CN111318283A - Wastewater treatment catalyst and preparation method thereof - Google Patents
Wastewater treatment catalyst and preparation method thereof Download PDFInfo
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- CN111318283A CN111318283A CN201811522010.6A CN201811522010A CN111318283A CN 111318283 A CN111318283 A CN 111318283A CN 201811522010 A CN201811522010 A CN 201811522010A CN 111318283 A CN111318283 A CN 111318283A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005751 Copper oxide Substances 0.000 claims abstract description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000000975 co-precipitation Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000009279 wet oxidation reaction Methods 0.000 abstract description 5
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 7
- 238000007865 diluting Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical class [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 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
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a wastewater treatment catalyst and a preparation method thereof, wherein the catalyst comprises a granular precursor and a CuZnM composite oxide loaded on the granular precursor, wherein M is selected from at least one of Ce, Ru and La; the catalyst comprises 50-75% of alumina, 15-30% of copper oxide, 6-15% of zinc oxide and 2-10% of M oxide by weight of the total weight of the final catalyst. The catalyst prepared by the method has concentrated granularity distribution, higher active metal dispersibility and hydration resistance, meets the performance requirement of high-concentration industrial wastewater treatment, and has good catalytic performance and stability in the catalytic wet oxidation process.
Description
Technical Field
The invention relates to a wastewater treatment catalyst and a preparation method thereof, in particular to a wastewater treatment catalyst especially suitable for catalytic wet oxidation and a preparation method thereof.
Background
With the rapid development of industrial technology and the continuous expansion of production scale, various industrial wastewater containing high-concentration hardly biodegradable organic pollutants, ammonia nitrogen compounds and suspended matters is increasing. The global environmental protection regulations are increasingly strict, the control index requirements of up-to-standard sewage discharge are higher and higher, and the catalytic oxidation treatment method of the wastewater is more and more valued and adopted by people. The high-concentration sewage treatment mainly comprises a catalytic wet oxidation method, an electrolytic catalytic oxidation method, a photocatalytic oxidation method, an advanced oxidation method and the like. The wet catalytic oxidation method is an effective method for treating high-concentration wastewater, a gaseous oxygen source is used as an oxidant, so that part of macromolecular organic matters are oxidized into biodegradable organic matters or completely mineralized into water and carbon dioxide, and the used catalysts are mainly homogeneous catalysts and heterogeneous catalysts. The homogeneous catalyst has mild reaction temperature, specific reaction performance and specific selectivity. The activity and selectivity of the homogeneous catalyst can be finely prepared and designed by factors such as the selection of ligands, the transformation of solvents, the addition of promoters and the like. In the homogeneous catalysis wet oxidation process, the catalyst is dissolved in the wastewater, so that the catalyst is easy to lose, economic loss and secondary pollution to the environment are caused, and subsequent treatment and recovery are needed, so that the process flow is complicated, the cost of wastewater treatment is increased, and the competitiveness is lost. The heterogeneous catalyst mainly takes active carbon, molecular sieve, amorphous alumina and titanium dioxide as carriers, takes single oxides or composite oxides of Cu, Fe, Mn, Co, V, Mo, Ni, Sn and the like as active metals, and among a plurality of metal oxide catalysts, the copper-containing catalyst shows higher catalytic activity, and CuO/gamma-Al 2O3 shows better catalytic activity due to the extremely high surface reduction activity.
CN105709776A discloses a preparation method of a catalytic wet catalyst, the catalyst is prepared by taking active carbon loaded with transition metal and rare earth metal as a core and alumina containing noble metal or amorphous silica-alumina containing noble metal as a shell by adopting a coprecipitation method, the water resistance of the catalyst is weak, and the loss of active metal of the catalyst is easy to cause.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a wastewater treatment catalyst and a preparation method thereof, and the catalyst prepared by the method has concentrated particle size distribution, higher active metal dispersibility and hydration resistance, meets the performance requirement of high-concentration industrial wastewater treatment, and has good catalytic performance and stability in the catalytic wet oxidation process.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a wastewater treatment catalyst comprising a particulate precursor and a CuZnM composite oxide supported on the particulate precursor, the particulate precursor containing:
75-90% of alumina
5-12% of copper oxide
1-4% of zinc oxide
0.5% -2% of M oxide;
the particulate precursor has the following particle size distribution:
less than 30 μm 2% -20%
30~60μm 40%~60%
15% -40% of particles with the diameter of more than 60 mu m;
the M is selected from at least one of Ce, Ru and La; the catalyst contains, based on the total weight of the final catalyst:
50-75% of alumina
15-30% of copper oxide
6-15% of zinc oxide
2% -10% of M oxide.
