CN114289034A - Noble metal catalyst, preparation method and application thereof in preparation of toluenediamine by catalyzing dinitrotoluene hydrogenation - Google Patents
Noble metal catalyst, preparation method and application thereof in preparation of toluenediamine by catalyzing dinitrotoluene hydrogenation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 54
- 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 34
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 144
- 150000003839 salts Chemical class 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 44
- 239000010703 silicon Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 12
- 150000003376 silicon Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 150000002940 palladium Chemical class 0.000 claims description 9
- 150000003057 platinum Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 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
- 239000002904 solvent Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 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
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 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
- 238000007598 dipping method Methods 0.000 claims description 3
- 150000002828 nitro derivatives Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 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
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 208000012839 conversion disease Diseases 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 42
- 238000012360 testing method Methods 0.000 description 22
- 239000006227 byproduct Substances 0.000 description 20
- 238000005070 sampling Methods 0.000 description 18
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 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
- 238000011068 loading method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 230000008021 deposition 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011521 glass Substances 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
- 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
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 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
- 230000007774 longterm Effects 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
- 238000004064 recycling Methods 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
- 239000002910 solid waste Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a noble metal catalyst, a preparation method and application thereof in catalyzing dinitrotoluene hydrogenation to prepare toluenediamine, 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 comprises Pd, Pt, Fe and Zn. The catalyst is prepared by adopting an impregnation method, silicon-containing salt in a sulfuric acid boiler is taken as a carrier, and the catalyst is obtained by reducing at a lower temperature, filtering, washing and drying after being impregnated by a noble metal salt solution. The catalyst has stronger hydrogenation activity and selectivity, is very suitable for catalyzing the application of dinitrotoluene hydrogenation to prepare toluenediamine, and can improve the catalytic reaction speed, the reaction conversion rate 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, the prepared polyurethane material is applied to industries such as construction, medical treatment and the like.
Tolylenediamine is generally converted from Dinitrotoluene (DNT) and is currently produced industrially mainly by liquid-phase catalytic hydrogenation. The catalyst is an important core for preparing toluenediamine by catalytic hydrogenation of dinitrotoluene, and two types are commonly used in the industry at present: 1) the supported noble metal catalyst has mainly Pd and Pt as the main supported metal and is supported on porous carrier, such as alumina, active carbon, carbon black, etc. Generally, the catalyst has mild reaction conditions and high reaction activity under low pressure, but the cost is high due to the content of the supported noble metal and the loss; 2) the Raney-Ni catalyst has low cost, but the reaction pressure in catalytic hydrogenation is high (more than 2 MPa), impurities are remained 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 loaded noble metal is easy to lose after being used for many times. In patent CN 110538651 a, modified ultrafine carbon black carrier loaded noble metal Pt is used as a catalyst, and is applied in hydrogenation of nitro compounds, but the noble metal used is of a single kind, and there is no other metal to assist in dispersing and strengthening the noble metal, so that the catalytic action of the noble metal is not fully exerted, and the metal loading strength needs to be further enhanced. Meanwhile, in the existing process for preparing toluenediamine mainly by using a noble metal catalyst, the tar content is generally over 1 percent, and an optimization space for further reducing the tar content is provided.
In the process of preparing dinitrotoluene, toluene and concentrated nitric acid react under the catalytic action 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 the concentrated sulfuric acid by a sulfuric acid boiler so as to be recycled. However, in the process of sulfuric acid concentration, because the boiler is in the sulfuric acid environment for a long time, salt deposition can occur inside the boiler, the components of the salt deposition are mainly silicon salt, the annual production amount of silicon-containing salt in the sulfuric acid boiler can reach about 500kg by a set of dinitrotoluene production device with the scale of 36 ten thousand tons, but the silicon-containing salt deposition is mainly treated as solid waste at present, and the problems of resource waste and environmental pollution exist. Therefore, it is of great significance to seek a reasonable way to recover the silicon-containing salt in the sulfuric acid boiler and realize resource recycling.
