CN1616408A - Hydrogenation reducing method for aromatic nitro-compound - Google Patents
Hydrogenation reducing method for aromatic nitro-compound Download PDFInfo
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- CN1616408A CN1616408A CN 200310113487 CN200310113487A CN1616408A CN 1616408 A CN1616408 A CN 1616408A CN 200310113487 CN200310113487 CN 200310113487 CN 200310113487 A CN200310113487 A CN 200310113487A CN 1616408 A CN1616408 A CN 1616408A
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- 238000000034 method Methods 0.000 title claims abstract description 43
- -1 aromatic nitro-compound Chemical class 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 18
- 230000001603 reducing effect Effects 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- 239000006249 magnetic particle Substances 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001566 austenite Inorganic materials 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002506 iron compounds Chemical class 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000011344 liquid material Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003822 preparative gas chromatography Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- PXWYZLWEKCMTEZ-UHFFFAOYSA-N 1-ethyl-2-nitrobenzene Chemical compound CCC1=CC=CC=C1[N+]([O-])=O PXWYZLWEKCMTEZ-UHFFFAOYSA-N 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000006731 degradation reaction Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910001691 hercynite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The method of hydrogenising aromatic nitro compound is that inside slurry bed or fluidized bed, in the presence of magnetic noble catalyst and under the conditions of reaction temperature 25-150 deg.c, reaction pressure 0.1-3.0 MPa and hydrogen/liquid material volume ratio of 5-300, aromatic nitro compound and hydrogen are contact reacted. The magnetic noble catalyst consists of spherical carrier comprising alumina and magnetic grain and one or several of noble Pt, Pd, Ru and Rh as active component, and the magnetic grain consists of SiO2 coating layer and ferric material kernal. The catalyst with superparamagnetism may be separated and recovered easily from reaction product under the action of magnetic field.
Description
Technical field
The invention relates to a kind of hydrogenation reduction method for aromatic nitro compound.More particularly, be about a kind of method of magnetic noble metal catalyst of in slurry bed or fluidized-bed, using to the aromatic nitro compound hydrogenating reduction.
Background technology
Aromatic nitro compound is carried out the very important unit process that hydrogenation is dyestuff, medicine and perfume industry.More existing adopt reports that homogeneous catalyst catalysis should reaction, yet these homogeneous catalysts are unstable and be not easy Separation and Recovery from reactant in air.In recent years, the palladium of loading type, platinum, rhodium catalyst and Raney nickel catalyst are used for aromatic nitro compound hydrogenation system aromatic amine and are subject to people's attention.
USP5,877,350 disclose a kind of method of aromatic nitro compound hydrogenation system aromatic amine, this method is in the gas phase fixed bed, is hydrogenation catalyst, reacts that with metals such as the palladium of alumina load, lead reaction conditions is under adiabatic condition: temperature 200-400 ℃, maximum catalyst temperature are 500 ℃ in pressure 1-30 crust, the device.
CN1252787A also discloses a kind of method of aromatic nitro compound hydrogenation system aromatic amine, and this method is in the gas phase fixed bed, to load on the BET surface-area less than 40m
2Metals such as the palladium on the ceramic monolith of/g, vanadium, lead, rhenium are hydrogenation catalyst, are 3-30 in the mol ratio of hydrogen pressure 0.5-5 crust, temperature of reaction 180-500 ℃, hydrogen and nitryl group: react under 1 the condition.
Summary of the invention
The purpose of this invention is to provide a kind of magnetic noble metal catalyst that in slurry bed or fluidized-bed, uses to hydrogenation reduction method for aromatic nitro compound.
Method provided by the invention is that to make aromatic nitro compound and magnetic noble metal catalyst in slurry bed or fluidized-bed be 25-150 ℃ in temperature of reaction, reaction pressure is 0.1-3.0MPa, hydrogen is 5-300 with the liquid phase feeding volume ratio: contact under 1 the condition, said magnetic catalyst is made up of ball type carrier and one or more the noble metal active component that is selected from platinum, palladium, ruthenium, the rhodium, ball type carrier wherein is made up of aluminum oxide and magnetic-particle, and magnetic-particle wherein is by SiO
2The kernel of coating layer and iron compound is formed.
