CN112108139B - 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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- CN112108139B CN112108139B CN202011058106.9A CN202011058106A CN112108139B CN 112108139 B CN112108139 B CN 112108139B CN 202011058106 A CN202011058106 A CN 202011058106A CN 112108139 B CN112108139 B CN 112108139B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 157
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 72
- 239000007791 liquid phase Substances 0.000 title claims abstract description 68
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 123
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000002245 particle Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000007833 carbon precursor Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 108
- 239000002243 precursor Substances 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000002041 carbon nanotube Substances 0.000 claims description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 46
- 238000001914 filtration Methods 0.000 claims description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 30
- 239000011268 mixed slurry Substances 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 20
- 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
- 239000002253 acid Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000007664 blowing 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
- 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
- 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
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000002071 nanotube Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 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
- 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
- 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
- 239000011734 sodium Substances 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
- 230000000536 complexating effect Effects 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
- 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
- 239000006172 buffering agent Substances 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
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 34
- 239000007864 aqueous solution Substances 0.000 description 26
- 239000012159 carrier gas Substances 0.000 description 22
- 238000004321 preservation Methods 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000012465 retentate Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 239000011651 chromium Substances 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000010668 complexation reaction Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000000889 atomisation Methods 0.000 description 11
- 238000010926 purge Methods 0.000 description 11
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 10
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 8
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 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
- 239000012071 phase Substances 0.000 description 3
- 230000001681 protective effect Effects 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 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
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 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
- 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
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 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
- 230000008676 import Effects 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
- 229910017604 nitric acid Inorganic materials 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
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 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, which comprises surface-modified carbon nanotubes 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 the mass of the catalyst. In addition, the invention also provides a method for preparing the catalyst. The catalyst raw material comprises surface modified carbon nano tubes 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 catalyst is applied to the reaction of synthesizing aniline by catalyzing nitrobenzene liquid phase hydrogenation, 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 liquid phase hydrogenation of nitrobenzene and a preparation method thereof.
Background
Aniline is also called aminobenzene and anilin oil, is one of the most important amine substances, is mainly used for manufacturing polyurethane raw material MDI in chemical production, has a plurality of 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 current aniline production process route is mainly based on a nitrobenzene catalytic hydrogenation method, and the nitrobenzene catalytic hydrogenation method 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 generally requires higher reaction temperature and hydrogen pressure, has high equipment requirement, high energy consumption and operation danger, while the liquid phase hydrogenation has the advantages of low reaction temperature, less side reaction, high catalytic load, high equipment production capacity, low total investment and the like, and has attracted attention in recent years.
The hydrogenation catalyst plays a core role in the nitrobenzene liquid-phase hydrogenation process, wherein non-noble metal Ni, co, noble metal Pd, pt, rh and other catalysts are common hydrogenation catalysts in the prior art, and are also core technologies in aniline production. For example, patent CN101259414a discloses a method for preparing a supported nickel nanocrystalline catalyst by using a carrier loaded with an inducer as a precursor and inducing and reducing a nickel-containing solution, wherein the activity of the supported nickel nanocrystalline catalyst can meet the nitrobenzene hydrogenation requirement, but the dispersion of the supported nickel nanocrystalline catalyst in a liquid phase hydrogenation slurry bed reactor is poor, and the service life of the supported nickel nanocrystalline catalyst is short. Patent application document US2823235 proposes an activated carbon with low specific surface area and high oil absorption as a carrier and Pd, pt or Pd-Pt bimetallic as an active component of nitro hydrogenation, but the catalyst has complex preparation process and higher cost.
At present, nitrobenzene liquid-phase hydrogenation is carried out in a slurry bed, the service life requirement of a catalyst is very strict, domestic aniline production devices and the catalyst are all dependent on import, and the catalytic cost is very high. The general activated carbon supported catalyst has insufficient spreading performance in a slurry bed reactor, more 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 invention aims to solve the technical problem of providing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and a preparation method thereof. The catalyst raw material comprises a catalyst of surface-modified carbon nano tubes 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 synthesizing aniline by catalyzing liquid-phase hydrogenation of nitrobenzene is 100%, the selectivity of aniline is more than 99.7%, the initial activity is high, the service life is long, the tar byproducts are less, and the catalyst is easy to industrially popularize.
In order to solve the technical problems, the invention adopts the following technical scheme: the catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene is characterized in that raw materials of the catalyst comprise surface-modified carbon nanotubes 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 the mass of the catalyst.
The catalyst for synthesizing the aniline by the nitrobenzene liquid phase hydrogenation is characterized in that the precursor atomized particles containing the active components and the auxiliary agents are atomized precursor complexes containing the active components and the auxiliary agents, and the precursor complexes containing the active components and the auxiliary agents are precursor complexes containing the active components and the auxiliary agents formed by the meridian combination reaction of the mixed solution containing the active components and the auxiliary agents 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.
The catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene 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:
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, dropwise adding 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;
Step two, mixing the carbon nano tube with the surface modified, oleylamine and water to obtain carbon nano tube-containing slurry;
step three, sequentially adding a buffering agent and a reducing agent into the carbon-containing nanotube slurry in the step two to obtain a mixed material;
and step four, under the condition of microwave heating at 60-100 ℃, atomizing and blowing the precursor complex containing the active components and the auxiliary agent in the step one into the mixed material in the step three, reacting at the temperature of 60-100 ℃, filtering, washing and drying the reacted material, and obtaining the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation.
The method is characterized in that the preparation method of the carbon nano tube after the surface modification in the second step 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, regulating the pH 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 nanotube.
The method is characterized in that in the first step, the complexing agent is citric acid, tartaric acid, oxalic acid or nitrilotriacetic acid, and the mass of the complexing agent is 5-10 times of that of the active component; step one, the soluble salt solution of the active component is chloroplatinic acid solution; step one, wherein the soluble salt solution of the auxiliary agent is RuCl 3 Solution, niCl 2 Solution, crCl 2 Solution, laNO 3 Solution and Na 2 WO 4 More than two of the solutions; in the first step, the solvent is one or more of water, isopropanol, glycol and oleic acid.
The method is characterized in that the volume of the oleylamine in the second step is 0.02-0.1 times of the mass of the carbon nano tube after surface modification, the volume of the oleylamine is in mL, and the mass of the carbon nano tube after surface modification is in g.
The method is characterized in that the buffer in the step three is NaHCO with the mass concentration of 10 percent 3 Solution with mass concentration of 10% NaH 2 PO 3 Solution, naAC solution with mass concentration of 10% orThe mass concentration is 10% of Na 3 C 6 H 5 O 7 The volume of the buffer is 0.5-1 time of the mass of the surface-modified carbon nano tube in the second step, the volume unit of the buffer is mL, and the mass unit of the surface-modified carbon nano tube is g; and step three, 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 particle size of atomization in the fourth step is 1.8-3.5 μm.
The method is characterized in that the average particle diameter of the carbon nanotubes in step 101 is 12-15 μm and the specific surface area is 1000cm 2 /g～1600cm 2 And/g, wherein the average pore diameter is 7 nm-10 nm; in the step 101, the sum of the mass of iron element in the soluble ferric salt solution and the mass of vanadium element in the soluble vanadium salt solution is 0.025-0.14 times of the mass of the carbon nano tube, 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 roasting temperature in the step 102 is 500-900 ℃.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a catalyst with raw materials comprising surface modified carbon nano tubes 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 synthesizing aniline by catalyzing nitrobenzene liquid phase hydrogenation is 100%, the selectivity of aniline is more than 99.7%, the initial activity is high, the service life is long, the tar byproducts are less, and the catalyst is easy to industrially popularize.
2. The invention takes the carbon nano tube with the surface modified by the metallic iron and the vanadium as the carrier, has high strength and electronegativity after surface change, can effectively avoid the loss of surface active components and auxiliary metal, prolongs the service life of the catalyst, simultaneously can ensure that the product aniline is quickly desorbed from the catalyst, prevents side reaction and improves the selectivity.
3. The invention provides a method for preparing a catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation, which comprises the steps of complexing an active component and an auxiliary agent, atomizing, then carrying out adsorption reduction, and forming a catalyst which is an eggshell-like catalyst with high metal dispersity, wherein the active component and the auxiliary agent are in metal electronic cooperation, and the catalytic activity is high.
4. The method has the advantages of simplified steps, easy industrialization, uniform and controllable size of the active component and the auxiliary agent metal particles, high utilization rate and good economy.
The technical scheme of the invention is further described in detail below with reference to the examples.