Disclosure of Invention
In view of the above problems in the prior art, the main object of the present invention is to provide a reinforced noble metal catalyst and a preparation method thereof, wherein the catalyst uses a silicon-containing salt of a sulfuric acid boiler as a carrier, can realize reasonable resource reuse, and can obtain a highly dispersed supported noble metal catalyst at a lower reduction temperature by an impregnation method, wherein the supported noble metal catalyst has the advantages of high active component loading strength, low noble metal loss rate, high specific surface area, high mechanical strength, low cost, etc.
The catalyst has stronger hydrogenation activity and selectivity, is very suitable for catalyzing the application of dinitrotoluene hydrogenation to prepare toluenediamine, and can improve the catalytic reaction speed, the reaction conversion rate and the selectivity.
Experiments show that a container (hereinafter, referred to as a sulfuric acid boiler) made of glass lining materials and the like in contact with sulfuric acid reacts with hot concentrated sulfuric acid, silicate is gradually separated out on the surface, the thickness of salt is gradually increased along with the accumulation of the salt, the salt structure generated in the environment is uniform, the preparation requirement of a 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 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, when calculating the mass percentage composition, the mass percentage of the metal active component refers to the mass of the metal element represented by the active component in the compound containing the active component in the compound, for example, if the palladium element exists in the form of chloride (palladium chloride), the mass percentage of the palladium is 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 percentage of the palladium is calculated by the mass of the simple substance thereof. In the noble metal catalyst of the present invention, the palladium element, the platinum element, the iron element, and the zinc element are mainly present in the form of pure metal simple substances.
The noble metal catalyst takes the 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 of the sulfuric acid boiler is salt generated in equipment which is 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 catalytic action 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 the concentrated sulfuric acid through the sulfuric acid boiler so as to be recycled. However, in the process of concentrating sulfuric acid, salt formation occurs inside the boiler due to the long-term sulfuric acid environment, wherein the salt formation mainly comprises silicon salt, is derived from a boiler lining made of glass-lined materials, and also comprises 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 device may contain a trace amount of elements such as Ta depending on the material of the device. The content of each component in the silicon-containing salt of the sulfuric acid boiler has great difference due to different types, materials and processes of the boiler. The composition of the silicon-containing salt of the sulfuric acid boiler in the invention can only realize the catalytic effect of the invention 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 of the invention, the sulfuric acid boiler contains pretreated silicon salt, and the pretreatment comprises processes of acidification, oxidation and roasting;
preferably, in some embodiments, the pretreatment method comprises: grinding the coarse material containing silicon 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 a carrier containing silicon salt of the sulfuric acid boiler;
preferably, the coarse material containing silicon 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 to 1; the acidification treatment temperature is 15-30 ℃, and the time is 4-6 h; the acetic acid is aqueous solution with the concentration of 10-50 wt%;
preferably, 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, more preferably 1: 0.5 to 1; the oxidation treatment temperature is 15-30 ℃, and the time is 4-6 h; the concentration of the hydrogen peroxide is 20-40 wt%;
the washing, drying and roasting are conventional operations in the field, preferably the drying temperature is 100-150 ℃, and the drying time is 2-3 h; the roasting temperature is preferably 300-500 ℃, and the roasting time is preferably 4-7 h.
In the invention, the silicon-containing salt carrier of the sulfuric acid boiler pretreated by the method has the average particle size of 10-20 microns, preferably 13-17 microns; specific surface area of 100-300m2G, preferably 150-230m2(ii)/g; the pore volume is 0.8-1.6cm3In g, preferably 1.2 to 1.6cm3/g。
The invention also provides a preparation method of the noble metal catalyst, which comprises the following steps:
pretreating the sulfuric acid boiler to obtain a sulfuric acid boiler silicon-containing salt carrier;
mixing palladium salt, platinum salt, ferric salt, zinc salt and a solvent to prepare a mixed metal salt solution, adding a pretreated sulfuric acid boiler silicon-containing salt carrier, adding ammonia water to adjust the pH value, and stirring and dipping;
adding a reducing agent into the mixture at the temperature of between 0 and 10 ℃ for reduction reaction, then ultrasonically standing, washing with water and drying to obtain the noble metal catalyst.