When adopting slurry bed reactor to implement the inventive method, suitable catalyst concn is 0.2-12 weight %, preferred 0.5-8 weight %.
When adopting fluidized-bed reactor to implement the inventive method, when the appropriate volume air speed is 3-50
-1, during preferred 5-20
-1
The aromatic nitro compound that is applicable to the inventive method can be benzene, C
1-C
6A nitro or many nitro-compounds of alkyl substituted benzene.
Said magnetic noble metal catalyst is made up of one or more the ball type carrier of precious metal, preferred platinum and/or palladium and surplus that is selected from platinum, palladium, ruthenium, the rhodium that accounts for the heavy % of catalyzer 0.2-10, the heavy % of preferred 0.3-7 in the inventive method.For the ease of the use in slurry bed or fluidized-bed reactor, the particle diameter of this catalyzer should be advisable between 10 μ m to 6mm.
Wherein said ball type carrier is formed by accounting for the heavy % of carrier 1-50, the magnetic-particle of the heavy % of preferred 2-15 and the aluminum oxide of surplus.Magnetic-particle wherein is (0.05-6) by weight ratio: 1, preferred (0.3-4.0): 1 SiO
2Coating layer and be dispersed in wherein, one or more particle diameters be the 3-30 nanometer, its chemical constitution is for being selected from Fe
3O
4, Fe and γ-Fe
2O
3In the kernel of single domain superparamagnetism particulate of one or more iron compounds form.Aluminum oxide wherein can be any crystalline phase, can be selected from the ρ of various low temperature transition phases-, χ-, η-, gama-alumina, also can be selected from the κ of various high temperature transition phases-, δ-, one or more the mixture in θ-aluminum oxide and the Alpha-alumina.
In above-mentioned said magnetic-particle, closely coat the amorphous Si O of kernel
2Coating layer and kernel mortise form magnetic-particle.For the magnetic-particle that kernel has a plurality of particulates, between each particulate because SiO
2Obstruct and uniform distribution.
By vibrating sample magnetometer said ball type carrier is measured, its magnetic hysteresis loop does not have hysteresis; When outside magnetic field exists, good magnetic property is arranged; Adding magnetic field H=0 o'clock, residual magnetization Mr and coercivity H are zero, have superparamagnetism.
The ball type carrier of being made up of magnetic-particle and aluminum oxide has good thermostability and erosion resistance, and because SiO
2The buffer action of coating layer can avoid kernel iron component and alumina catalyst support component at high temperature to form hercynite.
The preparation method of said ball type carrier is as follows in the inventive method:
The preparation of step 1-carrier kernel magnetic-particle: the Fe that contains that alkali is added 50-100 ℃
2+With Fe
3+In the aqueous solution of salt, with sedimentary Fe
3O
4Particle changes in the sodium silicate aqueous solution, under the protection of rare gas element, transfers to pH≤7 with acid, promptly obtains SiO
2Coat Fe
3O
4The particulate magnetic particle.Wherein, said alkali is selected from KOH, NaOH, NH
4OH, Na
2CO
3Or NaHCO
3A kind of or its mixture wherein; Fe in the said iron salt solutions
2+With Fe
3+Mol ratio be 1: (0.5-2.5), preferred 1: (1.5-2); The OH of said alkali
-With ∑ (Fe
2++ Fe
3+) mol ratio be 1: (0.1-1.0); Said water glass and Fe
3O
4Mol ratio be 1: (0.04-5), preferred 1: (0.06-1); Said acid is selected from one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid or the acetate.
