CN114289016A - Catalyst and preparation method and application thereof - Google Patents
Catalyst and preparation method and application thereof Download PDFInfo
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- CN114289016A CN114289016A CN202111678716.3A CN202111678716A CN114289016A CN 114289016 A CN114289016 A CN 114289016A CN 202111678716 A CN202111678716 A CN 202111678716A CN 114289016 A CN114289016 A CN 114289016A
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- activated carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 21
- 239000002351 wastewater Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011269 tar Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 37
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- -1 alumina Chemical class 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 229910052761 rare earth metal Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910052747 lanthanoid Inorganic materials 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002602 lanthanoids Chemical class 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 235000009827 Prunus armeniaca Nutrition 0.000 description 5
- 244000018633 Prunus armeniaca Species 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
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- 230000001070 adhesive effect Effects 0.000 description 4
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- 238000005303 weighing Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000002006 petroleum coke Substances 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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- 150000003624 transition metals Chemical group 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
Images
Abstract
The invention discloses a catalyst and a preparation method and application thereof. The catalyst of the invention comprises: a matrix and a metal oxide dispersed in the matrix; the preparation raw materials of the matrix comprise active carbon with the particle size of 100-500 meshes and a binder for binding the active carbon; the metal oxides include at least one transition metal oxide and at least one rare earth metal oxide. The catalyst of the invention can catalyze the ozone oxidation to decompose the organic matters in the water for a long time and with high efficiency through special structure and component design. The invention also provides a preparation method and application of the catalyst.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a catalyst, and a preparation method and application thereof.
Background
The ozone advanced oxidation has the advantages of high efficiency, no secondary pollution and the like, is often used for degrading organic matters which are difficult to degrade in organic wastewater, and is a common technical means in sewage treatment. However, since the ozone advanced oxidation is a gas-liquid two-phase reaction, the utilization rate of ozone is very low, and how to improve the utilization rate of ozone becomes a problem of concern in the industry.
At present, two methods are mainly used for improving the utilization rate of ozone: firstly, the size of ozone bubbles is reduced, the surface area of the bubbles is increased, namely the gas-liquid contact area is increased, and the effective reaction rate is improved; secondly, a catalyst is used to improve the ozone reaction efficiency.
There have been many studies on a catalyst for advanced oxidation of ozone, and the catalyst can be mainly classified into a simple metal, a metal oxide, a metal having a carrier, and a metal oxide having a carrier; the catalytic ozone advanced oxidation method is also used for degrading organic matters such as dimethyl phthalate, methyl orange, high-concentration humic acid and the like in water; the catalyst shows higher catalytic activity in the process of initial use. However, conventional catalysts generally deactivate rapidly with increasing time of use.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a catalyst which can catalyze the ozone oxidation decomposition of organic matters in water for a long time and with high efficiency through special structure and component design.
The invention also provides a preparation method of the catalyst.
The invention also provides an application of the catalyst or the catalyst prepared by the preparation method.
According to one aspect of the present invention, there is provided a catalyst comprising: a matrix and a metal oxide dispersed in the matrix;
the preparation raw materials of the matrix comprise activated carbon particles with the particle size of 100-500 meshes and a binder for binding the activated carbon;
the metal oxides include at least one transition metal oxide and at least one rare earth metal oxide.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
(1) the active carbon in the matrix has a porous structure, and the comparative area of the active carbon is as high as 800-1100 m2In terms of volume per gram, while other porous materials, such as diatomaceous earth, molecular sieves, zeolites, etc., have a specific surface area of up to 200m2Therefore, the activated carbon can load more metal oxides and can better fix and disperse the metal oxides.
In metal oxides, divalent or trivalent transition metals form lattice defects after doping with trivalent or tetravalent rare earth metals, on which lattice defects ozone can be rapidly decomposed to O2And HO, O2And HO is two free radicals, has very high oxidation-reduction potential, can attack organic matters, and can break chains (damage) of the organic matters, and further oxidize and even carbonize the organic matters, thereby finally improving the reaction efficiency of ozone.
In the metal oxide, lanthanide metal also has a unique lanthanide contraction phenomenon, which can promote the characteristic of complex stability constant increase when lanthanide metal forms a ligand, can promote the binding capacity of lanthanide metal and ozone in the process of catalyzing ozone oxidation, promote ozone molecules adsorbed on the catalyst, and further catalytically decompose more O2HO, which greatly improves the utilization rate of ozone.
