CN104817109A - Preparation method of tetragonal-phase-based sulfur-rich sulfated zirconia - Google Patents
Preparation method of tetragonal-phase-based sulfur-rich sulfated zirconia Download PDFInfo
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Abstract
The invention discloses a preparation method of tetragonal-phase-based sulfur-rich sulfated zirconia, which comprises the following steps: dissolving zirconium n-butoxide and ammonium persulfate in benzyl alcohol to obtain a solid phase, carrying out vapor-phase reaction by using distilled water as a liquid phase, and carrying out high-temperature roasting on the obtained solid product to obtain the sulfated zirconia. The sulfated zirconia has the characteristics of rich sulfur, tetragonal phase and uniform acidic potential distribution, and has excellent catalytic activity in the field of acid catalysis application.
Description
Technical field
The present invention relates to a kind of preparation method of sulfidation-oxidation zirconium, particularly relate to a kind of preparation method with high-sulphur Tetragonal sulfidation-oxidation zirconium.
Background technology
Liquid acid catalyst (sulfuric acid, hydrofluoric acid etc.) in use exist as produce a large amount of liquid and waste slag produced, equipment corrosion serious, catalyzer and raw material and product is not easily separated, technique is difficult to realize the series of problems such as continuous seepage.And solid acid has not etching apparatus, low in the pollution of the environment, catalyzer and the easily separated recovery of liquid-phase reaction system, acid catalyzed reaction can carry out within the scope of comparatively high temps and reactive behavior comparatively advantages of higher.Therefore, research and development replace the novel environmental friendly solid acid catalyst of liquid acid, just become popular research topic in recent years.
Sulfidation-oxidation zirconium solid acid catalyst, because having superior acidity and chemical stability, is widely used in many acid catalyzed reactions such as Organoalkyl reaction, isomerization reaction, scission reaction and transesterification reaction.At present, the preparation method of sulfidation-oxidation zirconium mainly contains two-step approach and single stage method two kinds of methods.Wherein, traditional two-step approach is first by inorganic or organic zirconium source hydrolysis amorphous zirconium hydroxide, then carries out flooding with dilute sulphuric acid or vitriol and obtain sulfidation-oxidation zirconium through high-temperature calcination.The method preparation process is loaded down with trivial details and sulfur species charge capacity is low, makes catalyzer activity in catalytic reaction process not high.And single stage method generally adopts is sol-gel method, by organic zirconium source, propyl alcohol and sulfuric acid aqueous solution and form gel through vigorous stirring, after at room temperature aging, drier through CO 2 supercritical method, obtain sulfidation-oxidation zirconium finally by high-temperature roasting.
Compared with traditional two-step approach, single stage method clearly avoid complicated dipping process, simplifies preparation process.Sulfidation-oxidation zirconium is carried on the Metaporous silicon dioxide material of good thermal stability by single stage method by some investigators, thus has prepared sulfidation-oxidation zirconium-mesoporous SiO 2 catalystic material.But the mesopore orbit of catalyzer is but blocked along with the increase of sulphur charge capacity, and then causes catalyst activity to reduce.Therefore, most researchers is then more paid close attention to and is adopted single stage method to prepare sulfidation-oxidation Zr catalyst material.
(Monoclinic and tetragonal high surface area sulfated zirconias in butane isomerization:CO adsorption and catalytic results. J Catal, 2001 such as Stichert; 198:277 – 85.) adopt single stage method, under hydrothermal system, successfully prepare sulfidation-oxidation zirconia material.Result shows, the crystalline phase of prepared sample all coexists with Tetragonal and monoclinic phase, and finds the low sulfur content of sample that content of tetragonal phase is the highest only load 2.4%, the high sulfur content of the less sample of content of tetragonal phase then load 8%.(One-step synthesis of mesoporous nanosized sulfated zirconia via liquid-crystal template (LCT) method. Mater Res Bull, 2012 such as Zhang; 47:3931 – 36.) also report and utilize liquid crystal templating route one step direct synthesis of nano sulfidation-oxidation zirconium, sample crystalline phase still coexists with the mixed phase of Tetragonal and monoclinic phase, and its surperficial sulphur content reaches as high as 5.22%.
(Crystal phase, spectral features, and catalytic activity of sulfated-doped zirconia systems. J Catal, 1995 such as Morterra; 157:109 – 23.) research shows, sulfidation-oxidation zirconium is the highest with pure Tetragonal catalytic activity, take second place, and the catalytic activity of pure monoclinic phase sulfidation-oxidation zirconium is minimum with the catalytic activity of sulfidation-oxidation zirconium of four directions and monocline two-phase coexistent.In fact, Stichert etc. also find in catalyzed reaction research, and the catalytic activity of the 2.4% low-sulfur charge capacity sample high-sulfur charge capacity apparently higher than 8%, its reason is just that the former content of tetragonal phase is higher than the latter.