A preparation method of a wastewater treatment catalyst comprises the following steps of firstly preparing a granular precursor and then loading metal:
(1) soaking alumina in a soluble salt solution containing Cu, Zn and M, and then drying and roasting to obtain a granular precursor; wherein M is selected from at least one of Ce, Ru and La, and at least one of the soluble salt solutions of Cu, Zn and M is a nitrate solution;
(2) adding water into the granular precursor obtained in the step (1) to form a suspension, adding soluble salt solutions of Fe, Zn and M and a precipitant solution into the suspension in parallel, carrying out coprecipitation reaction and gelling reaction, aging after finishing dropwise adding, washing, drying, forming and roasting a solid product to obtain the catalyst.
In the preparation method, when the impregnation is carried out in the step (1), the impregnation liquid also contains an organic complexing agent selected from at least one of polyethylene glycol, triethanolamine, urea, ethylene diamine tetraacetic acid, hexamethylenetetramine and citric acid; the content of the compound in the immersion liquid is 3-15 g/100mL, preferably 5-13 g/100 mL.
In the above preparation method, when the impregnation is performed in the step (1), the total concentration of the metal ions in the impregnation liquid is 0.5 to 1.5mol/L, and the total weight of the particulate precursor after the impregnation contains:
75-90% of alumina
5-12% of copper oxide
1-4% of zinc oxide
0.5% -2% of M oxide.
In the preparation method, the drying temperature in the step (1) is 100-120 ℃, and the time is 3-6 hours; the roasting adopts a sectional roasting mode, firstly, the roasting temperature is increased to 140-180 ℃ at the heating rate of 1.5-2.5 ℃/min, then, the temperature is increased to 200-220 ℃ at the heating rate of 0.1-0.8 ℃/min, then, the temperature is increased to 260-280 ℃ at the heating rate of 3.0-8.0 ℃/min, then, the temperature is increased to 500-600 ℃ at the heating rate of 1.5-2.5 ℃/min, and the temperature is kept for 3-5 hours.
As a further preference, the roasting operation process is as follows: the temperature is raised to 120-140 ℃ at the rate of 1.5-2.5 ℃/min, the roasting temperature is raised to 160-180 ℃ at the rate of 0.8-1.7 ℃/min, the temperature is raised to 200-220 ℃ at the rate of 0.1-0.8 ℃/min, the temperature is raised to 260-280 ℃ at the rate of 4.0-7.0 ℃/min, the temperature is raised to 500-600 ℃ at the rate of 1.5-2.5 ℃/min, and the temperature is kept for 3-5 hours.
In the preparation method, in the step (1) of the invention, an impregnation method is adopted to load active metal on alumina, and nitrate of the metal is utilized to be decomposed when being heated in the roasting process, so that gas is generated, the catalyst carrier is split into fine particles, an organic complexing agent in an impregnation liquid is loaded on the carrier and also is split into gas, the splitting is further intensified, the temperature is raised in a programmed manner, the slow temperature raising rate is controlled in the early stage of roasting, the temperature is slowly raised, after the gas is slowly released, cracks are formed on the surface of the catalyst, the temperature raising rate is rapidly raised, the nitrate and the organic complexing agent are rapidly decomposed, a large amount of gas is released, and the carrier is crushed to form particles with uniform size; with the above process, a particulate precursor having the following particle size distribution was obtained:
less than 30 μm 2% -20%
30~60μm 40%~60%
More than 60 μm 15% -40%.
In the preparation method, the alumina carrier adopted in the step (1) is a carrier commonly used in the field, and the hydration resistance of the carrier is improved by roasting at 850-950 ℃. Preferably, the molded alumina carrier is spherical, strip-shaped, flake-shaped or particle-shaped, and the specific surface area is 220-330 m2The pore volume is 0.8-1.2 mL/g.
In the above production method, the precipitant in step (2) is at least one selected from the group consisting of ammonium bicarbonate, ammonium carbonate, aqueous ammonia and urea, and NH is in the precipitant solution3And NH4 +The total concentration of (a) is 4.0-6.0 mol/L. Controlling the pH value of the coprecipitation reaction system to be 7.0-9.0, the reaction temperature to be 40-80 ℃, and the reaction time to be 30-45 min. The aging temperature is 40-80 ℃, the aging pH value is 7.0-9.0, and the aging time is 90-120 min.
