CN102744086B - Preparation method of ZrO2-TiO2/SO42-solid acid catalyst - Google Patents
Preparation method of ZrO2-TiO2/SO42-solid acid catalyst Download PDFInfo
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- CN102744086B CN102744086B CN2012102559497A CN201210255949A CN102744086B CN 102744086 B CN102744086 B CN 102744086B CN 2012102559497 A CN2012102559497 A CN 2012102559497A CN 201210255949 A CN201210255949 A CN 201210255949A CN 102744086 B CN102744086 B CN 102744086B
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Abstract
The invention discloses a preparation method of a ZrO2-TiO2/SO42-solid acid catalyst. The preparation method of the ZrO2-TiO2/SO42-solid acid catalyst is characterized by comprising the following steps of: firstly, stirring in water inside a thermostatic waterbath to dissolve ZrOCl2.8H2O, then adding polyethylene glycol, standing to obtain a clear and transparent solution A, regulating the pH value of the solution A by using ammonia water to obtain white sediments, filtering, and washing to obtain wet filter cakes; secondly, dissolving Ti(OC4H9)4 into concentrated sulfuric acid in the thermostatic waterbath to obtain a solution B, and then adding dilute sulphuric acid to the solution B to obtain a solution C; finally, stirring to dissolve the wet filter cakes into the solution C in the thermostatic waterbath to obtain a mixed solution, evaporating the mixed solution to obtain white solids, and calcining in a muffle furnace to obtain ZrO2-TiO2/SO42-solid acid catalyst. The invention has simple and easy preparation process and short time; and the ZrO2-TiO2/SO42-solid acid catalyst is regular in structure and can be produced in batches and used for preparing inorganic materials with other functions.
Description
Technical field
The invention belongs to the technology of preparing of inorganic material, particularly a kind of ZrO
2-TiO
2/ SO
4 2-The preparation method of solid acid catalyst.
Background technology
Chemical precipitation method refers to and at a certain temperature precipitating reagent is joined in metal salt solution and precipitated, and then by Separation of Solid and Liquid, washing, drying and heat treated etc., obtains solid powder sample.The method is without complicated Processes and apparatus, and easy operating, be one of chemical method extensively prepared inorganic nano material.Sol-gel process is a kind of effective method that preparation has the ordered micro-configuration material equally.By these two kinds of method combinations, the function complex chemical compound tool that has ordered structure for preparation is of great significance.
Tradition preparation ZrO
2-metal oxide/SO
4 2-The method of solid acid catalyst mainly comprises sol-gel process, precipitation-infusion process, hydro-thermal method, coprecipitation, self-assembly method etc., and these methods can effectively design ZrO
2-metal oxide/SO
4 2-The structure of solid acid catalyst and pattern, but usually have some defects, as the reaction time length, complex operation, not can manufacture etc.
Summary of the invention
The object of the invention is to: a kind of ZrO is provided
2-TiO
2/ SO
4 2-The preparation method of solid acid catalyst, in conjunction with sol-gel and chemical precipitation technical advantage, the ZrO that preparation in enormous quantities has ordered structure and specific morphology fast
2-TiO
2/ SO
4 2-Solid acid catalyst.
Technical solution of the present invention is that this preparation method comprises following concrete steps: at first, in water bath with thermostatic control, stirring and dissolving ZrOCl in water
28H
2O, then add polyethylene glycol, standing, obtain the solution A of clear; The pH value of ammoniacal liquor regulator solution A, obtain white precipitate, filters, washs, and obtains wet cake; Secondly, in water bath with thermostatic control, by Ti (OC
4H
9)
4Be dissolved in the concentrated sulfuric acid and obtain solution B, add again dilute sulfuric acid in solution B, obtain solution C; Finally, in water bath with thermostatic control, the wet cake stirring and dissolving, in solution C, is obtained to mixed solution, the evaporation mixed solution obtains white solid, in Muffle furnace, calcines, and obtains ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst; Wherein, water bath with thermostatic control temperature is 50-80
oC; The dispersant addition is ZrOCl
28H
2The 0.5%-3% of O addition; Wherein, the adjustable range of pH value is 8-9; Wherein, ZrOCl
28H
2O and Ti (OC
4H
9)
4Mole than for 1:0.5-2.0, ZrOCl
28H
2O and Ti (OC
4H
9)
4Mole sum and sulfuric acid mole than being 1:2.0-3.0; Wherein, the mass concentration of dilute sulfuric acid is 10%-30%; Calcining heat is 450
oC-700
oC.
Wherein, dispersant polyethylene glycol (PEG) is PEG-600, PEG-2000, PEG-20000.
Compared with prior art, its remarkable advantage: one, this solid acid catalyst preparation process are simple and easy, and the time is short in the present invention; Two, this solid acid catalyst has regular structure, can manufacture; Three, this technology of preparing has certain promotional value, can be for the preparation of other functional inorganic materials.
The specific embodiment
Further illustrate technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is the restriction to technical scheme.
Embodiment 1: according to following concrete steps, prepare ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst
Step 1,50
oIn the C water bath with thermostatic control, 0.02mol ZrOCl
28H
2The O stirring and dissolving is in 50mL H
2O, add 0.19g polyethylene glycol PEG-600, standing, obtains the solution A of clear;
Drip ammoniacal liquor in step 2, solution A and regulate pH value to 8, a large amount of white precipitates occur, standing, filter, wash, obtain wet cake;
Step 3,50
oIn the C water-bath, by 0.02mol Ti (OC
4H
9)
4Join 0.05mol mass concentration 98%H
2SO
4In, stirring and dissolving obtains solution B, adds subsequently 0.03mol mass concentration 10%H again
2SO
4, stir to obtain solution C;
Step 4,50
oIn the C water-bath, wet cake is joined in solution C, stirring and dissolving, obtain mixed solution;
Step 5,110
oIn the C baking oven, the above-mentioned mixed solution of evaporation, obtain white solid;
Step 6,450
oIn the C Muffle furnace, the calcining white solid, remove residual organic matter, obtains ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst.