Detailed Description
Example 1
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 1.5% of that of the catalyst, the active components are Pt, the auxiliary agents 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 embodiment provides a method for preparing a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene by taking 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 mixture with an average particle diameter of 12 mu m and a specific surface area of 1000cm 2 Mixing/g, namely mixing a carbon nano tube with an 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 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 used 2 CO 3 Adjusting the pH of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at the temperature of 500 ℃ in a nitrogen protection atmosphere to obtain the carbon nanotube after surface modification;
step three, mixing 12mL of platinous chloride solution with the platinum concentration of 0.05g/mL, ruthenium trichloride solution with the 4mLRu concentration of 0.05g/mL, chromium chloride solution with the 2mLCr concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume to 50mL by water to obtain a mixed system containing active components and auxiliary agents, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and the auxiliary agents at the dropwise speed of 1mL/min under the temperature condition of 55 ℃, and carrying out heat preservation and stirring for 12h under the temperature condition of 55 ℃ to carry out complexation reaction to obtain a precursor complex containing the active components and the auxiliary agents;
Step four, mixing 19.1g of the surface-modified carbon nanotube obtained in the step two, 0.382mL of oleylamine and 477.5mL of water to obtain carbon nanotube-containing slurry;
step five, adding 9.55mL of NaHCO with mass concentration of 10% into the carbon-containing nanotube slurry in the step four 3 Adding 3mL of formaldehyde into the solution to obtain a mixed material;
step six, heating the mixed material in the step five to 60 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 60 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Example 2
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 1% of that of the catalyst, the active components are Pt, the auxiliary agents are Ni and W, the mass of the Ni is 0.5% of that of the catalyst, and the mass of the W is 0.5% of that of the catalyst;
The embodiment provides a method for preparing a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene by taking 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 mixture has an average particle diameter of 12 mu m and a specific surface area of 1300cm 2 Mixing/g, namely mixing carbon nano tubes with the average pore diameter of 8nm, 15mL of ferric chloride solution with the concentration of iron element of 0.1g/mL and 5mL of ammonium metavanadate 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 used 2 CO 3 Adjusting the pH of the mixed slurry in the first step to 8.5 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at 600 ℃ in a nitrogen protective atmosphere to obtain the carbon nanotube with the modified surface;
mixing 12mL of platinum chloride acid solution with the concentration of 0.05g/mL, 2mL of nickel chloride solution with the concentration of Ni of 0.05g/mL, 2mL of sodium tungstate solution with the concentration of W of 0.05g/mL and 10mL of isopropanol, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliaries, dropwise adding 48mL of tartaric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and the auxiliaries at the dropwise speed of 1mL/min at the temperature of 75 ℃, and carrying out heat preservation and stirring for 10h at the temperature of 75 ℃ to carry out complexation reaction to obtain a precursor complex containing the active components and the auxiliaries;
Mixing 19.2g of the surface-modified carbon nanotube obtained in the second step, 0.96mL of oleylamine and 480mL of water to obtain carbon nanotube-containing slurry;
step five, adding 15.36mL of NaAC solution with mass concentration of 10% into the carbon-containing nanotube slurry in the step four, and then adding 4.8mL of formic acid to obtain a mixed material;
step six, heating the mixed material in the step five to 70 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 70 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Example 3
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 0.6% of that of the catalyst, the active components are Pt, the auxiliary agents are 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 liquid-phase hydrogenation of nitrobenzene by taking 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 mixture with an average particle diameter of 14 μm and a specific surface area of 1400cm 2 Mixing/g, namely mixing a carbon nano tube with the average pore diameter of 9nm, 5mL of ferric sulfate solution with the concentration of iron element of 0.1g/mL and 30mL of 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 used 2 CO 3 Adjusting the pH of the mixed slurry in the first step to be 10.0 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at the temperature of 700 ℃ in a nitrogen protection atmosphere to obtain the carbon nanotube after surface modification;
step three, mixing 12mL of platinum chloride acid solution with the concentration of 0.05g/mL, 2mL of ruthenium trichloride solution with the concentration of Ru of 0.05g/mL, 0.4mL of lanthanum nitrate solution with the concentration of La of 0.05g/mL and 10mL of ethylene glycol, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliaries, dropwise adding 60mL of nitrilotriacetic acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing active components and auxiliaries at the dropwise adding speed of 1mL/min under the temperature of 85 ℃, and carrying out heat preservation and stirring for 6h under the temperature of 85 ℃ to carry out complexation reaction to obtain a precursor complex containing active components and auxiliaries;
Mixing 19.28g of the surface-modified carbon nanotube obtained in the second step, 1.54mL of oleylamine and 482mL of water to obtain carbon nanotube-containing slurry;
step five, adding 15.42mL of NaH with mass concentration of 10% into the carbon-containing nanotube slurry in the step four 2 PO 3 Then adding 50mL of sodium formate aqueous solution with the concentration of 0.12g/mL to obtain a mixed material;
step six, heating the mixed material obtained in the step five to 90 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent obtained in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 90 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Example 4
