CN100447085C - Mesoporous Zr-Si molecular sieve and its synthesis - Google Patents

Mesoporous Zr-Si molecular sieve and its synthesis Download PDF

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CN100447085C
CN100447085C CNB2004100645027A CN200410064502A CN100447085C CN 100447085 C CN100447085 C CN 100447085C CN B2004100645027 A CNB2004100645027 A CN B2004100645027A CN 200410064502 A CN200410064502 A CN 200410064502A CN 100447085 C CN100447085 C CN 100447085C
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molecular sieve
zirconium
mesoporous
mol ratio
crystallization
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CN1636873A (en
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李福祥
李瑞丰
张香娣
郭群
谢克昌
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Taiyuan University of Technology
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Abstract

The present invention relates to a Zr-Si mesoporous molecular sieve and a systhesis method thereof, which belongs to the fields of inorganic material synthesis and catalytic science. The present invention is characterized in that the Zr-Si mesoporous molecular sieve provides a mesoporous molecular sieve with large specific surface area, high thermal stability and high Zr-Si ratio; in the synthesis method of the mesoporous molecular sieve, zirconium nitrate is used as a zirconium source, tetraethyl orthosilicate is used as a silicon source, and CTAB and P123 are used as template agents, and then the zirconium source, the silicon source and the template agents are synthesized by two-step crystallization method in an alcohol water system; when the ratio of zirconium to silicon is 1:2, the specific surface area reaches 500m<2>/g after the synthesized sample is roasted for 3 hours at 600 DEG C. The Zr-Si mesoporous molecular sieve can be used in the fields of adsorption, catalysis, etc.