In the preparation method of the present invention, the pretreatment is performed by the processes of acidification, oxidation and roasting, and details are not repeated herein.
In the preparation method, the palladium salt is selected from palladium chloride (PdCl)2) Sodium palladium tetrachloride (Na)2PdCl4) Either one or a combination of both;
the platinum salt is selected from chloroplatinic acid (H)2PtCl6·6H2O), platinum tetrachloride (PtCl)4) Either one or a combination of both;
the iron salt is selected from ferric chloride (FeCl)3·6H2O), iron (Fe (SO) sulfate4)3·7H2O) or a combination of two of them;
the zinc salt is selected from zinc chloride (ZnCl)2) Zinc sulfate (ZnSO)4) Either one or a combination of both;
preferably, the mass ratio of the palladium salt, the platinum salt, the iron salt and the zinc salt 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 at least two combinations of water, ethanol, glycol and the like, preferably a water-ethanol solution;
preferably, the amount of the solvent is 50 to 200 times, preferably 50 to 160 times of the total mass of the palladium salt, the platinum salt, the iron salt and the zinc salt.
In the preparation method, the concentration of the ammonia water is 10-50 wt%, preferably 20-50 wt%, and the PH value is adjusted to 8-12, preferably 9-11;
in the preparation method, the dipping process is carried out at the temperature of 15-30 ℃, preferably 20-25 ℃ for 2-6h, preferably 4-6 h.
Preferably, the mass ratio of the silicon-containing salt carrier to the mixed metal salt solution of the sulfuric acid boiler during impregnation 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 prepared into an aqueous solution with the concentration of 10-50 wt% for use;
preferably, the mass ratio of the adding amount of the reducing agent to the silicon-containing salt carrier of the sulfuric acid boiler is 1: 0.02 to 0.1, preferably 1: 0.05-0.1.
In the preparation method, the reduction reaction is carried out at the temperature of 0-20 ℃, preferably at the temperature of 5-15 ℃ for 2-6h, preferably for 3-5 h.
In the preparation method, after the reduction reaction is finished, ultrasonic standing, water washing and drying are further included, which is a conventional operation in the field, wherein the preferable conditions of the ultrasonic standing are as follows: the frequency is 28-40KHz, the temperature is 15-30 ℃, and the time is 1-2 h.
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 particularly suitable for preparing toluenediamine by catalyzing the hydrogenation of dinitrotoluene.
Preferably, the invention provides a method for preparing toluenediamine by hydrogenating dinitrotoluene, which is carried out in a continuous full-mixing kettle type reactor, and the catalyst of the noble metal catalyst is adopted to prepare the toluenediamine by hydrogenation reaction of dinitrotoluene and hydrogen raw materials.
Preferably, the mass ratio of hydrogen to dinitrotoluene (hydrogen oil) is 1: 10-15.
Preferably, the pressure of the hydrogen is from 0.65 to 1.0MPa (A), preferably from 0.7 to 0.9MPa (A);
preferably, the temperature of the hydrogenation reaction is 100-120 ℃, preferably 110-120 ℃; a mass space velocity of 5-30kg dnt/(kg catalyst h), preferably 5-20kg dnt/(kg catalyst h);
preferably, the hydrogenation reaction is carried out under stirring at a stirring speed of 800-. The preparation process of the noble metal catalyst can greatly enhance the performance of the catalyst, reduce the problem of high use cost of the prior noble metal catalyst, and can achieve the conversion rate and the selectivity of over 99 percent and reduce the selectivity of byproduct tar to below 1 percent when the dinitrotoluene is catalyzed and hydrogenated to prepare the toluenediamine.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the silicon-containing salt in the treated sulfuric acid boiler as the catalyst carrier, the salt is uniform in texture, the treated porous catalyst carrier with concentrated particle size distribution and high specific surface area can be more easily obtained, and the salt in the sulfuric acid boiler also simultaneously has other metal elements such as Fe, AL, Mn, Ni, Cr and the like which have synergistic effect with noble metals Pd and Pt, so that better hydrogenation performance can be realized, simultaneously the loading strength of active components can be enhanced, the service life of the catalyst is prolonged, waste recovery and resource reutilization are realized, and the cost is reduced.
