CN107285330A - A kind of preparation method of NU-88 molecular sieves - Google Patents
A kind of preparation method of NU-88 molecular sieves Download PDFInfo
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Abstract
A kind of preparation method of the molecular sieves of NU 88, comprises the following steps：(1) it is the template shown in inorganic base, silicon source, formula (I) is soluble in water well mixed, n=1~4 in formula (I),Silicon source is added into the mixed solution of (1) step, is well mixed, the mol ratio that each material in reactant mixture, the reactant mixture is made is SiO2/Al2O3=20~150, R/SiO2=0.05~0.2, M2O/SiO2=0.1~0.5, H2O/SiO2=10~50, wherein M2O is alkali metal oxide, and R is template, and reactant mixture made from (2) step is moved in crystallizing kettle, carries out hydrothermal crystallizing at autogenous pressures 1~20 day in 120~200 DEG C, collects solid product, drying.Molecular sieve crystallinity obtained by the method is high, one-pot high income.
Description
Technical field
The present invention is a kind of preparation method of Si-Al molecular sieve, is a kind of NU-88 molecular sieves specifically
Preparation method.
Background technology
NU-88 molecular sieves synthesized (US6027707) first by John Leonell Casci etc. in 1997,
The structure of the molecular sieve is not yet parsed completely, may belong to BEA families.At present, on NU-88 molecules
The synthesis patent and document of sieve are less.
US6027707 discloses the synthetic method of NU-88 molecular sieves：It is double (N- crassitudes) with 1, n-
Alkylene base bromide (n=4~6) is structure directing agent, dynamic crystallization 9~22 days under 160 DEG C of reaction temperature.
The mol ratio of its reactant is：n(SiO2)：n(Al2O3)：n(Na2O)：n(R)：n(H2O)=60：1.7~2.0：
10~20：10~20：3000~5000.In addition, also reporting NU-88 molecular sieves in patent US6117307
Good activity is shown in hydrocracking reaction and to the high selectivity of gasoline.
Document (Lee S H, Lee D K, Shin C H, et al.Synthesis, characterization, and
catalytic properties of zeolites IM-5and NU-88[J].Journal of Catalysis,2003,
215(1):NU-88 synthesis and catalytic performance 151-170.) is also reported, is closed using the method for document report
Into nanometer NU-88 molecular sieves heat endurance it is good, and with very high 1- butene conversions and normal octane
Lytic activity.The specific synthetic schemes of NU-88 molecular sieves is as follows in the document, using double (the N- methyl of 1,6-
Pyrrolidines) hexane bromide is structure directing agent, aluminum nitrate is silicon source, and white carbon is that silicon source and sodium hydroxide are made
Synthesized for inorganic base, be 9R in charge ratio：21.9Na2O：1Al2O3：60SiO2：2400H2O's
Under the conditions of 160 DEG C of dynamic crystallizations react 14 days, through washing, dry and roasting obtains NU-88 points of pure phase
Son sieve.Though this method can synthesize pure phase NU-88 molecular sieves, the material proportion narrow range of synthetic system,
Such as the SiO that feeds intake of synthetic system2/Al2O3Mol ratio can just synthesize pure phase product, mistake only under the conditions of 60
The high or too low mercerising molecular sieve that has occurs；The alkali silicon ratio of synthetic system also can only be 0.73 or so, too high meeting
There is the appearance of mercerising stray crystal, it is too low to have the appearance of ZSM-12 stray crystals.In addition, the compound body of NU-88 molecular sieves
The water content of system is too high, causes the product yield of synthetic system low, is unfavorable for industry amplification synthesis.
The content of the invention
It is an object of the invention to provide a kind of preparation method of NU-88 molecular sieves, this method uses phenodiazine oxa-
Cycloalkanes dibromo salt is template, and NU-88 molecular sieves, one-pot high income, gained are prepared in the presence of an inorganic base
Molecular sieve crystallinity is high.
