CN114289034B - Noble metal catalyst, preparation method and application thereof in preparation of toluenediamine by catalyzing hydrogenation of dinitrotoluene - Google Patents
Noble metal catalyst, preparation method and application thereof in preparation of toluenediamine by catalyzing hydrogenation of dinitrotoluene Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 63
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 151
- 150000003839 salts Chemical class 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052697 platinum Inorganic materials 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 150000002940 palladium Chemical class 0.000 claims description 11
- 150000003057 platinum Chemical class 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 150000003751 zinc Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 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 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- 150000003376 silicon Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000002828 nitro derivatives Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 49
- 229910052763 palladium Inorganic materials 0.000 abstract description 29
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005470 impregnation Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 25
- 239000006227 byproduct Substances 0.000 description 20
- 208000012839 conversion disease Diseases 0.000 description 18
- 238000005070 sampling Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013058 crude material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a noble metal catalyst and a preparation method thereof and application thereof in preparing toluenediamine by catalyzing dinitrotoluene hydrogenation, wherein the catalyst comprises a carrier and a metal active component; wherein the carrier is silicon-containing salt of a sulfuric acid boiler; the metal active component includes Pd, pt, fe, zn. The catalyst is prepared by adopting an impregnation method, takes silicon-containing salt in a sulfuric acid boiler as a carrier, is reduced at a lower temperature after being impregnated by a noble metal salt solution, and is obtained after filtration, washing and drying. The catalyst has stronger hydrogenation activity and selectivity, is very suitable for catalyzing dinitrotoluene hydrogenation to prepare toluenediamine, and can improve the catalytic reaction speed, the conversion rate of the reaction and the selectivity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a noble metal catalyst, a preparation method and application thereof in production of toluenediamine.
Background
Toluene Diamine (TDA), also known as diaminotoluene, is a main raw material for preparing Toluene Diisocyanate (TDI), and further, polyurethane materials are prepared and applied to industries such as construction, medical treatment and the like.
Toluenediamine is generally converted from Dinitrotoluene (DNT) and is currently produced industrially mainly by liquid-phase catalytic hydrogenation. Wherein the catalyst is an important core for preparing toluenediamine by catalytic hydrogenation of dinitrotoluene, and two types of catalysts are commonly used in the industry at present: 1) The supported noble metal catalyst has Pd and Pt as main metals and is supported on porous alumina, active carbon, carbon black and other carrier. Generally, the catalyst has mild reaction conditions and higher reaction activity at low pressure, but the cost is higher due to the content of the supported noble metal and the loss amount; 2) Raney nickel (Raney-Ni) catalyst has low price, but has high reaction pressure (more than 2 MPa) in catalytic hydrogenation, impurities remain in the preparation process, and the catalyst has natural risk.
Patent CN 105435808A proposes a carbon black catalyst for preparing palladium, platinum and iron, which has higher conversion rate when being applied to nitrobenzene hydrogenation, but the preparation method adopts one-time adsorption and reduction, and the noble metal loaded is easy to run off after multiple uses. In the patent CN 110538651A, the noble metal Pt supported by the modified superfine carbon black carrier is used as a catalyst and applied to the hydrogenation of nitro compounds, but the noble metal is single in type, no other metal is used for assisting in dispersing and reinforcing the noble metal, the catalysis of the noble metal is not fully exerted, and the metal supporting strength is required to be further reinforced. Meanwhile, in the existing process for preparing toluenediamine by taking a noble metal catalyst as a main component, the tar content is generally more than 1%, and the optimization space for further reducing the tar content is also provided.
In the process of preparing dinitrotoluene, toluene and concentrated nitric acid react under the catalysis of concentrated sulfuric acid to generate dinitrotoluene, and then the concentrated sulfuric acid is changed into dilute sulfuric acid, and the dilute sulfuric acid is concentrated into concentrated sulfuric acid by a sulfuric acid boiler so as to be recycled. However, in the sulfuric acid concentration process, because the boiler is in a sulfuric acid environment for a long time, salt formation occurs in the boiler, the components of the boiler are mainly silicon salt, the annual generation amount of the silicon-containing salt formation in the sulfuric acid boiler can reach about 500kg by one set of dinitrotoluene production device with the scale of 36 ten thousand tons, but the silicon-containing salt formation is mainly used as solid waste treatment at present, and the problems of resource waste and environmental pollution exist. Therefore, a reasonable mode is sought to recover the silicon-containing salt in the sulfuric acid boiler, and the method has important significance in realizing the reutilization of resources.
Disclosure of Invention
Aiming at the problems in the prior art, the main purpose of the invention is to provide a reinforced noble metal catalyst and a preparation method thereof, wherein the catalyst takes silicon-containing salt of a sulfuric acid boiler as a carrier, so that reasonable recycling of resources can be realized, the highly dispersed supported noble metal catalyst is obtained at a lower reduction temperature by an impregnation method, and the catalyst has the advantages of high loading strength of active components, low loss rate of noble metals, high specific surface area, high mechanical strength, low cost and the like.
The catalyst has stronger hydrogenation activity and selectivity, is very suitable for catalyzing dinitrotoluene hydrogenation to prepare toluenediamine, and can improve the catalytic reaction speed, the conversion rate of the reaction and the selectivity.