In the preparation method, in the step (2), the drying is carried out at 100-120 ℃ for 2-12 hours, and the roasting is carried out at 400-800 ℃ for 3-10 hours; preferably, the roasting is carried out for 4 to 7 hours at 500 to 600 ℃.
In the above preparation method, it is necessary to ensure that the solution does not contain Na during the preparation process+、Cl-And SO4 2-Ions.
In the above preparation method, the gas released during the calcination in step (2) may be conventional NOXThe absorption is carried out by an absorption mode.
In the above preparation method, the metal is deposited on the surface of the particulate precursor by coprecipitation in step (2), and contains, based on the total weight of the catalyst:
50-75% of alumina
15-30% of copper oxide
6-15% of zinc oxide
2% -10% of M oxide.
In the invention, the coprecipitation reaction is carried out on the granular precursor with dispersed ideal grain diameter, so that the active metals Cu, Zn and M are adsorbed on the surface of the granular precursor, which is not only beneficial to forming larger grains, but also beneficial to the dispersion of the active metals. Because the precipitate is deposited on the surface of the active metal adsorption particle precursor and does not enter Al and a metal crystal nucleus framework, the content of active metal on the surface of a crystal grain is increased, the interaction between the active metal and the Al is weakened, the catalyst is easier to activate, and the hydrogenation activity of the catalyst is favorably exerted. Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
(1) 160.7g of Cu (NO) are weighed out3)2 .3H2O、81 g Zn(NO3)2 .6H2O and 33.6gCe (NO)3)3 .6H2Preparing 200mL of solution by using O, measuring 40mL of the solution, diluting to 90mL, adding 12g of polyethylene glycol, uniformly mixing, soaking 100g of alumina carrier, drying at 120 ℃ for 4 hours, and roasting, wherein the temperature rise rate before 140 ℃ is 2.0 ℃/min, the temperature rise rate at 140-170 ℃ is 1.3 ℃/min, the temperature rise rate at 170-210 ℃ is 0.7 ℃/min, the temperature rise rate at 210-270 ℃ is 5.5 ℃/min, the temperature rise rate at 270-600 ℃ is 2.0 ℃/min, and the temperature of 600 ℃ is kept constant for 3 hours to obtain a granular precursor a1, and the particle size distribution of the granular precursor is shown in Table 1;
(2) a prepared in (1)1Adding 200mL of water, heating to 65 ℃, taking 156mL (1) of metal soluble salt solution to dilute to 500mL, taking the solution and ammonia water solution (as precipitator) with the molar concentration of 4.58mol/L in parallel flow and dropwise adding for coprecipitation, and carrying out precipitation reactionIn the process, the reaction pH value is 8.0, stirring and aging are continuously carried out at constant temperature for 70 minutes after the dropwise addition is finished, filtration is carried out after the aging is finished, a filter cake is dried for 3 hours at the temperature of 130 ℃, a peptizing agent is added, a strip is extruded and formed, and then roasting is carried out for 3 hours at the temperature of 600 ℃ to obtain the catalyst A1The physicochemical properties thereof are shown in Table 2.
Example 2
The other conditions were the same as in example 1 except that 33.6gCe (NO) in step (1)3)3 .6H2O is changed to 17.7La (NO)3)3 .6H2O, changing the precipitator into ammonium carbonate solution, changing the mass of polyethylene glycol into 11g, in the roasting process, setting the temperature rise rate to be 1.8 ℃/min before 140 ℃, setting the temperature rise rate to be 1.2 ℃/min between 140 and 175 ℃, setting the temperature rise rate to be 0.4 ℃/min between 175 and 215 ℃, setting the temperature rise rate to be 6.0 ℃/min between 215 and 275 ℃ and setting the temperature rise rate to be 1.8 ℃/min between 275 and 600 ℃ to obtain a granular precursor a2The particle size distribution is shown in table 1; in the step (2), the precipitation reaction temperature is 75 ℃, the precipitation reaction pH is 8.3, and the catalyst A is obtained2The physicochemical properties thereof are shown in Table 2.