The preparation of step 2-ball type carrier: under 10-35 ℃, with aluminum hydroxide sol, the magnetic particle that organic amine solution and step 1 obtain is according to aluminum hydroxide sol and organic amine solution 1: volume ratio (0.4-3.5), aluminum hydroxide sol and magnetic particle 1: weight ratio (0.02-0.2), the three is mixed and be uniformly dispersed, be 1 with itself and kerosene or vegetables oil with volume ratio then: (3-20), preferred 1: mixed (4-10) forms the water-in-oil-type drop, heating systems makes the aluminum hydroxide sol cure of aqueous phase, pass through again and the identical hydrothermal treatment consists of conventional forming oil column oxygenerating alumina supporter, ageing, dry and calcination steps is handled the ball type carrier that can obtain using in the inventive method.Wherein said organic amine is meant that the pH value is near neutral at normal temperatures, but can discharge the nitrogen-containing organic compound of alkaline matter through thermal degradation, as urea or hexamethylenetetramine, they can be used singly or in combination, and the concentration of organic amine solution is that the heavy % of 12-40 is advisable; Said dispersion means can be selected from conventional variety of way, as: stirring, vibration, ultrasonic etc.
Used catalyzer is that drying, roasting, reduction make then with the above-mentioned ball type carrier that makes of steeping fluid dipping that contains precious metal in the inventive method.Said steeping fluid is made into by precious metal salt (as Palladous chloride, Platinic chloride etc.), mineral acid and deionized water, the preferred hydrochloric acid of said mineral acid, and the pH value of steeping fluid is 2-6; Said drying temperature is a room temperature-120 ℃; Said maturing temperature is 150-600 ℃; Said reduction is to carry out under 50-500 ℃ in hydrogen atmosphere, or reduces with reductive agents such as formaldehyde, hydrazines.
Hydrogenation reduction method for aromatic nitro compound provided by the present invention because catalyst system therefor has adopted the ball type carrier with magnetic, thereby has the following advantages:
1, catalyzer has superparamagnetism.Good magnetic property is arranged when outside magnetic field exists, therefore in externally-applied magnetic field, can control easily, separate and reclaim; The remanent magnetism of catalyzer and coercive force were not zero when foreign field did not exist, so particle is difficult for assembling good dispersity in reaction system.
2, catalyzer has good chemical stability, thermostability and erosion resistance.The SiO on magnetic-particle surface
2Coating layer makes the ferromegnetism component not be exposed to catalyst surface, can avoid the loss of ferromegnetism component like this and to the pollution and toxic hazard of material.
3, catalyst grain size is little, so the surface-area of contact reacts thing is big, rate of mass transfer is fast, and its catalytic performance is fully utilized.
Embodiment
The present invention is further illustrated below by embodiment, but not thereby limiting the invention.
Embodiment 1
The preparation process of the ball type carrier of catalyst system therefor in present embodiment explanation the inventive method.
With 189g Na
2SiO
39H
2O is dissolved in the 1000mL distilled water, slowly drips 3mol/L HCl solution under agitation condition, and the pH value of solution is transferred to 13, filters afterwards standby.
In the 3L stirring tank that 1200mL distilled water is housed, add 42.2g FeCl
36H
2O and 20.6gFeCl
24H
2O is warming up to 85-90 ℃, adds the NH of 60mL25% in the high-speed stirring process
3H
2O solution, high-speed stirring adopted magnetic separator to isolate Fe after 3 minutes
3O
4Nano-particle product.With the precipitated product ultra-sonic dispersion after cleaning above-mentioned through pretreated Na
2SiO
3In the solution, move into then in the 3L stirring tank, be warming up to 85 ℃, under nitrogen protection and agitation condition, in solution, slowly drip the HCl solution of the about 2mol/L of concentration, in about 3 hours, the pH value of solution is reduced to 6 by 13.Obtain SiO
2Coat Fe
3O
4The particulate magnetic particle.The about 60g of above-mentioned product magnetic particle gross weight wherein contains Fe
3O
4About 20g is coated on Fe
3O
4The SiO on surface
2About 40g is amorphous Si O
2Detect the magnetic hysteresis loop that obtains through vibrating sample magnetometer (VSM) and show that magnetic particle has superparamagnetism.This component brief note is SF.