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 1.5% of that of the catalyst, the active components are Pt, the auxiliary agents are 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 liquid-phase hydrogenation of nitrobenzene by taking 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 mixture with an average particle diameter of 15 mu m and a specific surface area of 1600cm 2 Mixing/g, namely mixing a carbon nano tube with an 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 used 2 CO 3 Adjusting the pH value of the mixed slurry in the first step to 9 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering in a nitrogen protective atmosphere at 900 ℃ for 0.5 hour to obtain the carbon nanotube with the modified surface;
step three, mixing 12mL of chloroplatinic acid solution with the platinum concentration of 0.05g/mL, 4mL of chromium chloride solution with the Cr concentration of 0.05g/mL, 2mL of nickel chloride solution with the Ni concentration of 0.05g/mL and 10mL of isopropanol, and fixing the volume to 50mL by water to obtain a mixed system containing active components and auxiliaries, dropwise adding 36mL of oxalic acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and the auxiliaries at the dropwise speed of 1mL/min at the temperature of 95 ℃, and carrying out a complexation reaction by heat preservation and stirring for 0.5h at the temperature of 95 ℃ to obtain a precursor complex containing the active components and the auxiliaries;
Step four, mixing 19.1g of the surface-modified carbon nanotube obtained in the step two, 1.91mL of oleylamine and 477.5mL of water to obtain carbon nanotube-containing slurry;
step five, adding 19.1mL of Na with mass concentration of 10% into the carbon-containing nanotube slurry in the step four 3 C 6 H 5 O 7 Then adding 100mL of sodium hypophosphite aqueous solution with the concentration of 0.12g/mL to obtain a mixed material;
step six, heating the mixed material in the step five to 100 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 100 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Example 5
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 1.5% of that of the catalyst, the active components are Pt, the auxiliary agents 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 embodiment provides a method for preparing a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene by taking 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 mixture is subjected to average particle diameter of 12 mu m and specific surface area of 1200cm 2 Mixing/g, namely adding water to a constant volume of 500mL, and transferring into a 1L beaker to obtain mixed slurry, wherein the average pore diameter of the mixed slurry is 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 0.1 g/mL;
step two, na with the mass percentage of 2 percent is used 2 CO 3 Adjusting the pH of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at the temperature of 500 ℃ in a nitrogen protection atmosphere to obtain the carbon nanotube after surface modification;
step three, mixing 12mL of chloroplatinic acid solution with the platinum concentration of 0.05g/mL, 4mL of ruthenium trichloride solution with the Ru concentration of 0.05g/mL, 2mL of chromium chloride solution with the Cr concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliaries, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and auxiliaries at the temperature of 55 ℃ at the dropwise speed of 1mL/min, and carrying out a complexation reaction under the temperature of 55 ℃ under the condition of heat preservation and stirring for 12h to obtain a precursor complex containing the active components and the auxiliaries;
Step four, mixing 19.1g of the surface-modified carbon nanotube obtained in the step two, 0.382mL of oleylamine and 477.5mL of water to obtain carbon nanotube-containing slurry;
step five, adding 9.55mL of NaHCO with mass concentration of 10% into the carbon-containing nanotube slurry in the step four 3 Adding 3mL of formaldehyde into the solution to obtain a mixed material;
step six, heating the mixed material in the step five to 60 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 60 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Example 6
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 0.8% of that of the catalyst, the active components are Pt, the auxiliary agents are 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 liquid-phase hydrogenation of nitrobenzene by taking 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 mixture with an average particle diameter of 15 mu m and a specific surface area of 1300cm 2 Mixing/g, namely adding water into a carbon nano tube with the average pore diameter of 9nm, 18mL of ferric nitrate solution with the concentration of iron element of 0.1g/mL and 12mL of ammonium pyrovanadate solution with the concentration of vanadium element of 0.1g/mL, and transferring into a 1L beaker after adding water to a constant volume of 500mL to obtain mixed slurry;
step two, na with the mass percentage of 2 percent is used 2 CO 3 Adjusting the pH of the mixed slurry in the first step to 8.5 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at 600 ℃ in a nitrogen protective atmosphere to obtain the carbon nanotube with the modified surface;
mixing 12mL of platinum chloride acid solution with the concentration of 0.05g/mL, 2mL of nickel chloride solution with the concentration of Ni of 0.05g/mL, 0.8mL of ruthenium trichloride solution with the concentration of Ru of 0.05g/mL, 0.4mL of sodium tungstate solution with the concentration of W of 0.05g/mL and 10mL of isopropanol, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliaries, dropwise adding 50mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and the auxiliaries at the dropwise adding speed of 1mL/min at the temperature of 80 ℃, and carrying out a complexation reaction under the temperature of 80 ℃ while preserving heat and stirring for 6h to obtain a precursor complex containing the active components and the auxiliaries;
Step four, mixing 19.24g of the surface-modified carbon nanotube obtained in the step two, 0.962mL of oleylamine and 481mL of water to obtain a carbon nanotube-containing slurry;
step five, adding 15.392mL of NaH with mass concentration of 10% into the carbon-containing nanotube slurry in the step four 2 PO 3 Then adding 100mL of sodium hypophosphite aqueous solution with the concentration of 0.12g/mL to obtain a mixed material;
step six, heating the mixed material in the step five to 65 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 65 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Example 7
