CN107285334B - A kind of method and catalyst of synthesis in solid state AEI type molecular sieve - Google Patents
A kind of method and catalyst of synthesis in solid state AEI type molecular sieve Download PDFInfo
- Publication number
- CN107285334B CN107285334B CN201710618009.2A CN201710618009A CN107285334B CN 107285334 B CN107285334 B CN 107285334B CN 201710618009 A CN201710618009 A CN 201710618009A CN 107285334 B CN107285334 B CN 107285334B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- crystallization
- solid
- aei
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of molecular sieve solid phase synthesis process of AEI type structure, silicon source and Alkylpiperidine class organic formwork agent are subjected to hybrid reaction processing, excessive moisture is removed in vacuum distillation, meta-aluminic acid ammonium compounds gelinite is obtained, then crystallization is carried out with the mixture of silicon source, alkali source and molecular sieve seed mixed grinding and obtains AEI type structure molecular screen original powder.This Zeolite synthesis yield provided by the invention is high, required crystallization time is short, reduces the dosage of solvent and template, is suitable for large-scale industrial application.AEI molecular screen primary powder is swapped with metal cation, available metal-AEI molecular sieve can be used for tail gas NOx catalytic reduction reaction；AEI molecular screen primary powder is exchanged with ammonium ion, activate after obtain the AEI molecular sieve of Hydrogen, can be used for MTO and react to obtain the low-carbon alkene of high yield.
Description
Technical field
The invention belongs to porous orderly microporous inorganic materials synthesis fields, and in particular to have AEI type molecular sieve to a kind of
Solid phase synthesis process and catalyst.
Background technique
Molecular sieve primary synthetic methods include hydro-thermal or organic solvent thermal synthesis method, xerogel transformation approach, ionothermal synthesis.Water
Heat and solvent-thermal process method are to prepare the most classic method of molecular sieve, but the method low yield, environmental pollution are big；Xerogel conversion
Method preparation process is complicated, and ionothermal synthesis has significant improvement in terms of reducing reaction pressure, but the price of ionic liquid valuableness makes
This extensive industrial application of method is restricted.In addition, these methods require the effect of a large amount of solvents, it can not be fundamentally
Solve waste solvent, pollution this major issue of environment.
2012, Ren etc. reported a kind of and need to not need to add any by solid material mixed grinding, heating crystallization
Solvent, 10~20min of grinding can directly fill new method-solid phase thermal method that kettle crystallization prepares molecular sieve, for synthesize it is more cheap,
More green novel molecular sieve opens new air route.
Traditional water (solvent) thermal synthesis zeolite molecular sieve process, needs to consume a large amount of solvent (water or alcohols), product is washed
Wash the wastes and pollution for also resulting in great lot of water resources.On the other hand, due to the presence of a large amount of solvents, high-temperature heating process can draw
The pressure in kettle that reacts is higher, increases the quality requirement for equipment.
By the way that solid material is carried out simple physical mixed, grinding, crystallization in kettle, crystallization time can be shortened, greatly
Ground increases one-pot utilization rate, this can not only be conducive to the more products of plant produced, can also reduce the production cost of each product.
The zeolite product being prepared shows the physicochemical properties consistent with solvent structure sample, and this method
Material yield is high, reduces energy consumption, saves time and the energy, reduces solvent contamination.
Solid phase molecules sieve synthetic method does not need a kind of synthetic method that a large amount of solvents participate in, it is only needed in raw material containing few
It measures the crystallization water to participate in, and avoids generating reaction high pressure completely in reaction.A kind of energy conservation and environmental protection, safety non-pollution it is green
Color synthetic route.This provides very favorable support for the industrialized production of zeolite molecular sieve.
Summary of the invention
The object of the present invention is to provide a kind of methods of solid-phase grinding mixing method synthesis AEI molecular sieve, improve AEI molecular sieve
Combined coefficient and yield reduce the usage amount of template, solvent, reduce discharge of wastewater and reduce AEI Zeolite synthesis cost.
