CN113289637A - Hydrotalcite-like catalyst, preparation method and application thereof - Google Patents
Hydrotalcite-like catalyst, preparation method and application thereof Download PDFInfo
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- CN113289637A CN113289637A CN202110659554.2A CN202110659554A CN113289637A CN 113289637 A CN113289637 A CN 113289637A CN 202110659554 A CN202110659554 A CN 202110659554A CN 113289637 A CN113289637 A CN 113289637A
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- hydrotalcite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 22
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 22
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 150000005181 nitrobenzenes Chemical class 0.000 claims abstract description 20
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
- RFIJBZKUGCJPOE-UHFFFAOYSA-N [Fe].[Ni].[Zn] Chemical group [Fe].[Ni].[Zn] RFIJBZKUGCJPOE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000003513 alkali Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 16
- GLMGLOKOFVECMS-UHFFFAOYSA-K C(C)O.[Ru](Cl)(Cl)Cl Chemical compound C(C)O.[Ru](Cl)(Cl)Cl GLMGLOKOFVECMS-UHFFFAOYSA-K 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- -1 platinum group metals Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000000877 morphologic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 9
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 1
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- NEOOEFDJRSCWOU-UHFFFAOYSA-N iron(2+);dinitrate;hydrate Chemical compound O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NEOOEFDJRSCWOU-UHFFFAOYSA-N 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/8953—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 zinc, cadmium or mercury
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- 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
- B01J23/80—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 zinc, cadmium or mercury
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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- 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
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Abstract
The invention relates to the technical field of catalysts, and particularly relates to a hydrotalcite-like catalyst, a preparation method and application thereof. The hydrotalcite-like catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is nickel-zinc-iron hydrotalcite, and the active component is selected from one or two of platinum or ruthenium. The catalyst has unique morphological characteristics, can be used for multiple times, has excellent catalytic activity in catalyzing hydrogenation reaction of halogenated nitrobenzene, can ensure that the reaction is carried out under the condition of no solvent, and has high reaction charge ratio and moderate reaction temperature.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a hydrotalcite-like catalyst, a preparation method and application thereof.
Background
The demand of the halogenated aniline chemical raw material as an important chemical intermediate widely used in agriculture, animal husbandry and medical industry is also rising year by year. The main preparation methods for industrially preparing the halogenated aniline at present have different problems, wherein a catalytic hydrogenation reduction method which is relatively extensive is used at present, but due to the problem of selective adsorption of a catalyst, free hydrogen can attack carbon halogen bonds to cause dehalogenation, so that the free hydrogen reacts with hydrogen to generate corrosive hydrogen chloride, and equipment and pipelines are corroded, so that the solvent-free hydrogenation is more and more prone to be used for hydrogenating the halogenated arylamine.
The platinum group metal includes platinum (Pt), palladium (Pd), osmium (Os), iridium (Ir), ruthenium (Ru), rhodium (Rh), the excellent hydrogen evolution performance of the platinum group metal leads the platinum group metal to have extremely wide application in the field of catalytic hydrogenation, wherein the platinum-based catalyst has good catalytic activity and higher selectivity in the selective hydrogenation field, so that the catalyst has more application in the field of hydrogenation of halogenated nitrobenzene, the platinum catalyst which is most commonly used in the industry at present is the platinum-carbon catalyst with the load of 1-5 percent, but the price of the noble metal is increased due to epidemic situation, so that the price of the catalyst is increased along with the water rise of the ship, and since the carbon catalyst is easily lost at a higher temperature and the catalyst is difficult to separate from the sample due to low mechanical strength, people also aim to find a catalyst with lower loading and simple separation.
The hydrotalcite-like material is used as a layered multi-metal hydroxide, and has extremely wide application in the field of catalysis due to the special structure and adjustable modification of metal and interlayer anions of a layered plate of hydrotalcite. And because the laminate is composed of metal ions, the composite has strong SMSI effect (strong metal-carrier interaction).
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide a hydrotalcite-like catalyst, which is a solvent-free catalyst with good catalytic activity and has excellent selectivity at an extremely low loading amount. Solves the problem of dehalogenation in the hydrogenation of the halogenated nitrobenzene under the catalysis of no solvent, solves the problem of over low hydrogenation activity of low-content noble metal, and solves the problem of high temperature required by a solvent-free method.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
the hydrotalcite-like catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is nickel-zinc-iron hydrotalcite, and the active component is selected from one or more of platinum group metals. The platinum group metal includes platinum (Pt), palladium (Pd), osmium (Os), iridium (Ir), ruthenium (Ru), and rhodium (Rh).
