CN110975879A - Metal-doped ceramsite catalyst and preparation method and application thereof - Google Patents
Metal-doped ceramsite catalyst and preparation method and application thereof Download PDFInfo
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- CN110975879A CN110975879A CN201911061136.2A CN201911061136A CN110975879A CN 110975879 A CN110975879 A CN 110975879A CN 201911061136 A CN201911061136 A CN 201911061136A CN 110975879 A CN110975879 A CN 110975879A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 119
- 239000002184 metal Substances 0.000 claims abstract description 116
- 150000003839 salts Chemical class 0.000 claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- 239000010455 vermiculite Substances 0.000 claims abstract description 27
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 27
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 18
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 17
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 30
- 239000004927 clay Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- 229940099596 manganese sulfate Drugs 0.000 claims description 12
- 239000011702 manganese sulphate Substances 0.000 claims description 12
- 235000007079 manganese sulphate Nutrition 0.000 claims description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 238000004090 dissolution Methods 0.000 abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 235000014380 magnesium carbonate Nutrition 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 ceramsite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- B01J35/397—
-
- B01J35/60—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
Abstract
The invention discloses a metal-doped ceramsite catalyst, which is prepared by sintering metal salt with an ozone catalysis effect and a ceramic matrix component, wherein the ceramic matrix component comprises argil, a pore-forming agent, vermiculite and a fluxing agent, and the fluxing agent is a composition of calcium carbonate and magnesium carbonate; the catalyst has the advantages of large specific surface area, high porosity, good catalytic oxidation effect, low metal dissolution rate, high utilization rate and low secondary pollution; the invention also discloses a preparation method of the metal-doped ceramsite catalyst, which optimizes the preparation method of the ceramsite core, improves the doping mode of the active component, can load high-content metal salt, has the advantages of low raw material consumption, low production cost, high safety and repeatability, and can realize large-scale production and application; the invention also discloses the application of the doped metal ceramsite catalyst, the catalytic oxidation effect is good, organic pollutants in various sewage can be more effectively removed, the utilization rate is high, the secondary pollution is reduced, and the subsequent treatment is not needed.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a metal-doped ceramsite catalyst and a preparation method and application thereof.
Background
With the development and progress of the society in all aspects, the water environment system which people rely on to live is damaged more and more seriously, and the water treatment is extremely urgent. Based on the consideration of treatment cost, most of industrial wastewater is mainly treated by a biological treatment method at present, but because the industrial wastewater has complex components and contains organic matters which are difficult to degrade, the water quality of the biological treatment method is often unstable after reaching the standard; especially, under the large background that the drainage standard is continuously improved, the quality of the effluent is improved by continuously adopting a biological treatment method, which is extremely difficult.
Ozone is used as a strong green oxidant, has strong capability of decomposing organic matters, and has the effects of decoloring, deodorizing and disinfecting, so the ozone oxidation technology is used for water treatment as one of advanced oxidation technologies. The key of the ozone oxidation effect lies in the utilization rate and the utilization amount of ozone, and the prior ozone has low utilization rate and limits the effect of degrading organic matters. Therefore, the catalytic ozone is used for improving the utilization rate of ozone, improving the removal rate of organic matters and saving the water treatment cost.
Most of the catalysts used for catalyzing ozone in the prior art are transition metal compounds, including homogeneous catalysts and heterogeneous catalysts. The homogeneous catalyst is prepared through preparing solution of catalytically active matter, adding the catalyst into waste water in ionic state, and introducing ozone for catalytic reaction. Although the liquid catalyst can improve the oxidation capacity of ozone, the liquid catalyst has the defects that the catalyst cannot be reused, secondary pollution is easily caused, the difficulty of subsequent treatment is increased, and the like.