The invention is realized by the following technical scheme:
A kind of method of solid-phase sequencing synthesis AEI structure molecular screen, synthetic method are characterized in that:
(1) silicon source is reacted 6~24 at a temperature of 100~180 DEG C with the organic compound aqueous solution of Alkylpiperidine class
Hour, preferably 120~180 DEG C of reaction temperature, then 30~80 DEG C of vacuum distillations remove extra moisture, obtain gelatinous inclined
Aluminic acid ammonium compounds.
(2) meta-aluminic acid ammonium compounds gelatinous in (1) and silicon source, alkali source, crystal seed mixed grinding is uniform, obtain solid phase
Mixture, which is placed in crystallizing kettle, divides temperature section dynamic crystallization to react, and 125~200 DEG C of temperature range, the reaction time 48~96 hours.
Sudden cold suspension crystallization, isolates solid product, is filtered, washed with deionized water to neutrality, at 100~130 DEG C after the completion of crystallization
It air drying 12~48 hours, is roasted 2~10 hours in 400~600 DEG C of air, obtains AEI molecular screen primary powder.
Further, in the above-mentioned technical solutions, Alkylpiperidine class organic compound described in synthesis step of the present invention
Selected from 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidine, acetyl group -2,2 1-,
6,6- tetramethyl -4- oxo-piperidine, 1,1,3,5- tetramethyl -4- oxo-piperidine, 1- hydroxyl -1,1,2,2,6,6- hexamethyl piperazine
Pyridine, 1,1- dimethyl -4,4- dipropoxy piperidines, 3,5- dimethoxy -1,1- lupetidine, 3,5- dihydroxy -
1,1- lupetidine, 4- ethyl -1,1- dimethyl -3,5- dioxopiperidine.1- ethyl -1- methyl -2,2,6,6- six
It is one or more in methyl piperidine, 1- glycidyl -1- methyl -2,2,6,6- pregnancy phenylpiperidines.
Further, in the above-mentioned technical solutions, silicon source described in synthesis step of the present invention is selected from boehmite, SB
One or more of powder, Aluminum sol, pseudobochmite, aluminium isopropoxide and aluminium hydroxide.
Further, in the above-mentioned technical solutions, silicon source described in synthesis step of the present invention may come from white carbon black, big
It is one or more in hole silica gel, silochrom, Kiselgel A, tlc silica gel, Type B silica gel, sodium metasilicate and diatomite.
The organic compound aqueous solution mass concentration of the Alkylpiperidine class is 5.0~50wt%.
Further, in the above-mentioned technical solutions, following groups centimorgans in crystallization predecessor solid-phase mixture of the present invention
Your ratio is silicon source (SiO2Calculate), silicon source (Al2O3Calculate), alkali source (Na2O calculate) and organic formwork agent (OSDA) according to
Na2O:SiO2:Al2O3: OSDA=0.1~0.5:1.0:0.004~0.083:0.05~0.5, it is mixed that crystal seed accounts for the crystallization solid that feeds intake
0.1~20wt% of polymer weight, wherein H2O content accounts for the 2.0~20.0% of solid-phase mixture weight.
Further, in the above-mentioned technical solutions, synthetic method of the present invention divides temperature section crystallization using dynamic, and first segment is brilliant
Changing temperature is 125~150 DEG C, and crystallization time is 12~72 hours；Second segment crystallization temperature is that 170~200 DEG C of crystallization times are
12~96 hours.
The present invention provides a kind of catalyst, carries out ion using the AEI molecular sieve and soluble metal solution of above-mentioned synthesis
Exchange, obtains the AEI molecular sieve catalyst of metal promoted, can be used as a kind of NOx selective catalytic reduction catalyst.The rush
Copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold are selected from into agent metal
Or silver one or more of combination in these.The preferred copper of the promoter metals, iron, cobalt, nickel, zinc, tungsten, molybdenum；Further preferably
Copper and iron.Nitrogen oxides (NOx), including multiple compounds, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide
(NO2), nitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4) and dinitrogen pentoxide (N2O5) etc..
