CN105833864B - A kind of support type nano spherical particle palladium catalyst and its preparation method and application - Google Patents
A kind of support type nano spherical particle palladium catalyst and its preparation method and application Download PDFInfo
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- CN105833864B CN105833864B CN201610282146.9A CN201610282146A CN105833864B CN 105833864 B CN105833864 B CN 105833864B CN 201610282146 A CN201610282146 A CN 201610282146A CN 105833864 B CN105833864 B CN 105833864B
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- palladium
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 61
- 239000012798 spherical particle Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- -1 nitro aromatic amine Chemical class 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000001257 hydrogen Substances 0.000 description 20
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 description 1
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method 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
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/51—
-
- 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
-
- 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
- C07C209/365—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 by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
Abstract
A kind of support type nano spherical particle palladium catalyst and its preparation method and application, the catalyst is made of carrier and the active component being supported on carrier, the carrier is active carbon, aluminium oxide, silica or titanium dioxide, the active component is simple substance palladium, the pattern of the simple substance palladium is spheroidal particle, and particle diameter is between 5~50nm；Based on carrier quality, the load capacity of simple substance palladium is 0.10~15.0wt%.The present invention provides the applications in the catalytic hydrogenation reaction of nitro aromatic amine shown in catalyst Polynitroaramatics selective synthesizing accepted way of doing sth (II) shown in formula (I)；In formula (I), R1、R2、R3、R4、R5、R6In at least there are two being nitro, remaining group respectively stands alone as H, Cl, F, CH3、OH、CH2CH3、NH2、OCH3、OCH2CH3、C6H5, COOH or COOCH3；In formula (II), an only nitro is reduced to amino, corresponds in other groups and formula (I), and react front and back and remain unchanged.
Description
(1) technical field
The present invention relates to a kind of support type nano spherical particle palladium catalyst and its preparation method and application, the catalyst
It can be applied to the catalytic hydrogenation reaction of Polynitroaramatics selectivity synthesis nitro aromatic amine.
(2) technical background
Nitro aromatic amine is a kind of important organic synthesis intermediate, is widely used in pigment, dyestuff, medicine, pesticide and rubber
The synthesis of the fine chemicals such as glue auxiliary agent, resin, photosensitive material.Currently, nitro aromatic amine is mainly by corresponding more nitro aromatics
It is produced with object partial reduction.More mature technique is chemical reduction method.The method is using akali sulphide, iron powder etc. in acid medium
Nitro moiety is restored, nitro aromatic amine is made, this technological operation is easy, but can generate waste residue largely containing organic poison, is not easy to locate
It manages seriously polluted.Liquid phase catalytic hydrogenation reduction method is due to its, superior product quality few with the three wastes and low power consumption and other advantages by pass
Note, is an environmental-friendly friendly process.But during Polynitroaramatics hydrogenating reduction, although multiple nitros
Group usually has the characteristics that gradually to restore, but the Nitro group reduction reaction process energy barrier difference of different location is smaller, adds hydrogen
Process is difficult to rest on the nitro aromatic amine stage.Therefore, the selectivity and stability of catalyst are always Polynitroaramatics
Selective hydrogenation key technology difficulty urgently to be resolved.
In published document report, active constituent or auxiliary agent with Polynitroaramatics selective hydrogenation performance
The predominantly metals such as Au, Ni, Pd, Pt, Ru, Ir and Se, are usually supported on aluminium oxide, silica and active carbon etc.
Support type monometallic or bimetallic catalyst, such as Au/Al are prepared on carrier2O3、Au-Ni/Al2O3、Au/TiO2、Pt/SiO2、
Pt/TiO2、Pt/Al2O3, Pd/C and PVP-Ru/Al2O3Deng.These catalyst all show preferable more nitryl aromatic chemical combination
Object conversion ratio or nitro aromatic amine selectivity, but be difficult to reach conversion ratio and selectivity to be all 100%, i.e. nitro aromatic amine yield is low
In 100%.[Hou Jie, ruthenium-based catalyst paradinitrobenzene class compound selective hydrogenation prepare grinding for nitroaniline to open source literature
Study carefully, doctoral thesis, 2008.] report, the high-dispersion nano support type Ru/C catalyst prepared using surfactant Protection Code,
Under preferred reaction conditions, selective catalysis 2,4-DNP, 2,4- dinitroaniline and 3,5- dinitrosalicylic acid add
Hydrogen conversion ratio and nitro aromatic amine selectively can reach 100%.But the nitro aromatic amine of generation in the reaction system can hardly
Stablize stop, it can continue to be hydrogenated to arylamine quickly, and reaction end is unobvious to be difficult to determine, be only capable of by theoretical hydrogen-consuming volume come
Control reaction process.This greatly improves the requirements of precision and difficulty to hydrogenation reaction operational process of craft, hinder its work
The breakthrough of industry production technology.