The catalyst is prepared into a solid form for catalyzing ozone to treat wastewater, a liquid-solid heterogeneous catalysis system is formed, and the problems that the catalyst cannot be recycled and is difficult to recover are well solved. One of the schemes used in the currently prepared heterogeneous catalysts is loading, i.e. the carrier is immersed in a metal salt solution by an immersion method, and then the supported catalyst is prepared by drying and roasting. The catalyst is mainly applied to the catalyst of metal oxide loaded by carriers such as active carbon, alumina, ceramsite, silicon dioxide and the like. However, in the supported catalyst, the acting force between the metal oxide and the carrier is weak, and a certain amount of transition metal ions are dissolved in water in the catalytic reaction, so that secondary pollution is caused. Loss of transition metal ions not only results in waste of raw materials, but also results in reduced catalyst effectiveness.
Another method for preparing heterogeneous ozone catalysts is doping, i.e., mixing metal oxides or metal salts with the carrier raw materials, and then drying and roasting to obtain the doped catalyst. However, when the metal oxide catalyst is mixed with the carrier raw material, the particles of the oxide are limited by mechanical grinding, and the particles are often thicker, so that the catalytic oxidation effect of the metal oxide catalyst is influenced; in the prior art, the metal salt loaded ceramsite catalyst usually has a limited specific surface area, influences the ozone catalysis effect, and the common potassium permanganate belongs to a dangerous article easy to prepare viruses and explode and has a high market price, so that the catalyst is difficult to realize large-scale industrial production, and practical application is limited. In addition, the existing doping method for preparing the metal type ceramsite catalyst also has the problems of uneven distribution of active components, limited solubility of metal salt, easy dissolution of metal and the like, and influences the catalytic effect and popularization and application of the catalyst.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a metal-doped ceramsite catalyst which has the advantages of large specific surface area, high porosity, capability of loading high-content metal salt, low dissolution rate, good catalytic oxidation effect, cheap, easily-obtained and safe raw materials, low cost, reusability, high utilization rate and reduction of secondary pollution;
the second purpose of the invention is to provide a preparation method of the metal-doped ceramsite catalyst, optimize the preparation method of the ceramsite core, improve the doping mode of the active component, and obtain the catalyst with excellent catalytic performance, saved raw material consumption, low production cost and repeatability, thereby realizing large-scale production and application;
the invention also aims to provide the application of the metal-doped ceramsite catalyst, which has good catalytic oxidation effect, can effectively remove organic pollutants in various sewage, has high utilization rate, reduces secondary pollution, and does not need subsequent treatment.
One of the purposes of the invention is realized by adopting the following technical scheme:
a metal-doped ceramsite catalyst is prepared by sintering metal salt and ceramic matrix components, wherein the mass ratio of metal elements in the metal salt to the ceramic matrix components is (0.02-0.3): 1;
the ceramic matrix comprises the following raw materials in percentage by mass: 75-90% of pottery clay, 5-20% of pore-forming agent, 0.1-2% of vermiculite and 1-6% of fluxing agent, wherein the sum of the mass percentages of all the raw materials in the ceramic matrix component is 100%;
the metal salt can be decomposed into metal oxide with the function of catalyzing ozone through sintering;
the fluxing agent is a composition of calcium carbonate and magnesium carbonate.
Preferably, the ceramic matrix component comprises the following raw materials in percentage by mass: 85.71% of argil, 9.15% of pore-forming agent, 1.14% of vermiculite and 4% of fluxing agent.
Further, the air conditioner is provided with a fan,
the pore-forming agent is one of starch and coal powder.
The metal salt is one or a mixture of two of sulfate of iron and sulfate of manganese.
The mass ratio of the iron element to the manganese element is 1: (0.1-5).
Preferably, the sulfate of iron is ferrous sulfate heptahydrate, and the sulfate of manganese is manganese sulfate.