Example 3
The other conditions are the same as example 1, except that the mass of the polyethylene glycol in the step (1) is changed to 10g, the temperature is increased to 130 ℃ at the temperature rise rate of 2.1 ℃/min, the temperature rise rate of 130-165 ℃ is 1.4 ℃/min, the temperature rise rate of 165-205 ℃ is 0.4 ℃/min, the temperature rise rate of 205-265 ℃ is 5.8 ℃/min, the temperature rise rate of 265-600 ℃ is 2.1 ℃/min in the roasting process, and the granular precursor a is obtained3The particle size distribution is shown in table 1; in the step (42), the precipitation reaction temperature is 60 ℃, the precipitation reaction pH is 7.8, and the catalyst A is obtained3The physicochemical properties thereof are shown in Table 2.
Example 4
(1) Weighing 187.4g Cu (NO)3)2 .3H2O、64.8 g Zn(NO3)2 .6H2O and 16.8gCe (NO)3)3 .6H2Preparing 200mL of solution from O, measuring 40mL of the solution, diluting to 90mL, adding 12.5g of polyethylene glycol, uniformly mixing, taking 100g of alumina carrier, soaking, drying at 120 ℃ for 4 hours, and after drying, performingRoasting, wherein the temperature rise rate of 0-140 ℃ is 2.0 ℃/min, the temperature rise rate of 140-170 ℃ is 1.3 ℃/min, the temperature rise rate of 170-210 ℃ is 0.7 ℃/min, the temperature rise rate of 210-270 ℃ is 5.5 ℃/min, the temperature rise rate of 270-600 ℃ is 2.0 ℃/min, and the temperature of 600 ℃ is kept constant for 3 hours to obtain a granular precursor a4The particle size distribution is shown in table 1;
(2) a prepared in (1)4Adding 200mL of water, diluting a metal soluble salt solution in 156mL (1) to 500mL, co-flowing and dropwise precipitating with an ammonia water solution (as a precipitant) with the molar concentration of 4.98mol/L at 65 ℃, wherein the reaction pH value is 8.0 in the precipitation reaction process, continuously stirring and aging at constant temperature for 75 minutes after the dropwise addition is finished, filtering after the aging is finished, drying a filter cake at 130 ℃, adding a peptizing agent, extruding and molding the filter cake, and roasting at 600 ℃ for 3 hours to obtain a catalyst A4The physicochemical properties thereof are shown in Table 2.
Example 5
(1) 133.9g of Cu (NO) were weighed out3)2 .3H2O、97.2g Zn(NO3)2 .6H2O and 39.2g Ce (NO)3)3 .6H2Preparing 200mL of solution by using O, measuring 40L of the solution, diluting to 90mL, adding 12g of polyethylene glycol, uniformly mixing, soaking 100g of alumina carrier, drying at 120 ℃ for 4 hours after soaking, and roasting after drying, wherein the heating rate of 0-140 ℃ is 2.0 ℃/min, the heating rate of 140-170 ℃ is 1.3 ℃/min, the heating rate of 170-210 ℃ is 0.7 ℃/min, the heating rate of 210-270 ℃ is 5.5 ℃/min, the heating rate of 270-600 ℃ is 2.0 ℃/min, and the temperature of 600 ℃ is kept constant for 3 hours to obtain a granular precursor a5The particle size distribution is shown in table 1;
(2) a prepared in (1)5Adding 200mL of water, diluting a metal soluble salt solution in 156mL (1) to 500mL, co-flowing and dropwise adding the solution and an ammonia water solution (as a precipitant) with the molar concentration of 4.98mol/L at 63 ℃, wherein the reaction pH value is 8.0 in the precipitation reaction process, continuously stirring and aging at constant temperature for 100 minutes after the dropwise adding is finished, filtering after the aging is finished, drying a filter cake for 3 hours at 130 ℃, and adding a peptizing agentRoasting for 3 hours at 600 ℃ after extrusion molding to obtain catalyst A5The physicochemical properties thereof are shown in Table 2.
