CN105347359A - Synthesis and application of zeolite molecular sieve with solid acid contained in porous channels - Google Patents
Synthesis and application of zeolite molecular sieve with solid acid contained in porous channels Download PDFInfo
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Abstract
The invention provides a synthesis method of a zeolite molecular sieve with solid acid contained in porous channels. The synthesis method includes the steps that firstly, an aqueous solution containing metal salt is prepared, and the aqueous solution contains one or two of zirconium hydroxide, ammonium molybdate, ammonium tungstate, ZrSO4 and TiCl4; the aqueous solution containing metal salt, a silicon source and/or an aluminum source, a template agent, a pH value regulator and water are mixed, gel is obtained through stirring, and dry glue is obtained through drying; thirdly, a dry gel steam auxiliary method is adopted, the dry gel is crystallized at the temperature of 400-500 K; fourthly, products obtained through crystallization are sintered for 5-8 h at the air atmosphere, and exchange treatment is performed through ammonium ions. According to the synthesis method, precursors of solid super acid are introduced in the synthesis process of the molecular sieve through a dry glue method, the zeolite molecular sieve with oxide solid acid contained in the porous channels is successfully synthesized, and therefore the catalytic performance of the molecular sieve in esterification of biological levulinic acid and an isomerization reaction of light paraffin is improved.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of containing the zeolite molecular sieve of solid acid and the application in catalyzed reaction thereof.
Background technology
Zeolite molecular sieve to be a class apply in petrochemical complex and fine chemistry industry are produced solid acid catalyst material widely and catalyzer.Utilize the unique pore passage structure of zeolite molecular sieve, and distinctive shape selective catalysis performance, can the Efficient Conversion of realization response product.But, the acid of zeolite molecular sieve can not meet by force the requirement of some important reaction (as light paraffins isomerization, biomass intermediate esterification etc.), therefore, the acid how improving zeolite molecular sieve is strong, has very important significance to the application promoting zeolite molecular sieve.
At present, to the modification of zeolite molecular sieve, the method mainly through aftertreatment realizes.Such as, introduced the positively charged ion of high price by ion exchange method, the acid that can improve molecular sieve is strong.Be exactly the most typically the widespread use of Y molecular sieve in FCC catalytic cracking of rare earth exchanged.In addition, acid or alkali treatment modifying are (as patent CN103848438A, CN101722022A, CN102795634A, CN103521257A), surfactant-modified (CN104338553A), complexing agent modification (CN103769201A), silylating reagent (CN104477933A), mechanically mixing phosphorus or metal oxide modified (CN104211083A), original position load phosphorus or rare earth oxide (CN102744094A), pickling process prepares phosphorus or metal oxide modified (CN101450318, etc. CN1593759) also for improving pore structure and the Acidity of molecular sieve, and then improve activity and the reactivity worth of molecular sieve.
For the zeolite molecular sieve of ten-ring and twelve-ring, due to the aperture size of molecular sieve itself less (0.5 ~ 0.7nm), and the presoma of modified material (lewis' acid) size is larger, cause it cannot fully enter into molecular sieve pore passage inside, therefore often easily cause modification species in molecular sieve outer surface enrichment.On the other hand, the strength of acid of molecular sieve generally cannot with solid super-strong acid (as SO
4 2-/ ZrO
2, SO
4 2-/ ZrO
2, WO
3/ ZrO
2, MoO
3/ ZrO
2) compare, for the acid improving molecular sieve is strong, by soild oxide load at zeolite molecular sieve on the surface, then by vitriolization, (Chen Tongyun, Aging Temperature and doping are to molecular sieve carried SO to obtain the molecular sieve of super acids modification for people
4 2-/ ZrO
2-Co
2o
3the research of solid super-strong acid performance impact, Journal of Molecular Catalysis, 2006,20,311-315).Obviously, super acids cannot enter in the duct of zeolite molecular sieve.In order to address this problem, the mesopore molecular sieve (as MCM-41) that scientist aperture is larger, is successfully incorporated into (Chen Jing, Sun Rui, Han Mei, Guo Wei, Wang Jintang, MCM-41 load S in molecular sieve pore passage by oxide compound
2o
8 2-/ TiO
2the preparation of solid super-strong acid and esterification performance study, Chinese Journal of Inorganic Chemistry, 2006,22,421-425).After solid super-strong acid is introduced molecular sieve pore passage, can make in duct, to produce more B acid and L acid site, and strength of acid distribution gradient, to the reactive behavior and shape selectivity improving molecular sieve, there is important promoter action.
At present for the zeolite molecular sieve of ten-ring (as ZSM-5) and twelve-ring (as beta and mordenite), how by simple method soild oxide super acids introduced in its duct and have not been reported.On the one hand, adopt the method for aftertreatment modification, soild oxide super acids presoma size is greater than molecular sieve bore diameter, cannot enter in molecular sieve pore passage.On the other hand, adopt and introduce transition metal precursor in Hydrothermal Synthesis process, due under hydrothermal condition and alkali system, easily generate precipitation of hydroxide fast, and size is comparatively large, cannot enter into molecular sieve pore passage inside equally.