(2) In the traditional catalyst, active substances are mostly loaded on the surface of a matrix or exist in the near surface of the matrix, and the types of the matrix mostly comprise active alumina spheres, molecular sieves, zeolites and the like; in the process of catalytically oxidizing organic matters by ozone, the catalyst is subjected to double washing of water and gas, active substances on the surface are easy to separate from a matrix, and finally inactivation is caused;
in the catalyst provided by the invention, active substances (metal oxides) are dispersed in the matrix, the active carbon with moderate particle size in the matrix is bonded by the binder and then granulated and formed, and the components in the interior and on the surface of the obtained catalyst are relatively uniform, so that even if the surface layer is stripped in a long-term washing process, the catalyst with a fresh inner layer can play a role in catalyzing again, the catalytic activity is maintained, and the service life of the catalyst is greatly prolonged.
(3) Compared with other types of matrixes, the activated carbon adopted by the invention has extremely low bulk density, and when the activated carbon is used for treating organic wastewater, the catalyst can be in a fluidized state in a reactor, so that the consumption is less, and the comprehensive cost is lower.
(4) In the process of catalyzing the ozone to oxidize and decompose organic matters, compared with the catalyst sold in the market (comprising the catalyst formed by loading metal oxides such as alumina, zeolite, molecular sieve and the like), the removal rate of COD can be improved by about 10 percent; and the high-salt-concentration wastewater has no obvious adverse effect on the catalyst provided by the invention.
In some embodiments of the invention, the metal oxide comprises at least two of the rare earth metal oxides.
Due to the specific lanthanide contraction phenomenon of rare earth elements, different types of rare earth metal oxides are adopted to dope the transition metal oxides, so that different types of high-density lattice defects can be generated; in addition, the energy level of the f-orbit of the rare earth metal is narrow, so that the low energy after ozone oxidation is easily absorbed to generate electron transition from a ground state to a high energy state, and then the high energy is released when the high energy state returns to the ground state to excite the ozone to be decomposed into free radicals; because the energy levels of the f orbitals of the rare earth metals with different atomic numbers are different, the f orbitals of the rare earth metals can be complementary; in conclusion, the synergistic effect between the various rare earth metal oxides and the transition metal oxides can improve the adsorption and decomposition (generating free radicals) of the obtained catalyst on ozone, and finally improve the utilization efficiency of the ozone.
In some embodiments of the invention, the weight of the metal element in the metal oxide accounts for 1-20% of the weight of the activated carbon.
In some embodiments of the present invention, the total weight of the rare earth metal oxide is 1 to 10% of the weight of the transition metal oxide.
In some embodiments of the invention, the transition metal oxide comprises iron oxide, aluminum oxide, manganese oxide, nickel oxide, and copper oxide.
In some embodiments of the invention, the rare earth metal oxide comprises yttrium oxide and lanthanide metal oxide.
In some embodiments of the invention, the rare earth metal oxide comprises cerium oxide and europium oxide.
In some embodiments of the invention, the metal oxide is a nano-scale metal oxide.
In some embodiments of the present invention, the raw material for preparing the activated carbon comprises at least one of fruit shell, wood material and coal material.
In some embodiments of the invention, the bulk density of the activated carbon is 0.4g/ml or more.
In some embodiments of the invention, the comparative area of the activated carbon is 800m or more2/g。
In some embodiments of the invention, the binder comprises at least one of a phosphate, a pyrophosphate, a silicate, a polycellulose ether, pitch, coal tar and petroleum tar.
In some embodiments of the invention, the mass ratio of the activated carbon to the binder is 0.4-10: 1.
In some embodiments of the invention, the catalyst has a service life of 108h or more.
According to a further aspect of the present invention, there is provided a method for preparing the catalyst, comprising the steps of:
s1, sequentially dipping the activated carbon in a metal salt solution and an alkali solution, and then carrying out solid-liquid separation;
s2, mixing the solid obtained in the step S1 with the binder and then granulating;
and S3, calcining the solid obtained in the step S2 in an air-isolated state.
The principle of the preparation method is as follows:
in step S1, the activated carbon is immersed in a metal salt solution, and metal ions are adsorbed in the activated carbon by the adsorption capacity of the activated carbon;
the active carbon is dipped in alkali solution, so that the metal ions adsorbed on the active carbon can form metal hydroxide.
In step S3, the calcination pyrolyzes the metal hydroxide formed in step S1 to form metal oxide and water vapor, and the water vapor can further play a role in pore formation; calcination on the other hand can pyrolyze the binder introduced in step S2 to form a chemically stable material, and binders such as cellulose, cellulose ether, pitch, coal tar, petroleum coke, etc. are carbonized during calcination to form a carbon-based material with similar properties to activated carbon.