Comparative example 1
(1) 160.7g of Cu (NO) are weighed out3)2 .3H2O、81 g Zn(NO3)2 .6H2O and 33.6gCe (NO)3)3 .6H2Preparing 200mL of solution by using O, measuring 40mL of the solution, diluting to 90mL, adding 12g of polyethylene glycol, uniformly mixing, taking 100g of alumina carrier, carrying out solution impregnation, drying for 4 hours at 120 ℃, then roasting, raising the temperature to 600 ℃ at the speed of 2.0 ℃/min in the roasting process, keeping the temperature at 600 ℃ for 3 hours, and obtaining a granular precursor b1The particle size distribution is shown in table 1;
(2) b to preparation in (1)1Adding 200mL of water, heating to 65 ℃, taking 156mL (1) of metal soluble salt solution to dilute to 500mL, co-flowing and dropwise adding the solution and ammonia water solution (as precipitant) with the molar concentration of 4.58mol/L for coprecipitation, wherein the reaction pH value is 8.0 in the precipitation reaction process, continuously stirring and aging at constant temperature for 70 minutes after the dropwise adding is finished, filtering after the aging is finished, drying a filter cake for 3 hours at the temperature of 130 ℃, adding a peptizing agent for extrusion molding, and roasting at the temperature of 600 ℃ for 3 hours to obtain a catalyst B1The physicochemical properties thereof are shown in Table 2.
Comparative example 2
(1) 160.7g of Cu (NO) are weighed out3)2 .3H2O、81 g Zn(NO3)2 .6H2O and 33.6gCe (NO)3)3 .6H2Preparing 200mL of solution from O, measuring 44mL of the solution to dilute to 100mL, taking 100g of alumina carrier to carry out solution impregnation, drying for 4 hours at 120 ℃ after impregnation, and then roasting, wherein the heating rate before 140 ℃ is 2.0 ℃/min, the heating rate at 140-170 ℃ is 1.3 ℃/min, the heating rate at 170-210 ℃ is 0.7 ℃/min, the heating rate at 210-270 ℃ is 5.5 ℃/min, the heating rate at 270-600 ℃ is 2.0 ℃/min, and the constant temperature at 600 ℃ is 3 hours to obtain a granular precursor b2The particle size distribution is shown in table 1;
(2) to (1)1) B of (1)2Adding 200mL of water, heating to 65 ℃, taking 312mL of metal soluble salt solution in (1) to dilute to 500mL, co-flowing and dropwise adding the solution with ammonia water solution (as precipitant) with the molar concentration of 4.58mol/L for coprecipitation, wherein the reaction pH value is 8.0 in the precipitation reaction process, continuously stirring and aging at constant temperature for 70 minutes after the dropwise adding is finished, filtering after the aging is finished, drying a filter cake for 3 hours at the temperature of 130 ℃, adding a peptizing agent for extrusion molding, and roasting at the temperature of 600 ℃ for 3 hours to obtain a catalyst B2The physicochemical properties thereof are shown in Table 2.
TABLE 1 particle size distribution of particulate precursors
TABLE 2 physicochemical Properties of the catalyst
The catalysts prepared in the above-described examples of the present invention and comparative examples were evaluated. The catalyst is filled in a fixed bed reactor, and elemental oxygen is used as an oxidation medium and is contained in a certain oil refinery. . The wastewater is continuously treated. Main pollutants COD in wastewater: 12000 mg/L, free cyanogen: 780. mu.g/g. The treatment conditions are as follows: the temperature is 200 ℃, the pressure is 6.0MPa, the gas-liquid volume ratio is 150, and the liquid hourly volume space velocity is 1.5h-1. The properties of the treated wastewater after 7 hours of catalyst use are shown in Table 3.
TABLE 3 evaluation results of catalysts
The evaluation results of the above-mentioned wastewater treated under the same process conditions for 1000 hours using the catalysts prepared in the examples of the present invention and the comparative examples are shown in Table 4.
Table 4 stability test results
| Catalyst numbering | A1 | A2 | A3 | A4 | A5 | B1 | B2 |
| COD removal rate% | 95.6 | 96.7 | 97.2 | 96.4 | 97.3 | 83.2 | 86.4 |
| Free cyanogen,. mu.g/g | 3.65 | 4.23 | 3.65 | 3.47 | 4.12 | 15.6 | 18.5 |
As can be seen from the results in Table 4, the catalyst of the present invention still maintains high activity after 1000h of use, and has good stability.
Claims (12)
1. A wastewater treatment catalyst characterized by: the catalyst comprises a particulate precursor and a CuZnM composite oxide supported on the particulate precursor, the particulate precursor containing:
75-90% of alumina
5-12% of copper oxide
1-4% of zinc oxide
0.5% -2% of M oxide;
the particulate precursor has the following particle size distribution:
less than 30 μm 2% -20%
30~60μm 40%~60%
15% -40% of particles with the diameter of more than 60 mu m;
the M is selected from at least one of Ce, Ru and La; the catalyst contains, based on the total weight of the final catalyst:
50-75% of alumina
15-30% of copper oxide
6-15% of zinc oxide
2% -10% of M oxide.
