CN102744086A - Preparation method of ZrO2-TiO2/SO42-solid acid catalyst - Google Patents

Preparation method of ZrO2-TiO2/SO42-solid acid catalyst Download PDF

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CN102744086A
CN102744086A CN2012102559497A CN201210255949A CN102744086A CN 102744086 A CN102744086 A CN 102744086A CN 2012102559497 A CN2012102559497 A CN 2012102559497A CN 201210255949 A CN201210255949 A CN 201210255949A CN 102744086 A CN102744086 A CN 102744086A
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solution
acid catalyst
solid acid
preparation
tio2
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CN102744086B (en
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季红军
董云
万金方
付伟忠
厉业敏
朱旭东
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Jiangsu Huaihe Chemicals Co Ltd
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Jiangsu Huaihe Chemicals Co Ltd
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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

ZrO 2-TiO 2/ SO 42-The preparation method of solid acid catalyst
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 is meant at a certain temperature, precipitating reagent is joined in the metal salt solution precipitate, and obtains the pressed powder sample through Separation of Solid and Liquid, washing, drying and heat treated etc. then.This method need not complicated Processes and apparatus, and easy operating is one of chemical method that extensively prepares inorganic nano material.Sol-gel process is a kind of effective method that preparation has the ordered micro-configuration material equally.These two kinds of methods are combined, and the function complex chemical compound that has ordered structure for preparation has crucial meaning.
Traditional preparation process ZrO 2-metal oxide/SO 4 2-The method of solid acid catalyst mainly comprises sol-gel process, deposition-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 have some defectives usually, as the reaction time length, complex operation, not can manufacture etc.
Summary of the invention
The objective 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 fast has ordered structure and specific morphology 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 the water bath with thermostatic control, stirring and dissolving ZrOCl in the water 28H 2O adds polyethylene glycol again, leaves standstill, and gets the solution A of clear; The pH value of ammoniacal liquor regulator solution A gets white precipitate, filters, washs, and gets wet cake; Secondly, in the water bath with thermostatic control, with Ti (OC 4H 9) 4Be dissolved in and obtain solution B in the concentrated sulfuric acid, add dilute sulfuric acid in the solution B again, solution C; At last, in the water bath with thermostatic control, the wet cake stirring and dissolving in solution C, is got mixed solution, the evaporation mixed solution gets white solid, in Muffle furnace, calcines, and gets 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.
The present invention compared with prior art, its remarkable advantage: one of which, that this solid acid catalyst prepares process is simple and easy, the time is short; Two, this solid acid catalyst has regular structure, can manufacture; Three, this technology of preparing has certain popularization value, can be used to prepare other functional inorganic materials.
The specific embodiment
Further specify 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: prepare ZrO according to following concrete steps 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 adds 0.19g polyethylene glycol PEG-600, leaves standstill, and obtains the solution A of clear;
Dropping ammonia is regulated pH value to 8 in step 2, the solution A, a large amount of white precipitates occur, leaves standstill, and filters, washs, and obtains wet cake;
Step 3,50 oIn the C water-bath, with 0.02mol Ti (OC 4H 9) 4Join 0.05mol mass concentration 98%H 2SO 4In, stirring and dissolving gets solution B, adds 0.03mol mass concentration 10%H subsequently again 2SO 4, stir solution C;
Step 4,50 oIn the C water-bath, wet cake is joined in the solution C, stirring and dissolving gets mixed solution;
Step 5,110 oThe above-mentioned mixed solution of evaporation gets white solid in the C baking oven;
Step 6,450 oIn the C Muffle furnace, the calcining white solid is removed residual organic matter, obtains ZrO 2-TiO 2/ SO 4 2-Solid acid catalyst.
Embodiment 2: prepare ZrO according to following concrete steps 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 adds 1.0g polyethylene glycol PEG-600, leaves standstill, and obtains the solution A of clear;