Summary of the invention
For this area Problems existing, the object of the invention is proposition a kind of containing the ten-ring of solid super-strong acid position and the synthetic method of twelve-ring zeolite molecular sieve: utilize dry glue steam auxiliary law, by introducing transition metal ion in building-up process, it is made to enter into molecular sieve pore passage inside, by processing include the zeolite molecular sieve of solid acid to duct, the Acidity of this molecular sieve improves, and has higher catalytic activity in catalyzed reaction.
The solution of the present invention is: propose a kind of duct and include the ten-ring of solid strong acid and the synthetic method of twelve-ring zeolite molecular sieve, be exactly utilize in sieve synthesis procedure specifically, by introducing transition metal ion, soild oxide presoma being incorporated into inside zeolite cavity, then in molecular sieve pore passage, producing solid strong acid by precipitation, roasting, ion-exchange etc. process.
Described ten-ring molecular sieve and twelve-ring molecular sieve refer to the one in the zeolite molecular sieve with MFI, BEA and MOR skeleton structure.One or both mixing in the salt of the transition metal zirconium that described transition metal ion refers to, titanium, molybdenum, tungsten.In described duct, solid strong acid refers to SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2, WO
3/ ZrO
2, MoO
3/ ZrO
2deng one or both mixing in oxide compound.In duct, in solid acid, oxide content accounts for the 0.1wt.% ~ 5.0wt.% of molecular sieve gross weight.
Another object of the present invention proposes the molecular sieve catalyst that obtains of described method or molecular sieve carrier.
3rd object of the present invention is the application proposing described molecular sieve catalyst or molecular sieve carrier.
The technical scheme realizing above-mentioned purpose of the present invention is:
Duct includes a synthetic method for the zeolite molecular sieve of solid acid, comprises step:
1) aqueous solution of metal-containing salt is prepared, containing zirconium hydroxide, ammonium molybdate, ammonium tungstate, ZrSO in the described aqueous solution
4and TiCl
4in one or two kind, the concentration of metal-salt is 0.01 ~ 1mol/L;
2) aqueous solution of metal-containing salt and the silicon source of molecular sieve and/or aluminium source, template, pH value regulator, water mix, and obtain gel, and drying obtain dry glue through stirring;
3) dry glue steam auxiliary law is adopted, by gel crystallization 5 ~ 72 hours at 400 ~ 500K temperature;
4) by the roasting 5 ~ 8 hours in air atmosphere of crystallization products therefrom, then exchange with ammonium ion, then through roasting; The reagent carrying out ammonium ion exchange is ammonium sulfate, ammonium chloride or ammonium nitrate.
Wherein, described step 2) in, the silicon source of molecular sieve is one or both in white carbon black, silicon-dioxide, two (triethoxy is silica-based) methane, tetraethoxy; Aluminium source is NaAlO
2, aluminium hydroxide, one in Tai-Ace S 150; Described template is one or more in tetraethyl ammonium hydroxide, TPAOH, polyoxyethylene glycol, Neutral ammonium fluoride, and described pH value regulator is in NaOH and/or ammoniacal liquor.
As one of the preferred technical solution of the present invention, described step 2) in, the silicon source of molecular sieve and/or aluminium source, template, pH value regulator, water mixing, then with the aqueous solution of metal-containing salt, the mass ratio of silicon source and/or aluminium source, template, pH value regulator, water is 7.125:5 ~ 20:0.01 ~ 0.1:5 ~ 10.
As another optimal technical scheme of the present invention, described step 2) in, by NaOH, tetraethyl ammonium hydroxide, water mix, in mixture, add NaAlO
2, high degree of agitation, to clarification, then with aqueous solution, the stirring of metal-containing salt, adds white carbon black, stir 2 hours again, obtain gel, gel is dried, ground to form fine powder, for dry glue steam auxiliary law crystallization, wherein, NaOH, tetraethyl ammonium hydroxide, water, NaAlO
2the mass ratio added is 0.75:2 ~ 3:10 ~ 12:0.1 ~ 0.5.
Or, described step 2) be: white carbon black, tetraethyl ammonium hydroxide and NH
4f mixing also, after vigorous stirring, with the aqueous solution of metal-containing salt, continues to be stirred to and obtains gel; Gel is dried, ground to form fine powder, for dry glue steam auxiliary law crystallization; Wherein, white carbon black, TEAOH and NH
4the mass ratio of F mixing is 6:18 ~ 20:2 ~ 3.
Or, described step 2) be: by NaAlO
2be dissolved in the water with NaOH, obtain clear soln, then add two (triethoxy is silica-based) methane, after mixing, add the aqueous solution of metal-containing salt, stir 1 ~ 2 hour, form the gel of thickness; Wherein, NaAlO
2, NaOH, the mass ratio of two (triethoxy is silica-based) methane is 1 ~ 2:1 ~ 2:20.
