CN113145093A - Application of waste SCR catalyst in preparation of silicon dioxide-titanium dioxide composite photocatalyst - Google Patents
Application of waste SCR catalyst in preparation of silicon dioxide-titanium dioxide composite photocatalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000002699 waste material Substances 0.000 title claims abstract description 81
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000004115 Sodium Silicate Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 18
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 15
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 9
- 238000007781 pre-processing Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 38
- 238000004064 recycling Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004408 titanium dioxide Substances 0.000 abstract description 8
- 229940043267 rhodamine b Drugs 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 235000010215 titanium dioxide Nutrition 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides an application of a waste SCR catalyst in preparation of a silicon dioxide-titanium dioxide composite photocatalyst, and relates to the technical field of waste resource recycling. The invention takes the waste SCR catalyst as the raw material, and prepares the waste SCR catalyst into SiO with higher industrial added value2‑TiO2The composite photocatalyst product is used for degrading organic pollutants in the environment and has higher social and economic significance. The photocatalyst has better photocatalytic performance, and experiments prove that rhodamine B can be completely degraded within 30 minutes under the irradiation of ultraviolet light, and the photocatalytic performance of the photocatalyst under visible light is superior to the catalytic effect of Germany Digaosha P25 nanometer titanium dioxide.
Description
Technical Field
The invention relates to the technical field of waste resource recycling, in particular to application of a waste SCR catalyst in preparation of a silicon dioxide-titanium dioxide composite photocatalyst.
Background
Most of thermal power plants in China currently use flue gas denitration devices, and the device adopts SCR (Selective Catalytic Reduction) technology to convert nitrogen oxides into N harmless to environment2And O2. The method has high denitration efficiency and low cost, and is NO of the existing coal-fired power plantXThe mainstream technology of the control technology.
The SCR catalyst mainly comprises the following components: vanadium pentoxide (main active component), titanium dioxide (carrier), tungsten trioxide or molybdenum trioxide (additive), wherein the content of titanium dioxide is about 80-85% generally. The technical denitration principle is as follows: under the action of a catalyst, ammonia is sprayed into the flue gas with the temperature of about 280-420 ℃, and NOx is reduced into N2And H2And O. Under an ideal state, the denitration catalyst can be used for a long time, but due to the fact that the actual operation process is complex, the activity of the catalyst is reduced due to various factors, the service life is shortened, and the design operation life of the current domestic honeycomb type SCR denitration catalyst is 24000 h. The main causes of the reduction of the activity of the SCR catalyst and thus the deactivation can be summarized into four types: (1) catalyst poisoning by arsenic (As), alkali metals (mainly K, Na), and the like; (2) plugging of the catalyst; (3) sintering and active component volatilization caused by high temperature; (4) mechanical wear. As the catalyst is used for a longer period of time, the activity of the catalyst is lowered due to the above-mentioned problems, and after the activity is lowered to a certain extent, it is necessary to add or replace a layer of the catalyst. When the catalyst is replaced, regeneration or waste catalyst recycling treatment is carried out according to the actual condition of the catalyst. At present, few companies specialized in recycling the waste SCR catalyst are in China, the technology and equipment are not very mature, and the recycling treatment of the waste ineffective SCR catalyst is still in the research and test stage.
For the recovery of the SCR waste catalyst, besides the reactivation and reuse, in the face of a large amount of waste catalysts which cannot be reactivated and reused, researchers at home and abroad have proposed some treatment schemes, which mainly tend to treat the waste catalysts as wastes, including: (1) landfill disposal, (2) use as cement raw material or aggregate, (3) mix-burning with coal after grinding, and (4) recycle useful metal material therein.