Dropping ammonia is regulated pH value to 8.5 in step 2, the solution A, a large amount of white precipitates occur, leaves standstill, and filters, washs, and obtains wet cake;
Step 3,60 oIn the C water-bath, with 0.1mol Ti (OC 4H 9) 4Join 0.5mol mass concentration 98%H 2SO 4In, stirring and dissolving gets solution B, adds 0. 4mol mass concentration 20%H subsequently 2SO 4, stir and obtain solution C;
Step 4,60 oIn the C water-bath, wet cake is joined in the solution C, stirring and dissolving gets mixed solution;
Step 5,110 oThe above-mentioned mixed solution of evaporation obtains white solid in the C baking oven;
Step 6,500 oIn the C Muffle furnace, the calcining white solid is removed residual organic matter, obtains ZrO 2-TiO 2/ SO 4 2-Solid acid catalyst.
Embodiment 3: prepare ZrO according to following concrete steps 2-TiO 2/ SO 4 2-Solid acid catalyst
Step 1,70 oIn the C water bath with thermostatic control, with 0.02mol ZrOCl 28H 2The O stirring and dissolving is in 50mL H 2O adds 0.033g polyethylene glycol PEG-2000, obtains the solution A of clear;
Dropping ammonia is regulated pH value to 9 in step 2, the solution A, a large amount of white precipitates occur, leaves standstill, and filters, washs, and obtains wet cake;
Step 3,70 oIn the C water-bath, with 0.04mol Ti (OC 4H 9) 4Join 0.09mol mass concentration 98%H 2SO 4In, stirring and dissolving obtains solution B, adds 0.03mol mass concentration 30%H subsequently 2SO 4, stir and obtain solution C;
Step 4,70 oIn the C water-bath, wet cake is joined in the solution C, stirring and dissolving obtains mixed solution;
Step 5,110 oThe above-mentioned mixed solution of evaporation obtains white solid in the C baking oven;
Step 6,700 oIn the C Muffle furnace, the calcining white solid is removed residual organic matter, obtains ZrO 2-TiO 2/ SO 4 2-Solid acid catalyst.
Embodiment 4: prepare ZrO according to following concrete steps 2-TiO 2/ SO 4 2-Solid acid catalyst
Step 1,80 oIn the C water bath with thermostatic control, with 0.02mol ZrOCl 28H 2The O stirring and dissolving is in 50mL H 2O adds 0.1g polyethylene glycol PEG-20000, obtains the solution A of clear;
Dropping ammonia is regulated pH value to 9 in step 2, the solution A, a large amount of white precipitates occur, leaves standstill, and filters, washs, and obtains wet cake;
Step 3,80 oIn the C water-bath, with 0.02mol Ti (OC 4H 9) 4Join 0.05mol mass concentration 98%H 2SO 4In, stirring and dissolving obtains solution B, adds 0.05mol mass concentration 20%H subsequently 2SO 4, stir and obtain solution C;
Step 4,80 oIn the C water-bath, wet cake is joined in the solution C, stirring and dissolving obtains mixed solution;
Step 5,110 oThe above-mentioned mixed solution of evaporation obtains white solid in the C baking oven;
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 may further comprise the steps: at first, in the water bath with thermostatic control, stirring and dissolving ZrOCl in the water 28H 2O adds polyethylene glycol again, leaves standstill, and gets the solution A of clear; The pH value of ammoniacal liquor regulator solution A gets white precipitate, filters, washs, and gets wet cake; Secondly, in the water bath with thermostatic control, with Ti (OC 4H 9) 4Be dissolved in and obtain solution B in the concentrated sulfuric acid, add dilute sulfuric acid in the solution B again, solution C; At last, in the water bath with thermostatic control, the wet cake stirring and dissolving in solution C, is got mixed solution, the evaporation mixed solution gets white solid, in Muffle furnace, calcines, and gets 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.
CN2012102559497A 2012-07-24 2012-07-24 Preparation method of ZrO2-TiO2/SO42-solid acid catalyst Expired - Fee Related CN102744086B (en)

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CN103980737A (en) * 2013-12-25 2014-08-13 季红军 Modified titanium dioxide pigment and preparation method thereof
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
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
CN106349026A (en) * 2016-08-24 2017-01-25 安徽金邦医药化工有限公司 Synthesis technology of o-hydroxy phenyl ethyl ether
CN106397111A (en) * 2016-08-29 2017-02-15 吴琦琪 Catalytic preparation method of cyclohexanol

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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
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
CN106349026A (en) * 2016-08-24 2017-01-25 安徽金邦医药化工有限公司 Synthesis technology of o-hydroxy phenyl ethyl ether
CN106397111A (en) * 2016-08-29 2017-02-15 吴琦琪 Catalytic preparation method of cyclohexanol

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