CN105347359B - A kind of duct includes the synthesis and its application of the zeolite molecular sieve of solid acid - Google Patents
A kind of duct includes the synthesis and its application of the zeolite molecular sieve of solid acid Download PDFInfo
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Abstract
The present invention provides the synthetic method that a kind of duct includes the zeolite molecular sieve of solid acid, including step：1) prepare and contain zirconium hydroxide, ammonium molybdate, ammonium tungstate, ZrSO in the aqueous solution of metalline, the aqueous solution4And TiCl4In one or two kind, 2) aqueous solution of metalline mixes with silicon source and/or silicon source, template, pH value regulator, water, agitated gel, is dried to obtain dry glue；3) use dry glue water vapour auxiliary law, by dry glue at a temperature of 400~500K crystallization, 4) crystallization products therefrom is calcined 5~8 hours in air atmosphere, processing is then swapped with ammonium ion.Synthetic method proposed by the present invention, utilize dry gum method, the presoma of solid super-strong acid is introduced in the building-up process of molecular sieve, the synthesis that duct includes the zeolite molecular sieve of mixed oxide solid acid is successfully realized, and then improves molecular sieve and is esterified and the catalytic performance in light paraffins isomerization reaction in biological levulic acid.
Description
Technical field
The invention belongs to catalyst field, and in particular to a kind of zeolite molecular sieve containing solid acid and its in catalytic reaction
Application.
Background technology
Zeolite molecular sieve is a class in petrochemical industry and fine chemistry industry production using solid acid catalysis material widely
Material and catalyst.Using the unique pore passage structure of zeolite molecular sieve, and its distinctive shape selective catalysis performance, reaction product can be realized
Efficient Conversion.But, the acid of zeolite molecular sieve can not meet by force some important reaction (such as light paraffins isomerization, biologies
Matter intermediate esterification etc.) requirement, therefore, the acid for how improving zeolite molecular sieve is strong, answers promoting zeolite molecular sieve
With having very important significance.
At present, to the modification of zeolite molecular sieve, mainly realized by the method for post processing.For example, passing through ion-exchange
The cation of high price is introduced, the acid that can improve molecular sieve is strong.The most typical is exactly that the Y molecular sieve of rare earth exchanged is urged in FCC
Change the extensive use in cracking.In addition, acid or alkali treatment modifying (such as patent CN103848438A, CN101722022A,
CN102795634A, CN103521257A), surfactant-modified (CN104338553A), complexing agent are modified
(CN103769201A), silylating reagent (CN104477933A), mechanical mixture phosphorus or metal oxide modified
(CN104211083A), load phosphorus or rare earth oxide (CN102744094A) in situ, infusion process prepare phosphorus or metal oxide
Modified (CN101450318, CN1593759) etc. is also used for improving the pore structure and Acidity of molecular sieve, and then improves molecule
The activity and reactivity worth of sieve.
For ten-ring and the zeolite molecular sieve of twelve-ring, due to the aperture size of molecular sieve in itself it is smaller (0.5~
0.7nm), and presoma (lewis' acid) size of modified material is larger, cause it can not be well into molecular sieve pore passage
Inside, therefore tend to cause to be modified species in molecular sieve outer surface enrichment.On the other hand, the general nothing of the acid strength of molecular sieve
Method and solid super-strong acid (such as SO4 2-/ZrO2、SO4 2-/ZrO2、WO3/ZrO2、MoO3/ZrO2) compare, to improve the acid of molecular sieve
By force, soild oxide is supported on zeolite molecular sieve surface by people, then by sulfuric acid treatment, obtains point of super acids modification
(Chen Tongyun, Aging Temperature and doping are to molecular sieve carried SO for son sieve4 2-/ZrO2-Co2O3The research of solid super-strong acid performance influence,
Journal of Molecular Catalysis, 2006,20,311-315).Obviously, super acids cannot be introduced into the duct of zeolite molecular sieve.In order to solve this
Oxide is successfully incorporated into molecular sieve pore passage by one problem, scientist with the larger mesopore molecular sieve in aperture (such as MCM-41)
It is interior that (Chen Jing, Sun Rui, Han Mei, Guo Wei, Wang Jintang, MCM-41 load S2O8 2-/TiO2The preparation of solid super-strong acid and esterification performance are ground
Study carefully, Chinese Journal of Inorganic Chemistry, 2006,22,421-425).Solid super-strong acid is introduced after molecular sieve pore passage, enabled in duct
More B acid and L acid sites, and acid strength distribution gradient are produced, is had to the reactivity and shape selectivity for improving molecular sieve
There is important facilitation.