(3) summary of the invention
The object of the present invention is to provide a kind of support type nano spherical particle palladium catalyst and its preparation method and application, institutes
Stating catalyst can be applied to the catalytic hydrogenation reaction of Polynitroaramatics selectivity synthesis nitro aromatic amine.
To achieve the above object, the present invention adopts the following technical scheme:
The present invention provides a kind of support type nano spherical particle palladium catalyst, the catalyst is by carrier and is supported on load
Active component composition on body, the carrier is active carbon, aluminium oxide, silica or titanium dioxide, and the active component is
The pattern of simple substance palladium, the simple substance palladium is subsphaeroidal particle, and particle diameter is between 5~50nm；Based on carrier quality, simple substance palladium
Load capacity be 0.10~15.0wt%.
Further, in the catalyst, it is based on carrier quality, the load capacity of simple substance palladium is preferably 0.5~10.0wt%.
Further, in the catalyst, palladium particle diameter is preferably between 8~45nm.
Further, the carrier is active carbon, and ash is 0.01~5.0wt%, and specific surface area is 500~2000m2/
0.4~1.5mL/g of g, Kong Rongwei；The material of the active carbon can be coconut husk or wooden.
Further, the carrier is aluminium oxide, silica or titanium dioxide, and specific surface area is 100~800m2/ g,
0.2~1.0mL/g of Kong Rongwei.
The present invention also provides the preparation method of the support type nano spherical particle palladium catalyst, the preparation method is pressed
Following steps carry out:
(a) carrier is taken to be dried and dehydrated；
(b) palladium liquid is prepared；Palladium chloride or palladium nitrate are dissolved in ammonium hydroxide, is stirred at room temperature to being completely dissolved, obtains palladium
Liquid；
(c) not by the ethylene glycol or mass content that are immersed in -10.0~0.0 DEG C by the carrier of step (a) drying and dehydrating
In glycol water lower than 50%, the palladium liquid that (b) is obtained the step of instillation amount corresponding with load capacity after stirring to constant temperature,
And the reducing agent for reducing the palladium ion to simple substance palladium, continue stirring to being thoroughly mixed and maintain the temperature at -10.0~0.0
℃；Then this slurries is sealed up for safekeeping in closed pressure resistant container, and displaced air is filled with chemically inactive gas, first with 0.01~2.0
DEG C/heating rate of h is warming up to 50~100 DEG C, then is warming up to 150~500 DEG C by 2.0~10 DEG C/h, constant temperature 1 at a temperature of final temperature
~10 days；Later, open closed pressure resistant container, filter slurries, filter cake be washed with deionized to no chloride ion or nitrate anion from
Son is sealed up for safekeeping after vacuum drying to get support type nano spherical particle palladium catalyst.
Further, in preparation method step (a) of the present invention, the carrier is recommended to carry out vacuum at 100~150 DEG C
1~10h of drying and dehydrating.
Further, ammonia concn described in step (b) is preferably 25~28wt%, and dosage is that dissolution palladium metal is theoretical
1.0~5.0 times of dosage.
Further, the volumetric usage of ethylene glycol described in step (c) or glycol water is with carrier after drying and dehydrating
Quality is calculated as 2~10mL/g；
Further, in step (c), after the inventory of the palladium liquid is calculated as drying and dehydrating with the quality of wherein palladium metal element
The 0.10%~15.0% of carrier quality, preferably 0.5%~10.0%.
Further, reducing agent described in step (c) is preferably ascorbic acid, ethylene glycol, ethyl alcohol or glucose；The reduction
The amount of the substance of agent is 1.0~100 times of the amount of the theoretical substance of palladium metal element in palladium liquid, preferably 1.5~80 times.