The first solution has a large environmental impact and is wasteful and most undesirable. The second and third economic benefits are low, the process is complex, and the research significance is not great. Compared with the first three modes, the method for recycling the metal material in the SCR waste catalyst is a more environment-friendly treatment mode. Because the waste SCR catalyst contains high value-added metal elements, the recycling of the metal elements is a hot spot of current research. V in the waste SCR catalyst can be realized by separation and purification technology2O5、WO3、TiO2The separation and recovery of the flue gas denitration industry are realized. Most of the current research mainly involves two processes, leaching and separation. The leaching process mainly comprises acid leaching, alkali leaching, salt leaching or roasting leaching, and the obtained leachate is further separated and purified to realize the separation and recycling of vanadium, tungsten and titanium. However, the specific recovery method is very complex, the required recovery conditions are quite strict, and the defects exist, so that the actual production is not realized at present.
Therefore, a novel method for recycling the waste SCR catalyst is researched and developed, the waste SCR catalyst is changed into valuable, and the SiO with higher industrial added value is prepared2-TiO2The production of composite photocatalyst becomes necessary and urgent.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for preparing SiO by using a waste SCR catalyst2-TiO2Application in composite photocatalyst. The invention takes the waste SCR catalyst as the raw material, and prepares the waste SCR catalyst into SiO with higher industrial added value2-TiO2The composite photocatalyst product is used for degrading organic pollutants in the environment and has higher social and economic significance.
The second purpose of the invention is to provide a SiO prepared by the application method2-TiO2A composite photocatalyst is provided.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a method for preparing SiO by using waste SCR catalyst2-TiO2Application in composite photocatalyst.
Further, the application method comprises the following steps:
(a) pre-processing the waste SCR catalyst, wherein the process comprises the steps of blowing dust on the surface of the waste SCR catalyst by a high-pressure air gun, soaking the waste SCR catalyst in a sulfuric acid solution, cleaning the waste SCR catalyst by clear water, and then crushing, grinding and drying the waste SCR catalyst;
(b) reacting the pretreated waste SCR catalyst powder with concentrated sulfuric acid to obtain a solution A containing titanyl sulfate;
(c) providing a sodium silicate solution, then adding the sodium silicate solution into the solution A in the step (b), controlling the pH value of the solution, and carrying out hydrolysis reaction under a certain temperature condition and a continuous stirring state to obtain a photocatalyst intermediate;
(d) washing, drying, calcining and grinding the photocatalyst intermediate obtained in the step (c) in sequence to obtain SiO2-TiO2A composite photocatalyst is provided.
Further, a 72% -95% sulfuric acid solution is adopted for soaking in the preprocessing process of the waste SCR catalyst, the soaking time is 0.5-3 h, and after water washing and drying procedures, the waste SCR catalyst is ground into powder with the particle size of 100-325 meshes;
preferably, the concentrated sulfuric acid in the step (b) is a sulfuric acid solution with a concentration of 87%, the soaking time is 1h, and after washing with water and drying at 105 ℃ for 2h, the powder with a particle size of 200 meshes is ground.
Further, the reaction temperature of the reaction between the waste SCR catalyst and concentrated sulfuric acid in the step (b) is 120-250 ℃, and the reaction time is 1-6 hours;
preferably, the concentrated sulfuric acid added in the step (b) is added with TiO in the waste SCR catalyst raw material2The molar ratio of (A) to (B) is 2: 1.
Preferably, the reaction temperature of the reaction between the waste SCR catalyst and the concentrated sulfuric acid in the step (b) is 200 ℃ and the reaction time is 3 hours.
Further, the mass concentration of the sodium silicate solution in the step (c) is 1-20 g/L;
further, the mixing volume ratio of the sodium silicate solution to the titanyl sulfate-containing solution in the hydrolysis reaction in the step (c) is 300-400: 1.
Further, the pH value of the hydrolysis reaction in the step (c) is 1-3, and the time is 2-6 h;
preferably, the pH value of the hydrolysis reaction is 2, and the time is 3 h;
preferably, the hydrolysis reaction is carried out under stirring conditions, and the stirring speed is 300 r/min.
Further, the drying method in step (d) is as follows: firstly, drying for 1-3 h at 105-110 ℃, and then roasting for 2-5 h at 400-750 ℃.
Preferably, the drying method of step (d) is drying at 105 ℃ for 2h, and then baking at 550 ℃ for 3 h.
