CN104069874B - A kind of is that SO prepared by raw material by wollastonite42-/ TiO2-SiO2the method of solid super-strong acid - Google Patents
A kind of is that SO prepared by raw material by wollastonite42-/ TiO2-SiO2the method of solid super-strong acid Download PDFInfo
- Publication number
- CN104069874B CN104069874B CN201410257109.3A CN201410257109A CN104069874B CN 104069874 B CN104069874 B CN 104069874B CN 201410257109 A CN201410257109 A CN 201410257109A CN 104069874 B CN104069874 B CN 104069874B
- Authority
- CN
- China
- Prior art keywords
- sio
- tio
- strong acid
- wollastonite
- solid super
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to solid super-strong acid preparing technical field, being specifically related to a kind of is that SO prepared by raw material by wollastonite4 2‑/TiO2‑SiO2The method of solid super-strong acid.The method comprises the following steps: wollastonite 1) is placed in Ti (SO4)2In solution, stirring, dropping ammoniacal liquor regulation pH to 1.5 4；2) then system is placed in water-bath, has been stirred continuously crystallization process, then reactant filtration washing is dried to obtain compound；3) finally by compound sulfuric acid dipping stirring, filtration drying, SO is obtained4 2‑/TiO2‑SiO2Solid super-strong acid.The raw silicon lime stone of the present invention is cheap and easy to get, completes the while of synthesis and crystallization in water-bath more than 80 degree, simple to operate, is easily controlled.
Description
Technical field
The invention belongs to solid super-strong acid preparing technical field, being specifically related to a kind of is that SO prepared by raw material by wollastonite4 2-/TiO2-SiO2The method of solid super-strong acid.
Background technology
Solid super-strong acid has that catalysis activity is high, do not corrode consersion unit, pollute without " three wastes ", prepare catalyst of reusing convenient, renewable separates the advantage such as simply with product.Its research and application become the hot fields seeking new green environment protection type catalyst, have great importance to promoting that chemical industry develops to environmental protection direction, become one of focus of current catalyticing research.The SO wherein promoted by sulfate radical4 2-/WxOyType y inorganic solid superacids all shows higher reactivity and preferable selectivity of product to almost all of acid catalyzed reaction.
Binary oxide TiO2-SiO2Type solid acid, compared with its one-component, has bigger specific surface area, more preferable stability, higher surface acidity, is widely used in elimination, dehydrogenation and dehydrocyclization, dehydration of alcohols, isomerization and the esterification etc. of organic pollution are reacted.But, application wollastonite is that SO prepared by raw material4 2-/
TiO2-SiO2The research of catalyst have not been reported.
Summary of the invention
It is an object of the invention to provide one to synthesize under cryogenic, on the premise of not roasting, utilize wollastonite to prepare SO for raw material4 2-/TiO2-SiO2
The method of solid super-strong acid.
For achieving the above object, the present invention is by the following technical solutions:
A kind of is that SO prepared by raw material by wollastonite4 2-/TiO2-SiO2The method of solid super-strong acid, comprises the following steps: wollastonite 1) is placed in Ti (SO4)2In solution, stirring, dropping ammoniacal liquor regulation pH to 3；2) then system is placed in water-bath, is stirred continuously so that titanium continues deposition and realizes crystallization, then reactant filtration washing is dried (80-100 DEG C) and obtains Detitanium-ore-type TiO2-SiO2Compound；3) finally by dried Detitanium-ore-type TiO2-SiO2Compound sulfuric acid dipping stirring, filtration drying (100-110 DEG C), obtain SO4 2-/TiO2-SiO2Solid super-strong acid.
Wollastonite and Ti (SO4)2Mol ratio be 2:1-2.
Mixing time in step 1) is more than 24h.
Step 2) in mixing time be more than 2h.
The rate of addition of ammoniacal liquor is 1-5mL/min, and the concentration of ammoniacal liquor is 0.25-2.5mol/L.
The temperature of water-bath is more than 80 DEG C.
Ti(SO4)2The concentration of solution is 0.05-2mol/L.
The concentration of sulfuric acid is 0.5-3mol/L.
The present invention aims at and synthesizes SO with wollastonite for raw material low temperature not roasting4 2-/TiO2-SiO2Solid super-strong acid, compared with the production method of existing solid acid catalyst, its feature, advantage and good effect are mainly reflected in the following aspects:
One is with wollastonite as reaction raw materials, and raw material is natural products, cheap and easy to get；
Two be that synthesis completes in water-bath more than 80 degree while of crystallization, it is to avoid the roasting process in traditional preparation process；
Synthesis crystallization process is shown in Fig. 3.
