CN116022865A - Nanoscale Ni 2 O 3 Nano Ni 2 O 3 Preparation method and application of base heterogeneous catalyst - Google Patents
Nanoscale Ni 2 O 3 Nano Ni 2 O 3 Preparation method and application of base heterogeneous catalyst Download PDFInfo
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 154
- 238000002156 mixing Methods 0.000 claims abstract description 54
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 102
- 239000000843 powder Substances 0.000 claims description 76
- 239000012792 core layer Substances 0.000 claims description 75
- 238000010438 heat treatment Methods 0.000 claims description 68
- 239000003054 catalyst Substances 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000005507 spraying Methods 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 32
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 25
- 238000005096 rolling process Methods 0.000 claims description 24
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 24
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 24
- 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 23
- 239000002994 raw material Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 46
- 239000005708 Sodium hypochlorite Substances 0.000 description 38
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000005995 Aluminium silicate Substances 0.000 description 20
- 235000012211 aluminium silicate Nutrition 0.000 description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 20
- 238000000227 grinding Methods 0.000 description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 18
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PSVXRBRATLTFCD-UHFFFAOYSA-N [Cl+].Cl[O-] Chemical compound [Cl+].Cl[O-] PSVXRBRATLTFCD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 breaks ether bonds Chemical compound 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention relates to the field of heterogeneous catalysts, and discloses a nano Ni 2 O 3 Nano Ni 2 O 3 Preparation of a heterogeneous catalystMethods and applications. The nano Ni 2 O 3 The preparation method of the (C) comprises the following steps: taking bivalent nickel salt aqueous solution and hypochlorite alkaline aqueous solution, mixing by a turbine, stirring for reaction, and collecting solid products to prepare nano-scale Ni 2 O 3 . Ni was prepared by the method of the present invention 2 O 3 Ni can be used as 2 O 3 Is controlled to be in the nanometer scale when it is directly used for catalyzing ClO ‑ Degradation, or reuse after formation of heterogeneous catalyst for catalyzing ClO ‑ When degrading, can realize higher catalytic activity.
Description
Technical Field
The invention relates to the field of heterogeneous catalysts, in particular to a nano Ni 2 O 3 Nano Ni 2 O 3 A preparation method and application of a heterogeneous catalyst.
Background
The catalytic activity of the nickel sesquioxide can promote the decomposition of hypochlorite to generate oxygen free radicals, so that the oxidation performance of the nickel sesquioxide is enhanced. With this reaction, residual chlorine (hypochlorite) in the wastewater can be removed, and in addition, oxygen radicals generated therefrom can be used in various oxidation reactions such as oxidative degradation of COD in the wastewater, and the like. The existing preparation method of the nickel sesquioxide often has the problems that the particle size is difficult to control and nano-sized particles cannot be obtained, so that the catalytic activity of the nickel sesquioxide is limited, and particularly after the nickel sesquioxide is loaded into a carrier to prepare a heterogeneous catalyst, the catalytic activity is further reduced.
For example, patent CN102030377a discloses a method for preparing analytically pure nickel sesquioxide, after iron, calcium and magnesium ions are removed from nickel nitrate, nickel oxalate is prepared, then the nickel oxalate is moved into a nickel plate to be calcined at 200-300 ℃ for 3-4 hours, and then the nickel oxalate is subjected to closed cooling, grinding and sieving. The patent adopts a high-temperature sintering method to prepare the nickel sesquioxide, cannot obtain nano particles, and cannot control granularity.
In addition, patent CN102030377a discloses cobalt oxide, nickel oxide catalytic material, preparation method and application, wherein it relates to a preparation method of nickel oxide: adding sodium carbonate solution into nitrate or sulfate solution of nickel, centrifugally separating precipitate, washing until pH value of washing solution is about 7, adding nickel chloride aqueous solution, heating in water bath at a certain temperature, regulating pH value to form hydrated nickel chloride colloid, adding sodium dodecyl benzene sulfonate surfactant, extracting with organic solvent, extracting and separating colloid particles containing bound water and adsorption hydration layer, refluxing and dewatering, distilling under reduced pressure to remove organic solvent, and vacuum drying at 170-200deg.C to obtain nickel oxide powder. By this method, although a nano-scale catalyst can be obtained, the product is essentially a mixture of nickel oxide and nickel sesquioxide, the nickel oxide of both forms cannot be separated, and the ratio cannot be regulated.
Disclosure of Invention
To solve the existing pure Ni 2 O 3 The invention provides a nano Ni, which is difficult to control the grain diameter of the product in nano grade 2 O 3 Nano Ni 2 O 3 A preparation method and application of a heterogeneous catalyst. Ni was prepared by the method of the present invention 2 O 3 Ni can be used as 2 O 3 Is controlled to be in the nanometer scale when it is directly used for catalyzing ClO - Degradation, or reuse after formation of heterogeneous catalyst for catalyzing ClO - When degrading, can realize higher catalytic activity.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides a nano-scale Ni 2 O 3 The preparation method of (2) comprises the following steps: taking bivalent nickel salt aqueous solution and hypochlorite alkaline aqueous solution, mixing by a turbine, stirring for reaction, and collecting solid products to prepare nano-scale Ni 2 O 3 。
The invention adopts a reaction crystallization method through Ni 2+ And ClO - Reaction between them to prepare Ni 2 O 3 The reaction mechanism is as follows: 2Ni 2+ +ClO - +4OH - →Ni 2 O 3 +Cl - +2H 2 O. The team of the invention found that Ni can be controlled during the above-mentioned reactive crystallization by turbo mixing 2 O 3 Is to realize nano Ni 2 O 3 Is prepared by the following steps. Nano Ni 2 O 3 Has larger specific surface area when used for catalyzing ClO - The catalyst has higher catalytic activity during degradation; and when Ni is used 2 O 3 When loaded into a carrier to prepare a heterogeneous catalyst, compared with Ni with larger particle size in the prior art 2 O 3 In other words, the nano Ni prepared in the invention 2 O 3 Can give the heterogeneous catalyst higher catalytic activity.
