CN106745032B - The method that Al-MCM-41 mesopore molecular sieve is directly synthesized by kaolin or Hanggin 2# soil - Google Patents
The method that Al-MCM-41 mesopore molecular sieve is directly synthesized by kaolin or Hanggin 2# soil Download PDFInfo
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- 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
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Abstract
The present invention relates to the methods for directly synthesizing Al-MCM-41 mesopore molecular sieve by kaolin or Hanggin 2# soil.Specific steps specifically include that (1) 4mol/L aqueous sulfuric acid acid activation lamellar clay raw ore obtains acid-treated clay；(2) after the alkaline solution of acid-treated clay and certain density cetyl trimethylammonium bromide being mixed 1 hour in 70 DEG C of water-baths, pH value of solution=10 are adjusted, are further continued for stirring 1 hour；(3) gained mixture in hydrothermal reaction kettle, 110 DEG C standing crystallization 12 hours；(4) product is washed, and drying, roasting etc. post-processes up to Al-MCM-41 mesopore molecular sieve.The method of the present invention avoids that template usage amount is greatly reduced using highly energy-consumings pretreatment procedures such as high-temperature roasting, high speed ball milling or high temperature alkali fuses, also can get Patent alum by-product.Therefore this method is simple and easy to do, has saved cost.
Description
Technical field
The present invention relates to a kind of low energy consumption by kaolin or Hanggin 2#The layered clay minerals such as soil directly synthesize Al-
The method of MCM-41 mesopore molecular sieve, belongs to field of inorganic nonmetallic material.
Background technique
1992, Mobil (Mobil) company research staff used structure self-assembling technique, with cetyl trimethyl bromination
Ammonium (CTABr) is template, synthesis for the first time obtain duct uniformly, the MCM-41 mesopore molecular sieves of six side's ordered arrangements
(Nature,1992,359,710-712).The declaration of ordered mesoporous molecular sieve epoch is arrived.MCM-41 mesopore molecular sieve is being urged because of it
The extensive use in fields such as change, adsorb, isolating and purifying, and being paid close attention to by researcher.It is closed by raw material of organic or inorganic silica reagent
It emerges one after another at the report of MCM-41 mesopore molecular sieve.Also there are many hetero atom (such as Al3+, Fe3+, Ga3+Deng) doping MCM-41 Jie
Porous molecular sieve is synthesized (Chem.Rev., 1997,97,2373-2419) in succession.But there are expensive starting materials, technique mistakes for these methods
The defects of journey is complicated.Therefore, lot of domestic and international researcher has turned one's attention to is situated between using natural clay mineral synthesis MCM-41
The research work of porous molecular sieve.Wherein for kaolin because of the advantage of its global rich reserves, correlative study is extremely more.But in these work
Common problem mainly has: (1) the acidification soil after raw ore or acidified removal of impurities cannot be used directly as silicon and aluminum source, must
The pre-treatment steps rears such as 500 DEG C or more high-temperature roastings, high speed ball milling or high temperature alkali fuse must must be carried out to it can be used for synthesizing Jie
Porous molecular sieve (Appl.Clay Sci., 2015,107,182-187；J.Colloid Interface Sci.,2012,369,
216-222；CN102602954A), not only energy consumption is considerable, and product yield is low；(2) it when aluminium content is higher, must additionally mend
Add silicon source (Appl. Clay Sci., 2007,35,155-161), increases synthesis cost.
Summary of the invention
The object of the present invention is to provide one kind with layered clay mineral for unique silicon and aluminum source, only acidified pre-treatment, and nothing
The highly energy-consumings steps such as high-temperature roasting, high speed ball milling or high temperature alkali fuse are needed, quick hydrothermal synthesis Al-MCM-41 mesopore molecular sieve
Method.This method is by accurately controlling the conditions such as template agent concentration, synthesis temperature and synthesis pH value and existing technology being overcome to lack
It falls into.
Lamellar clay raw ore of the present invention can be Coaseries kaolin 1 (Ordos of Inner Mongolia Jungar Banner,
Mainly contain kaolinite, 80 meshes point, primary chemical forms (wt%): SiO243.99 Al2O339.51), Coaseries kaolin 2 is (interior
Mongolian Huhehaote City Qingshuihe County mainly contains kaolinite, boehmite, 80 meshes point, and primary chemical forms (wt%):
SiO235.17 Al2O347.05 TiO2Or Hanggin 2 1.75)#(Ordos of Inner Mongolia Hangjin Banner mainly contains concave convex rod to soil
Stone, illite, chlorite, 200 meshes point, primary chemical form (wt%): SiO251.57 Al2O322.72 Fe2O38.19
CaO 5.83, MgO 5.61, K2One of O 4.02).
Main technological steps of the invention are as follows:
S1. one of above-mentioned lamellar clay is mixed with 4mol/L sulfuric acid in 1g:10mL ratio, boiling reflux 2 hours, from
It is so cooling, it is once washed to neutrality, is filtered, 60 DEG C obtain acid-treated clay in drying 6 hours；
S2. 0.2mol/L sodium hydrate aqueous solution 100mL constant temperature in 70 DEG C of water-baths is taken；
S3. cetyl trimethylammonium bromide (CTABr) is added in the solution of step 2, stirring dissolves it all, control
The mass ratio of the material of CTABr and water processed are 1:1350；
S4. 4g step 1 gained acid-treated clay is added in the solution of step 3, continues stirring 1 hour；
S5. 1mol/L sulfuric acid is added dropwise in the solution of step 4, adjusts pH value of solution=10, continues stirring 1 hour；
S6. step 5 gained mixture is moved into the hydrothermal reaction kettle for having polytetrafluoroethyllining lining, 110 DEG C of standing crystallization
12 hours；
S7. step 6 products therefrom is filtered, and with being once washed to neutrality, after the drying 6 hours of 60 DEG C of solid product,
4 hours are roasted in 550 DEG C of air atmospheres up to Al-MCM-41 mesopore molecular sieve.
The major advantage of synthetic method according to the present invention has: (1) 4mol/L sulfuric acid used in step 1 filters solid-liquid through heat
After separation not only can crystallisation by cooling be precipitated Patent alum by-product, and recycle sulfuric acid it is reusable in acidification raw ore；(2) it keeps away
Exempt from not only to shorten generated time using highly energy-consumings pretreatment procedures such as high-temperature roasting, high speed ball milling or high temperature alkali fuses, hence it is evident that drop
Low process energy consumption, and product yield is greater than 95%；(3) items such as template agent concentration, synthesis temperature and synthesis pH value are accurately controlled
Part realizes and directly synthesizes Al-MCM-41 mesopore molecular sieve by acidification lamellar clay under low template agent concentration, significantly reduces mould
The usage amount of plate agent CTABr, has saved synthesis cost.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail；It should be understood that the following example is solely for the purpose of illustration
Technical solution of the invention, rather than limit the scope of the invention in any way.
Embodiment 1
Al-MCM-41 mesopore molecular sieve is synthesized by Coaseries kaolin 1: by Coaseries kaolin 1 and 4mol/L sulfuric acid by 1g:
The mixing of 10mL ratio, boiling reflux 2 hours, natural cooling was once washed to neutrality, filtered, and 60 DEG C of dryings must be acidified height in 6 hours
Ridge soil 1.Take 0.2mol/L sodium hydrate aqueous solution 100mL constant temperature in 70 DEG C of water-baths；CTABr 1.5g is added, stirring makes it
All dissolutions；4g acidification kaolin 1 is added, stirring 1 hour is continued；1mol/L sulfuric acid is added dropwise, adjusts pH value of solution=10, continues
Stirring 1 hour.Gained mixture immigration have in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, 110 DEG C standing crystallization 12 hours.From
So after cooling, products therefrom is filtered, and is washed to neutrality with primary；After the drying 6 hours of 60 DEG C of solid product, in 550 DEG C of skies
4 hours are roasted in gas atmosphere up to Al-MCM-41 mesopore molecular sieve.Product yield and characterization result are shown in Table 1.
Embodiment 2
Al-MCM-41 mesopore molecular sieve is synthesized by Coaseries kaolin 2: by Coaseries kaolin 2 and 4mol/L sulfuric acid by 1g:
The mixing of 10mL ratio, boiling reflux 2 hours, natural cooling was once washed to neutrality, filtered, and 60 DEG C of dryings must be acidified height in 6 hours
Ridge soil 2.Take 0.2mol/L sodium hydrate aqueous solution 100mL constant temperature in 70 DEG C of water-baths；CTABr 1.5g is added, stirring makes it
All dissolutions；4g acidification kaolin 2 is added, stirring 1 hour is continued；1mol/L sulfuric acid is added dropwise, adjusts pH value of solution=10, continues
Stirring 1 hour.Gained mixture immigration have in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, 110 DEG C standing crystallization 12 hours.From
So after cooling, products therefrom is filtered, and is washed to neutrality with primary；After the drying 6 hours of 60 DEG C of solid product, in 550 DEG C of skies
4 hours are roasted in gas atmosphere up to Al-MCM-41 mesopore molecular sieve.Product yield and characterization result are shown in Table 1.
Embodiment 3
By Hanggin 2#Soil synthesis Al-MCM-41 mesopore molecular sieve: by Hanggin 2#Soil is with 4mol/L sulfuric acid in 1g:10mL ratio
Mixing, boiling reflux 2 hours, natural cooling was once washed to neutrality, filtered, and 60 DEG C of dryings must be acidified Hanggin 2 in 6 hours#Soil
(atlapulgite).Take 0.2mol/L sodium hydrate aqueous solution 100mL constant temperature in 70 DEG C of water-baths；CTABr 1.5g, stirring is added
Dissolve it all；4g atlapulgite is added, stirring 1 hour is continued；1mol/L sulfuric acid is added dropwise, adjusts pH value of solution=10, after
Continuous stirring 1 hour.Gained mixture immigration have in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, 110 DEG C standing crystallization 12 hours.