2. A preparation method of a wastewater treatment catalyst is characterized by comprising the following steps: firstly, preparing a granular precursor, and then loading metal, wherein the method specifically comprises the following steps:
(1) soaking alumina in a soluble salt solution containing Cu, Zn and M, and then drying and roasting to obtain a granular precursor; wherein M is selected from at least one of Ce, Ru and La, and at least one of the soluble salt solutions of Cu, Zn and M is a nitrate solution;
(2) adding water into the granular precursor obtained in the step (1) to form a suspension, adding soluble salt solutions of Cu, Zn and M and a precipitant solution into the suspension in parallel, carrying out coprecipitation reaction and gelling reaction, aging after finishing dropwise adding, washing, drying, forming and roasting a solid product to obtain the final catalyst.
3. The method of claim 2, wherein: when in the step (1), the impregnation liquid also contains an organic complexing agent selected from at least one of polyethylene glycol, triethanolamine, urea, ethylene diamine tetraacetic acid, hexamethylenetetramine and citric acid; the content of the compound in the dipping solution is 3-15 g/100 mL.
4. The method of claim 2, wherein: in the step (1), during impregnation, the total concentration of metal ions in the impregnation liquid is 0.5-1.5 mol/L, and after impregnation, the total weight of the granular precursor comprises:
75-90% of alumina
5-12% of copper oxide
1-4% of zinc oxide
0.5% -2% of M oxide;
and M is selected from at least one of Ce, Ru and La.
5. The method of claim 2, wherein: in the step (1), the drying temperature is 100-120 ℃, and the time is 3-6 hours; the roasting adopts a sectional roasting mode, firstly, the roasting temperature is increased to 140-180 ℃ at the heating rate of 1.5-2.5 ℃/min, then, the temperature is increased to 200-220 ℃ at the heating rate of 0.1-0.8 ℃/min, then, the temperature is increased to 260-280 ℃ at the heating rate of 3.0-8.0 ℃/min, then, the temperature is increased to 500-600 ℃ at the heating rate of 1.5-2.5 ℃/min, and the temperature is kept for 3-5 hours.
6. The method of claim 5, wherein: the roasting operation process comprises the following steps: the temperature is raised to 120-140 ℃ at the rate of 1.5-2.5 ℃/min, the roasting temperature is raised to 160-180 ℃ at the rate of 0.8-1.7 ℃/min, the temperature is raised to 200-220 ℃ at the rate of 0.1-0.8 ℃/min, the temperature is raised to 260-280 ℃ at the rate of 4.0-7.0 ℃/min, the temperature is raised to 500-600 ℃ at the rate of 1.5-2.5 ℃/min, and the temperature is kept for 3-5 hours.
7. The method of claim 2, wherein: the particulate precursor had the following particle size distribution:
less than 30 μm 2% -20%
30~60μm 40%~60%
More than 60 μm 15% -40%.
8. The method of claim 2, wherein: roasting the alumina adopted in the step (1) at 850-950 ℃, wherein the alumina is spherical, strip-shaped, flake-shaped or granular, and the specific surface area is 220-330 m2The pore volume is 0.8-1.2 mL/g.
9. The method of claim 2, wherein: in the step (2), the precipitant is at least one selected from ammonium bicarbonate, ammonium carbonate, ammonia water and urea, and NH is contained in the precipitant solution3And NH4 +The total concentration of (a) is 4.0-6.0 mol/L.
10. The method of claim 2, wherein: controlling the pH value of the coprecipitation reaction system to be 7.0-9.0, the reaction temperature to be 40-80 ℃ and the reaction time to be 30-45 min in the step (2); the aging temperature is 40-80 ℃, the aging pH value is 7.0-9.0, and the aging time is 90-120 min.
11. The method of claim 2, wherein: in the step (2), the drying is carried out for 2-12 hours at 100-120 ℃, and the roasting is carried out for 3-10 hours at 400-800 ℃; .
12. The method of claim 2, wherein: based on the total weight of the final catalyst, comprises:
50-75% of alumina
15-30% of copper oxide
6-15% of zinc oxide
2% -10% of M oxide.
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