The present invention is not the reaction of simple wollastonite and acid, it is titanium sulfate reacting pretreatment stage due to participate in reaction, the introducing of sulfate radical makes to generate a large amount of sl. sol. calcium sulfate in course of reaction, simultaneously because the hydrolyzation system of titanium also will there be substantial amounts of titanium colloidal sol exist simultaneously, and plant process is had a significant impact by the existence of the generation of calcium sulfate and a large amount of titanium colloidal sol, finally give the acid of porous composite solids.
Accompanying drawing explanation
Fig. 1 is the XRD of embodiment 1 product (a) and reference examples 1 product (b)；
Fig. 2 is the TPD spectrogram of embodiment 1 product；
Fig. 3 is the figure of synthesis crystallization process.
Detailed description of the invention
Embodiment 1
Weigh 0.01mol325 mesh wollastonite in powder and be placed in the Ti (SO of 100 ml 0.05mol/L4)2In solution, stir 24h, in system, drip the pH to 2 of the ammoniacal liquor regulation system of 0.5mol/L with the speed of 1mL/min；It is 80 that system is placed in temperatureoIn the water-bath of C, and constantly stirring 2h, centrifuge washing reactant liquor is until detecting without SO with dichloride barium4 2-Till ion, will be deposited in after washing in baking oven 80oDetitanium-ore-type TiO is dried to obtain under C2-SiO2Compound.The TiO that will obtain2-SiO2The sulfuric acid of compound 0.5mol/L impregnates stirring, filtration drying in the ratio of 20ml/g, obtains SO4 2-/TiO2-SiO2Solid super-strong acid, as it is shown in figure 1, this solid acid degree of crystallization is good, the XRD peak of anatase is obvious；As in figure 2 it is shown, the acidity of solid acid meets standard.
Embodiment 2
Weigh 0.01mol325 mesh wollastonite in powder and be placed in the Ti (SO of 150 ml 0.05mol/L4)2In solution, stir 26h, in system, drip the pH to 3 of the ammoniacal liquor regulation system of 0.5mol/L with the speed of 2mL/min；It is 85 that system is placed in temperatureoIn the water-bath of C, and constantly stirring 3h, centrifuge washing reactant liquor is until detecting without SO with dichloride barium4 2-Till ion, will be deposited in after washing in baking oven 80oDetitanium-ore-type TiO is dried to obtain under C2-SiO2Compound.The TiO that will obtain2-SiO2The sulfuric acid of compound 0.5mol/L impregnates stirring, filtration drying in the ratio of 20ml/g, obtains SO4 2-/TiO2-SiO2Solid super-strong acid, XRD and the TPD spectrogram of product are same as in Example 1.
Embodiment 3
Weigh 0.01mol325 mesh wollastonite in powder and be placed in the Ti (SO of 200ml 0.05mol/L4)2In solution, stir 28h, in system, drip the pH to 4 of the ammoniacal liquor regulation system of 0.5mol/L with the speed of 3mL/min；It is 85 that system is placed in temperatureoIn the water-bath of C, and constantly stirring 4h, centrifuge washing reactant liquor is until detecting without SO with dichloride barium4 2-Till ion, will be deposited in after washing in baking oven 80oDetitanium-ore-type TiO is dried to obtain under C2-SiO2Compound.The TiO that will obtain2-SiO2The sulfuric acid of compound 0.5mol/L impregnates stirring, filtration drying in the ratio of 20ml/g, obtains SO4 2-/TiO2-SiO2Solid super-strong acid, XRD and the TPD spectrogram of product are same as in Example 1.
Reference examples 1
Weigh 0.01mol325 mesh wollastonite in powder and be placed in the Ti (SO of 100 ml 0.05mol/L4)2In solution, stir 24h, in system, drip the pH to 3 of the ammoniacal liquor regulation system of 0.5mol/L with the speed of 1mL/min；It is 70 that system is placed in temperatureoIn the water-bath of C, and constantly stirring 2h, centrifuge washing reactant liquor is until detecting without SO with dichloride barium4 2-Till ion, will be deposited in after washing in baking oven 80oDetitanium-ore-type TiO is dried to obtain under C2-SiO2Compound.The TiO that will obtain2-SiO2The sulfuric acid of compound 0.5mol/L impregnates stirring, filtration drying in the ratio of 20ml/g, obtains SO4 2-/TiO2-SiO2Solid super-strong acid, this solid acid degree of crystallization is the highest, and the XRD peak of anatase is inconspicuous.