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 0.8% of that of the catalyst, the active components are Pt, the auxiliary agents are 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 liquid-phase hydrogenation of nitrobenzene by taking 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 mixture with an average particle diameter of 13 μm and a specific surface area of 1500cm 2 Mixing/g, namely adding water into a carbon nano tube with the average pore diameter of 8nm, 24mL of ferric nitrate solution with the concentration of iron element of 0.1g/mL and 12mL of ammonium pyrovanadate solution with the concentration of vanadium element of 0.1g/mL, and transferring into a 1L beaker after adding water to a constant volume of 500mL to obtain mixed slurry;
step two, na with the mass percentage of 2 percent is used 2 CO 3 Adjusting the pH value of the mixed slurry in the first step to 8 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at the temperature of 750 ℃ in a nitrogen protection atmosphere to obtain the carbon nano tube after surface modification;
step three, mixing 12mL of platinum chloride acid solution with the concentration of 0.05g/mL, 2mL of ruthenium trichloride solution with the concentration of Ru of 0.05g/mL, 0.8mL of chromium chloride solution with the concentration of Cr of 0.05g/mL, 0.4mL of lanthanum nitrate solution with the concentration of La of 0.05g/mL and 10mL of ethylene glycol, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliary agents, dropwise adding 60mL of tartaric acid water solution with the concentration of 0.1g/mL into the mixed system containing active components and auxiliary agents at the dropwise adding speed of 1mL/min at the temperature of 65 ℃, and carrying out a complexation reaction under the temperature of 65 ℃ while preserving heat and stirring for 8h to obtain a precursor complex containing active components and auxiliary agents;
Mixing 19.24g of the surface-modified carbon nanotube obtained in the second step, 0.577mL of oleylamine and 4811mL of water to obtain a carbon nanotube-containing slurry;
step five, adding 7.69mL of NaH with mass concentration of 10% into the carbon-containing nanotube slurry in the step four 2 PO 3 Then adding 80mL of potassium borohydride aqueous solution with the concentration of 0.12g/mL to obtain a mixed material;
step six, heating the mixed material in the step five to 65 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 65 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Example 8
The embodiment provides a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, wherein the catalyst raw material comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 2.0% of that of the catalyst, the active components are Pt, the auxiliary agents are Ru, cr, ni, la and W, the mass of Ru is 1.0% of that of the catalyst, the mass of Cr is 0.5% of that of the catalyst, the mass of Ni is 0.3% of that of the catalyst, and the mass of La is 0.15% of that 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 liquid-phase hydrogenation of nitrobenzene by taking 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 mixture with an average particle diameter of 12 mu m and a specific surface area of 1000cm 2 Mixing/g, namely mixing a carbon nano tube with an 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 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 used 2 CO 3 Adjusting the pH of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at the temperature of 500 ℃ in a nitrogen protection atmosphere to obtain the carbon nanotube after surface modification;
mixing 12mL of platinum chloride acid solution with the concentration of 0.05g/mL, ruthenium trichloride solution with the concentration of 4mLRu of 0.05g/mL, chromium chloride solution with the concentration of 2mLCr of 0.05g/mL, nickel chloride solution with the concentration of 1.2mLNi of 0.05g/mL, lanthanum nitrate solution with the concentration of 0.6mLLa of 0.05g/mL, sodium tungstate solution with the concentration of 0.22mLW of 0.05g/mL and 10mL of oleic acid, and fixing the volume to 50mL by water to obtain a mixed system containing active components and auxiliary agents, dropwise adding 30mL of citric acid water solution with the concentration of 0.1g/mL into the mixed system containing active components and auxiliary agents at the dropwise adding speed of 1mL/min at the temperature of 55 ℃, and carrying out heat preservation and stirring for 12h at the temperature of 55 ℃ to obtain a precursor complex containing active components and auxiliary agents;
Step four, mixing 19.1g of the surface-modified carbon nanotube obtained in the step two, 0.382mL of oleylamine and 477.5mL of water to obtain carbon nanotube-containing slurry;
step five, adding 9.55mL of NaHCO with mass concentration of 10% into the carbon-containing nanotube slurry in the step four 3 Adding 3mL of formaldehyde into the solution to obtain a mixed material;
step six, heating the mixed material in the step five to 60 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 60 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Comparative example 1
The influence of the catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene without adding an auxiliary agent is examined in the comparative example, the raw materials of the catalyst of the comparative example comprise surface modified carbon nanotubes and precursor atomized particles containing active components, the mass of the active components is 3% of that of the catalyst, and the active components are Pt;
This comparative example provides a method for preparing the above catalyst as in example 1, with the exception of step three, step four and step six:
step three, mixing 12mL of chloroplatinic acid solution with the platinum concentration of 0.05g/mL and 10mL of oleic acid, and carrying out constant volume with water to 50mL to obtain a mixed system containing active components, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing active components at the dropwise speed of 1mL/min at the temperature of 55 ℃, and carrying out thermal insulation stirring for 12h at the temperature of 55 ℃ to carry out complexation reaction to obtain a precursor complex containing active components;
mixing 19.4g of the surface-modified carbon nanotube obtained in the second step, 0.388mL of oleylamine and 485mL of water to obtain carbon nanotube-containing slurry;
step six, heating the mixed material in the step five to 60 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components in the step three by an atomizer with the atomizing granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 60 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, drying the washed material in a vacuum oven at 75 ℃ until the weight is constant, and obtaining the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Comparative example 2