Further, chemically inactive gas described in step (c) is the gas not chemically reacted with reaction system, preferably
For the mixed gas of nitrogen, argon gas, helium, carbon dioxide or their arbitrary proportions, pressure is 0.1~3.0MPa.
Further, in step (c), recommending vacuum drying temperature is 25~120 DEG C, and the time is 2~5h.
Invention further provides the support type nano spherical particle palladium catalyst more nitro virtues shown in formula (I)
Application in the catalytic hydrogenation reaction of nitro aromatic amine shown in an aroma compounds selective synthesizing accepted way of doing sth (II)；
In formula (I), R1、R2、R3、R4、R5、R6In at least there are two be nitro, remaining group respectively stand alone as H, Cl, F,
CH3、OH、CH2CH3、NH2、OCH3、OCH2CH3、C6H5, COOH or COOCH3；In formula (II), only a nitro is reduced to ammonia
Base, other groups and formula (I) middle one-to-one correspondence, and react front and back and remain unchanged.
Further, formula (I) compound represented is selected from one of following:
Specifically, the application are as follows: urge compound shown in formula (I), solvent and the support type nano spherical particle palladium
Agent is put into high-pressure hydrogenation reaction kettle, closed reactor, is stirred with opening after hydrogen displaced air, is 20~100 in temperature
DEG C, Hydrogen Vapor Pressure be 0.1~3.0MPa under conditions of carry out catalytic hydrogenation reaction；When no longer declining in Hydrogen Vapor Pressure 5 minutes,
Stop stirring, hydrogenation liquid is post-treated to obtain compound shown in product formula (II).
In the application method, recommend compound shown in the formula (I) and the support type nano spherical particle palladium chtalyst
The mass ratio that feeds intake of agent is 100:0.1~4, preferably 100:0.2~2.0.
In the application method, preferable reaction temperature is 25~80 DEG C, and preferably Hydrogen Vapor Pressure is 0.2~2.5MPa.
The application can also carry out in fixed bed, method particularly includes: catalyst carrier is chosen for graininess, having a size of
1/10 or less reaction tube diameter.When reaction, compound shown in formula (I) and solvent are squeezed by evaporator using micro pump, used
Mass flowmenter controls hydrogen flowing quantity, is sufficiently mixed in mixing tube, urges subsequently into equipped with support type nano spherical particle palladium
The fixed bed reactors of agent.Tail gas obtains compound shown in product i.e. formula (II) after cooling, gas-liquid separation, Liquid liquid Separation.
During reaction, chromatography is used mutually to analyze to monitor reaction process organic matter.
In the fixed bed reaction, the gas space velocity of the sum of hydrogen and Polynitroaramatics is 0.05~10*
104h-1, hydrogen and Polynitroaramatics molar ratio are 30~100:1.
In the fixed bed reaction, temperature is 25~100 DEG C, and Hydrogen Vapor Pressure is 0.1~3.0MPa.
Compound shown in the formula (I) carries out hydrogenation reaction in a solvent, and applicable solvent is methanol, ethyl alcohol, water, positive third
The mixed solvent of one or more of alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, tert-butyl alcohol arbitrary proportion, pushes away
It recommends the volumetric usage of the solvent and 0.5~15mL/g, preferably 1~10mL/ is calculated as with the quality of compound shown in substrate formula (I)
g。
When carrying out hydrogenation reaction in a kettle, the method for the hydrogenation liquid post-processing are as follows: hydrogenation liquid filters to isolate
Catalyst, filtrate is after vacuum distillation recovered solvent and dehydration up to product；Also, in last handling process, hydrogenation liquid is filtered
To catalyst cake may return to reaction kettle carry out catalyst apply.It is described to add when carrying out hydrogenation reaction in fixed bed
The method of hydrogen liquid post-processing are as follows: by the tail gas of catalyst bed after cooling and gas-liquid separation, obtain similar in identical reaction kettle
Hydrogenation liquid, subsequent processing method successively carries out, and obtains compound shown in product formula (II).