The preparation method according to a preferred embodiment of the present invention has at least the following advantageous effects:
(1) due to the special effect of the dipping method, the metal oxide in the catalyst obtained by the invention has small grain diameter and is uniformly dispersed in a matrix; therefore, the catalytic activity is higher.
(2) Because the metal salt is dipped in the alkali solution again, the anions in the metal salt are replaced by hydroxyl, the risk of producing oxysulfide, nitric oxide or halogen gas in the calcining process is avoided, and the method has higher environmental protection property.
(3) The impurities in the catalyst are further removed by calcining, the homogeneity of the obtained catalyst is improved, and the service life of the catalyst is prolonged.
In some embodiments of the invention, step S1 further comprises activating the activated carbon prior to the impregnating.
In some embodiments of the invention, the method of activation comprises soaking the activated carbon with acid and alkali in sequence, followed by washing with water and drying.
In some embodiments of the present invention, the acid is used in the activation at a concentration of 1 to 10% by mass.
In some embodiments of the invention, the acid employed in the activation comprises at least one of sulfuric acid, hydrochloric acid and nitric acid.
In some embodiments of the invention, the activation is carried out by soaking in the acid for 1-24 hours.
In some embodiments of the present invention, the activation is performed with a base concentration of 1-10% by mass.
In some embodiments of the invention, the base employed in the activation comprises at least one of sodium hydroxide, potassium hydroxide and ammonia.
In some embodiments of the invention, the activation is carried out by soaking in the alkali for a period of time of about 1 to 24 hours.
In some embodiments of the invention, the end point of the water wash in the activation is pH 7.5 or less.
In some embodiments of the present invention, in the activation, solid-liquid separation is performed after the water washing to obtain a solid.
In some embodiments of the invention, the temperature of the drying is 80-125 ℃ and the time is 1-5 h.
In some embodiments of the present invention, the immersion time in the metal salt solution in step S1 is 1 to 24 hours.
During this time, the metal ions in the metal salt solution can be sufficiently adsorbed into the activated carbon.
In some embodiments of the invention, the pH of the metal salt solution in step S1 is about 2.
In some embodiments of the present invention, in step S1, the metal salt solution includes at least one transition metal salt and at least one rare earth metal salt.
In some embodiments of the invention, the transition metal salt (Me) comprises iron, aluminum, manganese, nickel and copper salts.
In some embodiments of the invention, the rare earth metal salt (Ln) comprises a yttrium salt and a lanthanide metal salt.
In some embodiments of the present invention, in step S1, the mass concentration of the transition metal salt in the metal salt solution is 1-10%.
In some embodiments of the present invention, in step S1, the rare earth metal salt in the metal salt solution is 1 to 20% by mass of the transition metal salt, i.e., Me: Ln ═ 100:1 to 20 (weight ratio).
In some preferred embodiments of the present invention, in step S1, the metal salt solution includes at least one transition metal salt and at least two rare earth metal salts.
In some preferred embodiments of the present invention, in step S1, the metal salt solution includes at least one transition metal salt and two rare earth metal salts.
In some embodiments of the invention, the mass ratio of the two rare earth metal salts is 1-10: 10.
In some embodiments of the present invention, in step S1, after the activated carbon is immersed in the metal salt solution, the activated carbon is dried and then immersed in the alkali solution.
In some embodiments of the present invention, the immersion time in the alkali solution in step S1 is about 1 to 24 hours.
In some embodiments of the invention, in step S1, the lye comprises at least one of potassium hydroxide, sodium hydroxide and ammonia.
In some embodiments of the present invention, in step S2, the obtained shape by the granulation is spherical, block-like or irregular.
In some embodiments of the present invention, step S3 further comprises drying before sintering.
In some embodiments of the invention, the drying before sintering is carried out at a temperature of 80-200 ℃ for 0.5-1.0 h.
In some embodiments of the present invention, in step S3, the calcining includes a first constant temperature calcining and a second constant temperature calcining.
In some embodiments of the invention, the temperature of the first isothermal calcination stage is 500 to 550 ℃.
In some embodiments of the invention, the duration of the first constant-temperature calcination is 0.5 to 1.0 h.
In some embodiments of the present invention, the temperature of the second isothermal calcination is 700 to 1200 ℃.
In some preferred embodiments of the present invention, the temperature of the second constant temperature calcination is 700 to 800 ℃.