The invention provides SiO2-TiO2The composite photocatalyst is mainly prepared by the application method.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing SiO by using waste SCR catalyst2-TiO2Application in composite photocatalyst. The content of titanium dioxide in the waste SCR catalyst exceeds 80 percent, although the crystal state of the waste SCR catalyst is changed and the activity is reduced, the element composition is not changed, the waste SCR catalyst is used as a raw material, and the waste SCR catalyst is prepared into SiO with higher industrial added value2-TiO2The composite photocatalyst product is used for degrading organic pollutants in the environment and has higher social and economic significance.
The SiO provided by the invention2-TiO2Composite photocatalyst of SiO2-TiO2The composite photocatalyst is mainly prepared from a waste SCR catalyst. The photocatalyst has good photocatalytic performance, experiments prove that rhodamine B can be completely degraded within 30 minutes under ultraviolet irradiation, and the visible light photocatalytic performance of the photocatalyst is superior to that of rhodamine BThe catalytic effect of the national di gaosha P25 nanometer titanium dioxide.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the invention, a waste SCR catalyst is used for preparing SiO2-TiO2Application in composite photocatalyst.
The invention provides a method for preparing SiO by using waste SCR catalyst2-TiO2Application in composite photocatalyst. The content of titanium dioxide in the waste SCR catalyst exceeds 80 percent, although the crystal state of the waste SCR catalyst is changed and the activity is reduced, the element composition is not changed, the waste SCR catalyst is used as a raw material, and the waste SCR catalyst is prepared into SiO with higher industrial added value2-TiO2The composite photocatalyst product is used for degrading organic pollutants in the environment and has higher social and economic significance.
In a preferred embodiment of the present invention, the application method comprises the steps of:
(a) carrying out preprocessing treatment on the waste SCR catalyst, wherein the preprocessing treatment process comprises the steps of blowing dust on the surface of the waste SCR catalyst by using a high-pressure air gun, soaking the waste SCR catalyst in a sulfuric acid solution, cleaning the waste SCR catalyst by using clear water, and then crushing, grinding and drying the waste SCR catalyst;
(b) reacting the pretreated waste SCR catalyst powder with concentrated sulfuric acid to obtain a solution A containing titanyl sulfate;
(c) providing a sodium silicate solution, then adding the sodium silicate solution into the solution A in the step (b), controlling the pH value of the solution, and carrying out hydrolysis reaction under a certain temperature condition and a continuous stirring state to obtain a photocatalyst intermediate;
(d) and (c) sequentially reacting the photocatalyst intermediates obtained in step (c)Washing, drying, calcining and grinding to obtain SiO2-TiO2A composite photocatalyst is provided.
As a preferred embodiment, the application method described above: firstly, preprocessing a waste SCR catalyst, and then reacting the preprocessed waste SCR catalyst powder with concentrated sulfuric acid to obtain a solution A containing titanyl sulfate; then adding a sodium silicate solution into the solution A, controlling the pH value of the solution, and carrying out hydrolysis reaction under a certain temperature condition and a continuous stirring state to obtain a photocatalyst intermediate; due to mesoporous SiO2Good mechanical strength of the carrier, SiO produced after loading2-TiO2The strength of the photocatalyst intermediate is also relatively increased. At the same time, in SiO2A layer of TiO is uniformly dispersed on the surface2Can effectively improve the interaction between the active component and the carrier, and improve the dispersing ability of the active component, and SiO2The production of anatase titania is further promoted. Finally, washing, drying, calcining and grinding the photocatalyst intermediate in sequence to obtain SiO2-TiO2A composite photocatalyst is provided.
Further, the above SiO2-TiO2The composite photocatalyst has SiO2Is thermally and mechanically stable and has TiO2The catalytic performance of (2). Research shows that a small amount of exposed TiO in corroded parts in the composite material2The intrinsic activity of the composite material is not changed, and the photocatalytic activity of the composite material is not obviously reduced. The titanium-silicon composite oxide shows great difference in performance due to different preparation methods and process conditions, and the difference brings bright prospect for the application of the composite oxide catalytic material.
