CN113042052B - TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof - Google Patents
TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000011258 core-shell material Substances 0.000 title claims abstract description 79
- 238000000926 separation method Methods 0.000 title claims abstract description 79
- 229910018540 Si C Inorganic materials 0.000 title claims abstract description 38
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000002245 particle Substances 0.000 claims abstract description 52
- 238000001354 calcination Methods 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 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 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000011068 loading method Methods 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 20
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 15
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 13
- 239000007789 gas Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 230000006872 improvement Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000010412 oxide-supported catalyst Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/51—
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention provides a TiO2An Al/Si-C based porous core-shell separation spherical catalyst, a preparation method and application thereof. Mixing and granulating the activated carbon particles with ferric oxide powder and alumina-containing powder in sequence, and preparing a sphere with a porous core-shell separation structure after primary calcination; the obtained porous core-shell separation sphere is dipped in a titanium-containing solution and is calcined for the second time to obtain TiO2An Al/Si-C based porous core-shell separation spherical catalyst is loaded. Through the mode, the method can utilize the reaction of the activated carbon particles and the ferric oxide in the calcining process to convert part of activated carbon into gas to escape, form a permanent spherical pore channel, reduce the volume of the residual activated carbon kernel, separate the residual activated carbon kernel from a shell layer formed by powder containing alumina, and form a porous core-shell separation spherical structure, thereby effectively improving the TiO content2The loading capacity and the catalytic effect of the catalyst realize the high-efficiency catalytic oxidation of the ozone and the hydrogen peroxide.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a TiO compound2An Al/Si-C based porous core-shell separation spherical catalyst, a preparation method and application thereof.
Background
With the rapid development of the chemical industry, a great amount of high-concentration refractory organic wastewater is continuously generated, and if the wastewater cannot be timely and effectively treated, the wastewater can irreversibly affect the surrounding environment. In order to find a method for treating high-concentration refractory organic wastewater efficiently and cheaply, people begin to pay attention to catalytic oxidation technology, reduce the cost of water treatment agents of a chemical oxidation method through catalysis, shorten reaction time, and convert refractory organic pollutants into easily degradable pollutants or completely oxidize the easily degradable pollutants into carbon dioxide and water so as to reach the emission or recycling standard.
Among various catalytic oxidation technologies for organic wastewater, catalytic oxidation of ozone and catalytic oxidation of hydrogen peroxide have attracted extensive attention due to the advantages of wide range of action, rapidness, high efficiency, no pollution and the like, wherein the preparation and application of the catalyst are the key points of the catalytic oxidation technology. At present, the catalysts commonly used in the catalytic oxidation process of ozone and the catalytic oxidation process of hydrogen peroxide mainly comprise metals, metal oxides, metal supported catalysts and metal oxide supported catalysts. Among them, the metal oxide supported catalyst has received extensive attention from researchers due to its advantages of high catalytic activity, good stability, and easy separation from water.
For example, patent publication No. CN109550503A provides a catalyst applied to a multi-catalytic ozonation system and a preparation method thereof, in which activated carbon is pretreated with acid, then placed in a mixed solution of ferromanganese oxide and titanium dioxide for water bath, cleaned, dried, then placed in an inert gas environment for calcination, cooled, and then placed in air for aging, so as to obtain a target oxidation catalyst, and multiple active substances are synergistic to effectively oxidize organic matters difficult to biodegrade. However, the patent only uses the activated carbon to adsorb active ingredients such as manganese, iron, titanium and the like, the content of the active ingredients capable of being loaded is limited, and the actual catalytic effect of the catalyst is further influenced; meanwhile, in practical application, the catalyst can only adsorb wastewater, ozone and hydrogen peroxide by utilizing pores of the active carbon, the adsorption effect is limited, and the ozone or the hydrogen peroxide is difficult to fully react with the wastewater under the action of the catalyst, so that the degradation efficiency of organic matters in the wastewater is low.