In some embodiments of the invention, the second constant temperature period is 3-5 h.
In some embodiments of the invention, in step S3, the method of isolating air includes one of atmospheric protection and vacuum.
According to another aspect of the invention, the application of the catalyst or the catalyst prepared by the preparation method in organic wastewater treatment is provided.
In some embodiments of the invention, the organic wastewater comprises coal enterprise scrubber wastewater.
In some embodiments of the invention, the coal enterprise scrubber wastewater includes tar therein.
The tar comprises at least one of a nitrogen heterocyclic compound, a nitrogen heterocyclic compound and a polycyclic compound, and is difficult to degrade by adopting a common ozone oxidation method.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 shows the results of durability tests of catalysts obtained in example 3 of the present invention and comparative example 1.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The catalyst is prepared by the following specific process:
D1. activated carbon activation:
d1a, taking 1000g of apricot shell activated carbon powder with the particle size of 100-200 meshes, adding 5 wt% of hydrochloric acid, soaking for 2h, and performing solid-liquid separation (draining water in the solid);
d1b, soaking the solid obtained in the step D1a with 5 wt% sodium hydroxide for 1h, and washing the solid with water to be neutral (pH is approximately equal to 7) after solid-liquid separation;
d1c, drying the solid obtained in the step D1b at 125 ℃ for 2 h;
D2. preparing an immersion liquid: measuring 1000ml of water, adding hydrochloric acid to adjust the pH value to 2, and adding 30g of manganese sulfate and 2g of cerium nitrate into the water with the pH value adjusted to dissolve for later use;
D3. d1, introducing the activated carbon obtained in the step D2 into the impregnation liquid obtained in the step D2, slowly stirring for 30min, standing for 8h, and performing solid-liquid separation after the completion;
D4. pouring the solid obtained in the step D3 into 500ml of ammonia water solution (the solution is obtained by diluting 25-28% ammonia water with water according to the volume ratio of 1: 1), stirring for 30min, standing for 30min, and carrying out solid-liquid separation;
D5. mixing the solid obtained in the step D4 and the adhesive for 4 hours in a kneader according to the weight ratio of 10:3.5 by taking coal tar as the adhesive, extruding the mixture into cylindrical strips with the diameter of 3mm in an extruder, and cutting the cylindrical strips into short strips with the length of 2 cm;
D6. and D5, placing the substance obtained in the step D5 into a dry pot, sintering by using a vacuum calciner, wherein the specific sintering system is that the temperature is increased to 200 ℃ at the speed of 50 ℃/h, the temperature is kept for 1h (the stage is dry), the temperature is increased to 550 ℃ at the speed of 30 ℃/h, the temperature is kept for 0.5h, the temperature is increased to 750 ℃ at the speed of 30 ℃/h, the temperature is kept for 4h, finally, the power supply is cut off, the temperature is naturally reduced to below 250 ℃, the furnace door is opened, the temperature is reduced to the room temperature, and then the product is obtained by packaging.
In this embodiment, the sequence between the step D1 and the step D2 may be changed or performed in parallel.
Example 2
The catalyst is prepared by the following specific process:
D1. activated carbon activation:
d1a, taking 1000g of apricot shell activated carbon powder with the particle size of 200-500 meshes, adding 5 wt% of hydrochloric acid, soaking for 2h, and carrying out solid-liquid separation;
d1b, soaking the solid obtained in the step D1a with 5 wt% sodium hydroxide for 1h, and washing the solid with water to be neutral (pH is approximately equal to 7) after solid-liquid separation;
D2. preparing an immersion liquid: weighing 1000ml of water, adding hydrochloric acid to adjust the pH value to 2, weighing 40g of manganese sulfate, 4g of cerium nitrate and 4g of europium nitrate, and adding the manganese sulfate, the 4g of cerium nitrate and the 4g of europium nitrate into the water with the adjusted pH value to dissolve for later use;
D3. d1, introducing the activated carbon obtained in the step D2 into the impregnation liquid obtained in the step D2, slowly stirring for 30min, standing for 8h, and performing solid-liquid separation after the completion; drying the obtained solid at 120 ℃ for 3 h;
D4. d3, pouring the solid obtained in the step D3 into 500ml of 10 wt% sodium hydroxide solution, stirring for 30min, standing for 30min, and carrying out solid-liquid separation;
D5. taking coal tar as a binder, uniformly mixing the solid obtained in the step D4 and the binder according to the weight ratio of 5:2, and extruding the mixture into particles with the diameter of 3mm and the length of 1 cm;
D6. and D5, placing the substance obtained in the step D5 into a dry pot, and sintering by adopting a vacuum calciner, wherein the specific sintering system is as follows: heating to 150 deg.C at a speed of 50 deg.C/h, maintaining for 1h, heating to 500 deg.C at a speed of 30 deg.C/h, maintaining for 0.7h, heating to 800 deg.C at a speed of 30 deg.C/h, maintaining for 3h, turning off power supply, naturally cooling to below 250 deg.C, opening the oven door, ventilating, cooling to room temperature, and packaging.