The present invention provides another catalyst, using the AEI molecular sieve and soluble ammonium salting liquid of above-mentioned synthesis carry out from
Then son exchange obtains the AEI molecular sieve of Hydrogen by dry, roasting, can be used as a kind of preparation for MTO catalyst.
Soluble ammonium salting liquid is the aqueous solution of ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium hydrogen carbonate, the concentration of ammonium ion is 0.5~
5.0mol/L, preferably 0.5~1.5mol/L.
The method of synthesis AEI molecular sieve of the present invention is relative to conventional method advantage:
(1) shorten generated time, reduce organic formwork agent usage amount, reduce synthesis cost；
(2) the AEI molecular sieve yield that synthesis obtains is high, and grain size distribution is more uniform；
(3) by carried metal promotor, it is also original for the catalysis of NOx to obtain the SCR catalyst containing AEI molecular sieve
Relatively high activity；
(4) after by ammonium ion exchange roasting, obtained Hydrogen AEI molecular sieve can be used for MTO reaction, have good
Activity and selectivity.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawings and embodiments:
Fig. 1 is the XRD diffraction pattern of 1 method of embodiment synthesis AEI molecular sieve；
Fig. 2 is the SEM figure of 1 method of embodiment synthesis AEI molecular sieve.
Specific embodiment
Embodiment of the present invention and generated effect are further illustrated by embodiment and comparative example, but of the invention
Protection scope is not limited to content listed by embodiment.
Embodiment 1
(1) by quantitative boehmite (Al2O3: 65.1wt%) and 1- ethyl -1- methyl -2,2,6,6- hexamethyl piperazine
Pyridine aqueous solution (concentration: 20.0wt%), is stirred to react 12 hours at a temperature of 150 DEG C, by 60 DEG C of mixture after reaction into
Row vacuum distillation, removes extra moisture, obtains gelatinous meta-aluminic acid ammonium compounds.
(2) by gelatinous meta-aluminic acid ammonium compounds and silochrom (SiO2: 91.40wt%), NaOH (purity:
It 96wt%) mixes and grinds uniformly with AEI molecular sieve seed, then mixture moves toLining 2000ml crystallizing kettle
In, and stirred under 60rpm speed, 130 DEG C crystallization 24 hours, then 175 DEG C crystallization 60 hours.Wherein AEI molecular sieve seed
The 5.0% of the total butt quality of Zhan, following component molar ratios of crystallization forerunner's solid-phase mixture:
Na2O:SiO2: Al2O3: OSDA=0.27:1.0:0.0562:0.24；
After crystallization is complete, product is cooled down rapidly, is to dry at 8.0~9.0,120 DEG C by filtering separation, washing to pH value
4 hours are roasted at 12 hours and 540 DEG C dry, can be obtained AEI molecular screen primary powder, product is denoted as A.
