CN117960173A - Preparation method of load-blending type ozone catalyst - Google Patents
Preparation method of load-blending type ozone catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 68
- 238000002156 mixing Methods 0.000 title claims abstract description 63
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 57
- 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 56
- 230000008569 process Effects 0.000 claims abstract description 45
- 239000010881 fly ash Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 239000010440 gypsum Substances 0.000 claims abstract description 33
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 33
- 239000000292 calcium oxide Substances 0.000 claims abstract description 31
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 31
- 230000000284 resting effect Effects 0.000 claims abstract description 31
- 238000003825 pressing Methods 0.000 claims abstract description 24
- 238000010025 steaming Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- 239000011398 Portland cement Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 26
- 239000003469 silicate cement Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 15
- 239000005695 Ammonium acetate Substances 0.000 claims description 15
- 229940043376 ammonium acetate Drugs 0.000 claims description 15
- 235000019257 ammonium acetate Nutrition 0.000 claims description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 14
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 14
- 239000001099 ammonium carbonate Substances 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical group 0.000 claims description 6
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 17
- 238000003911 water pollution Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 85
- 238000005469 granulation Methods 0.000 description 17
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- 239000011800 void material Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
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- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
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- 238000006385 ozonation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229910018516 Al—O Inorganic materials 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910020632 Co Mn Inorganic materials 0.000 description 2
- 229910020678 Co—Mn Inorganic materials 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 238000006703 hydration reaction Methods 0.000 description 2
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- 239000010865 sewage Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000011161 development Methods 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
- 230000009977 dual effect Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The invention is applicable to the technical field of catalysts for water pollution treatment, and provides a preparation method of a load-blending type ozone catalyst, which comprises the following steps: mixing the raw materials, and granulating in a granulating disc of a granulator, wherein the inclination angle of the granulating disc is 43-50 degrees, and the rotating speed of the granulating disc is 35-40 rpm/min; the obtained original catalyst is subjected to resting, steaming, pressing and drying to obtain a load-blending type ozone catalyst; the steaming and pressing process comprises a heating and boosting stage, a constant temperature and constant pressure stage and a cooling and depressurization stage which are sequentially carried out; the preparation raw materials comprise 35-55 parts of fly ash, 2-5 parts of quicklime, 4-8 parts of calcined gypsum, 15-25 parts of alumina, 9-15 parts of Portland cement, 5-10 parts of catalyst, 0.5-2 parts of foaming agent and 0.2-1 part of homogenizing agent. In conclusion, the preparation process of the ozone catalyst does not adopt high-temperature roasting, the activity and specific surface area of aggregate are high, the catalytic performance of the obtained ozone catalyst is high, and the preparation raw material cost is low.
Description
Technical Field
The invention relates to the technical field of catalysts for water pollution treatment, in particular to a preparation method of a load-blending type ozone catalyst.
Background
With the rapid development of modern industry, the amount of industrial wastewater is increased, and the trend of complex components, high inorganic salt content and the like is toward. At present, the industrial wastewater treatment process at home and abroad is mostly treated by adopting a biological method with good economical efficiency.
Ozone oxidation processes have gained increasing attention in recent years, with ozone having an oxidation-reduction potential of 2.07V in water, next to fluorine. Although simple ozone oxidation can remove organic matters to a certain extent, it is difficult to further oxidize oxidized small molecular substances. Research shows that by adding a certain proportion of metal catalyst into an ozone system, the capability of the ozone system for generating hydroxyl free radicals can be obviously improved, so that the performance of directly oxidizing organic matters by ozone is improved. Ozone catalytic oxidation can be classified into homogeneous catalytic oxidation and heterogeneous ozone catalytic oxidation according to the mode of adding a metal catalyst. The homogeneous catalyst is generally transition metal ion, and can be lost along with water after sewage treatment, and can not be used continuously, so that the cost of sewage treatment is high, and in addition, secondary pollution of water body can be caused. The catalyst in the heterogeneous ozone catalytic oxidation process is mainly activated carbon, zeolite, metal oxide (MnO 2、Fe2O3、Al2O3 and the like). Compared with the homogeneous ozone catalytic oxidation, the heterogeneous catalytic oxidation has the advantages of simple preparation, easy recovery and treatment, no secondary pollution and the like, thereby becoming a hot spot of current research.
The current common heterogeneous ozone catalyst preparation methods comprise an impregnation method and a blending method, but have certain problems. For example, the impregnated ozone catalyst has the defects of low catalyst content, easy loss, high cost and the like, and the usage amount is reduced year by year; although the blending type ozone catalyst solves the two problems of low catalyst content and catalyst loss, the blending type ozone catalyst adopts a high-temperature roasting process, the temperature reaches above 600 ℃, under the high-temperature condition, the crystal form of alumina is changed, the original activity and large specific surface characteristics of a base material are lost, the supported catalyst is less, and the ozone catalytic performance is lower; in order to improve the ozone catalytic performance in the prior art, the consumption of alumina is increased, and in the preparation raw materials of the ozone catalyst, the consumption of alumina reaches about 90 percent, so that the raw material cost is higher; meanwhile, the high-temperature roasting causes larger energy consumption and higher cost.
Paper article: preparation of Co-Mn/gamma-Al 2O3 catalyst and its catalytic performance. China water supply and drainage 2023.39 (17). The publication discloses that the Co-Mn/gamma-Al 2O3 composite catalyst is prepared by adopting an impregnation method, taking gamma-Al 2O3 as a carrier, taking manganese oxide and cobalt oxide as active components and calcining at 500 ℃. In the simulated wastewater reaction of the catalytic ozonation of aniline, the removal rate of COD reaches 84.79 percent. After the catalyst is reused for 8 times, the removal rate of COD is still stable between 82.15% and 84.79%. In the technology in the paper, active components are easy to lose, and the catalyst loading is low; the alumina is calcined at high temperature to form gamma-activated alumina, and the catalyst performance is still to be improved although the removal rate of COD of the catalyst is relatively high.