The preparation method of the hydrotalcite-like catalyst comprises the following steps:
(1) preparation of nickel-zinc-iron hydrotalcite: preparing nitrates of metal nickel, zinc and iron into mixed salt solution according to a proportion; preparing sodium carbonate and sodium hydroxide into an alkali solution according to a proportion; then preparing nickel-zinc-iron hydrotalcite by adopting a coprecipitation method or a hydrothermal synthesis method; the nitrate herein includes a nitrate of a metal or a hydrate thereof;
(2) alkali washing: putting the nickel-zinc-iron hydrotalcite obtained in the step (1) into a sodium hydroxide solution of 2-5 mol/L, stirring for 10-50 min, filtering, washing with water, and drying to obtain Ni-Zn-Fe-LDH-A; a herein represents the concentration of the alkali-washed sodium hydroxide solution, for example, Ni-Zn-Fe-LDH-5mol/L when the concentration of the alkali-washed sodium hydroxide solution is 5 mol/L.
(3) Loading active components: loading an active component by an ultrasonic impregnation method to obtain an active component-Ni-Zn-Fe-LDH-A;
(4) reduction: reducing the active component-Ni-Zn-Fe-LDH-A obtained in the step (3) by using a reducing solution to obtain a target hydrotalcite-like catalyst; the reducing solution is selected from potassium borohydride, sodium borohydride or ascorbic acid.
Preferably, in the mixed salt solution in the step (1), the concentration of the nitrate of nickel is 0.9mol/L to 1.1mol/L, the concentration of the nitrate of zinc is 0.18mol/L to 0.22mol/L, and the concentration of the nitrate of iron is 0.36mol/L to 0.44 mol/L.
Further preferably, in the mixed salt solution in the step (1), the concentration of the nitrate of nickel is 1mol/L, the concentration of the nitrate of zinc is 0.2mol/L, and the concentration of the nitrate of iron is 0.4 mol/L.
Preferably, the nickel-zinc-iron hydrotalcite is prepared by adopting a coprecipitation method in the step (1), the mixed salt solution and the alkali solution are subjected to ultrasonic treatment at 10-30 ℃ for 15min respectively, a certain amount of distilled water is added into a container in advance to serve as a base solution, the mixed salt solution and the alkali solution are simultaneously dripped into the base solution, the temperature during dripping is 60-100 ℃, the pH is controlled at 9-10, stirring is carried out, after dripping is finished, stirring and crystallization are carried out at 60-100 ℃ for 6-10 h, and filtering, washing and drying are carried out, so that the nickel-zinc-iron hydrotalcite is obtained.
Preferably, the active component in the step (3) is platinum or ruthenium, and the supporting method is an ultrasonic impregnation method.
Preferably, the active components in the step (3) are platinum and ruthenium, and the loading step comprises:
A. preparing chloroplatinic acid aqueous solution by taking chloroplatinic acid, putting Ni-Zn-Fe-LDH-A in the chloroplatinic acid aqueous solution, wherein the mass ratio of platinum in the chloroplatinic acid aqueous solution to Ni-Zn-Fe-LDH-A added into the chloroplatinic acid aqueous solution is 0.3-2%, and carrying out ultrasonic impregnation to obtain Pt/Ni-Zn-Fe-LDH-A;
B. configuration threeDissolving Pt/Ni-Zn-Fe-LDH-A in ruthenium trichloride ethanol solution, wherein the mass ratio of the ruthenium in the ruthenium trichloride ethanol solution to the Ni-Zn-Fe-LDH-A added in the ruthenium trichloride ethanol solution is 0.3-2%, and performing ultrasonic impregnation to obtain Pt-Rux/Ni-Zn-Fe-LDH-A。
The hydrotalcite-like catalyst is applied to catalyzing hydrogenation reaction of halogenated nitrobenzene.
Further preferably, the hydrogenation reaction of the halogenated nitrobenzene is the hydrogenation reaction of the halogenated nitrobenzene under the solvent-free condition.
Preferably, in the hydrogenation reaction of the halogenated nitrobenzene, the mass ratio of the halogenated nitrobenzene to the hydrotalcite-like catalyst is 130-200: 1.