The 10.0g AEI molecular screen primary powder of above-mentioned synthesis is added to the Cu that 100.0g concentration is 0.2mol/L
(CH3COO)2·H2In O aqueous solution, its pH to 6.5 is adjusted, is placed in heatproof container after stirring evenly 1 hour, and be put into togerther
In drier with pressure reducing valve；After the pressure in drier is extracted into 10Torr or less with vacuum pump, room temperature is carried out 1 hour
Degassing process, it is 12 hours dry to be then warming up to 90 DEG C of conditions, by the sample after drying under normal atmosphere pressure 500 DEG C of temperature
Roasting 4 hours；It obtains the copper and is modified AEI molecular sieve, in the catalyst prepared according to icp analysis result, copper (II) ion
The 2.1% of molecular sieve catalyst total weight is accounted for, i.e. copper load capacity is 2.1wt%, and Na ion concentration is lower than 200ppm, and product is denoted as
A1。
By AEI molecular screen primary powder with 1.0 DEG C/min heating rate, it is warming up to 550 DEG C of roastings in Muffle furnace and removes within 6 hours
Template.The ammonium nitrate solution ratio that the 10.0wt% of 10.0g is corresponded to every gram of AEI molecular screen primary powder is small in 80 DEG C of exchanges 1
When, an ammonium ion exchange is repeated after solid is recovered by filtration.Na ion is removed by ion exchange, solid product is again 120
DEG C drying 12 hours, 550 DEG C roasted 2 hours, obtain the Hydrogen AEI molecular sieve of high-crystallinity, and it is 11.5 that XRF, which measures silica alumina ratio,
Product is denoted as A2
Embodiment 2~10
The process of Solid phase synthesis AEI molecular sieve, Cu ion exchange and ammonium ion exchange is analogous to embodiment 1, institute
Unlike the type of silicon source in step (1), organic base Template Types, the type of silicon source, crystallization forerunner's solid-phase mixture
Component ratio, crystallization temperature and crystallization time etc., as shown in Tables 1 and 2.
Table 1
Table 2
Table 3
Comparative example 1
The AEI molecular sieve powder that SAR is 19.4 is synthesized according to US2017128921A1 patent Example 1:
It is the USY molecular sieve (Al of 10.7 de-aluminates by the molecule silica alumina ratio (SAR) of 35.0g2O3: 11.79wt%,
SiO2: 74.31%) it is stirred in stainless steel kettle with 945.7g deionized water, then under stiring by the N of 303.15g, N-
Diethyl -3,5- lupetidine solution (20.0wt%) and 416.15g sodium silicate solution (Na2O:9.00wt%, SiO2:
It 28.8wt%) is taken up in order of priority and slowly pours into said mixture, the mixed sols finally obtained is placed in 2L crystallizing kettle instead
It answers.Under 60rpm revolving speed stirring state, crystallizing kettle is heated to 145 DEG C of set temperature in 40min, and keeps this temperature,
49 hours completion crystallization, solid product are recovered by filtration, and are rinsed until pH value less than 10 with deionized water hereinafter, the filter of filtering
It is 12 hours dry in 120 DEG C of baking ovens of cake, obtain the AEI molecular screen primary powder containing organic formwork agent.
The 10.0g AEI molecular screen primary powder of above-mentioned synthesis is added to the Cu (NO that 100.0g concentration is 0.3mol/L3)2·
In 3H2O aqueous solution, its pH to 6.5 is adjusted, is placed in heatproof container after stirring evenly 1 hour, and be put into togerther with pressure reducing valve
Drier in；After the pressure in drier is extracted into 10Torr or less with vacuum pump, room temperature carries out 1 hour degassing process,
Then it is 12 hours dry that 90 DEG C of conditions are warming up to, 500 DEG C of temperature calcinations 4 are small under normal atmosphere pressure by the sample after drying
When；The modified AEI molecular sieve of the copper is obtained, according in the catalyst of icp analysis result preparation, copper (II) ion accounts for molecular sieve
The 2.5% of total catalyst weight, i.e. copper load capacity are 2.1wt%, and Na ion concentration is lower than 200ppm, and product is denoted as CP-1.