The experiment of the invention finds that a container (hereinafter collectively referred to as a sulfuric acid boiler) made of glass lining material and the like contacted with sulfuric acid can react with hot concentrated sulfuric acid, silicate is gradually precipitated on the surface, and the thickness of salt is gradually increased as time is accumulated, so that the salt-forming structure generated in the environment is uniform, the preparation requirement of the catalyst carrier is met, and the catalyst carrier with concentrated particle size distribution and high specific surface area can be obtained more easily under high-temperature roasting.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a noble metal catalyst, which comprises a carrier and a metal active component;
wherein the carrier is silicon-containing salt of a sulfuric acid boiler;
the metal active component comprises palladium (Pd), platinum (Pt), iron (Fe) and zinc (Zn).
The noble metal catalyst comprises the following components in percentage by mass:
in the present invention, the above-mentioned mass percentages of the metal active components in calculating the composition of the mass percentages refer to the mass of the metal element represented by the active component in the compound containing the active component, for example, if the palladium element exists in the form of chloride (palladium chloride), the mass percentages of the palladium are calculated only by the mass of the "palladium element" therein, for example, if the palladium element exists in the form of pure metal simple substance, the mass percentages of the palladium are calculated by the mass of the simple substance thereof. In the noble metal catalyst of the invention, the palladium element, the platinum element, the iron element and the zinc element mainly exist in the form of pure metal simple substances.
The noble metal catalyst takes silicon-containing salt of a sulfuric acid boiler as a carrier, and the silicon-containing salt of the sulfuric acid boiler comprises, by mass, 100% of silicon (Si) 40-50%, iron (Fe) 0.9-2%, aluminum (AL) 0.9-2%, manganese (Mn) 0.01-0.1%, nickel (Ni) 0.01-0.1% and chromium (Cr) 0.01-0.1%. The silicon-containing salt formation of the sulfuric acid boiler refers to salt formation generated in equipment in a sulfuric acid environment for a long time, for example, in the process of preparing dinitrotoluene, toluene and concentrated nitric acid react under the catalysis of concentrated sulfuric acid to generate dinitrotoluene, then the concentrated sulfuric acid is changed into dilute sulfuric acid, and the dilute sulfuric acid is concentrated into concentrated sulfuric acid through a sulfuric acid boiler so as to be recycled. However, in the sulfuric acid concentration process, since the boiler is in a sulfuric acid environment for a long time, salt formation occurs in the boiler, and the salt formation takes silicon salt as a main component, and is derived from a boiler lining made of glass lining materials, and also contains other metal elements such as Fe, AL, mn, ni, cr and the like derived from a reactor and a pipeline made of stainless steel and the like. In addition, the alloy may contain trace elements such as Ta, etc. depending on the material of the device. The contents of various components in the siliceous salt deposit of the sulfuric acid boiler are greatly different due to the different furnace types, materials and processes. The silicon-containing salt-forming composition of the sulfuric acid boiler can realize the catalytic effect only if the composition meets the requirements.
Preferably, the sulfuric acid boiler contains silicon salt, and when the sulfuric acid boiler is used for preparing the catalyst, the sulfuric acid boiler contains silicon salt after pretreatment, wherein the pretreatment comprises acidification, oxidation and roasting treatment processes;
preferably, in some embodiments, the pretreatment method comprises: grinding the crude silicon-containing salt of the sulfuric acid boiler into powder, then adding acetic acid for acidification treatment, washing with water, then adding hydrogen peroxide for oxidation treatment, and finally washing with water, drying and roasting to obtain the silicon-containing salt carrier of the sulfuric acid boiler;
preferably, the crude material containing silicon and salt of the sulfuric acid boiler is ground into powder with the particle size of 10-20 mu m;
preferably, when acetic acid acidification treatment is adopted, the mass ratio of the acetic acid to the silicon-containing salt of the sulfuric acid boiler is 1:0.5-2, more preferably 1:0.5-1; the acidification treatment temperature is 15-30 ℃ and the time is 4-6h; the acetic acid is aqueous solution with the concentration of 10-50wt%;
preferably, when hydrogen peroxide is adopted for oxidation treatment, the mass ratio of the hydrogen peroxide to the silicon-containing salt of the sulfuric acid boiler is 1:0.5-2, more preferably 1:0.5-1; the oxidation treatment temperature is 15-30 ℃ and the time is 4-6h; the concentration of the hydrogen peroxide is 20-40wt%;
the water washing, drying and roasting are conventional in the field, preferably the drying temperature is 100-150 ℃ and the drying time is 2-3h; preferably, the roasting temperature is 300-500 ℃ and the roasting time is 4-7h.
In the invention, the silicon-containing salt-forming carrier of the sulfuric acid boiler pretreated by the method has an average particle size of 10-20 mu m, preferably 13-17 mu m; specific surface area of 100-300m 2 /g, preferably 150-230m 2 /g; pore volume of 0.8-1.6cm 3 Preferably 1.2-1.6cm 3 /g。
The invention also provides a preparation method of the noble metal catalyst, which comprises the following steps:
pretreating the siliceous salt of the sulfuric acid boiler to obtain a siliceous salt carrier of the sulfuric acid boiler;
mixing palladium salt, platinum salt, ferric salt and zinc salt with a solvent to prepare a mixed metal salt solution, adding a pretreated silicon-containing salt-forming carrier of a sulfuric acid boiler into the mixed metal salt solution, adding ammonia water to regulate the PH, and stirring and impregnating;
adding a reducing agent into the mixture at the temperature of 0-10 ℃ for reduction reaction, then carrying out ultrasonic standing, washing with water and drying to obtain the noble metal catalyst.