Or, described step 2) be: by NaAlO
2be dissolved in the water with NaOH, obtain clear soln, then add two (triethoxy is silica-based) methane, after mixing, add the aqueous solution of metal-containing salt, stir 1 ~ 2 hour, obtain solution A, wherein, NaAlO
2, NaOH, the mass ratio of two (triethoxy is silica-based) methane is 0.05 ~ 0.1:0.05 ~ 0.1:1 ~ 2; By NaAlO
2be dissolved in water with NaOH, add white carbon black, obtain solution B, solution A and the rear high degree of agitation of solution B mixing, form the gel of thickness; Wherein, NaAlO
2, NaOH, the mass ratio of white carbon black is 0.05 ~ 0.1:0.05 ~ 0.1:0.1 ~ 1.
Wherein, described step 4) in, crystallization products therefrom is through washing and dry roasting, and the temperature of roasting is 800 ~ 900K.
Synthetic method of the present invention synthesizes the molecular sieve obtained.This molecular sieve can be molecular sieve catalyst or molecular sieve carrier.
The application of molecular sieve of the present invention in the esterification reaction of catalysis levulinic acid and light paraffins isomerization reaction.
Beneficial effect of the present invention is:
The synthetic method that the present invention proposes, utilize dry glue process (dry-gelconversionmethod, DGC) feature of synthesis of molecular sieve, the presoma of solid super-strong acid is introduced in the building-up process of molecular sieve, successfully achieve the synthesis that duct includes the zeolite molecular sieve of mixed oxide solid acid, and then improve the catalytic performance of molecular sieve in biological levulinic acid esterification and light paraffins isomerization reaction.
And this law adopts dry glue process synthesis of molecular sieve, in the process of dry glue process synthesis zeolite, pass through sol-gel method, the presoma of mixed oxide solid acid was introduced before dry glue generates, make it can high dispersing in silica-alumina gel, in the process of follow-up water vapor auxiliary crystallization, the high dispersing of producing under high-temperature water heat condition, tiny oxyhydroxide, the duct that can be evenly distributed on molecular sieve is inner.
The duct that the present invention proposes, containing the synthetic method of the zeolite molecular sieve of solid strong acid, can significantly improve the strength of acid of molecular sieve and sour density, expands the application of zeolite molecular sieve in the reaction needing strong acidic site.Synthesize the molecular sieve obtained, compare with traditional molecular sieve catalyst, in levulinic acid and ethyl esterification reaction, can improve the activity 30% of catalyzer, and traditional solid super-strong acid is close, catalyzer has higher reaction preference and work-ing life simultaneously.In addition, using it as carrier, be used for light paraffins isomerization reaction for supporting Pt precious metal, the isomerization rate of light paraffins can be improved, and then improve the octane value of product.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of catalyst A ~ H.
Embodiment
Following embodiment for illustration of the present invention, but should not be construed as limitation of the present invention.
If no special instructions, the technique means in embodiment is means known in those skilled in the art.
Embodiment 1 is containing WO
3, MoO
3, WO
3/ ZrO
2or MoO
3/ ZrO
2the synthesis of Beta zeolite molecular sieve of BEA structure
First, get 0.75gNaOH and 2.3gTEAOH, vigorous stirring production clear soln after the mixing of 11.7g water.Then the NaAlO of 0.27g is added
2to in solution, high degree of agitation production clear soln A.The ammonium tungstate solution of preparation 5mL0.2mol/L, obtains mixed liquid B.Get the solution A of 13mL and the B mixing of 6mL, high degree of agitation, then adds the white carbon black of 5.0g, high degree of agitation 2h, obtains uniform gel.The mol ratio composition SiO of gained colloidal sol
2: 0.014Al
2o
3: 0.125Na
2o:0.060TEAOH:30H
2o:0.0013WO
3.Gel is dried in 333K and is obtained dry glue in air atmosphere.By for subsequent use for dry glue grind into powder.Take the dry glue fine powder of 5g, be placed in the middle part that solvent is the crystallizing kettle of 150mL, then add 1.0mL water bottom it again, dry glue does not directly contact with water at the bottom of still.Under 413K crystallization temperature, be converted into water vapor at the bottom of still, under certain temperature, crystallization 48h, after reaction terminates, gained sample, through washing, oven dry, in 823K roasting 6h in air atmosphere, obtains containing WO
3beta molecular sieve, its structure is verified through XRD spectra (Fig. 1).XRD diffraction peak just shows the characteristic diffraction peak of Beta, and XRF result display solid acid oxide content is as follows: molecular sieve-4 A: 2.2wt.%WO
3.Ammonium tungstate solution is made into the ammonium molybdate of same concentration, obtain containing MoO
3beta molecular sieve, XRF result display solid acid oxide content is as follows: molecular sieve B:3.2wt.%MoO
3.
0.02 ~ 0.1g zirconium hydroxide is added in the ammonium tungstate solution of 5mL0.2mol/L, controls the ratio of W and Zr in solution (by WO
3and ZrO
2weight ratio) be greater than 0.1, a series of different WO can be obtained
3and ZrO
2the catalyzer of content, as:
In the aqueous solution of metal-containing salt, by WO
3and ZrO
2weight ratio 1:6, other operations are the same, and obtained molecular sieve XRF result display solid acid oxide content is molecular sieve C:0.3wt.%WO
3, 1.8wt.%ZrO
2.In the aqueous solution of metal-containing salt, by WO
3and ZrO
2weight ratio 3:5, other operations are the same, obtained molecular sieve D:1.5wt.%WO
3, 2.5wt.%ZrO
2.
In the aqueous solution of metal-containing salt, ammonium tungstate changes ammonium molybdate into, and the ratio of Mo and Zr is (by MoO
3and ZrO
2weight ratio) to be respectively 1:8 and 1:1.15 obtained containing MoO
3/ ZrO
2beta molecular sieve, XRF result display solid acid oxide content is: molecular sieve E:0.4wt.%MoO
3, 2.9wt.%ZrO
2; Molecular sieve F:2.3wt.%MoO
3, 2.7wt.%ZrO
2.
By molecular sieve-4 A, B, C, D, E, F after calcination process, carry out ammonium sulfate and exchange process, 723K roasting 4h obtains the molecular sieve of Hydrogen.
Comparative example 1
Adopt commercial Hydrogen Beta zeolite, adopt pickling process load to account for catalyst weight 5wt.%WO
3-ZrO
2(mass ratio 1:1) and 5wt%MoO
3-ZrO
2(mass ratio 1:1) catalyzer, obtains catalyst I and II.
As a comparison, conventional hydrothermal synthesis method is adopted to prepare Beta molecular sieve.0.15gNaOH, 0.27gNaAlO
2be dissolved in the water mixing of 9.6gTEAOH and 3.8g, high degree of agitation generates clear soln A.In ammonium molybdate 0.05g zirconium hydroxide being added the 0.2mol/L of 5mL or ammonium tungstate solution, control the ratio of W and Zr in solution (by WO
3and ZrO
2weight ratio) be 1/2, obtain mixed liquid B.Solution A and B mixing, high degree of agitation, then adds the white carbon black of 5.0g, high degree of agitation 2h, obtains uniform gel.Gel composition SiO
2: 0.014Al
2o
3: 0.032Na
2o:0.20TEAOH:15H
2o:0.002ZrO
2: 0.001WO
3gel.Then bottom crystallizing kettle gained gel being joined 150mL.Crystallization 48h under 413K crystallization temperature, after reaction terminates, gained sample, through washing, oven dry, in 823K roasting 6h in air atmosphere, obtains containing Beta molecular sieve.XRF diffraction patterns shows, in gained molecular sieve, and WO
3/ ZrO
2content extremely low, <0.05wt.%.This illustrates, adopts traditional hydrothermal synthesis method, soild oxide acid cannot be incorporated in molecular sieve pore passage.
Application Example 1
The generation of the solid acid in molecular sieve pore passage adopts toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene (molecular dimension 0.85nm) isomerization reaction to prove.
The condition of probe reaction is as follows: 20mg hydrogen type catalyst, 4kPa toluene and the equal tri-isopropyl benzene of 4kPa, temperature 573K, 96kPaN
2(being the rare gas element introduced to reduce reactant partial pressure), the molecular sieve of the made Hydrogen of embodiment 1, zeolite and the comparative example molecular sieve conversion profile to toluene and equal tri-isopropyl benzenes is as follows: A (92% and 3.5%), B (95% and 2.5%), C (95% and 2.7%), D (98% and 2.5%), E (95% and 3.1%), F (97% and 2.1%), I (92% and 97%), II (97% and 95%), Beta zeolite (commercial) (74% and 5.2%).
Because toluene can enter in the duct in Beta molecular sieve (0.7nm aperture), therefore, in all catalyzer, transformation efficiency is all higher, and, A ~ F and I, II catalyzer, owing to there is soild oxide acid, acid is better than by force simple Beta zeolite, so transformation efficiency is higher.And all tri-isopropyl benzene size is greater than Beta zeolite cavity size, cannot enter in molecular sieve pore passage, therefore the activity of Beta zeolite is lower, transformation efficiency only has 5.2%, but, after steep solids acid, because most solid acid is collected in molecular sieve outer surface, can contact with equal tri-isopropyl benzene, therefore catalyst I and II transformation efficiency bring up to more than 95%.And for catalyst A ~ F, because soild oxide majority is present in molecular sieve pore passage, cannot contact with equal tri-isopropyl benzene, reactive behavior is lower, and transformation efficiency is between 2.1 ~ 3.5%.This proves that most soild oxide solid acid is present in the duct of Beta zeolite.
Embodiment 2 is containing SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2the synthesis of Beta zeolite molecular sieve of BEA structure
Get 6.00g white carbon black, 19.88g40wt.%TEAOH and 2.00gNH
4vigorous stirring 2h after F mixing.Then a certain amount of ZrSO is got
4be dissolved in 1.6mL deionized water and form 0.5mol/L solution, be added drop-wise in above-mentioned system, then continue to stir 2h, obtain uniform gel.Then, gel is dried in 333K and is obtained dry glue in air atmosphere.By for subsequent use for dry glue grind into powder.Take the dry glue fine powder of 2g, be placed in the middle part that volume is the crystallizing kettle of 150mL, then bottom it, add 1.5mL water, dry glue does not directly contact with water at the bottom of still.Under 453K crystallization temperature, produce water vapor, crystallization 6h at the bottom of still, after reaction terminates, gained sample, through washing, oven dry, in 823K roasting 6h in air atmosphere, obtains containing ZrO
2beta molecular sieve.Molecular sieve adopts ammonium sulfate to carry out ion-exchange, and 723K roasting 4h finally obtains catalyzer G, and XRF analysis result shows, ZrO in catalyzer G
2content be 1.5wt.%,
By ZrSO
4be changed to TiCl
4, other operations are the same, obtained containing TiO
2catalyzer H.TiO in XRF analysis result display catalyzer H
2content be 2.1wt.%.
Comparative example 2
Adopt commercial Hydrogen Beta zeolite, adopt pickling process load to account for catalyst weight 5wt.%SO
4 2-/ ZrO
2(mol ratio 2:1) and 5wt.%SO
4 2-/ TiO
2(mol ratio 2:1) catalyzer, obtains catalyst I II and IV.
As a comparison, similar template is adopted to utilize conventional hydrothermal synthesis method to synthesize Beta molecular sieve: 12.0g white carbon black to be joined 44.2g tetraethyl-hydroxide by solution (TEAOH40wt.%), stir about 2h, entirely molten to white carbon black.By ZrSO
4be dissolved in after in 0.5g deionized water, be added drop-wise in above-mentioned glue, then 5ml ethanolic soln is joined in above-mentioned synthesis liquid.Stir 1h, add and fluoridize by being dissolved in 1.5g solution that deionized water is formed, vigorous stirring 30min by 4.44g, form viscous gel.Final gel mole consist of lSiO
2: 0.0065ZrO
2: 0.6TEAOH:O.6NH
4f:7.5H
2o:0.5EtOH.Above-mentioned gel to be moved in small-sized crystallizing kettle static crystallization under 423K and takes out cooling after 12 days, after filtration, wash paint, 373K is dried and 823K roasting 6h, obtain containing ZrO
2beta molecular sieve.Molecular sieve adopts ammonium sulfate to carry out ion-exchange, and 723K roasting 4h, finally obtains Beta molecular sieve.XRF diffraction patterns shows, in gained molecular sieve, and ZrO
2content extremely low, <0.02wt.%.This illustrates, adopts traditional hydrothermal synthesis method, soild oxide acid cannot be incorporated in molecular sieve pore passage.
Application Example 2
The generation of the solid acid in molecular sieve pore passage adopts toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene (molecular dimension 0.85nm) isomerization reaction to prove.The condition of probe reaction is as follows: 20mg catalyzer, 4kPa toluene and the equal tri-isopropyl benzene of 4kPa, temperature 573K, 96kPaN
2the conversion profile of toluene and equal tri-isopropyl benzene is as follows: G (99% and 2.1%), H (98% and 2.7%), III (96% and 99%), IV (98% and 99%), Beta zeolite (commercial) (74% and 5.2%).This proves most mixed oxide solid acid SO
4 2-/ ZrO
2and SO
4 2-/ TiO
2be present in the duct of Beta zeolite.
Embodiment 3 duct includes SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2the synthesis of mordenite of MOR structure
By 1.13gNaAlO
2be dissolved in 10mL water with the NaOH of 1.32g, production clear soln.Then two (triethoxy the is silica-based) methane (BTESM) of 20.1g is added.After mixing 3h, then toward wherein adding 2mL0.4mol/LZrSO
4.Stir 1h, vigorous stirring 30min, form viscous gel, 333K is dried to dry glue.Above-mentioned dry glue is moved into the middle part of volume 150mL crystallizing kettle, then bottom it, add 10mL water, dry glue does not directly contact with water at the bottom of still.Under 453K, static crystallization took out cooling after 3 days, and after filtration, washing, 373K dry and 823K roasting 6h, obtains containing ZrO
2and TiO
2mordenite.Molecular sieve adopts ammonium sulfate to carry out ion-exchange, and 723K roasting 4h, finally obtains catalyst I, and XRF analysis result shows, ZrO in catalyst I
2content be 2.5wt.%.
By ZrSO
4change TiCl into
4, additive method is the same, obtains containing TiO
2mordenite catalyst J.TiO in XRF analysis result display catalyzer J
2content be 2.4wt.%.
Application Example 3
Commercial h-mordenite got by the catalyzer of contrast, adopts pickling process load to account for catalyst weight 5wt%SO
4 2-/ ZrO
2(mol ratio 2:1) and 5wt%SO
4 2-/ TiO
2(mol ratio 2:1) catalyzer, obtains catalyst V and VI.