The patent with the publication number of CN 103007954B discloses a heterogeneous catalytic ozonation catalyst and a preparation method thereof, wherein the heterogeneous catalytic ozonation catalyst comprises the following components in percentage by weight: 61-64% of fly ash, 6-9% of metal oxide, 5-6% of cement, 5-6% of gypsum and 15-20% of lime, wherein the addition amount of aluminum powder is 0.06-0.07% of the total weight of the raw materials; the aggregate in the technology is mainly fly ash, aluminum powder is mainly used as a foaming agent, and cement is mainly used as a gelatinizing agent; the preparation method also comprises autoclaved air entrainment and a traditional blending technology, but the COD removal efficiency, the compressive strength and the total porosity of the ozone oxidation catalyst prepared by the technology are not ideal.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a load-blending type ozone catalyst, which solves the problems of low catalytic performance of the ozone catalyst, high preparation raw material cost and reduced aggregate activity and specific surface area caused by high-temperature roasting in the preparation process in the prior art.
The technical scheme of the invention is realized as follows:
in a first aspect, the invention provides a load-blending type ozone catalyst, which comprises the following preparation raw materials in parts by weight: 35-55 parts of fly ash, 2-5 parts of quicklime, 4-8 parts of calcined gypsum, 15-25 parts of alumina, 9-15 parts of Portland cement, 5-10 parts of a catalyst, 0.5-2 parts of a foaming agent and 0.2-1 part of a homogenizing agent.
Fly ash: the fly ash consists of glass body, crystal and a small part of unburned carbon, the main chemical components of the glass body are silicon dioxide and aluminum oxide, the total content of the silicon dioxide and the aluminum oxide is more than 60%, and the glass body is a main active component of the fly ash. Compared with cement, the activity of the fly ash is low, the hydration speed of the cement can be delayed, and under the same condition, the more glass bodies are, the higher the activity of the fly ash is, so that the fly ash activity is required to be excited by exciting the activity of the glass bodies in order to fully play the role of the fly ash.
Quicklime: the quicklime is used as a material for exciting the potential activity of the fly ash, the quicklime can generate heat and generate calcium hydroxide in the mixture, the fly ash is an acidic substance and is eroded under the action of strong alkali, so that the chemical bonds of Si-O and Al-O between glass bodies can be broken, the activity of the glass bodies is excited, and the activity of the fly ash is improved.
Plaster of paris: the calcined gypsum has the dual functions of an exciting agent and an accelerator, and the main components of the calcined gypsum contain sulfate, so that the hydration reaction of the fly ash and the quicklime can be accelerated, and the reaction process is as follows: firstly, calcined gypsum reacts with water to generate CaSO 4·2H2 O, quicklime is uniformly dispersed in the water to generate OH - and Ca 2+;OH- which promote the breaking of chemical bonds in a glass body, and secondly, under the influence of sulfate, ca 2+ interacts with Si-O and Al-O bonds which are broken before to generate a hydraulic cementing material, so that the strength of a prepared catalyst can be improved.
In the preparation raw materials, besides basic framework materials such as fly ash, quicklime, calcined gypsum and the like, alumina is added as a framework material, and has high chemical stability, can increase the specific surface area of the preparation materials, and can be used as a catalyst for catalytic oxidation reaction; through the cooperation of basic framework material and alumina, the consumption of alumina is reduced, and the cost of raw materials is reduced.
The addition amount of the silicate cement is 9-15 parts, so that the compressive strength of the ozone catalyst can be improved, and the continuous service time of the ozone catalyst can be prolonged.
In the invention, the catalyst is metal oxide, including any one or more of ferric oxide, cupric oxide, manganese oxide, cerium oxide and cobalt oxide, for example, the metal oxide can be ferric oxide and manganese oxide; or a mixture of copper oxide and manganese oxide, and a mixture of cerium oxide and iron oxide; or a mixture of iron oxide, copper oxide and manganese oxide. The foaming agent is ammonium salt, including any one of ammonium acetate and ammonium bicarbonate. The homogenizing agent is any one of potassium oxide and sodium oxide.
Preferably, the particle size of the fly ash, the silicate cement, the quicklime, the calcined gypsum and the catalyst is more than or equal to 100 meshes.
In a second aspect, the present invention also provides a method for preparing a load-blending type ozone catalyst, comprising the steps of:
s1: mixing fly ash, alumina, silicate cement, quicklime, calcined gypsum and a catalyst, and putting the mixture into a granulating disc of a granulator for granulating; in the granulating process, spraying the foaming agent solution into the mixture in a granulating disc in a mist form to prepare the original catalyst.
In the granulating process of the granulator, the inclination angle of the granulating disc is 43-50 degrees, and the rotating speed of the granulating disc is 35-40 rpm/min.
The framework material of the ozone catalyst comprises a basic framework material and alumina, wherein the addition amount of the alumina is controlled to be 15-25 parts, and 9-15 parts of silicate cement is added to influence the anti-pressure intensity; because the disc granulator needs to be provided with an inclination angle during operation, the size and shape of particles can be influenced by the synergistic effect of the inclination angle and the rotating speed, and the requirements of different material compositions or different proportions on the inclination angle are also different; aiming at the improved preparation raw materials and the proportion thereof, the invention needs to adjust the related parameters of a granulator, the inclination angle of a granulation disc is 43-50 degrees, the rotating speed is 35-40 rpm/min, and the invention is suitable for the balance of the centrifugal force and the gravity of the raw materials through parameter adjustment, so that the ozone catalyst forms proper particle size, more gaps are formed, and the compression strength is better.
In the invention, the preparation method of the foaming agent solution comprises the following steps: the foaming agent and water are mixed according to a certain proportion and are fully and uniformly stirred, and the mass concentration of the foaming agent solution is 1-5%.
