CN108636422A - Manganese cobalt spinel catalyst and preparation method thereof - Google Patents
Manganese cobalt spinel catalyst and preparation method thereof Download PDFInfo
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- CN108636422A CN108636422A CN201810316363.4A CN201810316363A CN108636422A CN 108636422 A CN108636422 A CN 108636422A CN 201810316363 A CN201810316363 A CN 201810316363A CN 108636422 A CN108636422 A CN 108636422A
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- Prior art keywords
- manganese
- cobalt
- salt
- cobalt spinel
- catalyst
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 129
- 239000011029 spinel Substances 0.000 title claims abstract description 129
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000919 ceramic Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 32
- 229910001437 manganese ion Inorganic materials 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 29
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 150000001868 cobalt Chemical class 0.000 claims description 27
- 150000002696 manganese Chemical class 0.000 claims description 26
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 25
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 25
- 239000003085 diluting agent Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- KQFUCKFHODLIAZ-UHFFFAOYSA-N manganese Chemical compound [Mn].[Mn] KQFUCKFHODLIAZ-UHFFFAOYSA-N 0.000 claims 1
- 239000011656 manganese carbonate Substances 0.000 claims 1
- 235000006748 manganese carbonate Nutrition 0.000 claims 1
- 229940093474 manganese carbonate Drugs 0.000 claims 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 28
- 230000009467 reduction Effects 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001257 hydrogen Substances 0.000 abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 17
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 239000003518 caustics Substances 0.000 abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 abstract description 11
- 239000010941 cobalt Substances 0.000 abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 10
- 239000011572 manganese Substances 0.000 abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052748 manganese Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910007676 ZnO—SiO2 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/61—
Abstract
The invention discloses manganese cobalt spinel catalyst and preparation method thereof, wherein manganese cobalt spinel catalyst is using manganese cobalt spinel as active component, using micropore ceramics as carrier.Manganese cobalt spinel catalyst proposed by the present invention not only has excellent mechanical strength, high temperature resistant and caustic corrosion resistance performance and preferable storage stability, but also has preferable catalytic activity in hydrogen reduction catalysis.
Description
Technical field
The invention belongs to catalyst fields, specifically, the present invention relates to manganese cobalt spinel catalyst and preparation method thereof.
Background technology
The catalytic performance of oxygen reduction catalyst it is best should be platinum and noble metal catalyst, but it is expensive；Perovskite
The catalytic performance of type composite catalyst and transition metal chelate catalyst is unstable, preparation process is complex and high cost；It prepares
Pure Mn oxide is generally more difficult and its complexity of reaction mechanism of oxygen, to limit the application of Mn oxide.Therefore,
Current existing oxygen reduction catalyst is further improved.
Invention content
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, the present invention
One purpose is to propose manganese cobalt spinel catalyst and preparation method thereof.Manganese cobalt spinel catalyst proposed by the present invention is not only
With excellent mechanical strength, high temperature resistant and caustic corrosion resistance performance and preferable storage stability, and in hydrogen reduction catalysis
With preferable catalytic activity.
According to an aspect of the present invention, the present invention proposes a kind of manganese cobalt spinel catalyst, the manganese cobalt spinel
Catalyst is using manganese cobalt spinel as active component, using micropore ceramics as carrier.
The manganese cobalt spinel catalyst of the above embodiment of the present invention is by using manganese cobalt spinel as active component, not only may be used
To significantly improve the hydrogen reduction catalytic performance and electric conductivity of catalyst, it can also make catalyst that there is preferable alkali resistance；Meanwhile
By being the micropore ceramics of main phase as carrier using micro- stomata, it can not only make manganese cobalt spinel catalyst that there is higher hardness
And excellent high temperature resistant, wear-resistant and corrosion resistance, moreover it is possible to significantly increase the manganese cobalt spinel as active component in oxygen
Specific surface area in reduction catalysts.The manganese cobalt spinel catalyst of the above embodiment of the present invention not only has excellent machine as a result,
Tool intensity, high temperature resistant and caustic corrosion resistance performance and preferable storage stability, and have in hydrogen reduction catalysis and preferably urge
Change activity, and reaction can be catalyzed for hydrogen reduction, the reaction compartment of bigger is provided, while being also less prone to be crushed in use, effectively
Specific surface area small disadvantage when active component manganese cobalt spinel is used alone is overcome, there is good industrial value.