Take by weighing AlCl
36H
2O 80g, be dissolved in the 600ml deionized water, add the 44g high-purity aluminum foil, kept 60-72 hour down at 80-100 ℃, after making aluminium foil fully be dissolved in the solution, the liquor capacity heating is concentrated into 300ml, obtains clarifying translucent colloidal sol, wherein aluminium/chlorine weight ratio is about 1.5: 1.0, and the aluminium in the colloidal sol is converted to aluminum oxide and is about 100g.This colloidal sol brief note is AL1.
Under 10 ℃, measure 100ml AL1 aluminum hydroxide sol, mix with the organic amine solution (containing hexamethylenetetramine 300g/L and urea 150g/L) of 90ml, stir, add 7.3g SF cladded type magnetic component particle again, pour in the 3L stirring tank that fills 1600ml sulfonated kerosene (the tensio-active agent Span80 that contains 0.05 volume %) after fully stirring, at room temperature, under the rotating speed of 700rpm, be uniformly dispersed, form water-in-oil emulsion, system is warming up to 85-90 ℃ subsequently, keep after 15 minutes, cool off, isolate product, obtain the spherical Al (OH) of magnetic
3This spherical products brief note is AL2.
With the spherical Al (OH) of above-mentioned magnetic
3Product A L2 packs into and fills in the 1L autoclave of 0.7L sulfonated kerosene medium; the following 180 ℃ of hydrothermal treatment consists of nitrogen protection 2 hours; after the product cleaning oil removing; subsequently in the weak ammonia of pH10 (measuring under the room temperature) in 80 ℃ of ageings 5 hours to remove wherein partial impurities; after 60 ℃ of oven dry, can obtain boehmite structure (the spherical Al (OH) of the magnetic of α-AlOOH)
3Product.This product brief note is AL3.AL3 is by α-AlOOH, Fe
3O
4And γ-Fe
2O
3Deng composition, in hydrothermal treatment consists, ageing and drying process, the Fe in the product
3O
4Partial oxidation is γ-Fe
2O
3
Above-mentioned boehmite product A L3 can obtain about 45g and contain γ-Fe through 580 ℃ of air atmosphere sintering 2 hours
2O
3Spherical gamma-the Al of magnetic kernel
2O
3Carrier.
The median size of this ball type carrier is about 200 μ m, and wherein the weight ratio of each component is: γ-Fe
2O
3: SiO
2: Al
2O
3=6: 12: 82, this carrier had the superparamagnetism feature, and specific saturation magnetization is 2.97Am
2/ Kg, BET specific surface are 200m
2/ g, pore volume are 0.75mL/g.
Embodiment 2
The preparation process of used palladium catalyst in present embodiment explanation the inventive method.
Get the ball type carrier 10g of embodiment 1 preparation, with PdCl
2Add the dipping solution 30ml that hydrochloric acid is made into Pd content 0.35wt%, pH4.5, impregnated carrier is 2 hours at normal temperatures, will flood PdCl
2Carrier 70 ℃ of dryings 2 hours in baking oven, 120 ℃ of dryings 2 hours, 300 ℃ of roastings 4 hours in retort furnace then, in 100 ℃ of following hydrogen reducings 4 hours, the catalyzer of preparing note was made catalyzer-1 again, the Pd content in this catalyzer is 1.0wt%.
Embodiment 3
The preparation process of used platinum catalyst in present embodiment explanation the inventive method.
Get the ball type carrier 10g of embodiment 1 preparation, with H
2PtCl
6Add the dipping solution 30ml that hydrochloric acid is made into Pt content 0.35wt%, pH4.5, impregnated carrier is 2 hours at normal temperatures, will flood H
2PtCl
6Carrier 70 ℃ of dryings 2 hours in baking oven, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 4 hours in retort furnace then, in 400 ℃ of following hydrogen reducings 4 hours, the catalyzer of preparing note was made catalyzer-2 again, the Pt content in this catalyzer is 1.0wt%.
Embodiment 4
Present embodiment explanation the inventive method is carried out the effect of nitrobenzene hydrogenation in slurry bed reactor.