Preferably, the fly ash, alumina, silicate cement, quicklime, calcined gypsum and catalyst are mixed and added into a granulator, and the inner wall of the granulator can be pre-wetted by adopting the prepared foaming agent solution. Firstly, wetting the inner wall of a granulator by using a foaming agent solution, then wetting a granulation disc, and pouring a mixture of fly ash, alumina, silicate cement, quicklime, calcined gypsum and a catalyst into the wetted granulation disc to facilitate granulation.
S2: the original catalyst is subjected to resting, autoclaved curing and drying to obtain the load-blending type ozone catalyst.
The resting temperature is 30-50 ℃, the resting time is 12-24 hours, and the resting pressure is normal pressure. The steaming and pressing process comprises a heating and boosting stage, a constant temperature and constant pressure stage and a cooling and depressurization stage which are sequentially carried out; the temperature and pressure rise stage is to raise the temperature from room temperature to 175-200 deg.c and the pressure from normal pressure to 0.8-1MPa within 1.5-2 hr; the constant temperature and constant pressure stage is carried out for 8-12h, the temperature is maintained at 175-200 ℃, and the pressure is maintained at 0.8-1Mpa; the temperature and pressure reduction time is 3-5h, the temperature is reduced from 175-200 ℃ to room temperature, and the pressure is reduced from 0.8-1Mpa to normal pressure. The drying temperature is 30-50deg.C, and the drying time is 12-24h.
The room temperature is 22-25 ℃; the normal pressure is 101.325kPa.
According to the invention, through the control of the resting temperature and the resting time, the ozone catalyst has better compressive strength and stability, and is not easy to crack; through the control of three stages in the autoclaved process, the ozone catalyst has larger specific surface area, higher porosity, better compressive strength and stability and is not easy to crack, thereby greatly improving the catalytic performance of the ozone catalyst.
Compared with the prior art, the preparation method of the load-blending type ozone catalyst has the following beneficial effects:
1. Alumina is added into the preparation raw materials, so that the specific surface area of the ozone catalyst is increased, the catalytic effect is improved, and the raw material cost is reduced through the cooperation of the alumina and the basic aggregate; 9-15 parts of silicate cement is also added into the preparation raw materials, so that the compressive strength of the ozone catalyst is improved.
2. The catalytic efficiency is improved to a certain extent by improving the preparation raw materials, and the proportion, density, granularity, plasticity and compression resistance of the preparation raw materials are changed, so that the granulation quality of the ozone catalyst is influenced by the change of the indexes, therefore, the preparation method is required to be adjusted for the improved preparation raw materials, the parameters of a granulator are improved firstly, the inclination angle of the granulation disc is 43-50 degrees, the rotating speed of the granulation disc is 35-40 rpm/min, so that the ozone catalyst has proper particle size, uniform particle size, more gaps are formed, and better compression strength is achieved. Secondly, the processing temperature of autoclaved aerated gas is controlled to be 200 ℃ at most, even if the calcining temperature is only 200 ℃ due to the improvement of the preparation raw materials and the improvement of parameters of a granulator, the requirement of compressive strength can be met, and the alpha active alumina with high activity and high specific surface area is always maintained due to the fact that the calcining temperature is only 200 ℃, so that the performance of the ozone catalyst is remarkably improved; because the processing temperature is relatively low, the energy consumption of the system can be saved. Finally, through the control of three stages in the autoclaved process, the ozone catalyst has larger specific surface area, higher porosity, better compressive strength and stability and is not easy to crack, thereby greatly improving the catalytic performance of the ozone catalyst.
3. The alumina has high activity, large specific surface area, uniform particle size and high porosity, so that the metal oxide catalyst can be uniformly distributed in the carrier, accumulation on the surface of the carrier is avoided, a series of problems of continuous use efficiency reduction and the like caused by loss of the surface catalyst in the application process are solved, the continuous use efficiency is improved, and the COD removal rate after repeated use for 10 times is still high.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope picture of a supported-blended ozone catalyst of example 2;
Fig. 2 is another scanning electron microscope picture of the supported-blended ozone catalyst of example 2.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1
The load-blending type ozone catalyst comprises the following preparation raw materials in parts by weight: 35 parts of fly ash, 2 parts of quicklime, 4 parts of calcined gypsum, 15 parts of alumina, 9 parts of silicate cement, 5 parts of ferric oxide, 0.5 part of ammonium acetate and 0.2 part of potassium oxide.
The preparation method of the load-blending type ozone catalyst comprises the following steps:
S1: before the fly ash, alumina, silicate cement, quicklime, calcined gypsum and ferric oxide are mixed and added into a granulator, the inner wall of the granulator is pre-wetted by adopting prepared ammonium acetate solution. The preparation method of the ammonium acetate solution comprises the following steps: mixing ammonium acetate and water according to a certain proportion, and fully and uniformly stirring, wherein the mass concentration of the ammonium acetate solution is 1%.
S2: mixing fly ash, alumina, silicate cement, quicklime, calcined gypsum and ferric oxide, and putting the mixture into a granulating disc of a granulator for granulating; in the granulating process, spraying an ammonium acetate solution into the mixture in a granulating disc in a mist form to prepare the original catalyst.
In the granulating process of the granulator, the inclination angle of the granulating disc is 43 degrees, and the rotating speed of the granulating disc is 35 rpm/min.
S3: taking out the original catalyst from the granulator, standing, placing the catalyst in an autoclave, vacuumizing the autoclave for 30 min, starting introducing high-temperature steam into the autoclave for autoclaved curing, and finally drying to obtain the load-blending type ozone catalyst.
The resting temperature is 30 ℃ and the resting time is 12 hours. The steaming and pressing process comprises a heating and boosting stage, a constant temperature and constant pressure stage and a cooling and depressurization stage which are sequentially carried out; the temperature and pressure rise stage is to raise the temperature from room temperature 22 ℃ to 175 ℃ within 1.5h, and the pressure is raised from normal pressure to 0.8Mpa; the constant temperature and constant pressure stage is carried out for 8 hours, the temperature is maintained at 175 ℃, and the pressure is 0.8Mpa; the temperature and pressure reduction time is 3 hours, the temperature is reduced from 175 ℃ to 22.5 ℃ at room temperature, and the pressure is reduced from 0.8Mpa to normal pressure. The drying temperature condition is 30 ℃ and the drying time is 12h.