Embodiment 2: according to following concrete steps, prepare ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst
Step 1,60
oIn the C water bath with thermostatic control, 0.2mol ZrOCl
28H
2The O stirring and dissolving is in 250mL H
2O, add 1.0g polyethylene glycol PEG-600, standing, obtains the solution A of clear;
Drip ammoniacal liquor in step 2, solution A and regulate pH value to 8.5, a large amount of white precipitates occur, standing, filter, wash, obtain wet cake;
Step 3,60
oIn the C water-bath, by 0.1mol Ti (OC
4H
9)
4Join 0.5mol mass concentration 98%H
2SO
4In, stirring and dissolving obtains solution B, adds subsequently 0. 4mol mass concentration 20%H
2SO
4, stir and obtain solution C;
Step 4,60
oIn the C water-bath, wet cake is joined in solution C, stirring and dissolving, obtain mixed solution;
Step 5,110
oIn the C baking oven, the above-mentioned mixed solution of evaporation, obtain white solid;
Step 6,500
oIn the C Muffle furnace, the calcining white solid, remove residual organic matter, obtains ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst.
Embodiment 3: according to following concrete steps, prepare ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst
Step 1,70
oIn the C water bath with thermostatic control, by 0.02mol ZrOCl
28H
2The O stirring and dissolving is in 50mL H
2O, add 0.033g polyethylene glycol PEG-2000, obtains the solution A of clear;
Drip ammoniacal liquor in step 2, solution A and regulate pH value to 9, a large amount of white precipitates occur, standing, filter, wash, obtain wet cake;
Step 3,70
oIn the C water-bath, by 0.04mol Ti (OC
4H
9)
4Join 0.09mol mass concentration 98%H
2SO
4In, stirring and dissolving obtains solution B, adds subsequently 0.03mol mass concentration 30%H
2SO
4, stir and obtain solution C;
Step 4,70
oIn the C water-bath, wet cake is joined in solution C, stirring and dissolving, obtain mixed solution;
Step 5,110
oIn the C baking oven, the above-mentioned mixed solution of evaporation, obtain white solid;
Step 6,700
oIn the C Muffle furnace, the calcining white solid, remove residual organic matter, obtains ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst.
Embodiment 4: according to following concrete steps, prepare ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst
Step 1,80
oIn the C water bath with thermostatic control, by 0.02mol ZrOCl
28H
2The O stirring and dissolving is in 50mL H
2O, add 0.1g polyethylene glycol PEG-20000, obtains the solution A of clear;
Drip ammoniacal liquor in step 2, solution A and regulate pH value to 9, a large amount of white precipitates occur, standing, filter, wash, obtain wet cake;
Step 3,80
oIn the C water-bath, by 0.02mol Ti (OC
4H
9)
4Join 0.05mol mass concentration 98%H
2SO
4In, stirring and dissolving obtains solution B, adds subsequently 0.05mol mass concentration 20%H
2SO
4, stir and obtain solution C;
Step 4,80
oIn the C water-bath, wet cake is joined in solution C, stirring and dissolving, obtain mixed solution;
Step 5,110
oIn the C baking oven, the above-mentioned mixed solution of evaporation, obtain white solid;
Step 6,600
oIn the C Muffle furnace, calcine this solid, remove residual organic matter, obtain ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst.
Claims (2)
1.ZrO
2-TiO
2/ SO
4 2-The preparation method of solid acid catalyst is characterized in that this preparation method comprises the following steps: at first, in water bath with thermostatic control, stirring and dissolving ZrOCl in water
28H
2O, then add polyethylene glycol, standing, obtain the solution A of clear; The pH value of ammoniacal liquor regulator solution A, obtain white precipitate, filters, washs, and obtains wet cake; Secondly, in water bath with thermostatic control, by Ti (OC
4H
9)
4Be dissolved in the concentrated sulfuric acid and obtain solution B, add again dilute sulfuric acid in solution B, obtain solution C; Finally, in water bath with thermostatic control, the wet cake stirring and dissolving, in solution C, is obtained to mixed solution, the evaporation mixed solution obtains white solid, in Muffle furnace, calcines, and obtains ZrO
2-TiO
2/ SO
4 2-Solid acid catalyst; Wherein, water bath with thermostatic control temperature is 50-80
oC; Dispersant polyethylene glycol addition is ZrOCl
28H
2The 0.5%-3% of O addition; Wherein, the adjustable range of pH value is 8-9; Wherein, ZrOCl
28H
2O and Ti (OC
4H
9)
4Mole than for 1:0.5-2.0, ZrOCl
28H
2O and Ti (OC
4H
9)
4Mole sum and sulfuric acid mole than being 1:2.0-3.0; Wherein, the mass concentration of dilute sulfuric acid is 10-30%; Calcining heat is 450
oC-700
oC.
2. ZrO according to claim 1
2-TiO
2/ SO
4 2-The preparation method of solid acid catalyst is characterized in that: dispersant polyethylene glycol (PEG) is PEG-600, PEG-2000, PEG-20000.
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| CN106345495A (en) * | 2016-08-24 | 2017-01-25 | 安徽金邦医药化工有限公司 | Solid acid catalyst and method for preparing 1,4-dioxane by using solid acid catalyst |
| CN106311286A (en) * | 2016-08-24 | 2017-01-11 | 安徽金邦医药化工有限公司 | Solid acid catalyst and preparing method of diethyl ether by using the same |
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