CN112108139A - Catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and preparation method thereof - Google Patents
Catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and preparation method thereof Download PDFInfo
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- CN112108139A CN112108139A CN202011058106.9A CN202011058106A CN112108139A CN 112108139 A CN112108139 A CN 112108139A CN 202011058106 A CN202011058106 A CN 202011058106A CN 112108139 A CN112108139 A CN 112108139A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 173
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 68
- 239000007791 liquid phase Substances 0.000 title claims abstract description 64
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002243 precursor Substances 0.000 claims abstract description 78
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 75
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 75
- 239000002245 particle Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000004048 modification Effects 0.000 claims abstract description 29
- 238000012986 modification Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 110
- 239000000463 material Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 238000002156 mixing Methods 0.000 claims description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 238000001914 filtration Methods 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 30
- 239000011268 mixed slurry Substances 0.000 claims description 23
- 239000012266 salt solution Substances 0.000 claims description 21
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000000536 complexating effect Effects 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003681 vanadium Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 5
- 239000007833 carbon precursor Substances 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 239000012159 carrier gas Substances 0.000 description 22
- 238000004321 preservation Methods 0.000 description 22
- 229910052697 platinum Inorganic materials 0.000 description 21
- 239000011651 chromium Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 11
- 238000007664 blowing Methods 0.000 description 11
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 11
- 239000012465 retentate Substances 0.000 description 11
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/42—Platinum
-
- 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
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B01J35/33—
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- B01J35/394—
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- B01J35/397—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation, wherein the raw materials of the catalyst comprise a surface-modified carbon nano tube and precursor atomized particles containing an active component and an auxiliary agent, the active component is Pt, the auxiliary agent is more than two of Ru, Ni, Cr, La and W, and the mass of each auxiliary agent is 0.05-1.0% of the mass of the catalyst. In addition, the invention also provides a method for preparing the catalyst. The catalyst provided by the invention comprises the raw materials of the carbon nano tube after surface modification and precursor atomized particles containing active components and auxiliaries, wherein the active components are Pt, the auxiliaries are more than two of Ru, Ni, Cr, La and W, and the catalyst is provided in the reaction of catalyzing liquid phase hydrogenation of nitrobenzene to synthesize aniline, has high initial activity, long service life and less tar byproducts, and is easy to industrially popularize.
Description
Technical Field
The invention belongs to the technical field of industrial catalysts, and particularly relates to a catalyst for synthesizing aniline by nitrobenzene liquid-phase hydrogenation and a preparation method thereof.
Background
Aniline is also called aminobenzene and aniloline oil, is one of the most important amine substances, is mainly used for manufacturing polyurethane raw material MDI in chemical production, has various applications in industries such as pigment, dye, medicine, pesticide, rubber and the like, and has more than 300 chemical products and intermediates prepared from aniline. The prior aniline production process route mainly adopts a nitrobenzene catalytic hydrogenation method, which is divided into fixed bed gas-phase catalytic hydrogenation, fluidized bed gas-phase catalytic hydrogenation and slurry bed liquid-phase catalytic hydrogenation. The gas phase hydrogenation reaction usually requires higher reaction temperature and hydrogen pressure, has high requirements on equipment, large energy consumption and dangerous operation, while the liquid phase hydrogenation has the advantages of low reaction temperature, less side reactions, high catalytic load, large equipment production capacity, low total investment and the like, and has attracted attention in recent years.
The nitrobenzene liquid phase hydrogenation process plays a core role in the hydrogenation catalyst, wherein non-noble metals such as Ni and Co and noble metals such as Pd, Pt and Rh are commonly used hydrogenation catalysts in the prior art and are also core technologies in aniline production. For example, patent CN101259414A discloses a supported nickel nanocrystalline catalyst prepared by using a carrier loaded with an inducer as a precursor and inducing reduction of a nickel-containing solution, wherein the activity of the supported nickel nanocrystalline catalyst can meet the hydrogenation requirement of nitrobenzene, but the supported nickel nanocrystalline catalyst has poor dispersibility and short service life in a liquid phase hydrogenation slurry bed reactor. Patent application document US2823235 proposes that activated carbon with low specific surface area and high oil absorption is used as a carrier, and Pd, Pt or Pd-Pt bimetal is used as an active component for nitro hydrogenation, but the preparation process of the catalyst is complex and the cost is high.
At present, nitrobenzene liquid phase hydrogenation is carried out in a slurry bed, the requirement on the service life of a catalyst is very strict, domestic aniline production devices and catalysts are all imported, and the catalytic cost is very high. The common active carbon-carried catalyst has insufficient diffusion performance in a slurry bed reactor, a plurality of byproducts such as tar, azobenzene and the like, poor high-temperature resistance and tar poisoning resistance, short service life and difficult industrial production.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and a preparation method thereof aiming at the defects of the prior art. The catalyst raw material comprises a carbon nano tube with a modified surface and a catalyst of precursor atomized particles containing an active component and an auxiliary agent, wherein the active component is Pt, the auxiliary agent is more than two of Ru, Ni, Cr, La and W, the conversion rate of nitrobenzene in the reaction of catalyzing nitrobenzene liquid phase hydrogenation to synthesize aniline is 100%, the selectivity of aniline is more than 99.7%, the initial activity is high, the service life is long, the tar byproduct is less, and the catalyst is easy to industrially popularize.