Example 2
The load-blending type ozone catalyst comprises the following preparation raw materials in parts by weight: 41 parts of fly ash, 2.5 parts of quicklime, 4.6 parts of calcined gypsum, 18 parts of alumina, 11 parts of Portland cement, 3 parts of copper oxide, 4 parts of manganese oxide, 0.8 part of ammonium bicarbonate and 0.5 part of sodium oxide.
The preparation method of the load-blending type ozone catalyst comprises the following steps:
S1: before fly ash, alumina, silicate cement, quicklime, calcined gypsum and copper oxide are mixed and added into a granulator, the inner wall of the granulator is pre-wetted by adopting prepared ammonium bicarbonate solution. The preparation method of the ammonium bicarbonate solution comprises the following steps: mixing ammonium bicarbonate and water according to a certain proportion, and fully and uniformly stirring, wherein the mass concentration of the ammonium bicarbonate solution is 2.5%.
S2: mixing fly ash, alumina, silicate cement, quicklime, calcined gypsum and copper oxide, and putting the mixture into a granulating disc of a granulator for granulating; in the granulating process, spraying ammonium bicarbonate solution into the mixture in a granulating disc in a mist form to prepare the original catalyst.
In the granulating process of the granulator, the inclination angle of the granulating disc is 45 degrees, and the rotating speed of the granulating disc is 37 rpm/min.
S3: taking out the original catalyst from the granulator, standing, placing the original catalyst in an autoclave, vacuumizing the autoclave for 30min, starting introducing high-temperature steam into the autoclave for autoclaved curing, and finally drying to obtain the load-blending type ozone catalyst (the scanning electron microscope pictures of the load-blending type ozone catalyst are shown in fig. 1 and 2, and only two pictures of the embodiment 2 are shown because of more scanning electron microscope pictures).
The resting temperature is 36 ℃ and the resting time is 18h. The steaming and pressing process comprises a heating and boosting stage, a constant temperature and constant pressure stage and a cooling and depressurization stage which are sequentially carried out; the temperature and pressure rise stage is to raise the temperature from room temperature 23 ℃ to 182 ℃ within 1.8h, and the pressure is raised from normal pressure to 0.85Mpa; the constant temperature and constant pressure stage is carried out for 10 hours, the pressure is maintained at 0.85Mpa, and the temperature is maintained at 182 ℃; the temperature and pressure reduction time is 3.5h, the temperature is reduced from 182 ℃ to 22.8 ℃ at room temperature, and the pressure is reduced from 0.85Mpa to normal pressure. The drying temperature condition is 38 ℃ and the drying time is 20h.
Example 3
The load-blending type ozone catalyst comprises the following preparation raw materials in parts by weight: 51 parts of fly ash, 4 parts of quicklime, 6 parts of calcined gypsum, 21 parts of alumina, 12 parts of silicate cement, 4 parts of cerium oxide, 4 parts of ferric oxide, 1.5 parts of ammonium acetate and 0.6 part of potassium oxide.
The preparation method of the load-blending type ozone catalyst comprises the following steps:
S1: before the fly ash, alumina, silicate cement, quicklime, calcined gypsum and manganese oxide are mixed and added into a granulator, the inner wall of the granulator is pre-wetted by adopting prepared ammonium acetate solution. The preparation method of the ammonium acetate solution comprises the following steps: mixing ammonium acetate and water according to a certain proportion, and fully and uniformly stirring, wherein the mass concentration of the ammonium acetate solution is 3.8%.
S2: mixing fly ash, alumina, silicate cement, quicklime, calcined gypsum and manganese oxide, and putting the mixture into a granulating disc of a granulator for granulating; in the granulating process, spraying an ammonium acetate solution into the mixture in a granulating disc in a mist form to prepare the original catalyst.
In the granulating process of the granulator, the inclination angle of the granulating disc is 47 degrees, and the rotating speed of the granulating disc is 38 rpm/min.
S3: taking out the original catalyst from the granulator, standing, placing the catalyst in an autoclave, vacuumizing the autoclave for 30 min, starting introducing high-temperature steam into the autoclave for autoclaved curing, and finally drying to obtain the load-blending type ozone catalyst.
The resting temperature is 41 ℃ and the resting time is 20h. The steaming and pressing process comprises a heating and boosting stage, a constant temperature and constant pressure stage and a cooling and depressurization stage which are sequentially carried out; the temperature and pressure rise stage is to raise the temperature from 23.6 ℃ to 190 ℃ in 1.8h, and the pressure is raised from normal pressure to 0.9Mpa; the constant temperature and constant pressure stage is carried out for 11.6 hours, the pressure is 0.9Mpa, and the temperature is maintained at 190 ℃; the temperature and pressure reduction time is 4.2h, the temperature is reduced from 190 ℃ to 22.5 ℃ at room temperature, and the pressure is reduced from 0.9Mpa to normal pressure. The drying temperature condition is 45 ℃ and the drying time is 19h.
Example 4
The load-blending type ozone catalyst comprises the following preparation raw materials in parts by weight: 55 parts of fly ash, 5 parts of quicklime, 8 parts of calcined gypsum, 25 parts of aluminum oxide, 15 parts of silicate cement, 2 parts of ferric oxide, 4 parts of copper oxide, 4 parts of manganese oxide, 2 parts of ammonium bicarbonate and 1 part of potassium oxide.
The preparation method of the load-blending type ozone catalyst comprises the following steps:
S1: before fly ash, alumina, silicate cement, quicklime, calcined gypsum and copper oxide are mixed and added into a granulator, the inner wall of the granulator is pre-wetted by adopting prepared ammonium bicarbonate solution. The preparation method of the ammonium bicarbonate solution comprises the following steps: mixing ammonium bicarbonate and water according to a certain proportion, and fully and uniformly stirring, wherein the mass concentration of the ammonium bicarbonate solution is 5%.