Further, the fluxing agent is a mixture of calcium carbonate and magnesium carbonate, wherein the mass ratio of the calcium carbonate to the magnesium carbonate is (0.1-1): 1.
the second purpose of the invention can be achieved by adopting the following technical scheme:
the preparation method of the metal-doped ceramsite catalyst is characterized by comprising the following steps of:
material preparation: weighing pottery clay, pore-forming agent, vermiculite and fluxing agent according to the formula ratio, and respectively grinding the pottery clay, pore-forming agent, vermiculite and fluxing agent to below 200 meshes to obtain a ceramic matrix component; the pottery clay in the pottery matrix component is divided into two parts which are respectively as follows: a first portion of clay and a second portion of clay;
metal salt treatment: weighing metal salt according to the formula ratio, dividing the metal salt into two parts, and respectively marking the two parts as a first part of metal salt and a second part of metal salt; dissolving the first part of metal salt in water to obtain a metal salt solution, and grinding the second part of metal salt into dry powder with the particle size of less than 50 meshes to obtain metal salt dry powder;
the preparation steps of the ceramsite core are as follows: taking the first part of pottery clay, and preparing a pottery granule core with the particle size of 3mm by a pelleting machine;
a material mixing step: mixing a second part of argil, metal salt dry powder, a pore-forming agent, vermiculite and a fluxing agent according to the formula amount to obtain a dry powder ingredient;
balling: coating the dry powder ingredients on the ceramsite core by using a metal salt solution as a binder through a disc granulator to generate a ceramsite catalyst with the particle size of 5-6 mm;
aging and drying: sequentially aging and drying the prepared ceramsite catalyst;
and (3) roasting: and roasting the ceramsite catalyst subjected to the aging and drying step to obtain the metal-doped ceramsite catalyst.
Further, the mass ratio of the first part of argil to the second part of argil is 1: 2.
the mass ratio of the first part of metal salt to the second part of metal salt is 1: (0.1-5).
Further, in the aging and drying step, the aging conditions are as follows: aging for 22-26h at room temperature, wherein the drying conditions are as follows: drying at 100-110 ℃ for 2-3 hours; in the roasting step, the roasting conditions are as follows: baking at 1100-1200 deg.C for 20-40 min.
An application of the metal-doped ceramsite catalyst in catalyzing ozone to treat wastewater.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, the metal salt and the ceramic matrix component are prepared into the ceramsite blank, and in the high-temperature sintering process, the metal salt can be decomposed to obtain metal oxide particles with ozone catalytic activity, wherein the particles are fine and are uniformly distributed in the ceramsite; the ceramsite catalyst is also added with a composition of calcium carbonate and magnesium carbonate as a fluxing agent, so that the loading capacity of metal salt can be improved, the dissolution rate of metal substances can be reduced, and the effective time of catalytic activity can be prolonged; meanwhile, vermiculite is added to reduce the shrinkage problem of the ceramsite catalyst in the roasting process, so that the porosity is increased, the load of a catalytic active substance is promoted, and the porous structure is more favorable for adsorbing organic pollutants in water and increasing the reaction activity.
2. The catalyst is prepared by combining two doping modes of active metal salt solution and metal salt powder, the metal salt is dissolved in water as a binder, and is used together with a ceramic matrix component added with metal salt powder to prepare the ceramsite catalyst, so that the doping of high-content metal can be realized, the limitation of the solubility of the metal salt is avoided, the problems of uneven distribution of active components and easy dissolution of the metal are effectively solved, the content of active components of metal oxides is improved, the catalytic activity is high, the loss rate of effective components is low, the utilization rate of catalytic active substances is high, the catalyst can be repeatedly used, and secondary pollution can be prevented.
3. The invention only uses the argil to prepare the ceramsite core, thereby saving the consumption of raw materials for producing the catalyst; the ceramsite with the core-shell structure and the catalyst active component on the surface layer is prepared by taking the pure argil as a raw material and the aqueous solution of the metal salt as a binder and taking the active component as the raw material of the ceramsite, so that the production cost is greatly reduced.
4. The preparation method has simple process, the used metal oxide precursors are all cheap, easily available and safe metal salts, the prepared ceramsite catalyst can be repeatedly used, the preparation process is simple, the operation controllability is strong, no pollution is caused, and large-scale industrial production can be realized.