Preferably, ni in the divalent nickel salt aqueous solution 2+ The concentration of ClO in the hypochlorite alkaline aqueous solution is not higher than 0.5mmol/L - The concentration is not higher than 0.6mmol/L.
The concentration of the reactant solution will affect the Ni produced 2 O 3 When the concentration of the divalent nickel salt aqueous solution or the hypochlorite alkaline solution is too large, ni is caused 2 O 3 The crystallization rate is too high, resulting in the production of Ni 2 O 3 The particle size is too large.
Preferably, the volume ratio of the divalent nickel salt aqueous solution to the hypochlorite alkaline aqueous solution is 1:0.5-1.5.
Preferably, the stirring reaction time is 0.5 to 1 hour.
Preferably, the nano-scale Ni 2 O 3 The preparation method of the composition specifically comprises the following steps: introducing the divalent nickel salt aqueous solution and the hypochlorite alkaline aqueous solution into a turbine mixer at the flow rate of 100-400 mL/min, performing turbine mixing, stirring for reaction, and collecting solid products to obtain nano-grade Ni 2 O 3 。
Preferably, the solute in the aqueous divalent nickel salt solution comprises one or more of nickel nitrate, nickel chloride and nickel sulfate.
Preferably, the solute in the hypochlorite alkaline aqueous solution comprises one or more of hypochlorous acid, sodium hypochlorite and potassium hypochlorite.
In a second aspect, the present invention provides a nano-scale Ni 2 O 3 A process for the preparation of a heterogeneous catalyst comprising the steps of:
(1) By using the nano Ni 2 O 3 Is prepared by the preparation method of nano Ni 2 O 3 ；
(2) At nano-scale Ni 2 O 3 Is a catalytic active component, and is made into nano Ni by granulating and shaping 2 O 3 Based on heterogeneous catalysts.
Preferably, the specific process of step (2) comprises the following steps:
(2.1) mixing the core layer raw materials, adding water, and performing rolling granulation to obtain core layer green body particles; the nuclear layer raw material comprises nano Ni 2 O 3 A core layer carrier powder, sodium carboxymethyl cellulose, and a core layer binder;
(2.2) mixing shell raw materials, adding the mixture into core layer green body particles, spraying water, and continuously rolling and granulating to obtain catalyst green body particles; the shell layer raw material comprises nano Ni 2 O 3 Shell carrier powder, alCl 3 Powder and shell binder;
(2.3) spraying bicarbonate solution on the surfaces of the catalyst blank particles, standing for 30-40 min, performing heat treatment at 145-155 ℃ for 1-2 h, then heating to 300-310 ℃ and preserving heat for 10-30 min, then heating to 450-550 ℃ and preserving heat for 2-3 h to obtain nano-scale Ni 2 O 3 Based on heterogeneous catalysts.
Ni prepared in the invention 2 O 3 The heterogeneous catalyst has pore canal structure with large outside and small inside, and the large pore canal in the shell layer is communicated with the small pore canal in the nuclear layer. When Ni with special pore structure is used 2 O 3 Based heterogeneous catalysts for catalyzing ClO - When degrading, the larger pore diameter in the shell layer is beneficial to ClO - The ions enter to generate enrichment effect to promote ClO - Into a core layer pore canal which is communicated with the shell layer pore canal and has smaller pore diameter, and the pore canal with smaller size in the core layer can slow down ClO - Desorbing ClO - At Ni 2 O 3 Is fully reacted to release oxygen free radicals under the catalysis of the catalyst. Through the mode, the Ni with the special pore canal structure 2 O 3 The heterogeneous based catalyst enables better catalytic performance.
The invention adopts carboxymethyl respectively in the core layer and the shell layerSodium cellulose base and AlCl 3 The powder is used as a pore-forming agent and is matched with a special pore-forming process to endow Ni 2 O 3 The special pore channel structure of the heterogeneous catalyst is specifically: in the process of pore-forming, firstly spraying bicarbonate solution on the surfaces of the catalyst blank particles, penetrating the bicarbonate solution into the shell layer, contacting with aluminum chloride and reacting to generate water-insoluble aluminum hydroxide which is retained in the shell layer, and simultaneously releasing CO 2 The gas diffuses outwards, and pore channels are formed in the shell layer; then heat treatment is carried out at 145-155 ℃, at this time, sodium carboxymethylcellulose in the core layer is not heat decomposed, aluminum hydroxide in the shell layer is decomposed into gamma-alumina, and the released vapor enlarges the pore canal in the shell layer further; in the process of heating to 300-310 ℃ and preserving heat, sodium carboxymethyl cellulose in the core layer is decomposed, and the released water vapor and CO are utilized 2 The gas can form pore channels in the core layer, further expand the original pore channels in the shell layer, and simultaneously communicate the pore channels in the core layer and the shell layer; in the process of heating to 450-550 ℃ and preserving heat, sodium carboxymethyl cellulose is further decomposed to form pores, and meanwhile, the catalyst is gradually sintered, so that the mechanical strength is improved.