(2) In the catalyst, Fe and Zn in a proper proportion are added to assist the dispersion of the noble metal, so that the catalyst prepared at a lower temperature has higher noble metal loading strength and noble metal dispersion, the noble metal loss rate in the using process of the catalyst is reduced, the hydrogenation selectivity is enhanced, the addition of the Fe and Zn assists the addition of the metal, the cost is further reduced, the hydrogenation activity of the noble metal is enhanced, and when the catalyst is used for preparing the toluenediamine by hydrogenation, the reaction activity and the selectivity are high, and the selectivity of the tar serving as a byproduct can be reduced to below 1%.
Detailed Description
The technical solutions and advantages of the present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The embodiment of the invention adopts the following main raw material source information:
coarse material containing silicon salt of sulfuric acid boiler: the salt is produced from the inner salt of glass lining boiler in Wanhua dinitrotoluene apparatus and consists of Si40-50 wt%, Fe0.9-2 wt%, Al0.9-2 wt%, Mn0.01-0.1 wt%, Ni0.01-0.1 wt% and Cr0.01-0.1 wt%.
Other principles such as palladium salt, platinum salt, iron salt, zinc salt, acetic acid, hydrogen peroxide and the like are purchased from commercial routes and are all chemical pure grades unless specially stated.
The catalyst characterization method adopted by the embodiment of the invention comprises the following steps:
specific surface area and pore volume: carrying out N2 adsorption-desorption test on the catalyst by adopting a BELSORP-II type adsorption instrument of BEL company in Japan, dehydrating a sample at 250 ℃ in vacuum for 4h, calculating the specific surface area by a BET equation, and calculating the pore volume of the catalyst by using a BJH model;
average particle size: the catalyst particle size was analyzed using a HELOS 1BF type particle sizer from napa tach, germany.
Example 1
1) Preparing a noble metal catalyst:
taking 10g of silicon-containing salt of the sulfuric acid boiler (comprising 44.8 wt% of Si, 1.09 wt% of Fe, 1.27 wt% of AL, 0.04 wt% of Mn, 0.02 wt% of Ni and 0.01 wt% of Cr), grinding into powder with the particle size of 10-20 microns, adding 200g of 10 wt% acetic acid aqueous solution, carrying out acidification treatment for 4h at 25 ℃, washing with deionized water, adding 100g of 20 wt% hydrogen peroxide, carrying out oxidation treatment for 4h at 25 ℃, drying for 2h at 150 ℃ after washing with deionized water, and then roasting at 300 ℃ for 4h to obtain the silicon-containing salt carrier of the sulfuric acid boiler.
The average particle diameter of the carrier is 14 mu m and the specific surface area of the carrier is 200m2G, pore volume of the carrier 1.2cm3/g。
0.73g of palladium chloride, 0.12g of chloroplatinic acid, 2.42g of ferric chloride hexahydrate and 1.04g of zinc chloride were weighed and dissolved in 250g of a water-ethanol solution (the mass ratio of water to ethanol was 1: 4), and stirred to sufficiently dissolve the metal salt, thereby forming about 252g of a mixed metal salt solution. Then 10g of pretreated sulfuric acid boiler silicon-containing salt carrier is added, 20 wt% of ammonia water is dripped under stirring to adjust the pH value to 9, and the mixture is stirred and soaked for 4 hours at 25 ℃.
The system was cooled to 5 ℃ and 200g of 50 wt% hydrazine hydrate solution was slowly added thereto and the reduction reaction was stirred at 5 ℃ for 3 h. Then ultrasonic standing is carried out for 1h at the frequency of 40KHz at the temperature of 25 ℃, and then washing and drying are carried out to prepare the noble metal catalyst.