In order to solve the technical problems, the invention adopts the technical scheme that: the catalyst for synthesizing aniline through nitrobenzene liquid phase hydrogenation is characterized in that raw materials of the catalyst comprise a carbon nano tube with a modified surface and precursor atomized particles containing active components and auxiliary agents, wherein the active components are Pt, the auxiliary agents are more than two of Ru, Ni, Cr, La and W, and the mass of each auxiliary agent is 0.05-1.0% of that of the catalyst.
The catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene is characterized in that the atomized particles of the precursor containing the active component and the auxiliary agent are atomized precursor complexes containing the active component and the auxiliary agent, and the precursor complexes containing the active component and the auxiliary agent are precursor complexes containing the active component and the auxiliary agent, which are formed by the complex reaction of a mixed solution containing the active component and the auxiliary agent and a complexing agent; the particle size of the precursor atomized particles containing the active component and the auxiliary agent is 1.8-3.5 mu m.
The catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation is characterized in that the total mass of the auxiliary agent and Pt is 3.6-5% of the mass of the catalyst, and the total mass of the auxiliary agent is 0.2-0.7 times of the mass of Pt.
The method for synthesizing the catalyst for aniline by liquid-phase hydrogenation of nitrobenzene is characterized by comprising the following steps of:
step one, mixing a soluble salt solution of an active component, a soluble salt solution of an auxiliary agent and a solvent to obtain a mixed system containing the active component and the auxiliary agent, dripping a complexing agent into the mixed system containing the active component and the auxiliary agent at the temperature of 55-95 ℃, and stirring and complexing for 0.5-12 h at the temperature of 55-95 ℃ to obtain a precursor complex containing the active component and the auxiliary agent;
mixing the carbon nano tube subjected to surface modification, oleylamine and water to obtain carbon nano tube-containing slurry;
thirdly, adding a buffering agent and a reducing agent into the slurry containing the carbon nano tubes obtained in the second step in sequence to obtain a mixed material;
and step four, atomizing and purging the precursor complex containing the active component and the auxiliary agent in the step one into the mixed material in the step three under the microwave heating condition of 60-100 ℃, reacting at the temperature of 60-100 ℃, filtering, washing and drying the reacted material to obtain the catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene.
The method is characterized in that the preparation method of the carbon nano tube after the surface modification in the step two comprises the following steps:
step 101, mixing a carbon nano tube, a soluble ferric salt solution, a soluble vanadium salt solution and water to obtain mixed slurry;
and 102, adjusting the pH value of the mixed slurry in the step 101 to 7.5-10, standing and aging at normal temperature, and roasting to obtain the surface-modified carbon nano tube.
The method is characterized in that in the step one, the complexing agent is citric acid, tartaric acid, oxalic acid or nitrilotriacetic acid, and the mass of the complexing agent is 5-10 times that of the active component; step one, the soluble salt solution of the active component is a platinic chloride solution; the soluble salt solution of the auxiliary agent in the step one is RuCl3Solution, NiCl2Solution, CrCl2Solution, LaNO3Solution and Na2WO4Two or more of the solutions; the solvent in the first step is one or more of water, isopropanol, glycol and oleic acid.
The method is characterized in that, in the second step, the volume of the oleylamine is 0.02 to 0.1 times of the mass of the carbon nanotube after surface modification, the unit of the volume of the oleylamine is mL, and the unit of the mass of the carbon nanotube after surface modification is g.
The method is characterized in that in the third step, the buffer is NaHCO with the mass concentration of 10%3Solution, 10% NaH by mass concentration2PO3A solution, a NaAC solution with a mass concentration of 10% or Na with a mass concentration of 10%3C6H5O7A solution, wherein the volume of the buffer is 0.5 to 1 time of the mass of the carbon nanotubes after the surface modification in the second step, the volume unit of the buffer is mL, and the mass unit of the carbon nanotubes after the surface modification is g; and thirdly, the mass of the reducing agent is 5-20 times of that of the active component, and the reducing agent is formaldehyde, formic acid, sodium formate, sodium hypophosphite or potassium borohydride.
The method is characterized in that the atomized particle size in the fourth step is 1.8-3.5 μm.
The method described above, wherein the carbon nanotubes have an average particle diameter of 12 to 15 μm and a specific surface area of 1000cm in step 1012/g～1600cm2(ii)/g, the average pore diameter is 7nm to 10 nm; in step 101, the sum of the mass of the iron element in the soluble ferric salt solution and the mass of the vanadium element in the soluble vanadium salt solution is 0.025-0.14 times of the mass of the carbon nanotube, the soluble ferric salt solution is ferric nitrate solution, ferric chloride solution or ferric sulfate solution, and the soluble vanadium salt solution is vanadiumAn ammonium salt solution, an ammonium metavanadate solution or an ammonium pyrovanadate solution; the temperature of the calcination in the step 102 is 500-900 ℃.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a catalyst of which the raw materials comprise a carbon nano tube with a modified surface and precursor atomized particles containing active components and auxiliary agents, wherein the active components are Pt, the auxiliary agents are more than two of Ru, Ni, Cr, La and W, the conversion rate of nitrobenzene in the reaction of catalyzing nitrobenzene liquid phase hydrogenation to synthesize aniline is 100%, the selectivity of aniline is more than 99.7%, the initial activity is high, the service life is long, the tar byproduct is less, and the catalyst is easy to industrially popularize.