Compared with prior art, the beneficial effects of the present invention are embodied in:
(1) the active component palladium particle almost spherical on support type nano spherical particle palladium catalyst surface of the present invention, ruler
It is very little, regular appearance is uniform, size concentrates on 8~45nm, especially suitable for Polynitroaramatics selective catalytic hydrogenation；
(2) support type nano spherical particle palladium catalyst of the present invention, not only hydrogenation conversion and nitro aromatic amine are selectively equal
It can reach 100%.Moreover, reaction end is easy to judge, the nitro aromatic amine stage of generation can be rested on, work can be satisfied with completely
Industry production requirement；
(3) catalyst circulation use process mild condition of the present invention, stability is good, applies often；
(4) method for preparing catalyst of the present invention is simple, easy to operate.
In conclusion particle almost spherical when catalyst of the present invention is applied, size, regular appearance are uniform, and particle size is special
Not Shi He Polynitroaramatics selective hydrogenation, higher reaction rate can be kept, but can reach hydrogenation reaction turn
Rate 100%, nitro aromatic amine selectivity 100%, and reaction end is easy to judge, has the technical conditions of industrialized production,
With significant progress.
(4) Detailed description of the invention
Fig. 1 is the TEM figure of catalyst made from the embodiment of the present invention 1.
Fig. 2 is the TEM figure of catalyst made from the embodiment of the present invention 8.
Fig. 3 is the TEM figure of catalyst made from comparative example 1 of the present invention.
Fig. 4 is the TEM figure of catalyst made from comparative example 2 of the present invention.
Fig. 5 is the reaction mechanism mechanism of reaction figure of the embodiment of the present invention 16.
(5) specific embodiment
Below with specific embodiment to further illustrate the technical scheme of the present invention, but protection scope of the present invention is not limited to
This.
1~embodiment of embodiment 15
Provide catalyst activity component content, proportion and its preparation condition (as shown in table 1).
The specific preparation process of catalyst is following (by taking embodiment 1 as an example):
1) by coconut husk preparing active carbon in 120 DEG C of vacuum dehydration 3h；
2) palladium chloride is dissolved in concentrated ammonia liquor (25~28wt%), dosage is that just dissolution can (the 1.0 of theoretical amount
Times), it is stirred at room temperature to being completely dissolved, is then diluted with water the palladium liquid for being configured to that concentration is 0.05g/ml.
3) take the ethylene glycol solution that 25ml mass content is 80% in 100ml hydrothermal synthesis kettle, controlled at -8.0
℃.The 10g active carbon Jing Guo vacuum dehydration is poured into synthesis reactor afterwards, stirring to slurry temperature reaches -8.0 DEG C；It instills
10ml palladium liquid obtained above and 1.0ml ethylene glycol, stirring to slurry temperature reach -8.0 DEG C, close kettle, pour after displaced air
Nitrogen is to 0.5MPa；Temperature program is set:Synthesis reactor is opened, filter pulp is crossed
Liquid, filter cake are washed with deionized to no chloride ion, seal up for safekeeping after 80 DEG C of vacuum drying 3h to get the support type ball shaped nano grain
Sub- palladium catalyst.Load capacity is 5%, 10~35nm of Pd nano particle.
Comparative example 1
Conventional carbon-carried palladium catalyst preparation method: being 1350m by specific surface area2/ g, Kong Rongwei 0.65mL/g, ash are
3.5% coconut husk preparing active carbon is in 120 DEG C of vacuum dehydration 3h；Pipette the chlorine palladium acid solution that 10mL concentration is 0.05g/mL
(wherein concentration of hydrochloric acid 0.1mol/L) makes its pH value in 0.8 in 50mL deionized water, with hydrochloric acid adjusting；Then it will pass through vacuum
The 10g active carbon of drying and dehydrating is dipped in palladium liquid, and 80 DEG C are sufficiently stirred dipping 5h, adjusts pH value to 8~10 with sodium hydroxide；Half
After hour, 2.5mL hydrazine hydrate, 35 DEG C of reductase 12 h are added dropwise.It is down to room temperature, reaction system filtering, filter cake deionized water later
To neutrality, 105 DEG C of drying and dehydrating 3h obtain simple substance supported palladium catalyst for washing.Through high power transmissioning electric mirror determining palladium particle
Mean size is 6nm, and pattern is irregular.
Comparative example 2
The preparation of catalyst preparation process method as disclosed in Chinese patent [CN1817455A], palladium load capacity are 2.0%.