In the preparation method of the invention, the pretreatment is the process of acidification, oxidation and roasting, and is not repeated here.
In the preparation method of the invention, the palladium salt is selected from palladium chloride (PdCl 2 ) Sodium palladium tetrachloride (Na) 2 PdCl 4 ) Any one or two of the following combinations;
the platinum salt is selected from chloroplatinic acid (H) 2 PtCl 6 ·6H 2 O), platinum tetrachloride (PtCl) 4 ) Any one or two of the following combinations;
the ferric salt is selected from ferric chloride (FeCl) 3 ·6H 2 O), ferric sulfate (Fe (SO) 4 ) 3 ·7H 2 O) any one or two combinations;
the zinc salt is selected from zinc chloride (ZnCl) 2 ) Zinc sulfate (ZnSO) 4 ) Any one or two of the following combinations;
preferably, the palladium salt, platinum salt, ferric salt and zinc salt are calculated according to the metal active component elements, and the mass ratio is (0.5-10): (0.44-10): (0.8-10): (0.2-10), preferably (0.7-5): (0.44-3): (3-5): (3-5).
In the preparation method of the invention, the solvent is selected from any one or a combination of at least two of water, ethanol, glycol and the like, and is preferably water-ethanol solution;
preferably, the solvent is used in an amount of 50 to 200 times, preferably 50 to 160 times, the total mass of the palladium salt, the platinum salt, the iron salt and the zinc salt.
In the preparation method of the invention, the concentration of the ammonia water is 10-50wt%, preferably 20-50wt%, and the pH value is adjusted to 8-12, preferably 9-11;
in the preparation method of the invention, the temperature of the dipping process is 15-30 ℃, preferably 20-25 ℃ and the time is 2-6 hours, preferably 4-6 hours.
Preferably, during impregnation, the mass ratio of the silicon-containing salt-forming carrier to the mixed metal salt solution of the sulfuric acid boiler is 1:20-50, preferably 1:20-30.
In the preparation method of the invention, the reducing agent is selected from any one or at least two of formaldehyde, hydrazine hydrate, sodium sulfite and the like; preferably, the reducing agent is formulated for use as an aqueous solution having a concentration of 10-50 wt%;
preferably, the mass ratio of the addition amount of the reducing agent to the silicon-containing salt-forming carrier of the sulfuric acid boiler is 1:0.02-0.1, preferably 1:0.05-0.1.
In the preparation method of the invention, the reduction reaction is carried out at a temperature of 0-20 ℃, preferably 5-15 ℃ for 2-6 hours, preferably 3-5 hours.
In the preparation method, after the reduction reaction is completed, ultrasonic standing, water washing and drying treatment are further included, and the preparation method is a conventional operation in the field, wherein the ultrasonic standing preferably comprises the following conditions: the frequency is 28-40KHz, the temperature is 15-30 ℃ and the time is 1-2h.
The invention also provides the application of the noble metal catalyst, which can be used for the catalytic hydrogenation reaction of nitro compounds, and is especially suitable for preparing toluenediamine by catalyzing the hydrogenation of dinitrotoluene.
Preferably, the invention provides a method for preparing toluenediamine by hydrogenation of dinitrotoluene, which is carried out in a continuous full-mixing kettle type reactor, and the toluenediamine is prepared by hydrogenation reaction of dinitrotoluene and hydrogen raw materials by adopting the noble metal catalyst.
Preferably, the mass ratio of hydrogen to dinitrotoluene (hydrogen oil) is 1:10-15.
Preferably, the pressure of the hydrogen is 0.65-1.0Mpa (a), preferably 0.7-0.9Mpa (a);
preferably, the temperature of the hydrogenation reaction is 100-120 ℃, preferably 110-120 ℃; the mass space velocity is 5-30kg dnt/(kg catalyst) h, preferably 5-20kg dnt/(kg catalyst) h;
preferably, the hydrogenation reaction is carried out with stirring at a rotational speed of 800-1000rpm. The preparation process of the noble metal catalyst can greatly strengthen the performance of the catalyst, reduce the problem of higher use cost of the conventional noble metal catalyst, and can reduce the conversion rate and selectivity to more than 99% and the selectivity of byproduct tar to less than 1% when catalyzing the hydrogenation of dinitrotoluene to prepare toluenediamine.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method adopts the silicon-containing salt in the treated sulfuric acid boiler as the catalyst carrier, the salt has uniform texture, the catalyst porous carrier with concentrated particle size distribution and high specific surface area is easier to obtain after treatment, the salt of the sulfuric acid boiler also has other metal elements such as Fe, AL, mn, ni, cr and the like, and the salt cooperates with noble metals Pd and Pt, so that better hydrogenation performance can be realized, the loading strength of active components can be enhanced, the service life of the catalyst is prolonged, the waste recovery and the resource recycling are realized, and the cost is reduced.