In addition, manganese cobalt spinel catalyst according to the above embodiment of the present invention can also have following additional technology special
Sign：
In some embodiments of the invention, the quality that manganese cobalt spinel loads in the manganese cobalt spinel catalyst is 2-
50%.Thus, it is possible to further increase the catalytic activity of manganese cobalt spinel catalyst, and provide for hydrogen reduction catalysis reaction larger
Reaction compartment.
According to the second aspect of the invention, the invention also provides a kind of sides preparing above-mentioned manganese cobalt spinel catalyst
Method, including：
(1) manganese salt and cobalt salt are mixed to and are carried out the first milled processed, to obtain mixing salt powder；
(2) the mixing salt powder is mixed with micropore ceramics, diluent and water and carries out the second milled processed and carries out old
Change, to obtain compound intermediate；
(3) processing is dried to the compound intermediate, to obtain presoma；
(4) calcination process is carried out to the presoma, to obtain the manganese cobalt spinel catalyst.
The method for preparing manganese cobalt spinel catalyst of the above embodiment of the present invention is by by manganese salt, cobalt salt, micropore ceramics
It is aged, the active component manganese cobalt spinel being prepared can successfully be loaded to after diluent and water mixed grinding
On micropore ceramics, and then manganese cobalt spinel catalyst can be finally obtained with calcination process by being subsequently dried.As a result, originally
The method for preparing manganese cobalt spinel catalyst of invention above-described embodiment is not only simple for process, easily realizes industrialized production, but also
Be prepared prepare manganese cobalt spinel catalyst also have excellent mechanical strength, high temperature resistant and caustic corrosion resistance performance and preferably
Storage stability, and hydrogen reduction catalysis in have preferable catalytic activity, and can be hydrogen reduction catalysis react provide more
Big reaction compartment, while being also less prone to be crushed in use, effectively overcome the exclusive use of active component manganese cobalt spinel
When the small disadvantage of specific surface area, have good industrial value.
In some embodiments of the invention, the manganese salt is selected from manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, carbonic acid
At least one of manganese and manganese oxalate；The cobalt salt is selected from cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate, cobalt carbonate and oxalic acid
At least one of cobalt.Manganese ion and cobalt ions are not only contributed to as a result, and reacts and formed spinel structure in aqueous solution, also
The yield and purity of active component manganese cobalt spinel can be further increased, and then the catalysis of manganese cobalt spinel can be further increased
The catalytic activity of agent.
In some embodiments of the invention, the micropore ceramics are selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、
TiO2With in SiC at least two high temperature sintering product.Thus, it is possible to make manganese cobalt spinel catalyst that there is larger specific surface
Long-pending, excellent catalytic activity, mechanical strength, high temperature resistant and caustic corrosion resistance performance and storage stability.
In some embodiments of the invention, the diluent is selected from glucose, trisodium citrate, potassium chloride, poly- second
At least one of enol, Pehanorm and citric acid.The manganese cobalt spinel that can not only enable reaction generate as a result,
Equably load to the surface and inside of micropore ceramics, moreover it is possible to which the combination for further increasing manganese cobalt spinel and micropore ceramics is strong
Degree, and then the catalytic activity of manganese cobalt spinel catalyst can be further increased.
In some embodiments of the invention, in step (1), manganese ion and cobalt ions in the cobalt salt in the manganese salt
Molar ratio is (1-3)：1.Thus, it is possible to further increase the catalytic activity for the manganese cobalt spinel being finally prepared.