2. The invention takes the carbon nano tube with the modified surface of the metallic iron and the vanadium as the carrier, has high strength and electronegativity after surface modification, can effectively avoid the loss of surface active components and auxiliary metal, prolongs the service life of the catalyst, simultaneously can lead the product aniline to be quickly desorbed from the catalyst, prevents side reaction from occurring, and improves the selectivity.
3. The invention provides a method for preparing a catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene.
4. The method has the advantages of simplified steps, easy industrialization, uniform and controllable sizes of the active components and the metal particles of the auxiliary agent, high utilization rate and good economical efficiency.
The technical solution of the present invention is further described in detail with reference to the following examples.
Detailed Description
Example 1
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a carbon nano tube subjected to surface modification and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 1.5% of that of the catalyst, the active component is Pt, the auxiliary agent is Ru and Cr, the mass of Ru is 1.0% of that of the catalyst, and the mass of Cr is 0.5% of that of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 12 mu m and the specific surface area of 1000cm2Mixing per gram, 2.5mL of carbon nano tube with the average pore diameter of 7nm, 2.5mL of ferric nitrate solution with the concentration of iron element being 0.1g/mL and 10mL of ammonium vanadate solution with the concentration of vanadium element being 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at the temperature of 500 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 4mLRu of ruthenium trichloride solution with concentration of 0.05g/mL, 2mLCr of chromium chloride solution with concentration of 0.05g/mL and 10mL of oleic acid, fixing the volume to 50mL with water to obtain a mixed system containing the active component and the auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out complex reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.1g of the carbon nano tube subjected to surface modification in the step two, 0.382mL of oleylamine and 477.5mL of water to obtain slurry containing the carbon nano tube;
step five, adding 9.55mL of NaHCO with the mass concentration of 10% into the slurry containing the carbon nano tubes in the step four3Adding 3mL of formaldehyde into the solution to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 60 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 microns to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of heat preservation at 60 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Example 2
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a surface-modified carbon nanotube and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 1% of that of the catalyst, the active component is Pt, the auxiliary agent is Ni and W, the mass of Ni is 0.5% of that of the catalyst, and the mass of W is 0.5% of that of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 12 mu m and the specific surface area of 1300cm2Mixing 15mL of iron element ferric chloride solution with the average pore diameter of 8nm, 5mL of vanadium element ammonium metavanadate solution with the concentration of 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 8.5 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at 600 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 2mL of nickel chloride solution with Ni concentration of 0.05g/mL, 2mL of sodium tungstate solution with W concentration of 0.05g/mL and 10mL of isopropanol, adding water to a constant volume of 50mL to obtain a mixed system containing an active component and an auxiliary agent, dropwise adding 48mL of tartaric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at a dropwise adding speed of 1mL/min at a temperature of 75 ℃, and carrying out heat preservation and stirring for 10 hours at a temperature of 75 ℃ to carry out a complex reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.2g of the carbon nano tube subjected to surface modification in the step two, 0.96mL of oleylamine and 480mL of water to obtain carbon nano tube-containing slurry;
step five, adding 15.36mL of NaAC solution with the mass concentration of 10% into the slurry containing the carbon nano tubes obtained in the step four, and then adding 4.8mL of formic acid to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 70 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of heat preservation at 70 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Example 3
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a carbon nano tube with a modified surface and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 0.6% of that of the catalyst, the active component is Pt, the auxiliary agent is Ru and La, the mass of Ru is 0.5% of that of the catalyst, and the mass of La is 0.1% of that of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 14 μm and the specific surface area of 1400cm2Mixing a carbon nano tube with an average pore diameter of 9nm, 5mL of ferric sulfate solution with an iron element concentration of 0.1g/mL and 30mL of ammonium pyrovanadate solution with a vanadium element concentration of 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 10.0 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at 700 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 2mL of ruthenium trichloride solution with Ru concentration of 0.05g/mL, 0.4mL of lanthanum nitrate solution with La concentration of 0.05g/mL and 10mL of ethylene glycol, adding water to a constant volume of 50mL to obtain a mixed system containing an active component and an auxiliary agent, dropwise adding 60mL of nitrilotriacetic acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at a dropwise adding speed of 1mL/min at a temperature of 85 ℃, and carrying out heat preservation and stirring for 6 hours at a temperature of 85 ℃ to carry out a complexing reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.28g of the carbon nano tube subjected to surface modification in the step two, 1.54mL of oleylamine and 482mL of water to obtain carbon nano tube-containing slurry;
step five, adding 15.42mL of NaH with the mass concentration of 10% into the slurry containing the carbon nano tubes in the step four2PO3Adding 50mL of sodium formate aqueous solution with the concentration of 0.12g/mL to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 90 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 microns to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of heat preservation at 90 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Example 4
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a carbon nano tube subjected to surface modification and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 1.5% of that of the catalyst, the active component is Pt, the auxiliary agent is Cr and Ni, the mass of Cr is 1.0% of that of the catalyst, and the mass of Ni is 0.5% of that of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 15 mu m and the specific surface area of 1600cm2Mixing per gram, carbon nano tubes with the average pore diameter of 10nm, 20mL of ferric chloride solution with the concentration of iron element of 0.1g/mL and 50mL of ammonium vanadate solution with the concentration of vanadium element of 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 9 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at the temperature of 900 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of platinic chloride solution with platinum concentration of 0.05g/mL, 4mL of chromium chloride solution with Cr concentration of 0.05g/mL, 2mL of nickel chloride solution with Ni concentration of 0.05g/mL and 10mL of isopropanol, adding water to a constant volume of 50mL to obtain a mixed system containing the active component and the auxiliary agent, dropwise adding 36mL of oxalic acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at a dropwise adding speed of 1mL/min at a temperature of 95 ℃, and carrying out heat preservation and stirring for 0.5h at a temperature of 95 ℃ to carry out a complex reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.1g of the carbon nano tube subjected to surface modification in the step two, 1.91mL of oleylamine and 477.5mL of water to obtain carbon nano tube-containing slurry;