Preferably, the reaction temperature of the hydrogenation reaction of the halogenated nitrobenzene is 50-80 ℃.
Advantageous effects
(1) According to the catalyst adopted by the invention, the sodium hydroxide is used for treating the surface of the hydrotalcite-like compound, so that cation vacancies and active sites are exposed, the active components of the noble metal can be anchored better, and the loss is not easy to occur, so that the finally obtained target catalyst has excellent stability in hydrogenation reaction, and still has excellent conversion efficiency and selectivity after repeated use. And as the cation vacancy is used for anchoring the noble metal active component, the noble metal active center and the halogenated nitrobenzene generate an electronic effect, and the activation of a carbon-halogen bond is reduced, so that dehalogenation is reduced.
(2) The catalyst adopted by the invention is used for catalyzing the hydrogenation reaction of the halogenated nitrobenzene to prepare the o-chloroaniline, and the selectivity and the conversion rate are high.
(3) The catalyst adopted by the invention for preparing o-chloroaniline does not need to add a solvent or a dehalogenation inhibitor, thereby reducing the economic loss caused by the subsequent steps.
(4) The catalyst adopted by the invention has extremely low content of noble metal, high feeding ratio and high utilization ratio of the noble metal.
(5) The invention can complete the solvent-free hydrogenation of o-chloronitrobenzene at low temperature, the required temperature is 50-80 ℃, and the catalyst can still keep good selectivity and conversion rate at low temperature.
(6) The catalyst of the invention is easier to separate after catalyzing hydrogenation reaction of halogenated nitrobenzene.
Drawings
FIG. 1 SEM micrograph of Ni-Zn-Fe-LDH obtained in example 1 without alkali washing at 500 nm.
FIG. 2 Electron micrograph of 1. mu. SEM of Ni-Zn-Fe-LDH obtained in example 1 without alkaline washing.
FIG. 3 SEM photograph of 1 μm of alkali-washed Ni-Zn-Fe-LDH-5mol/L obtained in example 1.
FIG. 4 SEM photograph of Ni-Zn-Fe-LDH-5mol/L obtained in example 1 after alkali washing at 100 nm.
FIG. 5 XRD patterns of hydrotalcite-like catalysts or carriers according to examples 1 to 5.
FIG. 6 XRD pattern of Ni-Fe-LDH-5mol/L obtained in comparative example 6.
FIG. 7XRD pattern of Ni-Zn-Fe-LDH-5mol/L obtained in comparative example 7.
FIG. 8 is an eds scanning of the platinum element of the target catalyst obtained in example 4.
FIG. 9 eds surface scan of the ruthenium element of the target catalyst obtained in example 4.
FIG. 10 eds scanning chart of zinc element of the target catalyst obtained in example 4.
FIG. 11 is a scanning layered image of the platinum, ruthenium and zinc three-element eds of the target catalyst obtained in example 4.
Detailed Description
The following will clearly and completely describe the technical solutions in the specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Wherein the terms in the present specification have the following meanings:
halogenated nitrobenzene: can be chloronitrobenzene, bromonitrobenzene or iodonitrobenzene, and can be ortho-halogenated nitrobenzene, meta-halogenated nitrobenzene and para-halogenated nitrobenzene.
The present invention will be described in detail with reference to examples below to facilitate understanding of the present invention by those skilled in the art.
First, embodiments within the scope of the invention
Example 1
Preparation of the target catalyst:
preparing nickel-zinc-iron hydrotalcite in step (1): weighing 0.05mol of nickel nitrate hexahydrate, 0.01mol of zinc nitrate hexahydrate and 0.02mol of ferric nitrate nonahydrate, dissolving the three nitrates in 50mL of water to obtain a mixed salt solution, and carrying out ultrasonic oscillation for 15 minutes;
weighing 0.128mol of sodium hydroxide and 0.04mol of sodium carbonate, and dissolving in 50mL of water to obtain an alkali solution;
taking a 150mL three-neck flask, adding 40mL of distilled water as a base solution, respectively adding the mixed salt solution and the alkali solution into two constant-pressure titration funnels, controlling the pH of the solution in the flask to be 9-10 (controlling the flow rate of alkali), gradually dropwise adding the mixed salt solution and the alkali solution into the three-neck flask, stirring at the speed of 300rpm, controlling the temperature at 60 ℃ during dropwise adding, covering a cover after dropwise adding, continuously stirring and crystallizing at the speed of 300rpm at 60 ℃ for six hours, taking out a sample, washing with deionized water to be neutral, washing with alcohol once, drying the sample at the temperature of 80 ℃ to obtain the nickel-zinc-iron hydrotalcite, namely Ni-Zn-Fe-LDH, weighing and grinding for later use. SEM electron micrographs of the Ni-Zn-Fe-LDH obtained in the step are shown in figures 1 and 2, and as can be seen from figures 1 and 2, the Ni-Zn-Fe-LDH has a clear laminate structure, is clear and visible in appearance and is nano-scale;
XRD of Ni-Zn-Fe-LDH is shown in the bottom line of FIG. 5.