The comparative example examines the influence of liquid phase hydrogenation of nitrobenzene to aniline catalyst performance by using an unmodified carbon nanotube as a carrier, wherein the catalyst raw material comprises carbon nanotubes 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 nanotubes, 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 comparative example provides a method for preparing the catalyst, which specifically comprises the following steps:
step one, mixing 12mL of platinum chloride acid solution with the concentration of 0.05g/mL, ruthenium trichloride solution with the concentration of 4mLRu of 0.05g/mL, chromium chloride solution with the concentration of 2mLCr of 0.05g/mL and 10mL of oleic acid, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliaries, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing active components and auxiliaries at the temperature of 55 ℃ at the dropwise speed of 1mL/min, and carrying out a complexation reaction under the temperature of 55 ℃ under the condition of heat preservation and stirring for 12h to obtain a precursor complex containing the active components and the auxiliaries;
Step two, mixing 19.1g of carbon nano tube, 0.382mL of oleylamine and 477.5mL of water to obtain carbon nano tube-containing slurry; the average grain diameter of the carbon nano tube is 12 mu m, and the specific surface area is 1200cm 2 /g, average pore size 7nm;
step three, adding 9.55mL of NaHCO with mass concentration of 10% into the carbon-containing nanotube slurry in the step two 3 Adding 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 microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent obtained in the step one by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 60 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Comparative example 3
The comparative example examines the influence of non-atomized precursor raw materials containing active components and auxiliary agents on the performance of a catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene, wherein the catalyst raw materials of the comparative example comprise surface-modified carbon nanotubes and precursors containing the active components and the auxiliary agents, the mass of the active components is 3% of that of the catalyst, the mass of the auxiliary agents is 1.5% of that of the catalyst, the active components are Pt, the auxiliary agents 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 for preparing the above catalyst of this comparative example is the same as in example 1, except that:
step six, heating the mixed material obtained in the step five to 60 ℃ by microwaves and preserving heat, pouring the precursor complex containing the active components and the auxiliary agent obtained in the step three into the preserved mixed material, carrying out reduction reaction for 45min at the temperature of 60 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material to constant weight in a vacuum oven at 75 ℃ to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation.
Comparative example 4
The comparative example examined the effect 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 was the same as that of example 1, except that the auxiliary was Cu and Zn, the mass of Cu being 1.0% of the mass of the catalyst, and the mass of Zn being 0.5% of the mass of the catalyst;
the method for preparing the above catalyst of this comparative example is the same as in example 1, except that,
the third step is: mixing 12mL of chloroplatinic acid solution with the platinum concentration of 0.05g/mL, copper nitrate solution with the 4mLCu concentration of 0.05g/mL, zinc nitrate solution with the 2mLZn concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliaries, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and the auxiliaries at the dropwise speed of 1mL/min at the temperature of 55 ℃, and carrying out heat preservation and stirring for 12h at the temperature of 55 ℃ to carry out complexation reaction to obtain a precursor complex containing the active components and the auxiliaries.
Comparative example 5
The influence of the active carbon serving as a carrier on the performance of the catalyst for synthesizing the aniline by liquid phase hydrogenation of the nitrobenzene is examined in the comparative example, wherein the catalyst raw material of the comparative example comprises surface modified active carbon 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 method for preparing the catalyst in the comparative example comprises the following steps:
step one, 50g of the mixture having an average particle diameter of 27 μm and a specific surface area of 1400cm 2 Mixing/g of active carbon with an 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 used 2 CO 3 Adjusting the pH value of the mixed slurry in the first step to 7.5 by using an aqueous solution, standing and ageing for 12 hours at normal temperature, filtering, and roasting the retentate obtained by filtering for 0.5 hour at the temperature of 500 ℃ in a nitrogen protection atmosphere to obtain the surface modified activated carbon;
Step three, mixing 12mL of platinous chloride solution with the platinum concentration of 0.05g/mL, ruthenium trichloride solution with the 4mLRu concentration of 0.05g/mL, chromium chloride solution with the 2mLCr concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume to 50mL by water to obtain a mixed system containing active components and auxiliary agents, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and the auxiliary agents at the dropwise speed of 1mL/min under the temperature condition of 55 ℃, and carrying out heat preservation and stirring for 12h under the temperature condition of 55 ℃ to carry out complexation reaction to obtain a precursor complex containing the active components and the auxiliary agents;
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 mass concentration of 10% into the activated carbon-containing slurry in the step four 3 Adding 3mL of formaldehyde into the solution to obtain a mixed material;
step six, heating the mixed material in the step five to 60 ℃ by microwaves and preserving heat, atomizing the precursor complex containing the active components and the auxiliary agent in the step three by an atomizer with the atomization granularity of 1.8-3.5 mu m to obtain precursor atomized particles containing the active components and the auxiliary agent, blowing the precursor atomized particles into the preserved mixed material, carrying out reduction reaction for 45min under the heat preservation condition of 60 ℃, cooling the reacted material, filtering, washing the retentate obtained by filtering by pure water until the conductivity of the filtrate is less than 25us/cm, and drying the washed material in a vacuum oven at 75 ℃ until the weight is constant to obtain the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation; the purging is performed by using nitrogen as carrier gas, and the flow rate of the carrier gas is 100mL/min.