After natural cooling, products therefrom is filtered, and is washed to neutrality with primary；After the drying 6 hours of 60 DEG C of solid product, at 550 DEG C
4 hours are roasted in air atmosphere up to Al-MCM-41 mesopore molecular sieve.Product yield and characterization result are shown in Table 1.
Embodiment 4
Al-MCM-41 mesopore molecular sieve (sulfuric acid reuse experiment) is synthesized by Coaseries kaolin 2: by Coaseries kaolin 2 and being returned
It receives sulfuric acid to mix in 1g:15mL ratio, boiling reflux 2 hours, natural cooling was once washed to neutrality, filtered, 60 DEG C of dryings 6
Hour obtains reuse and is acidified kaolin 2.Take 0.2mol/L sodium hydrate aqueous solution 100mL constant temperature in 70 DEG C of water-baths；CTABr is added
1.5g, stirring dissolve it all；4g reuse acidification kaolin 2 is added, stirring 1 hour is continued；1mol/L sulfuric acid is added dropwise, adjusts
PH value of solution=10 are saved, stirring 1 hour is continued.The immigration of gained mixture has in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, and 110 DEG C
Stand crystallization 12 hours.After natural cooling, products therefrom is filtered, and is washed to neutrality with primary；60 DEG C of dryings 6 of solid product
After hour, 4 hours are roasted in 550 DEG C of air atmospheres up to Al-MCM-41 mesopore molecular sieve.Product yield and characterization result are shown in
Table 1.
Table 1 synthesizes Al-MCM-41 mesopore molecular sieve yield and characterization result
Claims (4)
1. the method for directly synthesizing Al-MCM-41 mesopore molecular sieve by kaolin or Hanggin 2# soil, it is characterised in that: this method with
Low dosage cetyl trimethylammonium bromide is template, by accurately controlling template agent concentration, synthesis temperature and synthesis pH value
Condition, without the highly energy-consumings pre-treatment steps such as high-temperature roasting, high speed ball milling or high temperature alkali fuse, quick hydrothermal synthesis Al-MCM-41
Mesopore molecular sieve；Specific step is as follows for this method,
S1 is mixed lamellar clay and 4mol/L sulfuric acid in 1g:10mL ratio, and boiling reflux 2 hours, natural cooling was primary to wash
It to neutrality, filters, 60 DEG C obtain acid-treated clay in drying 6 hours；
S2 takes 0.2mol/L sodium hydrate aqueous solution 100mL constant temperature in 70 DEG C of water-baths；
Cetyl trimethylammonium bromide is added in S3 in the solution of step S2, and stirring dissolves it all, controls CTABr and water
The mass ratio of the material be 1:1350；
4g step 1 gained acid-treated clay is added in S4 in the solution of step S3, continues stirring 1 hour；
1mol/L sulfuric acid is added dropwise in S5 in the solution of step S4, adjusts pH value of solution=10, continues stirring 1 hour；
S6 moves into mixture obtained by step S5 in the hydrothermal reaction kettle for having polytetrafluoroethyllining lining, and 110 DEG C of standing crystallization 12 are small
When；
S7 filters step S6 products therefrom, and with once neutrality is washed to, after the drying 6 hours of 60 DEG C of solid product, at 550 DEG C
4 hours are roasted in air atmosphere up to Al-MCM-41 mesopore molecular sieve.
2. the method according to claim 1 that Al-MCM-41 mesopore molecular sieve is directly synthesized by kaolin or Hanggin 2# soil,
It is characterized by: silicon and aluminum source used is entirely Coaseries kaolin I, Coaseries kaolin II or Hanggin 2#One of soil is not necessarily to volume
Outer other silicon and aluminum sources of addition；Coaseries kaolin I mainly contains kaolinite, 80 meshes point；Coaseries kaolin II mainly contains kaolinite, soft
Diaspore, 80 meshes point；Hanggin 2#It is native mainly to contain attapulgite, illite, chlorite, 200 meshes point.
3. the method according to claim 1 that Al-MCM-41 mesopore molecular sieve is directly synthesized by kaolin or Hanggin 2# soil,
It is characterized by: this method can obtain Patent alum by-product.
4. the method according to claim 1 that Al-MCM-41 mesopore molecular sieve is directly synthesized by kaolin or Hanggin 2# soil,
It is characterized by: accurately controlling in template agent concentration, the mass ratio of the material of CTABr and water is 1:1350, and synthesis temperature is 70 DEG C
And synthesis pH value=10.
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