Through tests, the noble metal catalyst comprises the following components in percentage by mass: 85.16% of carrier, 4.4% of palladium element, 0.44% of platinum element, 5% of iron element and 5% of zinc element, wherein palladium, platinum, iron and zinc exist in the form of pure metal simple substance.
2) Preparation of toluenediamine by hydrogenation of dinitrotoluene:
in the continuous full-mixing kettle type reactor, the hydrogen is fed at 0.54NL/min, the hydrogen pressure is 0.75MPa, and the mass ratio of the fed hydrogen to the fed dinitrotoluene is 1: 14, 3g of the noble metal catalyst prepared in step 1) above were added, the reaction temperature was 115 ℃, the stirring speed was 800rpm, and the mass space velocity was 13.4kg dnt/(kg catalyst · h). After reacting for 15h, sampling and testing, the reaction conversion rate is 99.99%, the selectivity is 99.2%, the selectivity of the byproduct tar 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 shows that the reaction conversion rate is 99.99%, the selectivity is 99.2%, the selectivity of the byproduct tar 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) Preparing a noble metal catalyst:
taking 10g of silicon-containing salt of a sulfuric acid boiler (containing 44.1 wt% of Si, 1.71 wt% of Fe, 1.42 wt% of Al, 0.02 wt% of Mn, 0.04 wt% of Ni and 0.05 wt% of Cr), grinding into powder with the particle size of 10-20 microns, adding 150g of 10 wt% acetic acid aqueous solution, carrying out acidification treatment at 20 ℃ for 5h, washing with deionized water, adding 75g of 20 wt% hydrogen peroxide, carrying out oxidation treatment at 20 ℃ for 5h, washing with deionized water, drying at 100 ℃ for 3h, and then roasting at 400 ℃ for 5h to obtain the silicon-containing salt carrier of the sulfuric acid boiler.
The average particle diameter of the carrier is 13 μm and the specific surface area of the carrier is 215m2G, pore volume of the carrier 1.5cm3/g
1.33g of palladium chloride, 0.79g of chloroplatinic acid, 1.45g of ferric chloride hexahydrate and 0.63g of zinc chloride were weighed and dissolved in 250g of a water-ethanol solution (the mass ratio of water to ethanol was 1: 4), and stirred to sufficiently dissolve the metal salt, thereby forming about 254g of a mixed metal salt solution. Then 10g of pretreated sulfuric acid boiler silicon-containing salt carrier is added, 30 wt% of ammonia water is dripped under stirring to adjust the pH value to 10, and the mixture is stirred and soaked for 5 hours at the temperature of 20 ℃.
The system was cooled to 10 ℃ and 300g of 50 wt% hydrazine hydrate solution was slowly added thereto and the reduction reaction was stirred at 10 ℃ for 4 h. Then ultrasonic standing is carried out for 2 hours at the temperature of 15 ℃ and the frequency of 35KHz, and then washing and drying are carried out to prepare the noble metal catalyst.
Through tests, the noble metal catalyst comprises the following components in percentage by mass: 83% of carrier, 8% of palladium element, 3% of platinum element, 3% of iron element and 3% of zinc element, wherein the palladium, the platinum, the iron and the zinc exist in the form of pure metal simple substance.