step five, adding 19.1mL of Na with the mass concentration of 10% into the slurry containing the carbon nano tubes in the step four3C6H5O7Adding 100mL of sodium hypophosphite aqueous solution with the concentration of 0.12g/mL into the solution to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 100 ℃ by microwave, preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 100 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Example 5
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a carbon nano tube subjected to surface modification and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 1.5% of that of the catalyst, the active component is Pt, the auxiliary agent is Ru and Cr, the mass of Ru is 1.0% of that of the catalyst, and the mass of Cr is 0.5% of that of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 12 mu m and the specific surface area of 1200cm2Mixing per gram, carbon nano tubes with the average pore diameter of 7nm, 2.5mL of ferric nitrate solution with the concentration of iron element of 0.1g/mL and 10mL of ammonium vanadate with the concentration of vanadium element of 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at the temperature of 500 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of platinic chloride solution with platinum concentration of 0.05g/mL, 4mL of ruthenium trichloride solution with Ru concentration of 0.05g/mL, 2mL of chromium chloride solution with Cr concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume to 50mL with water to obtain a mixed system containing the active component and the auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out complex reaction, and obtaining a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.1g of the carbon nano tube subjected to surface modification in the step two, 0.382mL of oleylamine and 477.5mL of water to obtain slurry containing the carbon nano tube;
step five, adding 9.55mL of NaHCO with the mass concentration of 10% into the slurry containing the carbon nano tubes in the step four3Adding 3mL of formaldehyde into the solution to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 60 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 microns to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of heat preservation at 60 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Example 6
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a surface-modified carbon nanotube and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 0.8% of that of the catalyst, the active component is Pt, the auxiliary agent is Ni, Ru and W, the mass of Ni is 0.5% of that of the catalyst, the mass of Ru is 0.2% of that of the catalyst, and the mass of W is 0.1% of that of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 15 mu m and the specific surface area of 1300cm2Mixing 18mL of ferric nitrate solution with the average pore diameter of 9nm, 12mL of ammonium pyrovanadate solution with the vanadium element concentration of 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 8.5 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at 600 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 2mL of nickel chloride solution with Ni concentration of 0.05g/mL, 0.8mL of ruthenium trichloride solution with Ru concentration of 0.05g/mL, 0.4mL of sodium tungstate solution with W concentration of 0.05g/mL and 10mL of isopropanol, adding water to a constant volume of 50mL to obtain a mixed system containing an active component and an auxiliary agent, dropwise adding 50mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at a dropwise adding speed of 1mL/min at a temperature of 80 ℃, and carrying out heat preservation and stirring for 6 hours at the temperature of 80 ℃ to carry out a complexing reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.24g of the carbon nano tube subjected to surface modification in the step two, 0.962mL of oleylamine and 481mL of water to obtain carbon nano tube-containing slurry;
step five, firstly adding 15.392mL of NaH with the mass concentration of 10% into the slurry containing the carbon nano tubes in the step four2PO3Adding 100mL of sodium hypophosphite aqueous solution with the concentration of 0.12g/mL into the solution to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 65 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 microns to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 65 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Example 7
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a carbon nano tube subjected to surface modification and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 0.8% of that of the catalyst, the active component is Pt, the auxiliary agent is Ru, Cr and La, the mass of Ru is 0.5% of that of the catalyst, the mass of Cr is 0.2% of that of the catalyst, and the mass of La is 0.1% of that of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 13 mu m and the specific surface area of 1500cm2Mixing per gram, carbon nano tubes with the average pore diameter of 8nm, 24mL ferric nitrate solution with the concentration of iron element of 0.1g/mL and 12mL ammonium pyrovanadate solution with the concentration of vanadium element of 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 8 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at the temperature of 750 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of platinic chloride solution with platinum concentration of 0.05g/mL, 2mL of ruthenium trichloride solution with Ru concentration of 0.05g/mL, 0.8mL of chromium chloride solution with Cr concentration of 0.05g/mL, 0.4mL of lanthanum nitrate solution with La concentration of 0.05g/mL and 10mL of ethylene glycol, adding water to a constant volume of 50mL to obtain a mixed system containing an active component and an auxiliary agent, dropwise adding 60mL of tartaric acid aqueous solution with concentration of 0.1g/mL at a dropwise adding speed of 1mL/min into the mixed system containing the active component and the auxiliary agent at a temperature of 65 ℃, and carrying out heat preservation and stirring for 8 hours at the temperature of 65 ℃ to carry out a complexing reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.24g of the carbon nano tube subjected to surface modification in the step two, 0.577mL of oleylamine and 4811mL of water to obtain carbon nano tube-containing slurry;
step five, adding 7.69mL of NaH with the mass concentration of 10% into the slurry containing the carbon nano tubes in the step four2PO3Adding 80mL of potassium borohydride aqueous solution with the concentration of 0.12g/mL to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 65 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 microns to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 65 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Example 8