Reference examples 2
Weigh 0.01mol325 mesh wollastonite in powder and be placed in the Ti (SO of 100 ml 0.05mol/L4)2In solution, stir 12h, in system, drip the pH to 3 of the ammoniacal liquor regulation system of 0.5mol/L with the speed of 1mL/min；It is 80 that system is placed in temperatureoIn the water-bath of C, and constantly stirring 2h, centrifuge washing reactant liquor is until detecting without SO with dichloride barium4 2-Till ion, will be deposited in after washing in baking oven 80oDetitanium-ore-type TiO is dried to obtain under C2-SiO2Compound.The TiO that will obtain2-SiO2The sulfuric acid of compound 0.5mol/L impregnates stirring, filtration drying in the ratio of 20ml/g, obtains SO4 2-/TiO2-SiO2Solid super-strong acid, this solid acid is short due to pretreatment time so that wollastonite can not completely remove, and this catalyst has relatively low specific surface area.
Reference examples 3
Weigh 0.01mol325 mesh wollastonite in powder and be placed in the Ti (SO of 100 ml 0.05mol/L4)2In solution, stir 12h, in system, drip the pH to 8 of the ammoniacal liquor regulation system of 0.5mol/L with the speed of 10mL/min；It is 80 that system is placed in temperatureoIn the water-bath of C, and constantly stirring 2h, centrifuge washing reactant liquor is until detecting without SO with dichloride barium4 2-Till ion, will be deposited in after washing in baking oven 80oDetitanium-ore-type TiO is dried to obtain under C2-SiO2Compound.The TiO that will obtain2-SiO2The sulfuric acid of compound 0.5mol/L impregnates stirring, filtration drying in the ratio of 20ml/g, obtains SO4 2-/TiO2-SiO2Solid super-strong acid, this solid acid is many due to speed, the amount of dropping alkali so that titanium and silicon deposit the most simultaneously, so while the existence of silicon makes the space between titanium increase, are unfavorable for nucleation and the carrying out of crystallization.
Reference examples 4
Weigh 0.01mol325 mesh wollastonite in powder and be placed in the Ti (SO of 100 ml 0.05mol/L4)2In solution, stir 12h, in system, drip the pH to 3 of the ammoniacal liquor regulation system of 0.5mol/L with the speed of 1mL/min；It is 80 that system is placed in temperatureoIn the water-bath of C, and constantly stirring 1h, centrifuge washing reactant liquor is until detecting without SO with dichloride barium4 2-Till ion, will be deposited in after washing in baking oven 80oDetitanium-ore-type TiO is dried to obtain under C2-SiO2Compound.The TiO that will obtain2-SiO2The sulfuric acid of compound 0.5mol/L impregnates stirring, filtration drying in the ratio of 20ml/g, obtains SO4 2-/TiO2-SiO2Solid super-strong acid, this solid acid is short due to crystallization time, it is impossible to formed anatase structured, less stable.
Claims (5)
1. one kind is that SO prepared by raw material by wollastonite4 2-/TiO2-SiO2The method of solid super-strong acid, it is characterised in that comprise the following steps: 1) wollastonite is placed in Ti (SO4)2In solution, wollastonite and Ti (SO4)2Mol ratio be 2:1-2, stirring, dropping ammoniacal liquor regulation pH to 1.5-4；2) then system is placed in the water-bath of more than 80 DEG C, has been stirred continuously crystallization process, then reactant filtration washing is dried to obtain compound；3) finally by compound concentration be 0.5-3mol/L sulfuric acid dipping stirring, filtration drying, obtain SO4 2-/TiO2-SiO2Solid super-strong acid.
2. as claimed in claim 1 is that SO prepared by raw material by wollastonite4 2-/TiO2-SiO2The method of solid super-strong acid, it is characterised in that: the mixing time in step 1) is more than 24h.
3. as claimed in claim 1 is that SO prepared by raw material by wollastonite4 2-/TiO2-SiO2The method of solid super-strong acid, it is characterised in that: step 2) in mixing time be more than 2h.
4. as claimed in claim 1 is that SO prepared by raw material by wollastonite4 2-/TiO2-SiO2The method of solid super-strong acid, it is characterised in that: the rate of addition of ammoniacal liquor is 1-5mL/min, and the concentration of ammoniacal liquor is 0.25-2.5mol/L.