Alkali washing in step (2): preparing a 5mol/L sodium hydroxide aqueous solution, adding Ni-Zn-Fe-LDH into the sodium hydroxide aqueous solution according to the proportion of 1g of Ni-Zn-Fe-LDH-10mL of the sodium hydroxide aqueous solution, stirring at the rotating speed of 300rpm for 30min, filtering, washing with deionized water to be neutral, washing residual organic matters with ethanol, drying and weighing the sample at 80 ℃, and grinding to obtain the Ni-Zn-Fe-LDH-5 mol/L. SEM images of Ni-Zn-Fe-LDH-5mol/L are shown in FIGS. 3 and 4, and it can be seen from the SEM images that the structure of the laminate itself is clearly visible without significant debris, although alkali washing is performed.
XRD of Ni-Zn-Fe-LDH-5mol/L is shown in FIG. 5, which is the second line from bottom to top.
Loading active components in the step (3): taking 1g of Ni-Zn-Fe-LDH-5mol/L prepared in the step (2), taking chloroplatinic acid to prepare 4mL of chloroplatinic acid aqueous solution with platinum content of 0.3 percent, (wherein 0.3 percent refers to the mass ratio of platinum in the chloroplatinic acid aqueous solution to Ni-Zn-Fe-LDH-5mol/L added into the chloroplatinic acid aqueous solution), soaking 1g of Ni-Zn-Fe-LDH-5mol/L in the prepared 4mL of chloroplatinic acid aqueous solution, performing ultrasonic treatment for 15 minutes, soaking overnight, taking out the obtained product the next day, and drying to obtain Pt/Ni-Zn-Fe-LDH-5 mol/L;
preparing 4mL of ruthenium trichloride ethanol solution with the ruthenium content of 0.3 percent, (wherein 0.3 percent refers to the mass ratio of the mass of ruthenium in the ruthenium trichloride ethanol solution to the mass of Ni-Zn-Fe-LDH-5mol/L in the platinum-loaded catalyst added into the ruthenium trichloride ethanol solution, namely Ru/Ni-Zn-Fe-LDH-5mol/L), soaking the obtained Pt/Ni-Zn-Fe-LDH-5mol/L in 4mL of ruthenium trichloride ethanol solution, carrying out ultrasonic treatment for 15 minutes, soaking overnight, taking out and drying the obtained Pt-Rux/Ni-Zn-Fe-LDH-5mol/L。
And (4) reduction: after 0.5mol/L potassium borohydride solution is prepared, 1g of Pt-Ru is addedxadding/Ni-Zn-Fe-LDH-5 mol/L into the prepared 25ml potassium borohydride solution for reduction, and after reduction for 4 to 8 hours, removingWashing the product with water and ethanol, and drying to obtain the target catalyst.
The application comprises the following steps: catalytic hydrogenation of halonitrobenzene
0.05g of the target catalyst is taken, 8g of o-chloronitrobenzene is added, the mixture is added into a hydrogenation reaction kettle, the reaction temperature is set to be 50 ℃, the hydrogen pressure is set to be 1Mpa, the rotating speed is set to be 500rpm, the reaction lasts for 4 hours, and the conversion rate and the selectivity are shown in table 1.
Example 2
The content of the ruthenium trichloride ethanol solution in the step (3) of the preparation of the target catalyst was changed to 0.4%, and other preparation steps, conditions, the amounts of the related compounds, and other experimental operations of the target catalyst were completely the same as those in example 1.
The experimental procedure, conditions and the amounts of the relevant compounds employed were exactly the same as in example 1, the conversions and the selectivities are shown in Table 1.