The embodiment provides a catalyst for synthesizing aniline through nitrobenzene liquid-phase hydrogenation, wherein raw materials of the catalyst comprise a carbon nano tube subjected to surface modification and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of the mass of the catalyst, the mass of the auxiliary agent is 2.0% of the mass of the catalyst, the active component is Pt, the auxiliary agent is Ru, Cr, Ni, La and W, the mass of Ru is 1.0% of the mass of the catalyst, the mass of Cr is 0.5% of the mass of the catalyst, the mass of Ni is 0.3% of the mass of the catalyst, and the mass of La is 0.15% of the mass of the catalyst; the mass of W is 0.05% of the mass of the catalyst;
the embodiment provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation by using surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries as raw materials, which specifically comprises the following steps:
step one, 50g of the powder with the average particle size of 12 mu m and the specific surface area of 1000cm2Mixing per gram, 2.5mL of carbon nano tube with the average pore diameter of 7nm, 2.5mL of ferric nitrate solution with the concentration of iron element being 0.1g/mL and 10mL of ammonium vanadate solution with the concentration of vanadium element being 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at the temperature of 500 ℃ in a nitrogen protective atmosphere to obtain a surface-modified carbon nano tube;
step three, mixing 12mL of platinic chloride solution with platinum concentration of 0.05g/mL, 4mLRu of ruthenium trichloride solution with concentration of 0.05g/mL, 2mLCr of chromium chloride solution with concentration of 0.05g/mL, 1.2mLNi of nickel chloride solution with concentration of 0.05g/mL, 0.6mLLa of lanthanum nitrate solution with concentration of 0.05g/mL, 0.22mLW of sodium tungstate solution with concentration of 0.05g/mL and 10mL of oleic acid, fixing the volume to 50mL by water to obtain a mixed system containing the active component and the auxiliary agent, dripping 30mL of citric acid solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min under the temperature condition of 55 ℃, stirring for 12 hours under the temperature condition of 55 ℃ to carry out complexing reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.1g of the carbon nano tube subjected to surface modification in the step two, 0.382mL of oleylamine and 477.5mL of water to obtain slurry containing the carbon nano tube;
step five, adding 9.55mL of NaHCO with the mass concentration of 10% into the slurry containing the carbon nano tubes in the step four3Adding 3mL of formaldehyde into the solution to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 60 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 microns to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of heat preservation at 60 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Comparative example 1
The comparative example inspects the influence of the performance of the catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene without adding an auxiliary agent, the raw materials of the catalyst of the comparative example comprise a surface modified carbon nano tube and precursor atomized particles containing an active component, the mass of the active component is 3% of the mass of the catalyst, and the active component is Pt;
this comparative example provides a process for preparing the above catalyst identical to example 1, except for step three, step four, and step six:
step three, mixing 12mL of platinic chloride solution with platinum concentration of 0.05g/mL and 10mL of oleic acid, fixing the volume to 50mL by using water to obtain a mixed system containing an active component, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component at a dripping speed of 1mL/min at the temperature of 55 ℃, preserving heat and stirring for 12 hours at the temperature of 55 ℃ to carry out a complexing reaction to obtain a precursor complex containing the active component;
step four, mixing 19.4g of the carbon nano tube subjected to surface modification in the step two, 0.388mL of oleylamine and 485mL of water to obtain carbon nano tube-containing slurry;
sixthly, heating the mixed material obtained in the fifth step to 60 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active component, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min at the temperature of 60 ℃, cooling and filtering the reacted material, washing the retentate obtained by filtering with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Comparative example 2
The comparative example investigates the influence of the performance of the catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene by using an unmodified carbon nanotube as a carrier, wherein the raw materials of the catalyst comprise the carbon nanotube and precursor atomized particles containing an active component and an auxiliary agent, the mass of the active component is 3% of that of the carbon nanotube, the mass of the auxiliary agent is 1.5% of that of the catalyst, the active component is Pt, the auxiliary agent is Ru and Cr, the mass of Ru is 1.0% of that of the catalyst, and the mass of Cr is 0.5% of that of the catalyst;
the present comparative example provides a method for preparing the above catalyst, specifically:
step one, mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 4mLRu of ruthenium trichloride solution with concentration of 0.05g/mL, 2mLCr of chromium chloride solution with concentration of 0.05g/mL and 10mL of oleic acid, fixing the volume to 50mL with water to obtain a mixed system containing an active component and an auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out complex reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step two, mixing 19.1g of carbon nano tube, 0.382mL of oleylamine and 477.5mL of water to obtain slurry containing the carbon nano tube; the average grain diameter of the carbon nano tube is 12 mu m, and the specific surface area is 1200cm2(ii)/g, average pore diameter 7 nm;
step three, adding 9.55mL of NaHCO with mass concentration of 10% into the slurry containing the carbon nano tube in step two3Adding 3mL of formaldehyde into the solution to obtain a mixed material;
step four, heating the mixed material obtained in the step three to 60 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the step one by an atomizing machine with the atomizing granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of preserving heat at 60 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Comparative example 3
The influence of non-atomized precursor raw materials containing active components and auxiliaries on the performance of the catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene is examined in the comparative example, the catalyst raw materials in the comparative example comprise surface-modified carbon nanotubes and precursors containing the active components and the auxiliaries, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliaries is 1.5% of that of the catalyst, the active components are Pt, the auxiliaries are Ru and Cr, the mass of Ru is 1.0% of that of the catalyst, and the mass of Cr is 0.5% of that of the catalyst;
the method of this comparative example for preparing the above catalyst is the same as example 1, except that:
and step six, heating the mixed material obtained in the step five to 60 ℃ by microwave and preserving heat, pouring the precursor complex containing the active component and the auxiliary agent obtained in the step three into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of preserving heat at 60 ℃, cooling and filtering the reacted material, washing the filtered trapped substance by pure water until the conductivity of the filtrate is less than 25us/cm, drying the washed material in a vacuum oven at 75 ℃ to constant weight, and obtaining the catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase.