Further, in the step (2.3), the specific process of heating to 300-310 ℃ and preserving heat for 10-30 min, heating to 450-550 ℃ and preserving heat for 2-3 h comprises the following steps: heating to 220-240 ℃, then heating to 300-310 ℃ at the speed of 3-5 ℃/min, preserving heat for 10-30 min, heating to 450-550 ℃ at the speed of 10-20 ℃/min, and preserving heat for 2-3 h.
The thermal decomposition process of sodium carboxymethyl cellulose mainly comprises two stages: the first stage is to raise the temperature from about 245 ℃ to about 310 ℃, and the sodium carboxymethyl cellulose mainly breaks ether bonds, so that the gas generation speed is high; the second stage starts around 310 ℃, and the sodium carboxymethyl cellulose is mainly subjected to the cleavage of glycosidic bonds, and the gas generation speed of the process is slower. In accordance with the method, different heating rates are adopted in two stages respectively, so that the formation of pore channel structures with large outside and small inside can be better ensured, and specifically: the first stage adopts a slower heating rate to prevent the oversized pore canal in the nucleation layer and collapse of the porous structure in the shell layer caused by the excessively high gas release rate; the second stage adopts a faster heating rate to prevent the gas release rate from being too slow to effectively enlarge the pore canal in the shell.
Further, in the step (2.1), the core layer raw material comprises the following components in percentage by mass: nano Ni 2 O 3 10-20 parts of core layer carrier powder, 3-6 parts of sodium carboxymethyl cellulose, 0.2-0.4 part of core layer adhesive and 8-15 parts of core layer adhesive.
Further, in the step (2.2), the shell raw materials comprise the following components in percentage by mass: nano Ni 2 O 3 10 to 20 portions of shell carrier powder, 3 to 6 portions of AlCl 3 0.7 to 1.0 part of powder and 8 to 15 parts of shell adhesive.
Further, the particle size ratio of the core layer green body particles to the catalyst green body particles is 1:1.5 to 2.5.
Further, in the steps (2.1) and (2.2), the core layer carrier powder and the shell layer carrier powder are Al 2 O 3 Powder and/or MgO powder.
Further, in the steps (2.1) and (2.2), the core layer binder and the shell layer binder are independently selected from one or more of kaolin powder, bentonite powder and attapulgite.
In a second aspect, the present invention provides Ni 2 O 3 Use of a base catalyst for catalyzing hypochlorite decomposition to produce oxygen radicals, said Ni 2 O 3 The base catalyst is composed of the nano Ni 2 O 3 Is prepared by the preparation method of (1) or from the nano-scale Ni 2 O 3 A method for preparing a heterogeneous catalyst.
Compared with the prior art, the invention has the following advantages:
(1) The invention uses Ni 2+ And ClO - As raw material, adopting a reaction crystallization method to prepare Ni 2 O 3 And by combining turbine mixing, ni can be controlled 2 O 3 Is to realize nano Ni 2 O 3 Is prepared by the steps of (1);
(2) The invention adopts a special process to endow Ni 2 O 3 The heterogeneous catalyst has pore channel structure with large outside and small inside, and the large pore channel in the shell layer is communicated with the small pore channel in the core layer, so that the catalytic performance of the heterogeneous catalyst can be improved.
Detailed Description
The invention is further described below with reference to examples.
General examples
Nanoscale Ni 2 O 3 The preparation method of (2) comprises the following steps: taking bivalent nickel salt aqueous solution and hypochlorite alkaline aqueous solution, mixing by a turbine, stirring for reaction, and collecting solid products to prepare nano-scale Ni 2 O 3 。
As a specific embodiment, the nano-scale Ni 2 O 3 The preparation method of the composition specifically comprises the following steps: introducing the divalent nickel salt aqueous solution and the hypochlorite alkaline aqueous solution into a turbine mixer at the flow rate of 100-400 mL/min, performing turbine mixing, stirring for reaction, and collecting solid products to obtain nano-grade Ni 2 O 3 。
As a specific embodiment, ni in the divalent nickel salt aqueous solution 2+ The concentration of ClO in the hypochlorite alkaline aqueous solution is not higher than 0.5mmol/L - The concentration is not higher than 0.6mmol/L.
As a specific embodiment, the volume ratio of the divalent nickel salt aqueous solution to the hypochlorite alkaline aqueous solution is 1:0.5-1.5.
As a specific embodiment, the stirring reaction time is 0.5-1 h.
As a specific embodiment, the solute in the aqueous solution of divalent nickel salt comprises one or more of nickel nitrate, nickel chloride and nickel sulfate; the solute in the hypochlorite alkaline aqueous solution comprises one or more of hypochlorous acid, sodium hypochlorite and potassium hypochlorite.