S2: mixing fly ash, alumina, silicate cement, quicklime, calcined gypsum and copper oxide, and putting the mixture into a granulating disc of a granulator for granulating; in the granulating process, spraying ammonium bicarbonate solution into the mixture in a granulating disc in a mist form to prepare the original catalyst.
In the granulating process of the granulator, the inclination angle of the granulating disc is 50 degrees, and the rotating speed of the granulating disc is 40 rpm/min.
S3: taking out the original catalyst from the granulator, standing, placing the catalyst in an autoclave, vacuumizing the autoclave for 30 min, starting introducing high-temperature steam into the autoclave for autoclaved curing, and finally drying to obtain the load-blending type ozone catalyst.
The resting temperature is 50 ℃ and the resting time is 24 hours. The steaming and pressing process comprises a heating and boosting stage, a constant temperature and constant pressure stage and a cooling and depressurization stage which are sequentially carried out; the temperature and pressure rise stage is to raise the temperature from 24 ℃ to 200 ℃ at room temperature within 2h, and the pressure is raised from normal pressure to 1Mpa; the constant temperature and constant pressure stage is carried out for 12 hours, the pressure is 1Mpa, and the temperature is maintained at 200 ℃; the temperature and pressure reduction time is 5h, the temperature is reduced from 200 ℃ to 23.8 ℃ at room temperature, and the pressure is reduced from 1Mpa to normal pressure. The drying temperature condition is 50 ℃ and the drying time is 24 hours.
The supported-blended ozone catalysts prepared in the examples 1, 2, 3 and 4 are respectively used in an ozone catalytic oxidation reaction tower, 1000 mL ozone catalysts are respectively arranged in the reaction tower, 5g ozone generators (oxygen sources) are selected, the aeration flow is 0.25L/min, the ozone concentration is 100 parts, 350 mL wastewater is taken for starting an experiment, the reaction time is 1h, the COD concentration of the water is sampled and detected, and the COD removal efficiency is calculated. The type of wastewater is selected from chemical wastewater.
For the present invention of example 1, example 2, example 3, example 4 prepared in the load-blending type ozone catalyst, according to the application method, repeated use 10 times, calculated COD removal efficiency.
The compressive strength, particle diameter, and total void fraction of the ozone catalyst particles were measured for the supported-blended ozone catalysts prepared in examples 1,2, 3, and 4 of the present invention.
In the invention, the detection method of COD removal efficiency is the national environmental protection standard HJ 828-2017; the detection method of the compressive strength is the national environmental protection standard HG/T3927-2020; the particle size detection method is national standard GB/T12496.2-1999; the detection method of the total void fraction is Q/0705 LAT 001-2023 (enterprise standard).
The detection method in Q/0705 LAT 001-2023 comprises the following steps:
About 1000mL of the ozone catalyst sample is weighed by using a measuring cup, weighed to the accuracy of 0.01g, placed into a beaker, immersed by adding water, continuously stirred, separated from the sample by using a funnel after 1h, placed for 10min, and weighed to the accuracy of 0.01g after water absorption. The water-absorbed sample was then placed in a 1000mL beaker and water was added just after the ozone catalyst was removed, and water volume V was noted. And observing for 30min, and determining that the liquid level is not lower than the uppermost surface of the ozone catalyst.
The total porosity is calculated as Y 3, the value is expressed as%, and the total porosity is calculated according to the formula:
Wherein: y 3 is the water absorption (%) of the sample; m is the mass (g) of the dried sample; m 1 is the mass (g) of the water-absorbing saturated sample; v is water addition volume (mL).
The various indices of the load-blending ozone catalysts of examples 1-4 are shown in Table I.
Table-ozone catalyst index in examples 1-4
| COD removal efficiency (%) | COD removal efficiency after 10 times of repeated use (%) | Compressive Strength (N/particle) | Particle size (mm) | Total void fraction (%) | |
| Example 1 | 89.2 | 88.7 | 166 | 3.4 | 71 |
| Example 2 | 91.3 | 90.5 | 172 | 3.8 | 78 |
| Example 3 | 90.8 | 90.0 | 175 | 3.7 | 76 |
| Example 4 | 89.7 | 88.3 | 170 | 3.5 | 73 |
The data show that the COD removal efficiency of the ozone catalyst is above 89%, the COD removal efficiency after repeated use for 10 times is little in reduction, and is also above 88%, the compressive strength is more than 165N/granule, and the total void ratio is more than 70%, which indicates that the ozone catalyst prepared by the invention has higher catalytic efficiency.
Because the blending type ozone catalyst adopts a high-temperature roasting process, the temperature reaches above 600 ℃, the activity and the large specific surface property of the alumina are lost, the consumption of the alumina can be increased to improve the ozone catalytic performance, the raw material cost is higher, and the invention sets a comparative example 1 for verifying the increase of the consumption of the alumina and the improvement of the cost.
Comparative example 1
Based on example 1, the preparation raw materials of the ozone catalyst were modified: 56 parts of aluminum oxide, 9 parts of silicate cement, 5 parts of ferric oxide, 0.5 part of ammonium acetate and 0.2 part of potassium oxide. Other conditions were consistent.
In the present invention, the addition amount of alumina was 15 to 25 parts, and in order to verify that the addition amount of the present invention was the optimal addition amount, comparative example 2 and comparative example 3 were set.
Comparative example 2
Based on example 1, the preparation raw materials of the ozone catalyst were modified: the alumina content is increased to 35 parts and the fly ash is reduced to 15 parts. Other conditions were consistent.
Comparative example 3
Based on example 1, the preparation raw materials of the ozone catalyst were modified: the alumina content is reduced to 8 parts and the fly ash is increased to 42 parts. Other conditions were consistent.