5. as claimed in claim 1 is that SO prepared by raw material by wollastonite4 2-/TiO2-SiO2The method of solid super-strong acid, it is characterised in that: Ti (SO4)2The concentration of solution is 0.05-2mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410257109.3A CN104069874B (en) | 2014-06-11 | 2014-06-11 | A kind of is that SO prepared by raw material by wollastonite42-/ TiO2-SiO2the method of solid super-strong acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410257109.3A CN104069874B (en) | 2014-06-11 | 2014-06-11 | A kind of is that SO prepared by raw material by wollastonite42-/ TiO2-SiO2the method of solid super-strong acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104069874A CN104069874A (en) | 2014-10-01 |
| CN104069874B true CN104069874B (en) | 2016-09-07 |
Family
ID=51591712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410257109.3A Expired - Fee Related CN104069874B (en) | 2014-06-11 | 2014-06-11 | A kind of is that SO prepared by raw material by wollastonite42-/ TiO2-SiO2the method of solid super-strong acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104069874B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807472A (en) * | 2012-08-21 | 2012-12-05 | 南京工业大学 | Novel process for synthesizing 1, 2-cyclohexanediol by hydrolyzing epoxy cyclohexane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5642337B2 (en) * | 2008-02-27 | 2014-12-17 | 中部電力株式会社 | Halogen-containing compound decomposer |
-
2014
- 2014-06-11 CN CN201410257109.3A patent/CN104069874B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807472A (en) * | 2012-08-21 | 2012-12-05 | 南京工业大学 | Novel process for synthesizing 1, 2-cyclohexanediol by hydrolyzing epoxy cyclohexane |
Non-Patent Citations (2)
| Title |
|---|
| 固体酸SO2-/TiO2-SiO2对甲苯硝化的选择性催化作用;阳年发等;《化学研究与应用》;19961231;第8卷(第4期);第543-546页 * |
| 锐钛矿型TiO2/SiO2复合氧化物的制备;苑美荣等;《吉林大学学报（理学版）》;20070930;第45卷(第5期);第857-860页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104069874A (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101913586B (en) | Preparation method of ferric phosphate and product thereof | |
| US10898888B2 (en) | Preparation and application of magnetic metallic oxide cross-linked acidic polyionic liquid | |
| CN103730259B (en) | A kind of nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film and preparation method thereof | |
| CN110776418B (en) | Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid | |
| CN104549439B (en) | A kind of catalyst of high activity Synthesis of dimethyl carbonate and its preparation method and application | |
| CN105772057B (en) | A kind of preparation method of acetic acid and the order mesoporous catalyst of formaldehyde acrylic acid synthesizing | |
| CN105327709A (en) | Preparation method of catalyst used for synthesizing diphenyl carbonate by ester exchange method | |
| CN104492495A (en) | Ionic liquid immobilized magnetic solid acid material catalyst and preparation method thereof | |
| CN104492493A (en) | Magnetic solid acid material catalyst and preparation method thereof | |
| CN103394370A (en) | Silica gel supported sulfonic acid dual-core ionic liquid catalyst, preparation method and application | |
| CN111545225A (en) | Heterostructure photocatalyst for enhancing visible light response and preparation method thereof | |
| CN111875493B (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN104069874B (en) | A kind of is that SO prepared by raw material by wollastonite42-/ TiO2-SiO2the method of solid super-strong acid | |
| CN101869847A (en) | Micro-spherical polymer solid acid esterification catalyst and preparation method thereof | |
| CN101774637A (en) | Method for preparing self-assembly Bi12TiO20 micro-spheres by solution method | |
| CN101265180B (en) | Method for preparing lactic acid | |
| CN110354882B (en) | BiVO4@ZnIn2S4/g-C3N4Visible light response photocatalyst and preparation method thereof | |
| CN104525271A (en) | Ionic liquid supported magnetic iron oxide solid acid catalyst and preparation method thereof | |
| CN103073447B (en) | Synthesis method for 2-para-fluorobenzoylbut benzamide | |
| CN111087027A (en) | Flower-shaped Co3O4Preparation method of micro-sodium structure | |
| CN104556210A (en) | Method for preparing Sm2Sn2O7/SnO2 nano composite by microwave-assisted solvothermal two-step process | |
| CN106378163A (en) | Preparation method of KF modified zinc-aluminum hydrotalcite catalyst | |
| CN102730726B (en) | Method for preparing boehmite powder by using esterification reaction hydrothermal method | |
| CN110354883B (en) | BiVO4@CuIn2S4/g-C3N4Visible light response photocatalyst and preparation method thereof | |
| CN105195122A (en) | Preparation method for synthesizing propylene carbonate catalyst with urea and 1,2-propylene glycol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160907 Termination date: 20200611 |