By molecular screen primary powder with 1.0 DEG C/min heating rate, 550 DEG C of roastings, 6 hours removing moulds are warming up in Muffle furnace
Plate agent.The ammonium acetate solution ratio that the 10.0wt% of 10.0g is corresponded to every gram molecule sieve powder, exchanges 1 hour, filtering at 80 DEG C
An ammonium ion exchange is repeated after recycling solid.Na ion is removed by ion exchange, solid product dries 12 at 120 DEG C again
Hour, 550 DEG C roast 2 hours, obtain the Hydrogen AEI molecular sieve of high-crystallinity, and it is 19.4 that XRF, which measures silica alumina ratio, is named as VS-
1。
Comparative example 2
3.94g NaOH (purity: 98%) is dissolved into 49.5g deionized water, is stirred in rustless steel container, then
Continue the business HY molecular sieve powder (Al for being 5.4 by the molecule silica alumina ratio (SAR) of 13.83g under stirring2O3: 18.32wt%,
SiO2: 58.71%, Na2O:0.08wt% the slurries for forming white uniformity) are added, next, by 9.29g N, diethyl -3 N-,
5- dimethyl hydrogen Oxypertine (concentration: 55.8wt% is denoted as OSDA) and 324.3g sodium silicate solution (Na2O:9.00wt%, SiO2:
It 28.8wt%) sequentially adds in above-mentioned mixed serum.The colloidal sol eventually formed, corresponding mole of composition are as follows:
68.0SiO2: 1.00Al2O3: 21.0Na2O:1.00OSDA:580H2O
Continue to stir 30min, be subsequently placed in 120 DEG C of stirring crystallization in 0.6L kettle, crystallization is completed after 45 hours, solid product
Recycling, and the progress of the program as described in comparative example 1 Cu ion exchange obtains copper (II) ion accounts for molecular sieve catalyst total weight
2.5%, product is denoted as CP-2.
Na ion is activated and removed with AEI molecular screen primary powder of the technical process identical in comparative example 1 to synthesis, is obtained
To the Hydrogen AEI molecular sieve of high-crystallinity, it is 11.7 that XRF, which measures silica alumina ratio, is named as VS-2.
Embodiment 11~18
SCR catalyst test:
10~20 mesh A1~F1 catalyst granules prepared in Example 1~6 and comparative example 1~2 are mounted in reactorIn, it include 500ppm NO, 500ppm NH3, 10 volume %O2, 5 volume % steam and Ar be Balance Air
Mixed airflow 160mL/min first passes through preheater (being set as 250 DEG C), subsequently into SCR reactor.At 150~650 DEG C
Reaction temperature and be based on 48000h-1Sample is tested under volume gas hourly space velocity.The temperature is by being located at sample position
Interior thermocouple monitoring.
Fresh SCR catalyst each in used above-described embodiment and comparative example is carried out the durable processing of hydro-thermal to be aged
SCR catalyst, hydro-thermal it is durable processing test condition are as follows:
Space velocity SV:30000/h, temperature: 800 DEG C, the time: 16 hours, moisture concentration: 10%, oxygen concentration: 10%,
Nitrogen concentration: balance.
After carrying out hydro-thermal ripening according to above-mentioned parameter, continue to comment as SCR catalyst for NOx catalytic reduction reaction
Valence test:
NO conversion ratio or " de- NOx " activity are under steady state conditions, a reactor by using 55 type FT-IR spectrum of Bruker EQUINOX
Instrument measures NOx, NH3 and N2O concentration in exit and determines.
Using above-mentioned SCR catalyst activity laboratory evaluation device, the loaded Cu that embodiment and comparative example is prepared
SCR catalyst carry out NOx selective catalytic reduction performance evaluation, the results are shown in Table 4.
Table 4
Can be as seen from Table 4 under all test temperatures, the SCR of A1~F1 catalyst sample of preparation of the embodiment of the present invention is living
Property is substantially better than CP-1 the and CP-2 catalyst sample in comparative example, no matter its " fresh " state or " ageing " state.Therefore,
Cu-AEI molecular sieve catalytic agent material of the invention is clearly shown by the result that embodiment 11~18 obtains and is obtained with it
Catalyst have improveds SCR catalytic activity, especially such as diesel locomotive application in processing NOx when cold start
Under specific low conversion temperature.