In some embodiments of the invention, in step (2), the micropore ceramics mix manganese ion in salt powder with described
Molar ratio with cobalt ions summation is 2:1.Thus, it is possible to which the catalysis for further increasing the manganese cobalt spinel being finally prepared is lived
Property.
In some embodiments of the invention, the diluent mixes manganese ion and cobalt ions quality in salt powder with described
The 5-20% of summation.Thus, it is possible to further increase the catalytic activity of manganese cobalt spinel catalyst.
In some embodiments of the invention, in step (1) and step (2), first milled processed and the second grinding
The temperature of processing is respectively 25-60 degrees Celsius.
In some embodiments of the invention, in step (2), the ageing is that progress 2-24 is small under 25-90 degrees Celsius
When complete.Thus, it is possible to further increase the yield of manganese cobalt spinel, and then it can further increase and finally be prepared
The catalytic activity of manganese cobalt spinel catalyst.
In some embodiments of the invention, in step (3), the drying process is that 5- is carried out under 50-150 degrees Celsius
It completes within 24 hours.Thus, it is possible to fully remove the water phase contained by compound intermediate.
In some embodiments of the invention, in step (4), the calcination process is with the heating rate of 2-10 DEG C/min
It is warming up to 500-1500 DEG C and maintains 5-20h, then room temperature completion is cooled to the rate of temperature fall of 5-20 DEG C/min.As a result, may be used
To further increase the stability of manganese cobalt spinel catalyst.
In some embodiments of the invention, the calcination process be under the protective atmosphere of argon gas, nitrogen or helium into
Capable.It is possible thereby to effectively avoid active component manganese cobalt spinel oxygenolysis.
Description of the drawings
Fig. 1 is the method flow diagram according to an embodiment of the invention for preparing manganese cobalt spinel catalyst.
Specific implementation mode
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes a kind of manganese cobalt spinel catalyst, the catalysis of manganese cobalt spinel
Agent is using manganese cobalt spinel as active component, using micropore ceramics as carrier.
The manganese cobalt spinel catalyst of the above embodiment of the present invention is by using manganese cobalt spinel as active component, not only may be used
To significantly improve the hydrogen reduction catalytic performance and electric conductivity of catalyst, it can also make catalyst that there is preferable alkali resistance；Meanwhile
By being the micropore ceramics of main phase as carrier using micro- stomata, it can not only make manganese cobalt spinel catalyst that there is higher hardness
And excellent high temperature resistant, wear-resistant and corrosion resistance, moreover it is possible to significantly increase the manganese cobalt spinel as active component in oxygen
Specific surface area in reduction catalysts.The manganese cobalt spinel catalyst of the above embodiment of the present invention not only has excellent machine as a result,
Tool intensity, high temperature resistant and caustic corrosion resistance performance and preferable storage stability, and have in hydrogen reduction catalysis and preferably urge
Change activity, and reaction can be catalyzed for hydrogen reduction, the reaction compartment of bigger is provided, while being also less prone to be crushed in use, effectively
Specific surface area small disadvantage when active component manganese cobalt spinel is used alone is overcome, there is good industrial value.
According to a particular embodiment of the invention, the quality that manganese cobalt spinel loads in manganese cobalt spinel catalyst is 2-
50%.Inventor has found, when the load capacity of manganese cobalt spinel in manganese cobalt spinel catalyst is very few, in hydrogen reduction catalytic process
In catalytic effect unobvious can not only increase production cost and cause resource and when the load capacity of manganese cobalt spinel is excessive
Waste, and the manganese cobalt spinel loaded is also easy to fall off.As a result, by controlling manganese in manganese cobalt spinel catalyst in the present invention
The quality of cobalt spinel load is 2-50%.It can not only enable what manganese cobalt spinel stablized to load on micropore ceramics, and
Make manganese cobalt spinel catalyst that there is excellent mechanical strength, high temperature resistant and caustic corrosion resistance performance and preferable storage stability,
The specific surface area of manganese cobalt spinel can also be significantly improved, and then the catalysis that can further increase manganese cobalt spinel catalyst is lived
Property, and provide larger response area for hydrogen reduction catalysis reaction.