Example 3
This example prepares a catalyst, and the specific process differs from example 2 in that:
(1) in the step D1a, the grain size of the adopted shell activated carbon is 200-300 meshes;
(2) in the step D2, the metal salt is added in the following proportion: 30g of manganese sulfate, 20g of ferric chloride, 10g of aluminum sulfate, 8g of cerium nitrate and 4g of europium nitrate;
(3) the sintering system in the step D6 is as follows: heating to 200 ℃ at the speed of 50 ℃/h, preserving heat for 1h, heating to 550 ℃ at the speed of 30 ℃/h, preserving heat for 0.5h, heating to 800 ℃ at the speed of 30 ℃/h, preserving the temperature for 5h, cutting off a power supply, naturally cooling to below 250 ℃, opening a furnace door, ventilating and cooling to room temperature.
Comparative example 1
This comparative example prepared a catalyst, which differs from example 3 in that the specific procedure was: the apricot shell activated carbon with the diameter of 1-5 mm, the thickness of 0.1-1.0 mm and an irregular shape is adopted, and the apricot shell activated carbon is not powdered activated carbon, so that an adhesive is not needed for carrying out adhesive forming on the apricot shell activated carbon, and other steps are the same as those in the embodiment 3.
Test example 1
This test example tested the performance of the catalysts prepared in examples 1-3 and comparative example 1. The testing steps are as follows:
A1. preparing organic wastewater: the method comprises the following steps of (1) coal enterprise gas washing wastewater, wherein the COD (chemical oxygen demand) content in the coal enterprise gas washing wastewater is 5600mg/L, the TDS (total dissolved solids, which is equivalent to providing a high-salt environment) content is 87g/L, and the pH value is 8.3;
A2. after the pH value of the organic wastewater prepared in the step A1 is adjusted to 9, carrying out pretreatment (the pretreatment mainly comprises the working procedures of homogenization adjustment, flocculation precipitation, filter pressing and the like, and removing suspended matters in the organic wastewater);
A3. respectively adopting the catalyst obtained in the embodiment 1-3 and a commercially available alumina microsphere catalyst to catalyze the organic wastewater obtained in the ozone oxidation step A2; the commercial alumina microsphere catalyst takes active alumina with the diameter of 2-3 mm as a carrier, and metal oxides such as manganese oxide, iron oxide, copper oxide and the like are loaded on the carrier;
the specific method comprises the following steps: adding 1000ml of the wastewater obtained in the step A2 into an ozone reactor, adding 300ml (about 150g) of catalyst, starting an air source ozone generator, and introducing ozone into the ozone reactor, wherein the amount of the introduced ozone is 1L/min;
A4. and (4) testing the COD content of the water sample obtained in the step A3, and carrying out the test by referring to a national standard document with the reference number of GB 1191489.
The test example used the test of step A3 without catalyst addition as a control test. The COD content of the water sample obtained in step A3 and the corresponding removal rate of COD are shown in Table 1.
TABLE 1 catalytic Effect of catalysts obtained in examples 1 to 3
The method for calculating the degradation rate comprises the following steps: 1-COD in the water sample/COD in the organic wastewater obtained in the step A3.
The results in table 1 show that the catalyst provided by the invention has a significantly improved catalytic oxidation removal rate of COD in organic wastewater compared with the commercially available catalyst.
Test example 2
This test example tested the durability of the catalysts prepared in example 3 and comparative example. The testing steps are as follows: the treated wastewater was the same as that obtained in step A2 of example 1; an ozone reactor with continuous feeding and continuous discharging is adopted; in which is disposed a catalyst (loose volume) occupying approximately the volume 1/3 of the ozone reactor; the treatment rate of the organic wastewater is 5L/h, and ozone is introduced into the ozone reactor at the rate of 1L/min in the process.
The test results are shown in table 2 and fig. 1.