5. The invention can be used for treating water independently and can also be used together with other methods. After being catalyzed by the catalyst, the ozone can effectively remove organic pollutants in water, and the oxidation capacity of the ozone is obviously improved, so that the adding amount of the ozone is reduced, and the operation cost is saved.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
A metal-doped ceramsite catalyst is prepared by sintering metal salt and ceramic matrix components, wherein the mass ratio of metal elements in the metal salt to the ceramic matrix components is (0.02-0.3): 1; the metal salt can be decomposed into metal oxide with the function of catalyzing ozone through sintering;
the ceramic matrix comprises the following raw materials in percentage by mass: 75-90% of pottery clay, 5-20% of pore-forming agent, 0.1-2% of vermiculite and 1-6% of fluxing agent, wherein the sum of the mass percentages of all the raw materials in the ceramic matrix component is 100%;
wherein, the fluxing agent is a composition of calcium carbonate and magnesium carbonate.
As a further preferred embodiment, the ceramic matrix component comprises the following raw materials in percentage by mass: 85.71% of argil, 9.15% of pore-forming agent, 1.14% of vermiculite and 4% of fluxing agent.
Wherein the pore-forming agent is one of starch and coal powder, the fluxing agent is a mixture of calcium carbonate and magnesium carbonate, and the mass ratio of the calcium carbonate to the magnesium carbonate is (0.1-1): 1.
starch or coal powder is added as a pore-forming agent, so that the specific surface area of the ceramsite catalyst is increased; calcium carbonate and magnesium carbonate are added as fluxing agents, so that the dissolution rate of metal substances is reduced; the vermiculite is added to reduce the shrinkage problem of the ceramsite catalyst in the roasting process, so that the porosity is increased, and the reaction activity is increased.
The metal salt is one or a mixture of two of iron sulfate and manganese sulfate.
As a further preferred embodiment, the mass ratio of the iron element to the manganese element in the metal salt is 1: (0.1-5).
As a further preferred embodiment, the sulfate of iron is ferrous sulfate heptahydrate and the sulfate of manganese is manganese sulfate.
A preparation method of a metal-doped ceramsite catalyst comprises the following steps:
material preparation: weighing pottery clay, pore-forming agent, vermiculite and fluxing agent according to the formula ratio, and respectively grinding the pottery clay, pore-forming agent, vermiculite and fluxing agent to below 200 meshes to obtain a ceramic matrix component; the pottery clay in the pottery matrix component is divided into two parts which are respectively as follows: a first portion of clay and a second portion of clay;
metal salt treatment: weighing metal salt according to the formula ratio, dividing the metal salt into two parts, and respectively marking the two parts as a first part of metal salt and a second part of metal salt; dissolving the first part of metal salt in water to obtain a metal salt solution, and grinding the second part of metal salt into dry powder with the particle size of less than 50 meshes to obtain metal salt dry powder;
the preparation steps of the ceramsite core are as follows: taking the first part of pottery clay, and preparing a pottery granule core with the particle size of 3mm by a pelleting machine;
a material mixing step: mixing a second part of argil, metal salt dry powder, a pore-forming agent, vermiculite and a fluxing agent according to the formula amount to obtain a dry powder ingredient;
balling: coating the dry powder ingredients on the ceramsite core by using a metal salt solution as a binder through a disc granulator to generate a ceramsite catalyst with the particle size of 5-6 mm;
aging and drying: sequentially aging and drying the prepared ceramsite catalyst; the aging conditions are as follows: aging at room temperature for 22-26 h; the drying conditions were: drying at 100-110 ℃ for 2-3 hours;
and (3) roasting: roasting the ceramsite catalyst subjected to the aging and drying step to prepare a metal-doped ceramsite catalyst; the roasting conditions are as follows: baking at 1100-1200 deg.C for 20-40 min.
In a further preferred embodiment, the mass ratio of the first part of clay to the second part of clay is 1: 2; the mass ratio of the first part of metal salt to the second part of metal salt is 1: (0.1-5).