In a preferred embodiment of the present invention, the step (a) preprocessing method comprises: blowing dust on the surface of the waste SCR catalyst by using a high-pressure air gun, soaking for 0.5-3 h by using 72-95% sulfuric acid solution, washing with water, drying, and grinding to obtain powder with the particle size of 100-325 meshes.
In a preferred embodiment of the present invention, the concentrated sulfuric acid in step (b) is a 87% sulfuric acid solution, the reaction time of the waste SCR catalyst powder and the concentrated sulfuric acid is 1-6 hours, and after washing with water and drying at 105 ℃ for 2 hours, the waste SCR catalyst powder is ground into 200-mesh powder;
in the above preferred embodiment, the reaction temperature of the reaction between the waste SCR catalyst and the concentrated sulfuric acid in the step (b) is 120 to 250 ℃, and the reaction time is 1 to 6 hours.
In a preferred embodiment of the present invention, the concentrated sulfuric acid is added in the step (b) in an amount corresponding to the amount of TiO in the waste SCR catalyst feedstock2The molar ratio of (A) to (B) is 2: 1.
In a preferred embodiment of the invention, the sodium silicate solution in the step (c) has a mass concentration of 1-20 g/L;
in the above preferred embodiment, the concentration of sodium silicate in the sodium silicate solution is 12 g/L.
In a preferred embodiment of the present invention, the mixing volume ratio of the sodium silicate solution to the titanyl sulfate-containing solution in the hydrolysis reaction in the step (c) is 300-400: 1.
In the preferred embodiment, the pH value of the hydrolysis reaction in the step (c) is 1-3, and the time is 2-6 h;
preferably, the pH value of the hydrolysis reaction is 2, and the time is 3 h;
in the preferred embodiment, the hydrolysis reaction is carried out under stirring at a speed of 300 r/min.
In a preferred embodiment of the present invention, the drying step (d) comprises: firstly, drying for 1-3 h at 105-110 ℃, and then roasting for 2-5 h at 400-750 ℃;
preferably, the drying method of step (d) is drying at 105 ℃ for 2h, and then baking at 550 ℃ for 3 h.
According to one aspect of the invention, a SiO2-TiO2Composite photocatalyst of said SiO2-TiO2The composite photocatalyst is mainly prepared from a waste SCR catalyst.
The photocatalyst has better photocatalytic performance, experiments prove that rhodamine B can be completely degraded within 30 minutes under the irradiation of ultraviolet light, and the visible photocatalytic performance of the photocatalyst is superior to the catalytic effect of Germany Digaosha P25 nanometer titanium dioxide.
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
SiO (silicon dioxide)2-TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) the specific process of the early-stage surface cleaning treatment of the waste SCR catalyst comprises the steps of blowing dust attached to the surface by a high-pressure air gun, soaking the surface for 2 hours by using 5% dilute sulfuric acid, washing the surface for 2-3 times by using water, drying the surface for 2 hours at 105 ℃ by using an oven, grinding the surface to be more than 200 meshes by using a ball mill, and then drying and grinding the surface to be powder of 100-325 meshes;
(2) 6.26g of concentrated sulfuric acid is taken to be placed in a beaker, 6.8 g of the waste SCR catalyst powder obtained in the step (1) is placed in the beaker, 6g of concentrated sulfuric acid is added, the temperature is raised to 200 ℃, and the reaction is carried out for 3 hours to obtain solution A containing titanyl sulfate;
(3) slowly dripping 100mL of solution containing 21 g of water glass with the modulus of 3 into the solution A containing the titanyl sulfate under the condition of fully stirring to perform hydrolysis reaction; stirring all the time in the reaction process, and adding ammonia water to adjust the pH value to 2.0; continuously stirring for reacting for 3 hours, and standing for 1 d;
(4) filtering the solution after the hydrolysis reaction, washing the solution with deionized water until the pH value is neutral, and washing the solution for 2 times with absolute ethyl alcohol; then drying at 105 ℃, roasting at 550-700 ℃ for 1 hour, grinding to 325 meshes to obtain white powdery SiO2-TiO2A composite photocatalyst is provided.