The generation of the solid acid in molecular sieve pore passage adopts toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene (molecular dimension 0.85nm) isomerization reaction to prove.
The condition of probe reaction is as follows: 20mg catalyzer, 4kPa toluene and the equal tri-isopropyl benzene of 4kPa, temperature 300 DEG C, 96kPaN
2the conversion profile of toluene and equal tri-isopropyl benzene is as follows: I (96% and 3.5%), J (97% and 2.1%), V (99% and 98%), VI (99% and 98%), mordenite (85% and 6.1%).
Toluene can enter in the duct in mordenite (0.7nm aperture), therefore, in all catalyzer, transformation efficiency is all higher, and, I, J, V and VI catalyzer, owing to there is soild oxide acid, acid strong due to simple mordenite, so transformation efficiency is higher.And all tri-isopropyl benzene size is greater than mordenite pore size, cannot enter in molecular sieve pore passage, therefore the activity of mordenite is lower, transformation efficiency only has 6.1%, but, after steep solids acid, because most solid acid is collected in molecular sieve outer surface, can contact with equal tri-isopropyl benzene, therefore catalyst V and VI transformation efficiency bring up to more than 99%.And for catalyst I and J, because soild oxide majority is present in molecular sieve pore passage, cannot contact with equal tri-isopropyl benzene, reactive behavior is lower, and transformation efficiency is between 2.1 ~ 3.5%.This proves most mixed oxide solid acid SO
4 2-/ ZrO
2and SO
4 2-/ TiO
2be present in the duct of mordenite.
Embodiment 4 duct includes SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2the synthesis of mordenite of MOR structure
By 0.083gNaAlO
2be dissolved in 5mL water with the NaOH of 0.092g, production clear soln.Then two (triethoxy the is silica-based) methane (BTESM) of 1.39g is added.After mixing 3h, then toward wherein adding 1mL0.1mol/LZrSO
4.Stir 1h and obtain solution A.The NaOH of 0.092g is dissolved in 6mL water, then adds 0.49g white carbon black, obtain solution B.Solution A joined in solution B, high degree of agitation, form viscous gel, 333K is dried to dry glue.Above-mentioned dry glue is moved into the middle part of volume 150mL crystallizing kettle, then bottom it, add 1mL water, dry glue does not directly contact with water at the bottom of still.Under 453K, static crystallization took out cooling after 3 days, and after filtration, washing, 373K dry and 823K roasting 6h, obtains containing ZrO
2mordenite.Molecular sieve adopts ammonium sulfate to carry out ion-exchange, and 723K roasting 4h, finally obtains catalyzer K.XRF analysis result shows, ZrO in catalyzer K
2content be 1.1wt.%.
By ZrSO
4solution changes 0.18mol/LTiCl into
4solution, other operations are the same, obtain containing TiO
2mordenite.Molecular sieve adopts ammonium sulfate to carry out ion-exchange, finally obtains catalyzer L.XRF analysis result shows, TiO in catalyzer L
2content be 1.4wt.%.
Application Example 4
The generation of the solid acid in molecular sieve pore passage adopts toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene (molecular dimension 0.85nm) isomerization reaction to prove.The condition of probe reaction is as follows: 20mg catalyzer, 4kPa toluene and the equal tri-isopropyl benzene of 4kPa, 573K, 96kPaN
2the conversion profile of toluene and equal tri-isopropyl benzene is as follows: K (95% and 2.0%), L (94% and 1.5%), V (99% and 98%), VI (99% and 98%), mordenite (85% and 6.1%).This proves most mixed oxide solid acid SO
4 2-/ ZrO
2and SO
4 2-/ TiO
2be present in the duct of mordenite.
Embodiment 5 duct includes SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2the synthesis of ZSM-5 zeolite of MFI structure
0.066gNaOH, 0.125gNaAlO
2, 1.0g polyoxyethylene glycol is dissolved in the 40wt.%TPAOH solution of 10.8g, then adds the TEOS of 7.0g.Mixing solutions stirs 2h, then toward wherein adding 4mL0.4mol/LZrSO
4or 0.6mol/LTiCl
4solution, then obtains dry glue through the dry 24h of 333K.Above-mentioned gel is moved into the middle part of 150mL crystallizing kettle, then bottom it, add 1mL water, dry glue does not directly contact with water at the bottom of still.Under 433K, static crystallization took out cooling after 3 days again, after filtration, washed paint, 373K oven dry and 773K roasting 6h, obtained containing ZrO
2and TiO
2mordenite.Molecular sieve adopts ammonium sulfate to carry out ion-exchange, and 723K roasting 4h, finally obtains catalyzer M.XRF analysis result shows, ZrO in catalyzer M
2content be 2.1wt.%.
ZrSO
4change TiCl into
4, other operations are the same, obtain containing TiO
2mordenite.Adopt ammonium sulfate to carry out ion-exchange, finally obtain catalyst n.XRF analysis result shows, TiO in catalyst n
2content be 2.5wt.%.
