CN107285337B - A kind of 4A molecular sieve and preparation method thereof - Google Patents

A kind of 4A molecular sieve and preparation method thereof Download PDF

Info

Publication number
CN107285337B
CN107285337B CN201610228003.XA CN201610228003A CN107285337B CN 107285337 B CN107285337 B CN 107285337B CN 201610228003 A CN201610228003 A CN 201610228003A CN 107285337 B CN107285337 B CN 107285337B
Authority
CN
China
Prior art keywords
weight
rich
silicon
molecular sieve
product
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
Application number
CN201610228003.XA
Other languages
Chinese (zh)
Other versions
CN107285337A (en
Inventor
张中华
王宝冬
孙琦
肖永丰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
Original Assignee
Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenhua Group Corp Ltd, National Institute of Clean and Low Carbon Energy filed Critical Shenhua Group Corp Ltd
Priority to CN201610228003.XA priority Critical patent/CN107285337B/en
Publication of CN107285337A publication Critical patent/CN107285337A/en
Application granted granted Critical
Publication of CN107285337B publication Critical patent/CN107285337B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C01B39/14—Type A
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Silicon Compounds (AREA)

Abstract

The present invention relates to coal resources to utilize field, discloses a kind of 4A molecular sieve and preparation method thereof, this method comprises: white clay is reacted with lye, obtains Silicon-rich filtrate；And liquor alumini chloridi is successively crystallized and roasted, it obtains rich aluminium and consolidates product；Then under the conditions of hydrothermal synthesis reaction, the Silicon-rich filtrate is consolidated product with the rich aluminium to contact, and the product obtained after the contact is successively subjected to crystallization and filtering, wherein, the liquor alumini chloridi and the white clay are respectively and successively carry out acid system by the material containing flyash to mention the filtrate obtained after aluminium and filtering and filter residue.Method of the invention can obtain the 4A molecular sieve of high heap density, significantly reduce production cost, and improve the comprehensive utilization ratio of flyash avoiding or reduce the by-product after making full use of flyash acid system to mention aluminium under the premise of the generation of NaCl.

Description

A kind of 4A molecular sieve and preparation method thereof
Technical field
The present invention relates to coal resources to utilize field, and in particular, to a kind of method for preparing 4A molecular sieve and by the party The 4A molecular sieve that method is prepared.
Background technique
The three-dimensional framework shape structural compounds that 4A zeolite is made of silicon oxygen and aluminum-oxygen tetrahedron belong to cubic system, structure cell Center is that a diameter isHole, it is formed by connecting by 8 member rings and 6 similar holes, this 8 member ring knot The free hole diameter being configured to isTherefore referred to as 4A zeolite.It is that a kind of nontoxic, odorless, tasteless and mobility is preferable White powder, adsorption ability is strong, is ideal adsorbent and desiccant.
Flyash is the main waste of firepower electrical plant, and discharge amount increases year by year.The utilization rate of China's flyash is not high, The flyash largely accumulated causes to seriously endanger to environment.In certain coalfields, coal and kaolin association, such coal burning There is very high aluminium content in obtained flyash afterwards, have reached the aluminium content in medium taste bauxite.
The mineral resources such as aluminium oxide are extracted from flyash numerous studies, and wherein acidity extraction aluminium oxide has work The features such as skill is simple, recovery rate is high, is widely used.After this method extracts aluminium oxide, the residue of residue about 56%, usually this is residual The problem of slag is referred to as white clay, therefore the effective use and consumption of white clay are also urgent need to resolve.
The main component of white clay is SiO2And Al2O3And oxide after inorganic mineral calcination etc., wherein SiO2Content It is up to about 70%, is the suitable silicon sources of synthesis zeolite.Meanwhile containing a large amount of Al in the filtrate after acidleach, and with AlCl3There are in filtrate for form.
Current synthesis technology is directly to use AlCl3Molecular sieve is prepared as silicon source, but the reaction is generating molecular sieve Meanwhile a large amount of salt can be generated, when 1 ton of 4A zeolite of generation, while generating 1.2 tons of NaCl.It is shown below:
2SiO2+2AlCl3+ 8NaOH=Na2Si2Al2O8(Na-A)+6NaCl+4H2O
CN103738977A, which is disclosed, a kind of to be prepared the method for 4A type molecular sieve using white clay as raw material and is prepared by this method Product, and specifically disclose that use additional sodium metaaluminate be that the method for silicon source avoids the generation of NaCl with synthetic zeolite.So And the heap density of the 4A molecular sieve synthesized using the method for the prior art is usually within the scope of 0.43-0.72g/mL, and And this method production cost is higher.
Summary of the invention
The heap of the existing 4A molecular sieve being prepared is close when preparing 4A molecular sieve by white clay the purpose of the present invention is overcoming Lower defect is spent, under the premise of avoiding generating a large amount of sodium chloride, provides a kind of 4A molecular sieve for preparing higher heap density Method.
To achieve the goals above, in a first aspect, the present invention provides a kind of method for preparing 4A molecular sieve, this method packet It includes: white clay being reacted with lye, obtains Silicon-rich filtrate；And liquor alumini chloridi is successively crystallized and roasted, it obtains Rich aluminium consolidates product；Then under the conditions of hydrothermal synthesis reaction, the Silicon-rich filtrate is consolidated into product with the rich aluminium and is contacted, and The product obtained after the contact is successively subjected to crystallization and filtering, wherein the liquor alumini chloridi and the white clay are respectively Acid system is successively carried out by the material containing flyash mentions the filtrate obtained after aluminium and filtering and filter residue.
Second aspect, the present invention provide the 4A molecular sieve being prepared by preceding method.
The present invention, which passes through, to be utilized as coal ash for manufacturing for AlCl obtained in white clay process3By-product and acid system mention during aluminium The white clay of acquisition is prepared to obtain 4A molecular sieve.Heap density by the 4A molecular sieve of this method acquisition is higher, and by The static water absorption for the 4A molecular sieve that this method of the invention obtains is higher.
The present inventor by many experiments and the study found that the important factor in order of heap density first is that controlling it Particle diameter distribution prepares the suitable particle size distribution range that existing big partial size also has small particle 4A molecular sieve.To solid-state The crystallization and roasting of silicon source optimize with it is improved on the basis of, when adding silicon source, controlling crystallizing condition is in preferred range When, the heap density for the 4A molecular sieve for enabling to method of the invention to be prepared is higher.
In addition, preceding method of the invention can make full use of fine coal under the premise of avoiding or reducing the generation of NaCl Grey acid system mentions the by-product after aluminium, significantly reduces production cost, and improves the comprehensive utilization ratio of flyash.
For the existing technology for preparing 4A molecular sieve, method of the invention significantly improves industrial reaction kettle The heap density of middle 4A molecular sieve, has the advantages that economic, practical.In addition, it is not necessarily to additional sodium metaaluminate in the present invention, thus into One step reduces production cost.
Preceding method of the invention also has that simple process, output per single reactor be high, low in cost and advantages of environment protection.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the XRD diagram for the 4A molecular sieve being prepared by the method for the embodiment of the present invention 1.
Fig. 2 is the SEM figure for the 4A molecular sieve being prepared by the method for the embodiment of the present invention 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of methods for preparing 4A molecular sieve, this method comprises: by white clay and lye into Row reaction, obtains Silicon-rich filtrate；And liquor alumini chloridi is successively crystallized and roasted, it obtains rich aluminium and consolidates product；Then exist Under the conditions of hydrothermal synthesis reaction, the Silicon-rich filtrate is consolidated into product with the rich aluminium and is contacted, and will be obtained after the contact Product successively carry out crystallization and filtering, wherein the liquor alumini chloridi and the white clay are respectively by the object containing flyash Material successively carries out acid system and mentions the filtrate obtained after aluminium and filtering and filter residue.