Nanoscale Ni 2 O 3 A process for the preparation of a heterogeneous catalyst comprising the steps of:
(1) The nano-scale is adoptedNi 2 O 3 Is prepared by the preparation method of nano Ni 2 O 3 ；
(2) At nano-scale Ni 2 O 3 Is a catalytic active component, and is made into nano Ni by granulating and shaping 2 O 3 Based on heterogeneous catalysts.
Optionally, the specific process of step (2) includes the following steps:
(2.1) mixing the core layer raw materials, adding water, and performing rolling granulation to obtain core layer green body particles; the nuclear layer raw material comprises nano Ni 2 O 3 A core layer carrier powder, sodium carboxymethyl cellulose, and a core layer binder;
(2.2) mixing shell raw materials, adding the mixture into core layer green body particles, spraying water, and continuously rolling and granulating to obtain catalyst green body particles; the shell layer raw material comprises nano Ni 2 O 3 Shell carrier powder, alCl 3 Powder and shell binder;
(2.3) spraying bicarbonate solution on the surfaces of the catalyst blank particles, standing for 30-40 min, performing heat treatment at 145-155 ℃ for 1-2 h, then heating to 300-310 ℃ and preserving heat for 10-30 min, then heating to 450-550 ℃ and preserving heat for 2-3 h to obtain nano-scale Ni 2 O 3 Based on heterogeneous catalysts.
As a specific embodiment, the particle size ratio of the core layer green body particles to the catalyst green body particles is 1:1.5 to 2.5.
In step (2.3), as a specific implementation manner, the specific process of heating to 300-310 ℃ and preserving heat for 10-30 min, heating to 450-550 ℃ and preserving heat for 2-3 h comprises the following steps: heating to 220-240 ℃, then heating to 300-310 ℃ at the speed of 3-5 ℃/min, preserving heat for 10-30 min, heating to 450-550 ℃ at the speed of 10-20 ℃/min, and preserving heat for 2-3 h.
As a specific embodiment, in the step (2.1), the core layer raw material comprises the following components in percentage by mass: nano Ni 2 O 3 10-20 parts of core layer carrier powder, 3-6 parts of sodium carboxymethyl cellulose, 0.2-0.4 part of core layer adhesive and 8-15 parts of core layer adhesive; in the step (2.2), the step of (c) is performed,the shell raw materials comprise the following components in percentage by mass: nano Ni 2 O 3 10 to 20 portions of shell carrier powder, 3 to 6 portions of AlCl 3 0.7 to 1.0 part of powder and 8 to 15 parts of shell adhesive.
As a specific embodiment, in the steps (2.1) and (2.2), the core layer carrier powder and the shell layer carrier powder are Al 2 O 3 Powder and/or MgO powder; the core layer binder and the shell layer binder are independently selected from one or more of kaolin powder, bentonite powder and attapulgite clay.
Ni 2 O 3 Use of a base catalyst for catalyzing hypochlorite decomposition to produce oxygen radicals, said Ni 2 O 3 The base catalyst is composed of the nano Ni 2 O 3 Is prepared by the preparation method of (1) or from the nano-scale Ni 2 O 3 A method for preparing a heterogeneous catalyst.
Example 1
The nano-scale Ni is prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of nanoscale Ni 2 O 3 ：
An aqueous solution of nickel nitrate (0.5 mmol/L) and an aqueous solution of sodium hypochlorite (0.6 mmol/L) containing sodium hypochlorite and sodium hydroxide (0.6 mmol/L) were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 100mL/min, and then stirred for reaction for 0.5h, thus obtaining nano-scale Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle size analyzer, the monodisperse polymer is obtained, and the particle size distribution is 600-900 nm. After centrifugal separation, water washing and drying, nano Ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 3 parts of powder, 0.2 part of sodium carboxymethyl cellulose and 8 parts of kaolin powder, grinding, and adding nano-grade Ni 2 O 3 And (3) uniformly mixing 20 parts, spraying water in a spray mode, and rolling and granulating to prepare core layer green body particles with the particle size of about 1.5 mm.
(3) And (3) coating a shell:
al is added with 2 O 3 3 parts of powder, alCl 3 Mixing 0.7 part of powder and 8 parts of kaolin powder, grinding, and adding nano Ni 2 O 3 Mixing 20 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.3mL/cm 2 Roasting in an air atmosphere after standing for 30min, heating to 145 ℃ at a speed of 25 ℃ per minute and preserving heat for 2h, heating to 220 ℃ at a speed of 15 ℃ per minute, heating to 310 ℃ at a speed of 3 ℃ per minute and preserving heat for 10min, heating to 450 ℃ at a speed of 10 ℃ per minute and preserving heat for 3h to obtain nano-scale Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 32ppm.
Example 2
The nano-scale Ni is prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of nanoscale Ni 2 O 3 ：
An aqueous solution of 0.4mmol/L nickel chloride and an aqueous solution of sodium hypochlorite containing 0.6mmol/L sodium hypochlorite and 0.6mmol/L sodium hydroxide were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 400mL/min, and then stirred for reaction for 0.5h, thus obtaining nano-scale Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle size analyzer, the monodisperse polymer is obtained, and the particle size distribution is 300-700 nm. After centrifugal separation, water washing and drying, nano Ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 5 parts of powder, 0.3 part of sodium carboxymethyl cellulose and 10 parts of kaolin powder, grinding, and adding nano-scale Ni 2 O 3 15 parts of the components are evenly mixed, and then water is sprayed in a spray mode for rolling granulation, so that core layer green body particles with the particle size of about 1.5mm are prepared.