Application Example 5
The generation of the solid acid in molecular sieve pore passage adopts toluene (molecular dimension 0.55nm) and sym-trimethylbenzene (molecular dimension 0.7nm) disproportionation reaction to prove.
Adopt commercial ZSM-5 zeolite, adopt pickling process load to account for catalyst weight 5wt%SO
4 2-/ ZrO
2(mol ratio 2:1) and 5wt%SO
4 2-/ TiO
2(mol ratio 2:1) catalyzer, obtains catalyst V II and VIII.
The condition of probe reaction is as follows: 20mg catalyzer, 4kPa toluene and 4kPa sym-trimethylbenzene, temperature 573K, 96kPaN
2the conversion profile of toluene and sym-trimethylbenzene is as follows: M (97% and 6.5%), N (98% and 5.1%), VII (99% and 98%), VIII (99% and 98%), ZSM-5 zeolite (74% and 8.1%).Toluene can enter in the duct in ZSM-5 zeolite (0.55nm aperture), therefore, in all catalyzer, transformation efficiency is all higher, and, M, N, VII and VIII catalyzer, owing to there is soild oxide acid, acid strong due to simple ZSM-5 zeolite, so transformation efficiency is higher.And sym-trimethylbenzene size is greater than ZSM-5 zeolite pore size, cannot enter in molecular sieve pore passage, therefore the activity of ZSM-5 zeolite is lower, transformation efficiency only has 8.1%, but, after steep solids acid, because most solid acid is collected in molecular sieve outer surface, can contact with sym-trimethylbenzene, therefore catalyst V II and VIII transformation efficiency bring up to more than 98%.And for catalyzer M and N, because soild oxide majority is present in molecular sieve pore passage, cannot contact with equal tri-isopropyl benzene, reactive behavior is lower, and transformation efficiency is between 5.1 ~ 6.5%.This proves that most mixed oxide solid acid is present in the duct of ZSM-5 zeolite.
Embodiment 6
Synthesized molecular sieve catalyst is used for levulinic acid esterification reaction.Reaction conditions is as follows: 351K, levulinic acid and ethanol mol ratio 1:6, in the reactor of 500mL volume, 2.0g catalyzer, catalyzer accounts for the 30wt.% of levulinic acid quality, react 12 hours, the selectivity of all acid catalysts is all close to 100%, therefore the performance of catalyzer quality is mainly reflected on the transformation efficiency of reaction.Reaction result is as table 1 (last three molecular sieves of table 1 are commercial):
Table 1 levulinic acid esterification reaction result compares
| Catalyzer | Transformation efficiency % |
| A | 51 |
| B | 50 |
| C | 49 |
| D | 54 |
| E | 56 |
| F | 57 |
| G | 62 |
| H | 61 |
| I | 61 |
| J | 64 |
| K | 63 |
| L | 62 |
| M | 45 |
| N | 45 |
| I | 42 |
| II | 43 |
| III | 46 |
| IV | 45 |
| V | 46 |
| VI | 45 |
| VII | 42 |
| VIII | 42 |
| Mordenite | 38 |
| Beta zeolite | 37 |
| ZSM-5 zeolite | 32 |
Embodiment 7
Synthesized molecular sieve is used for as the isomerized carrier of light paraffins, and by molecular sieve C ~ N, molecular sieve carried acid catalyst I ~ VIII, commercial Beta zeolite, mordenite and ZSM-5 zeolite adopt pickling process, the Pt metal of load 0.3wt.%.Reaction conditions is as follows: 1g catalyzer, the H of 523K, 2.1MP
2, normal hexane and Skellysolve A (mass ratio 1:1), reaction-ure feeding air speed 1h
-1, hydrogen/hydrocarbon molecule is than 4.Reaction result is as follows:
Table 2: light paraffins Isomerization Results compares
| Catalyzer | C 5Isomerization rate, quality % | C 6Isomerization rate, quality % |
| C | 75 | 85 |
| D | 76 | 86 |
| E | 75 | 84 |
| F | 74 | 85 |
| G | 75 | 85 |
| H | 74 | 86 |
| I | 75 | 86 |
| J | 74 | 86 |
| K | 73 | 86 |
| L | 75 | 86 |
| M | 71 | 65 |
| N | 72 | 63 |
| I | 71 | 80 |
| II | 72 | 82 |
| III | 73 | 81 |
| IV | 72 | 81 |
| V | 72 | 81 |
| VI | 71 | 80 |
| VII | 65 | 58 |
| VIII | 66 | 57 |
| Mordenite | 71 | 80 |
| Beta zeolite | 71 | 79 |
| ZSM-5 zeolite | 62 | 45 |
Constitutional features:
Fig. 1 is the XRD spectra of catalyst A ~ H. all catalyzer have all embodied the characteristic diffraction peak (JCPDSNo.47-0183) of BEA skeleton structure.Explanation successfully synthesizes Beta zeolite molecular sieve.Meanwhile, except characteristic diffraction peak, do not find the diffraction peak of soild oxide.