Example 2
SiO (silicon dioxide)2-TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) the specific process of the early-stage surface cleaning treatment of the waste SCR catalyst comprises the steps of blowing dust attached to the surface by a high-pressure air gun, soaking the surface for 2 hours by using 5% dilute sulfuric acid, washing the surface for 2-3 times by using water, drying the surface for 2 hours at 105 ℃ by using an oven, and grinding the surface into powder of 100-325 meshes;
(2) taking 12.26g of concentrated sulfuric acid in a beaker, heating to 200 ℃, putting 6.8 g of waste into the beaker, and reacting for 3 hours to obtain a solution A containing titanyl sulfate;
(3) slowly pouring 100mL of sodium silicate solution with the concentration of 2.5mol/L into the solution A containing titanyl sulfate under the condition of stirring for hydrolysis reaction; keeping the temperature at 100 ℃ in the reaction process, stirring all the time, and adding ammonia water to adjust the pH value to 2.0; continuously stirring for reacting for 3 hours, and standing for 1 d;
(4) filtering the solution after the hydrolysis reaction, washing the solution with deionized water until the pH value is neutral, and washing the solution for 2 times with absolute ethyl alcohol; then drying at 110 ℃, roasting at 550-700 ℃ for 1-2 hours, and grinding to 325 meshes to obtain white powdery SiO2-TiO2A composite photocatalyst is provided.
Example 3
SiO (silicon dioxide)2-TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) the specific process of the early-stage surface cleaning treatment of the waste SCR catalyst comprises the steps of blowing dust attached to the surface by a high-pressure air gun, soaking the surface for 2 hours by using 10% oxalic acid, then washing the surface for 2-3 times by using water, drying the surface for 2 hours at 105 ℃ by using an oven, and grinding the surface to powder of 325 meshes by using a ball mill;
(2) 50g of concentrated sulfuric acid is taken to be put into a beaker, the temperature is raised to 200 ℃, 28 g of waste is put into the beaker to react for 3 hours, and solution A containing titanyl sulfate is obtained;
(3) slowly pouring 200mL of a water glass saturated solution with the modulus of 3.2 into a solution A containing titanyl sulfate under the condition of stirring for hydrolysis reaction, keeping the temperature of 85-95 ℃ in the reaction process, stirring all the time, and adding ammonia water to adjust the pH value to 2.0; continuously stirring for reacting for 3 hours, and standing for 1 d;
(4) filtering the solution after the hydrolysis reaction, washing with deionized water until the pH is neutral, and washing with deionized water for 2-3 times; then drying the mixture at 110 ℃, and then drying the mixture at 550-700 DEG CRoasting for 2 hours, grinding to 325 meshes to obtain white powdery SiO2-TiO2A composite photocatalyst is provided.
Example 4
SiO (silicon dioxide)2-TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) the specific process of the early-stage surface cleaning treatment of the waste SCR catalyst comprises the steps of blowing dust attached to the surface by a high-pressure air gun, soaking the surface for 3 hours by using 5% sulfuric acid, then washing the surface for 2-3 times by using water, drying the surface for 3 hours at 105 ℃ by using an oven, and grinding the surface to 200 meshes by using a ball mill;
(2) taking 500g of concentrated sulfuric acid in a beaker, heating to 180 ℃, putting 300 g of waste into the beaker, and reacting for 3 hours to obtain a solution A containing titanyl sulfate;
(3) slowly pouring 1000mL of saturated sodium silicate solution into a solution A containing titanyl sulfate under the condition of stirring for hydrolysis reaction, keeping the temperature at 85-95 ℃ in the reaction process, stirring all the time, and adding ammonia water to adjust the pH value to 1.0; continuously stirring for reacting for 3 hours, and standing for 1 d;
(4) filtering the solution after the hydrolysis reaction, washing with deionized water until the pH is neutral, and washing with deionized water for 2-3 times; then drying at 110 ℃, roasting at 550-600 ℃ for 2-3 hours, and depolymerizing and scattering the product to obtain white powdery SiO2-TiO2A composite photocatalyst is provided.
Comparative example 1
The commercial German Digaosha P25 nanometer titanium white photocatalyst.
Experimental example 1
In order to show that the photocatalyst prepared by the method has a good photocatalytic effect, the photocatalysts of examples 1-3 and comparative example 1 are detected in a rhodamine B aqueous solution:
the specific detection method comprises the following steps: ultraviolet light and full-gloss rhodamine B solution degradation detection are carried out by adopting a photochemical reaction instrument;
and (3) detection results: the photocatalyst prepared in the embodiment 1-3 can completely degrade rhodamine B within 30 minutes, the rhodamine B degradation under the ultraviolet light condition can reach more than 90% within 30 minutes, and the visible light catalysis performance is superior to that of Germany Digaosha P25 nanometer titanium dioxide.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An application of a waste SCR catalyst in preparing a silicon dioxide-titanium dioxide composite photocatalyst.
2. The application according to claim 1, characterized in that the application method comprises the following steps:
(a) carrying out preprocessing treatment on the waste SCR catalyst, wherein the preprocessing treatment process comprises the steps of blowing dust on the surface of the waste SCR catalyst by using a high-pressure air gun, soaking the waste SCR catalyst in a sulfuric acid solution, cleaning the waste SCR catalyst by using clear water, and then crushing, grinding and drying the waste SCR catalyst;
(b) reacting the pretreated waste SCR catalyst powder with concentrated sulfuric acid to obtain a solution A containing titanyl sulfate;
(c) providing a sodium silicate solution, then adding the sodium silicate solution into the solution A in the step (b), controlling the pH value of the solution, and carrying out hydrolysis reaction under a certain temperature condition and a continuous stirring state to obtain a photocatalyst intermediate;
(d) washing, drying, calcining and grinding the photocatalyst intermediate obtained in the step (c) in sequence to obtain SiO2-TiO2A composite photocatalyst is provided.
3. The use of claim 2, wherein said step (a) preprocessing process comprises: blowing dust on the surface of the waste SCR catalyst by using a high-pressure air gun, soaking for 0.5-3 h by using 72-95% sulfuric acid solution, washing with water, drying, and grinding to obtain powder with the particle size of 100-325 meshes.
4. The use of claim 2, wherein the concentrated sulfuric acid in the step (b) is a sulfuric acid solution with a concentration of 87%, the reaction time of the waste SCR catalyst powder and the concentrated sulfuric acid is 1-6 h, and after washing with water and drying at 105 ℃ for 2h, the waste SCR catalyst powder is ground into powder with a particle size of 200 meshes;
preferably, the reaction temperature of the reaction between the waste SCR catalyst and the concentrated sulfuric acid in the step (b) is 120-250 ℃, and the reaction time is 1-6 hours.
5. The use of claim 2, wherein the concentrated sulfuric acid is added in step (b) in an amount corresponding to the amount of TiO in the spent SCR catalyst feedstock2The molar ratio of (A) to (B) is 2: 1.
6. The use according to claim 2, wherein the sodium silicate solution in the step (c) has a mass concentration of 1-20 g/L;
preferably, the concentration of sodium silicate in the sodium silicate solution is 12 g/L.
7. The use according to claim 2, wherein the mixing volume ratio of the sodium silicate solution to the titanyl sulfate-containing solution in the hydrolysis reaction in the step (c) is 300-400: 1.
8. The use of claim 7, wherein the hydrolysis reaction of step (c) has a pH of 1-3 for 2-6 h;
preferably, the pH value of the hydrolysis reaction is 2, and the time is 3 h;
preferably, the hydrolysis reaction is carried out under stirring conditions, and the stirring speed is 300 r/min.
9. The use of claim 2, wherein the drying of step (d) is performed by: firstly, drying for 1-3 h at 105-110 ℃, and then roasting for 2-5 h at 400-750 ℃;
preferably, the drying method of step (d) is drying at 105 ℃ for 2h, and then baking at 550 ℃ for 3 h.
10. The silicon dioxide-titanium dioxide composite photocatalyst is characterized by being mainly prepared from a waste SCR catalyst.
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