Contain a large amount of SiO with reactivity in the white clay2, by the way that with after alkaline reaction and filtering, filtrate is Containing a large amount of Na2SiO3Solution.
Preferably, by the condition that the liquor alumini chloridi crystallizes include: temperature be 100-160 DEG C, more preferably 120-140℃。
Preferably, the condition that products therefrom roasts after the liquor alumini chloridi being crystallized includes: that temperature is 150-400 DEG C, time 10-100min.It is further preferred that products therefrom roasts after the liquor alumini chloridi is crystallized Condition includes: that temperature is 200-350 DEG C, time 20-60min.
The Silicon-rich filtrate is consolidated into the production obtained after product is contacted under the conditions of hydrothermal synthesis reaction with the rich aluminium Object is silicon-aluminum sol.Preferably, in the hydrothermal synthesis reaction, the Silicon-rich filtrate consolidates the dosage of product with the rich aluminium So that containing respectively with Na in the product (i.e. silicon-aluminum sol) obtained after the contact2O、Al2O3And SiO2The molar ratio of meter is 1.2-7:1:1.2-2.5 Na element, Al element and Si element；It is further preferred that containing respectively with Na in the silicon-aluminum sol2O、 Al2O3And SiO2The molar ratio of meter is Na element, Al element and the Si element of 2.4-3.2:1:1.8-2.1；And in the contact In the product obtained afterwards, with Al2O3The Al element and H of meter2The molar ratio of O is 1:40-420；More preferably 1:190-375.
The Silicon-rich filtrate, which consolidates product with the rich aluminium, to be contacted under alkaline condition.Preferably, by the richness It include: temperature is 0-50 DEG C that silicon filtrate and the rich aluminium, which consolidate the condition that product is contacted, time 2-60min；More preferable institute It is 15-40 DEG C that the condition for stating contact, which includes: temperature, time 15-30min.
It preferably, include: temperature by the condition that the product obtained after the contact carries out crystallization is 80-120 DEG C, the time is 6-24h。
The step of acid system mentions aluminium may include: to mix the material containing flyash in acid condition.It is excellent Selection of land, the acid condition are formed by the presence of acid solution, and the hydrogen ion concentration in the acid condition is 1-12mol/L. The acid solution can generate hydrionic solution to be various, such as can be hydrochloric acid, sulfuric acid, nitric acid etc..The present invention is preferred The acid solution is hydrochloric acid and/or sulfuric acid.To the concentration of hydrochloric acid and sulfuric acid, there is no particular limitation, as long as can pass through the hydrochloric acid And/or sulfuric acid to obtain present invention acid condition above-mentioned.
Preferably, by the condition that the material containing flyash mixes in acid condition include: temperature be 60-200 DEG C, time 0.2-2h.
What the white clay and lye carried out react can by by white clay and alkaline matter in the presence of solvent such as water It is reacted to realize.Preferably, by the condition that white clay is reacted with lye include: temperature be 40-200 DEG C, time 5- 150min；More preferably by the condition that white clay is reacted with lye include: temperature be 80-120 DEG C, time 15-60min.
Preferably, the dosage of the lye makes in the Silicon-rich filtrate being prepared element silicon with SiO2The content of meter is 80-160g/L。
Preferably, method of the invention further comprises: before carrying out hydrothermal synthesis reaction, adjusting the Silicon-rich filtrate Basicity be 1-5mol/L；Preferably 2.9-3.3mol/L.
Preferably, containing with the Al of the 15-45 weight % of white clay total weight in the white clay2O3, 40-70 weight % SiO2, 0-5 weight % P2O5, 0-3 weight % K2O, the TiO of CaO, 0-5 weight % of 0-4 weight %2, 0-3 weight % Fe2O3, 0-2 weight % SrO, 0-2 weight % ZrO2, 0-3 weight % Na2The C of O and 0.01-8 weight %.