(3) And (3) coating a shell:
al is added with 2 O 3 5 parts of powder, alCl 3 Mixing 0.8 part of powder and 10 parts of kaolin powder, grinding, and adding nano Ni 2 O 3 Mixing 15 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.5mL/cm 2 Roasting in an air atmosphere after standing for 30min, heating to 150 ℃ at a speed of 20 ℃/min and preserving heat for 1.5h, heating to 230 ℃ at a speed of 20 ℃/min, heating to 310 ℃ at a speed of 3 ℃/min and preserving heat for 30min, heating to 500 ℃ at a speed of 15 ℃/min and preserving heat for 2.5h to obtain the nano-grade Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 39ppm.
Example 3
The nano-scale Ni is prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of nanoscale Ni 2 O 3 ：
An aqueous solution of nickel sulfate (0.1 mmol/L) and an aqueous solution of sodium hypochlorite (0.1 mmol/L) containing sodium hypochlorite and sodium hydroxide (0.1 mmol/L) were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 200mL/min, and then stirred for reaction for 0.5h, thus obtaining nano-scale Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle size analyzer, the monodisperse polymer is obtained, and the particle size distribution is 40-200 nm. After centrifugal separation, water washing and drying, nano Ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 6 parts of powder, 0.4 part of sodium carboxymethyl cellulose and 15 parts of kaolin powder, grinding, and adding nano-grade Ni 2 O 3 10 parts of the components are evenly mixed, and then water is sprayed in a spray mode for rolling granulation, so that core layer green body particles with the particle size of about 2.0mm are prepared.
(3) And (3) coating a shell:
al is added with 2 O 3 6 parts of powder, alCl 3 Mixing 1.0 part of powder and 15 parts of kaolin powder, grinding, and adding nano Ni 2 O 3 Mixing 10 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.5mL/cm 2 After standing for 40min, roasting in an air atmosphere, heating to 155 ℃ at a speed of 25 ℃ per minute and preserving heat for 1h, heating to 240 ℃ at a speed of 25 ℃ per minute, heating to 300 ℃ at a speed of 5 ℃ per minute and preserving heat for 30min, and heating to 550 ℃ at a speed of 20 ℃ per minute and preserving heat for 2h to obtain the nano-grade Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 45ppm.
Example 4
The nano-scale Ni is prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of nanoscale Ni 2 O 3 ：
An aqueous solution of 0.4mmol/L nickel chloride and an aqueous solution of sodium hypochlorite containing 0.6mmol/L sodium hypochlorite and 0.6mmol/L sodium hydroxide were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 400mL/min, and then stirred for reaction for 0.5h, thus obtaining nano-scale Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle analyzer to obtainTo be monodisperse, and the particle size distribution is 300-700 nm. After centrifugal separation, water washing and drying, nano Ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 5 parts of powder, 0.3 part of sodium carboxymethyl cellulose and 10 parts of kaolin powder, grinding, and adding nano-scale Ni 2 O 3 15 parts of the components are evenly mixed, and then water is sprayed in a spray mode for rolling granulation, so that core layer green body particles with the particle size of about 1.5mm are prepared.
(3) And (3) coating a shell:
al is added with 2 O 3 Mixing 5 parts of powder, 0.8 part of sodium carboxymethyl cellulose and 10 parts of kaolin powder, grinding, and adding nano-scale Ni 2 O 3 Mixing 15 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
roasting the catalyst blank particles in an air atmosphere, firstly heating to 150 ℃ at the speed of 20 ℃/min and preserving heat for 1.5 hours, then heating to 230 ℃ at the speed of 20 ℃/min, then heating to 310 ℃ at the speed of 3 ℃/min and preserving heat for 30 minutes, and finally heating to 500 ℃ at the speed of 15 ℃/min and preserving heat for 2.5 hours to obtain the nano-grade Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 126ppm.
In comparison with example 2, example 4 uses AlCl as the porogen in the shell 3 The catalyst is replaced by sodium carboxymethyl cellulose, and the prepared heterogeneous catalyst has poor catalytic performance on the decomposition of hypochlorite. The reason for this is presumed to be: EXAMPLE 2 sodium carboxymethylcellulose and AlCl were used in the core and outer shells, respectively 3 As a pore-forming agent, the pore-forming agent is matched with a special pore-forming process, so that a pore-channel structure with large outside and small inside can be obtained, and a large pore channel in a shell layer is communicated with a small pore channel in a core layer, and the pore-channel structure is larger in the shell layerPore size favors ClO - The ions enter to generate enrichment effect to promote ClO - Into a core layer pore canal which is communicated with the shell layer pore canal and has smaller pore diameter, and the pore canal with smaller size in the core layer can slow down ClO - Desorbing ClO - At Ni 2 O 3 Oxygen free radicals are released by the full reaction under the catalysis of the catalyst, and in this way, the catalytic performance of the heterogeneous catalyst can be improved. In example 4, sodium carboxymethylcellulose is used as the pore-forming agent in both the core layer and the shell, and the pore structure of "big pore canal outside and small pore canal inside and big pore canal inside and small pore canal in the shell layer are mutually communicated" is not formed, although the structure of big pore canal inside and big pore canal outside can be formed (by controlling the adding amount of the pore-forming agent), so that the ClO can not be promoted by the big pore canal in the shell - Adsorption, too, cannot slow down ClO by small pore channels in the core layer - And (5) desorption.