Above embodiment is only be described the specific embodiment of the present invention; not scope of the present invention is limited; those skilled in the art also can do numerous modifications and variations on the basis of existing technology; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering technical personnel in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (10)
1. duct includes a synthetic method for the zeolite molecular sieve of solid acid, it is characterized in that, comprises step:
1) aqueous solution of metal-containing salt is prepared, containing zirconium hydroxide, ammonium molybdate, ammonium tungstate, ZrSO in the described aqueous solution
4and TiCl
4in one or two kind, the concentration of metal-salt is 0.01 ~ 1mol/L;
2) aqueous solution of metal-containing salt and the silicon source of molecular sieve and/or aluminium source, template, pH value regulator, water mix, and obtain gel, and drying obtain dry glue through stirring;
3) dry glue steam auxiliary law is adopted, by dry glue crystallization 5 ~ 72 hours at 400 ~ 500K temperature;
4) by the roasting 5 ~ 8 hours in air atmosphere of crystallization products therefrom, then exchange with ammonium ion, then through roasting; The reagent carrying out ammonium ion exchange is ammonium sulfate, ammonium chloride or ammonium nitrate.
2. synthetic method according to claim 1, it is characterized in that, described step 2) in, the silicon source of molecular sieve is one or both in white carbon black, silicon-dioxide, two (triethoxy is silica-based) methane, tetraethoxy (TEOS); Aluminium source is NaAlO
2, aluminium hydroxide, one in Tai-Ace S 150; Described template is one or more in tetraethyl ammonium hydroxide, TPAOH, polyoxyethylene glycol, Neutral ammonium fluoride, and described pH value regulator is NaOH and/or ammoniacal liquor.
3. synthetic method according to claim 1 and 2, it is characterized in that, described step 2) in, the silicon source of molecular sieve and/or aluminium source, template, pH value regulator, water mixing, then with the aqueous solution of metal-containing salt, the mass ratio of silicon source and/or aluminium source, template, pH value regulator, water is 7.125:5 ~ 20:0.01 ~ 0.1:5 ~ 10.
4. synthetic method according to claim 1 and 2, is characterized in that, described step 2) in, by NaOH, tetraethyl ammonium hydroxide, water mixing, in mixture, add NaAlO
2, high degree of agitation, to clarification, then with aqueous solution, the stirring of metal-containing salt, adds white carbon black, stir 2 hours again, obtain gel, gel is dried, ground to form fine powder, for dry glue steam auxiliary law crystallization, wherein, NaOH, tetraethyl ammonium hydroxide, water, NaAlO
2the mass ratio added is 0.75:2 ~ 3:10 ~ 12:0.1 ~ 0.5.
5. synthetic method according to claim 1 and 2, is characterized in that, described step 2) be: white carbon black, tetraethyl ammonium hydroxide and NH
4f mixing also, after vigorous stirring, with the aqueous solution of metal-containing salt, continues to be stirred to and obtains gel; Gel is dried, ground to form fine powder, for dry glue steam auxiliary law crystallization; Wherein, white carbon black, TEAOH and NH
4the mass ratio of F mixing is 6:18 ~ 20:2 ~ 3.
6. synthetic method according to claim 1 and 2, is characterized in that, described step 2) be: by NaAlO
2be dissolved in the water with NaOH, obtain clear soln, then add two (triethoxy is silica-based) methane, after mixing, add the aqueous solution of metal-containing salt, stir 1 ~ 2 hour, form the gel of thickness; Wherein, NaAlO
2, NaOH, the mass ratio of two (triethoxy is silica-based) methane is 1 ~ 2:1 ~ 2:20.
7. synthetic method according to claim 1 and 2, is characterized in that, described step 2) be: by NaAlO
2be dissolved in the water with NaOH, obtain clear soln, then add two (triethoxy is silica-based) methane, after mixing, add the aqueous solution of metal-containing salt, stir 1 ~ 2 hour, obtain solution A, wherein, NaAlO
2, NaOH, the mass ratio of two (triethoxy is silica-based) methane is 0.05 ~ 0.1:0.05 ~ 0.1:1 ~ 2; By NaAlO
2be dissolved in water with NaOH, add white carbon black, obtain solution B, solution A and the rear high degree of agitation of solution B mixing, form the gel of thickness; Wherein, NaAlO
2, NaOH, the mass ratio of white carbon black is 0.05 ~ 0.1:0.05 ~ 0.1:0.1 ~ 1.
8. synthetic method according to claim 1 and 2, is characterized in that, described step 4) in, crystallization products therefrom is through washing and dry roasting, and the temperature of roasting is 800 ~ 900K.
9. the arbitrary described synthetic method of claim 1 ~ 8 synthesizes the molecular sieve obtained.
10. the application of molecular sieve described in claim 9 in the esterification reaction of catalysis levulinic acid and light paraffins isomerization reaction.
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