Preferably, containing with the Al of the 20-55 weight % of flyash total weight in the flyash2O3, 10-45 weight Measure the SiO of %2, 0-5 weight % P2O5, 0-3 weight % K2O, the TiO of CaO, 0-5 weight % of 0-10 weight %2, 0-5 weight Measure the Fe of %2O3, 0-2 weight % SrO, 0-1 weight % ZrO2, 0-2 weight % Na2The C of O and 0.01-30 weight %.
Second aspect, the present invention provides the 4A molecular sieves being prepared by preceding method.
Preferably, the unit volume water absorption rate of the 4A molecular sieve is 230-290g/L, and heap density is 0.8-1.0g/mL, institute Unit volume water absorption rate is stated to calculate by the static water absorption measured by 6287 molecular sieve Static Water determining adsorption method of GB/T It obtains.
The present invention will be described in detail by way of examples below.
In case of no particular description, various raw materials used below are all from commercially available.
Every part of expression 1g below.
Flyash used below is from quasi- Ge Er limited energy company, Shenhua Gangue Power Plant.
The composition of flyash used below and its content (weight %) are shown in the table 1.
The heap density of following molecular sieve uses " 6286 molecular sieve sedimentating density measuring method of GB/T " to measure；Static Water is inhaled Attached rate uses " 6287 molecular sieve Static Water determining adsorption method of GB/T " to measure.
Table 1
Element Al2O3 SiO2 P2O5 K2O CaO TiO2 Fe2O3 Na2O C It is other
Content 51.99 38.83 0.80 0.26 1.79 2.15 0.56 0.48 2.49 0.65
Preparation example 1-3 is used for by coal ash for manufacturing for white clay；Embodiment 1-6 is used to illustrating the of the invention 4A molecular sieve for preparing Method and the 4A molecular sieve being prepared by this method.
Preparation example 1
Flyash in 100 parts of table 1 is placed in the aqueous hydrochloric acid solution of 400 parts of 28 weight % and is reacted, reacted Temperature be 80 DEG C, time 1h；Then the mixture obtained after reaction is filtered, respectively obtains the chlorination as filtrate Aluminum solutions and white clay as filter residue, the composition of the white clay and content (weight %) are shown in the table 2.
Preparation example 2
Flyash in 100 parts of table 1 is placed in the aqueous hydrochloric acid solution of 400 parts of 25 weight % and is reacted, reacted Temperature be 60 DEG C, time 2h；Then the mixture obtained after reaction is filtered, respectively obtains the chlorination as filtrate Aluminum solutions and white clay as filter residue, the composition of the white clay and content (weight %) are shown in the table 2.
Preparation example 3
Flyash in 100 parts of table 1 is placed in the aqueous sulfuric acid of 400 parts of 40 weight % and is reacted, reacted Temperature be 120 DEG C, time 0.8h；Then the mixture obtained after reaction is filtered, is respectively obtained as filtrate Liquor alumini chloridi and white clay as filter residue, the composition of the white clay and content (weight %) are shown in the table 2.
Table 2
Al2O3 SiO2 P2O5 K2O CaO TiO2 TFe2O3 Na2O C It is other
Preparation example 1 27.87 63.66 1.10 0.40 2.03 2.74 0.62 0.52 0.35 0.71
Preparation example 2 27.52 63.98 1.08 0.50 1.98 2.78 0.71 0.49 0.31 0.65
Preparation example 3 27.34 64.02 1.12 0.45 2.09 2.70 0.68 0.56 0.36 0.68
Embodiment 1
50 parts are mixed by white clay, 40 parts of solid NaOH (also referred to as piece alkali), the 200 parts of water that preparation example 1 obtains (quality meter) reacts 30min at 95 DEG C, and filtering obtains element silicon with SiO2The content of meter is the Silicon-rich filtrate of 120g/L.It adopts The liquor alumini chloridi in preparation example 1 crystallize at 120 DEG C with triple effect evaporation, obtains Aluminium chloride hexahydrate；Then The Aluminium chloride hexahydrate is roasted into 60min at 300 DEG C, rich aluminium is obtained and consolidates product.