Alumina is used as a framework material, has higher chemical stability, can increase the specific surface area of a preparation material, can be used as a catalyst for catalytic oxidation reaction, and is provided with a comparative example 4 in order to verify the function of alumina in an ozone catalyst.
Comparative example 4
Based on example 1, the preparation raw materials of the ozone catalyst were modified: alumina is not added in the formula, the fly ash is increased to 48 parts, and the quicklime is increased to 4 parts. Other conditions were consistent.
The portland cement can improve the compressive strength of the ozone catalyst, and comparative example 5 was set in order to verify the effect of the portland cement in the ozone catalyst.
Comparative example 5
Based on example 2, the preparation raw materials of the ozone catalyst were modified: portland cement is not added in the formula. Other conditions were consistent.
The addition amount of the Portland cement of the present invention was 9 to 15 parts, and comparative example 6 and comparative example 7 were set in order to verify that the addition amount of the present invention was the optimum addition amount.
Comparative example 6
Based on example 2, the preparation raw materials of the ozone catalyst were modified: the addition amount of the silicate cement is 6 parts. Other conditions were consistent.
Comparative example 7
Based on example 2, the preparation raw materials of the ozone catalyst were modified: the addition amount of the silicate cement is 20 parts. Other conditions were consistent.
The preparation raw materials of the ozone catalyst of the present invention are adjusted, and therefore, parameters of the disk granulator need to be adjusted for the special raw materials of the present invention, and in order to verify the parameters of the disk granulator used in the present invention, comparative example 8, comparative example 9, comparative example 10 and comparative example 11 are set for the optimal parameters of the special raw materials of the present invention.
Comparative example 8
In the preparation process of the load-blending type ozone catalyst based on the embodiment 3, the inclination angle of the granulation disc is changed to 35 degrees, and other conditions are consistent.
Comparative example 9
In the preparation process of the load-blending type ozone catalyst based on the embodiment 3, the inclination angle of the granulation disc is changed to 60 degrees, and other conditions are consistent.
Comparative example 10
In the preparation process of the load-blending type ozone catalyst based on the example 3, the rotation speed of the granulation disc is 28 rpm/min, and other conditions are consistent.
Comparative example 11
In the preparation process of the load-blending type ozone catalyst based on the example 3, the rotation speed of the granulation disc is 67 rpm/min, and other conditions are consistent.
Comparative example 12
In the preparation of the load-blending type ozone catalyst based on example 3, the inclination angle of the granulation disk was 30 °, and the rotation speed of the granulation disk was 25 rpm/min (a parameter frequently used in the prior art).
According to the invention, through the control of the resting temperature and the resting time, the ozone catalyst has better compressive strength and stability, and is not easy to crack; in order to verify that the resting temperature and the resting time of the present invention are optimal parameters, comparative example 13, comparative example 14, comparative example 15 and comparative example 16 were set.
Comparative example 13
On the basis of the embodiment 4, in the preparation process of the load-blending type ozone catalyst, the resting temperature is changed to 22 ℃, and other conditions are consistent.
Comparative example 14
On the basis of the embodiment 4, in the preparation process of the load-blending type ozone catalyst, the resting temperature is changed to 58 ℃, and other conditions are consistent.
Comparative example 15
On the basis of the embodiment 4, in the preparation process of the load-blending type ozone catalyst, the rest time is changed to 8 hours, and other conditions are consistent.
Comparative example 16
On the basis of the embodiment 4, in the preparation process of the load-blending type ozone catalyst, the resting time is changed to 30 hours, and other conditions are consistent.
The ozone catalyst has larger specific surface area, higher porosity, better compressive strength and stability and is not easy to crack through the control of three stages of the steaming and pressing process, so that the catalytic performance of the ozone catalyst is greatly improved, and in order to verify the necessity of the three stages of the steaming and pressing process, the comparative examples 17, 18, 19, 20 and 21 are arranged.
Comparative example 17
On the basis of the embodiment 2, the steaming and pressing process is modified, wherein the steaming and pressing process only comprises a heating and boosting stage, and a constant temperature and constant pressure processing stage and a cooling stage are not needed. Other conditions were consistent.
Comparative example 18
On the basis of the embodiment 2, the steaming and pressing process is modified, wherein the steaming and pressing process only comprises a heating and pressurizing stage and a cooling stage, and constant temperature and constant pressure treatment is not carried out. Other conditions were consistent.
Comparative example 19
On the basis of the embodiment 2, the autoclaved process is modified, wherein the autoclaved process only comprises a temperature rising and pressure rising stage and a constant temperature and pressure stage, the temperature and pressure reduction is not carried out, and the original catalyst directly enters the room temperature environment after the constant temperature and pressure treatment at 175-200 ℃. Other conditions were consistent.
Comparative example 20
On the basis of the embodiment 2, the steaming and pressing process is modified, wherein the steaming and pressing process only comprises a constant temperature and constant pressure stage and a cooling stage, and the heating and boosting stage is not adopted.
Directly placing the catalyst into a autoclave at 175-200 ℃ for constant temperature and constant pressure treatment (vacuumizing the autoclave to 30min, then introducing high-temperature steam into the autoclave for preheating in advance and heating to 175-200 ℃, and placing the original catalyst after resting into the autoclave for constant temperature and constant pressure treatment).
Other conditions were consistent.
Comparative example 21
On the basis of the embodiment 2, the steaming and pressing process is modified, and the heating and boosting stage comprises the following steps: the temperature is raised from room temperature to 500 ℃ in 1.5-2 h. Other conditions were consistent.
Each index of the load-blending type ozone catalyst in comparative examples 1 to 21 is shown in Table II.