Example 3
The content of the ruthenium trichloride ethanol solution in the step (3) of the preparation of the target catalyst was changed to 0.5%, and other preparation steps, conditions, the amounts of the related compounds, and other experimental operations of the target catalyst were completely the same as those in example 1.
The experimental procedure, conditions and the amounts of the relevant compounds employed were exactly the same as in example 1, the conversions and the selectivities are shown in Table 1.
Example 4
The content of the ruthenium trichloride ethanol solution in the step (3) of the preparation of the target catalyst was changed to 0.6%, and the experimental operations such as other preparation steps, conditions, and the amounts of the related compounds of the target catalyst were completely the same as those in example 1.
The experimental procedure, conditions and the amounts of the relevant compounds employed were exactly the same as in example 1, the conversions and the selectivities are shown in Table 1.
As shown in FIGS. 8 to 11, eds surface scans of the platinum element, ruthenium element, zinc element and the three elements of the target catalyst obtained in example 4 are respectively shown. As can be seen from the figure, both the platinum element and the ruthenium element show better dispersity on the surface scanning picture. It is demonstrated that even at lower loadings, higher dispersion of the active component can be achieved.
Example 5
The content of the ruthenium trichloride ethanol solution in the step (3) of the preparation of the target catalyst was changed to 0.7%, and other preparation steps, conditions, the amounts of the related compounds, and other experimental operations of the target catalyst were completely the same as those in example 1.
The experimental procedure, conditions and the amounts of the relevant compounds employed were exactly the same as in example 1, the conversions and the selectivities are shown in Table 1.
The XRD patterns of the target catalysts prepared in examples 1-5 are shown in FIG. 5, and the XRD curves of the target catalyst obtained in example 5, the target catalyst obtained in example 4, the target catalyst obtained in example 3, the target catalyst obtained in example 2, the target catalyst obtained in example 1, Ni-Zn-Fe-LDH obtained in example 1 and Ni-Zn-Fe-LDH-5mol/L obtained in example 1 are shown in the sequence from top to bottom in FIG. 5.
The target catalyst obtained in example 5, the target catalyst obtained in example 4, the target catalyst obtained in example 3, the target catalyst obtained in example 2, the target catalyst obtained in example 1, Ni-Zn-Fe-LDH obtained in example 1, and the specific surface area, pore volume and average pore diameter of Ni-Zn-Fe-LDH-5mol/L obtained in example 1 are shown in the following tables:
| crystal | Specific surface area | Pore volume | Average pore diameter |
| Ni-Zn-Fe-LDH | 78.0 | 0.378 | 16.2 |
| Ni-Zn-Fe-LDH-5mol/L | 110.1 | 0.326 | 11.1 |
| Catalyst obtained in example 1 | 88.5 | 0.317 | 12.3 |
| Example 2 the target catalyst | 88.4 | 0.316 | 12.3 |
| Catalyst obtained in example 3 | 100.6 | 0.384 | 13.0 |
| Example 4 the target catalyst | 97.7 | 0.422 | 14.3 |
| Catalyst obtained in example 5 | 94.8 | 0.390 | 13.4 |
Example 6
The preparation of the target catalyst was exactly the same as in example 4.
The experimental procedure, conditions and quantities of related compounds used were exactly the same as in example 4, except that in this example the temperature for catalyzing the hydrogenation of the halonitrobenzene was chosen to be 60 ℃ and the final conversion and selectivity are shown in table 1.
Example 7
The preparation of the target catalyst was exactly the same as in example 4.
The experimental procedure, conditions and quantities of related compounds used were exactly the same as in example 4, except that in this example the temperature for the catalytic hydrogenation of the halonitrobenzene was chosen to be 70 ℃ and the final conversion and selectivity are shown in table 1.
Example 8
The preparation of the target catalyst was exactly the same as in example 4.
The experimental procedure, conditions and quantities of related compounds used were exactly the same as in example 4, except that in this example the temperature for the catalytic hydrogenation of the halonitrobenzene was chosen to be 80 ℃ and the final conversion and selectivity are shown in table 1.
Example 9
In the preparation step (3) of the target catalyst, no platinum catalyst was supported, only 0.7% of ruthenium was supported, and the experimental operations of other preparation steps, conditions, and amounts of related compounds of the target catalyst were completely identical to those of example 1.
The experimental procedure, conditions and the amounts of the relevant compounds employed were exactly the same as in example 1, the conversions and the selectivities are shown in Table 1.