2) Preparation of toluenediamine by hydrogenation of dinitrotoluene:
in the continuous full-mixing kettle type reactor, the hydrogen is fed at 0.54NL/min, the hydrogen pressure is 0.7MPa, and the mass ratio of the fed hydrogen to the fed dinitrotoluene is 1: 12, 2g of the noble metal catalyst prepared in step 1) above were added, the reaction temperature was 120 ℃, the stirring speed was 800rpm, and the mass space velocity was 17.3kg dnt/(kg catalyst · h). After reacting for 15h, sampling and testing, the reaction conversion rate is 99.99%, the selectivity is 99.3%, the selectivity of the byproduct tar 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 tests show that the reaction conversion rate is 99.99%, the selectivity is 99.2%, the selectivity of the byproduct tar 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) Preparing a noble metal catalyst:
taking 10g of silicon-containing salt of a sulfuric acid boiler (containing 44.81 wt% of Si, 1.42 wt% of Fe, 0.95 wt% of Al, 0.03 wt% of Mn, 0.01 wt% of Ni and 0.02 wt% of Cr), grinding into powder with the particle size of 10-20 microns, adding 100g of 10 wt% acetic acid aqueous solution, carrying out acidification treatment at 15 ℃ for 6h, washing with deionized water, adding 50g of 20 wt% hydrogen peroxide, carrying out oxidation treatment at 15 ℃ for 6h, washing with deionized water, drying at 130 ℃ for 2.5h, and then roasting at 500 ℃ for 6h to obtain the silicon-containing salt carrier of the sulfuric acid boiler.
Tested, carrier averagedThe particle diameter is 15 μm, and the specific surface area of the carrier is 190m2G, pore volume of the carrier 1.3cm3/g。
0.33g of palladium chloride, 0.80g of chloroplatinic acid, 0.48g of ferric chloride hexahydrate and 0.21g of zinc chloride were weighed and dissolved in 250g of a water-ethanol solution (the mass ratio of water to ethanol was 1: 4), and stirred to sufficiently dissolve the metal salt, thereby forming about 252g of a mixed metal salt solution. Then 10g of pretreated sulfuric acid boiler silicon-containing salt carrier is added, 50 wt% ammonia water is added dropwise under stirring to adjust the pH value to 11, and the mixture is stirred and soaked for 6 hours at 25 ℃.
The system was cooled to 15 ℃ and 400g of 50 wt% hydrazine hydrate solution was slowly added thereto and the reduction reaction was stirred at 15 ℃ for 5 h. Then ultrasonic standing is carried out at the frequency of 30KHz at the temperature of 20 ℃ for 2 hours, and then washing and drying are carried out to prepare the noble metal catalyst.
Through tests, the noble metal catalyst comprises the following components in percentage by mass: 94% of carrier, 1% of palladium element, 3% of platinum element, 1% of iron element and 1% of zinc element, wherein palladium, platinum, iron and zinc exist in the form of pure metal simple substance.
2) Preparation of toluenediamine by hydrogenation of dinitrotoluene:
in the continuous full-mixing kettle type reactor, the hydrogen is fed at 0.54NL/min, the hydrogen pressure is 0.85MPa, and the mass ratio of the fed hydrogen to the fed dinitrotoluene is 1: 10, 5g of the noble metal catalyst prepared in step 1) above was added, the reaction temperature was 110 ℃, the stirring speed was 800rpm, and the mass space velocity was 5.7kg dnt/(kg catalyst · h). After reacting for 15h, sampling and testing, the reaction conversion rate is 99.99%, the selectivity is 99.1%, the selectivity of the byproduct tar 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 tests show that the reaction conversion rate is 99.99%, the selectivity is 99.1%, the selectivity of the byproduct tar 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 referred to in example 1 differs only in that: in the step 1), the pretreated sulfuric acid boiler silicon-containing salt carrier is replaced by active carbon with equal mass as a carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by hydrogenating 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 selectivity of byproduct tar is 1.39%, and the loss rates of Pd and Pt in the catalyst after reaction are respectively 0.03 wt% and 0.01 wt%.
After the reaction is continued for 100 hours, sampling tests show that the reaction conversion rate is 99.98%, the selectivity is 98.4%, the selectivity of the byproduct tar 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 referred to in example 1 differs only in that: in the step 1), the pretreated sulfuric acid boiler silicon-containing salt carrier is replaced by silicon dioxide with equal mass as a carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by hydrogenating 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 selectivity of byproduct tar is 1.39%, and the loss rates of Pd and Pt in the catalyst after reaction are respectively 0.04 wt% and 0.01 wt%.