Comparative example 4
The comparative example examines the influence of other auxiliary components on the performance of the catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, and the catalyst of the comparative example is the same as that of example 1, wherein the difference is that the auxiliary components are Cu and Zn, the mass of Cu is 1.0% of that of the catalyst, and the mass of Zn is 0.5% of that of the catalyst;
this comparative example the process for preparing the above catalyst was the same as in example 1, except that,
the third step is: mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 4mL of copper nitrate solution with platinum concentration of 0.05g/mL, 2mL of zinc nitrate solution with zinc nitrate concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume to 50mL by using water to obtain a mixed system containing the active component and the auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, and carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out complexing reaction to obtain a precursor complex containing the active component and the auxiliary agent.
Comparative example 5
The catalyst raw materials of the comparative example comprise surface-modified activated carbon and precursor atomized particles containing an active component and an auxiliary agent, wherein the mass of the active component is 3% of that of the catalyst, the mass of the auxiliary agent is 1.5% of that of the catalyst, the active component is Pt, the auxiliary agent is Ru and Cr, the mass of Ru is 1.0% of that of the catalyst, and the mass of Cr is 0.5% of that of the catalyst;
the method of this comparative example for preparing the above catalyst comprises the steps of:
step one, 50g of the powder with the average particle size of 27 mu m and the specific surface area of 1400cm2Mixing activated carbon with the average pore diameter of 3.4nm, 2.5mL of ferric nitrate solution with the concentration of iron element of 0.1g/mL and 10mL of ammonium vanadate solution with the concentration of vanadium element of 0.1g/mL, adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry;
step two, Na with the mass percentage of 2 percent is used2CO3Adjusting the pH value of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and aging for 12h at normal temperature, filtering, and roasting the intercepted substance obtained by filtering for 0.5h at the temperature of 500 ℃ in a nitrogen protective atmosphere to obtain surface-modified activated carbon;
step three, mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 4mLRu of ruthenium trichloride solution with concentration of 0.05g/mL, 2mLCr of chromium chloride solution with concentration of 0.05g/mL and 10mL of oleic acid, fixing the volume to 50mL with water to obtain a mixed system containing the active component and the auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out complex reaction to obtain a precursor complex containing the active component and the auxiliary agent;
step four, mixing 19.1g of the surface-modified activated carbon obtained in the step two, 0.382mL of oleylamine and 477.5mL of water to obtain activated carbon-containing slurry;
step five, adding 9.55mL of NaHCO with the mass concentration of 10% into the slurry containing the activated carbon in the step four3Adding 3mL of formaldehyde into the solution to obtain a mixed material;
sixthly, heating the mixed material obtained in the fifth step to 60 ℃ by microwave and preserving heat, atomizing the precursor complex containing the active component and the auxiliary agent obtained in the third step by an atomizing machine with the atomizing granularity of 1.8-3.5 microns to obtain precursor atomized particles containing the active component and the auxiliary agent, blowing the precursor atomized particles into the heat-preserved mixed material, carrying out reduction reaction for 45min under the condition of heat preservation at 60 ℃, cooling and filtering the reacted material, washing the filtered retentate with pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a 75 ℃ vacuum oven to constant weight to obtain a catalyst for synthesizing aniline by hydrogenation of nitrobenzene liquid phase; the purging is performed by using nitrogen as a carrier gas, and the flow rate of the carrier gas is 100 mL/min.
Comparative example 6
The comparative example examines the influence of Ti and Co as carbon nano tube modified metal on the performance of the catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene. The catalyst of this comparative example was the same as example 1, and the method of preparing the above catalyst of this comparative example was the same as example 1, except that:
step one, 50g of the powder with the average particle size of 12 mu m and the specific surface area of 1000cm2Mixing carbon nano tubes with the average pore diameter of 7nm, 2.5mL of titanium tetrachloride solution with the titanium element concentration of 0.1g/mL and 10mL of cobalt nitrate solution with the cobalt element concentration of 0.1g/mL, adding water to a constant volume of 500mL, and transferring the mixture into a 1L beaker to obtain mixed slurry.
Comparative example 7
The comparative example examines the influence of the performance of the catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene as an auxiliary agent, and the catalyst of the comparative example is the same as that of example 1, wherein the difference is that the auxiliary agent is Ru, and the mass of the auxiliary agent is 1.0 percent of that of the catalyst.