According to the second aspect of the invention, the invention also provides a kind of sides preparing above-mentioned manganese cobalt spinel catalyst
Method, including：
(1) manganese salt and cobalt salt are mixed to and are carried out the first milled processed, to obtain mixing salt powder；(2) by salt-mixture
Powder mixes and is carried out with micropore ceramics, diluent and water the second milled processed and is aged, to obtain among compound
Body；(3) processing is dried to compound intermediate, to obtain presoma；(4) calcination process is carried out to presoma, so as to
Obtain manganese cobalt spinel catalyst.
The method for preparing manganese cobalt spinel catalyst of the above embodiment of the present invention is by by manganese salt, cobalt salt, micropore ceramics
It is aged, the active component manganese cobalt spinel being prepared can successfully be loaded to after diluent and water mixed grinding
On micropore ceramics, and then manganese cobalt spinel catalyst can be finally obtained with calcination process by being subsequently dried.As a result, originally
The method for preparing manganese cobalt spinel catalyst of invention above-described embodiment is not only simple for process, easily realizes industrialized production, but also
Be prepared prepare manganese cobalt spinel catalyst also have excellent mechanical strength, high temperature resistant and caustic corrosion resistance performance and preferably
Storage stability, and hydrogen reduction catalysis in have preferable catalytic activity, and can be hydrogen reduction catalysis react provide more
Big reaction compartment, while being also less prone to be crushed in use, effectively overcome the exclusive use of active component manganese cobalt spinel
When the small disadvantage of specific surface area, have good industrial value.
The method for preparing manganese cobalt spinel catalyst of the above embodiment of the present invention is retouched in detail below with reference to Fig. 1
It states.
S100：Manganese salt and cobalt salt are mixed to and are carried out the first milled processed, to obtain mixing salt powder
According to an embodiment of the invention, by mixing and carrying out at the first grinding by manganese salt and cobalt salt in advance in the present invention
Reason, can not only enable manganese salt powder and cobalt salt powder be sufficiently mixed, and also help the grain of further control mixing salt powder
Diameter, and then being conducive to the active component manganese cobalt spinel being subsequently formed can be on payload to micropore ceramics.
According to a particular embodiment of the invention, manganese salt can be selected from manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, carbonic acid
At least one of manganese and manganese oxalate, cobalt salt can be selected from cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate, cobalt carbonate and oxalic acid
At least one of cobalt.Inventor has found, above-mentioned manganese salt and cobalt salt is not only soluble easily in water and purity is higher, and manganese ion and cobalt from
The valence state of son is more stable, by selecting above-mentioned manganese salt and cobalt salt in the present invention, not only contributes to manganese ion and cobalt ions in water
It is reacted in solution and forms spinel structure, moreover it is possible to further increase the yield and purity of active component manganese cobalt spinel, in turn
The catalytic activity for the manganese cobalt spinel being finally prepared can be further increased.
According to a particular embodiment of the invention, the molar ratio of manganese ion and cobalt ions in cobalt salt is (1-3) in manganese salt：1.This
By controlling manganese ion and cobalt ions it is above-mentioned molar ratio in invention, not only can further advantageously forms manganese cobalt spinel
Structure, moreover it is possible to further increase the yield and purity of manganese cobalt spinel, and then the manganese being finally prepared can be further increased
The catalytic activity of cobalt spinel.Preferably, the molar ratio of manganese ion and cobalt ions in cobalt salt can be (1.5-2.5) in manganese salt：
1, it is highly preferred that the molar ratio of manganese ion and cobalt ions in cobalt salt can be 2 in manganese salt:1, thus, it is possible to make finally to be prepared into
The manganese cobalt spinel arrived has better catalytic activity.
According to a particular embodiment of the invention, the temperature of the first milled processed can be 25-60 degrees Celsius.Thus, it is possible to
It is that catalyst structure changes to avoid grinding under higher temperature.