The ceramic kernel of the invention takes pure argil as raw material and water as binder, thus reducing the cost of raw material.
The method comprises the steps of doping metal salts of iron and manganese into a ceramsite raw material, wherein the metal salts are added by taking ferrous sulfate, manganese sulfate or a mixed aqueous solution of ferrous sulfate and manganese sulfate as a binder. When high content metal is mixed, the limitation of metal salt solubility is avoided, and the rest metal salt is added in a powder form and is dry-mixed with the ceramsite base material. The two doping modes of solution and dry mixing are combined, so that the problems of uneven distribution of active components and easy dissolution of metal are effectively solved.
An application of a metal-doped ceramsite catalyst in catalyzing ozone to treat wastewater.
The metal-doped ceramsite catalyst is added into an ozone catalytic reaction device to catalyze organic pollutants in ozone oxidation water, so that the application of the metal-doped ceramsite catalyst in catalyzing ozone to treat wastewater is realized. Wherein the adding amount of the catalyst is the degree of full contact with water. The ozone catalytic reaction device consists of a water inlet, an air inlet, an aeration sand core, a catalytic reaction layer, a water outlet and a tail gas absorber from bottom to top. Ozone is directly generated by the ozone generator and enters the reaction device through the flow control valve.
The technological parameters of the ozone catalytic reactor are as follows: the catalyst is filled into the water outlet of the catalytic reaction device, a certain height is reserved between the catalyst and the air outlet, and the contact time of the catalyst and the catalyst is 10-60 min.
Example 1
A metal-doped ceramsite catalyst comprises 80g of metal salt and 350g of ceramic matrix component;
wherein, the ceramic matrix comprises the following components: 300g of argil, 32g of starch, 4g of vermiculite, 8g of magnesium carbonate and 6g of calcium carbonate.
The metal-doped ceramsite catalyst is prepared by the following method:
material preparation: weighing pottery clay, starch, vermiculite, magnesium carbonate and calcium carbonate according to the formula ratio, and respectively grinding the pottery clay, starch, vermiculite, magnesium carbonate and calcium carbonate to below 200 meshes to obtain ceramic matrix components; dividing argil in the argil matrix component into two parts, namely 100g of argil in the first part and 200g of argil in the second part;
metal salt treatment: dissolving 30g of ferrous sulfate heptahydrate and 15g of manganese sulfate in 70ml of water to prepare a metal salt solution; then 20g of ferrous sulfate heptahydrate and 15g of manganese sulfate are ground into metal salt dry powder with the particle size of less than 50 meshes.
The preparation steps of the ceramsite core are as follows: taking the first part of pottery clay, and preparing a pottery granule core with the particle size of 3mm by a pelleting machine;
a material mixing step: mixing a second part of argil, metal salt dry powder and the argil, starch, vermiculite, magnesium carbonate and calcium carbonate with the formula amount to obtain a dry powder ingredient;
balling: coating the dry powder ingredients on the ceramsite core by using a metal salt solution as a binder through a disc granulator to generate a ceramsite catalyst with the particle size of 5-6 mm;
aging and drying: aging the prepared ceramsite catalyst at room temperature for 24 hours, and then drying at 105 ℃ for 2-3 hours;
and (3) roasting: and roasting the aged and dried ceramsite catalyst at 1100-1200 ℃ for 20-40min to obtain the metal-doped ceramsite catalyst.
Example 2
A metal-doped ceramsite catalyst comprises 200g of metal salt and 350g of ceramic matrix component;
wherein, the ceramic matrix comprises the following components: 300g of argil, 32g of coal powder, 4g of vermiculite, 8g of magnesium carbonate and 6g of calcium carbonate.
The doped metal type ceramsite catalyst of this example was prepared by the method of example 1, with the difference that:
metal salt treatment: dissolving 30g of ferrous sulfate heptahydrate and 25g of manganese sulfate in 70ml of water to prepare a metal salt solution; the remaining 95g of ferrous sulfate heptahydrate and 50g of manganese sulfate were ground to a dry powder of metal salts of 50 mesh or less.