The preparation method for the NU-88 molecular sieves that the present invention is provided, comprises the following steps：
(1) it is the template shown in inorganic base, silicon source, formula (I) is soluble in water well mixed, formula (I)
Middle n=1~4,
(2) silicon source is added into the mixed solution of (1) step, is well mixed, reactant mixture is made, institute
The mol ratio for stating each material in reactant mixture is SiO2/Al2O3=20~150, R/SiO2=0.05~0.2,
M2O/SiO2=0.1~0.5, H2O/SiO2=10~45, wherein M2O is alkali metal oxide, and R is template,
(3) reactant mixture made from (2) step is moved in crystallizing kettle, in 120~200 DEG C in spontaneous pressure
Hydrothermal crystallizing is carried out under power 1~20 day, collect solid product, drying.
The inventive method is template using the phenodiazine oxa- cycloalkanes dibromo salt shown in formula (I), in inorganic base
In environment, the high NU-88 molecular sieves of crystallinity can be prepared, and single-autoclave yield rate is improved.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of NU-88 molecular sieves prepared by comparative example 2,
Fig. 2 is the X-ray diffractogram (XRD) of NU-88 molecular sieves prepared by present example 4,
Fig. 3 is the X-ray diffractogram (XRD) of NU-88 molecular sieves prepared by present example 5,
Fig. 4 is the ESEM shape appearance figure (SEM) of NU-88 molecular sieves prepared by present example 6,
Fig. 5 is the transmission electron microscope shape appearance figure (TEM) of NU-88 molecular sieves prepared by present example 7.
Embodiment
The inventive method is template using the phenodiazine oxa- cycloalkanes dibromo salt shown in formula (I), in inorganic base
Environment in, control appropriate raw material proportioning, prepare NU-88 molecular sieves.The method can be widened effectively
The material proportion of synthetic system, reduces the water silicon ratio fed intake, shortens crystallization time, and the NU-88 synthesized
Molecular sieve particle diameter is smaller, better heat stability, crystallinity high.
It is in (1) step of the invention, inorganic base, silicon source, template is soluble in water well mixed, preferably
Even stirring at least 30 minutes.
(1) silicon source described in step is selected from aluminium chloride, aluminum sulfate, aluminium hydroxide, sodium metaaluminate or Alumina gel.
Described inorganic base is selected from NaOH and/or KOH.
(1) template of formula described in step (I) structure, is 4,4,9,9- tetramethyl -1- oxygen -4,9- as n=2
Two azo-cycle hendecane -4,9- dibromo salts, are the azo-cycle ten of 4,4,10,10- tetramethyl -1- oxygen -4,10- bis- as n=3
Dioxane -4,10- dibromo salt (R2), is the azo-cycle tridecane of 4,4,11,11- tetramethyl -1- oxygen -4,11- bis- as n=4
- 4,11- dibromo salt, described template are also the mixture of any two or three of above-mentioned three kinds of templates.
(2) step is to add silicon source in mixed liquor made from (1) step, and described silicon source is Ludox, admittedly
Body silica gel, tetraethyl orthosilicate, waterglass or white carbon.Described solid silicone includes silochrom, pore
One or more in silica gel or spherical silica gel.Wherein, described white carbon is that average pore size is 30-60nm,
Specific surface area is 150-400m2/ g, pore volume is 0.7-1.0ml/g amorphous silica gel.Described solid silicon
Glue refers to Na2O content ﹤ 1%, solid content>80wt% impure less silica gel.The silochrom
Average pore size is 8-12nm, and specific surface area is 300-400m2/ g, pore volume is 0.7-1.0ml/g；Pore silicon
The average pore size of glue is 2-3nm, and specific surface area is 650-800m2/ g, pore volume is 0.35-0.45ml/g；Ball
The pore structure of shape silica gel is between silochrom and Kiselgel A, and pore volume is 0.60-0.85ml/g, average
Aperture is 4.5-7.0nm, and specific surface area is 450-650m2/g。
(2) in step, the mol ratio of each material is SiO in mixture preferably2/Al2O3=20~90,
R/SiO2=0.08~0.2, M2O/SiO2=0.1~0.5, H2O/SiO2=20~45.
(3) reactant mixture is is carried out hydro-thermal process by step, and hydrothermal crystallizing treatment temperature preferably is
140~180 DEG C, at autogenous pressures hydrothermal crystallizing time preferably 6~15 days.
(3) hydrothermal crystallizing described in step can also be divided to two sections of progress, first by described reactant mixture in 80~
160 DEG C, first paragraph hydrothermal crystallizing, preferably 1~6 day hydrothermal crystallizing time are carried out under self-generated pressure, then heat up
To 170~220 DEG C, second segment hydrothermal crystallizing, hydrothermal crystallizing time preferably 2~10 are carried out at autogenous pressures
My god.After crystallization terminates, kettle is cooled, solid product is collected, dries, that is, obtains NU-88 molecules
The former powder of sieve.Preferably 80~110 DEG C of described drying temperature, preferably 5~15 hours drying time.
After NU-88 molecular sieves obtained by the present invention are exchanged through hydrogen ion or ammonium, then it is calcined and can obtain Hydrogen molecule
Sieve, preferably 450~700 DEG C, more preferably 500~600 DEG C of described sintering temperature.
Described Hydrogen NU-88 molecular sieves are anti-suitable for hydrocarbon compound cracking reaction, alkylation of toluene methanol
Should, the catalyst of the alkylated reaction of benzene and ethene.
The present invention is further described below by example, but the present invention is not limited thereto.
In example and comparative example, the one-pot yield for preparing molecular sieve is calculated according to the following formula：
Comparative example 1
Press《Petroleum journal》(PETROLEUM PROCESSING), in August, 2010,26 (4) .P493-498 method system
Standby NU-88 molecular sieves.
By following molar ratio of material SiO2/Al2O3=60, NaOH/SiO2=0.73, R/SiO2=0.15,
H2O/SiO2=40 mix alkaline silica sol, sodium aluminate solution, template R, NaOH and water, its
Middle template R is double (N- crassitudes) the hexamethylene base dibromo salts of 1,6-
Specifically charging process is：Template is slowly added in silicon source under stirring, is added dropwise in right amount
Water dilutes, then silicon source is slowly added dropwise obtains mixture, and stir about 8h obtains white gum thing, then be added dropwise
NaOH, stirs 4h, until forming colloid.In the high pressure crystallizing kettle that colloid is moved into polytetrafluoroethyllining lining,
Reactant is taken out in crystallization 14 days under 160 DEG C of stirrings, after cooling and filters and uses deionized water cyclic washing,
By obtained solid in 100 DEG C of dryings, 7.3g NU-88 molecular sieve M are obtained, one-pot yield is 80 matter
% is measured, crystallinity is 86.3%, the BET specific surface area and pore volume (BJH measured with N2 adsorption-desorption method
Algorithm is calculated) 1 is shown in Table, similarly hereinafter.
Comparative example 2
NU-88 molecular sieves are prepared by the method for USP6027707 examples 1.
By 4.37g sodium metaaluminates (NaAlO2) solid and 8.53g NaOH be dissolved in 720.0g deionized waters,
Under stirring, white carbon 48.0g is added, 55.2g templates -1,6- are then added double (N- crassitudes)
Hexamethylene base dibromo salt, the well mixed mol ratio for obtaining each material in colloid, reactant mixture is SiO2：
Al2O3：Na2O：R：H2O=30：1：5：5：1500, wherein R are template.
Above-mentioned colloid is transferred in 1L stainless steel cauldron, 160 DEG C are stirred crystallization 13 days, stopped brilliant
Change reaction, product is scrubbed, filtering, gained solid is dried 12 hours in 110 DEG C, obtains 6.4g NU-88
Molecular sieve N, one-pot yield is 70 mass %, and crystallinity is 85.6%, and specific surface area and pore volume are shown in Table 1.
Example 1
Double (dimethylaminoethyl) ethers of 15g (0.094mol) are added in two-mouth bottle, 100mL isopropyls are added
Alcohol, the lower Isosorbide-5-Nitrae-dibromobutane that 10.2g (0.047mol) is added dropwise of 25 DEG C of stirrings, completion of dropping is warming up to
Reflux temperature flows back 30min, and solution becomes white opacity by colourless, then reacts 12h at a reflux temperature,
25 DEG C are cooled to, 50mL ethyl acetate stirring 15min formation white opacity liquid, filtering, gained is added
Solid is washed with ethyl acetate, obtains azo-cycle hendecane -4, the 9- dibromo of 4,4,9,9- tetramethyl -1- oxygen -4,9- bis-
N is 2 compound in salt 15.6g, i.e. formula (I), is template R1, and its fusing point is 294.4 DEG C,1H-NMR
Spectrogram chemical shift (300MHz, internal standard TMS, solvent C DCl3) δ (ppm) is：1.82(2H,s),2.53(2H,
m),3.09(12H,s),3.56(8H,m),3.94(4H,m)。
Example 2
Phenodiazine oxa- cycloalkanes dibromo salt is prepared by the method for example 1, the difference is that using 10.8g (0.047mol)
1, pentamethylene bromide replace Isosorbide-5-Nitrae-dibromobutane, obtain the azo-cycle of 4,4,10,10- tetramethyl -1- oxygen -4,10- bis-
N is 3 compound in dodecane -4,10- dibromo salt 14.5g, i.e. formula (I), is template R2, and it melts
Point is 270.2 DEG C,1H-NMR spectrum chemical shift (300MHz, internal standard TMS, solvent C DCl3)δ(ppm)
For：1.22(2H,m),1.82(4H,m),3.26(4H,t),3.56(12H,t),3.61(4H,t),3.79(4H,t).
Example 3
Double (dimethylaminoethyl) ethers of 7.5g (0.047mol) and 100mL isopropanol are added in two-mouth bottle,
Stir.At 25 DEG C, 11.4g (0.047mol) 1,6- dibromo-hexanes are slowly added dropwise, are warming up to back
Temperature reflux 30min is flowed, solution becomes white opacity by colourless, then reacts 12h at a reflux temperature, drop
Temperature adds 50mL ethyl acetate stirring 15min to 25 DEG C.Filtering, gained solid is washed with ethyl acetate
Wash, obtain 13.1g white solid, be the azo-cycle tridecane -4,11- of 4,4,11,11- tetramethyl -1- oxygen -4,11- bis-
N is 4 compound in dibromo salt, i.e. formula (I), is template R3, and its fusing point is 230 DEG C,1H-NMR
Spectrogram chemical shift (300MHz, internal standard TMS, solvent D2O) it is：1.36(4H,t),1.17(4H,t),
3.06(12H,s),3.33(4H,t),3.56(4H,t),3.93(4H,t)。
Example 4
Following instance prepares NU-88 molecular sieves with the inventive method.
By 0.21g NaAlO2, 1.40g NaOH, 2.93g templates R2 be dissolved in 36g deionized waters, mix
Close uniform, under conditions of stirring, add white carbon 3.00g, stir.Each material in reactant mixture
Mol ratio be：SiO2/Al2O3=40, R2/SiO2=0.15, Na2O/SiO2=0.35, H2O/SiO2=40.
Reactant mixture colloid is transferred in autoclaves of the 45ml with polytetrafluoroethyllining lining, 160 DEG C
Hydrothermal crystallizing 14 days, reaction product is dried 12 hours in 80 DEG C, obtained through washing, filtering, gained solid
NU-88 molecular sieve-4 As, its XRD diffraction spectrogram see Fig. 2 (its crystallinity is set to 100%, and as
The relative crystallinity of the other sieve samples of benchmark), NU-88 one-pot yield is 85.5 mass %,
NU-88 molecular sieves are shown in Table 1 through 550 DEG C of specific surface areas and pore volume for being calcined 6h.
Example 5
By 0.14g NaAlO2, 1.60g NaOH, 3.03g R3 be dissolved in 27g deionized waters, be well mixed,
Under conditions of stirring, Ludox 10g (SiO are added2Mass fraction 30%), stir.Reaction
The mol ratio of each material is in mixture：SiO2/Al2O3=60, R3/SiO2=0.15, Na2O/SiO2=0.4,
H2O/SiO2=40.
Reactant mixture colloid is transferred in autoclaves of the 45ml with polytetrafluoroethyllining lining, 140 DEG C
Hydrothermal crystallizing 6 days, 180 DEG C of hydrothermal crystallizings 8 days, reaction product is through washing, filtering, and gained solid is in 80 DEG C
Dry 12 hours, then obtain NU-88 molecular sieve B then at 550 DEG C of roasting 6h, its XRD diffraction spectra
Figure is shown in Fig. 3, and NU-88 one-pot yield is 88.6 mass %, and crystallinity is 93.6%, specific surface area and hole
Volume is shown in Table 1.
Example 6
By 0.57g Al2(SO4)3, 0.60g NaOH, 1.88g R1 be dissolved in 35.74g deionized waters, mix
Uniformly, under conditions of stirring, solid silochrom 3.26g (SiO are added2Mass fraction 92.17%),
Stir.The mol ratio of each material is in reactant mixture：SiO2/Al2O3=30, R1/SiO2=0.1,
Na2O/SiO2=0.15, H2O/SiO2=20.
Reactant mixture colloid is transferred in autoclaves of the 45ml with polytetrafluoroethyllining lining, 40 DEG C
Hydrothermal crystallizing 3 days, 170 DEG C of hydrothermal crystallizings 3 days, reaction product is through washing, filtering, and gained solid is in 80 DEG C
Dry 10 hours, obtain NU-88 molecular sieve C, wherein NU-88 one-pots yield is 92.2 mass %, knot
Brilliant degree is 106.0%.Gained molecular sieve is calcined 5 hours in 550 DEG C, the SEM figures of gained sample are shown in Fig. 4,
Specific surface area and pore volume are shown in Table 1.
Example 7
By 0.27g Al (NO3)3, 1.60g NaOH, 1.95g R2 and 1.01g R3 be dissolved in 35.94g go from
In sub- water, it is well mixed, under conditions of stirring, adds solid Kiselgel A 3.06g (solid content 98.17%),
Stir.The mol ratio of each material is in reactant mixture：SiO2/Al2O3=80, R/SiO2=0.15,
Na2O/SiO2=0.4, H2O/SiO2=40, wherein R=R2+R3.
Reactant mixture colloid is transferred in autoclaves of the 45ml with polytetrafluoroethyllining lining, 160 DEG C
Hydrothermal crystallizing 6 days, 180 DEG C of hydrothermal crystallizings 8 days, reaction product is through washing, filtering, and gained solid is in 80 DEG C
Dry 15 hours, obtain NU-88 molecular sieve D, its one-pot yield is 84.3 mass %, crystallinity is
101.0%.Gained molecular sieve is calcined 3 hours in 600 DEG C, the SEM figures of gained sample are shown in Fig. 5, compare table
Area and pore volume are shown in Table 1.
Example 8~13
The NU-88 molecular sieves and comparative example 1 and comparative example 2 of the preparation of example 4~7 in the 10g present invention is taken to prepare
NU-88 molecular sieves, carry out ammonium exchange with 200mL concentration for 5 mass % ammonium chloride solution respectively,
Swap time is 3 hours, and solid after washing, is dried 12 hours, 550 DEG C of roastings 3 in 90 DEG C after exchange
Hour, obtain Hydrogen NU-88 molecular sieves.
Take 2g Hydrogen NU-88 molecular sieves to be placed in micro-reactor, be passed through benzene and ethene, in 250 DEG C,
3.6MPa, feed volume air speed 3h-1, benzene ethylene mol ratio be 12 under conditions of carry out liquid-phase alkylation it is anti-
Should, molecular sieve and reaction result are shown in Table 2 used in each example.
From the data in table 1, it can be seen that molecular sieve prepared by the present invention has higher micro pore surface area and pore volume.
The data display of table 2, molecular sieve prepared by the present invention is than molecular sieve prepared by comparative example, with higher second
Alkene conversion ratio and ethylbenzene selectivity.
Table 1
* micropore is the hole that aperture is less than 2nm.
Table 2
Claims (8)
1. a kind of preparation method of NU-88 molecular sieves, comprises the following steps：
(1) it is the template shown in inorganic base, silicon source, formula (I) is soluble in water well mixed, formula (I)
Middle n=1~4,
(2) silicon source is added into the mixed solution of (1) step, is well mixed, reactant mixture is made, institute
The mol ratio for stating each material in reactant mixture is SiO2/Al2O3=20~150, R/SiO2=0.05~0.2,
M2O/SiO2=0.1~0.5, H2O/SiO2=10~45, wherein M2O is alkali metal oxide, and R is template,
(3) reactant mixture made from (2) step is moved in crystallizing kettle, in 120~200 DEG C in spontaneous pressure
Hydrothermal crystallizing is carried out under power 1~20 day, collect solid product, drying.
2. in accordance with the method for claim 1, it is characterised in that (2) each material rubs in step mixture
You are than being SiO2/Al2O3=20~90, R/SiO2=0.08~0.2, M2O/SiO2=0.1~0.5,
H2O/SiO2=20~45.
3. according to the method described in claim 1 or 2, it is characterised in that (1) by inorganic base, aluminium in step
Source, template are soluble in water, uniform stirring at least 30 minutes.
4. according to the method described in claim 1 or 2, it is characterised in that (1) silicon source described in step is chlorine
Change aluminium, aluminum sulfate, aluminium hydroxide, sodium metaaluminate or Alumina gel.
5. according to the method described in claim 1 or 2, it is characterised in that (1) inorganic base described in step is
NaOH and/or KOH.
6. according to the method described in claim 1 or 2, it is characterised in that (2) silicon source described in step is silicon
Colloidal sol, solid silicone, tetraethyl orthosilicate, waterglass or white carbon.
7. according to the method described in claim 1 or 2, it is characterised in that (3) hydrothermal crystallizing described in step
Temperature is 140~180 DEG C, and the hydrothermal crystallizing time is 6~14 days.
, will be described anti-8. according to the method described in claim 1 or 2, it is characterised in that (3) in step
Mixture is answered in 80~160 DEG C, first paragraph hydrothermal crystallizing is carried out under self-generated pressure and is reacted 1~6 day, is warming up to
170~220 DEG C, second segment hydrothermal crystallizing is carried out at autogenous pressures and is reacted 2~10 days, solid product is collected,
Dry.
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| CN110407222A (en) * | 2018-04-26 | 2019-11-05 | 中国石油化工股份有限公司 | The method for synthesizing NU-88 molecular sieve |
| US10737945B2 (en) | 2016-04-27 | 2020-08-11 | China Petroleum & Chemical Corporation | Molecular sieve, its preparation and application thereof |
| CN112010325A (en) * | 2019-05-30 | 2020-12-01 | 中国石油化工股份有限公司 | Method for synthesizing EMM-23 molecular sieve |
| CN115140747A (en) * | 2021-03-30 | 2022-10-04 | 中国石油化工股份有限公司 | Granular NU-88 molecular sieve and preparation method thereof |
| CN116102574A (en) * | 2022-09-27 | 2023-05-12 | 苏州百灵威超精细材料有限公司 | 4-nitrophthaloyl nitrogen oxygen heterocyclic compound, preparation method and application thereof |
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| US10737945B2 (en) | 2016-04-27 | 2020-08-11 | China Petroleum & Chemical Corporation | Molecular sieve, its preparation and application thereof |
| US11091372B2 (en) | 2016-04-27 | 2021-08-17 | China Petroleum & Chemical Corporation | Molecular sieve, its preparation and application thereof |
| CN110407222A (en) * | 2018-04-26 | 2019-11-05 | 中国石油化工股份有限公司 | The method for synthesizing NU-88 molecular sieve |
| CN112010325A (en) * | 2019-05-30 | 2020-12-01 | 中国石油化工股份有限公司 | Method for synthesizing EMM-23 molecular sieve |
| CN115140747A (en) * | 2021-03-30 | 2022-10-04 | 中国石油化工股份有限公司 | Granular NU-88 molecular sieve and preparation method thereof |
| CN115140747B (en) * | 2021-03-30 | 2023-11-10 | 中国石油化工股份有限公司 | Granular NU-88 molecular sieve and preparation method thereof |
| CN116102574A (en) * | 2022-09-27 | 2023-05-12 | 苏州百灵威超精细材料有限公司 | 4-nitrophthaloyl nitrogen oxygen heterocyclic compound, preparation method and application thereof |
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