml beaker, it is dense that 30ml is added
Degree is the Ca (NO of 0.1mol/L3)2Solution moves into porcelain crucible after mixing suction uniformly with carrier, dries 3 in 120 DEG C in Muffle furnace
Hour, 530 DEG C roast 4 hours, and on the basis of dry carrying alumina body weight, the CaO appendix amount in resulting vehicle is about
0.56wt%.
Carrier by above-mentioned dipping calcium nitrate and after roasting is placed in 1000ml beaker, and 30ml concentration is added and is
The Na of 0.03227mol/L2CO3Solution is moved into porcelain crucible after mixing suction uniformly, is dried 4 hours in 120 DEG C in an oven.With dry
Carrying alumina body weight on the basis of, the Na in resulting vehicle2O appendix amount is about 0.2wt%.
The alumina support containing double auxiliary agents after above-mentioned drying is placed in 250ml beaker, pouring into 70ml concentration is
0.00851mol/L, the H that temperature is room temperature2PdCl4Solution, remaining operation is the same as embodiment 1.It is with dry carrying alumina body weight
Benchmark, the palladium content of catalyst are about 0.2wt%.
The activity rating device of the catalyst of the present embodiment 4, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Embodiment 5
The operation of embodiment 4 is repeated, is only with 30ml concentration when adding the precursor salt solution of alkaline earth oxide
Ba (the NO of 0.03913mol/L3)2Solution substitutes Ca (NO3)2, 30g alumina support impregnate barium salt after 120 DEG C in Muffle furnace
Drying 4 hours, 650 DEG C roast 4 hours, and on the basis of dry carrying alumina body weight, the content of BaO is in resulting vehicle
0.6wt%.The precursor salt solution of alkali metal oxide uses the NaHCO that 30ml concentration is 0.03872mol/L instead3Solution, carrier leaching
Stain NaHCO3It is dried 4 hours in baking oven in 120 DEG C after solution, on the basis of dry carrying alumina body weight, Na in resulting vehicle2O
Content be 0.12wt%.
The Metal Palladium precursor type of the present embodiment 5, dosage and leaching palladium operation are same as Example 4, with dry carrying alumina
On the basis of body weight, the palladium content of catalyst is about 0.2wt%.
The activity rating device of the catalyst of the present embodiment 5, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 1
Weighing 30g partial size is 2.2~2.8mm, impurity Na2O < 0.05wt%, average pore radius 22nm, specific surface area
About 95m2The spherical δ of/g, θ-Al2O3, it is placed in 250ml glass beaker, the Mg that 30ml concentration is 0.49628mol/L is added
(NO3)2Aqueous solution moves into porcelain crucible after mixing suction uniformly, dries in an oven in 120 DEG C 4 hours, 350 DEG C roast 4 hours, institute
The MgO appendix amount on carrier is obtained on the basis of dry carrying alumina body weight, about 2wt%.
The Metal Palladium precursor type of the catalyst of this comparative example 1, dosage and leaching palladium operation are same as Example 1, with dry
On the basis of carrying alumina body weight, the palladium content of catalyst is about 0.23wt%.
The activity rating device of the catalyst of this comparative example 1, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 2
The process of comparative example 1 is repeated, the precursor salt solution of alkaline earth oxide, which is only changed to 30ml concentration, is
Ca (the NO of 0.1mol/L3)2Solution moves into porcelain crucible after mixing suction uniformly with carrier, small in 120 DEG C of drying 3 in Muffle furnace
When, 530 DEG C roast 4 hours, and on the basis of dry alumina support, the CaO of 0.56wt% is contained on carrier.
The Metal Palladium precursor type of the catalyst of this comparative example 2, dosage and leaching palladium operation are same as Example 1, with dry
On the basis of carrying alumina body weight, the palladium content of catalyst is about 0.23wt%.
The activity rating device of the catalyst of this comparative example 1, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 3
The process of comparative example 1 is repeated, the precursor salt solution of alkaline earth oxide, which is only changed to 30ml concentration, is
Ba (the NO of 0.03913mol/L3)2, it is moved into porcelain crucible after mixing suction uniformly with carrier, it is small in 120 DEG C of drying 3 in Muffle furnace
When, 630 DEG C roast 4 hours, and on the basis of dry alumina support, the BaO of 0.6wt% is contained on carrier.