At present for ten-ring (such as ZSM-5) and the zeolite molecular sieve of twelve-ring (such as beta and modenite), how
Soild oxide super acids are introduced by simple method and had not been reported in its duct.On the one hand, it is modified using post processing
Method, the superpower acid precursor size of soild oxide be more than molecular sieve bore diameter, it is impossible to enter molecular sieve pore passage in.The opposing party
Face, it is easily quick due under hydrothermal condition and alkali system using transition metal precursor is introduced during Hydrothermal Synthesiss
Hydroxide precipitation is generated, and size is larger, equally cannot be introduced into inside molecular sieve pore passage.
The content of the invention
The problem of existing for this area, the purpose of the present invention is to propose to a kind of ten-ring and ten of the position containing solid super-strong acid
The synthetic method of two yuan of rings zeolite molecular sieves：Using dry glue water vapour auxiliary law, by introducing transition metal in building-up process
Ion, is made it into inside molecular sieve pore passage, and the zeolite molecular sieve that duct includes solid acid must be arrived by handling, the molecular sieve
Acidity improved, in catalytic reaction have higher catalytic activity.
The solution of the present invention is：Propose that a kind of duct includes the ten-ring and twelve-ring zeolite molecular sieve of solid strong acid
Synthetic method, is specifically exactly using in sieve synthesis procedure, by introducing transition metal ions by soild oxide
Presoma is incorporated into inside zeolite cavity, is then handled by precipitation, roasting, ion exchange etc. and is produced solid in molecular sieve pore passage
Body strong acid.
The ten-ring molecular sieve and twelve-ring molecular sieve refer to the zeolite with MFI, BEA and MOR framework structure point
One kind in son sieve.One or both of transition metal zirconium that the transition metal ions refers to, titanium, molybdenum, the salt of tungsten
Mixing.Solid strong acid refers to SO in the duct4 2-/ZrO2、SO4 2-/TiO2、WO3/ZrO2、MoO3/ZrO2Deng one in oxide
Plant or two kinds of mixing.Oxide content accounts for 0.1wt.%~5.0wt.% of molecular sieve gross weight in solid acid in duct.
It is another object of the present invention to propose molecular sieve catalyst or molecular sieve carrier that methods described is obtained.
Third object of the present invention is to propose the application of the molecular sieve catalyst or molecular sieve carrier.
The technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of duct includes the synthetic method of the zeolite molecular sieve of solid acid, including step：
1) prepare and contain zirconium hydroxide, ammonium molybdate, ammonium tungstate, ZrSO in the aqueous solution of metalline, the aqueous solution4With
TiCl4In one or two kind, the concentration of metal salt is 0.01~1mol/L；
2) aqueous solution of metalline is mixed with the silicon source of molecular sieve and/or silicon source, template, pH value regulator, water, warp
Stirring to obtain gel, and it is dried to obtain dry glue；
3) use dry glue water vapour auxiliary law, by gel at a temperature of 400~500K crystallization 5~72 hours；
4) crystallization products therefrom is calcined 5~8 hours in air atmosphere, then swapped with ammonium ion, then passed through
Roasting；The reagent for carrying out ammonium ion exchange is ammonium sulfate, ammonium chloride or ammonium nitrate.
Wherein, the step 2) in, the silicon source of molecular sieve is white carbon, silica, double (triethoxy silicon substrate) methane,
One or both of tetraethyl orthosilicate；Silicon source is NaAlO2, aluminium hydroxide, one kind in aluminum sulfate；The template is four
One or more in ethyl ammonium hydroxide, TPAOH, polyethylene glycol, ammonium fluoride, the pH value regulator is
In NaOH and/or ammoniacal liquor.
As one of the preferred technical solution of the present invention, the step 2) in, silicon source and/or silicon source, the template of molecular sieve
Agent, pH value regulator, water mixing, are then mixed with the aqueous solution of metalline, silicon source and/or silicon source, template, pH value regulation
Agent, the mass ratio of water are 7.125：5~20：0.01~0.1：5~10.
It is used as another optimal technical scheme of the present invention, the step 2) in, by NaOH, tetraethyl ammonium hydroxide, water are mixed
Close, NaAlO is added into mixture2, high degree of agitation to clarify, then mix, stir with the aqueous solution of metalline, addition in vain
Carbon black, is stirred for 2 hours, obtains gel, gel is dried, fine powder is ground to form, for dry glue water vapour auxiliary law crystallization, wherein,
NaOH, tetraethyl ammonium hydroxide, water, NaAlO2The mass ratio of addition is 0.75：2~3:10~12：0.1~0.5.
Or, the step 2) be：White carbon, tetraethyl ammonium hydroxide and NH4After F is mixed and is stirred vigorously, and containing metal
The aqueous solution mixing of salt, continues to stir to obtaining gel；Gel is dried, fine powder is ground to form, for dry glue water vapour auxiliary law
Crystallization；Wherein, white carbon, TEAOH and NH4The mass ratio of F mixing is 6：18~20：2~3.