(2) In the catalyst, the proper proportion of Fe and Zn is added to assist in noble metal dispersion, so that the catalyst prepared at a lower temperature has higher noble metal loading strength and noble metal dispersibility, the noble metal loss rate in the use process of the catalyst is reduced, the hydrogenation selectivity is enhanced, the addition of Fe and Zn is assisted, the cost is further reduced, and the hydrogenation activity of the noble metal is enhanced, so that when the catalyst is used for preparing toluene diamine through hydrogenation, the reaction activity and selectivity are high, and the selectivity of byproduct tar can be reduced to below 1%.
Detailed Description
The technical scheme and beneficial effects of the present invention are further described below with reference to examples, but the present invention is not limited to the following examples.
The embodiment of the invention adopts main raw material source information:
the crude material containing silicon and salt for the sulfuric acid boiler is as follows: the composition of the internal salt deposit from the lining boiler made of glass lining material in the Wanhua dinitrotoluene device comprises 40-50wt% of Si, 0.9-2wt% of Fe, 0.9-2wt% of AL, 0.01-0.1wt% of Mn, 0.01-0.1wt% of Ni and 0.01-0.1wt% of Cr.
Other principles such as palladium salt, platinum salt, ferric salt, zinc salt, acetic acid, hydrogen peroxide and the like are all obtained by purchasing through commercial paths and are all of chemical purity grade unless specifically indicated.
The catalyst characterization method adopted by the embodiment of the invention comprises the following steps:
specific surface area and pore volume: performing N2 adsorption-desorption test on the catalyst by adopting a BELSORP-II type adsorption instrument of BEL company in Japan, firstly dehydrating a sample in vacuum at 250 ℃ for 4 hours, calculating the specific surface area by a BET equation, and calculating the pore volume of the catalyst by using a BJH model;
average particle diameter: the catalyst particle size was analyzed using a HELOS 1BF type particle sizer from New Patag, germany.
Example 1
1) Preparation of noble metal catalyst:
10g of siliceous salt of a sulfuric acid boiler (comprising 44.8wt% of Si, 1.09wt% of Fe, 1.27wt% of AL, 0.04wt% of Mn, 0.02wt% of Ni and 0.01wt% of Cr) is ground into powder with the particle size of 10-20 mu m, 200g of aqueous solution of acetic acid with the concentration of 10wt% is added, acidizing treatment is carried out at 25 ℃ for 4 hours, deionized water is washed, 100g of hydrogen peroxide with the concentration of 20wt% is added, oxidizing treatment is carried out at 25 ℃ for 4 hours, deionized water is washed, drying is carried out at 150 ℃ for 2 hours, and high-temperature roasting is carried out at 300 ℃ for 4 hours, thus obtaining the siliceous salt carrier of the sulfuric acid boiler.
The test shows that the average grain diameter of the carrier is 14 mu m, and the specific surface area of the carrier is 200m 2 Per g, pore volume of the support is 1.2cm 3 /g。
0.73g of palladium chloride, 0.12g of chloroplatinic acid, 2.42g of ferric chloride hexahydrate, 1.04g of zinc chloride were weighed and dissolved in 250g of a water-ethanol solution (the mass ratio of water to ethanol is 1:4), and the metal salt was sufficiently dissolved by stirring to form about 252g of a mixed metal salt solution. Then 10g of pretreated siliceous salt-forming carrier of a sulfuric acid boiler is added, 20wt% ammonia water is added dropwise under stirring to adjust the PH value to 9, and the mixture is stirred and immersed for 4 hours at 25 ℃.
The system was cooled to 5℃and 200g of a 50wt% hydrazine hydrate solution was slowly added thereto and the reduction reaction was stirred at 5℃for 3 hours. Then, after ultrasonic standing for 1h at the frequency of 40KHz at 25 ℃, washing with water and drying to obtain the noble metal catalyst.
The noble metal catalyst comprises the following components in percentage by mass through testing: the carrier 85.16%, 4.4% of palladium element, 0.44% of platinum element, 5% of iron element and 5% of zinc element, and the palladium, platinum, iron and zinc exist in the form of pure metal simple substances.
2) Hydrogenation of dinitrotoluene to produce toluenediamine:
in a continuous full-mixing kettle reactor, feeding hydrogen at 0.54NL/min and 0.75MPa, and feeding hydrogen to dinitrotoluene at a mass ratio of 1:14, adding 3g of the noble metal catalyst prepared in the step 1), wherein the reaction temperature is 115 ℃, the stirring rotation speed is 800rpm, and the mass space velocity is 13.4kg DNT/(kg catalyst). After 15h of reaction, sampling and testing, the reaction conversion rate is 99.99%, the selectivity is 99.2%, the byproduct tar selectivity is 0.76%, and Pd and Pt in the catalyst are basically not lost after the reaction.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 99.2%, the byproduct tar selectivity is 0.78%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.05% and 0.02%.