Example 5
The nano-scale Ni is prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of nanoscale Ni 2 O 3 ：
An aqueous solution of 0.4mmol/L nickel chloride and an aqueous solution of sodium hypochlorite containing 0.6mmol/L sodium hypochlorite and 0.6mmol/L sodium hydroxide were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 400mL/min, and then stirred for reaction for 0.5h, thus obtaining nano-scale Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle size analyzer, the monodisperse polymer is obtained, and the particle size distribution is 300-700 nm. After centrifugal separation, water washing and drying, nano Ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 5 parts of powder, 0.3 part of sodium carboxymethyl cellulose and 10 parts of kaolin powder, grinding, and adding nano-scale Ni 2 O 3 15 parts of the components are evenly mixed, and then water is sprayed in a spray mode for rolling granulation, so that core layer green body particles with the particle size of about 1.5mm are prepared.
(3) And (3) coating a shell:
al is added with 2 O 3 5 parts of powder, alCl 3 Mixing 0.8 part of powder and 10 parts of kaolin powder, grinding, and adding nano Ni 2 O 3 Mixing 15 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.5mL/cm 2 After standing for 30min, roasting in an air atmosphere, heating to 230 ℃ at a speed of 20 ℃/min, heating to 310 ℃ at a speed of 3 ℃/min, and preserving heat for 30min, heating to 500 ℃ at a speed of 15 ℃/min, and preserving heat for 2.5h to obtain Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 108ppm.
Compared with example 2, example 4 was not subjected to heat preservation at 150 ℃ for 1.5 hours during pore preparation, and the prepared heterogeneous catalyst had poor catalytic performance on the decomposition of hypochlorite. The reason for this is presumed to be: when heat treatment is carried out at 150 ℃, aluminum hydroxide (generated by reacting aluminum chloride with sodium bicarbonate solution) in the shell layer is decomposed into gamma-aluminum oxide, and released water vapor can further expand pore channels in the shell layer, so that the formation of pore channel structures with large outside and small inside is facilitated.
Example 6
The nano-scale Ni is prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of nanoscale Ni 2 O 3 ：
An aqueous solution of nickel sulfate (0.1 mmol/L) and an aqueous solution of sodium hypochlorite (0.1 mmol/L) containing sodium hypochlorite and sodium hydroxide (0.1 mmol/L) were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 200mL/min, and then stirred for reaction for 0.5h, thus obtaining nano-scale Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle size analyzer to obtain the monodisperse particle size distribution40-200 nm. After centrifugal separation, water washing and drying, nano Ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 6 parts of powder, 0.4 part of sodium carboxymethyl cellulose and 15 parts of kaolin powder, grinding, and adding nano-grade Ni 2 O 3 10 parts of the components are evenly mixed, and then water is sprayed in a spray mode for rolling granulation, so that core layer green body particles with the particle size of about 2.0mm are prepared.
(3) And (3) coating a shell:
al is added with 2 O 3 6 parts of powder, alCl 3 Mixing 1.0 part of powder and 15 parts of kaolin powder, grinding, and adding nano Ni 2 O 3 Mixing 10 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.5mL/cm 2 After standing for 40min, roasting in an air atmosphere, heating to 155 ℃ at a speed of 25 ℃ per minute and preserving heat for 1h, heating to 240 ℃ at a speed of 25 ℃ per minute, heating to 300 ℃ at a speed of 15 ℃ per minute and preserving heat for 30min, and heating to 550 ℃ at a speed of 20 ℃ per minute and preserving heat for 2h to obtain the nano-grade Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 102ppm.
Compared with example 3, in the pore-forming process of example 6, the temperature rising rate from 240 ℃ to 300 ℃ is changed from 5 ℃/min to 15 ℃/min, and the prepared heterogeneous catalyst has poorer catalytic performance on the decomposition of hypochlorite. The reason for this is presumed to be: in the process of heating from 240 ℃ to 300 ℃, the speed of generating gas by carboxymethyl decomposition is high, and if the heating speed is too high in the stage, the pore canal in the core layer is oversized, the porous structure in the shell layer is collapsed, and the formation of the pore canal structure with large outside and small inside is not facilitated.
Example 7
The nano-scale Ni is prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of nanoscale Ni 2 O 3 ：
An aqueous solution of nickel nitrate (0.5 mmol/L) and an aqueous solution of sodium hypochlorite (0.6 mmol/L) containing sodium hypochlorite and sodium hydroxide (0.6 mmol/L) were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 100mL/min, and then stirred for reaction for 0.5h, thus obtaining nano-scale Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle size analyzer, the monodisperse polymer is obtained, and the particle size distribution is 600-900 nm. After centrifugal separation, water washing and drying, nano Ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 3 parts of powder, 0.2 part of sodium carboxymethyl cellulose and 8 parts of kaolin powder, grinding, and adding nano-grade Ni 2 O 3 And (3) uniformly mixing 20 parts, spraying water in a spray mode, and rolling and granulating to prepare core layer green body particles with the particle size of about 1.5 mm.