Add 1g catalyzer, 10ml oil of mirbane in the stirring tank of 300ml, 60ml ethanol is made solvent.Reaction conditions is 30 ℃ of temperature, pressure 1.0MPa, mixing speed 630rpm, 40 minutes reaction times.Vapor-phase chromatography, hydrogen flame detector are adopted in the analysis of reaction product.The response data of catalyzer-1 and catalyzer-2 sees Table 1.
Table 1
Catalyzer oil of mirbane transformation efficiency % aniline selectivity %
Catalyzer-1 99.5 99.3
Catalyzer-2 99.8 99.2
Embodiment 5
Present embodiment explanation the inventive method is carried out the effect of nitrobenzene hydrogenation in fluidized-bed reactor.
In the fluidized-bed reactor of internal diameter 13.5mm, add the 8g catalyzer.The oil of mirbane of nitrobenzene-containing 12% (quality), alcohol mixture are raw material.When reaction conditions is 30 ℃ of temperature, pressure 1.0MPa, air speed 10
-1, hydrogen/liquid input material volume ratio 100: 1.Vapor-phase chromatography, hydrogen flame detector are adopted in the analysis of reaction product.The response data of catalyzer-1 and catalyzer-2 sees Table 2.
Table 2
Catalyzer oil of mirbane transformation efficiency % aniline selectivity %
Catalyzer-1 97.9 99.8
Catalyzer-2 98.3 99.2
Embodiment 6
Present embodiment explanation the inventive method is carried out the effect of para-nitrotoluene hydrogenation reaction in slurry bed reactor.
Add 2g catalyzer-1,10ml para-nitrotoluene in the reactor of 300ml, 60ml methyl alcohol is made solvent.Reaction conditions is 50 ℃ of temperature, pressure 1.0MPa, mixing speed 630rpm, 40 minutes reaction times.Vapor-phase chromatography, hydrogen flame detector are adopted in the analysis of reaction product.Reaction result is a para-nitrotoluene transformation efficiency 96.3%, phenylmethylamine selectivity 100%.
Embodiment 7
Present embodiment explanation the inventive method is carried out the effect to nitro ethylbenzene hydrogenation reaction in slurry bed reactor.
Add 2g catalyzer-1,10ml to nitro ethylbenzene in the reactor of 300ml, 60ml methyl alcohol is made solvent.Reaction conditions is 60 ℃ of temperature, pressure 1.0MPa, mixing speed 630rpm, 40 minutes reaction times.Vapor-phase chromatography, hydrogen flame detector are adopted in the analysis of reaction product.Reaction result is to nitro conversion of ethylbenzene 93.2%, p-Ethylaniline selectivity 100%.
Embodiment 8
Present embodiment explanation the inventive method is carried out the hydrogenation of dinitro toluene reaction in slurry bed reactor effect.
In the reactor of 300ml, add 2g catalyzer-1,10ml 3, the 5-dinitrotoluene (DNT), 60ml methyl alcohol is made solvent.Reaction conditions is 130 ℃ of temperature, pressure 1.5MPa, mixing speed 630rpm, 30 minutes reaction times.Vapor-phase chromatography, hydrogen flame detector are adopted in the analysis of reaction product.Reaction result is dinitrotoluene (DNT) transformation efficiency 95.3%, two an amido methylbenzene selective 100%.
Comparative Examples 1
This Comparative Examples illustrates the process with conventional preparing carriers palladium catalyst.
Employing pH value is 4.5 PdCl
2Solution is at the γ-Al of normal temperature to commodity WAY-253 by name
2O
3Carrier (produce, about 150 microns of particle diameter, specific surface area 290m by Wenzhou alumina producer
2/ g, pore volume 0.63mL/g) dipping is 2 hours, 70 ℃ of dryings 2 hours, and 120 ℃ of dryings are 2 hours then, 300 ℃ of roasts 2 hours, 100 ℃ of following hydrogen reducings 4 hours are prepared the Pd/Al of palladium content 1.0wt%
2O
3Catalyzer is noted by abridging and is contrast medium-1.