It is specific the preparation method comprises the following steps:
10g active carbon is weighed, the specific surface area of active carbon is 1200m2/ g, active carbon are immersed in 120 milliliters of concentration and are
6 hours in the KI solution of 2.5mol/L, filtering is washed with deionized to no iodide ion and detects.Then by the active carbon of processing
80 DEG C of temperature of 100mL slurries are configured to, 4 milliliters of H is slowly added dropwise2PdCl4Solution (Pd content is 0.05g/mL), stirs 6h,
Solution ph is adjusted to alkalescent (pH=8) with 10% NaOH solution again, and cools the temperature to room temperature, is filtered, deionized water
It washs to neutrality.Unreduced catalyst is configured to the slurries of 150mL at 30 DEG C, the 85% of 2 milliliters is then slowly added dropwise
Hydrazine hydrate solution continues stirring 2 hours.Catalyst after reduction through filtering, wash to neutrality by deionized water, finally exists in room temperature
Through preliminarily dried in air, it is sealed.Mean size through high power transmissioning electric mirror determining palladium particle is 25nm, and pattern is not advised
Then.
Embodiment 16~32 is to be applied to catalyst made from above-described embodiment 1~15,1~2 preparation method of comparative example
The example of Polynitroaramatics selectivity synthesis nitro aromatic amine catalytic hydrogenation reaction.The results are shown in Table 2 for its catalytic performance.
Embodiment 16~32
Support type prepared by 50g m-dinitrobenzene, 100ml methanol and 0.5g embodiment 1~15 or comparative example 1~2 is urged
Agent is added in 500mL autoclave, closes reaction kettle, displaces air in reactor with nitrogen, then replaced with hydrogen
Nitrogen opens stirring, and agitation revolution 1000r/min, 25~70 DEG C of maintaining reaction temperature, 1.0~1.5MPa of Hydrogen Vapor Pressure is carried out
Reaction.No longer decline when in hydrogen 5 minutes, be considered as reaction terminating, stops reaction, filtration catalytic agent.Filtrate is mutually separated a point water
And after vacuum distillation dehydration be product, through chromatographic quantitative analysis (molar percentage).
Embodiment 33
Catalyst prepared by embodiment 10 is chosen, carrier granular is chosen for 0.5-1.0mm, 8cm in fixed bed.Hydrogen and
The gas space velocity of the sum of dinitrobenzene is 2.0*104h-1, hydrogen and m-dinitrobenzene molar ratio are 40:1；Temperature is 70 DEG C, hydrogen
Atmospheric pressure is 2.0MPa.For product through chromatography, conversion ratio and selectivity are all 100%.
Embodiment 34
Catalyst prepared by embodiment 15 is chosen, carrier granular is chosen for 0.5-1.0mm, 8cm in fixed bed.Hydrogen and
The gas space velocity of the sum of dinitrobenzene is 0.5*104h-1, hydrogen and m-dinitrobenzene molar ratio are 40:1；Temperature is 60 DEG C, hydrogen
Atmospheric pressure is 2.0MPa.For product through chromatography, conversion ratio and selectivity are all 100%.
The catalytic performance result of 2 embodiment 1~15 of table and 1~2 prepared catalyst of comparative example
Embodiment 35~44 is that hydrogenation catalyst prepared by embodiment 1 is synthesized in Polynitroaramatics catalytic hydrogenation
Catalytic performance in corresponding nitro aromatic amine reaction, the results are shown in Table 3.
Catalyst prepared by 3 embodiment 1 of table is anti-in the corresponding nitro aromatic amine of Polynitroaramatics catalytic hydrogenation synthesis
Catalytic performance in answering
Embodiment 45
Embodiment 45 is under the operating condition of embodiment 16, and catalyst prepared by embodiment 1 is urged in m-dinitrobenzene
Change in hydrogenation reaction and apply experimental conditions, the results are shown in Table 4.