Or, the step 2) be：By NaAlO2It is dissolved in the water with NaOH, obtains the solution of clarification, then adds double (three second
Epoxide silicon substrate) methane, after mixing, the aqueous solution of metalline is added, is stirred 1~2 hour, sticky gel is formed；Wherein,
NaAlO2, NaOH, the mass ratio of double (triethoxy silicon substrate) methane is 1~2：1~2：20.
Or, the step 2) be：By NaAlO2It is dissolved in the water with NaOH, obtains the solution of clarification, then adds double (three second
Epoxide silicon substrate) methane, after mixing, the aqueous solution of metalline is added, stirs 1~2 hour, obtains solution A, wherein, NaAlO2,
NaOH, the mass ratio of double (triethoxy silicon substrate) methane is 0.05~0.1：0.05~0.1：1~2；By NaAlO2And NaOH
Water is dissolved in, white carbon is added, high degree of agitation after solution B, solution A and solution B mixing is obtained, forms sticky gel；Wherein,
NaAlO2, NaOH, the mass ratio of white carbon is 0.05~0.1：0.05~0.1：0.1~1.
Wherein, the step 4) in, crystallization products therefrom by washing and dry roasting, the temperature of roasting for 800~
900K。
The molecular sieve that synthetic method synthesis of the present invention is obtained.The molecular sieve can be molecular sieve catalyst or molecular sieve
Carrier.
Application of the molecular sieve of the present invention in catalysis levulic acid esterification reaction and light paraffins isomerization reaction.
The beneficial effects of the present invention are：
Synthetic method proposed by the present invention, utilizes dry gum method (dry-gel conversion method, DGC) synthesis point
The characteristics of son sieve, the presoma of solid super-strong acid is introduced in the building-up process of molecular sieve, duct is successfully realized and includes oxidation
The synthesis of the zeolite molecular sieve of thing solid acid, and then molecular sieve is improved in the esterification of biological levulic acid and light paraffins isomerization
Catalytic performance in reaction.
It is solidifying by colloidal sol during dry gum method synthesis zeolite and this law uses dry gum method synthesis of molecular sieve
Glue method, dry glue generation before introduce mixed oxide solid acid presoma so that its in silica-alumina gel can high degree of dispersion,
During follow-up water vapour auxiliary crystallization, the high degree of dispersion produced under high temperature hydrothermal condition, tiny hydroxide, Neng Goujun
It is even to be distributed in inside the duct of molecular sieve.
The synthetic method of zeolite molecular sieve of the duct proposed by the present invention containing solid strong acid, can significantly improve molecular sieve
Acid strength and sour density, expand application of the zeolite molecular sieve in the reaction of strong acidic site is needed.Obtained molecular sieve is synthesized, and is passed
The molecular sieve catalyst of system is compared, in levulic acid and ethanol esterification, it is possible to increase the activity 30% of catalyst, and is passed
The solid super-strong acid of system is approached, while catalyst has higher reaction selectivity and service life.In addition, being used as load using it
Body, is used for light paraffins isomerization reaction, it is possible to increase the isomerization rate of light paraffins for supporting Pt noble metal, and then improves
The octane number of product.
Brief description of the drawings
Fig. 1 is catalyst A~H XRD spectra.
Embodiment
Detailed description below is used to illustrate the present invention, but should not be construed as limiting the invention.
Unless otherwise instructed, the technological means in embodiment is means known in those skilled in the art.