Comparative Examples 2
This Comparative Examples illustrates the process with conventional preparing carriers platinum catalyst.
Employing pH value is 4.5 H
2PtCl
6Solution, at normal temperature to commercial goods γ-Al
2O
3Carrier (specification and Comparative Examples 1 with) dipping 2 hours, 70 ℃ of dryings 2 hours, 120 ℃ of dryings are 2 hours then, 500 ℃ of roasts 4 hours, 400 ℃ of following hydrogen reducings 4 hours are prepared the Pt/Al of palladium content 1.0wt%
2O
3Catalyzer is noted by abridging and is contrast medium-2.
Comparative Examples 3
Catalyst system therefor carries out the comparison of nitrobenzene hydrogenation effect in this Comparative Examples explanation contrast medium and the inventive method in slurry bed reactor.
Add 1g catalyzer, 10ml oil of mirbane in the reactor of 300ml, 60ml ethanol is made solvent.Reaction conditions is 30 ℃ of temperature, pressure 1.0MPa, mixing speed 630rpm, 40 minutes reaction times.Vapor-phase chromatography, hydrogen flame detector are adopted in the analysis of reaction product.The response data of catalyzer-1 and contrast medium-1 and catalyzer-2 and contrast medium-2 sees Table 3.
Table 3
Catalyzer oil of mirbane transformation efficiency % aniline selectivity %
Catalyzer-1 99.5 99.3
Contrast medium-1 99.0 99.1
Catalyzer-2 99.8 99.2
Contrast medium-2 99.3 98.6
Claims (12)
1, a kind of hydrogenation reduction method for aromatic nitro compound, be that to make aromatic nitro compound and magnetic noble metal catalyst in slurry bed or fluidized-bed be 25-150 ℃ in temperature of reaction, reaction pressure is 0.1-3.0MPa, hydrogen is 5-300 with the liquid phase feeding volume ratio: contact under 1 the condition, said magnetic noble metal catalyst is made up of ball type carrier and one or more the noble metal active component that is selected from platinum, palladium, ruthenium, the rhodium, ball type carrier wherein is made up of aluminum oxide and magnetic-particle, and magnetic-particle wherein is by SiO
2The kernel of coating layer and iron compound is formed.
2, according to the said method of claim 1, catalyst concn is 0.2-12 weight % in the wherein said slurry bed reactor.
3, according to the said method of claim 2, wherein said catalyst concn is 0.5-8 weight %.
4, according to the said method of claim 1, when the volume space velocity in the wherein said fluidized-bed reactor is 3-50
-1
5, according to the said method of claim 4, when wherein said volume space velocity is 5-20
-1
6, according to the said method of claim 1, wherein said aromatic nitro compound is benzene, C
1-C
6A nitro or many nitro-compounds of alkyl substituted benzene.
7, according to the said method of claim 1, it is characterized in that said magnetic noble metal catalyst by account for the heavy % of catalyzer 0.2-10 be selected from platinum, palladium, ruthenium, the rhodium one or more precious metal and the ball type carrier of surplus form.
8, according to the said method of claim 7, it is characterized in that precious metal is platinum and/or the palladium that accounts for the heavy % of catalyzer 0.3-7 in the said catalyzer.
9,, it is characterized in that carrier 1-50 weighs the magnetic-particle of % to said ball type carrier and the aluminum oxide of surplus is formed by accounting for according to the said method of claim 1.
10,, it is characterized in that magnetic-particle in the said ball type carrier accounts for the heavy % of 2-15 of carrier according to the said method of claim 9.
11,, it is characterized in that the magnetic-particle in the said ball type carrier is (0.05-6) by weight ratio: 1 SiO according to claim 1, one of 9 and 10 said methods
2Coating layer and be dispersed in wherein, one or more particle diameters be the 3-30 nanometer, its chemical constitution is for being selected from Fe
3O
4, Fe and γ-Fe
2O
3In the kernel of single domain superparamagnetism particulate of one or more iron compounds form.