4 embodiment of table, 1 prepared catalyst synthesizing nitryl aniline reaction applies experimental result
Claims (8)
1. a kind of support type nano spherical particle palladium catalyst, it is characterised in that: the catalyst is by carrier and is supported on carrier
On active component composition, the carrier is active carbon, aluminium oxide, silica or titanium dioxide, and the active component is single
The pattern of matter palladium, the simple substance palladium is spheroidal particle, and regular appearance, particle diameter is between 8-45nm；It is single based on carrier quality
The load capacity of matter palladium is 0.10wt%~15.0wt%；
The catalyst is prepared as follows:
(a) carrier is taken to be dried and dehydrated；
(b) palladium liquid is prepared；Palladium chloride or palladium nitrate are dissolved in ammonium hydroxide, are stirred at room temperature to being completely dissolved, palladium liquid is obtained；
(c) -10.0~0.0 DEG C of ethylene glycol will be immersed in by the carrier of step (a) drying and dehydrating or mass content is not less than
In 50% glycol water, stir to (b) the step of instilling amount corresponding with load capacity after constant temperature obtained palladium liquid and
For reducing the palladium ion to the reducing agent of simple substance palladium, continue stirring to being thoroughly mixed and maintain the temperature at -10.0~0.0 DEG C；
Then this slurries is sealed up for safekeeping in closed pressure resistant container, and displaced air is filled with chemically inactive gas, first with 0.01~2.0 DEG C/h
Heating rate be warming up to 50-100 DEG C, then be warming up to 150-500 DEG C by 2.0-10 DEG C/h, constant temperature 1-10 days at a temperature of final temperature；
Later, closed pressure resistant container is opened, slurries are filtered, filter cake is washed with deionized to no chloride ion or nitrate ion, vacuum
It is sealed up for safekeeping after drying to get support type nano spherical particle palladium catalyst.
2. support type nano spherical particle palladium catalyst as described in claim 1, it is characterised in that: the carrier is activity
Charcoal, ash are 0.01wt%~5.0wt%, and specific surface area is 500~2000m20.4~1.5mL/g of/g, Kong Rongwei；It is described
The material of active carbon is coconut husk or wooden.
3. support type nano spherical particle palladium catalyst as described in claim 1, it is characterised in that: the carrier is oxidation
Aluminium, silica or titanium dioxide, specific surface area are 100~800m20.2~1.0mL/g of/g, Kong Rongwei.
4. the support type nano spherical particle palladium catalyst as described in one of claims 1 to 3, it is characterised in that: the catalysis
In agent, it is based on carrier quality, the load capacity of simple substance palladium is 0.5wt%~10.0wt%.
5. support type nano spherical particle palladium catalyst as described in claim 1, it is characterised in that: described in step (c) also
Former agent is ascorbic acid, ethylene glycol, ethyl alcohol or glucose, and the amount of the substance of the reducing agent is the reason of palladium metal element in palladium liquid
By 1.0~100 times of the amount of substance.
6. support type nano spherical particle palladium catalyst as described in claim 1, it is characterised in that: the chemically inactive gas
For the mixed gas of nitrogen, argon gas, helium, carbon dioxide or their arbitrary proportions, pressure is 0.1~3.0MPa.
7. support type nano spherical particle palladium catalyst as described in claim 1 more nitryl aromatic chemical combination shown in formula (I)
Application in the catalytic hydrogenation reaction of nitro aromatic amine shown in an object selective synthesizing accepted way of doing sth (II),
In formula (I), R1、R2、R3、R4、R5、R6In at least there are two being nitro, remaining group respectively stands alone as H, Cl, F, CH3、OH、
CH2CH3、NH2、OCH3、OCH2CH3、C6H5, COOH or COOCH3；In formula (II), only a nitro is reduced to amino, other
It is corresponded in group and formula (I), and reacts front and back and remain unchanged.
8. the use as claimed in claim 7, it is characterised in that: formula (I) compound represented is selected from one of following:
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| US10384201B2 (en) | 2016-02-17 | 2019-08-20 | Korea Institute Of Energy Research | Direct synthesis method of nanostructured catalyst particles on various supports and catalyst structure produced by the same |
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| CN109395721A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | Load type palladium catalyst and preparation method thereof |
| CN111995503B (en) * | 2019-05-27 | 2022-10-25 | 华东师范大学 | Ethylene glycol monobutyl ether synthesis method, supported palladium catalyst and application thereof |
| CN110743590B (en) * | 2019-10-21 | 2023-01-24 | 西安凯立新材料股份有限公司 | High-selectivity catalyst for synthesizing vitamin A intermediate and preparation method thereof |
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| CN1817455A (en) * | 2006-03-21 | 2006-08-16 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
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| CN1817455A (en) * | 2006-03-21 | 2006-08-16 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
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