This comparative example the process for preparing the above catalyst is the same as in example 1, with the difference that step three is: mixing 12mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 4mL of ruthenium trichloride solution with platinum concentration of 0.05g/mL and 10mL of oleic acid, fixing the volume to 50mL by using water to obtain a mixed system containing an active component and an auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, and carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out a complexing reaction to obtain a precursor complex containing the active component and the auxiliary agent;
and step four, mixing 19.2g of the carbon nano tube subjected to surface modification in the step two, 0.96mL of oleylamine and 480mL of water to obtain carbon nano tube-containing slurry.
Comparative example 8
The comparative example investigates the influence of the content of the active component on the performance of the catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, and the catalyst is the same as the catalyst in the example 1, wherein the difference is that the mass of the active component is 2 percent of the mass of the catalyst;
this comparative example the process for preparing the above catalyst was the same as in example 1, except that step three was: mixing 8mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 4mL of ruthenium trichloride solution with platinum concentration of 0.05g/mL, 2mL of chromium chloride solution with chromium chloride concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume to 50mL by using water to obtain a mixed system containing the active component and the auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, and carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out complex reaction to obtain a precursor complex containing the active component and the auxiliary agent.
Comparative example 9
The comparative example investigates the influence of the content of the active component on the performance of the catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, and the catalyst is the same as the catalyst in the example 1, wherein the difference is that the mass of the active component is 5 percent of that of the catalyst;
this comparative example the process for preparing the above catalyst was the same as in example 1, except that step three was: mixing 20mL of chloroplatinic acid solution with platinum concentration of 0.05g/mL, 4mL of ruthenium trichloride solution with platinum concentration of 0.05g/mL, 2mL of chromium chloride solution with chromium chloride concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume to 50mL by using water to obtain a mixed system containing the active component and the auxiliary agent, dripping 30mL of citric acid aqueous solution with concentration of 0.1g/mL into the mixed system containing the active component and the auxiliary agent at the dripping speed of 1mL/min at the temperature of 55 ℃, and carrying out heat preservation and stirring for 12 hours at the temperature of 55 ℃ to carry out complexing reaction to obtain a precursor complex containing the active component and the auxiliary agent.
Performance evaluation:
the catalysts of the embodiments 1-8 and the comparative examples 1-9 are used for the liquid phase hydrogenation of nitrobenzene to prepare aniline, and the reaction process comprises the following steps: 150mL of nitrobenzene, 200mL of aniline and 0.3g of catalyst are placed in a continuous reaction kettle, the mixture is reacted for 20min under the conditions that the temperature is 200 ℃ and the pressure is 1.5MPa, the reaction liquid is extruded after the temperature is reduced to be lower than 70 ℃, a sample is taken and analyzed by a gas chromatograph, and the conversion rate of nitrobenzene and the selectivity of aniline are shown in Table 1.
The catalyst of example 1 was repeatedly used according to the performance evaluation method, the reaction was terminated without decreasing the hydrogen pressure in the reaction vessel, the reaction time was 20min to 30min for each use, the catalyst was separated from the reaction solution after each reaction, the catalyst was back-flushed into the reaction vessel with a mixture of 150mL nitrobenzene and 200mL aniline, and the results of repeated use are shown in table 2.
TABLE 1 Nitrobenzene conversion and Aniline Selectivity in Nitrobenzene liquid phase hydrogenation to Aniline reaction
Table 2 example 1 evaluation results of catalyst life
According to table 1, the initial activity of the catalyst of the present invention in the reaction of preparing aniline by liquid phase hydrogenation of nitrobenzene and the selectivity of aniline are superior to those of the comparative example, which shows that the catalyst of the present invention, which comprises the surface-modified carbon nanotubes and the precursor atomized particles containing the active component and the auxiliary agent, has excellent catalytic conversion performance.
According to the table 2, the catalyst prepared by the invention is repeatedly used for 20 times in the reaction of preparing aniline by liquid phase hydrogenation of nitrobenzene, the activity of the catalyst is basically not attenuated, and the catalyst has good aniline selectivity and service life.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The catalyst for synthesizing aniline through nitrobenzene liquid phase hydrogenation is characterized in that raw materials of the catalyst comprise a carbon nano tube with a modified surface and precursor atomized particles containing active components and auxiliary agents, wherein the active components are Pt, the auxiliary agents are more than two of Ru, Ni, Cr, La and W, and the mass of each auxiliary agent is 0.05-1.0% of that of the catalyst.
2. The catalyst for liquid-phase hydrogenation of nitrobenzene to aniline according to claim 1, wherein the atomized particles of the precursor containing the active ingredient and the auxiliary agent are atomized precursor complexes containing the active ingredient and the auxiliary agent, and the precursor complexes containing the active ingredient and the auxiliary agent are precursor complexes containing the active ingredient and the auxiliary agent, which are formed by the complex reaction of the mixed solution containing the active ingredient and the auxiliary agent and the complexing agent; the particle size of the precursor atomized particles containing the active component and the auxiliary agent is 1.8-3.5 mu m.
3. The catalyst for liquid-phase hydrogenation of nitrobenzene to aniline according to claim 1, wherein the total mass of the promoter and Pt is 3.6-5% of the mass of the catalyst, and the total mass of the promoter is 0.2-0.7 times of the mass of Pt.