Comparative example 6
The comparative example examined the effect of Ti and Co as carbon nanotube modified metal on the performance of catalyst for synthesizing aniline by liquid phase hydrogenation of nitrobenzene. The catalyst of this comparative example was the same as in example 1, and the method of preparing the above catalyst of this comparative example was the same as in example 1, except that:
step one, 50g of the mixture with an average particle diameter of 12 mu m and a specific surface area of 1000cm 2 Per gram, carbon nanotubes with an average pore diameter of 7nm, 2.5mL of titanium tetrachloride solution with a concentration of titanium element of 0.1g/mL, 10mL of nitric acid with a concentration of cobalt element of 0.1g/mLCobalt solution is mixed, water is added to fix the volume to 500mL, and then the mixture is transferred into a 1L beaker, so as to obtain mixed slurry.
Comparative example 7
The comparative example examined the effect of the auxiliary agent on the performance of the catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, and the catalyst of the comparative example was the same as that of example 1, except that the auxiliary agent was Ru, and the mass of the auxiliary agent was 1.0% of the mass of the catalyst.
The method for preparing the catalyst of this comparative example is the same as in example 1, except that step three is: mixing 12mL of chloroplatinic acid solution with the platinum concentration of 0.05g/mL, 4mLRu solution with the ruthenium trichloride with the concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliary agents, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and the auxiliary agents at the dropwise speed of 1mL/min at the temperature of 55 ℃, and carrying out a complexation reaction at the temperature of 55 ℃ under heat preservation and stirring for 12h to obtain a precursor complex containing the active components and the auxiliary agents;
And step four, mixing 19.2g of the surface-modified carbon nanotube obtained in the step two, 0.96mL of oleylamine and 480mL of water to obtain carbon nanotube-containing slurry.
Comparative example 8
This comparative example examined the effect of active component content on the performance of a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, the catalyst being the same as that of example 1, except that the mass of the active component was 2% of the mass of the catalyst;
the method for preparing the catalyst of this comparative example is the same as in example 1, except that step three is: 8mL of platinum chloride acid solution with the concentration of 0.05g/mL, 4mLRu solution with the concentration of 0.05g/mL, 2mLCr solution with the concentration of 0.05g/mL and 10mL of oleic acid are mixed and water is used for constant volume to 50mL, a mixed system containing active components and auxiliary agents is obtained, 30mL of aqueous solution of citric acid with the concentration of 0.1g/mL is dropwise added into the mixed system containing the active components and the auxiliary agents at the dropping speed of 1mL/min at the temperature of 55 ℃, and the mixture is subjected to heat preservation and stirring for 12h at the temperature of 55 ℃ to carry out complexation reaction, so that a precursor complex containing the active components and the auxiliary agents is obtained.
Comparative example 9
This comparative example examined the effect of active component content on the performance of a catalyst for synthesizing aniline by liquid-phase hydrogenation of nitrobenzene, the catalyst being the same as that of example 1 except that the mass of the active component was 5% of the mass of the catalyst;
The method for preparing the catalyst of this comparative example is the same as in example 1, except that step three is: mixing 20mL of platinum chloride acid solution with the platinum concentration of 0.05g/mL, ruthenium trichloride solution with the 4mLRu concentration of 0.05g/mL, chromium chloride solution with the 2mLCr concentration of 0.05g/mL and 10mL of oleic acid, and fixing the volume with water to 50mL to obtain a mixed system containing active components and auxiliaries, dropwise adding 30mL of citric acid aqueous solution with the concentration of 0.1g/mL into the mixed system containing the active components and auxiliaries at the dropwise speed of 1mL/min at the temperature of 55 ℃, and carrying out thermal insulation stirring for 12h at the temperature of 55 ℃ to carry out complexation reaction to obtain a precursor complex containing the active components and the auxiliaries.