Table II ozone catalyst index in comparative examples 1 to 21
| COD removal efficiency% | COD removal efficiency after 10 times of repeated use% | Compressive strength N/particle | Particle diameter mm | Total void fraction% | |
| Comparative example 1 | 86.92 | 86.03 | 165 | 3.5 | 72 |
| Comparative example 2 | 89.5 | 89 | 167 | 3.8 | 75 |
| Comparative example 3 | 75.4 | 71.8 | 161 | 3.3 | 70 |
| Comparative example 4 | 58 | 43.6 | 158 | 3.1 | 62 |
| Comparative example 5 | 54 | 41 | 155 | 3.2 | 69 |
| Comparative example 6 | 80.4 | 79.3 | 152 | 3.3 | 70 |
| Comparative example 7 | 89.5 | 75.6 | 182 | 3.7 | 75 |
| Comparative example 8 | 85.3 | 82.6 | 157 | 2.8 | 62 |
| Comparative example 9 | 84.7 | 81.3 | 155 | 2.4 | 58 |
| Comparative example 10 | 86.6 | 84.2 | 151 | 2.6 | 60 |
| Comparative example 11 | 87.0 | 84.9 | 156 | 2.0 | 52 |
| Comparative example 12 | 81.7 | 69.2 | 149 | 1.9 | 50 |
| Comparative example 13 | 85.1 | 80.6 | 150 | 3.7 | 70 |
| Comparative example 14 | 84.3 | 82 | 152 | 2.8 | 61 |
| Comparative example 15 | 82.6 | 75 | 147 | 3.2 | 69 |
| Comparative example 16 | 90.3 | 88.2 | 165 | 3.4 | 70 |
| Comparative example 17 | 81.2 | 78.5 | 168 | 2.7 | 62 |
| Comparative example 18 | 82.5 | 80.4 | 157 | 2.8 | 61 |
| Comparative example 19 | 84.6 | 81.7 | 153 | 3.2 | 69 |
| Comparative example 20 | 83.3 | 81.5 | 155 | 3.4 | 70 |
| Comparative example 21 | 76.5 | 63.9 | 171 | 3.0 | 65 |
In comparative example 1, the COD removing efficiency, the compressive strength, the total void ratio and other index effects are relatively good.
However, the amount of alumina was 79.2% and the amount of alumina in example 1 was 21.2%, so that comparative example 1 was 58% more than example 1. According to the annual output of the ozone catalyst of enterprises of 1 ten thousand tons, the comparative example 1 is 5800 tons more than the alumina of the example 1, the market alumina cost is about 5000 yuan/ton, and the cost of the alumina of the comparative example 1 is 2900 ten thousand yuan more.
In example 1, the ratio of fly ash to calcined gypsum is 49.5%, the ratio of quicklime to calcined gypsum is 2.8% and the ratio of calcined gypsum is 5.6%, and then, in example 1, the cost of example 1 is 172.25 ten thousand yuan per ton of quicklime, 1500 yuan per ton of calcined gypsum and 1000 yuan per ton of calcined gypsum according to 150 yuan per ton of fly ash and 280 tons of calcined gypsum as compared with the comparative example.
The cost of the preparation raw material in comparative example 1 was 2727.75 ten thousand yuan (2900 ten thousand yuan to 172.25 ten thousand yuan) more than that in example 1 in one year.
In comparative example 2, the alumina content was increased to 35 parts, the fly ash was reduced to 15 parts, and the index effects of COD removal efficiency, compressive strength, total void fraction, etc. were not substantially changed.
However, the amount of alumina used was 49.5%, which is 28.3% more than that of the alumina of example 1, 2830 tons more, and 1415 ten thousand yuan more.
The ratio of the fly ash is 21.2%, the ratio is 28.3% less than that of the embodiment, 2830 tons less, and the cost is 42.45 ten thousand yuan less
The cost of the preparation raw material in comparative example 2 was 1372.55 ten thousand yuan more than that in example 1 in one year.
In comparative example 3, the alumina content was reduced to 8 parts, the COD removal efficiency was lowered, and the COD removal efficiency after 10 times of repeated use was lowered faster. It is explained that the reduction of the alumina content has an effect on the catalytic performance of the ozone catalyst.
In comparative example 4, the formula was not added with alumina, the COD removal efficiency was only 58%, and the COD removal efficiency after 10 times of repeated use was very fast reduced, indicating that alumina in the ozone catalyst can promote the catalytic oxidation reaction.
In comparative example 5, the compressive strength was very low without adding portland cement to the formulation, and the COD removal efficiency and COD removal efficiency after 10 times of repeated use were also very low, and the influence was relatively large, indicating that portland cement affected the compressive strength of the ozone catalyst.
In comparative example 6, the addition amount of Portland cement in the formulation is 6 parts, and the compressive strength is very low; in comparative example 7, the addition amount of Portland cement in the formulation was 20 parts, and although the compressive strength of the ozone catalyst became large, the cracking was easy, and the COD removal efficiency after repeated use for 10 times was lowered relatively rapidly, probably because the addition amount of Portland cement was too large, and the parameters of the granulation disk and the parameters of the autoclaved process were not adapted to the raw material ratio in comparative example 7.
In comparative examples 8-11, the inclination angle and rotation speed of the granulation disk were changed, so that the compressive strength and total porosity of the ozone catalyst were reduced, and the COD removal efficiency after 10 repeated use were also affected, compared with the data in example 3, indicating that the parameters of the disk granulator used in the present invention are optimal parameters for the purpose-made raw materials of the present invention.
In comparative example 12, the inclination angle and rotation speed of the granulation disk all adopt parameters frequently used in the prior art, so that the compressive strength, the total porosity, the COD removal efficiency and the COD removal efficiency after 10 times of repeated use of the ozone catalyst are very low, the particle size of the ozone catalyst is uneven, the total porosity changes greatly and floats in the preparation process for a plurality of times, and the parameters of the granulation disk adopted by the invention are explained as optimal parameters for the special raw materials of the invention.
In comparative example 13, the resting temperature is lower than 30 ℃, resulting in greatly prolonged resting time, easy cracking of the ozone catalyst particles and reduced compressive strength; in comparative example 14, the resting temperature was higher than 50 ℃, and the evaporation of water in the ozone catalyst particles was too fast, so that the ozone catalyst particles were also liable to crack, the compressive strength was reduced, the porosity was reduced, and the COD removal efficiency after 10 times of repeated use were all affected.