Example 10
In the preparation step (3) of the target catalyst, no ruthenium catalyst was supported, only 0.3% of platinum was supported, and the experimental operations of other preparation steps, conditions, and amounts of related compounds of the target catalyst were completely identical to those of example 1.
The experimental procedure, conditions and the amounts of the relevant compounds employed were exactly the same as in example 1, the conversions and the selectivities are shown in Table 1.
Example 11
In the preparation step (3) of the target catalyst, no platinum catalyst was supported, only 0.6% of ruthenium was supported, and the experimental operations of other preparation steps, conditions, and amounts of related compounds of the target catalyst were completely identical to those of example 1.
The experimental procedure, conditions and the amounts of the relevant compounds employed were exactly the same as in example 1, the conversions and the selectivities are shown in Table 1.
Example 12
Catalytic hydrogenation of the halonitrobenzene was carried out using the catalyst prepared in example 4.
Taking 0.05g of the target catalyst, adding 10g of o-chloronitrobenzene, adding into a hydrogenation reaction kettle, setting the reaction temperature to be 50 ℃, the hydrogen pressure to be 1Mpa, setting the rotating speed to be 500rpm, reacting for 4 hours, and obtaining the conversion rate and the selectivity shown in table 1.
TABLE 1 catalytic Effect of the catalysts obtained in examples 1 to 12
The selectivities in the above table refer to: [ molar amount of o-chloroaniline/(molar amount of o-chloroaniline + molar amount of aniline) ]
The conversion in the above table refers to: [ molar amount of o-chloroaniline + molar amount of aniline)/(original molar amount of o-chloronitrobenzene-remaining molar amount of o-chloronitrobenzene ]
Yield-selectivity-conversion.
As can be seen from the above table, the catalyst of the present invention is used to catalyze the hydrogenation of nitrohalogenated benzene to obtain selectivity and conversion rate of over 66%, and yield of over 66%.
Especially, the yield of the catalyst is more than 93% in examples 2-6 and 10, wherein the yield of examples 4-5 is not less than 98.9%, which is an unexpected good effect for the field, and shows that Pt0.3% -Ru0.6-0.7%, and the catalyst of the invention has the best catalytic performance when the reaction temperature is maintained at 50 ℃.
Example 13
The first step is as follows: the catalyst prepared in example 4 was used to catalyze the hydrogenation of halogenated nitrobenzene, 0.05g of the above target catalyst was added to 8g of o-chloronitrobenzene and added to a hydrogenation reactor, the reaction temperature was set at 50 ℃, the hydrogen pressure was set at 1Mpa, the rotation speed was set at 500rpm, and the reaction was carried out for 4 hours.
The second step is that: after the reaction, the catalyst was separated by magnetic adsorption to obtain a used catalyst.
The third step: the catalytic reaction of the first step is repeated further using the catalyst obtained by the separation. Namely: and adding 10g of o-chloronitrobenzene into the separated catalyst, adding the catalyst into a hydrogenation reaction kettle, setting the reaction temperature to be 50 ℃, setting the hydrogen pressure to be 1Mpa, setting the rotating speed to be 500rpm, and reacting for 4 hours.
The fourth step: and repeating the second step and the third step, and circulating in sequence to explore the repeated use performance of the catalyst designed by the invention.
The catalytic performance of the above catalyst per re-use is shown in the following table:
TABLE 2 results of repeated experiments on catalysts of the invention
From the above table, it can be seen that the catalyst prepared by the present invention can be reused for multiple times, and when the catalyst is reused for eight times, the catalyst still maintains extremely high selectivity and conversion rate.
Second, comparative example group
Comparative example 1
The preparation of the target catalyst was exactly the same as in example 1 except that platinum or ruthenium was not supported; the experimental procedure, conditions and the amounts of the relevant compounds employed are exactly the same as in example 1, the conversions and the selectivities are shown in Table 3.
Comparative example 2
The experimental procedure, conditions and the amounts of the related compounds used were exactly the same as in example 1, except that the catalyst used in the experimental application of this comparative example was 1% of a commercial platinum-carbon catalyst, the amount of the catalyst added was 0.1g, and the final conversion and selectivity are shown in Table 3.