Description

A kind of mesoporous Zr-Si molecular sieve and synthetic method
One, technical field:
The present invention is a kind of mesoporous Zr-Si molecular sieve and synthetic method, belongs to the synthetic and catalytic science field of inorganic materials.
Two, background technology:
Mesoporous material is meant the porous material of aperture at 2～50nm, U.S. Mobil company in 1992 adopt tensio-active agent to make template first successfully to have synthesized the aperture be the M41S type quasi-crystalline state mesopore SiO of 2～10nm 2Material, such material have surface-area greatly (greater than 1000m 2), characteristics such as the narrow and high adsorption capacity of pore size distribution, caused chemists' intensive interest, and a series of these class materials have been synthesized, as SBA-15, MAS-5 etc., this class material has been obtained and big development, and thermostability and hydrothermal stability are greatly improved, the aperture is also adjustable within the specific limits, but a little less than this mesoporous material surface acidity of pure silicon, catalytic activity is low, must introduce other metal heteroatom, to increase its catalytic activity, so people expand to transition metal oxide (as ZrO with this synthetic thinking 2, WO 3, TiO 2Deng).Zirconium white has acidity, alkalescence, oxidisability and reductibility, and therefore the catalyzer of being made by it has unique catalytic activity and selectivity, and zirconium white can also be made multiple super acidic catalyst (as SO 4 2-/ ZrO 2, WO 3/ ZrO 2And MoO 3/ ZrO 2Deng), be used for reactions such as isomerization, alkylation and esterification.The simultaneous oxidation zirconium still is a kind of good support of the catalyst, but the zirconium white specific surface area of traditional method preparation is little, reactive behavior is low, and the poor heat stability of present synthetic pure zirconia mesoporous material, so the synthetic of the mesoporous Zr-Si molecular sieve of large specific surface, high thermal stability and high zirconium silicon ratio will be widely used aspect Industrial Catalysis.
Three, summary of the invention:
The present invention is a kind of mesoporous Zr-Si molecular sieve and synthetic method, purpose is to provide the mesoporous Zr-Si molecular sieve and the synthetic method of a kind of large specific surface, high thermal stability and high zirconium silicon ratio, thereby solves the low problems such as little and pure zirconia hole material poor heat stability of amassing with zirconium surface of pure silicon mesopore molecular sieve catalytic activity.
A kind of mesoporous Zr-Si molecular sieve of the present invention is characterized in that it being a kind of a kind of mesoporous Zr-Si molecular sieve of making according to following step method:
I, be the zirconium source, and cetyl trimethylammonium bromide with the zirconium nitrate, in zirconium nitrate and alcoholic acid mol ratio be 1: 30～200, cetyl trimethylammonium bromide and alcoholic acid mol ratio be that 1: 30～40 ratios are dissolved in respectively in the ethanol, makes A and B solution;
II, under agitation slowly add A solution in the B solution, the mol ratio of its zirconium nitrate and cetyl trimethylammonium bromide is 0.3～1.5, be sealed in the reactor of inner liner polytetrafluoroethylene after stirring 1h, pre-crystallization is 2～10 hours in 40～140 ℃ baking oven, taking-up is cooled to room temperature, the material that crystallization is good was poured in the beaker high degree of agitation into 1～8 hour, made material C;
III, simultaneously with triblock polymer template EO 20PO 70EO 20Molecular-weight average is 5800, under agitation be dissolved in the hydrochloric acid soln of 1.6mol/L, after 35～40 ℃ of following stirring and dissolving, join in the tetraethoxy, 35～40 ℃ of following stirring reactions 1～10 hour, under agitation slowly add material C then, the mol ratio of its zirconium silicon is 0.05～2.6, continues to stir after 0.5～6 hour, be sealed in the reactor of inner liner polytetrafluoroethylene, crystallization is 24～62 hours in 80～120 ℃ baking oven;
Take out after IV, crystallization are finished and be cooled to room temperature, filter, and with distilled water wash for several times, the dry faint yellow solid that gets in air at room temperature, this solid just obtained the mesoporous Zr-Si molecular sieve sample behind the removed template method in 3～10 hours 350～650 ℃ of following roastings, this molecular sieve its:
Zirconium silicon ratio is: 0.1～2.0
The aperture is: 6～10nm
Pore volume is: 0.3～0.7cm 3/ g
Specific surface area is: 180～700m 2/ g
ZrO 2It in molecular sieve the tetragonal structure structure.
The synthetic method of described mesoporous Zr-Si molecular sieve is to carry out according to above-mentioned step method, and its described (zirconium+silicon): P123: the mol ratio of water is 100～200: 1: 12000～13000.
The above-mentioned feature that contains the zirconium mesoporous material in view of this high zirconium silicon ratio of synthetic of the present invention, high thermal stability, can be used for different absorption and catalytic reaction process by different treatment processs, zirconium dioxide has acid and basic surface center, have oxidisability and reductibility simultaneously, therefore this material is even more important for the reaction of dual-function catalyst, all shows excellent catalytic performance in dehydration, hydrogenation, hydrogen exchange reaction; Zirconium dioxide has good ion-exchange performance, can produce stronger interaction with active ingredient as a kind of important catalyst carrier.The catalyzer of this material load rhodium can be used for CO 2With the hydrogenation reaction of CO, the catalyzer of load rhodium also can be used to catalytic decomposition N 2O; Flood in finite concentration sulphuric acid soln or Ammonium Persulfate 98.5 solution originally containing the zirconium mesoporous material, can be made into SO after high temperature (generally at 500 ℃～650 ℃) roasting then 4 2-/ M xO yType or S 2O 8 2-/ M xO yType solid super-strong acid material, it is simple that super acidic catalyst has preparation, etching apparatus not, Heat stability is good, people's attention to advantages such as water are stable and extremely, in organic synthesis industry, just obtaining application more and more widely, can be applied in the reactions such as cracking, isomerization, alkylation, esterification, acylations, polymerization; Utilize this material of absorption property of zirconium dioxide also be used for can processing environment sewage sexavalent chrome.
Four, description of drawings:
The nitrogen adsorption-desorption isothermal map of Fig. 1 sample is among the figure: a-Zr/Si=0.38, b-Zr/Si=0.92, c-Zr/Si=1.20.
The pore distribution figure of Fig. 2 sample is among the figure: a-Zr/Si=0.38, b-Zr/Si=0.92, c-Zr/Si=1.20.
The XRD figure of Fig. 3 sample (Zr/Si=1.2)
The TEM figure of Fig. 4 sample
Five, embodiment:
Embodiment one:
1.. at first get the Zr (NO of 0.75g 3) 43H 2O is dissolved in the ethanol of 25mL, and the cetyl trimethylammonium bromide (CTAB) of getting 1.0g is dissolved in the ethanol of 10ml, and the ethanolic soln with both mixes then, behind the stirring 1h, leaves standstill 10h in the 100ml reactor of the inner liner polytetrafluoroethylene of packing under 50 ℃ condition; 2.. other gets beaker, takes by weighing the hydrochloric acid soln that 1.0g triblock copolymer (P123) adds the 2mol/l of 40ml, and 40 ℃ of stirred in water bath 3h add the tetraethoxy (TEOS) of 2.3ml then, continue to stir 2h; 3.. the material is 1. poured out the adding 2. restir 5h in still; 4.. tighten in the reactor of the inner liner polytetrafluoroethylene of packing at last, in 110 ℃ of baking ovens, leave standstill 24h, washing, suction filtration, drying at room temperature.Behind 600 ℃ of roasting 3h, the BET surface-area of gained sample is 624m 2/ g, pore volume are 0.55cm 3/ g, the aperture is 7.78nm.
Embodiment two:
1.. at first get the Zr (NO of 1.5g 3) 43H 2O is dissolved in the ethanol of 40mL, and the cetyl trimethylammonium bromide (CTAB) of getting 2.0g is dissolved in the ethanol of 10ml, and the ethanolic soln with both mixes then, behind the stirring 1h, leaves standstill 8h in the 100ml reactor of the inner liner polytetrafluoroethylene of packing under 70 ℃ condition; 2.. other gets beaker, takes by weighing the hydrochloric acid soln that 1.0g triblock copolymer (P123) adds the 2mol/l of 40ml, and 40 ℃ of stirred in water bath 3h add the tetraethoxy (TEOS) of 2.3ml then, continue to stir 2h; 3.. the material is 1. poured out the adding 2. restir 5h in still; 4.. tighten in the reactor of the inner liner polytetrafluoroethylene of packing at last, in 110 ℃ of baking ovens, leave standstill 24h, washing, suction filtration, drying at room temperature.Behind 600 ℃ of roasting 3h, the BET surface-area of gained sample is 524m 2/ g, pore volume are 0.53cm 3/ g, the aperture is 7.68nm.
Embodiment three:
1.. at first get the Zr (NO of 2.6g 3) 43H 2O is dissolved in the ethanol of 40mL, and the cetyl trimethylammonium bromide (CTAB) of getting 2.0g is dissolved in the ethanol of 10ml, and the ethanolic soln with both mixes then, behind the stirring 1h, leaves standstill 8h in the 100ml reactor of the inner liner polytetrafluoroethylene of packing under 80 ℃ condition; 2.. other gets beaker, takes by weighing the hydrochloric acid soln that 1.0g triblock copolymer (P123) adds the 2mol/l of 40ml, and 40 ℃ of stirred in water bath 3h add the tetraethoxy (TEOS) of 2.3ml then, continue to stir 2h; 3.. the material is 1. poured out the adding 2. restir 5h in still; 4.. tighten in the reactor of the inner liner polytetrafluoroethylene of packing at last, in 100 ℃ of baking ovens, leave standstill 48h, washing, suction filtration, drying at room temperature.Behind 600 ℃ of roasting 3h, the BET surface-area of gained sample is 474m 2/ g, pore volume are 0.52cm 3/ g, the aperture is 7.66nm.
Embodiment four:
1.. at first get the Zr (NO of 3.7g 3) 43H 2O is dissolved in the ethanol of 40mL, and the cetyl trimethylammonium bromide (CTAB) of getting 2.0g is dissolved in the ethanol of 10ml, and the ethanolic soln with both mixes then, behind the stirring 1h, leaves standstill 4h in the 100ml reactor of the inner liner polytetrafluoroethylene of packing under 110 ℃ condition; 2.. other gets beaker, takes by weighing the hydrochloric acid soln that 1.0g triblock copolymer (P123) adds the 2mol/l of 40ml, and 40 ℃ of stirred in water bath 3h add the tetraethoxy (TEOS) of 2.3ml then, continue to stir 2h; 3.. the material is 1. poured out the adding 2. restir 5h in still; 4.. tighten in the reactor of the inner liner polytetrafluoroethylene of packing at last, in 100 ℃ of baking ovens, leave standstill 48h, washing, suction filtration, drying at room temperature.Behind 600 ℃ of roasting 3h, the BET surface-area of gained sample is 315m 2/ g, pore volume are 0.40cm 3/ g, the aperture is 6.76nm.
Embodiment five:
1.. at first get the Zr (NO of 4.8g 3) 43H 2O is dissolved in the ethanol of 40mL, and the cetyl trimethylammonium bromide (CTAB) of getting 2.0g is dissolved in the ethanol of 10ml, and the ethanolic soln with both mixes then, behind the stirring 1h, leaves standstill 4h in the 100ml reactor of the inner liner polytetrafluoroethylene of packing under 110 ℃ condition; 2.. other gets beaker, takes by weighing the hydrochloric acid soln that 1.0g triblock copolymer (P123) adds the 2mol/l of 40ml, and 40 ℃ of stirred in water bath 3h add the tetraethoxy (TEOS) of 2.3ml then, continue to stir 2h; 3.. the material is 1. poured out the adding 2. restir 5h in still; 4.. in the reactor of the inner liner polytetrafluoroethylene of packing at last, tighten, in 100 ℃ of baking ovens, leave standstill 48h, washing, suction filtration, drying at room temperature.Behind 600 ℃ of roasting 3h, the BET surface-area of gained sample is 226m 2/ g, pore volume are 0.30cm 3/ g, the aperture is 7.67nm.
Embodiment six:
1.. Zr (NO3) 43H2O that at first gets 6.9g is dissolved in the ethanol of 50mL, the cetyl trimethylammonium bromide (CTAB) of getting 2.6g is dissolved in the ethanol of 15ml, ethanolic soln with both mixes then, after stirring 1h, under 120 ℃ condition, leave standstill 4h in the 100ml reactor of the inner liner polytetrafluoroethylene of packing into; 2.. other gets beaker, takes by weighing the hydrochloric acid soln that 1.0g triblock copolymer (P123) adds the 2mol/l of 40ml, and 40 ℃ of stirred in water bath 3h add the tetraethoxy (TEOS) of 2.3ml then, continue to stir 2h; 3.. the material is 1. poured out the adding 2. restir 5h in still; 4.. in the reactor of the inner liner polytetrafluoroethylene of packing at last, tighten, in 100 ℃ of baking ovens, leave standstill 48h, washing, suction filtration, drying at room temperature.Behind 600 ℃ of roasting 3h, the BET surface-area of gained sample is 192m 2/ g, pore volume are 0.24cm 3/ g, the aperture is 7.67nm.
Embodiment seven:
1.. at first get the Zr (NO of 9.3g 3) 43H 2O is dissolved in the ethanol of 50mL, and the cetyl trimethylammonium bromide (CTAB) of getting 3.5g is dissolved in the ethanol of 18ml, and the ethanolic soln with both mixes then, behind the stirring 1h, leaves standstill 2h in the 100ml reactor of the inner liner polytetrafluoroethylene of packing under 140 ℃ condition; 2.. other gets beaker, takes by weighing the hydrochloric acid soln that 1.0g triblock copolymer (P123) adds the 2mol/l of 40ml, and 40 ℃ of stirred in water bath 3h add the tetraethoxy (TEOS) of 2.3ml then, continue to stir 2h; 3.. the material is 1. poured out the adding 2. restir 5h in still; 4.. in the reactor of the inner liner polytetrafluoroethylene of packing at last, tighten, in 90 ℃ of baking ovens, leave standstill 62h, washing, suction filtration, drying at room temperature.Behind 600 ℃ of roasting 3h,
The BET surface-area of gained sample is 176m 2/ g, pore volume are 0.20cm 3/ g, the aperture is 6.27nm.

Claims (2)

1, a kind of mesoporous Zr-Si molecular sieve is characterized in that it being a kind of a kind of mesoporous Zr-Si molecular sieve of making according to following step method:
I, be the zirconium source, and cetyl trimethylammonium bromide with the zirconium nitrate, in zirconium nitrate and alcoholic acid mol ratio be 1: 30～200, cetyl trimethylammonium bromide and alcoholic acid mol ratio be that 1: 30～40 ratios are dissolved in respectively in the ethanol, makes A and B solution;
II, under agitation slowly add A solution in the B solution, the mol ratio of its zirconium nitrate and cetyl trimethylammonium bromide is 0.3～1.5, be sealed in the reactor of inner liner polytetrafluoroethylene after stirring 1h, pre-crystallization is 2～10 hours in 40～140 ℃ baking oven, taking-up is cooled to room temperature, the material that crystallization is good was poured in the beaker high degree of agitation into 1～8 hour, made material C;
III, simultaneously with triblock polymer template EO 20PO 70EO 20Molecular-weight average is 5800, under agitation be dissolved in the hydrochloric acid soln of 1.6mol/L, after 35～40 ℃ of following stirring and dissolving, join in the tetraethoxy, 35～40 ℃ of following stirring reactions 1～10 hour, under agitation slowly add material C then, the mol ratio of its zirconium silicon is 0.05～2.6, continues to stir after 0.5～6 hour, be sealed in the reactor of inner liner polytetrafluoroethylene, crystallization is 24～62 hours in 80～120 ℃ baking oven;
Take out after IV, crystallization are finished and be cooled to room temperature, filter, and with distilled water wash for several times, the dry faint yellow solid that gets in air at room temperature, this solid just obtained the mesoporous Zr-Si molecular sieve sample behind the removed template method in 3～10 hours 350～650 ℃ of following roastings, this molecular sieve its:
Zirconium silicon ratio is: 0.1～2.0
The aperture is: 6～10nm
Pore volume is: 0.3～0.7cm 3/ g
Specific surface area is: 180～700m 2/ g
ZrO 2It in molecular sieve the tetragonal structure structure.
2, the synthetic method of the described mesoporous Zr-Si molecular sieve of claim 1 is characterized in that carrying out according to the described step method of claim 1, and its described (zirconium+silicon): P123: the mol ratio of water is 100～200: 1: 12000～13000.
CNB2004100645027A 2004-10-16 2004-10-16 Mesoporous Zr-Si molecular sieve and its synthesis Expired - Fee Related CN100447085C (en)

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CN101941878B (en) * 2009-07-06 2013-07-17 中国石油化工股份有限公司 Method for dehydrating ethanol
CN109694079B (en) * 2017-10-24 2020-10-23 中国科学院过程工程研究所 Method for preparing Zr-MSU mesoporous molecular sieve by using industrial zirconium-containing waste residues as raw materials and mesoporous molecular sieve
CN109115834A (en) * 2018-08-01 2019-01-01 华东师范大学 A kind of ppb grades of NO2Gas sheet type sensor and preparation method
CN112495359A (en) * 2020-12-24 2021-03-16 烟台大学 Zirconium-based gold catalyst for propylene epoxidation reaction and preparation method thereof

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CN1362363A (en) * 2001-01-05 2002-08-07 中国石油化工股份有限公司 Mesoporous aluminium phosphotitanate molecular sieve and its prepn
CN1118432C (en) * 2000-11-28 2003-08-20 中国科学院山西煤炭化学研究所 Composite dual-pure Si-Al molecular sieve and its preparing process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1118432C (en) * 2000-11-28 2003-08-20 中国科学院山西煤炭化学研究所 Composite dual-pure Si-Al molecular sieve and its preparing process
CN1362363A (en) * 2001-01-05 2002-08-07 中国石油化工股份有限公司 Mesoporous aluminium phosphotitanate molecular sieve and its prepn

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