Summary of the invention
The object of the invention is to solve prior art Problems existing, a kind of zirconic preparation method of rich sulfur vulcanization based on Tetragonal is provided.
The zirconic preparation method of rich sulfur vulcanization based on Tetragonal of the present invention is:
Using zirconium-n-butylate as zirconium source, both, as sulfur species, are dissolved in phenylcarbinol the solid phase obtaining solution system and react as vapor phase by ammonium persulphate;
The liquid phase of reacting using distilled water as vapor phase;
Under air-tight state, above-mentioned solid phase and liquid phase is kept directly not to carry out vapor phase transport process reaction contiguously;
Collect the solid product that described vapor phase is obtained by reacting, high-temperature roasting obtains sulfidation-oxidation zirconium.
Wherein, in the solid phase of described vapor phase reaction, the mol ratio that the amount ratio of zirconium-n-butylate and ammonium persulphate meets sulphur atom and zirconium atom is 2 ~ 8: 1.
In above-mentioned preparation method, the temperature of reaction of described vapor phase reaction is 130 ~ 150 DEG C, reaction times 20 ~ 30h.
The present invention utilizes one-step synthesis, in high-pressure sealed system, under the booster action of phenylcarbinol, be hydrolyzed the surface that formed directly to be hydrolyzed with ammonium persulphate the sulfate ion generated with the crystal zirconium white molecule of oh group to combine by zirconium-n-butylate, and after high-temperature heat treatment, prepare the sulfidation-oxidation Zr catalyst material that rich sulphur, Tetragonal, acidic site are evenly distributed, more sulphur is carried on Tetragonal crystal zirconium surface, thus made it in acid catalysis Application Areas, have more advantage.
After tested, the sulphur content of the sulfidation-oxidation zirconium that the present invention prepares can reach 8.6 ~ 10.4%, is significantly higher than the sulphur content of prior art the highest 8%.
The crystalline phase of sulfidation-oxidation zirconium prepared by the present invention is Tetragonal, demonstrates superior catalytic activity.The sulfidation-oxidation zirconium catalysis Viscotrol C using the present invention to prepare and the transesterification reaction of methyl alcohol, obtain the high yield of product Viscotrol C methyl esters 100%.
Sulfidation-oxidation zirconium acidic site prepared by the present invention is evenly distributed, and ammonia temperature programmed desorption(TPD) instrument measurement result shows, and its 200 DEG C, 400 DEG C and 600 DEG C of corresponding diffraction peaks prove that it has the characteristic of weak acid, middle strong acid and super acids simultaneously.
Accompanying drawing explanation
Fig. 1 is the energy dispersion spectrogram of sulfidation-oxidation zirconium prepared by embodiment 1.
Fig. 2 is the X ray diffracting spectrum of sulfidation-oxidation zirconium prepared by embodiment 1.
Fig. 3 is the ammonia temperature programmed desorption(TPD) figure of sulfidation-oxidation zirconium prepared by embodiment 1.
Fig. 4 is the energy dispersion spectrogram of sulfidation-oxidation zirconium prepared by embodiment 2.
Fig. 5 is the X ray diffracting spectrum of sulfidation-oxidation zirconium prepared by embodiment 2.
Fig. 6 is the ammonia temperature programmed desorption(TPD) figure of sulfidation-oxidation zirconium prepared by embodiment 2.
Fig. 7 is the energy dispersion spectrogram of sulfidation-oxidation zirconium prepared by embodiment 3.
Fig. 8 is the X ray diffracting spectrum of sulfidation-oxidation zirconium prepared by embodiment 3.
Fig. 9 is the ammonia temperature programmed desorption(TPD) figure of sulfidation-oxidation zirconium prepared by embodiment 3.
Embodiment
Embodiment 1
Taking 0.96g zirconium-n-butylate adds in 12mL phenylcarbinol, 25 DEG C of mix and blend 10min, then adds 1.14g ammonium persulphate mixing and stirring.
Above-mentioned solution is loaded with in teflon-lined stainless steel still, puts into the distilled water be not in direct contact with it simultaneously, 140 DEG C of reaction 24h.
The solid product be obtained by reacting is through washing with alcohol, centrifugation, and 60 DEG C of dry 24h, 500 DEG C of calcination process obtain sulfidation-oxidation zirconium.
Get a little sulfidation-oxidation zirconium powdered sample, measure sulphur content 10.2% through energy dispersion spectrogram, as shown in Figure 1.Get a little sulfidation-oxidation zirconium powdered sample, measure through X-ray diffractometer, occurred the characteristic diffraction peak of Tetragonal when 2 times of diffraction angle are 50 °, proved that its crystalline phase is Tetragonal, as shown in Figure 2.Get a little sulfidation-oxidation zirconium powdered sample, measure through ammonia temperature programmed desorption(TPD) instrument, its acidic site is evenly distributed, and as shown in Figure 3, presents weak acid peak, middle strong acid peak and super acids peak respectively 200 DEG C, 400 DEG C and 600 DEG C.