Embodiment 1 contains WO3、MoO3、WO3/ZrO2Or MoO3/ZrO2BEA structures Beta zeolite molecular sieve synthesis
First, 0.75g NaOH and 2.3g TEAOH, 11.7g water is taken to be stirred vigorously the solution of production clarification after mixing.So
0.27g NaAlO is added afterwards2Into solution, the solution A of high degree of agitation production clarification.Prepare 5mL 0.2mol/L ammonium tungstate
Solution, obtains mixed liquid B.13mL solution A and 6mL B mixing are taken, then high degree of agitation adds 5.0g white carbon, fierce
2h is stirred, uniform gel is obtained.The mol ratio composition SiO of gained colloidal sol2:0.014Al2O3:0.125Na2O：
0.060TEAOH：30H2O：0.0013WO3.Gel obtains dry glue in air atmosphere in 333K drying.By dry glue grind into powder
It is standby.5g dry glue fine powders are weighed, the middle part for the crystallizing kettle that solvent is 150mL is placed in, then its bottom adds 1.0mL water again, does
Glue and bottom water are simultaneously not directly contacted with.Under 413K crystallization temperatures, bottom is converted under water vapour, certain temperature, crystallization 48h,
After reaction terminates, gained sample is scrubbed, drying, is calcined 6h in 823K in air atmosphere, obtains containing WO3Beta molecules
Sieve, its structure is verified by XRD spectra (Fig. 1).XRD diffraction maximums are the characteristic diffraction peak for showing Beta, and XRF results show
Show that solid acid oxide content is as follows：Molecular sieve-4 A：2.2wt.%WO3.Ammonium tungstate solution is made into the ammonium molybdate of same concentration,
Obtain containing MoO3Beta molecular sieves, XRF results show solid acid oxide content it is as follows：Molecular sieve B：3.2wt.%MoO3。
In the ammonium tungstate solution that 0.02~0.1g zirconium hydroxides are added to 5mL 0.2mol/L, W and Zr in control solution
Ratio (presses WO3And ZrO2Weight ratio) it is more than 0.1, a series of different WO can be made3And ZrO2The catalyst of content, such as：
In the aqueous solution of metalline, by WO3And ZrO2Weight compares 1:6, ibid, obtained molecular sieve XRF is tied for other operations
Fruit shows that solid acid oxide content is molecular sieve C:0.3wt.%WO3, 1.8wt.%ZrO2.In the aqueous solution of metalline, press
WO3And ZrO2Weight compares 3:5, ibid, molecular sieve D is made in other operations:1.5wt.%WO3, 2.5wt.%ZrO2。
In the aqueous solution of metalline, ammonium tungstate is changed to ammonium molybdate, and Mo and Zr ratio (press MoO3And ZrO2Weight ratio) point
Wei 1:8 and 1:1.15 are made containing MoO3/ZrO2Beta molecular sieves, XRF results show solid acid oxide content be：Molecule
Sieve E:0.4wt.%MoO3, 2.9wt.%ZrO2；Molecular sieve F:2.3wt.%MoO3, 2.7wt.%ZrO2。
By molecular sieve-4 A, B, C, D, E, F after calcination process, ammonium sulfate exchange processing is carried out, 723K roastings 4h obtains hydrogen
The molecular sieve of type.
Comparative example 1
Using commercial Hydrogen Beta zeolites, catalyst weight 5wt.%WO is accounted for using infusion process load3-ZrO2(mass ratio
1：And 5wt%MoO 1)3-ZrO2(mass ratio 1：1) catalyst, obtains catalyst I and II.
As a comparison, Beta molecular sieves are prepared using conventional hydrothermal synthetic method.0.15g NaOH, 0.27g NaAlO2Dissolving
Mixed in 9.6g TEAOH and 3.8g water, the solution A of high degree of agitation generation clarification.0.05g zirconium hydroxides are added 5mL's
In 0.2mol/L ammonium molybdate or ammonium tungstate solution, W and Zr ratio (presses WO in control solution3And ZrO2Weight ratio) it is 1/2,
Obtain mixed liquid B.Solution A and B mixing, high degree of agitation, then add 5.0g white carbon, and high degree of agitation 2h obtains uniform
Gel.Gel constitutes SiO2:0.014 Al2O3:0.032Na2O：0.20TEAOH：15H2O：0.002 ZrO2：0.001WO3It is solidifying
Glue.Then gained gel is added to 150mL crystallizing kettle bottom.The crystallization 48h under 413K crystallization temperatures, after reaction terminates,
Gained sample is scrubbed, drying, is calcined 6h in 823K in air atmosphere, obtains molecular sieve containing Beta.XRF diffraction patterns show
Show, in gained molecular sieve, WO3/ZrO2Content it is extremely low,<0.05wt.%.This explanation, using traditional hydrothermal synthesis method, it is impossible to
Soild oxide acid is incorporated into molecular sieve pore passage.
Application Example 1
The generation of solid acid in molecular sieve pore passage (is divided using toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene
Sub- size 0.85nm) isomerization reaction proves.
The condition of probe reaction is as follows：20mg hydrogen type catalysts, 4kPa toluene and the equal tri-isopropyl benzenes of 4kPa, temperature 573K,
96kPa N2(being the inert gas introduced to reduce reactant partial pressure), the molecular sieve of the made Hydrogen of embodiment 1, zeolite with
And comparative example molecular sieve is as follows to the conversion profile of toluene and equal tri-isopropyl benzene：A (92% and 3.5%), B (95% Hes
2.5%), C (95% and 2.7%), D (98% and 2.5%), E (95% and 3.1%), F (97% and 2.1%), I (92% Hes
97%), II (97% and 95%), Beta zeolites (purchased in market) (74% and 5.2%).