In comparative example 15, the resting time is less than 12 hours, the compressive strength of the ozone catalyst particles is reduced, the ozone catalyst particles are easy to crack, and the COD removal efficiency is reduced rapidly after the ozone catalyst particles are repeatedly used for 10 times; in comparative example 16, the resting time was higher than 24 hours, and although the compressive strength of the ozone catalyst particles was not changed, the preparation time was prolonged and the production efficiency was lowered.
In comparative example 17, if the process of steaming and pressing is only to raise the temperature, the constant temperature and the constant pressure are not performed, and the temperature and the pressure are not lowered, so that the ozone catalyst is not expanded, the specific surface area is low, the porosity is low, and the COD removal efficiency of the ozone catalyst and the COD removal efficiency after 10 times of repeated use are finally affected.
In comparative example 18, the process of steaming and pressing does not have constant temperature and constant pressure treatment, so that various raw materials of the ozone catalyst are not thoroughly reacted, the expansion is insufficient, the specific surface area is low, the porosity is low, the compressive strength of the catalyst particles is insufficient, and the COD removal efficiency of the ozone catalyst and the COD removal efficiency after 10 times of repeated use are finally affected.
In comparative example 19, the process of steaming and pressing was not performed to cool down and reduce the pressure, the ozone catalyst particles directly enter the room temperature environment at a high temperature of 175-200 ℃, and sudden drop of the environmental temperature also causes cracking of the ozone catalyst particles, and compressive strength is reduced, which finally affects the COD removal efficiency of the ozone catalyst and the COD removal efficiency after 10 times of repeated use.
In comparative example 20, the steaming and pressing process only includes a constant temperature and constant pressure stage and a cooling stage, and no heating and boosting stage is provided. The process of steaming and pressing is directly carried out under the condition of 175-200 ℃ to carry out constant temperature and constant pressure treatment, so that the ozone catalyst particles can be cracked, the compressive strength is reduced, and the COD removal efficiency of the ozone catalyst and the COD removal efficiency after 10 times of repeated use are finally influenced.
In comparative example 21, the temperature and pressure rise stage was carried out by raising the temperature from room temperature to 500 ℃ within 1.5 to 2 hours, but the compressive strength reached the standard, but the original activity and large specific surface characteristics were lost due to the change of the alumina crystal form at high temperature, resulting in less supported catalyst, a decrease in COD removal efficiency, and a rapid decrease in COD removal efficiency after 10 uses. In addition, the calcination temperature of the invention is 200 ℃, and energy consumption can be saved relative to 500 ℃.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A preparation method of a load-blending type ozone catalyst is characterized by comprising the following steps: the load-blending type ozone catalyst comprises the following preparation raw materials in parts by weight: 35-55 parts of fly ash, 2-5 parts of quicklime, 4-8 parts of calcined gypsum, 15-25 parts of alumina, 9-15 parts of Portland cement, 5-10 parts of a catalyst, 0.5-2 parts of a foaming agent and 0.2-1 part of a homogenizing agent;
the preparation method of the load-blending type ozone catalyst comprises the following steps:
S1: mixing fly ash, alumina, silicate cement, quicklime, calcined gypsum and a catalyst, and putting the mixture into a granulating disc of a granulator for granulating; in the granulating process, spraying a foaming agent solution into the mixture in a granulating disc to prepare an original catalyst;
In the granulating process of the granulator, the inclination angle of a granulating disc is 43-50 degrees, and the rotating speed of the granulating disc is 35-40 rpm/min;
s2: the original catalyst is subjected to resting, steaming, pressing and drying to obtain a load-blending type ozone catalyst; the process of steaming and pressing comprises a heating and boosting stage, a constant temperature and constant pressure stage and a cooling and depressurization stage which are sequentially carried out.
2. The method for preparing the load-blending type ozone catalyst according to claim 1, characterized in that: the catalyst is metal oxide and comprises any one or more of ferric oxide, copper oxide, manganese oxide, cerium oxide and cobalt oxide; the foaming agent is ammonium salt, including any one of ammonium acetate and ammonium bicarbonate; the homogenizing agent is any one of potassium oxide and sodium oxide.
3. The method for preparing the load-blending type ozone catalyst according to claim 1, characterized in that: the particle size of the fly ash, the silicate cement, the quicklime, the calcined gypsum and the catalyst is more than or equal to 100 meshes.
4. The method for preparing the load-blending type ozone catalyst according to claim 1, characterized in that: the resting temperature in the preparation process is 30-50 ℃, and the resting time is 12-24 hours.
5. The method for preparing the load-blending type ozone catalyst according to claim 1, characterized in that: in the steaming and pressing process, the temperature and pressure rise stages are that the temperature is raised to 175-200 ℃ from room temperature within 1.5-2h, and the pressure is raised to 0.8-1Mpa from normal pressure; the constant temperature and constant pressure stage is carried out for 8-12h, the temperature is maintained at 175-200 ℃, and the pressure is maintained at 0.8-1Mpa; the temperature and pressure reduction time is 3-5h, the temperature is reduced from 175-200 ℃ to room temperature, and the pressure is reduced from 0.8-1Mpa to normal pressure.
6. The method for preparing the load-blending type ozone catalyst according to claim 1, characterized in that: the preparation method of the foaming agent solution comprises the following steps: mixing the foaming agent and water, and stirring uniformly, wherein the mass concentration of the foaming agent solution is 1-5%.
7. The method for preparing the load-blending type ozone catalyst according to claim 6, wherein: before the fly ash, alumina, silicate cement, quicklime, calcined gypsum and catalyst are mixed and added into a granulator, a foaming agent solution is adopted to pre-wet the inner wall of the granulator.
8. The method for preparing the load-blending type ozone catalyst according to claim 1, characterized in that: the temperature condition of the drying is 30-50 ℃ and the drying time is 12-24h.
Priority Applications (1)
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