12,, it is characterized in that the magnetic-particle in the said ball type carrier is (0.3-4.0) by weight ratio: 1 SiO according to the said method of claim 11
2Coating layer and magnetic particle kernel are formed.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274895B (en) * | 2007-03-30 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrogenation reduction method for aromatic nitro compound |
| CN102861573A (en) * | 2012-10-12 | 2013-01-09 | 康纳新型材料(杭州)有限公司 | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound |
| CN102872862A (en) * | 2012-10-12 | 2013-01-16 | 康纳新型材料(杭州)有限公司 | Carrier type platinum-ruthenium catalyst and application of carrier type platinum-ruthenium catalyst in hydrogenation of aromatic nitro compound |
| CN103304427A (en) * | 2013-05-17 | 2013-09-18 | 中国科学院宁波材料技术与工程研究所 | Method for preparing aniline through low-temperature liquid-phase catalytic hydrogenation |
| CN103819295A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院大连化学物理研究所 | Application of catalyst to selective hydrogenation reaction of aromatic nitro compound |
| CN104667945A (en) * | 2015-01-10 | 2015-06-03 | 安徽大学 | Preparation of supported palladium catalyst Fe3O4/SiO2/Pd and application of supported palladium catalyst Fe3O4/SiO2/Pd in Suzuki reaction |
| CN114644585A (en) * | 2020-12-18 | 2022-06-21 | 沈阳化工研究院有限公司 | Method for preparing indigo white by fluidized bed catalytic hydrogenation |
| CN114682288A (en) * | 2022-04-11 | 2022-07-01 | 西安凯立新材料股份有限公司 | Supported catalyst for hydrogenation of aromatic nitro compound and preparation method thereof |
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| US11452992B2 (en) | 2019-03-20 | 2022-09-27 | King Fahd University Of Petroleum And Minerals | Iron oxide supported rhodium catalyst for nitroarene reduction |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274895B (en) * | 2007-03-30 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrogenation reduction method for aromatic nitro compound |
| CN102861573A (en) * | 2012-10-12 | 2013-01-09 | 康纳新型材料(杭州)有限公司 | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound |
| CN102872862A (en) * | 2012-10-12 | 2013-01-16 | 康纳新型材料(杭州)有限公司 | Carrier type platinum-ruthenium catalyst and application of carrier type platinum-ruthenium catalyst in hydrogenation of aromatic nitro compound |
| CN102861573B (en) * | 2012-10-12 | 2014-11-05 | 康纳新型材料(杭州)有限公司 | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound |
| CN103819295A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院大连化学物理研究所 | Application of catalyst to selective hydrogenation reaction of aromatic nitro compound |
| CN103819295B (en) * | 2012-11-19 | 2016-04-27 | 中国科学院大连化学物理研究所 | The application of a kind of catalyzer in aromatic nitro compound selective hydrogenation |
| CN103304427A (en) * | 2013-05-17 | 2013-09-18 | 中国科学院宁波材料技术与工程研究所 | Method for preparing aniline through low-temperature liquid-phase catalytic hydrogenation |
| CN103304427B (en) * | 2013-05-17 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Method for preparing aniline through low-temperature liquid-phase catalytic hydrogenation |
| CN104667945A (en) * | 2015-01-10 | 2015-06-03 | 安徽大学 | Preparation of supported palladium catalyst Fe3O4/SiO2/Pd and application of supported palladium catalyst Fe3O4/SiO2/Pd in Suzuki reaction |
| CN114644585A (en) * | 2020-12-18 | 2022-06-21 | 沈阳化工研究院有限公司 | Method for preparing indigo white by fluidized bed catalytic hydrogenation |
| CN114644585B (en) * | 2020-12-18 | 2023-10-27 | 沈阳化工研究院有限公司 | Method for preparing indigo white by fluidized bed catalytic hydrogenation |
| CN114682288A (en) * | 2022-04-11 | 2022-07-01 | 西安凯立新材料股份有限公司 | Supported catalyst for hydrogenation of aromatic nitro compound and preparation method thereof |
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