Example 2
1) Preparation of noble metal catalyst:
10g of siliceous salt (comprising 44.1wt% of Si, 1.71wt% of Fe, 1.42wt% of AL, 0.02wt% of Mn, 0.04wt% of Ni and 0.05wt% of Cr) of a sulfuric acid boiler is ground into powder with the particle size of 10-20 mu m, 150g of acetic acid aqueous solution with the concentration of 10wt% is added, acidizing treatment is carried out at 20 ℃ for 5h, deionized water washing is carried out, 75g of hydrogen peroxide with the concentration of 20wt% is added, oxidizing treatment is carried out at 20 ℃ for 5h, deionized water washing is carried out, drying is carried out at 100 ℃ for 3h, and then high-temperature roasting is carried out at 400 ℃ for 5h, thus obtaining the siliceous salt carrier of the sulfuric acid boiler.
The test shows that the average grain diameter of the carrier is 13 μm, and the specific surface area of the carrier is 215m 2 Per g, pore volume of the support is 1.5cm 3 /g
1.33g of palladium chloride, 0.79g of chloroplatinic acid, 1.45g of ferric chloride hexahydrate, 0.63g of zinc chloride and dissolved in 250g of water-ethanol solution (the mass ratio of water to ethanol is 1:4) were weighed, and the metal salt was sufficiently dissolved by stirring to form about 254g of mixed metal salt solution. Then 10g of pretreated siliceous salt-forming carrier of a sulfuric acid boiler is added, 30wt% ammonia water is added dropwise under stirring to adjust the PH value to 10, and the mixture is stirred and immersed for 5h at 20 ℃.
The system was cooled to 10℃and 300g of a 50wt% hydrazine hydrate solution was slowly added thereto and the reduction reaction was stirred at 10℃for 4 hours. Then, after ultrasonic standing for 2 hours at the frequency of 35KHz at 15 ℃, washing with water and drying to prepare the noble metal catalyst.
The noble metal catalyst comprises the following components in percentage by mass through testing: 83% of carrier, 8% of palladium element, 3% of platinum element, 3% of iron element and 3% of zinc element, and palladium, platinum, iron and zinc exist in the form of pure metal simple substances.
2) Hydrogenation of dinitrotoluene to produce toluenediamine:
in a continuous full-mixing kettle reactor, feeding hydrogen at 0.54NL/min and 0.7MPa, and feeding hydrogen to dinitrotoluene at a mass ratio of 1:12, adding 2g of the noble metal catalyst prepared in the step 1), wherein the reaction temperature is 120 ℃, the stirring rotation speed is 800rpm, and the mass space velocity is 17.3kg DNT/(kg catalyst) h. After 15h of reaction, sampling and testing, the reaction conversion rate is 99.99%, the selectivity is 99.3%, the byproduct tar selectivity is 0.7%, and Pd and Pt in the catalyst are basically not lost after the reaction.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 99.2%, the byproduct tar selectivity is 0.75%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.06% and 0.03%.
Example 3
1) Preparation of noble metal catalyst:
10g of siliceous salt (comprising 44.81wt% of Si, 1.42wt% of Fe, 0.95wt% of AL, 0.03wt% of Mn, 0.01wt% of Ni and 0.02wt% of Cr) of a sulfuric acid boiler is ground into powder with the particle size of 10-20 mu m, 100g of acetic acid aqueous solution with the concentration of 10wt% is added, acidizing is carried out at 15 ℃ for 6 hours, deionized water is washed, 50g of hydrogen peroxide with the concentration of 20wt% is added, oxidizing treatment is carried out at 15 ℃ for 6 hours, deionized water is washed, drying is carried out at 130 ℃ for 2.5 hours, and then high-temperature roasting is carried out at 500 ℃ for 6 hours, thus obtaining the siliceous salt carrier of the sulfuric acid boiler.
The test shows that the average grain diameter of the carrier is 15 mu m, and the specific surface area of the carrier is 190m 2 Per g, pore volume of the support is 1.3cm 3 /g。
0.33g of palladium chloride, 0.80g of chloroplatinic acid, 0.48g of ferric chloride hexahydrate and 0.21g of zinc chloride are weighed and dissolved in 250g of water-ethanol solution (the mass ratio of water to ethanol is 1:4), and the metal salt is fully dissolved by stirring to form about 252g of mixed metal salt solution. Then 10g of pretreated siliceous salt-forming carrier of a sulfuric acid boiler is added, 50wt% ammonia water is added dropwise under stirring to adjust the PH value to 11, and the mixture is stirred and immersed for 6h at 25 ℃.
The system was cooled to 15℃and 400g of a 50wt% hydrazine hydrate solution was slowly added thereto and the reduction reaction was stirred at 15℃for 5 hours. Then, after ultrasonic standing for 2 hours at the frequency of 30KHz at 20 ℃, washing with water and drying to prepare the noble metal catalyst.
The noble metal catalyst comprises the following components in percentage by mass through testing: 94% of carrier, 1% of palladium element, 3% of platinum element, 1% of iron element and 1% of zinc element, and palladium, platinum, iron and zinc exist in the form of pure metal simple substances.