In view of the above, there is a need for an improved catalyst for improving the degradation efficiency of organic matters in wastewater by the efficient catalysis of the oxidation reaction of ozone and hydrogen peroxide, so as to solve the above problems.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to a TiO compound2An Al/Si-C based porous core-shell separation spherical catalyst, a preparation method and application thereof. The active carbon particles are sequentially mixed with ferric oxide powder and aluminum oxide-containing powder for granulation and calcination, so that part of active carbon is converted into gas to escape by utilizing the reaction of the active carbon particles and the ferric oxide in the calcination process, the gas escaping channel forms a permanent spherical pore channel, the volume of the residual active carbon core is reduced, the residual active carbon core is separated from a shell layer formed by the aluminum oxide-containing powder to form a porous core-shell separation spherical structure, and the TiO content is effectively improved2The loading capacity and the catalytic effect of the catalyst realize the high-efficiency catalytic oxidation of the ozone and the hydrogen peroxide.
In order to achieve the above object, the present invention provides a TiO compound2The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst comprises the following steps:
s1, screening the activated carbon particles, then carrying out acid washing, and drying for later use;
s2, fully mixing the dried activated carbon particles obtained in the step S1 with a predetermined amount of ferric oxide powder, adding powder containing alumina, blending, granulating and drying to obtain dry spheres;
s3, calcining the dried sphere obtained in the step S2 in an inert atmosphere for the first time, and reacting part of active carbon in the dried sphere with ferric oxide to form a porous core-shell separation sphere;
s4, placing the porous core-shell separation sphere obtained in the step S3 in a titanium-containing solution, taking out the porous core-shell separation sphere after full immersion, drying the porous core-shell separation sphere, and performing secondary calcination in an inert atmosphere to obtain TiO2An Al/Si-C based porous core-shell separation spherical catalyst is loaded.
In a further improvement of the invention, in step S2, the mass ratio of the activated carbon particles to the alumina-containing powder is 1 (2-10).
As a further improvement of the present invention, in step S2, the alumina-containing powder includes alumina, silica and sodium carboxymethyl cellulose; the aluminum oxide, the silicon oxide and the sodium carboxymethyl cellulose are mixed according to the mass ratio of 1 (0-1) to 0.1-0.3.
In a further improvement of the present invention, in step S2, the mass ratio of the activated carbon particles to the iron sesquioxide powder is (1-3): 1.
As a further improvement of the invention, the mesh number of the activated carbon particles obtained after screening is 60-100, the average particle size of the ferric oxide powder is 10-20 μm, and the average particle size of the alumina-containing powder is 0.5-1 μm.
In a further improvement of the present invention, in step S4, the titanium-containing solution is a titanium nitrate solution having a mass concentration of 2% to 20%, the mass ratio of the porous core-shell separation spheres to the titanium-containing solution is (0.1 to 0.2):1, and the obtained TiO is2TiO in Al/Si-C based porous core-shell separation sphere catalyst2The loading amount of the catalyst is 3.5 to 5.0 percent.
As a further improvement of the invention, in step S3, the calcination temperature of the primary calcination is 400-700 ℃, and the calcination time is 0.5-4 h.
As a further improvement of the invention, in step S4, the calcination temperature of the secondary calcination is 400-700 ℃, and the calcination time is 0.3-2 h.
In order to achieve the purpose, the invention also provides TiO2The Al/Si-C-based porous core-shell separation spherical catalyst is prepared according to any one of the technical schemes, and comprises active carbon which is used as a core and is loaded with iron, Al/Si oxide which is used as a shell, and TiO which is uniformly loaded in the shell and the core2(ii) a The particle size of the spherical catalyst is 0.5-2 mm, and the specific surface area is 150-200 m2/g。
In order to achieve the purpose, the invention also provides the TiO2Loaded Al/Si-C based porous core-shell separation spherical catalyst in ozoneThe catalytic oxidation and the hydrogen peroxide catalytic oxidation.
