CN102432032A - Nanometer all-silicon molecular sieve and its preparation method and use - Google Patents
Nanometer all-silicon molecular sieve and its preparation method and use Download PDFInfo
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Abstract
The invention provides a nanometer all-silicon molecular sieve. The nanometer all-silicon molecular sieve is prepared from tetrapropylammonium hydroxide, a silicon source, water and amino acids. A mole ratio of the silicon source to tetrapropylammonium hydroxide to water is 1: [0.05 to 0.50]: [15 to 65]. The mass of the used amino acids is 0.5 to 5% of that of the silicon source. A mole number and a mass number of silica represent a mole number and a mass number of the silicon source. The invention also provides a preparation method of the nanometer all-silicon molecular sieve, and a use of the nanometer all-silicon molecular sieve in a cyclohexanone-oxime gas phase beckmann rearrangement reaction. The nanometer all-silicon molecular sieve has a high degree of crystallization, regular morphology and adjustable particle sizes of 40 to 160 nanometers. In a cyclohexanone-oxime gas phase beckmann rearrangement reaction, the nanometer all-silicon molecular sieve shows excellent catalytic activity, selectivity and stability.
Description
[technical field]
The invention belongs to zeolite preparation and applied technical field.Relate in particular to a kind of nanometer total silicon molecular sieve and preparation method thereof and application.
[background technology]
Hexanolactam is the monomer of synthetic nylon-6, and has a wide range of applications in field of fine chemical such as leatheroid, medicine, coating and chemical assistants.2010, the apparent consumption of domestic hexanolactam reached 1124.7kt, but domestic hexanolactam ultimate production has only 493.9kt, and the degree of self-sufficiency is merely 43.9%, had bigger breach.
Current, synthetic main the passing through of hexanolactam realized as the OxiKhim-Styrol liquid phase Beckmann rearrangement of catalyzer and solvent with the vitriol oil.The use of the vitriol oil not only causes needing in the last handling process to neutralize with ammoniacal liquor, thus a large amount of low value-added ammonium sulfate of by-product; And causing equipment corrosion and hazardous emission, the utmost point does not meet the developing direction of production technique " environmental friendlinessization ".Solid acid catalysis OxiKhim-Styrol gas phase beckmann rearrangement both can have been avoided the use of the vitriol oil and liquefied ammonia; The hazardous emission that also can avoid post catalyst reaction to separate with reaction product causing and liquid acid be to problems such as equipment corrosions, and can realize the continuous production of hexanolactam.
Among the USP3639391, reported that the earliest the boron oxide catalyzer is used for Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement.B in the 0.5h before the reaction
2O
3/ ThO
2On OxiKhim-Styrol transformation efficiency and hexanolactam selectivity be respectively 99.1% and 92.0%; But OxiKhim-Styrol transformation efficiency and hexanolactam selectivity have all descended 30～40% behind reaction 5h.
Catalysis Today, 2000, among the 63:275, the report B of BoQing Xu research group
2O
3/ ZrO
2Rearrangement reaction had better katalysis, its catalytic effect even surpass B
2O
3/ Al
2O
3And B
2O
3/ SiO
2Catalyzer.(300 ℃ of temperature of reaction, benzene are that solvent, carbonic acid gas are carrier gas and OxiKhim-Styrol mass space velocity WHSV=0.32h in the reaction atmosphere of optimizing
-1), B
2O
3Content is that 10.0% catalyzer is kept the caprolactam productive rate and is not less than reaction times of 90% and can reaches 7h, and the decaying catalyst use of can regenerating.
Catalysis Letters 2001,77:119, Dongsen Mao has reported B
2O
3/ ZrO
2-TiO
2And B
2O
3/ Al
2O
3-TiO
2But the stability of these catalyzer is all than B
2O
3/ ZrO
2Low.
But based on the pore structure of molecular sieve rule and the surface acidity of modulation, many scholars attempt with molecular sieve as the Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement catalyzer.In these molecular sieves, the high-silica zeolite with two five-ring secondary structure units is particularly unique to the catalytic performance of rearrangement reaction, is the rearrangement reaction catalyzer with strong prospects for commercial application.
Catalysis Today 1997, T.Yashima etc. has reported at 350 ℃ of temperature of reaction, W/F=10.2g h mol among the 38:249
-1, helium is carrier gas, ethanol is under the reaction conditions of solvent, is catalyzer with Silicalite-1, and successive reaction 3h, the transformation efficiency of OxiKhim-Styrol and the selectivity of hexanolactam can reach 95%.
Journal of Catalysis 1999 is among the 186:12
Deng the NH of report with 0.7M
3And 3.7MNH
4NO
390 ℃ of treatment S ilicalite-1 of mixed solution catalyzer 1h is at 300 ℃ of temperature of reaction, WHSV=0.33h
-1, nitrogen is carrier gas, ethanol is under the reaction conditions of solvent, and during reaction 2h, transformation efficiency 93%, selectivity 98%.USP5403801 has also reported the si molecular sieves of handling through inorganic alkali solution, at WHSV=8h
-1, during reaction 6.25h, the OxiKhim-Styrol transformation efficiency is 99.5%, the hexanolactam selectivity is 96.5%; Feed the saturated air regeneration 23h of methyl alcohol then, proceed reaction, so be repeated to 30 times; Reaction 6.25h, the transformation efficiency of OxiKhim-Styrol is 95.3%, the selectivity of hexanolactam is 95.3%.But in alkaline solution handling of molecular sieve process, can cause about 20% catalyst attrition.
Bull.Chem.Soc.JPN.2007,80 (7): in 1280, Oshitaka Izumi etc. has reported that the SUMITOMO CHEMICAL chemical industry is that catalyzer has been set up the production equipment of producing 60000 ten thousand tons of OxiKhim-Styrol vapor phase rearrangements production hexanolactams per year with MFI type total silicon zeolite.For solving the rapid deactivation problem of catalyzer, this production equipment has adopted fluidization.
The R&D work result of many decades catalysts shows that loading type boron oxide catalyzer reveals higher hexanolactam selectivity (95～98%) to this reaction table, but the one way life-span has only several hours; Although high silicon even total silicon ZSM-5 and TS-1 molecular sieve have higher activity stability,, keep the high transformation efficiency of OxiKhim-Styrol (＞99%), the hexanolactam selectivity is difficult to surpass 95%.This shows that existing catalyst performance all is further improved.
In the Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, the formation of catalyst surface charcoal is the major cause of catalyst deactivation, and this mainly is because the carbon deposit meeting covering catalyst surface that forms is also blocking microporous, thereby has reduced the diffuser efficiency of reactant and product.And replace the zeolite of micron-scale may improve catalyst activity and the inactivation that improves catalyzer with the zeolite molecular sieve of nano-scale.
[summary of the invention]
The purpose of this invention is to provide a kind of nanometer total silicon molecular sieve that under organic molecule is auxiliary, utilizes the tetrapropyl aqua ammonia to prepare, and this molecular sieve is applied to the catalyzed gas Beckmann rearrangement for template.
For reaching the foregoing invention purpose; The invention provides a kind of nanometer total silicon molecular sieve; Its raw material comprises: TPAOH, silicon source, water, amino acid; Silicon source wherein: TPAOH: the molar ratio of water is 1: [0.05-0.50]: [15-65], amino acid whose consumption are the 0.5-5% of silicon source quality, and wherein the mole number in silicon source and total mass number are in silicon-dioxide.
Preferably, in the above-mentioned nanometer total silicon molecular sieve, said silicon source is to be selected from silica gel, silicon sol or the organosilicon acid esters one or more.
Preferably, in the above-mentioned nanometer total silicon molecular sieve, said organosilicon acid esters is that general formula is (OR
1)
4The silicon ester of Si, wherein R
1Alkyl for 1-4 carbon atom.
Preferably, in the above-mentioned nanometer total silicon molecular sieve, said silicon ester is a tetraethyl orthosilicate.
Preferably, in the above-mentioned nanometer total silicon molecular sieve, said amino acid is to be selected from Methionin, Histidine, L-glutamic acid, l-arginine, L-Ala or the leucine one or more.
The present invention also provides the preparation method of aforementioned nanometer total silicon molecular sieve, comprises following steps:
S1 gets TPAOH, silicon source and water by predetermined proportioning and mixes, and makes gel;
S2 adds amino acid in gel, fully stirs, and at 25-120 ℃ of following dynamic aging 6-72h;
S3 will wear out liquid in inserting autoclave, and after 100-180 ℃ of crystallization 1-7 days, filtration, washing, drying and roasting promptly get.
Preferably, among the preparation method of above-mentioned nanometer total silicon molecular sieve, in said step S2, will add amino acid whose gel at 40-100 ℃ of dynamic aging 12-48h.
Preferably, among the preparation method of above-mentioned nanometer total silicon molecular sieve, in said step S3, the liquid that will wear out was in 120-180 ℃ of hydrothermal crystallizing 2-4 days.
The present invention more provides the application of aforementioned nanometer total silicon molecular sieve in Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement.Said nanometer total silicon molecular sieve is in Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, at air speed WHSV=8h
-1, under the operational condition that temperature of reaction is 370 ℃, be solvent reaction 6h with ethanol, OxiKhim-Styrol transformation efficiency＞99%, hexanolactam selectivity＞96%.
Nanometer total silicon molecular sieve provided by the invention has the percent crystallinity height, and pattern is regular, and the particle characteristic size is characteristics such as adjustable in the 40-160nm scope.Nano molecular sieve wherein of the present invention has good catalytic performance when being used for Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, at air speed WHSV=8h
-1, under the operational condition that temperature of reaction is 370 ℃, reaction 6h, OxiKhim-Styrol transformation efficiency＞99%, hexanolactam selectivity＞96%.In air speed is WHSV=4.0h
-1, keep the OxiKhim-Styrol transformation efficiency be not less than 99% be not less than reaction times of 96% with the hexanolactam selectivity can be above 100 hours; And the catalyzer behind the inactivation can repeatedly utilize through roasting regeneration, and the accumulation reaction times was above 1000 hours.
[Brief Description Of Drawings]
Fig. 1, shown in Figure 2 be respectively the scanning electron microscope diagram of the nanometer total silicon molecular sieve that provides of one embodiment of the invention and comparative example.
[embodiment]
Below in conjunction with the embodiment of the invention and comparative example the present invention is further specified:
Embodiment 1
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.06g Methionin (L-Lys), fully stir, then at 80 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.5g by ordinary method filtration, washing, drying and roasting.Catalyzer pattern and particle size adopt Hitachi S-4800 sem to characterize, and sample is carrying out sem analysis test initial vacuum metal spraying.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 50nm.
Molecular sieve catalytic Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement performance is carried out in miniature fixed-bed quartz reactor; The fixed-bed reactor internal diameter is 10mm; The sieve catalyst 0.5g that filling 20-40 order prepares as stated above; The silica sand of the high same specification of filling 30mm below the catalyst bed floor height 12mm, the high 8-20 order of filling 70mm silica sand above the beds, beds.Used silica sand is through s.t., washing and high-temperature roasting.
At 400 ℃ of nitrogen purging catalyzer 0.5h, reduce to 370 ℃ of temperature of reaction then before the reaction with 40ml/min.Regulate flow rate of carrier gas to 20ml/min, incision 25%CHO-ethanolic soln, the mass space velocity WHSV=8h of control CHO
-1The product that from reactor drum, flows out cools off through mixture of ice and water, collects.Capillary gas chromatography, hydrogen flame detector.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.4%, and the selectivity of hexanolactam is 96.1%.
Embodiment 2
Change the CHO mass space velocity (WHSV) of catalyst performance evaluation among the embodiment 1 into 4h
-1, other method is analogous to embodiment 1, reaction times 100h, and the transformation efficiency of OxiKhim-Styrol is not less than 99%, and the selectivity of hexanolactam is not less than 96%., the catalyzer behind the inactivation recycles 10 times through roasting regeneration, and its performance is constant basically.
Embodiment 3
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.24g Methionin (L-Lys), fully stir, then at 80 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.4g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 40nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.6%, and the selectivity of hexanolactam is 96.1%.
Embodiment 4
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.24g Methionin (L-Lys), fully stir, then at 80 ℃ of dynamic aging 48h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.4g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 40nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.5%, and the selectivity of hexanolactam is 96.0%.
Embodiment 5
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 35 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M adds deionized water 28.57g, mechanical stirring in ice bath in two-mouth bottle.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.24g Methionin (L-Lys), fully stir, then at 80 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.4g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 50nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.3%, and the selectivity of hexanolactam is 96.2%.