The Metal Palladium precursor type of the catalyst of this comparative example 3, dosage and leaching palladium operation are same as Example 1, with dry
On the basis of carrying alumina body weight, the palladium content of catalyst is about 0.23wt%.
The activity rating device of the catalyst of this comparative example 3, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 4
The process of comparative example 3 is repeated, only this example catalyst leaching palladium uses H instead2PdCl4Solution, will be upper as Metal Palladium precursor
The alumina support containing double auxiliary agents after stating drying is placed in 250ml beaker, and pouring into 70ml concentration is 0.00851mol/L, temperature
For the H of room temperature2PdCl4Solution, remaining operation is with embodiment 1, and on the basis of dry carrying alumina body weight, the palladium of catalyst contains
Amount is about 0.2wt%.
The activity rating device of the catalyst of this comparative example 4, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 5
Weighing 30g partial size is 2.2~2.8mm, impurity Na2O < 0.05wt%, average pore radius 22nm, specific surface area
About 95m2The spherical δ of/g, θ-Al2O3, it is placed in 1000ml beaker, the Na that 28ml concentration is 0.03458mol/L is added2CO3It is molten
Liquid is moved into porcelain crucible after mixing suction uniformly with carrier, is dried 4 hours in 120 DEG C in an oven, with dry carrying alumina body weight
On the basis of, the Na in resulting vehicle2O appendix amount is about 0.2wt%.
This example catalyst soaks palladium and uses H2PdCl4Solution is as Metal Palladium precursor, by the oxygen containing single auxiliary agent after above-mentioned drying
Change alumina supporter to be placed in 250ml beaker, pours into the H that 70ml concentration is 0.00958mol/L, temperature is room temperature2PdCl4Solution,
Remaining operation is with embodiment 1, and on the basis of dry carrying alumina body weight, the palladium content of catalyst is about 0.23wt%.
The activity rating device of the catalyst of this comparative example 5, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 6
The alumina support for weighing the preparation of 30g embodiment 4 is placed in 1000ml beaker the (particle diameter of the alumina catalyst support
For 2.5~3.2mm, specific surface area 68.6m2/ g, specific pore volume product are 0.40cm3/ g, average pore radius 45nm), 30ml is added
Concentration is the Ba (NO of 0.03913mol/L3)2, move into porcelain crucible after mixing suction uniformly with carrier, dried in Muffle furnace in 120 DEG C
3 hours dry, 630 DEG C roast 4 hours, and on the basis of dry alumina support, the BaO of 0.6wt% is contained on carrier.
The 30g carrier containing auxiliary BaO after above-mentioned roasting is placed in 250ml beaker, pouring into 70ml concentration is
0.00958mol/L, the Na that temperature is room temperature2PdCl4Solution impregnates about 60 minutes under stiring, filters out catalyst and drain
Afterwards, the AgNO of wash water 2wt% is washed till with the deionized water of flowing3Until solution can't check chloride ion.It filters out catalyst and drips
It is dry, it is cooling after 80~150 DEG C dry 2 hours and roast about 4 hours in 450~550 DEG C, air atmosphere in high temperature furnace
To room temperature, required catalyst is obtained, on the basis of carrying alumina body weight, Metal Palladium weight content is about
0.23wt%.
The activity rating device of the catalyst of this comparative example 6, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 7
The alumina support for weighing the preparation of 30g embodiment 4 is placed in 1000ml beaker, and 70ml concentration is added and is
0.01208mol/L, the Na that temperature is room temperature2PdCl4Solution impregnates about 60 minutes under stiring, filters out catalyst and drain
Afterwards, wash water 2wt%AgNO is washed till with the deionized water of flowing3Until solution can't check chloride ion.It filters out catalyst and drains,
After 80~150 DEG C dry 2 hours and roast about 4 hours in 450~550 DEG C, air atmosphere in high temperature furnace, it is cooled to room
Temperature obtains required catalyst, and on the basis of carrying alumina body weight, Metal Palladium weight content is about 0.285wt%.
The activity rating device of the catalyst of this comparative example 7, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
Comparative example 8
The process of comparative example 7 is repeated, only be 0.01208mol/L with 70ml concentration when leaching palladium, temperature is room temperature
H2PdCl4Substitute Na2PdCl4Solution, obtained catalyst, on the basis of carrying alumina body weight, Metal Palladium weight content
About 0.288wt%.