Comparative example 3
The experimental procedure, conditions and amounts of related compounds used were exactly the same as in example 1, except that the catalyst used in the application experiment of this comparative example was 1% of commercial palladium on carbon catalyst, the amount of catalyst added was 0.1g, and the final conversion and selectivity are shown in Table 3.
Comparative example 4
The preparation of the target catalyst was the same as in example 4 except that the concentration of the sodium hydroxide solution in the alkali washing in step (2) was changed to 8mol/L and the other conditions were not changed.
The experimental procedure, conditions and the amounts of the related compounds applied using the catalyst obtained in this comparative example are exactly the same as in example 1, the final conversion and the selectivity are shown in table 3.
Comparative example 5
The preparation of the target catalyst was the same as in example 4, except that the alkaline washing step of step (2) was omitted and the other conditions were unchanged.
The experimental procedure, conditions and the amounts of the related compounds applied using the catalyst obtained in this comparative example are exactly the same as in example 1, the final conversion and the selectivity are shown in table 3.
Comparative example 6
The preparation of the objective catalyst was the same as in example 4 except that in this example, 0.06mol of nickel nitrate hydrate, 0mol of zinc nitrate hydrate, and 0.02mol of iron nitrate hydrate were used in step (1).
As shown in fig. 6, which is an XRD pattern of the nickel-iron hydrotalcite after alkaline washing obtained by using the above nitrate ratio, that is, an XRD pattern of Ni-Fe-LDH-5mol/L, it can be seen from observing the XRD pattern 6 that after the synthesized hydrotalcite is washed by sodium hydroxide in the absence of zinc, the characteristic peaks of the hydrotalcite still exist, but a large number of hetero-peaks appear, and the channels of the hydrotalcite are blocked by the debris with the appearance of a large number of hetero-crystals, and the carrier composition is complicated, so that the performance of the catalyst cannot be fully exerted.
The experimental procedure, conditions and the amounts of the related compounds applied using the target catalyst obtained in this comparative example are exactly the same as in example 1, and the final conversion and selectivity are shown in table 3.
Comparative example 7
The preparation of the objective catalyst was the same as in example 4 except that the mixed salt solution and the alkali solution in step (1) were gradually added dropwise into a three-necked flask, the dropping temperature and the crystallization temperature were controlled to 30 ℃, and the other conditions were not changed.
As shown in FIG. 7, which is an XRD pattern of the nickel-zinc-iron hydrotalcite after alkali washing obtained by using the above nitrate ratio, that is, an XRD pattern of Ni-Zn-Fe-LDH-5mol/L, when the XRD pattern of FIG. 7 is observed, it can be seen that there are too many hetero peaks, the peak positions are shifted to different degrees, the crystallinity is low, and a large amount of hetero crystals are included, so that it is not suitable for use as a catalyst carrier.
Comparative example 8
The preparation of the objective catalyst was the same as in example 4 except that the temperature of dropping the mixed salt solution and the alkali solution in step (1) was 100 ℃ and the crystallization temperature was also 100 ℃. In the dropping process, under the condition that the solution is continuously stirred, the concentration of the salt solution precursor fluctuates due to overhigh temperature, so that a large amount of impurity peaks appear in the hydrotalcite, and the crystallinity is also increased due to overhigh temperature, so that the further treatment is difficult.
TABLE 3 comparative examples 1-7 catalyst Performance tables
| Comparative example | Active component | Temperature of | Conversion rate of o-chloronitrobenzene | O-chloroaniline selectivity |
| Comparative example 1 | Is free of | 50 | 10.7％ | 99.3％ |
| Comparative example 2 | |
50 | 41.4％ | 97.0％ |
| Comparative example 3 | |
50 | 45.7％ | 97.0％ |
| Comparative example 4 | Pt0.3％-Ru0.6％ | 50 | 56.2％ | 81.1％ |
| Comparative example 5 | Pt0.3％-Ru0.6％ | 50 | 23.7％ | 99.6％ |
| Comparative example 6 | Pt0.3％-Ru0.6％ | 50 | 17.6％ | 99.7％ |
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The hydrotalcite-like catalyst is characterized by comprising a carrier and an active component loaded on the carrier, wherein the carrier is nickel-zinc-iron hydrotalcite, and the active component is selected from one or more of platinum group metals.