After the reaction is continued for 100 hours, sampling tests show that the reaction conversion rate is 99.98%, the selectivity is 98.4%, the selectivity of the byproduct tar 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 referred to in example 1 differs only in that: in the step 1), the pretreated sulfuric acid boiler silicon-containing salt carrier is replaced by silica gel with equal mass as a carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by hydrogenating 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 selectivity of byproduct tar is 1.40%, and the loss rates of Pd and Pt in the catalyst after reaction are respectively 0.03 wt% and 0.02 wt%.
After the reaction is continued for 100 hours, sampling tests show that the reaction conversion rate is 99.98%, the selectivity is 98.4%, the selectivity of the byproduct tar 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 referred to in example 1 differs only in that: in the step 1), the pretreated sulfuric acid boiler silicon-containing salt carrier is replaced by diatomite with equal mass as a carrier to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by hydrogenating 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 selectivity of byproduct tar is 1.49%, and the loss rates of Pd and Pt in the catalyst after reaction are respectively 0.05 wt% and 0.02 wt%.
After the reaction is continued for 100 hours, sampling tests show that the reaction conversion rate is 99.98%, the selectivity is 98.3%, the selectivity of the byproduct tar 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 referred to in example 1 differs only in that: and (2) adding no zinc chloride into the mixed metal salt solution in the step 1), and keeping other operations unchanged to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by hydrogenating 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 selectivity of byproduct tar is 1.45%, and the loss rates of Pd and Pt in the catalyst after reaction are respectively 0.05 wt% and 0.04 wt%.
After the reaction is continued for 100 hours, sampling tests show that the reaction conversion rate is 99.98%, the selectivity is 98.3%, the selectivity of the byproduct tar 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 referred to in example 1 differs only in that: in the step 1), no ferric chloride hexahydrate is added into the mixed metal salt solution, and other operations are unchanged to prepare the catalyst.
The prepared catalyst is used for preparing toluenediamine by hydrogenating 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 selectivity of byproduct tar is 1.42%, and the loss rates of Pd and Pt in the catalyst after reaction are respectively 0.04 wt% and 0.03 wt%.
After the reaction is continued for 100 hours, sampling tests show that the reaction conversion rate is 99.98%, the selectivity is 98.3%, the selectivity of the byproduct tar 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 (10)
1. A noble metal catalyst comprising a support and a metal active component;
wherein the carrier is silicon-containing salt of a sulfuric acid boiler;
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 comprises, in mass percent:
3. the noble metal catalyst of claim 1 or 2, wherein the composition of the silicon-containing salt of the sulfuric acid boiler comprises silicon 40-50%, iron 0.9-2%, aluminum 0.9-2%, manganese 0.01-0.1%, nickel 0.01-0.1%, chromium 0.01-0.1% by mass;
preferably, the sulfuric acid boiler contains silicon salt, which is pretreated, and the pretreatment comprises the processes of acidification, oxidation and roasting;
preferably, the pretreated silicon-containing carrier of the sulfuric acid boiler has an average particle size of 10-20 μm, preferably 13-17 μm; specific surface area of 100-300m2G, preferably 150-230m2(ii)/g; the pore volume is 0.8-1.6cm3In g, preferably 1.2 to 1.6cm3/g。
4. The noble metal catalyst of claim 3, wherein the pretreatment process comprises: grinding the coarse material containing silicon 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 a carrier containing silicon salt of the sulfuric acid boiler;
preferably, the coarse material containing silicon 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 to 1; the acidification treatment temperature is 15-30 ℃, and the time is 4-6 h; the acetic acid is aqueous solution with the concentration of 10-50 wt%;
preferably, 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, more preferably 1: 0.5 to 1; the oxidation treatment temperature is 15-30 ℃, and the time is 4-6 h; the concentration of the hydrogen peroxide is 20-40 wt%;
preferably, the drying temperature is 100-150 ℃, and the drying time is 2-3 h; the roasting temperature is 300-500 ℃, and the roasting time is 4-7 h.
5. A method for preparing the noble metal catalyst of any one of claims 1 to 4, comprising the steps of:
pretreating the sulfuric acid boiler to obtain a sulfuric acid boiler silicon-containing salt carrier;
mixing palladium salt, platinum salt, ferric salt, zinc salt and a solvent to prepare a mixed metal salt solution, adding a pretreated sulfuric acid boiler silicon-containing salt carrier, adding ammonia water to adjust the pH value, and stirring and dipping;
adding a reducing agent into the mixture at the temperature of between 0 and 10 ℃ for reduction reaction, then ultrasonically standing, washing with water and drying to obtain the noble metal catalyst.
6. The preparation method according to claim 5, wherein the palladium salt is selected from any one or two of palladium chloride and sodium palladium tetrachloride;
the platinum salt is selected from any one or two combinations of chloroplatinic acid and platinum tetrachloride;
the ferric salt is selected from any one or the combination of two of ferric chloride and ferric sulfate;
the zinc salt is selected from any one or two of zinc chloride and zinc sulfate;
preferably, the mass ratio of the palladium salt, the platinum salt, the iron salt and the zinc salt is (0.5-10): (0.44-10): (0.8-10): (0.2-10), preferably (0.7-5): (0.44-3): (3-5): (3-5).
7. The method according to claim 5 or 6, wherein the solvent is selected from any one or a combination of at least two of water, ethanol, and ethylene glycol, preferably a water-ethanol solution;
preferably, the dosage of the solvent is 50-200 times, preferably 50-160 times of the total mass of the palladium salt, the platinum salt, the iron salt and the zinc salt;
the concentration of the ammonia water is 10-50 wt%, preferably 20-50 wt%, and the PH value is adjusted to 8-12, preferably 9-11;
the mass ratio of the silicon-containing salt carrier of the sulfuric acid boiler to the mixed metal salt solution is 1: 20-50, preferably 1: 20-30 parts of;
the impregnation process is carried out at 15-30 deg.C, preferably 20-25 deg.C, for 2-6h, preferably 4-6 h.
8. The method according to any one of claims 5 to 7, wherein the reducing agent is selected from any one of formaldehyde, hydrazine hydrate, sodium sulfite, or a combination of at least two thereof; preferably, the reducing agent is prepared into an aqueous solution with the concentration of 10-50 wt% for use;
preferably, the mass ratio of the adding amount of the reducing agent to the silicon-containing salt carrier of the sulfuric acid boiler is 1: 0.02 to 0.1, preferably 1: 0.05-0.1;
the reduction reaction is carried out at the temperature of 0-20 ℃, preferably at the temperature of 5-15 ℃ for 2-6h, preferably for 3-5 h.
The ultrasonic standing condition is as follows: the frequency is 28-40KHz, the temperature is 15-30 ℃, and the time is 1-2 h.
9. Use of the noble metal catalyst according to any one of claims 1 to 4 or prepared by the process according to any one of claims 5 to 8 for catalytic hydrogenation of nitro compounds, in particular for catalytic hydrogenation of dinitrotoluene to toluenediamine.
10. A process for the hydrogenation of dinitrotoluene to toluenediamine, which is carried out in a continuous, all-mixed-tank reactor, using a noble metal catalyst according to any one of claims 1 to 4 or a noble metal catalyst prepared by a process according to any one of claims 5 to 8, to produce toluenediamine by hydrogenation from dinitrotoluene and a hydrogen feed;
preferably, the mass ratio of hydrogen to oil is 1: 10-15 parts of;
preferably, the pressure of the hydrogen is from 0.65 to 1.0MPa (A), preferably from 0.7 to 0.9MPa (A);
preferably, the temperature of the hydrogenation reaction is 100-120 ℃, preferably 110-120 ℃; a mass space velocity of 5-30kg dnt/(kg catalyst h), preferably 5-20kg dnt/(kg catalyst h);
preferably, the hydrogenation reaction is carried out under stirring at a stirring speed of 800-.
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