Embodiment 2
Take 1.92g zirconium-n-butylate and 2.28g ammonium persulphate adds in 23mL phenylcarbinol, 25 DEG C of mix and blend 15min are to evenly.
Above-mentioned solution is loaded with in teflon-lined stainless steel still, puts into the distilled water be not in direct contact with it simultaneously, 140 DEG C of reaction 24h.
The solid product be obtained by reacting is through washing with alcohol, centrifugation, and 60 DEG C of dry 24h, 500 DEG C of calcination process obtain sulfidation-oxidation zirconium.
Fig. 4 shows its sulphur content 10.4%, Fig. 5, and to show its crystalline phase be Tetragonal, and Fig. 6 shows it and presents weak acid peak, middle strong acid peak and super acids peak simultaneously, and acidic site is evenly distributed.
Embodiment 3
Taking 6.84g ammonium persulphate adds in 35mL phenylcarbinol, 25 DEG C of mix and blend 20min, then adds 2.28g zirconium-n-butylate mixing and stirring.
Above-mentioned solution is loaded with in teflon-lined stainless steel still, puts into the distilled water be not in direct contact with it simultaneously, 140 DEG C of reaction 24h.
The solid product be obtained by reacting is through washing with alcohol, centrifugation, and 60 DEG C of dry 24h, 500 DEG C of calcination process obtain sulfidation-oxidation zirconium.
Fig. 7 shows its sulphur content 8.6%, Fig. 8, and to show its crystalline phase be Tetragonal, and Fig. 9 shows its acidic site and is evenly distributed.
Claims (3)
1., based on the zirconic preparation method of rich sulfur vulcanization of Tetragonal, it is characterized in that:
Using zirconium-n-butylate as zirconium source, both, as sulfur species, are dissolved in phenylcarbinol the solid phase obtaining solution system and react as vapor phase by ammonium persulphate;
The liquid phase of reacting using distilled water as vapor phase;
Under air-tight state, above-mentioned solid phase and liquid phase is kept directly not to carry out vapor phase transport process reaction contiguously;
Collect the solid product that described vapor phase is obtained by reacting, high-temperature roasting obtains sulfidation-oxidation zirconium.
2. the preparation method of sulfidation-oxidation zirconium according to claim 1, is characterized in that in described solid phase, and the mol ratio that the amount ratio of zirconium-n-butylate and ammonium persulphate meets sulphur atom and zirconium atom is 2 ~ 8: 1.
3. preparation method according to claim 1 and 2, is characterized in that the temperature of reaction that described vapor phase is reacted is 130 ~ 150 DEG C, reaction times 20 ~ 30h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908232A1 (en) * | 1997-10-13 | 1999-04-14 | Total Raffinage Distribution S.A. | Sulfated zirconia containing acid catalyst and use thereof |
| JP2001129398A (en) * | 1999-11-04 | 2001-05-15 | Mitsubishi Heavy Ind Ltd | Catalyst for reforming methanol and method for preparing it |
| CN101041138A (en) * | 2007-03-15 | 2007-09-26 | 复旦大学 | Method for preparing tetragonal phase region sulphuric acid zirconia solid superacid |
| US20110105314A1 (en) * | 2009-11-05 | 2011-05-05 | Anatoly Sobolevskiy | Process of Activation of a Palladium Catalyst System |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908232A1 (en) * | 1997-10-13 | 1999-04-14 | Total Raffinage Distribution S.A. | Sulfated zirconia containing acid catalyst and use thereof |
| JP2001129398A (en) * | 1999-11-04 | 2001-05-15 | Mitsubishi Heavy Ind Ltd | Catalyst for reforming methanol and method for preparing it |
| CN101041138A (en) * | 2007-03-15 | 2007-09-26 | 复旦大学 | Method for preparing tetragonal phase region sulphuric acid zirconia solid superacid |
| US20110105314A1 (en) * | 2009-11-05 | 2011-05-05 | Anatoly Sobolevskiy | Process of Activation of a Palladium Catalyst System |
Non-Patent Citations (3)
| Title |
|---|
| SWAPAN K.DAS ET AL.: "Self-Assembled Mesoporous Zirconia and Sulfated Zirconia Nanoparticles Synthesized by Triblock Copolymer as Template", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| 但悠梦等: "S2O82-/ZrO2-Al2O3 固体超强酸催化剂的研制与应用", 《应用化学》 * |
| 张黎等: "S2O82-/ZrO2固体超强酸的研究", 《高等学校化学学报》 * |
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