The invention has the beneficial effects that:
(1) the invention mixes and granulates the active carbon particles with ferric oxide powder and alumina-containing powder in turn, and utilizes the reaction of the active carbon particles and ferric oxide in the primary calcining process to convert part of the active carbon into gas to escape, the passage of the escaping gas forms a permanent spherical pore channel, and the volume of the residual active carbon kernel is reduced, thereby separating the residual active carbon kernel from the shell layer formed by the alumina-containing powder to form a porous core-shell separation spherical structure. On the basis, the sphere with the porous core-shell separation structure is soaked in the titanium-containing solution, so that the titanium-containing solution can be loaded on the surface of the sphere and permeates into the sphere to form a three-dimensional uniform load, and TiO is effectively improved2The loading capacity of the catalyst is improved, the catalytic effect of the catalyst is improved, and the efficient catalytic oxidation of ozone and hydrogen peroxide is realized, so that the degradation efficiency of organic matters in the wastewater is obviously improved, and the consumption of the oxidant is reduced.
(2) According to the invention, the activated carbon particles are fully mixed with the ferric oxide powder, and the mass ratio of the activated carbon particles to the ferric oxide powder is regulated, so that part of the activated carbon particles can reduce the ferric oxide in the calcining process, gas is generated while the activated carbon particles are consumed, and not only can the gas escape be utilized to form a spherical pore channel, and the sphere has a porous structure, but also the activated carbon particles can be separated from Al/Si oxide serving as a shell layer by utilizing the reduction of the volume of the activated carbon particles to form a core-shell separation structure, so that the specific surface area of the catalyst is further improved. Meanwhile, the invention can regulate and control the reduction rate of the ferric oxide by controlling the temperature of the primary calcination process, not only can utilize the unreduced ferric oxide and titanium dioxide to catalyze ozone or hydrogen peroxide together, and improve the catalytic efficiency; and the iron elementary substance loaded on the activated carbon particles obtained after reduction can also enable the catalyst to be recovered through magnetic adsorption after use so as to recycle the catalyst, and the method has high economic value and environmental protection value.
(3) The invention is prepared byThe alumina, the silicon oxide and the sodium carboxymethyl cellulose are mixed in proportion to be used as a shell layer of a sphere with a core-shell structure, so that the alumina and the silicon oxide can be used as TiO2The loading capacity of the carrier is further improved, and the sodium carboxymethyl cellulose can be used as a binder to promote the binding of alumina and silicon oxide, so that the prepared spherical catalyst has better mechanical property, and the integrity of a spherical structure is ensured during core-shell separation. Meanwhile, on the basis that the active carbon particles loaded with the ferric oxide are used as the inner core of the catalyst sphere, the sodium carbonate generated in the calcining process of the sodium carboxymethyl cellulose can also promote the reduction of the ferric oxide by the active carbon, so that the reduction rate of the ferric oxide is improved at a lower calcining temperature, and the performance of a porous core-shell separation sphere structure is promoted.
(4) The method provided by the invention can utilize the synergistic effect among the raw materials to prepare the active carbon loaded with iron as the kernel, Al/Si oxide as the shell, and TiO is uniformly loaded in the shell and the kernel in a three-dimensional way2The spherical catalyst is in a porous core-shell separation structure. The porous core-shell separation structure of the spherical catalyst has a large specific surface area, so that ozone or hydrogen peroxide can be fully contacted and reacted with wastewater under the action of the catalyst, the degradation efficiency of the spherical catalyst on organic matters in the wastewater is effectively improved while the consumption of an oxidant is reduced, and the degradation rate of catalytic oxidation for 10min is over 95 percent. The method provided by the invention has the advantages of simple process and strong controllability, and the prepared spherical catalyst can be recycled after being used, can meet the requirements of actual production and application, and has higher application value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a TiO2The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst comprises the following steps:
s1, screening the activated carbon particles, then carrying out acid washing, and drying for later use;
s2, fully mixing the dried activated carbon particles obtained in the step S1 with a predetermined amount of ferric oxide powder, adding powder containing alumina, blending, granulating and drying to obtain dry spheres;
s3, calcining the dried sphere obtained in the step S2 in an inert atmosphere for the first time, and reacting part of active carbon in the dried sphere with ferric oxide to form a porous core-shell separation sphere;
s4, placing the porous core-shell separation sphere obtained in the step S3 in a titanium-containing solution, taking out the porous core-shell separation sphere after full immersion, drying the porous core-shell separation sphere, and performing secondary calcination in an inert atmosphere to obtain TiO2An Al/Si-C based porous core-shell separation spherical catalyst is loaded.
The mesh number of the active carbon particles obtained after screening is 60-100, the average particle size of the ferric oxide powder is 10-20 mu m, and the average particle size of the powder containing the alumina is 0.5-1 mu m.
In step S2, the mass ratio of the activated carbon particles to the ferric oxide powder is (1-3): 1; the mass ratio of the activated carbon particles to the alumina-containing powder is 1 (2-10); the powder containing the alumina comprises alumina, silicon oxide and sodium carboxymethyl cellulose; the aluminum oxide, the silicon oxide and the sodium carboxymethyl cellulose are mixed according to the mass ratio of 1 (0-1) to 0.1-0.3.
In step S3, the calcination temperature of the primary calcination is 400 to 700 ℃, and the calcination time is 0.5 to 4 hours.
In step S4, the titanium-containing solution is a titanium nitrate solution with a mass concentration of 2% -20%, the mass ratio of the porous core-shell separation spheres to the titanium-containing solution is (0.1-0.2): 1, and the obtained TiO is2Al/Si-C-based porous core shellSeparation of TiO from spherical catalyst2The load capacity of the catalyst is 3.5 to 5.0 percent; the calcination temperature of the secondary calcination is 400-700 ℃, and the calcination time is 0.3-2 h.
The invention also provides TiO2The spherical catalyst is prepared according to the technical scheme and comprises active carbon which is used as a core and is loaded with iron, Al/Si oxide which is used as a shell and TiO which is uniformly loaded in the shell and the core2(ii) a The particle size of the spherical catalyst is 0.5-2 mm, and the specific surface area is 150-200 m2/g。
The invention also provides the TiO2The Al/Si-C-loaded porous core-shell separation spherical catalyst is applied to the fields of catalytic oxidation of ozone and catalytic oxidation of hydrogen peroxide.
The following example is provided to illustrate a TiO compound of the present invention2A supported Al/Si-C based porous core-shell separation spherical catalyst, a preparation method and application thereof are explained.
Example 1
This example provides a TiO2The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst comprises the following steps:
s1, screening the activated carbon particles, selecting 60-100 meshes of activated carbon, putting the activated carbon into a weak acid solution with the pH of 4-6, ultrasonically cleaning for 30min at normal temperature, and drying for 3h at 100 ℃ for later use.
S2, fully mixing the dried activated carbon particles obtained in the step S1 with ferric oxide powder with the average particle size of 15 mu m according to the mass ratio of 2:1, and then adding alumina-containing powder with the average particle size of 0.8 mu m for blending. Wherein the alumina-containing powder is prepared by mixing alumina, silicon oxide and sodium carboxymethylcellulose according to the mass ratio of 1:0.5:0.2, and the mass ratio of the activated carbon particles to the alumina-containing powder is 1: 6. And granulating and drying the mixed materials by an integrated granulating dryer to obtain a dry sphere with the average diameter of 1 mm.
S3, calcining the dried sphere obtained in the step S2 in a nitrogen atmosphere at 600 ℃ for 3h, so that part of the activated carbon in the dried sphere and ferric oxide are subjected to reduction reaction under the action of sodium carbonate generated by decomposition of sodium carboxymethylcellulose, generated CO gas escapes to form a permanent sphere channel, the volume of a residual activated carbon core is reduced, and the residual activated carbon core is separated from a shell layer formed by Al/Si oxide serving as a shell layer to form a porous core-shell separation sphere.
S4, soaking the porous core-shell separation sphere obtained in the step S3 in a titanium nitrate solution with the mass concentration of 10%, enabling the mass ratio of the porous core-shell separation sphere to the titanium nitrate solution to be 0.15:1, taking out after full soaking, drying the porous core-shell separation sphere at 100 ℃ for 3 hours, then carrying out secondary calcination in a nitrogen atmosphere, setting the calcination temperature to be 600 ℃ and the calcination time to be 1 hour, and obtaining TiO2An Al/Si-C based porous core-shell separation spherical catalyst is loaded.
The ball catalyst prepared in this example was tested for TiO2Was supported at 4.73 wt%, and the specific surface area of the spherical catalyst was 176.51m2Per g, shows the TiO prepared in this example2The Al/Si-C-based porous core-shell separation spherical catalyst has higher TiO2The loading capacity and the large specific surface area can effectively improve the catalytic efficiency of ozone and hydrogen peroxide, and have high degradation efficiency on organic matters in wastewater.
Examples 2 to 9 and comparative examples 1 to 3
Examples 2 to 9 and comparative examples 1 to 2 each provide a TiO compound2A preparation method of a supported Al/Si-C based porous core-shell separation sphere catalyst is provided, and a comparative example 3 provides a TiO catalyst2Compared with example 1, the difference of the preparation method of the supported C-based porous sphere catalyst is that the mass ratio of each raw material is changed, the raw material mass ratios corresponding to each example and comparative example are shown in Table 1, and the rest steps and parameters are consistent with those of example 1, and are not repeated herein.
TABLE 1 Mass ratios of raw materials in examples 2 to 9 and comparative examples 1 to 3
In order to analyze the difference of the physical and chemical properties and the catalytic effect of the spherical catalysts prepared in the examples and the comparative examples, the specific surface area of the spherical catalyst and the TiO loaded on the spherical catalyst provided in the examples are analyzed2The mass fraction of (a) and the degradation effect on wastewater were tested, and the results are shown in table 2.
Wherein, the degradation effect is tested by taking a methyl orange solution as an example, 5g of the catalysts prepared in each example and comparative example are respectively added into 500mL of methyl orange solution with the concentration of 100mg/L, and the degradation efficiency of the catalysts after the catalysts are reacted with hydrogen peroxide and ozone for 10min is respectively tested; the mass fraction of the hydrogen peroxide is 20 percent, and the ozone introducing speed is 20 mg/L.min.
TABLE 2 physicochemical properties and catalytic effects of the spherical catalysts prepared in examples 1 to 9 and comparative examples 1 to 3
As can be seen from table 2, adjusting the mass ratio of each raw material has a greater influence on the physicochemical properties of the prepared spherical catalyst and the catalytic effect thereof.
As can be seen by comparing examples 1 to 3 with comparative example 1, the TiO content of the catalyst prepared increases with the relative content of the ferric oxide2The whole of the loading capacity, the specific surface area and the degradation efficiency of the loading capacity tend to increase firstly and then decrease. Mainly because the ferric oxide is added and can react with the active carbon particles, on one hand, the generated gas escapes to form a sphere pore channel, so that the sphere has a porous structure, and on the other hand, the active carbon particles reduce the volume along with the consumption of the reaction to form a core-shell separation structure, so that the active carbon particles can react with the active carbon particles to form a core-shell separation structureTo promote TiO2The catalyst is uniformly loaded from the outside of the sphere to the inside of the sphere in a three-dimensional manner, and the catalytic effect of the catalyst is improved. Comparative example 1, in which no iron trioxide was added, could not react with activated carbon, and the catalyst prepared therefrom did not have a porous and core-shell separation structure, the TiO of the catalyst provided in comparative example 1 was2The loading capacity, the specific surface area and the degradation efficiency are obviously lower than those of the embodiments of the invention. In addition, under the condition of certain calcining condition and certain content of sodium carboxymethyl cellulose, the content of ferric oxide which can be reduced by the activated carbon is certain, and excessive ferric oxide does not bring extra reaction and pore structure, but blocks the pores in the activated carbon. Therefore, in the present invention, the mass ratio of the activated carbon particles to the iron sesquioxide powder is preferably (1-3): 1.
As can be seen from comparative examples 1, 4 to 5 and 3, TiO content of the catalyst obtained increases with the relative content of the alumina-containing powder2The whole of the loading capacity, the specific surface area and the degradation efficiency of the loading capacity tend to increase firstly and then decrease. Mainly because the alumina-containing powder can form an Al/Si oxide shell and form a core-shell separation structure together with the active carbon particles as the inner core, thereby effectively improving TiO2The loading capacity and the specific surface area thereof, and further achieve better degradation efficiency. Therefore, the performance of the catalyst prepared by the comparative example 3 without adding alumina powder at all is significantly lower than that of the examples of the present invention. However, excessive alumina-containing powder can also result in too thick a shell layer, affecting the TiO2The three-dimensional uniform load from the outside to the inside.
It can be seen from comparison of examples 6 to 9 and comparative example 2 that appropriate increase in the contents of silica and sodium carboxymethylcellulose in the alumina-containing powder both contribute to increase in the specific surface area and catalytic effect of the catalyst. The sodium carboxymethyl cellulose not only has a bonding effect on alumina and silicon oxide, but also can promote the reaction of active carbon positioned in the inner core and ferric oxide, so that the formation of a porous core-shell separation structure is promoted, and the catalytic effect of the catalyst is further improved. In comparative example 2, the absence of sodium carboxymethylcellulose not only affects the mechanical properties and integrity of the whole sphere, but also affects the reaction between the activated carbon and ferric oxide, resulting in poor catalytic effect as in the examples of the present application.
Examples 10 to 15
Examples 10 to 15 provide a TiO compound2Compared with the preparation method of the Al/Si-C-loaded porous core-shell separation sphere catalyst in the embodiment 1, the difference is that the calcination temperature and time of the primary calcination and the secondary calcination, the mass concentration of the titanium nitrate solution and the mass ratio of the porous core-shell separation sphere to the titanium nitrate solution are changed, the corresponding parameters of each embodiment are shown in the table 3, and the rest steps and parameters are consistent with those of the embodiment 1 and are not repeated herein.
TABLE 3 preparation parameters for examples 10 to 15
TiO described in examples 10 to 152Specific surface area of Al/Si-C-based porous core-shell separation spherical catalyst and TiO loaded by same2The mass fraction of (a) and the degradation effect on wastewater were tested, and the results are shown in table 4.
TABLE 4 physicochemical properties and catalytic effects of the spherical catalysts prepared in examples 10 to 15
As can be seen from Table 4, TiO increases with the concentration of the titanium nitrate solution or the relative mass of the titanium nitrate solution2The loading of (A) is also gradually increased, but when TiO is used2When the load of the catalyst is saturated, the improvement of the catalytic efficiency of the catalyst is not obvious by continuously increasing the concentration or relative mass of the titanium nitrate solution.
Meanwhile, in the two calcining processes, the influence of the temperature and the time of the first calcining on the performance of the prepared catalyst is relatively larger, mainly because the reaction state of the activated carbon and the ferric oxide is directly influenced by the change of the temperature and the time during the first calcining, and the formation of a porous core-shell separation structure is further influenced.
Therefore, the invention can not only control the formation of the porous core-shell separation structure, but also catalyze ozone or hydrogen peroxide by using the unreduced ferric oxide and titanium dioxide together by regulating and controlling the temperature and time of primary calcination, thereby improving the catalytic efficiency; and the iron elementary substance loaded on the activated carbon particles obtained after reduction can also enable the catalyst to be recovered through magnetic adsorption after use so as to recycle the catalyst, and the method has high economic value and environmental protection value.
In summary, the present invention provides a TiO compound2An Al/Si-C based porous core-shell separation spherical catalyst, a preparation method and application thereof. Mixing and granulating the activated carbon particles with ferric oxide powder and alumina-containing powder in sequence, and preparing a sphere with a porous core-shell separation structure after primary calcination; the obtained porous core-shell separation sphere is dipped in a titanium-containing solution and is calcined for the second time to obtain TiO2An Al/Si-C based porous core-shell separation spherical catalyst is loaded. Through the mode, the method can utilize the reaction of the activated carbon particles and the ferric oxide in the calcining process to convert part of activated carbon into gas to escape, form a permanent spherical pore channel, reduce the volume of the residual activated carbon kernel, separate the residual activated carbon kernel from a shell layer formed by powder containing alumina, and form a porous core-shell separation spherical structure, thereby effectively improving the TiO content2The loading capacity and the catalytic effect of the catalyst realize the high-efficiency catalytic oxidation of the ozone and the hydrogen peroxide.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. TiO 22The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of:
s1, screening the activated carbon particles, then carrying out acid washing, and drying for later use;
s2, fully mixing the dried activated carbon particles obtained in the step S1 with a predetermined amount of ferric oxide powder, adding powder containing alumina, blending, granulating and drying to obtain dry spheres; the powder containing the alumina comprises alumina, silicon oxide and sodium carboxymethyl cellulose;
s3, calcining the dried sphere obtained in the step S2 in an inert atmosphere for the first time, and reacting part of active carbon in the dried sphere with ferric oxide to form a porous core-shell separation sphere;
s4, placing the porous core-shell separation sphere obtained in the step S3 in a titanium-containing solution, taking out the porous core-shell separation sphere after full immersion, drying the porous core-shell separation sphere, and performing secondary calcination in an inert atmosphere to obtain TiO2An Al/Si-C based porous core-shell separation spherical catalyst is loaded.
2. The TiO of claim 12The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of: in step S2, the mass ratio of the activated carbon particles to the alumina-containing powder is 1 (2-10).
3. The TiO of claim 12The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of: in step S2, the mass ratio of the aluminum oxide to the silicon oxide to the sodium carboxymethyl cellulose is 1 (0-1) to 0.1-0.3.
4. The TiO of claim 12The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of: in step S2, the mass ratio of the activated carbon particles to the iron sesquioxide powder is (1-3): 1.
5. The TiO of claim 12The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of: the mesh number of the active carbon particles obtained after screening is 60-100, the average particle size of the ferric oxide powder is 10-20 mu m, and the average particle size of the powder containing the alumina is 0.5-1 mu m.
6. The TiO of claim 12The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of: in step S4, the titanium-containing solution is a titanium nitrate solution with a mass concentration of 2-20%, the mass ratio of the porous core-shell separation spheres to the titanium-containing solution is (0.1-0.2): 1, and the obtained TiO is2TiO in Al/Si-C based porous core-shell separation sphere catalyst2The loading amount is 3.5% -5.0%.
7. The TiO of any one of claims 1 to 62The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of: in step S3, the calcination temperature of the primary calcination is 400 to 700 ℃, and the calcination time is 0.5 to 4 hours.
8. The TiO of any one of claims 1 to 62The preparation method of the Al/Si-C-based porous core-shell separation spherical catalyst is characterized by comprising the following steps of: in step S4, the calcination temperature of the secondary calcination is 400 to 700 ℃, and the calcination time is 0.3 to 2 hours.
9. TiO 22The Al/Si-C based porous core-shell separation spherical catalyst is characterized in that: the spherical catalyst is prepared by the preparation method of any one of claims 1 to 8, and comprises active carbon which is used as an inner core and is loaded with iron, Al/Si oxide which is used as an outer shell, and TiO which is uniformly loaded in the outer shell and the inner core2(ii) a The particle size of the spherical catalyst is 0.5-2 mm, and the specific surface area is 150-200 m2/g。
10. TiO prepared by the preparation method of any one of claims 1 to 82Supported Al/Si-C based porous core-shell separation sphere catalyst or TiO of claim 92The application of the Al/Si-C based porous core-shell separation spherical catalyst is characterized in that: the TiO is2The Al/Si-C-loaded porous core-shell separation spherical catalyst is applied to the fields of ozone catalytic oxidation and hydrogen peroxide catalytic oxidation.
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