The activity rating device of the catalyst of this comparative example 8, method are identical with embodiment 1 as condition.Activity evaluation
It is shown in Table 1.
The anthraquinone hydrogenation activity of the different palladium-aluminium oxide catalysts of table 1.
* the macropore alumina supporter of embodiment 4 is used
It is compared by the comparative example 3 and comparative example 6 of table 1 as it can be seen that in auxiliary agent type, dosage and the identical situation of palladium content,
The activity of the activity catalyst more lesser than carrier aperture of the biggish catalyst of carrier aperture is high.It is right from comparative example 7 and comparative example 8
Than as it can be seen that different Metal Palladium precursors is used in identical from the palladium content situation of catalyst carrier, to the shadow of catalyst activity
It rings little.The data of table 1 are also shown that the activity of double auxiliary agent catalyst is higher than the activity of single auxiliary agent catalyst, single auxiliary agent catalyst
Activity higher than no auxiliary agent catalyst activity.The present invention is using macroporous aluminium oxide as the double auxiliary agent palladium catalysts of the support type of carrier
Activity is that activity of the carrier without auxiliary agent or single auxiliary agent palladium catalyst is high than common aluminium oxide.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (3)
1. a kind of preparation method of carried palladium-aluminium oxide catalyst characterized by comprising
Prepare the Aluminum sol that Al/Cl mass ratio is 1.0 1.5, A1 content is 9 16wt%；
Premixed liquid is made in the precursor salt solution of alkaline earth oxide, hexamethylenetetramine solution and Aluminum sol mixture；
Premixed liquid is granulated by oil-drop method, obtains aluminium glue ball；
After the aging of aluminium glue ball warp, washing, successively dried in 100 120 °C 4 hours, 200 300 °C are handled 23 hours,
550 °C are handled 34 hours, and 960 1000 °C are handled 34 hours, obtain alumina support；
It is dried after the precursor salt solution of alumina support alkali metal oxide is impregnated；
Washing, drying after alumina support after drying is impregnated with Metal Palladium precursor solution, in 450 550 °C, air atmosphere
Middle roasting 35 hours, obtains carried palladium-aluminium oxide catalyst；
Wherein, the precursor salt solution of alkaline earth oxide is selected from one of magnesium, calcium, the acetate of barium or nitrate or more
Kind, the precursor salt solution of alkali metal oxide is selected from Na2CO3、NaHCO3、K2CO3And KHCO3One of or a variety of, Metal Palladium
Precursor solution is H2PdCl4Aqueous solution or Na2PdCl4Aqueous solution；
The Aluminum sol by metallic aluminium powder, deionized water and dilute hydrochloric acid not higher than 110 °C at a temperature of react to obtain, metallic aluminium
Purity >=99.0wt% of powder；
The aperture of the alumina support is 32 ~ 45nm；
The dosage for controlling the precursor salt solution of alkaline earth oxide, makes the content of the alkaline earth oxide in alumina support
For 0.3 2wt%；
For the dosage of the hexamethylenetetramine in terms of the chlorinity in Aluminum sol, the molar ratio of hexamethylenetetramine and chlorine is six times
Tetramine: chlorine=1.10 1.28: 4；
Oil temperature when aging is 120 150 °C, and pressure is 0.35 0.40MPa, and ageing time is 10 20 hours；
The dosage for controlling the precursor salt solution of alkali metal oxide, makes the content of the alkali metal oxide in alumina support
0.02〜lwt%；
The dosage for controlling Metal Palladium precursor solution, makes 0.15 0.32wt% of palladium content in catalyst.
2. the preparation method of carried palladium-aluminium oxide catalyst according to claim 1, it is characterised in that: forming oil column
When oil temperature be 85 98 °C.
3. the preparation method of carried palladium-aluminium oxide catalyst according to claim 1 or 2, it is characterised in that: molding oil
It is 10 12mm selected from 100 °C of lower kinematic viscosity2/SDiesel oil, lubricating oil, machine oil, transformer oil, bobbin oil, mineral base oil
Or synthetic base oil.
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| CN1623655A (en) * | 2004-10-26 | 2005-06-08 | 福州大学 | Palladium-aluminium oxide catalyst and its preparation process |
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| CN1623655A (en) * | 2004-10-26 | 2005-06-08 | 福州大学 | Palladium-aluminium oxide catalyst and its preparation process |
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