Embodiment 19~26
The evaluation of catalyst: A2~F2 catalyst raw powder obtained in Examples 1 to 6 is subjected to tabletting, is crushed to 20
~40 mesh.It weighs 0.5g catalyst (20~40 mesh) to be packed into stainless steel tubular reactor (length 45cm, internal diameter 8mm), both ends
Suitable quartz sand and silica wool are filled respectively, carry out MTO evaluation.Before test, first purged with carrier gas N2, on temperature of reactor
500 DEG C are risen to, is kept for 2 hours.After pretreatment, reactor is cooled to required reaction temperature i.e. 350 DEG C and keeps.Methanol is by nitrogen
It carries, nitrogen flow rate 15ml/min, methanol weight air speed 4.0h-1.Product gas composition uses 7890 chromatography of Agilent GC
On-line analysis, chromatograph are equipped with fid detector and HP-PONA chromatographic column.Selectivity of product, which is that the specific product is shared, removes diformazan
The mass percent of the outer total overall reaction product of ether (DME), the results are shown in Table 5.
Table 5
t50: conversion ratio was reduced to for 50% time experienced from 100%；t98: conversion ratio is reduced to 98% institute from 100%
The time of experience.
As can be seen from Table 5, the AEI molecular sieve catalyst of method preparation provided by the invention has more in MTO reaction
High low-carbon alkene (C2 =+C3 =) selectivity up to 85%, and conversion ratio drop to 50% before conversion life-span 13 hours with
On, conversion ratio was reduced to for 98% time experienced at 7.0 hours or more, illustrated the AEI molecular sieve catalyst that embodiment obtains
Compared with comparative example, there is better MTO reactivity worth and durability.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.Without departing from the premise in the spirit of the present invention, all essence according to the present invention is made equivalent transformation changes or repairs
Decorations, appended claims should all cover within the protection scope of spirit of that invention.
Claims (5)
1. a kind of method of solid-phase grinding mixing method synthesis AEI type molecular sieve, it is characterised in that:
(1) silicon source reacted at a temperature of 100~180 DEG C to 6 with the organic formwork agent compound water solution of Alkylpiperidine class~
24 hours, then room temperature~80 DEG C vacuum distillation removed extra moisture, obtained gelatinous meta-aluminic acid ammonium compounds；
(2) meta-aluminic acid ammonium compounds gelatinous in (1) and silicon source, alkali source, crystal seed mixed grinding is uniform, obtain solid phase mixing
Object, which is placed in crystallizing kettle, divides temperature section dynamic crystallization to react, and 125~200 DEG C of temperature range, the reaction time 48~96 hours；Crystallization
Sudden cold suspension crystallization after the completion, isolates solid product, is filtered, washed with deionized water to neutrality, in 100~130 DEG C of air
Middle drying 12~48 hours roasts 2~10 hours in 400~600 DEG C of air, obtains AEI molecular screen primary powder；
Following component molar ratios are silicon source with SiO in the crystallization predecessor solid-phase mixture2It calculates, silicon source is with Al2O3Meter
It calculates, alkali source is with Na2O is calculated and the organic formwork agent compound water solution of Alkylpiperidine class is calculated with OSDA, according to Na2O:
SiO2:Al2O3: OSDA=0.1~0.5:1.0:0.004~0.083:0.05~0.5 molar ratio is mixed, and crystal seed accounts for
0.1~20wt% of the crystallization that feeds intake predecessor solid-phase mixture weight, wherein H2O content account for solid-phase mixture weight 2.0~
20.0%.
2. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: alkyl piperidine
Pyridine class organic compound is selected from 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidine
, 1,1,3,5- tetramethyl -4- oxo-piperidine, 1- hydroxyl -1,1,2,2,6,6- pregnancy phenylpiperidines, dimethyl -4 1,1-,
4- dipropoxy piperidines, 3,5- dimethoxy -1,1- lupetidine, 3,5- dihydroxy -1,1- lupetidine, 4-
Ethyl -1,1- dimethyl -3,5- dioxopiperidine, 1- ethyl -1- methyl -2,2,6,6- pregnancy phenylpiperidines, 1- epoxy third
It is one or more in base -1- methyl -2,2,6,6- pregnancy phenylpiperidines.
3. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: silicon source choosing
From one or more of boehmite, SB powder, Aluminum sol, boehmite, aluminium isopropoxide and aluminium hydroxide.
4. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: silicon source can
From white carbon black, macro porous silica gel, silochrom, Kiselgel A, tlc silica gel, Type B silica gel, sodium metasilicate and diatom
It is one or more in soil.
5. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: use and divide
Temperature section dynamic crystallization, first segment crystallization temperature are 120~160 DEG C, and crystallization time is 12~72 hours；Second segment crystallization temperature
Be 170~200 DEG C of crystallization times be 12~96 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710618009.2A CN107285334B (en) | 2017-07-26 | 2017-07-26 | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710618009.2A CN107285334B (en) | 2017-07-26 | 2017-07-26 | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107285334A CN107285334A (en) | 2017-10-24 |
| CN107285334B true CN107285334B (en) | 2019-05-10 |
Family
ID=60103072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710618009.2A Active CN107285334B (en) | 2017-07-26 | 2017-07-26 | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107285334B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3749611A4 (en) * | 2018-02-06 | 2022-02-23 | Basf Se | A process for preparing a zeolitic material having a framework structure type rth |
| EP3781520A1 (en) * | 2018-04-20 | 2021-02-24 | Basf Se | A process for preparing a porous oxidic material which comprises micropores and mesopores and which comprises a zeolitic material having a framework type aei |
| JP2021535883A (en) * | 2018-08-29 | 2021-12-23 | パシフィック インダストリアル デベロップメント コーポレイション | Method for producing AEI-type zeolite having a high silica / alumina ratio (SAR) |
| CN109399664B (en) * | 2018-09-26 | 2022-02-18 | 山东国瓷功能材料股份有限公司 | Preparation method and application of AEI molecular sieve with controllable crystal grains |
| CN109336131B (en) * | 2018-11-01 | 2022-02-22 | 山东国瓷功能材料股份有限公司 | Method for quickly synthesizing AEI type molecular sieve |
| US20210403334A1 (en) * | 2018-11-05 | 2021-12-30 | Pacific Industrial Development Corporation | Method of making aei-type zeolites having a high silica to alumina molar ratio (sar) |
| 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 |
| US20220106192A1 (en) * | 2019-01-23 | 2022-04-07 | Basf Se | An oxidic material comprising a zeolite having framework type aei |
| CN110339809A (en) * | 2019-08-13 | 2019-10-18 | 淄博齐创化工科技开发有限公司 | A kind of adsorbent and preparation method for VOCs absorption |
| CN110961148A (en) * | 2019-12-14 | 2020-04-07 | 中触媒新材料股份有限公司 | AEI/LEV structure symbiotic composite molecular sieve, preparation method and SCR application thereof |
| CN113753915B (en) * | 2020-06-01 | 2023-04-07 | 中国石油化工股份有限公司 | Preparation method of small-crystal-grain SAPO-34 molecular sieve, prepared molecular sieve and application |
| CN114477209B (en) * | 2020-10-23 | 2023-10-13 | 中国石油化工股份有限公司 | Silicon-aluminum molecular sieve and preparation method and application thereof |
| CN112742411B (en) * | 2020-12-29 | 2023-04-11 | 安徽省福泰精细化工有限责任公司 | Preparation method of catalyst for methylal synthesis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016172128A1 (en) * | 2015-04-20 | 2016-10-27 | Johnson Matthey Public Limited Company | Method for preparing structured directing agent |
| CN106457144A (en) * | 2014-03-27 | 2017-02-22 | 庄信万丰股份有限公司 | SCR method for reducing oxides of nitrogen and method for producing a catalyst for such method |
| CN106745057A (en) * | 2017-03-10 | 2017-05-31 | 中触媒新材料股份有限公司 | The AEI/MFI eutectics Si-Al molecular sieve and synthetic method of a kind of binder free and application |