S200：Mixing salt powder is mixed with micropore ceramics, diluent and water and carried out the second milled processed and is carried out old
Change, to obtain compound intermediate
According to a particular embodiment of the invention, micropore ceramics can be added into mixing salt powder first to carry out with diluent
Mixing and grinding, then add water and continue to grind, liquid to be mixed by it is dilute fade to thick shape after be aged, wherein grinding temperature
It can be 25-60 degrees Celsius.Not only salt-mixture powder can be made to be come into full contact with micropore ceramics and diluent as a result, moreover it is possible to logical
Crossing ageing enables manganese ion and cobalt ions fully to be reacted on mixed liquor or micropore ceramics surface and inside and forms manganese cobalt point crystalline substance
Stone structure, and make the manganese cobalt spinel suspended matter uniform settlement of generation to micropore ceramics surface and inside, to realize that liquid divides admittedly
From and obtain compound intermediate, be then sintered and be thermally treated resulting in catalyst.
According to a particular embodiment of the invention, micropore ceramics can be selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、
TiO2With in SiC at least two high temperature sintering product.The above-mentioned micropore ceramics selected in the present invention using micro- stomata as main phase,
And there are the excellent performances such as high large specific surface area, hardness, wear-resistant, high temperature resistant, anticorrosive, pass through selection in the present invention as a result,
Carrier of the above-mentioned micropore ceramics as active component manganese cobalt spinel can not only provide more for the reaction of manganese ion and cobalt ions
Big reaction compartment can also enable active component manganese cobalt spinel obtained by the reaction steadily load to the table of micropore ceramics
Face and inside, and then can make the manganese cobalt spinel catalyst being finally prepared that there is larger specific surface area, excellent urge
Change activity, mechanical strength, high temperature resistant and caustic corrosion resistance performance and storage stability.
According to a particular embodiment of the invention, diluent can be selected from glucose, trisodium citrate, potassium chloride, poly- second
At least one of enol, Pehanorm and citric acid.By selecting the diluent of the above-mentioned type in the present invention, not only may be used
So that manganese ion and cobalt ions can be evenly dispersed in mixed liquor, and then enable the manganese cobalt spinel of reaction generation equably
Load to the surface and inside of micropore ceramics, moreover it is possible to further increase the bond strength of manganese cobalt spinel and micropore ceramics, as a result,
The catalytic activity for the manganese cobalt spinel catalyst being finally prepared can be further increased.
According to a particular embodiment of the invention, diluent can be preferably glucose and polyvinyl alcohol 1：The mixing of 1 mass
Object.
According to a particular embodiment of the invention, micropore ceramics and mole for mixing manganese ion and cobalt ions summation in salt powder
Than 2:1.Inventor has found, when above-mentioned molar ratio is excessive, can lead to manganese in the manganese cobalt spinel catalyst being finally prepared
The load capacity of cobalt spinel is very few, the catalytic effect unobvious in hydrogen reduction catalytic process, and when above-mentioned molar ratio is too small,
Production cost can not only be increased and resulted in waste of resources, but also the manganese cobalt spinel loaded is also easy to fall off.Pass through in the present invention
Control micropore ceramics are 2 with the molar ratio of manganese ion and cobalt ions summation in salt powder is mixed:1, it can not only make to be obtained by the reaction
Loading on micropore ceramics of can stablizing of manganese cobalt spinel, moreover it is possible to make in the manganese cobalt spinel catalyst being finally prepared
The load quality of manganese cobalt spinel reaches 2-50%, can not only make the manganese cobalt spinel catalyst being finally prepared as a result,
With excellent mechanical strength, high temperature resistant and caustic corrosion resistance performance and preferable storage stability, manganese cobalt can also be significantly improved
The specific surface area of spinelle, and then the catalytic activity of manganese cobalt spinel catalyst can be further increased, and can be urged for hydrogen reduction
Change the response area that reaction provides bigger.