Evaluation of performance:
the catalysts of examples 1 to 8 and comparative examples 1 to 9 are used for the aniline preparation reaction by nitrobenzene liquid phase hydrogenation, and the reaction process comprises: 150mL of nitrobenzene, 200mL of aniline and 0.3g of catalyst were placed in a continuous reaction kettle, reacted for 20min at a temperature of 200 ℃ and a pressure of 1.5MPa, the reaction solution was extruded after the temperature was reduced to below 70 ℃, and samples were analyzed by a gas chromatograph, and the nitrobenzene conversion and the aniline selectivity are shown in Table 1.
The catalyst of example 1 was repeatedly used according to the above performance evaluation method, the reaction was terminated without a decrease in hydrogen pressure in the reaction vessel, the reaction time was 20min to 30min per use, the catalyst was separated from the reaction solution after each reaction, and the catalyst was back-flushed into the reaction vessel with a mixture of 150mL of nitrobenzene and 200mL of aniline, and the repeated use results are shown in table 2.
TABLE 1 nitrobenzene conversion and aniline selectivity for the liquid phase hydrogenation of nitrobenzene to aniline
Table 2 example 1 catalyst life evaluation results
According to Table 1, the initial activity of the catalyst in the reaction for 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 invention, which comprises surface-modified carbon nanotubes and precursor atomized particles containing active components and auxiliaries, has excellent catalytic conversion performance.
According to 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 not attenuated basically, and the catalyst has good aniline selectivity and service life.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (6)
1. The method for synthesizing the catalyst for the aniline by the nitrobenzene liquid phase hydrogenation is characterized in that raw materials of the catalyst for the aniline synthesis by the nitrobenzene liquid phase hydrogenation comprise surface-modified carbon nanotubes 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 the mass of the catalyst; 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 comprises the following steps:
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, dropwise adding 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; the complexing agent is citric acid, tartaric acid, oxalic acid or nitrilotriacetic acid, and the mass of the complexing agent is 5-10 times of that of the active component;
step two, mixing the carbon nano tube with the surface modified, oleylamine and water to obtain carbon nano tube-containing slurry;
step three, sequentially adding a buffering agent and a reducing agent into the carbon-containing nanotube slurry in the step two to obtain a mixed material; the preparation method of the surface modified carbon nano tube 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; 102, regulating the pH 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 nanotube; in the step 101, the sum of the mass of iron element in the soluble ferric salt solution and the mass of vanadium element in the soluble vanadium salt solution is 0.025-0.14 times of the mass of the carbon nano tube, 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 roasting temperature in the step 102 is 500-900 ℃;
And step four, under the condition of microwave heating at 60-100 ℃, atomizing and blowing the precursor complex containing the active components and the auxiliary agent in the step one into the mixed material in the step three, reacting at the temperature of 60-100 ℃, filtering, washing and drying the reacted material, and obtaining the catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation.
2. The method for synthesizing the catalyst for aniline by liquid-phase hydrogenation of nitrobenzene according to claim 1, wherein the precursor atomized particles 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 formed by the meridian-complex reaction of a mixed solution containing the active component and the auxiliary agent with 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.
3. The method for synthesizing a catalyst for aniline by liquid-phase hydrogenation of nitrobenzene according to claim 1, wherein the soluble salt solution of the active component in the first step is chloroplatinic acid solution; step one, wherein the soluble salt solution of the auxiliary agent is RuCl 3 Solution, niCl 2 Solution, crCl 2 Solution, laNO 3 Solution and Na 2 WO 4 More than two of the solutions; in the first step, the solvent is one or more of water, isopropanol, glycol and oleic acid.
4. The method for synthesizing the catalyst for aniline by liquid-phase hydrogenation of nitrobenzene according to claim 1, wherein in the second step, the volume of the oleylamine is 0.02-0.1 times of the mass of the carbon nanotube after surface modification, the volume of the oleylamine is in mL, and the mass of the carbon nanotube after surface modification is in g.
5. The method for synthesizing aniline catalyst by liquid phase hydrogenation of nitrobenzene according to claim 1, wherein in step three, the buffer is NaHCO with a mass concentration of 10% 3 Solution with mass concentration of 10% NaH 2 PO 3 Solution, naAC solution with mass concentration of 10% or Na with mass concentration of 10% 3 C 6 H 5 O 7 The volume of the buffer is 0.5-1 time of the mass of the surface-modified carbon nano tube in the second step, the volume unit of the buffer is mL, and the mass unit of the surface-modified carbon nano tube is g; and step three, 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.
6. The method for synthesizing a catalyst for aniline by liquid-phase hydrogenation of nitrobenzene according to claim 1, wherein the atomized particle size in the fourth step is 1.8 μm to 3.5 μm.
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| 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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