Because toluene can be entered in the duct in Beta molecular sieves (0.7nm apertures), therefore, in all catalyst
In, conversion ratio is all higher, moreover, A~F and I, II catalyst, due to there is soild oxide acid, acid is better than by force simple Beta
Zeolite, so conversion ratio is higher.And tri-isopropyl benzene size is more than Beta zeolite cavity sizes, it is impossible to enter molecular sieve pore passage
It is interior, therefore Beta zeolites is active relatively low, conversion ratio only has 5.2%, still, after steep solids acid, due to most solid
Acid is collected in molecular sieve outer surface, can be contacted with equal tri-isopropyl benzene, therefore catalyst I and II conversion ratio brings up to more than 95%.
And for catalyst A~F, because soild oxide majority is present in molecular sieve pore passage, it is impossible to and the contact of equal tri-isopropyl benzene, instead
Should be active relatively low, conversion ratio is between 2.1~3.5%.This proves that most soild oxide solid acid is present in Beta boilings
In the duct of stone.
Embodiment 2 contains SO4 2-/ZrO2、SO4 2-/TiO2BEA structures Beta zeolite molecular sieve synthesis
Take 6.00g white carbons, 19.88g 40wt.%TEAOH and 2.00g NH42h is stirred vigorously after F mixing.Then take
A certain amount of ZrSO4Formation 0.5mol/L solution in 1.6mL deionized waters is dissolved in, is added drop-wise in above-mentioned system, stirring is further continued for
2h, obtains uniform gel.Then, gel obtains dry glue in air atmosphere in 333K drying.Dry glue grind into powder is standby
With.2g dry glue fine powders are weighed, the middle part for the crystallizing kettle that volume is 150mL is placed in, then adds 1.5mL water, dry glue in its bottom
With bottom water and being not directly contacted with.Under 453K crystallization temperatures, bottom produces water vapour, and crystallization 6h is reacted after terminating, gained sample
Product are scrubbed, drying, and 6h is calcined in 823K in air atmosphere, obtain containing ZrO2Beta molecular sieves.Molecular sieve uses sulfuric acid
Ammonium carries out ion exchange, and 723K roastings 4h finally gives catalyst G, and XRF analysis result is shown, ZrO in catalyst G2Content
For 1.5wt.%,
By ZrSO4It is changed to TiCl4, other operate ibid, are made and contain TiO2Catalyst H.XRF analysis result shows catalyst H
Middle TiO2Content be 2.1wt.%.
Comparative example 2
Using commercial Hydrogen Beta zeolites, catalyst weight 5wt.%SO is accounted for using infusion process load4 2-/ZrO2(mole
Than 2：And 5wt.%SO 1)4 2-/TiO2(mol ratio 2：1) catalyst, obtains catalyst III and IV.
As a comparison, Beta molecular sieves are synthesized using conventional hydrothermal synthetic method using similar template：By 12.0g hard charcoals
The black 44.2g tetraethyls hydroxide that is added to is by solution (TEAOH 40wt.%), and stir about 2h is entirely molten to white carbon.Will
ZrSO4After being dissolved in 0.5g deionized waters, it is added drop-wise in above-mentioned glue, 5ml ethanol solutions is then added to above-mentioned Synthesis liquid
In.1h is stirred, adds by 4.44g fluorinations and to form solution by being dissolved in 1.5g deionized waters, be stirred vigorously 30min, formation is sticky
Gel.A mole composition for final gel is l SiO2:0.0065 ZrO2:0.6TEAOH:O.6NH4F:7.5H2O:0.5EtOH.Will
Above-mentioned gel moves into small-sized crystallizing kettle and to take out cooling after 12 days in static crystallization under 423K, through filter, wash paint, 373K dry and
823K is calcined 6h, obtains containing ZrO2Beta molecular sieves.Molecular sieve carries out ion exchange using ammonium sulfate, and 723K is calcined 4h, most
Beta molecular sieves are obtained eventually.XRF diffraction patterns are shown, in gained molecular sieve, ZrO2Content it is extremely low,<0.02wt.%.This says
It is bright, using traditional hydrothermal synthesis method, it is impossible to which soild oxide acid is incorporated into molecular sieve pore passage.
Application Example 2
The generation of solid acid in molecular sieve pore passage (is divided using toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene
Sub- size 0.85nm) isomerization reaction proves.The condition of probe reaction is as follows：20mg catalyst, 4kPa toluene and 4kPa are equal
Tri-isopropyl benzene, temperature 573K, 96kPa N2, the 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 zeolites (purchased in market) (74% and 5.2%).This card
Bright most mixed oxide solid acid SO4 2-/ZrO2And SO4 2-/TiO2In the duct for being present in Beta zeolites.
The duct of embodiment 3 includes SO4 2-/ZrO2、SO4 2-/TiO2MOR structures modenite synthesis
By 1.13g NaAlO2It is dissolved in 1.32g NaOH in 10mL water, produces the solution of clarification.Then add
Double (triethoxy silicon substrate) methane (BTESM) of 20.1g.Mix after 3h, be then charged with 2mL 0.4mol/L ZrSO4.Stir
1h is mixed, 30min is stirred vigorously, viscous gel is formed, 333K is dried to dry glue.Above-mentioned dry glue is moved into volume 150mL crystallizing kettles
Middle part, 10mL water is then added in its bottom, dry glue and bottom water are simultaneously not directly contacted with.In after static crystallization under 453K 3 days
Cooling is taken out, 6h is calcined through filtering, washing, 373K drying and 823K, obtains containing ZrO2And TiO2Modenite.Molecular sieve is adopted
Ion exchange is carried out with ammonium sulfate, 723K roasting 4h finally give catalyst I, XRF analysis result is shown, ZrO in catalyst I2
Content be 2.5wt.%.
By ZrSO4Change TiCl into4, other method ibid, obtain contain TiO2Mordenite catalyst J.XRF analysis result
Show TiO in catalyst J2Content be 2.4wt.%.
Application Example 3
The catalyst of contrast is the h-mordenite for taking commercialization, and catalyst weight 5wt% is accounted for using infusion process load
SO4 2-/ZrO2(mol ratio 2：And 5wt%SO 1)4 2-/TiO2(mol ratio 2：1) catalyst, obtains catalyst V and VI.
The generation of solid acid in molecular sieve pore passage (is divided using toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene
Sub- size 0.85nm) isomerization reaction proves.
The condition of probe reaction is as follows：20mg catalyst, 4kPa toluene and the equal tri-isopropyl benzenes of 4kPa, 300 DEG C of temperature,
96kPa N2, the 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%), modenite (85% and 6.1%).
Toluene can be entered in the duct in modenite (0.7nm apertures), therefore, in all catalyst, conversion
Rate is all higher, moreover, I, J, V and VI catalyst, acid strong due to simple modenite due to there is soild oxide acid,
So conversion ratio is higher.And tri-isopropyl benzene size is more than modenite pore size, it is impossible to enter in molecular sieve pore passage, therefore
Modenite it is active relatively low, conversion ratio only has 6.1%, still, steep solids acid after, because most solid acid is collected in
Molecular sieve outer surface, can be contacted with equal tri-isopropyl benzene, therefore catalyst V and VI conversion ratio brings up to more than 99%.And for urging
Agent I and J, because soild oxide majority is present in molecular sieve pore passage, it is impossible to and equal tri-isopropyl benzene contact, reactivity compared with
Low, conversion ratio is between 2.1~3.5%.This proves most mixed oxide solid acid SO4 2-/ZrO2And SO4 2-/TiO2It is present in
In the duct of modenite.
The duct of embodiment 4 includes SO4 2-/ZrO2、SO4 2-/TiO2MOR structures modenite synthesis
By 0.083g NaAlO2It is dissolved in 0.092g NaOH in 5mL water, produces the solution of clarification.Then add
Double (triethoxy silicon substrate) methane (BTESM) of 1.39g.Mix after 3h, be then charged with 1mL 0.1mol/L ZrSO4.Stir
Mix 1h and obtain solution A.0.092g NaOH is dissolved in 6mL water, 0.49g white carbons is then added, obtains solution B.Will be molten
Liquid A is added in solution B, high degree of agitation, forms viscous gel, and 333K is dried to dry glue.Above-mentioned dry glue is moved into volume 150mL
The middle part of crystallizing kettle, then adds 1mL water in its bottom, and dry glue and bottom water are simultaneously not directly contacted with.In static crystallization 3 under 453K
Cooling is taken out after it, 6h is calcined through filtering, washing, 373K drying and 823K, obtains containing ZrO2Modenite.Molecular sieve uses sulphur
Sour ammonium carries out ion exchange, and 723K roasting 4h finally give catalyst K.XRF analysis result shows, ZrO in catalyst K2Contain
Measure as 1.1wt.%.
By ZrSO4Solution changes 0.18mol/L TiCl into4Solution, other operations ibid, obtain containing TiO2Modenite.
Molecular sieve carries out ion exchange using ammonium sulfate, finally gives catalyst L.XRF analysis result shows, TiO in catalyst L2's
Content is 1.4wt.%.
Application Example 4
The generation of solid acid in molecular sieve pore passage (is divided using toluene (molecular dimension 0.55nm) disproportionation and equal tri-isopropyl benzene
Sub- size 0.85nm) isomerization reaction proves.The condition of probe reaction is as follows：20mg catalyst, 4kPa toluene and 4kPa are equal
Tri-isopropyl benzene, 573K, 96kPa N2, the conversion profile of toluene and equal tri-isopropyl benzene is as follows：K (95% and 2.0%), L (94%
With 1.5%), V (99% and 98%), VI (99% and 98%), modenite (85% and 6.1%).This proves most oxygen
Compound solid acid SO4 2-/ZrO2And SO4 2-/TiO2It is present in the duct of modenite.
The duct of embodiment 5 includes SO4 2-/ZrO2、SO4 2-/TiO2MFI structure ZSM-5 zeolite synthesis
0.066g NaOH, 0.125g NaAlO2, 1.0g polyethylene glycol is dissolved in 10.8g 40wt.%TPAOH solution
In, then add 7.0g TEOS.Mixed solution stirs 2h, is then charged with 4mL 0.4mol/L ZrSO4Or
0.6mol/L TiCl4Solution, then dries 24h through 333K and obtains dry glue.Above-mentioned gel is moved into the middle part of 150mL crystallizing kettles,
1mL water is then added in its bottom, dry glue and bottom water are simultaneously not directly contacted with.Take out cold after 3 days then at static crystallization under 433K
But, 6h is calcined through filtering, washing paint, 373K drying and 773K, obtains containing ZrO2And TiO2Modenite.Molecular sieve uses sulfuric acid
Ammonium carries out ion exchange, and 723K roasting 4h finally give catalyst M.XRF analysis result shows, ZrO in catalyst M2Content
For 2.1wt.%.
ZrSO4Change TiCl into4, other are operated ibid, obtain containing TiO2Modenite.Ion friendship is carried out using ammonium sulfate
Change, finally give catalyst n.XRF analysis result shows, TiO in catalyst n2Content be 2.5wt.%.
Application Example 5
The generation of solid acid in molecular sieve pore passage uses toluene (molecular dimension 0.55nm) and mesitylene (molecular dimension
0.7nm) disproportionated reaction is proved.
Using commercial ZSM-5 zeolite, catalyst weight 5wt%SO is accounted for using infusion process load4 2-/ZrO2(mol ratio 2：
And 5wt%SO 1)4 2-/TiO2(mol ratio 2：1) catalyst, obtains catalyst VII and VIII.
The condition of probe reaction is as follows：20mg catalyst, 4kPa toluene and 4kPa mesitylene, temperature 573K, 96kPa
N2, the conversion profile of toluene and mesitylene is as follows：M (97% and 6.5%), N (98% and 5.1%), VII (99% Hes
98%), VIII (99% and 98%), ZSM-5 zeolite (74% and 8.1%).Toluene can enter ZSM-5 zeolite (0.55nm
Aperture) duct in, therefore, in all catalyst, conversion ratio is all higher, moreover, M, N, VII and VIII catalyst, by
It is acid strong due to simple ZSM-5 zeolite in there is soild oxide acid, so conversion ratio is higher.And mesitylene size is big
In ZSM-5 zeolite pore size, it is impossible to enter in molecular sieve pore passage, therefore ZSM-5 zeolite is active relatively low, and conversion ratio only has
8.1%, still, after steep solids acid, because most solid acid is collected in molecular sieve outer surface, it can be connect with mesitylene
Touch, therefore catalyst VII and VIII conversion ratio brings up to more than 98%.And for catalyst M and N, because soild oxide is more
Number is present in molecular sieve pore passage, it is impossible to and equal tri-isopropyl benzene contact, and reactivity is relatively low, conversion ratio 5.1~6.5% it
Between.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 levulic acid and is esterified reaction.Reaction condition is as follows：351K, levulic acid and
Ethanol mol ratio 1:6, in the reactor of 500mL volumes, 2.0g catalyst, catalyst accounts for the 30wt.% of levulic acid quality,
Reaction 12 hours, the selectivity of all acid catalysts is all close to 100%, therefore the performance quality of catalyst is mainly reflected in reaction
On conversion ratio.Reaction result such as table 1 (1 last three molecular sieve of table is purchased in market)：
The levulic acid of table 1 esterification reaction result compares
| Catalyst | Conversion ratio % |
| 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 |
| Modenite | 38 |
| Beta zeolites | 37 |
| ZSM-5 zeolite | 32 |
Embodiment 7
Synthesized molecular sieve is used for the carrier as light paraffins isomerization, by molecular sieve C~N, molecular sieve carried
Acid catalyst I~VIII, commercial Beta zeolites, modenite and ZSM-5 zeolite use infusion process, load 0.3wt.% Pt gold
Category.Reaction condition is as follows：1g catalyst, 523K, 2.1MP H2, n-hexane and pentane (mass ratio 1:1), reaction-ure feeding
Air speed 1h-1, hydrogen/hydrocarbon molecule compares 4.Reaction result is as follows：
Table 2：Light paraffins Isomerization Results compare
| Catalyst | C5Isomerization rate, quality % | C6Isomerization 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 |
| Modenite | 71 | 80 |
| Beta zeolites | 71 | 79 |
| ZSM-5 zeolite | 62 | 45 |
Architectural feature：
Fig. 1 is that catalyst A~H all catalyst of XRD spectra has all embodied the feature diffraction of BEA skeleton structures
Peak (JCPDS No.47-0183).Illustrate to successfully synthesize Beta zeolite molecular sieve.Meanwhile, in addition to characteristic diffraction peak, not
It was found that the diffraction maximum of soild oxide.