2. The method of preparing the hydrotalcite-like catalyst according to claim 1, wherein the method comprises the steps of:
(1) preparation of nickel-zinc-iron hydrotalcite: preparing nitrates of metal nickel, zinc and iron into mixed salt solution according to a proportion; preparing sodium carbonate and sodium hydroxide into an alkali solution according to a proportion; then preparing nickel-zinc-iron hydrotalcite by adopting a coprecipitation method or a hydrothermal synthesis method;
(2) alkali washing: putting the nickel-zinc-iron hydrotalcite obtained in the step (1) into a sodium hydroxide solution of 2-5 mol/L, stirring for 10-50 min, filtering, washing with water, and drying to obtain Ni-Zn-Fe-LDH-A;
(3) loading active components: loading an active component by an ultrasonic impregnation method to obtain an active component-Ni-Zn-Fe-LDH-A;
(4) reduction: reducing the active component-Ni-Zn-Fe-LDH-A obtained in the step (3) by using a reducing solution to obtain a target hydrotalcite-like catalyst; the reducing solution is selected from potassium borohydride, sodium borohydride or ascorbic acid.
3. The method of preparing hydrotalcite-like catalyst according to claim 2, wherein the mixed salt solution in step (1) has a concentration of nickel nitrate of 0.9mol/L to 1.1mol/L, a concentration of zinc nitrate of 0.18mol/L to 0.22mol/L, and a concentration of iron nitrate of 0.36mol/L to 0.44 mol/L.
4. The method of preparing hydrotalcite-like catalyst according to claim 3, wherein the mixed salt solution in step (1) has a concentration of nitrate of nickel of 1mol/L, a concentration of nitrate of zinc of 0.2mol/L, and a concentration of nitrate of iron of 0.4 mol/L.
5. The preparation method of the hydrotalcite-like catalyst according to any one of claims 2 to 4, wherein the nickel-zinc-iron hydrotalcite is prepared by a coprecipitation method in step (1), the mixed salt solution and the alkali solution are respectively subjected to ultrasound at 10 ℃ to 30 ℃ for 15min, a certain amount of distilled water is added into a container in advance as a base solution, the mixed salt solution and the alkali solution are simultaneously added into the base solution dropwise, the temperature during dropping is 60 ℃ to 100 ℃, the pH is controlled to be 9 to 10, stirring is performed, after the dropwise addition is completed, stirring and crystallization are continued at 60 ℃ to 100 ℃ for 6h to 10h, and filtering, washing and drying are performed to obtain the nickel-zinc-iron hydrotalcite.
6. The method for preparing hydrotalcite-like catalyst according to claim 2, wherein the active component in step (3) is one or both of platinum and ruthenium, and the supporting method is ultrasonic impregnation.
7. The method for preparing a hydrotalcite-like catalyst according to claim 6, wherein the active components in step (3) are platinum and ruthenium, and the supporting step comprises:
A. preparing chloroplatinic acid aqueous solution by taking chloroplatinic acid, putting Ni-Zn-Fe-LDH-A in the chloroplatinic acid aqueous solution, wherein the mass ratio of platinum in the chloroplatinic acid aqueous solution to Ni-Zn-Fe-LDH-A added into the chloroplatinic acid aqueous solution is 0.3-2%, and carrying out ultrasonic impregnation to obtain Pt/Ni-Zn-Fe-LDH-A;
B. preparing ruthenium trichloride ethanol solution, dissolving Pt/Ni-Zn-Fe-LDH-A in the ruthenium trichloride ethanol solution, and ultrasonically dipping, wherein the mass ratio of the mass of ruthenium in the ruthenium trichloride ethanol solution to the mass of Ni-Zn-Fe-LDH-A added into the ruthenium trichloride ethanol solution is 0.3-2%, so as to obtain Pt-Rux/Ni-Zn-Fe-LDH-A。
8. The use of the hydrotalcite-like catalyst of claim 1 for catalyzing the hydrogenation of halonitrobenzene.
9. The application of claim 8, wherein in the hydrogenation reaction of the halogenated nitrobenzene, the mass ratio of the halogenated nitrobenzene to the hydrotalcite-like catalyst is 130-200: 1.
10. The use according to claim 8, wherein the reaction temperature of the hydrogenation of the halogenated nitrobenzene is between 50 ℃ and 80 ℃.
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|---|---|---|---|---|
| CN114984977A (en) * | 2022-06-20 | 2022-09-02 | 重庆师范大学 | Hydrotalcite-like compound loaded PtM catalyst, and preparation method and application thereof |
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