Example 3
A doped metal type ceramsite catalyst comprises 88g of metal salt and 346g of ceramic matrix component;
wherein, the ceramic matrix comprises the following components: 300g of argil, 32g of starch, 4g of vermiculite, 6g of magnesium carbonate and 4g of calcium carbonate.
The doped metal type ceramsite catalyst of this example was prepared by the method of example 1, with the difference that:
metal salt treatment: dissolving 30g of ferrous sulfate heptahydrate and 8g of manganese sulfate in 70ml of water to prepare a metal salt solution; the remaining 40g of ferrous sulfate heptahydrate and 10g of manganese sulfate were ground to a dry powder of metal salts of 50 mesh or less.
Application example
The catalysts of examples 1 to 3 were used for catalytic ozone treatment of wastewater, in which the mass ratio of ozone addition to COD was O3: the COD was 1:1, and the properties of the wastewater and the treatment results are shown in Table 1.
Table 1 examples 1-6 application of catalyst in catalytic ozonation wastewater and removal efficiency table
As can be seen from Table 1, the catalysts of examples 1-3 of the present application have better catalytic activity on ozone when treating wastewater, and compared with the case of adding ozone alone, the treatment efficiency of COD in wastewater is improved by more than 20%; moreover, the product of this application embodiment can be applicable to the water sample of different compositions, for example contains phenol waste water, paper mill waste water and rubbish penetrant waste water, and is higher to the waste water treatment efficiency of high COD content. When examples 1 and 2 were used simultaneously for the treatment of waste water from the same paper mill, it can be seen from table 2 that example 2, which carries a higher content of metal salts, has a higher catalytic activity.
Comparative example 1
A metal-doped haydite catalyst, which comprises the same components and preparation method as example 1 except that the ceramic matrix component does not contain vermiculite.
Comparative example 2
A metal-doped haydite catalyst, which comprises the same components and preparation method as example 1 except that the ceramic matrix component does not contain magnesium sulfate and calcium carbonate.
Comparative example 3
A metal-doped haydite catalyst was prepared in the same manner as in example 1, except for the metal salt.
The metal salt of this comparative example was 50g of ferrous sulfate heptahydrate, and the metal salt treatment procedure was:
dissolving 30g of ferrous sulfate heptahydrate in 70ml of water to prepare a metal salt solution; the remaining 20g of ferrous sulfate heptahydrate was ground to a dry powder of metal salts below 50 mesh.
Test example
The catalysts of comparative examples 1-3 and example 1 are used for catalyzing ozone to treat phenolic wastewater, wherein the mass ratio of the ozone addition amount to COD is O3: COD 1:1, initial COD 130mg/l, COD after ozone treatment reduced to 105.7mg/l, COD removal rate was 18.7%. The porosity, breakage rate and removal efficiency of the catalysts of comparative examples 1 to 3 and example 1 were measured, and the results are shown in table 2.
TABLE 2 porosity, breakage and removal efficiency of doped haydite catalysts
As is apparent from Table 2, under the same ozone adding amount, the treatment effect of the doped ceramsite catalysts prepared in comparative examples 1-3 and example 1 on wastewater is obviously higher than the removal rate of ozone without the catalyst, i.e., the treatment efficiency of COD is improved by 14.9-24.8% in the presence of the doped metal ceramsite catalyst. Comparing example 1 with comparative example 1, the apparent porosity and COD removal effect of the ceramsite catalyst (added with vermiculite) in example 1 are obviously higher than those of the ceramsite catalyst (added with vermiculite) in comparative example 1; comparing example 1 with comparative example 2, the breakage dissolution rate of comparative example 2 (no flux added) is much higher than that of example 1 (flux added), the COD removal rate in a short time is increased, but the long-term use of the catalyst is not facilitated; comparing example 1 with comparative example 3, the COD removal effect of example 1 (adding both metal salts of iron and manganese) was higher than that of comparative example 3 (adding only iron salt), and the addition of manganese salt greatly reduced the dissolution of iron salt and the breakage rate of catalyst.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of the present invention claimed in the present invention.