Embodiment 6
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.20g L-glutamic acid (L-Glu), fully stir, then at 25 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.2g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 50nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.4%, and the selectivity of hexanolactam is 96.0%.
Embodiment 7
Change the CHO mass space velocity (WHSV) of catalyst performance evaluation among the embodiment 6 into 4h
-1, other method is analogous to embodiment 6, reaction times 100h, and the transformation efficiency of OxiKhim-Styrol is not less than 99%, and the selectivity of hexanolactam is not less than 96%., the catalyzer behind the inactivation recycles 10 times through roasting regeneration, and its performance is constant basically.
Embodiment 8
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.81g L-glutamic acid (L-Glu), fully stir, then at 25 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.3g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 50nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.3%, and the selectivity of hexanolactam is 96.5%.
Embodiment 9
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.07g l-arginine (L-Arg), fully stir, then at 80 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.2g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 60nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.2%, and the selectivity of hexanolactam is 96.1%.
Embodiment 10
Change the CHO mass space velocity (WHSV) of catalyst performance evaluation among the embodiment 9 into 4h
-1, other method is analogous to embodiment 9, reaction times 100h, and the transformation efficiency of OxiKhim-Styrol is not less than 99%, and the selectivity of hexanolactam is not less than 96%., the catalyzer behind the inactivation recycles 10 times through roasting regeneration, and its performance is constant basically.
Embodiment 11
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.28g l-arginine (L-Arg), fully stir, then at 25 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.1g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 50nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.4%, and the selectivity of hexanolactam is 96.2%.
Embodiment 12
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 35 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M adds deionized water 28.57g, mechanical stirring in ice bath in two-mouth bottle.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.28g l-arginine (L-Arg), fully stir, then at 80 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.1g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 50nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.4%, and the selectivity of hexanolactam is 96.2%.
Comparative Examples 1
The explanation of this Comparative Examples is according to USP4061724, and the USP0165425 reported method prepares Silicalite-1.According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 35 mole proportioning, the TPAOH that takes by weighing 33.92g 0.76M is in two-mouth bottle, and adding deionized water 25.33g mechanical stirring in ice bath is even.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid, then above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.6g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 120nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 90.8%, and the selectivity of hexanolactam is 93.9%.In addition, the mass space velocity WHSV=4h of control CHO
-1, other method is constant, reaction times 100h, and the transformation efficiency of OxiKhim-Styrol is lower than 90%, and the selectivity of hexanolactam is lower than 92%.
Comparative Examples 2
This Comparative Examples is explained according to USP0165425, Microporous and Mesoporous Materials43 (2001) 83-89 reported method treatment S ilicalite-1.Get molecular sieve 3g in the Comparative Examples 1, add 0.05M sodium hydroxide solution 200ml and stir 1h for 50 ℃, spinning goes out solid; Use 30ml80 ℃ of IX 3h of 1.5M ammonium nitrate solution again, exchange twice.Get the zeolite product 2.2g of alkaline purification by ordinary method filtration, washing, drying and roasting.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 99.3%, and the selectivity of hexanolactam is 94.9%.
Comparative Examples 3
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 16 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M in two-mouth bottle, mechanical stirring in ice bath.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.Then at 80 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.6g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 80nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 96.2%, and the selectivity of hexanolactam is 93.2%.
Comparative Examples 4
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 35 mole proportioning, the TPAOH that takes by weighing 33.92g0.76M is in two-mouth bottle, and adding deionized water 25.33g mechanical stirring in ice bath is even.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.06g Methionin (L-Lys), fully stir, the gained gel is at 80 ℃ of dynamic aging 24h.Then above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.5g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 70nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 96.5%, and the selectivity of hexanolactam is 93.5%.
Comparative Examples 5
Change the temperature of reaction of catalyst performance evaluation among the embodiment 1 into 350 ℃, other method is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 96.2%, and the selectivity of hexanolactam is 96.7%.
Comparative Examples 6
According to reaction mixture SiO
2: TPAOH: H
2O=1: 0.3: 35 mole proportioning, the TPAOH that takes by weighing 30.65g0.83M adds deionized water 25.33g, mechanical stirring in ice bath in two-mouth bottle.Take by weighing tetraethyl orthosilicate 18.39g and slowly splash into to above-mentioned solution, form clear liquid.In this clear liquid, add 0.07g l-arginine (L-Arg), fully stir, then at 25 ℃ of dynamic aging 24h.Above-mentioned reaction mixture is moved into autoclave, 170 ℃ of following hydrothermal crystallizing 72h.Get zeolite product 4.2g by ordinary method filtration, washing, drying and roasting.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 110nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 91.2%, and the selectivity of hexanolactam is 92.4%.
Comparative Examples 7
Change the organic additive among the embodiment 1 into leucine, other method is analogous to embodiment 1, gets zeolite product 4.1g.Stereoscan photograph shows that the gained molecular sieve is positive hexagon looks, and its length of side is approximately 120nm.
Prepared molecular sieve catalytic OxiKhim-Styrol gas phase beckmann rearrangement performance evaluation is analogous to embodiment 1.Reaction times 6h, the transformation efficiency of OxiKhim-Styrol are 93.7%, and the selectivity of hexanolactam is 90.5%.
Can find out from the foregoing description and comparative example; The total silicon molecular sieve that the inventive method makes has unique materialization constitutional features; The nano molecular sieve that wherein makes is applied in the vapor phase beckmann rearrangement reaction, can highly selective, high productivity prepares hexanolactam.
Claims (10)
1. nanometer total silicon molecular sieve; Its raw material comprises: TPAOH, silicon source, water, amino acid; Wherein said silicon source: TPAOH: the molar ratio of water is 1: [0.05-0.50]: [15-65]; Said amino acid whose consumption is the 0.5-5% of silicon source quality, and wherein the mole number in silicon source and total mass number are in silicon-dioxide.
2. nanometer total silicon molecular sieve according to claim 1 is characterized in that, said silicon source is to be selected from silica gel, silicon sol or the organosilicon acid esters one or more.
3. nanometer total silicon molecular sieve according to claim 2 is characterized in that, said organosilicon acid esters is that general formula is the silicon ester of (OR1) 4Si, and wherein R1 is the alkyl of 1-4 carbon atom.
4. the method for preparing nanometer total silicon molecular sieve according to claim 3 is characterized in that said silicon ester is a tetraethyl orthosilicate.
5. nanometer total silicon molecular sieve according to claim 1 is characterized in that, said amino acid is to be selected from Methionin, Histidine, L-glutamic acid, l-arginine, L-Ala or the leucine one or more.
6. the preparation method of any described nanometer total silicon molecular sieve of claim 1-5 comprises following steps:
S1 gets TPAOH, silicon source and water by predetermined proportioning and mixes, and makes gel;
S2 adds amino acid in gel, fully stirs, and at 25-120 ℃ of following dynamic aging 6-72h;
S3 will wear out, and liquid places autoclave and after 100-180 ℃ of crystallization 1-7 days, filtration, washing, drying and roasting promptly get.
7. the preparation method of nanometer total silicon molecular sieve according to claim 6 is characterized in that, among the said step S2, will add amino acid whose gel at 40-100 ℃ of dynamic aging 12-48h.
8. the preparation method of nanometer total silicon molecular sieve according to claim 6 is characterized in that, among the said step S3, the liquid that will wear out places autoclave and at 120-180 ℃ of crystallization 2-4 days.
9. the application of the described nanometer total silicon of claim 1 molecular sieve in Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement.
10. the application of nanometer total silicon molecular sieve according to claim 9 in Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement; It is characterized in that described nanometer total silicon molecular sieve is in Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, at air speed WHSV=8h-1; Under the operational condition that temperature of reaction is 370 ℃; With ethanol is solvent reaction 6h, OxiKhim-Styrol transformation efficiency＞99%, hexanolactam selectivity＞96%.In air speed is WHSV=4.0h-1, keep the OxiKhim-Styrol transformation efficiency be not less than 99% be not less than reaction times of 96% with the hexanolactam selectivity can be above 100 hours; And the catalyzer behind the inactivation can repeatedly utilize through roasting regeneration, and the accumulation reaction times was above 1000 hours.
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| CN104310413A (en) * | 2014-10-21 | 2015-01-28 | 太原理工大学 | Preparation method and application of thin-layer nano flaky total-silicon molecular sieve for preparing caprolactam |
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