2) Hydrogenation of dinitrotoluene to produce toluenediamine:
in a continuous full-mixing kettle reactor, feeding hydrogen at 0.54NL/min and 0.85MPa, and feeding hydrogen to dinitrotoluene at a mass ratio of 1:10, adding 5g of the noble metal catalyst prepared in the step 1), wherein the reaction temperature is 110 ℃, the stirring rotation speed is 800rpm, and the mass space velocity is 5.7kg DNT/(kg catalyst) h. After 15h of reaction, sampling and testing, the reaction conversion rate is 99.99%, the selectivity is 99.1%, the byproduct tar selectivity is 0.81%, and Pd and Pt in the catalyst are basically not lost after the reaction.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 99.1%, the byproduct tar selectivity is 0.83%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.02% and 0.04%.
Comparative example 1
The process of reference example 1 differs only in that: in the step 1), the pretreated silicon-containing salt-forming carrier of the sulfuric acid boiler is replaced by active carbon with the same mass as the carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by the hydrogenation of dinitrotoluene in the step 2), after 15 hours of reaction, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 98.5%, the byproduct tar selectivity is 1.39%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.03wt% and 0.01wt%.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.98%, the selectivity is 98.4%, the byproduct tar selectivity is 1.49%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.12% and 0.07%.
Comparative example 2
The process of reference example 1 differs only in that: in the step 1), the pretreated silicon-containing salt-forming carrier of the sulfuric acid boiler is replaced by silicon dioxide with the same mass as the carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by the hydrogenation of dinitrotoluene in the step 2), after 15 hours of reaction, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 98.5%, the byproduct tar selectivity is 1.39%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.04wt% and 0.01wt%.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.98%, the selectivity is 98.4%, the byproduct tar selectivity is 1.55%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.11% and 0.07%.
Comparative example 3
The process of reference example 1 differs only in that: in the step 1), the pretreated silicon-containing salt-forming carrier of the sulfuric acid boiler is replaced by silica gel with the same mass as the carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by the hydrogenation of dinitrotoluene in the step 2), after 15 hours of reaction, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 98.5%, the byproduct tar selectivity is 1.40%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.03wt% and 0.02wt%.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.98%, the selectivity is 98.4%, the byproduct tar selectivity is 1.53%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.13% and 0.08%.
Comparative example 4
The process of reference example 1 differs only in that: in the step 1), the pretreated siliceous salt carrier of the sulfuric acid boiler is replaced by diatomite with the same mass as the carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by the hydrogenation of dinitrotoluene in the step 2), after 15 hours of reaction, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 98.4%, the byproduct tar selectivity is 1.49%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.05wt% and 0.02wt%.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.98%, the selectivity is 98.3%, the byproduct tar selectivity is 1.55%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.13% and 0.07%.
Comparative example 5
The process of reference example 1 differs only in that: and (3) adding no zinc chloride into the mixed metal salt solution in the step (1), and carrying out other operation unchanged to obtain the catalyst.
The prepared catalyst is used for preparing toluenediamine by the hydrogenation of dinitrotoluene in the step 2), after 15 hours of reaction, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 98.4%, the byproduct tar selectivity is 1.45%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.05wt% and 0.04wt%.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.98%, the selectivity is 98.3%, the byproduct tar selectivity is 1.56%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.15% and 0.1%.
Comparative example 6
The process of reference example 1 differs only in that: and (3) adding no ferric chloride hexahydrate into the mixed metal salt solution in the step (1), and carrying out other operation unchanged to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by the hydrogenation of dinitrotoluene in the step 2), after 15 hours of reaction, sampling test is carried out, the reaction conversion rate is 99.99%, the selectivity is 98.4%, the byproduct tar selectivity is 1.42%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.04wt% and 0.03wt%.
After the reaction is continued for 100 hours, sampling test is carried out, the reaction conversion rate is 99.98%, the selectivity is 98.3%, the byproduct tar selectivity is 1.52%, and the loss rates of Pd and Pt in the catalyst after the reaction are respectively 0.11% and 0.09%.
Claims (39)
1. A noble metal catalyst characterized by comprising a carrier and a metal active component;
wherein the carrier is a siliceous salt of a sulfuric acid boiler, and the siliceous salt of the sulfuric acid boiler comprises 40-50% of silicon, 0.9-2% of iron, 0.9-2% of aluminum, 0.01-0.1% of manganese, 0.01-0.1% of nickel and 0.01-0.1% of chromium by taking the siliceous salt as 100% of the siliceous salt;
the metal active component comprises palladium element, platinum element, iron element and zinc element.
2. The noble metal catalyst of claim 1, wherein the composition by mass comprises:
3. the noble metal catalyst of claim 2, wherein the composition by mass comprises:
4. the noble metal catalyst of claim 1, wherein the sulfuric acid boiler comprises a siliceous salt, which has been pretreated, and wherein the pretreatment comprises acidification, oxidation, and calcination.
5. The noble metal catalyst according to claim 4, wherein the pretreated carrier of the sulfuric acid boiler containing silicon salt has an average particle diameter of 10-20 μm and a specific surface area of 100-300m 2 Per g, pore volume of 0.8-1.6cm 3 /g。
6. The noble metal catalyst of claim 5, wherein the average particle size is from 13 to 17 μm.
7. The noble metal catalyst of claim 5, wherein the specific surface area is 150-230m 2 /g。
8. The noble metal catalyst of claim 5, wherein the pore volume is from 1.2cm to 1.6cm 3 /g。
9. The noble metal catalyst of claim 4, wherein the pretreatment process comprises: grinding the crude silicon-containing salt of the sulfuric acid boiler into powder, adding acetic acid for acidification treatment, washing with water, adding hydrogen peroxide for oxidation treatment, and finally washing with water, drying and roasting to obtain the silicon-containing salt carrier of the sulfuric acid boiler.