Table 2 durability results for the catalysts obtained in example 3 and comparative example 1
The above results show that the catalysts obtained in example 1 and comparative example 1 of the present invention have a certain reduction in catalytic performance with the increase of reaction time, but the catalyst obtained in comparative example 1 has a more significant reduction trend, and the catalyst obtained in example 1 has a catalytic oxidation removal rate of COD as high as 68% after the catalyst is continuously reacted for 108 hours. The durability of the catalyst obtained in example 1 is significantly better than that of comparative example 1.
The reasons for the above results are: comparative example 1 granular (block) husk activated carbon has a large amount of metal oxide supported due to its abundant surface channels, and catalytic efficiency of ozone oxidation is high in a short time, while by impregnation methods (including conventional mechanical mixing methods), the amount of metal oxide entering the inside of the channels of activated carbon is small, and with the passage of surface metal oxide (under the combined action of water flow and ozone gas flow), its catalytic efficiency drops sharply. In the embodiment 1, the powdered activated carbon is loaded with metal oxides on the surface of the powdered activated carbon by an impregnation method, the metal oxides loaded on the surface and the inner part are basically consistent after the powdered activated carbon is bonded by a binder and extruded, and the inner layer of the powdered activated carbon is exposed on the surface along with the stripping of the surface layer due to water flow and air flow, so that the catalytic effect can still be achieved.
In conclusion, the catalyst obtained by the design of the structure and the components has excellent catalytic efficiency on ozone oxidation and outstanding durability.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A catalyst, comprising: a matrix and a metal oxide dispersed in the matrix;
the preparation raw materials of the matrix comprise active carbon with the particle size of 100-500 meshes and a binder for binding the active carbon;
the metal oxides include at least one transition metal oxide and at least one rare earth metal oxide.
2. The catalyst of claim 1 wherein the metal oxide comprises at least two of the rare earth metal oxides.
3. The catalyst according to claim 2, wherein the total weight of the rare earth metal oxide is 1 to 10% of the weight of the transition metal oxide.
4. The catalyst of claim 1, wherein the binder comprises at least one of a phosphate, a pyrophosphate, a silicate, a polycellulose ether, a pitch, a coal tar and a petroleum tar; preferably, the mass ratio of the activated carbon to the binder is 0.4-10: 1.
5. The catalyst according to any one of claims 1 to 4, wherein the service life of the catalyst is not less than 108 h.
6. A method for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:
s1, sequentially dipping the activated carbon in a metal salt solution and an alkali solution, and then carrying out solid-liquid separation;
s2, mixing the solid obtained in the step S1 with the binder and then granulating;
and S3, calcining the solid obtained in the step S2 in an air-isolated state.
7. The method according to claim 6, wherein the immersion time in the metal salt solution in step S1 is 1 to 24 hours.
8. The method according to claim 6 or 7, wherein in step S3, the calcination includes a first constant temperature calcination and a second constant temperature calcination; preferably, the temperature of the first-stage constant-temperature calcination is 500-550 ℃; preferably, the duration of the first-stage constant-temperature calcination is 0.5-1.0 h; preferably, the temperature of the second-stage constant-temperature calcination is 700-1200 ℃; preferably, the duration of the second constant-temperature calcination is 3-5 h.
9. Use of a catalyst according to any one of claims 1 to 5 or a catalyst prepared by a method according to any one of claims 7 to 9 in the treatment of organic waste water.
10. The use of claim 9, wherein the organic wastewater comprises coal industry scrubber wastewater.
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| CN109794260A (en) * | 2019-02-22 | 2019-05-24 | 上海电气集团股份有限公司 | A kind of preparation method and ozone oxidation catalyst of ozone oxidation catalyst |
| CN110975862A (en) * | 2019-11-22 | 2020-04-10 | 南京中衡元环保科技有限公司 | High-efficiency catalyst for ozone reactor and preparation method thereof |
| WO2020122808A1 (en) * | 2018-12-12 | 2020-06-18 | Sembcorp Industries Ltd | A metal doped catalyst |
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| CN1812835A (en) * | 2003-04-29 | 2006-08-02 | 约翰逊马西有限公司 | Manganese ozone decomposition catalysts and process for its preparation |
| WO2020122808A1 (en) * | 2018-12-12 | 2020-06-18 | Sembcorp Industries Ltd | A metal doped catalyst |
| CN109794260A (en) * | 2019-02-22 | 2019-05-24 | 上海电气集团股份有限公司 | A kind of preparation method and ozone oxidation catalyst of ozone oxidation catalyst |
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