(3) And (3) coating a shell:
al is added with 2 O 3 3 parts of powder, alCl 3 Mixing 0.7 part of powder and 8 parts of kaolin powder, grinding, and adding nano Ni 2 O 3 Mixing 20 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.3mL/cm 2 Roasting in an air atmosphere after standing for 30min, heating to 145 ℃ at a speed of 25 ℃ per minute and preserving heat for 2h, heating to 220 ℃ at a speed of 15 ℃ per minute, heating to 310 ℃ at a speed of 3 ℃ per minute and preserving heat for 10min, and heating to 450 ℃ at a speed of 3 ℃ per minute and preserving heat for 3h to obtain the nano-scaleNi 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to decrease to 94ppm.
Compared with example 1, in example 7, the temperature rising rate from 310 ℃ to 450 ℃ is changed from 10 ℃/min to 3 ℃/min in the pore preparation process, and the prepared heterogeneous catalyst has poorer catalytic performance on the decomposition of hypochlorite. The reason for this is presumed to be: in the process of heating from 310 ℃ to 450 ℃, the speed of generating gas by decomposing carboxymethyl cellulose is slower, and if the heating speed is too slow in the stage, the gas release speed is too slow, so that the pore channels in the shell layer are difficult to effectively expand, and the formation of pore channel structures with large outside and small inside is not facilitated.
Comparative example 1
Ni was prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of Ni 2 O 3 ：
An aqueous solution of nickel sulfate (0.1 mmol/L) and an aqueous solution of sodium hypochlorite (0.1 mmol/L) containing sodium hypochlorite and sodium hydroxide (0.1 mmol/L) were prepared, respectively. Mixing 500L of each solution, stirring and reacting for 0.5h, centrifuging, washing with water and drying to obtain Ni 2 O 3 . Through detection, ni is obtained 2 O 3 The particle size distribution is 10-100 mu m.
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 6 parts of powder, 0.4 part of sodium carboxymethyl cellulose and 15 parts of kaolin powder, grinding, and adding Ni 2 O 3 10 parts of the components are evenly mixed, and then water is sprayed in a spray mode for rolling granulation, so that core layer green body particles with the particle size of about 2.0mm are prepared.
(3) And (3) coating a shell:
al is added with 2 O 3 6 parts of powder, alCl 3 Mixing 1.0 part of powder and 15 parts of kaolin powder, grinding, and adding Ni 2 O 3 Mixing 10 parts, adding into core layer blank granule, spraying waterAnd (5) continuously rolling and granulating to prepare catalyst green body particles with the particle size of about 4.0mm, and drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.5mL/cm 2 After standing for 40min, roasting in an air atmosphere, heating to 155 ℃ at a speed of 25 ℃ per minute and preserving heat for 1h, heating to 240 ℃ at a speed of 25 ℃ per minute, heating to 300 ℃ at a speed of 5 ℃ per minute and preserving heat for 30min, and heating to 550 ℃ at a speed of 20 ℃ per minute and preserving heat for 2h to obtain the nano-grade Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 177ppm.
In comparison with comparative example 1, the reaction in step (1) of example 3 was carried out in a turbine mixer to obtain Ni 2 O 3 The particle size is obviously smaller and can reach the nanometer level, and the catalyst has better catalytic activity on the decomposition of hypochlorite after being prepared into a heterogeneous catalyst. The description is combined with the reactive crystallization method, and Ni can be controlled by simultaneously performing turbine mixing and reaction 2 O 3 Reducing Ni in terms of precipitation rate 2 O 3 Particle diameter of (2) to realize nano Ni 2 O 3 Is prepared by the following steps.
Comparative example 2
Ni was prepared by the following steps 2 O 3 Heterogeneous based catalyst:
(1) Preparation of Ni 2 O 3 ：
1mmol/L nickel sulfate aqueous solution and sodium hypochlorite aqueous solution containing 1mmol/L sodium hypochlorite and 1mmol/L sodium hydroxide were prepared, respectively. 500L of each of the two solutions is introduced into a turbine mixer for mixing at a flow rate of 400mL/min, and then stirred for reaction for 0.5h, thus obtaining Ni which is uniformly dispersed in the solution 2 O 3 And (3) particles. Tested by a nanometer particle size analyzer, the monodisperse polymer is obtained, and the particle size distribution is 900-3000 nm. After centrifugal separation, water washing and drying, ni is obtained 2 O 3 。
(2) Preparing core layer green body particles:
al is added with 2 O 3 Mixing 5 parts of powder, 0.3 part of sodium carboxymethyl cellulose and 10 parts of kaolin powder, grinding, and adding Ni 2 O 3 15 parts of the components are evenly mixed, and then water is sprayed in a spray mode for rolling granulation, so that core layer green body particles with the particle size of about 1.5mm are prepared.
(3) And (3) coating a shell:
al is added with 2 O 3 5 parts of powder, alCl 3 Mixing 0.8 part of powder and 10 parts of kaolin powder, grinding, and adding Ni 2 O 3 Mixing 15 parts, adding into core layer green body particles, spraying water while rolling to granulate, and oven drying.