10. The noble metal catalyst of claim 9, wherein the sulfuric acid boiler siliceous salt-forming coarse material is ground to a powder having a particle size of 10-20 μm.
11. The noble metal catalyst of claim 9, wherein when acetic acid acidification is adopted, the mass ratio of acetic acid to sulfuric acid boiler silicon-containing salt is 1:0.5-2; the acidification treatment temperature is 15-30 ℃ and the time is 4-6h; the acetic acid is aqueous solution with the concentration of 10-50wt%.
12. The noble metal catalyst of claim 11, wherein when acetic acid acidification is used, the mass ratio of acetic acid to sulfuric acid boiler siliceous salt is 1:0.5-1.
13. The noble metal catalyst of claim 9, wherein when the hydrogen peroxide is used for oxidation treatment, the mass ratio of the hydrogen peroxide to the silicon-containing salt of the sulfuric acid boiler is 1:0.5-2; the oxidation treatment temperature is 15-30 ℃ and the time is 4-6h; the concentration of the hydrogen peroxide is 20-40wt%.
14. The noble metal catalyst of claim 9, wherein when the hydrogen peroxide is used for oxidation treatment, the mass ratio of the hydrogen peroxide to the silicon-containing salt of the sulfuric acid boiler is 1:0.5-1.
15. The noble metal catalyst of claim 9, wherein the drying temperature is 100-150 ℃ and the drying time is 2-3 hours; the roasting temperature is 300-500 ℃ and the roasting time is 4-7h.
16. A process for preparing the noble metal catalyst of any one of claims 1 to 15, comprising the steps of:
pretreating the siliceous salt of the sulfuric acid boiler to obtain a siliceous salt carrier of the sulfuric acid boiler;
mixing palladium salt, platinum salt, ferric salt and zinc salt with a solvent to prepare a mixed metal salt solution, adding a pretreated silicon-containing salt-forming carrier of a sulfuric acid boiler into the mixed metal salt solution, adding ammonia water to regulate the PH, and stirring and impregnating;
adding a reducing agent into the mixture at the temperature of 0-10 ℃ for reduction reaction, then carrying out ultrasonic standing, washing with water and drying to obtain the noble metal catalyst.
17. The method according to claim 16, wherein the palladium salt is selected from any one or two of palladium chloride and sodium tetra-palladium chloride;
the platinum salt is selected from any one or two of chloroplatinic acid and platinum tetrachloride;
the ferric salt is selected from any one or two of ferric chloride and ferric sulfate;
the zinc salt is selected from any one or two of zinc chloride and zinc sulfate.
18. The preparation method according to claim 17, wherein the palladium salt, platinum salt, iron salt and zinc salt are in mass ratio (0.5-10) based on the metal active component element: (0.44-10): (0.8-10): (0.2-10).
19. The preparation method according to claim 18, wherein the palladium salt, platinum salt, iron salt and zinc salt are in mass ratio (0.7-5) based on the metal active component element: (0.44-3): (3-5): (3-5).
20. The method of claim 16, wherein the solvent is selected from any one or a combination of at least two of water, ethanol, and ethylene glycol;
the concentration of the ammonia water is 10-50wt% and the PH value is adjusted to 8-12;
the mass ratio of the silicon-containing salt-forming carrier to the mixed metal salt solution of the sulfuric acid boiler is 1:20-50 parts;
the dipping process is carried out at 15-30 ℃ for 2-6h.
21. The method of claim 20, wherein the solvent is a water-ethanol solution.
22. The process according to claim 20, wherein the aqueous ammonia concentration is 20 to 50wt% and the pH is adjusted to 9 to 11.
23. The preparation method of claim 20, wherein the mass ratio of the silicon-containing salt-forming carrier to the mixed metal salt solution of the sulfuric acid boiler is 1:20-30.
24. The method of claim 20, wherein the dipping process is performed at a temperature of 20-25 ℃ for a time of 4-6 hours.
25. The preparation method according to claim 16, wherein the solvent is used in an amount of 50 to 200 times the total mass of palladium salt, platinum salt, iron salt and zinc salt.
26. The preparation method according to claim 25, wherein the solvent is used in an amount of 50 to 160 times the total mass of palladium salt, platinum salt, iron salt and zinc salt.
27. The method according to claim 16, wherein the reducing agent is selected from any one or a combination of at least two of formaldehyde, hydrazine hydrate, sodium sulfite;
the reduction reaction is carried out at the temperature of 0-20 ℃ for 2-6 hours;
the ultrasonic standing conditions are as follows: the frequency is 28-40KHz, the temperature is 15-30 ℃ and the time is 1-2h.
28. The method of claim 27, wherein the reduction is carried out at a temperature of 5-15 ℃ for a period of 3-5 hours.
29. The method of claim 16, wherein the reducing agent is formulated for use as an aqueous solution having a concentration of 10-50 wt%.