| CN106745031A (en) * | 2016-11-28 | 2017-05-31 | 中海亚环保材料有限公司 | A kind of zeolites of high silica alumina ratio SSZ 39 and its synthesis and application |
-
2017
- 2017-07-26 CN CN201710618009.2A patent/CN107285334B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106457144A (en) * | 2014-03-27 | 2017-02-22 | 庄信万丰股份有限公司 | SCR method for reducing oxides of nitrogen and method for producing a catalyst for such method |
| WO2016172128A1 (en) * | 2015-04-20 | 2016-10-27 | Johnson Matthey Public Limited Company | Method for preparing structured directing agent |
| CN106745031A (en) * | 2016-11-28 | 2017-05-31 | 中海亚环保材料有限公司 | A kind of zeolites of high silica alumina ratio SSZ 39 and its synthesis and application |
| CN106745057A (en) * | 2017-03-10 | 2017-05-31 | 中触媒新材料股份有限公司 | The AEI/MFI eutectics Si-Al molecular sieve and synthetic method of a kind of binder free and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107285334A (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107285334B (en) | A kind of method and catalyst of synthesis in solid state AEI type molecular sieve | |
| CN105347359B (en) | A kind of duct includes the synthesis and its application of the zeolite molecular sieve of solid acid | |
| CN102049283B (en) | Hydro-cracking catalyst and preparation method thereof | |
| CN109174173A (en) | A kind of molecular sieve SCR catalyst preparation method and its catalyst of preparation | |
| CN107029781B (en) | Iron and cerium modified beta-molecular sieve selective reduction catalyst and preparation method and application | |
| CN107115888A (en) | A kind of preparation method and its usage of the catalyst of Cu SSZ 13 | |
| CN107804855A (en) | A kind of preparation method, the preparation method of SCR catalyst of the hydrogen type molecular sieves of SSZ 13 | |
| CN109985660A (en) | A kind of method and its application of the iron-based molecular sieve catalyst of one-step synthesis method | |
| WO2018010359A1 (en) | Method for preparing dual-function catalyst and application thereof | |
| CN103818927A (en) | One-step method for synthesizing copper-containing CHA type molecular sieve with high hydro-thermal stability | |
| CN109647500B (en) | Ammonia oxidation catalyst for internal combustion engine tail gas purification system and preparation method thereof | |
| CN105817259A (en) | Productive naphtha type hydrocracking catalyst and preparation method thereof | |
| CN106466642A (en) | A kind of Ce Base Metal organic framework catalyst, its preparation method and the application in Air Pollution prevention and control | |
| CN108906050A (en) | A kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst and its preparation method and application | |
| CN109999902A (en) | The supported porous grade titanium-silicon molecular sieve catalyst of encapsulation type platinum family sub-nanometer metal and its preparation and application | |
| CN110182827A (en) | A kind of preparation method and applications of CuM/SAPO-34 and Fe/Beta coupled molecule sieve | |
| CN102049308B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
| CN101440040B (en) | Process for synthesizing p-aminophenol by catalytic hydrogenation of nitrobenzene | |
| CN105964295B (en) | A kind of the Mn-SAPO-34 molecular sieve catalyst and preparation method thereof and purposes of richness manganese | |
| CN107344721A (en) | A kind of Modified Zeolite Y and its preparation method and application | |
| CN113751062A (en) | Porous copper-based catalyst for preparing ethanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN110508290B (en) | High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof | |
| CN103100402B (en) | Preparation method of hydrocracking catalyst | |
| CN109395772A (en) | A kind of isomerization catalyst and its preparation method and application | |
| CN109046324B (en) | Medium-low temperature denitration catalyst with mesoporous cerium oxide as carrier and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |