CN107185529B - A kind of template preparing anthraquinone hydrogenation production peroxidating catalyst for hydrogen - Google Patents
A kind of template preparing anthraquinone hydrogenation production peroxidating catalyst for hydrogen Download PDFInfo
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- CN107185529B CN107185529B CN201710471329.XA CN201710471329A CN107185529B CN 107185529 B CN107185529 B CN 107185529B CN 201710471329 A CN201710471329 A CN 201710471329A CN 107185529 B CN107185529 B CN 107185529B
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- catalyst
- pure water
- anthraquinone
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- ethyl alcohol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 52
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 235000019441 ethanol Nutrition 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 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 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000007605 air drying Methods 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 31
- 238000000034 method Methods 0.000 description 27
- 239000012224 working solution Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000274 adsorptive effect Effects 0.000 description 6
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000000658 coextraction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- 229910021277 Co3O4-Al2O3 Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 hydrogen anthraquinone Chemical class 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/308—Thermal decomposition of nitrates
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of templates for preparing anthraquinone hydrogenation production peroxidating catalyst for hydrogen.It the steps include: that ethyl alcohol is added in three-neck flask by (1), MgCl be then added2–NH4HCO3Mixed solution, it is agitated, stand after obtained white solid filtered into pure water, be redispersed in pure water and keep the temperature, refilter and alternately washed with pure water and ethyl alcohol, be dried to obtain Mg5(CO3)4(OH)2·4H2O, abbreviation MCH；(2) it takes MCH to be distributed in ethyl alcohol, Al (NO is added thereto under stiring3)3Ethanol solution, filtering ethyl alcohol is washed after hydro-thermal, up to γ-Al after dry, roasting2O3Microballoon powder；(3) with the γ-Al of preparation2O3Obtained catalyst by washing, drying, is roasted with equi-volume impregnating load active component Pd- for carrier.The catalyst has higher hydrogen efficiency in anthraquinone hydrogenation reaction, and it is 96.9% that highest anthraquinone, which is recycled back to yield,.
Description
Technical field
The invention belongs to anthraquinone hydrogenations to produce H2O2With the preparation field of catalyst, and in particular to classify mesoporous Al2O3It is micro-
The preparation method of ball and its preparing anthraquinone production H2O2Application in palladium catalyst.
Background technique
H2O2Chemical name is hydrogen peroxide, is commonly called as hydrogen peroxide, is to be formed by two kinds of hydrogen, oxygen elements with Covalent bonding together
Compound.Its product is widely used in chemicals synthesis, printing and dyeing, metallurgy, circuit board etching and food production processing.H2O2
Synthetic method have acidolysis peroxide method, electrolysis method, isopropanol method, anthraquinone and hydrogen-oxygen direct synthesis technique etc..The world at present
Upper 99% H2O2Using anthraquinone synthesis, hydrogen-oxygen direct synthesis technique is the fresh approach being concerned at present, but now also in
In the laboratory research stage, from industrial applications, there are also a distances.It is anthraquinone to generally use palladium catalyst fixed bed for the country at present
Produce H2O2, anthraquinone is mainly the control of entire production technology including three processes, hydrogenation process such as hydrogenation, oxidation and extractions
Process processed, because the hydrogen anthraquinone complete oxidation after hydrogenation can be H by oxidation process2O2。
Catalyst used in hydrogenation process mainly has Raney nickel and palladium catalyst two major classes.Raney nickel, which has, meets sky
Gas spontaneous combustion, hydrogenator are difficult to the disadvantages of regenerating after structure is complicated and failure, therefore palladium catalyst is present anthraquinone production H2O2's
Preferred hydrogenation catalyst, and palladium catalyst has many advantages, such as that dosage is few, active height, easily regeneration and use are safe.
The carrier of existing palladium catalyst mainly uses γ-Al2O3, γ-Al2O3Technology of preparing it is highly developed, at present
It is domestic mainly to use neutralisation and carbonizatin method, the γ-Al of different texture properties just can be obtained by controlling preparation condition2O3Carrier,
But few γ-Al for making specific microscopic appearance2O3Carrier, and there is higher catalytic activity in hydrogenation reaction.
CN101284227 is package core in 10~50 μm of nanostructure ball-aluminium oxide powder with partial size, and utilization is non-
Precipitation from homogeneous solution-roasting method obtains alumina group/nano dioxy in one layer of titanium dioxide nanoparticle film of its surface depositional packages
Change titanium-nucleus/shell structure composite microballoons, and is applied to photocatalysis field.
CN103101946A discloses a kind of preparation method of alumina nano-microsphere, using aluminium salt as precursor, by adding
Pyrohydrolysis prepares alumina sol, sequentially add obtain after solvent and high polymer can spinning solution, then obtained by electrostatic spinning
Precursor microsphere after heat treatment obtains alumina nano-microsphere.Electrospinning process is although simple and convenient, but it is by polymer
Molecular weight, SOLUTION PROPERTIES (concentration, viscosity, conductivity, surface tension etc.), electromotive force are affected, and prepare the behaviour of specific microballoon
It is not easy to control to make condition.Junying Tian et al. (Junying Tian, Peng Tian, Hongchang Pang, Guiling
Ning,Raji Feyisa Bogale,Hang Cheng,Shanwen Shen.Fabrication synthesis of
porous Al2O3hollow microspheres and its superior adsorption performance for
Organic dye [J] .Microporous and Mesoporous Materials, 2016,223:27-34.) have studied with
CaMg(CO3)2Al is prepared for template2O3Tiny balloon, Congo red absorption property with higher, this is attributed to the Al2O3It is empty
Heart microballoon has graduation pore structure abundant, to have biggish specific surface area, provides adsorption site abundant.
Xinpu Fu et al. (Xinpu Fu, Qikai Shen, Dong Shi, Ke Wu, Zhao Jin, Xu Wang, Rui Si,
Qisheng Song,Chunjiang Jia,Chunhua Yan.Co3O4-Al2O3mesoporous hollow spheres as
efficient catalyst for Fischer-Tropsch synthesis[J].Applied Catalysis B:
Environmental, 2017,211:176-187.) it points out, the catalyst of spherical nanostructure is in catalysis Fischer-Tropsch synthesis
With the advantage in terms of mass transfer and redox reaction.So far, it has no γ-Al2O3Graduation spherical shape is made to urge as palladium
The carrier of agent.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention prepares graduation spherical gamma-Al by template2O3It carries
Body, and it is used to prepare anthraquinone hydrogenation production H2O2Use catalyst.Obtained catalyst has height in anthraquinone hydrogenation reaction
Catalytic activity, high anthraquinone are recycled back to yield and higher stability.
In order to achieve the goal above, specific technical solution of the present invention is as follows:
In a first aspect, the present invention provides a kind of anthraquinone hydrogenation preparation H2O2With the preparation method of catalyst comprising following step
It is rapid:
(1) 95% ethyl alcohol of 50mL is added in three-neck flask, heated sealed is to 60 DEG C, then under 60r/min stirring
By MgCl2–NH4HCO3Three-neck flask is added in mixed aqueous solution, and stirring is stood, and obtained white solid is filtered pure water three
It is secondary, after be dispersed in 120mL pure water in 80 DEG C of heat preservation 2h, refilter and alternately washed with pure water and ethyl alcohol three times, it is dry through 60 DEG C of air blast
Dry 4h obtains Mg5(CO3)4(OH)2·4H2O, referred to as MCH.
(2) using MCH as template, the above-mentioned MCH of 0.3g is taken to be distributed in 95% ethyl alcohol of 20mL, to it under 50r/min stirring
It is middle that the Al (NO that 10mL concentration is 0.5mol/L is added3)3Ethanol solution, then 50r/min stir 30min, be transferred to water heating kettle water
Heat, cooled and filtered ethanol washing obtain Al three times, through 60 DEG C of forced air drying 4h2O3Predecessor, after being grinded with a mortar through 500 DEG C
Still air atmosphere roasts 4h, and heating rate is 2 DEG C/min to get γ-Al2O3Microballoon powder.
(3) a certain amount of above-mentioned γ-Al of tetrachloro-palladium acid sodium water solution incipient impregnation is used at 60 DEG C2O3Microballoon powder
2h is filtered, pure water is washed till in filtrate without Cl-, filter cake is roasted into 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, is risen
Warm rate is 2 DEG C/min, obtains the catalyst.
MgCl described in step (1)2–NH4HCO3Mixed aqueous solution volume is 60mL, wherein MgCl2Concentration is
0.4mol/L, NH4HCO3Concentration is 0.8mol/L, needs to be heated to 60 DEG C before three-neck flask is added.
Stirring condition described in step (1) is to stir 10min, mixing speed 60r/min at 60 DEG C；Static conditions are
1h is stood at 60 DEG C.
Hydrothermal temperature described in step (2) is 120 DEG C~180 DEG C, and the time is 8~18h.
The PdCl that tetrachloro-palladium acid sodium water solution described in step (3) is 1:2 by molar ratio2It is dissolved in pure water and making with NaCl
?.
Second aspect, the present invention provide the anthraquinone hydrogenation that the above method obtains and produce H2O2Catalyst, specific surface area are
209.6~336.3m20.48~0.77cm of/g, Kong Rongwei3/ g, average pore size are 4.5~6.5nm, the load of active component Pd-
Amount is 0.2~0.5wt%.
The third aspect, the catalyst of above method preparation provided by the invention, purposes is: preparing for anthraquinone hydrogenation
H2O2Hydrogenation process.
The activity rating of catalyst carries out in homemade paste state bed reactor.The reactor by water-bath, three-neck flask,
Condenser pipe, thermometer and some appurtenances composition, condenser pipe connect the intermediary interface of flask, other two interface is respectively
Gas input interface and sample tap.The working solution of experiment is industrial working solution, through liquid chromatographic detection, wherein effective anthraquinone
Content are as follows: 2- ethyl hydrazine 113.8g/L, tetrahydro 2- ethyl hydrazine 87.3g/L.Above-mentioned self-control slurry is added in 0.4g catalyst
In bed reactor, 6mL or so working solution is added and soaks catalyst, checks air-tightness, uses N2Replace the air in flask.In normal pressure
Under conditions of 60 DEG C, the H for being 60mL/min with flow velocity2/N2Mixed gas (V (N2):V(H2)=1:3) activated catalyst 2h, then
60mL working solution, low whipping speed 30r/min, H is added2Flow velocity is 75mL/min, temperature is that hydrogenation is carried out at 60 DEG C.
3mL reaction solution is pipetted every 30min, is put into centrifuge tube after cooling, 8000r/min is centrifuged 3min, removes solid catalyst, moves
It takes 2mL filtrate in separatory funnel, 20mL pure water is added, 2 drop concentrated phosphoric acids are added dropwise, are passed through the O that flow velocity is 35mL/min2It is aoxidized
Reaction generates H2O2, until after glassy yellow (time-consuming about 0.5~1h) is presented in working solution, with the H of pure water extraction generation2O2(coextraction 5
It is secondary) it is collected in conical flask, the sulfuric acid that 5mL concentration is 20wt% is added, then uses the KMnO of 0.02mol/L4Standard solution drop
It is fixed, calculate hydrogenation efficiency.
Hydrogenation efficiency calculation formula:
In formula: C KMnO4The actual concentrations (mol/L) of solution；V0To consume KMnO4The volume (mL) of solution；M is H2O2
Relative molecular weight (34g/mol)；V is the working solution volume (mL) for participating in oxidation.
The measurement that anthraquinone is recycled back to yield carries out liquid phase point to sample using Agilent HP1260 high performance liquid chromatograph
Analysis.Testing conditions are as follows: 25 DEG C of column temperature, chromatographic column zorbox Eclipse XDB-C18 (4.6mm × 250mm, 5 μm), mobile phase
Vol/vol methanol: water=90:10, flow velocity 1mL/min, Detection wavelength 254nm, 10 μ L of sample volume.Standard song is made using external standard method
2- ethyl hydrazine and tetrahydro -2- ethyl hydrazine content, are recycled back to yield data to obtain the anthraquinone of catalyst in line test sample,
Its calculation formula is:
In formula, n is the amount of substance (mol) of effective anthraquinone in working solution after oxidation reaction；n0It is effective in original working solution
The amount of substance (mol) of anthraquinone.This method efficiently avoids conversion ratio and is 100% hypothesis problem, and can reflect hydrogen strictly according to the facts
Change the variation of reaction selectivity.
The present invention has the advantages that below main compared with prior art:
(1) by successively having prepared γ-Al through hydro-thermal, roasting process using MCH as template2O3Sphere.And pass through control
Hydrothermal temperature and time are by γ-Al2O3The microstructure of sphere is adjusted to best.
(2) classify spherical gamma-Al2O3Carrier has biggish specific surface area, while can provide more in catalysis reaction
Active site, and with the advantage in terms of mass transfer.
(3) it is cheap and easy to get to prepare raw material used in MCH, and preparation condition is simple, mild.
(4) catalyst prepared by is in anthraquinone hydrogenation H2O2Application in there is higher hydrogen efficiency and anthraquinone to be recycled back to
Yield.
Detailed description of the invention
Fig. 1~2 are the N of Examples 1 to 6 catalyst2Adsorption-desorption isothermal and pore size distribution curve.
Fig. 3~4 are hydrogenation efficiency curve and anthraquinone circulation and stress of the Examples 1 to 6 catalyst in anthraquinone hydrogenation reaction
Rate histogram.
Fig. 5~6 are the SEM picture of 1 catalyst of embodiment.
Specific embodiment
By following detailed description combination attached drawing it will be further appreciated that the features and advantages of the invention.Provided implementation
Example is only the explanation to the method for the present invention, remaining content without limiting the invention in any way announcement.
N in following embodiment 1-62Adsorption-desorption curve determination, N used2Adsorption-desorption instrument is raw for Merck & Co., Inc, the U.S.
The II 3020 type Sorption Analyzer of TriStar of production.
Anthraquinone is recycled back to the measurement of yield using Agilent HP1260 high performance liquid chromatograph pair in following embodiment 1-6
Sample carries out liquid phase analysis.Testing conditions are as follows: 25 DEG C of column temperature, chromatographic column zorbox Eclipse XDB-C18 (4.6mm ×
250mm, 5 μm), mobile phase volume is than methanol: water=90:10, flow velocity 1mL/min, Detection wavelength 254nm, 10 μ L of sample volume.It adopts
Make 2- ethyl hydrazine and tetrahydro -2- ethyl hydrazine content in standard curve test sample with external standard method, to obtain the anthracene of catalyst
Quinone is recycled back to yield data.
You Han et al. (You Han, Zhiyuan He, Suli Wang, Wei Li and Jinli
Zhang.Performance of facet-controlled Pd nanocrystals in 2-ethylanthraquinone
Hydrogenation [J] .Catalysis Science&Technology, 2015,5 (5): 2630-2639.) once with following public affairs
Formula calculates the selectivity of anthraquinone hydrogenation reaction:
In formula, n is the amount of substance (mol) of effective anthraquinone in working solution after oxidation reaction；n0It is effective in original working solution
The amount of substance (mol) of anthraquinone.There are a hypothesis for the formula: eAQ can quickly and H2Reaction and conversion ratio are 100%, in this way
The target product H that anthraquinone hydrogenation reaction generates2EAQ and H6EAQ just can pass through regenerated eAQ and H after measurement oxidation reaction4eAQ
Amount carry out calculating of equal value, to calculate hydrogenation selectivity indirectly by above formula.But anthraquinone conversion ratio reaches in reaction
100% needs the regular hour, therefore can generate large error with this formula calculating hydrogenation selectivity.
And Huimei Chen et al. (Huimei Chen, Dengpo Huang, Xiyao Su, Jiale Huang,
Xiaolian Jing,Mingming Du,Daohua Sun,Lishan Jia,Qingbiao Li.Fabrication of
Pd/γ-Al2O3 catalysts for hydrogenation of 2-ethyl-9,10-anthraquinone
assisted by plant-mediated strategy[J].Chemical Engineering Journal,2015,262:
Hydrogenation selectivity then 356-363.) is observed indirectly with the content of catabolite in anthraquinone working solution after oxidation cycle, is calculated
Formula are as follows:
In formula, NDFor catabolite percentage；N is the amount of substance (mol) of effective anthraquinone in working solution after oxidation reaction；n0
For the amount of substance (mol) of effective anthraquinone in original working solution.
Here the research is used for reference, the selectivity that yield observes hydrogenation indirectly, calculation formula are recycled back to anthraquinone
Are as follows:
In formula, n is the amount of substance (mol) of effective anthraquinone in working solution after oxidation reaction；n0It is effective in original working solution
The amount of substance (mol) of anthraquinone.This method efficiently avoids conversion ratio and is 100% hypothesis problem, and can reflect hydrogen strictly according to the facts
Change the variation of reaction selectivity.
[embodiment 1]
(1) preparation of MCH
95% ethyl alcohol of 50mL is added in three-neck flask, heated sealed is to 60 DEG C, then by 0.024molMgCl2·6H2O
With 0.048mol NH4HCO3It is dissolved in 60mL pure water, is equally heated to 60 DEG C, then by MgCl under 60r/min stirring2–
NH4HCO3Mixed aqueous solution rapidly joins in three-neck flask, continues 60r/min stirring 10min at 60 DEG C, stands 1h, will obtain
White solid filtering pure water three times, after be dispersed in 120mL pure water in 80 DEG C of heat preservation 2h, refilter with pure water and ethyl alcohol
Alternating is washed three times, and last 60 DEG C of forced air drying 4h obtain MCH.
(2)γ-Al2O3The preparation of microballoon
It takes 0.3gMCH to be distributed in 95% ethyl alcohol of 20mL, the Al (NO of 10mL is added thereto under 50r/min stirring3)3
Ethanol solution (0.5mol/L), continue 50r/min and stir 30min, be then transferred in water heating kettle in 120 DEG C of hydro-thermal 18h, will
Obtained precipitating filtering ethanol washing three times, obtains Al through 60 DEG C of forced air drying 4h2O3Predecessor, after being grinded with a mortar at 500 DEG C
4h is roasted under still air atmosphere, heating rate is 2 DEG C/min to get γ-Al2O3Microballoon powder.
(3) preparation of Pd supported catalyst
Using equi-volume impregnating load active component Pd-.Take γ-Al2O3Microballoon powder 0.6g is negative by Pd- as carrier
Carrying capacity is that 0.3wt% weighs 0.003gPdCl2The corresponding saturated water adsorptive value of 0.6g carrier is dissolved in 0.002gNaCl, and tetrachloro is made
Palladium acid sodium solution instills γ-Al2O3In stir evenly, 60 DEG C of standing 2h of sealer are filtered, pure water is washed till in filtrate without Cl-, will filter
Cake roasts 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, and heating rate is to get Pd- load capacity for 2 DEG C/min
0.3wt% catalyst.
The activity rating of catalyst carries out in homemade paste state bed reactor.The reactor by water-bath, three-neck flask,
Condenser pipe, thermometer and some appurtenances composition, condenser pipe connect the intermediary interface of flask, other two interface is respectively
Gas input interface and sample tap.The working solution of experiment is industrial working solution, through liquid chromatographic detection, wherein effective anthraquinone
Content are as follows: 2- ethyl hydrazine 113.8g/L, tetrahydro 2- ethyl hydrazine 87.3g/L.Above-mentioned self-control slurry is added in 0.4g catalyst
In bed reactor, 6mL or so working solution is added and soaks catalyst, checks air-tightness, uses N2Replace the air in flask.In normal pressure
Under conditions of 60 DEG C, the H for being 60mL/min with flow velocity2/N2Mixed gas (V (N2):V(H2)=1:3) activated catalyst 2h, then
60mL working solution, low whipping speed 30r/min, H is added2Flow velocity is 75mL/min, temperature is that hydrogenation is carried out at 60 DEG C.
3mL reaction solution is pipetted every 30min, is put into centrifuge tube after cooling, 8000r/min is centrifuged 3min, removes solid catalyst, moves
It takes 2mL filtrate in separatory funnel, 20mL pure water is added, 2 drop concentrated phosphoric acids are added dropwise, are passed through the O that flow velocity is 35mL/min2It is aoxidized
Reaction generates H2O2, until after glassy yellow (time-consuming about 0.5~1h) is presented in working solution, with the H of pure water extraction generation2O2(coextraction 5
It is secondary) it is collected in conical flask, the sulfuric acid that 5mL concentration is 20wt% is added, then uses the KMnO of 0.02mol/L4Standard solution drop
It is fixed, calculate hydrogenation efficiency.
Hydrogenation efficiency calculation formula:
In formula: C KMnO4The actual concentrations (mol/L) of solution；V0To consume KMnO4The volume (mL) of solution；M is H2O2
Relative molecular weight (34g/mol)；V is the working solution volume (mL) for participating in oxidation.
Through detecting, by Fig. 1 and 3 and table 1 and 2 as it can be seen that gained specific surface area of catalyst is 272.9m2/ g, Kong Rongwei
0.62cm3/ g, average pore size 6.5nm.Hydrogenation efficiency is 9.76gH2O2/ L working solution, highest anthraquinone are recycled back to yield and are
96.9%.Many nanometer sheets constitute γ-Al it can be seen from Fig. 5,62O3Microballoon, the prepared γ-Al of this explanation2O3Microballoon
With graded structure.
[embodiment 2]
(1) preparation of MCH
MCH is prepared using embodiment 1 step (1) method.
(2)γ-Al2O3The preparation of microballoon
It takes 0.3gMCH to be distributed in 95% ethyl alcohol of 20mL, the Al (NO of 10mL is added thereto under 50r/min stirring3)3
Ethanol solution (0.5mol/L), continue 50r/min and stir 30min, be then transferred in water heating kettle in 150 DEG C of hydro-thermal 12h, will
Obtained precipitating filtering ethanol washing three times, obtains Al through 60 DEG C of forced air drying 4h2O3Predecessor, after being grinded with a mortar at 500 DEG C
4h is roasted under still air atmosphere, heating rate is 2 DEG C/min to get γ-Al2O3Microballoon powder.
(3) preparation of Pd supported catalyst
Using equi-volume impregnating load active component Pd-.Take γ-Al2O3Microballoon powder 0.6g is negative by Pd- as carrier
Carrying capacity is that 0.3wt% weighs 0.003gPdCl2The corresponding saturated water adsorptive value of 0.6g carrier is dissolved in 0.002gNaCl, and tetrachloro is made
Palladium acid sodium solution instills γ-Al2O3In stir evenly, 60 DEG C of standing 2h of sealer are filtered, pure water is washed till in filtrate without Cl-, will filter
Cake roasts 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, and heating rate is to get Pd- load capacity for 2 DEG C/min
0.3wt% catalyst.
Using the performance of catalytic performance test method detection prepared catalyst same as Example 1.
Through detecting, by Fig. 1 and 3 and table 1 and 2, as it can be seen that, gained specific surface area of catalyst is 209.6m2/ g, Kong Rongwei
0.54cm3/ g, average pore size 6.2nm.Hydrogenation efficiency is 6.69gH2O2/ L working solution, highest anthraquinone are recycled back to yield and are
92.5%.
[embodiment 3]
(1) preparation of MCH
MCH is prepared using embodiment 1 step (1) method.
(2)γ-Al2O3The preparation of microballoon
It takes 0.3gMCH to be distributed in 95% ethyl alcohol of 20mL, the Al (NO of 10mL is added thereto under 50r/min stirring3)3
Ethanol solution (0.5mol/L), continue 50r/min and stir 30min, be then transferred in water heating kettle in 180 DEG C of hydro-thermal 8h, will
Obtained precipitating filtering ethanol washing three times, obtains Al through 60 DEG C of forced air drying 4h2O3Predecessor, after being grinded with a mortar at 500 DEG C
4h is roasted under still air atmosphere, heating rate is 2 DEG C/min to get γ-Al2O3Microballoon powder.
(3) preparation of Pd supported catalyst
Using equi-volume impregnating load active component Pd-.Take 0.6g γ-Al2O3Microballoon powder is negative by Pd- as carrier
Carrying capacity is that 0.2wt% weighs 0.002gPdCl2The corresponding saturated water adsorptive value of 0.6g carrier is dissolved in 0.0013gNaCl, and tetrachloro is made
Palladium acid sodium solution instills γ-Al2O3In stir evenly, 60 DEG C of standing 2h of sealer are filtered, pure water is washed till in filtrate without Cl-, will filter
Cake roasts 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, and heating rate is to get Pd- load capacity for 2 DEG C/min
0.2wt% catalyst.
Using the performance of catalytic performance test method detection prepared catalyst same as Example 1.
Through detecting, by Fig. 1 and 3 and table 1 and 2 as it can be seen that gained specific surface area of catalyst is 263.1m2/ g, Kong Rongwei
0.48cm3/ g, average pore size 4.5nm.Hydrogenation efficiency is 5.88gH2O2/ L working solution, highest anthraquinone are recycled back to yield and are
96.3%.
[embodiment 4]
(1) preparation of MCH
MCH is prepared using embodiment 1 step (1) method.
(2)γ-Al2O3The preparation of microballoon
It takes 0.3gMCH to be distributed in 95% ethyl alcohol of 20mL, the Al (NO of 10mL is added thereto under 50r/min stirring3)3
Ethanol solution (0.5mol/L) continues 50r/min and stirs 30min, is then transferred in water heating kettle in 120 DEG C of hydro-thermal 18h, will
The precipitating filtering ethanol washing arrived three times, obtains Al through 60 DEG C of forced air drying 4h2O3Predecessor, it is quiet at 500 DEG C after being grinded with a mortar
4h is roasted under state air atmosphere, heating rate is 2 DEG C/min to get γ-Al2O3Microballoon powder.
(3) preparation of Pd supported catalyst
Using equi-volume impregnating load active component Pd-.Take γ-Al2O3Microballoon powder 0.6g is negative by Pd- as carrier
Carrying capacity is that 0.5wt% weighs 0.005gPdCl2The corresponding saturated water adsorptive value of 0.6g carrier is dissolved in 0.0033gNaCl, and tetrachloro is made
Palladium acid sodium solution instills γ-Al2O3In stir evenly, 60 DEG C of standing 2h of sealer are filtered, pure water is washed till in filtrate without Cl-, will filter
Cake roasts 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, and heating rate is to get Pd- load capacity for 2 DEG C/min
0.5wt% catalyst.
Using the performance of catalytic performance test method detection prepared catalyst same as Example 1.
Through detecting, by Fig. 2 and 4 and table 1 and 2 as it can be seen that gained specific surface area of catalyst is 265.3m2/ g, Kong Rongwei
0.59cm3/ g, average pore size 5.8nm.Hydrogenation efficiency is 3.22gH2O2/ L working solution, highest anthraquinone are recycled back to yield and are
92.0%.
[embodiment 5]
(1) preparation of MCH
MCH is prepared using embodiment 1 step (1) method.
(2)γ-Al2O3The preparation of microballoon
It takes 0.3gMCH to be distributed in 95% ethyl alcohol of 20mL, the Al (NO of 10mL is added thereto under 50r/min stirring3)3
Ethanol solution (0.5mol/L) continues 50r/min and stirs 30min, is then transferred in water heating kettle in 120 DEG C of hydro-thermal 18h, will
The precipitating filtering ethanol washing arrived three times, obtains Al through 60 DEG C of forced air drying 4h2O3Predecessor, it is quiet at 500 DEG C after being grinded with a mortar
4h is roasted under state air atmosphere, heating rate is 2 DEG C/min to get γ-Al2O3Microballoon powder.
(3) preparation of Pd supported catalyst
Using equi-volume impregnating load active component Pd-.Take γ-Al2O3Microballoon powder 0.6g is negative by Pd- as carrier
Carrying capacity is that 0.2wt% weighs 0.002gPdCl2The corresponding saturated water adsorptive value of 0.6g carrier is dissolved in 0.0013gNaCl, and tetrachloro is made
Palladium acid sodium solution instills γ-Al2O3In stir evenly, 60 DEG C of standing 2h of sealer are filtered, pure water is washed till in filtrate without Cl-, will filter
Cake roasts 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, and heating rate is to get Pd- load capacity for 2 DEG C/min
0.2wt% catalyst.
Using the performance of catalytic performance test method detection prepared catalyst same as Example 1.
Through detecting, by Fig. 2 and 4 and table 1 and 2 as it can be seen that gained specific surface area of catalyst is 246.2m2/ g, Kong Rongwei
0.60cm3/ g, average pore size 6.3nm.Hydrogenation efficiency is 7.63gH2O2/ L working solution, highest anthraquinone are recycled back to yield and are
98.5%.
[embodiment 6]
(1) preparation of MCH
MCH is prepared using embodiment 1 step (1) method.
(2)γ-Al2O3The preparation of microballoon
It takes 0.3gMCH to be distributed in 95% ethyl alcohol of 20mL, the Al (NO of 10mL is added thereto under 50r/min stirring3)3
Ethanol solution (0.5mol/L) continues 50r/min and stirs 30min, is then transferred in water heating kettle in 120 DEG C of hydro-thermal 8h, will
The precipitating filtering ethanol washing arrived three times, obtains Al through 60 DEG C of forced air drying 4h2O3Predecessor, it is quiet at 500 DEG C after being grinded with a mortar
4h is roasted under state air atmosphere, heating rate is 2 DEG C/min to get γ-Al2O3Microballoon powder.
(3) preparation of Pd supported catalyst
Using equi-volume impregnating load active component Pd-.Take γ-Al2O3Microballoon powder 0.6g is negative by Pd- as carrier
Carrying capacity is that 0.5wt% weighs 0.005gPdCl2The corresponding saturated water adsorptive value of 0.6g carrier is dissolved in 0.0033gNaCl, and tetrachloro is made
Palladium acid sodium solution instills γ-Al2O3In stir evenly, 60 DEG C of standing 2h of sealer are filtered, pure water is washed till in filtrate without Cl-, will filter
Cake roasts 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, and heating rate is to get Pd- load capacity for 2 DEG C/min
0.5wt% catalyst.
Using the performance of catalytic performance test method detection prepared catalyst same as Example 1.
Through detecting, by Fig. 2 and 4 and table 1 and 2 as it can be seen that gained specific surface area of catalyst is 336.3m2/ g, Kong Rongwei
0.77cm3/ g, average pore size 6.2nm.Hydrogenation efficiency is 9.15gH2O2/ L working solution, highest anthraquinone are recycled back to yield and are
97.7%.
The texture property of each embodiment prepared catalyst of table 1
| Sample | Specific surface area SBET(m2/g) | Hole holds Vt(cm3/g) | Average pore size D (nm) |
| Embodiment 1 | 272.9 | 0.62 | 6.5 |
| Embodiment 2 | 209.6 | 0.54 | 6.2 |
| Embodiment 3 | 263.1 | 0.48 | 4.5 |
| Embodiment 4 | 265.3 | 0.59 | 5.8 |
| Embodiment 5 | 246.2 | 0.60 | 6.3 |
| Embodiment 6 | 336.3 | 0.77 | 6.2 |
The hydrogenation efficiency and anthraquinone of each embodiment prepared catalyst of table 2 catalysis anthraquinone hydrogenation reaction are recycled back to yield
It is important to emphasize that above-described embodiment is used for the purpose of clearly demonstrating examples of the invention, and simultaneously
The non-complete restriction to embodiment.Those of ordinary skill in the art can also make other on the basis of the above description
Various forms of variations can not provide embodiment without to all embodiments here, but thus amplify out aobvious and
The variation being clear to is still in protection scope of the present invention.