According to a particular embodiment of the invention, diluent is the 5- for mixing manganese ion and cobalt ions quality summation in salt powder
20%.Inventor has found, when the addition of diluent is very few, is unfavorable for the manganese cobalt spinel of reaction generation in micropore ceramics
Surface and inner homogeneous dispersion, and when the addition of diluent is excessive, and excessive thinner composition is be easy to cause in micropore
Adhere on ceramics, influence micropore ceramics to the load capacity of active component manganese cobalt spinel and the specific surface area of manganese cobalt spinel,
The catalytic activity for the manganese cobalt spinel being finally prepared is influenced in turn.In the present invention by control diluent be mixing salt powder
The 5-20% of middle manganese ion and cobalt ions quality summation can not only enable the manganese cobalt spinel that reaction generates equably load
To the surface and inside of micropore ceramics, and further increase the bond strength of manganese cobalt spinel and micropore ceramics, moreover it is possible to ensure most
The manganese cobalt spinel catalyst being prepared eventually can further increase most the load capacity of active component manganese cobalt spinel
The catalytic activity for the manganese cobalt spinel catalyst being prepared eventually.
According to a particular embodiment of the invention, above-mentioned ageing is to carry out completing for 2-24 hours under 25-90 degrees Celsius.This
By being aged under these conditions in invention, each component in mixed liquor can be made fully to react, and make the manganese cobalt generated
Solid-liquor separation is realized on spinelle suspended substance sedimentation and the surface and inside for loading to micropore ceramics.Thus, it is possible to further increase
The yield of manganese cobalt spinel, and then the catalytic activity for the manganese cobalt spinel catalyst being finally prepared can be further increased.
It is possible to further which the mixed liquor after ageing is filtered and washed, compound intermediate is obtained.
S300：Processing is dried to compound intermediate, to obtain presoma
According to an embodiment of the invention, it can effectively be gone in the present invention by the way that processing is dried to compound intermediate
Except the water phase contained by compound intermediate, and then obtain presoma.Specifically, above-mentioned drying process can be at 50-150 degrees Celsius
Lower progress is completed for 5-24 hours, thus, it is possible to further increase drying effect.
S400：Calcination process is carried out to presoma, to obtain manganese cobalt spinel catalyst
According to a particular embodiment of the invention, above-mentioned calcination process can be warming up to the heating rate of 2-10 DEG C/min
500-1500 DEG C and 5-20h is maintained, then room temperature completion is cooled to the rate of temperature fall of 5-20 DEG C/min.Thus, it is possible into one
Step improves the stability of manganese cobalt spinel catalyst.
According to a particular embodiment of the invention, the calcination process can be under the protective atmosphere of argon gas, nitrogen or helium
It carries out.Thus, it is possible to effectively avoid active component manganese cobalt spinel oxygenolysis.
Embodiment 1
(1) at room temperature, manganese salt and cobalt salt are mixed to and carried out the first milled processed, obtains mixing salt powder.Wherein, manganese salt
For manganese sulfate, cobalt salt is cobaltous sulfate, and the molar ratio of manganese ion and cobalt ions in cobalt salt is 2 in manganese salt:1.
It (2) will mixing salt powder and micropore ceramics (ZrO2-Al2O3-SiO2), diluent (glucose) and water mixing carry out
Second milled processed, when mixed liquor by it is dilute fade to thick shape after be aged, obtain compound intermediate.Wherein, micropore ceramics with
It is 2 to mix the molar ratio of manganese ion and cobalt ions summation in salt powder:1, diluent be in mixing salt powder manganese ion and cobalt from
The 10% of protonatomic mass summation, ageing carry out 12h completions at 60 DEG C.
(3) processing is dried to compound intermediate, obtains presoma, the drying process is in vacuum drying chamber
15h completions are carried out at 120 DEG C.