(4) Hole making and sintering:
spraying 1mol/L sodium bicarbonate solution to the surfaces of the catalyst blank particles, wherein the spraying amount is 0.5mL/cm 2 Roasting in an air atmosphere after standing for 30min, heating to 150 ℃ at a speed of 20 ℃/min and preserving heat for 1.5h, heating to 230 ℃ at a speed of 20 ℃/min, heating to 310 ℃ at a speed of 3 ℃/min and preserving heat for 30min, heating to 500 ℃ at a speed of 15 ℃/min and preserving heat for 2.5h to obtain the nano-grade Ni 2 O 3 Based on heterogeneous catalysts.
Catalytic performance test: 500g of the catalyst prepared in this example was charged into a U-shaped tube, and 1L of 2000ppm sodium hypochlorite solution was introduced, and after 2 hours, the sodium hypochlorite concentration was detected to be reduced to 120ppm.
The reactant solutions used in step (1) of examples 1 to 3 had smaller concentrations than comparative example 2, and Ni was produced 2 O 3 The particle size is smaller, and the catalyst has better catalytic activity on the decomposition of hypochlorite after being prepared into a heterogeneous catalyst. Indicating that when the concentration of the reactant solution (including the aqueous solution of nickel divalent salt and the alkaline solution of hypochlorite) is too large, the Ni produced is caused 2 O 3 The particle size is too large, probably due to Ni 2 O 3 The crystallization rate is too high.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. Nanoscale Ni 2 O 3 The preparation method of (2) is characterized by comprising the following steps: taking bivalent nickel salt aqueous solution and hypochlorite alkaline aqueous solution, mixing by a turbine, stirring for reaction, and collecting solid products to prepare nano-scale Ni 2 O 3 。
2. The method of claim 1, wherein the Ni in the aqueous solution of divalent nickel salt 2+ The concentration of ClO in the hypochlorite alkaline aqueous solution is not higher than 0.5mmol/L - The concentration is not higher than 0.6mmol/L.
3. The preparation method according to claim 1 or 2, characterized by comprising the following steps: introducing a divalent nickel salt aqueous solution and a hypochlorite alkaline aqueous solution into a turbine mixer at a flow rate of 100-400 mL/min, performing turbine mixing, stirring for reaction, and collecting a solid product to obtain nano-grade Ni 2 O 3 。
4. The method of making as claimed in claim 1 or 2, wherein the solute in the aqueous divalent nickel salt solution comprises one or more of nickel nitrate, nickel chloride and nickel sulfate.
5. Nanoscale Ni 2 O 3 A process for the preparation of a heterogeneous catalyst, characterized in that it comprises the following steps:
(1) The method of claim 1 to 4, wherein nano Ni is obtained 2 O 3 ；
(2) At nano-scale Ni 2 O 3 Is a catalytic active component, and is made into nano Ni by granulating and shaping 2 O 3 Based on heterogeneous catalysts.
6. The preparation method according to claim 5, wherein the specific process of the step (2) comprises the steps of:
(2.1) mixing the core layer raw materials, adding water, and performing rolling granulation to obtain core layer green body particles; the nuclear layer raw material comprises nano Ni 2 O 3 A core layer carrier powder, sodium carboxymethyl cellulose, and a core layer binder;
(2.2) mixing shell raw materials, adding the mixture into core layer green body particles, spraying water, and continuously rolling and granulating to obtain catalyst green body particles; the shell layer raw material comprises nano Ni 2 O 3 Shell carrier powder, alCl 3 Powder and shell binder;
(2.3) spraying bicarbonate solution on the surfaces of the catalyst green body particles, standing for 30-40 min, performing heat treatment at 145-155 ℃ for 1-2 h, then heating to 300-310 ℃ and preserving heat for 10-30 min, then heating to 450-550 ℃ and preserving heat for 2-3 h to obtain nano-scale Ni 2 O 3 Based on heterogeneous catalysts.
7. The preparation method according to claim 6, wherein in the step (2.3), the specific process of heating to 300-310 ℃ and maintaining the temperature for 10-30 min, heating to 450-550 ℃ and maintaining the temperature for 2-3 h comprises the following steps: after the temperature is raised to 220-240 ℃, the temperature is raised to 300-310 ℃ at the speed of 3-5 ℃/min and kept for 10-30 min, and then the temperature is raised to 450-550 ℃ at the speed of 10-20 ℃/min and kept for 2-3 h.
8. The method of manufacturing according to claim 6, wherein:
in the step (2.1), the core layer raw material comprises the following components in percentage by mass: nano Ni 2 O 3 10-20 parts of core layer carrier powder 3-6 parts of sodium carboxymethyl cellulose0.2-0.4 parts of core layer adhesive, 8-15 parts of core layer adhesive; and/or
In the step (2.2), the shell raw materials comprise the following components in percentage by mass: nano Ni 2 O 3 10-20 parts of shell carrier powder, 3-6 parts of AlCl 3 0.7-1.0 parts of powder and 8-15 parts of shell adhesive.
9. The method of preparing as claimed in claim 6 wherein the particle size ratio of the core layer green particles to the catalyst green particles is 1: 1.5-2.5.
10.Ni 2 O 3 The use of a base catalyst for catalyzing hypochlorite decomposition to produce oxygen radicals, characterized in that the Ni 2 O 3 The base catalyst is produced by the production method according to one of claims 1 to 4 or by the production method according to one of claims 5 to 9.
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