Claims (3)
1. a kind of anthraquinone hydrogenation prepares H2O2With the preparation method of catalyst, which comprises the following steps:
(1) 95% ethyl alcohol of 50mL is added in three-neck flask, heated sealed will under 60r/min stirring to 60 DEG C, then
The MgCl of 60mL2–NH4HCO3Three-neck flask is added in mixed aqueous solution, wherein MgCl2–NH4HCO3MgCl in mixed aqueous solution2It is dense
Degree is 0.4mol/L, NH4HCO3Concentration is 0.8mol/L, MgCl2–NH4HCO3Mixed aqueous solution needs before three-neck flask is added
It is heated to 60 DEG C；Continue 60r/min stirring 10min at 60 DEG C and stands 1h；By the filtering of obtained white solid, pure water
It after three times, is dispersed in 120mL pure water, in 80 DEG C of heat preservation 2h, refilters and alternately washed three times with pure water and ethyl alcohol, through 60 DEG C of air blast
Dry 4h obtains Mg5(CO3)4(OH)2·4H2O, referred to as MCH；
(2) using MCH as template, the above-mentioned MCH of 0.3g is taken to be distributed in 95% ethyl alcohol of 20mL, added thereto under 50r/min stirring
Enter the Al (NO that 10mL concentration is 0.5mol/L3)3Ethanol solution, then 50r/min stir 30min, be transferred to water heating kettle hydro-thermal,
Hydrothermal temperature is 120 ~ 180 DEG C, and the time is 8 ~ 18h, and cooled and filtered, ethanol washing three times, are obtained through 60 DEG C of forced air drying 4h
Al2O3Predecessor roasts 4h through 500 DEG C of still air atmosphere, heating rate is 2 DEG C/min to get γ-after being grinded with a mortar
Al2O3Microballoon powder；
(3) a certain amount of above-mentioned γ-Al of tetrachloro-palladium acid sodium water solution incipient impregnation is used at 60 DEG C2O3Microballoon powder 2h, institute
The PdCl that the tetrachloro-palladium acid sodium water solution stated is 1:2 by molar ratio2It is dissolved in pure water and being made with NaCl；It is filtered, pure water is washed till
Without Cl in filtrate‒, filter cake is roasted into 4h in 120 DEG C of dry 2h, 450 DEG C of still air atmosphere, heating rate is 2 DEG C/min, is obtained
To the catalyst.
2. anthraquinone hydrogenation made from a kind of preparation method described in claim 1 produces H2O2Catalyst, which is characterized in that described
The specific surface area of catalyst is 209.6 ~ 336.3m20.48 ~ 0.77cm of/g, Kong Rongwei3/ g, average pore size is 4.5 ~ 6.5nm, living
Property component Pd load capacity be 0.2 ~ 0.5wt%.
3. anthraquinone hydrogenation made from preparation method described in claim 1 produces H2O2Catalyst prepares H in anthraquinone hydrogenation2O2Hydrogen
Application during change.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3635841A (en) * | 1969-06-16 | 1972-01-18 | Engelhard Min & Chem | Novel anthraquinone hydrogenation catalyst |
| CN1294941A (en) * | 1999-11-05 | 2001-05-16 | 吉化集团公司合成树脂厂 | Composite hydrogenating palladium catalyst for fixed bed in anthraquinone process of preparing hydrogen peroxide and its preparation |
| CN1544312A (en) * | 2003-11-19 | 2004-11-10 | 复旦大学 | Anthraquinone hydrogenation catalyzer of anthraquinone method oxydol preparation process and its preparation method |
| CN101229513A (en) * | 2007-01-24 | 2008-07-30 | 中国石油大学(北京) | Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3635841A (en) * | 1969-06-16 | 1972-01-18 | Engelhard Min & Chem | Novel anthraquinone hydrogenation catalyst |
| CN1294941A (en) * | 1999-11-05 | 2001-05-16 | 吉化集团公司合成树脂厂 | Composite hydrogenating palladium catalyst for fixed bed in anthraquinone process of preparing hydrogen peroxide and its preparation |
| CN1544312A (en) * | 2003-11-19 | 2004-11-10 | 复旦大学 | Anthraquinone hydrogenation catalyzer of anthraquinone method oxydol preparation process and its preparation method |
| CN101229513A (en) * | 2007-01-24 | 2008-07-30 | 中国石油大学(北京) | Supported palladium catalyst used for anthraquinone producing peroxid and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Fabrication synthesis of porous Al2O3 hollow microspheres and its superior adsorption performance for organic dye;Junying Tian，et al;《Microporous and Mesoporous Materials》;20151028;第223卷;第27-34页 * |
| NiO hierarchical structure: template-engaged synthesis and adsorption property;Peng Tian,et al;《RSC Advances》;20120914;第2卷(第27期);第10217-10221页 * |
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