(4) calcination process is carried out to presoma, obtains manganese cobalt spinel catalyst, the calcination process is in nitrogen protection
Under, it is that 5 DEG C/min is warming up to 950 DEG C with heating rate, is sintered 15h, is then that 10 DEG C/min is cooled to room temperature with rate of temperature fall,
It finally obtains with micropore ceramics ZrO2-Al2O3-SiO2For carrier, it is catalyzed by the manganese cobalt spinel of active component of manganese cobalt spinel
Agent.
Embodiment 2
(1) at room temperature, manganese salt and cobalt salt are mixed to and carried out the first milled processed, obtains mixing salt powder.Wherein, manganese salt
For manganese chloride, cobalt salt is cobalt chloride, and the molar ratio of manganese ion and cobalt ions in cobalt salt is 2 in manganese salt:1.
It (2) will mixing salt powder and micropore ceramics (ZrO2-ZnO-SiO2), diluent (polyvinyl alcohol) and water mixing carry out
Second milled processed, when mixed liquor by it is dilute fade to thick shape after be aged, obtain compound intermediate.Wherein, micropore ceramics with
It is 2 to mix the molar ratio of manganese ion and cobalt ions summation in salt powder:1, diluent be in mixing salt powder manganese ion and cobalt from
The 12% of protonatomic mass summation, ageing carry out 10h completions at 70 DEG C.
(3) processing is dried to compound intermediate, obtains presoma, the drying process is in vacuum drying chamber
15h completions are carried out at 120 DEG C.
(4) calcination process is carried out to presoma, obtains manganese cobalt spinel catalyst, the calcination process is in nitrogen protection
Under, it is that 5 DEG C/min is warming up to 950 DEG C with heating rate, is sintered 15h, is then that 10 DEG C/min is cooled to room temperature with rate of temperature fall,
It finally obtains with micropore ceramics ZrO2-ZnO-SiO2For carrier, it is catalyzed by the manganese cobalt spinel of active component of manganese cobalt spinel
Agent.
Embodiment 3
(1) at room temperature, manganese salt and cobalt salt are mixed to and carried out the first milled processed, obtains mixing salt powder.Wherein, manganese salt
For manganese oxalate, cobalt salt is cobalt oxalate, and the molar ratio of manganese ion and cobalt ions in cobalt salt is 2 in manganese salt:1.
It (2) will mixing salt powder and micropore ceramics (ZrO2-Al2O3-TiO2), diluent (citric acid) and water mixing carry out
Second milled processed, when mixed liquor by it is dilute fade to thick shape after be aged, obtain compound intermediate.Wherein, micropore ceramics with
It is 2 to mix the molar ratio of manganese ion and cobalt ions summation in salt powder:1, diluent be in mixing salt powder manganese ion and cobalt from
The 18% of protonatomic mass summation, ageing carry out 12h completions at 50 DEG C.
(3) processing is dried to compound intermediate, obtains presoma, the drying process is in vacuum drying chamber
15h completions are carried out at 120 DEG C.
(4) calcination process is carried out to presoma, obtains manganese cobalt spinel catalyst, the calcination process is in nitrogen protection
Under, it is that 5 DEG C/min is warming up to 950 DEG C with heating rate, is sintered 15h, is then that 10 DEG C/min is cooled to room temperature with rate of temperature fall,
It finally obtains with micropore ceramics ZrO2-Al2O3-TiO2For carrier, it is catalyzed by the manganese cobalt spinel of active component of manganese cobalt spinel
Agent.
The above embodiment of the present invention 1-3 prepares the method not only preparation process condition operation letter of manganese cobalt spinel catalyst
Manganese cobalt spinel catalyst that is single, easily realizing industrialized production, and be prepared all has high mechanical strength, high temperature resistant and resistance to
The feature that caustic corrosion performance is good and the larger catalytic activity of specific surface area of catalyst is high.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiments or example.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of manganese cobalt spinel catalyst, which is characterized in that the manganese cobalt spinel catalyst is using manganese cobalt spinel as work
Property component, using micropore ceramics as carrier.
2. catalyst according to claim 1, which is characterized in that manganese cobalt spinel is negative in the manganese cobalt spinel catalyst
The quality of load is 2-50%.