Embodiment above is only that the embodiment of the present invention is described, and not the scope of the present invention is entered
Row is limited, and those skilled in the art can also do numerous modifications and variations, be set not departing from the present invention on the basis of existing technology
On the premise of meter spirit, all variations and modifications that this area ordinary skill technical staff makes to technical scheme,
In the protection domain that claims of the present invention determination all should be fallen into.
Claims (4)
1. a kind of duct includes the synthetic method of the zeolite molecular sieve of solid acid, it is characterised in that including step：
1) prepare and contain zirconium hydroxide, ammonium molybdate, ammonium tungstate, ZrSO in the aqueous solution of metalline, the aqueous solution4And TiCl4
In one or two kind, the concentration of metal salt is 0.01~1mol/L；
2) NaOH, tetraethyl ammonium hydroxide, water are mixed, NaAlO is added into mixture2, high degree of agitation to clarification, Ran Houyu
Aqueous solution mixing, the stirring of metalline, add white carbon, are stirred for 2 hours, obtain gel, and gel is dried, ground to form carefully
Powder, for dry glue water vapour auxiliary law crystallization, wherein, NaOH, tetraethyl ammonium hydroxide, water, NaAlO2The mass ratio of addition
For 0.75：2~3：10~12：0.1~0.5；
Or, white carbon, tetraethyl ammonium hydroxide and NH4After F is mixed and is stirred vigorously, mix, continue with the aqueous solution of metalline
Stirring is to obtaining gel；Gel is dried, fine powder is ground to form, for dry glue water vapour auxiliary law crystallization；Wherein, white carbon,
TEAOH and NH4The mass ratio of F mixing is 6：18~20：2~3；
Or, by NaAlO2It is dissolved in the water with NaOH, obtains the solution of clarification, then adds double (triethoxy silicon substrate) methane, mixing
Afterwards, the aqueous solution of metalline is added, is stirred 1~2 hour, sticky gel is formed；Wherein, NaAlO2, NaOH, double (three second
Epoxide silicon substrate) methane mass ratio be 1~2：1~2：20；
3) use dry glue water vapour auxiliary law, by dry glue at a temperature of 400~500K crystallization 5~72 hours；
4) crystallization products therefrom is calcined 5~8 hours in air atmosphere, then swapped with ammonium ion, then by roasting；
The reagent for carrying out ammonium ion exchange is ammonium sulfate, ammonium chloride or ammonium nitrate.
2. synthetic method according to claim 1, it is characterised in that the step 4) in, crystallization products therefrom is by washing
Wash and dry roasting, the temperature of roasting is 800~900K.
3. the molecular sieve that synthetic method synthesis described in claim 1 or 2 is obtained.
4. application of the molecular sieve described in claim 3 in catalysis levulic acid esterification reaction and light paraffins isomerization reaction.
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| JP7340198B2 (en) | 2017-05-31 | 2023-09-07 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| WO2018221693A1 (en) | 2017-05-31 | 2018-12-06 | 国立大学法人北海道大学 | Functional structure and production method for functional structure |
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| EP3632548A4 (en) | 2017-05-31 | 2021-03-03 | National University Corporation Hokkaido University | Functional structure and production method for functional structure |
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| WO2018221690A1 (en) | 2017-05-31 | 2018-12-06 | 国立大学法人北海道大学 | Functional structure and production method for functional structure |
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| EP3632555A4 (en) | 2017-05-31 | 2021-01-27 | Furukawa Electric Co., Ltd. | Hydrodesulfurization catalyst structure, hydrodesulfurization device provided with said catalyst structure, and production method of hydrodesulfurization catalyst structure |
| CN109174172A (en) * | 2018-11-07 | 2019-01-11 | 南京大学连云港高新技术研究院 | A kind of preparation method of the low temperature catalyst for SCR reaction |
| CN113441175A (en) * | 2020-03-26 | 2021-09-28 | 中国石油天然气股份有限公司 | Molecular sieve supported metal catalyst and preparation method thereof |
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