Claims (10)
1. The metal-doped ceramsite catalyst is characterized by being prepared by sintering metal salt and ceramic matrix components, wherein the mass ratio of metal elements in the metal salt to the ceramic matrix components is (0.02-0.3): 1;
the ceramic matrix comprises the following raw materials in percentage by mass: 75-90% of pottery clay, 5-20% of pore-forming agent, 0.1-2% of vermiculite and 1-6% of fluxing agent, wherein the sum of the mass percentages of all the raw materials in the ceramic matrix component is 100%;
the metal salt can be decomposed into metal oxide with the function of catalyzing ozone through sintering;
the fluxing agent is a composition of calcium carbonate and magnesium carbonate.
2. The doped metal type ceramsite catalyst according to claim 1, wherein the ceramic matrix component comprises the following raw materials in percentage by mass: 85.71% of argil, 9.15% of pore-forming agent, 1.14% of vermiculite and 4% of fluxing agent.
3. The doped metal type ceramsite catalyst according to claim 1, wherein the metal salt is one or a combination of two of iron sulfate and manganese sulfate; the pore-forming agent is one of starch and coal powder.
4. The doped metal type ceramsite catalyst according to claim 3, wherein the mass ratio of the iron element to the manganese element in the metal salt is 1: (0.1-5).
5. The doped metal type ceramsite catalyst according to claim 1, wherein the mass ratio of the calcium carbonate to the magnesium carbonate is (0.1-1): 1.
6. a process for the preparation of the doped metal-type haydite catalyst according to any one of claims 1 to 5, which comprises:
material preparation: weighing pottery clay, pore-forming agent, vermiculite and fluxing agent according to the formula ratio, and respectively grinding the pottery clay, pore-forming agent, vermiculite and fluxing agent to below 200 meshes to obtain a ceramic matrix component; the pottery clay in the pottery matrix component is divided into two parts which are respectively as follows: a first portion of clay and a second portion of clay;
metal salt treatment: weighing metal salt according to the formula ratio, dividing the metal salt into two parts, and respectively marking the two parts as a first part of metal salt and a second part of metal salt; dissolving the first part of metal salt in water to obtain a metal salt solution, and grinding the second part of metal salt into dry powder with the particle size of less than 50 meshes to obtain metal salt dry powder;
the preparation steps of the ceramsite core are as follows: taking the first part of pottery clay, and preparing a pottery granule core with the particle size of 3mm by a pelleting machine;
a material mixing step: mixing a second part of argil, metal salt dry powder, a pore-forming agent, vermiculite and a fluxing agent according to the formula amount to obtain a dry powder ingredient;
balling: coating the dry powder ingredients on the ceramsite core by using a metal salt solution as a binder through a disc granulator to generate a ceramsite catalyst with the particle size of 5-6 mm;
aging and drying: sequentially aging and drying the prepared ceramsite catalyst;
and (3) roasting: and roasting the ceramsite catalyst subjected to the aging and drying step to obtain the metal-doped ceramsite catalyst.
7. The method for preparing the metal-doped ceramsite catalyst according to claim 6, wherein the mass ratio of the first part of argil to the second part of argil is 1: 2.
8. the method for preparing the doped metal type ceramsite catalyst according to claim 6, wherein the mass ratio of the first part of metal salt to the second part of metal salt is 1: (0.1-5).
9. The method for preparing the doped metal type ceramsite catalyst according to claim 6, wherein in the aging and drying step, the aging conditions are as follows: aging for 22-26h at room temperature, wherein the drying conditions are as follows: drying at 100-110 ℃ for 2-3 hours; in the roasting step, the roasting conditions are as follows: baking at 1100-1200 deg.C for 20-40 min.
10. The use of the doped metal type ceramsite catalyst according to any one of claims 1-5 in the catalysis of ozone treatment wastewater.
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