3. a kind of method preparing catalyst as claimed in claim 1 or 2, which is characterized in that including：
(1) manganese salt and cobalt salt are mixed to and are carried out the first milled processed, to obtain mixing salt powder；
(2) the mixing salt powder is mixed with micropore ceramics, diluent and water and carries out the second milled processed and is aged, with
Just compound intermediate is obtained；
(3) processing is dried to the compound intermediate, to obtain presoma；
(4) calcination process is carried out to the presoma, to obtain the manganese cobalt spinel catalyst.
4. according to the method described in claim 3, it is characterized in that, the manganese salt be selected from manganese nitrate, manganese sulfate, manganese chloride,
At least one of manganese acetate, manganese carbonate and manganese oxalate；The cobalt salt be selected from cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate,
At least one of cobalt carbonate and cobalt oxalate,
Optionally, the micropore ceramics are selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、TiO2With in SiC at least two height
Warm sintered product,
Optionally, the diluent is selected from glucose, trisodium citrate, potassium chloride, polyvinyl alcohol, Pehanorm and lemon
At least one of lemon acid.
5. method according to claim 3 or 4, which is characterized in that in step (1), in the manganese salt manganese ion with it is described
The molar ratio of cobalt ions is (1-3) in cobalt salt：1.
6. according to the method described in claim 5, it is characterized in that, in step (2), the micropore ceramics mix salt fines with described
The molar ratio of manganese ion and cobalt ions summation is 2 in end:1,
Optionally, the diluent is the 5-20% of manganese ion and cobalt ions quality summation in the mixing salt powder.
7. according to the method described in claim 3, it is characterized in that, in step (1) and step (2), first milled processed
Temperature with the second milled processed is separately 25-60 degrees Celsius.
8. according to the method described in claim 3, it is characterized in that, in step (2), the ageing is under 25-90 degrees Celsius
Carry out completion in 2-24 hours.
9. according to the method described in claim 3, it is characterized in that, in step (3), the drying process is Celsius in 50-150
Degree lower progress is completed for 5-24 hours.
10. according to the method described in claim 3, it is characterized in that, in step (4), the calcination process be with 2-10 DEG C/
The heating rate of min is warming up to 500-1500 DEG C and maintains 5-20h, then with the rate of temperature fall of 5-20 DEG C/min to be cooled to room temperature complete
At,
Optionally, the calcination process is carried out under the protective atmosphere of argon gas, nitrogen or helium.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114471606A (en) * | 2022-03-01 | 2022-05-13 | 南京先进生物材料与过程装备研究院有限公司 | Titanium dioxide modified manganese-cobalt spinel catalyst and preparation method and application thereof |
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| CN101664690A (en) * | 2008-09-04 | 2010-03-10 | 北京石油化工学院 | Catalyst and preparation method and application thereof |
| CN101939097A (en) * | 2008-06-27 | 2011-01-05 | 田中贵金属工业株式会社 | The catalyst of no platinum group metal |
| CN107790116A (en) * | 2016-09-07 | 2018-03-13 | 中国科学院福建物质结构研究所 | The preparation of spinel catalyst and the elimination applied to nitrogen oxides |
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| CN101939097A (en) * | 2008-06-27 | 2011-01-05 | 田中贵金属工业株式会社 | The catalyst of no platinum group metal |
| CN101664690A (en) * | 2008-09-04 | 2010-03-10 | 北京石油化工学院 | Catalyst and preparation method and application thereof |
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| CN114471606A (en) * | 2022-03-01 | 2022-05-13 | 南京先进生物材料与过程装备研究院有限公司 | Titanium dioxide modified manganese-cobalt spinel catalyst and preparation method and application thereof |
| CN114471606B (en) * | 2022-03-01 | 2024-02-13 | 南京先进生物材料与过程装备研究院有限公司 | Titanium dioxide modified manganese cobalt spinel catalyst and preparation method and application thereof |
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