4. A process for preparing the catalyst for liquid phase hydrogenation of nitrobenzene to aniline according to claim 1, comprising the steps of:
step one, mixing a soluble salt solution of an active component, a soluble salt solution of an auxiliary agent and a solvent to obtain a mixed system containing the active component and the auxiliary agent, dripping a complexing agent into the mixed system containing the active component and the auxiliary agent at the temperature of 55-95 ℃, and stirring and complexing for 0.5-12 h at the temperature of 55-95 ℃ to obtain a precursor complex containing the active component and the auxiliary agent;
mixing the carbon nano tube subjected to surface modification, oleylamine and water to obtain carbon nano tube-containing slurry;
thirdly, adding a buffering agent and a reducing agent into the slurry containing the carbon nano tubes obtained in the second step in sequence to obtain a mixed material;
and step four, atomizing and purging the precursor complex containing the active component and the auxiliary agent in the step one into the mixed material in the step three under the microwave heating condition of 60-100 ℃, reacting at the temperature of 60-100 ℃, filtering, washing and drying the reacted material to obtain the catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene.
5. The method of claim 4, wherein the step two of preparing the surface-modified carbon nanotubes comprises:
step 101, mixing a carbon nano tube, a soluble ferric salt solution, a soluble vanadium salt solution and water to obtain mixed slurry;
and 102, adjusting the pH value of the mixed slurry in the step 101 to 7.5-10, standing and aging at normal temperature, and roasting to obtain the surface-modified carbon nano tube.
6. The method according to claim 4, wherein the complexing agent in the first step is citric acid, tartaric acid, oxalic acid or nitrilotriacetic acid, and the mass of the complexing agent is 5-10 times that of the active component; step one, the soluble salt solution of the active component is a platinic chloride solution; the soluble salt solution of the auxiliary agent in the step one is RuCl3Solution, NiCl2Solution, CrCl2Solution, LaNO3Solution and Na2WO4Two or more of the solutions; the solvent in the first step is one or more of water, isopropanol, glycol and oleic acid.
7. The method as claimed in claim 4, wherein the volume of oleylamine in step two is 0.02 to 0.1 times the mass of the carbon nanotubes after surface modification, the volume of oleylamine is in mL, and the mass of the carbon nanotubes after surface modification is in g.
8. The method of claim 4, wherein in step three, the buffer is NaHCO with a mass concentration of 10%3Solution, 10% NaH by mass concentration2PO3A solution, a NaAC solution with a mass concentration of 10% or Na with a mass concentration of 10%3C6H5O7A solution, wherein the volume of the buffer is 0.5 to 1 time of the mass of the carbon nanotubes after the surface modification in the second step, the volume unit of the buffer is mL, and the mass unit of the carbon nanotubes after the surface modification is g; and thirdly, the mass of the reducing agent is 5-20 times of that of the active component, and the reducing agent is formaldehyde, formic acid, sodium formate, sodium hypophosphite or potassium borohydride.
9. The method of claim 4, wherein the atomized particles in step four have a size of 1.8 μm to 3.5 μm.
10. The method of claim 5, wherein the carbon nanotubes of step 101 have an average particle size of 12 to 15 μm and a specific surface area of 1000cm2/g～1600cm2(ii)/g, the average pore diameter is 7nm to 10 nm; in step 101, the sum of the mass of the iron element in the soluble ferric salt solution and the mass of the vanadium element in the soluble vanadium salt solution is 0.025-0.14 times of the mass of the carbon nanotube, the soluble ferric salt solution is ferric nitrate solution, ferric chloride solution or ferric sulfate solution, and the soluble vanadium salt solution is ammonium vanadate solution, ammonium metavanadate solution or ammonium pyrovanadate solution; the temperature of the calcination in the step 102 is 500-900 ℃.
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| US20060142148A1 (en) * | 2004-11-16 | 2006-06-29 | Hyperion Catalysis International, Inc. | Methods for preparing catalysts supported on carbon nanotube networks |
| CN103316676A (en) * | 2013-05-17 | 2013-09-25 | 中国科学院宁波材料技术与工程研究所 | Catalyst used in nitrobenzene liquid-phase hydrogenation aniline synthesis, and preparation method thereof |
| CN103349983A (en) * | 2013-07-27 | 2013-10-16 | 西安凯立化工有限公司 | Catalyst for preparing halogenated aniline through catalytic hydrogenation of halogenated nitrobenzene and application thereof |
| CN106732564A (en) * | 2016-12-03 | 2017-05-31 | 西安凯立新材料股份有限公司 | The preparation method and application of aromatic hydrogenation rhodium/activated-carbon catalyst |
| CN107649148A (en) * | 2017-10-26 | 2018-02-02 | 湘潭大学 | A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified |
| CN109126823A (en) * | 2018-10-23 | 2019-01-04 | 江西理工大学 | Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline |
| CN110465289A (en) * | 2019-08-23 | 2019-11-19 | 西安凯立新材料股份有限公司 | A kind of preparation method of carried by active carbon Pt nanocrystal catalyst |
| CN111330629A (en) * | 2020-04-08 | 2020-06-26 | 万华化学集团股份有限公司 | M-xylylenediamine hydrogenation catalyst, and preparation method and application thereof |
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