30. The preparation method according to claim 16, wherein the mass ratio of the addition amount of the reducing agent to the silicon-containing salt-forming carrier of the sulfuric acid boiler is 1:0.02-0.1.
31. The preparation method according to claim 30, wherein the mass ratio of the addition amount of the reducing agent to the silicon-containing salt-forming carrier of the sulfuric acid boiler is 1:0.05-0.1.
32. Use of the noble metal catalyst of any one of claims 1 to 15 or prepared by the process of any one of claims 16 to 31 for the catalytic hydrogenation of nitro compounds.
33. A process for the preparation of toluenediamine by hydrogenation of dinitrotoluene, characterized in that it is carried out in a continuous fully-mixed tank reactor and toluenediamine is prepared by hydrogenation of dinitrotoluene with hydrogen starting materials using the noble metal catalyst according to any one of claims 1 to 15 or prepared by the process according to any one of claims 16 to 31.
34. The method of claim 33, wherein the hydrogen to oil mass ratio is 1:10-15.
35. The method of claim 33, wherein the hydrogen gas is at a pressure of 0.65-1.0 mpa.
36. The method of claim 35, wherein the hydrogen gas is at a pressure of 0.7-0.9 mpa.
37. The process of claim 33 wherein the temperature of the hydrogenation reaction is from 100 ℃ to 120 ℃; the mass space velocity is 5-30kg DNT/(kg catalyst. H).
38. The process of claim 37 wherein the temperature of the hydrogenation reaction is 110-120 ℃; the mass space velocity is 5-20kg DNT/(kg catalyst. H).
39. The process of claim 33, wherein the hydrogenation reaction is carried out with stirring at a speed of 800 to 1000rpm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005143A (en) * | 1998-08-07 | 1999-12-21 | Air Products And Chemicals, Inc. | Use of a monolith catalyst for the hydrogenation of dinitrotoluene to toluenediamine |
| WO2003039743A1 (en) * | 2001-11-08 | 2003-05-15 | Degussa Ag | Supported catalyst for hydrogenation of nitroaromatics |
| CN102665900A (en) * | 2009-12-25 | 2012-09-12 | 东曹株式会社 | Hydrogenation catalyst, process for production thereof, and use thereof |
| CN103480370A (en) * | 2012-06-15 | 2014-01-01 | 中国石油化工股份有限公司 | Preparation method of carbon supported Pd-Pt metallic catalyst for catalytic hydrogenation |
| CN105080567A (en) * | 2014-04-22 | 2015-11-25 | 中国科学院长春应用化学研究所 | Catalyst and aromatic amino compound preparation method |
| CN105435808A (en) * | 2014-08-20 | 2016-03-30 | 中国石油化工股份有限公司 | Carbon black noble metal catalyst preparation method |
| CN106179400A (en) * | 2016-06-30 | 2016-12-07 | 浙江工业大学 | Activated carbon supported type composite metal catalyst and preparation method and application |
-
2021
- 2021-12-27 CN CN202111615330.8A patent/CN114289034B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6005143A (en) * | 1998-08-07 | 1999-12-21 | Air Products And Chemicals, Inc. | Use of a monolith catalyst for the hydrogenation of dinitrotoluene to toluenediamine |
| WO2003039743A1 (en) * | 2001-11-08 | 2003-05-15 | Degussa Ag | Supported catalyst for hydrogenation of nitroaromatics |
| CN1582199A (en) * | 2001-11-08 | 2005-02-16 | 德古萨股份公司 | Supported hydrogenating catalyst for hydrogenation of nitroaromatics |
| CN102665900A (en) * | 2009-12-25 | 2012-09-12 | 东曹株式会社 | Hydrogenation catalyst, process for production thereof, and use thereof |
| CN103480370A (en) * | 2012-06-15 | 2014-01-01 | 中国石油化工股份有限公司 | Preparation method of carbon supported Pd-Pt metallic catalyst for catalytic hydrogenation |
| CN105080567A (en) * | 2014-04-22 | 2015-11-25 | 中国科学院长春应用化学研究所 | Catalyst and aromatic amino compound preparation method |
| CN105435808A (en) * | 2014-08-20 | 2016-03-30 | 中国石油化工股份有限公司 | Carbon black noble metal catalyst preparation method |
| CN106179400A (en) * | 2016-06-30 | 2016-12-07 | 浙江工业大学 | Activated carbon supported type composite metal catalyst and preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| Unsupported Nanoporous Platinum−Iron Bimetallic Catalyst for the Chemoselective Hydrogenation of Halonitrobenzenes to Haloanilines;Yuxuan Geng;《ACS Appl. Mater. Interfaces》;第13卷;全文 * |
| 二硝基甲苯加氢制甲苯二胺催化剂的研究进展;闫少伟;《化工进展》;第32卷(第02期);全文 * |
| 对氯硝基苯加氢用骨架镍催化剂的改性研究;孙盛凯;《能源化工》;第37卷(第02期);全文 * |
| 混合二硝基苯催化加氢合成苯二胺;姚少华;《天津化工》(第2期);全文 * |
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