The Silicon-rich filtrate of 9.5 parts of the present embodiment is mixed with 34 parts of water, and 0.4 part of piece alkali is added, after mixing evenly, is added The rich aluminium of 1 part of the present embodiment consolidates product, is stirred to react 25min at 25 DEG C, obtains silicon-aluminum sol, distinguishes in gained silicon-aluminum sol With Na2O、Al2O3And SiO2Na element, Al element and the Si element and H of meter2The molar ratio of O is 2.8:1:2:280；By institute Silicon-aluminum sol is obtained to continue to stir, the crystallization 10h at 95 DEG C is filtered, and is washed, and it is dry, obtain 4A molecular sieve Z1.
As a result: the XRD diagram of 4A molecular sieve Z1 as shown in Figure 1, be by the crystallinity that XRD interpretation of result obtains Z1 99.2%；And the Na element by containing in terms of oxide 21.22 weight % in 4A molecular sieve Z1 known to XRF analysis, with The Al element of 36.87 weight % of oxide meter, the Si element of in terms of oxide 41.31 weight %, the chlorine element of 0.38 weight %, With Fe2O3Count the Fe element of 0.018 weight %, other objects of the Ca element of in terms of oxide 0.011 weight % and 0.19 weight % Matter；The SEM figure of 4A molecular sieve Z1 is as shown in Figure 2.Byproduct sodium chloride is obtained when preparing 4A molecular sieve Z1 by the method for the present embodiment 0.07 part.The heap density of Z1 is 1.0g/mL, and unit volume water absorption rate is 281.0g/L.
0.72g/mL is usually being not higher than using the heap density that identical measuring method tests commercially available 4A molecular screen primary powder, Generally within the scope of 0.4-0.72g/mL, unit volume water absorption rate is usually within the scope of 50-195g/L.
By comparison as can be seen that the unit volume water absorption rate of the 4A molecular sieve obtained using the method for the present embodiment compares city The unit volume water absorption rate for the 4A molecular screen primary powder sold is substantially higher, and illustrates the product of the 4A molecular sieve obtained by method of the invention Matter is higher compared with the quality of commercial product.
Embodiment 2
(quality meter) is mixed by white clay, 35 parts of solid NaOH, the 200 parts of water that preparation example 2 obtains by 50 parts, in 85 55min is reacted at DEG C, is filtered, is obtained element silicon with SiO2The content of meter is the Silicon-rich filtrate of 117g/L.It will using triple effect evaporation Liquor alumini chloridi progress in preparation example 2 is crystallized at 130 DEG C, obtains Aluminium chloride hexahydrate；Then by the six hydrations chlorine Change aluminium and roast 60min at 200 DEG C, obtains rich aluminium and consolidate product.
The Silicon-rich filtrate of 6.4 parts of the present embodiment is mixed with 24 parts of water, and 0.4 part of piece alkali is added, after mixing evenly, is added The rich aluminium of 1 part of the present embodiment consolidates product, is stirred to react 15min at 30 DEG C, obtains silicon-aluminum sol, distinguishes in gained silicon-aluminum sol With Na2O、Al2O3And SiO2Na element, Al element and the Si element and H of meter2The molar ratio of O is 2.4:1:1.8:190；It will Gained silicon-aluminum sol continues to stir, the crystallization 8h at 110 DEG C, filters, and washs, dry, obtains 4A molecular sieve Z2.
As a result: the XRD diagram and SEM of 4A molecular sieve Z2 schemes Fig. 1 and Fig. 2 with the 4A molecular sieve Z1 in embodiment 1 respectively It is similar, crystallinity 99.1%.0.08 part of byproduct sodium chloride is obtained when preparing 4A molecular sieve Z2 by the method for the present embodiment.The 4A The heap density of molecular sieve is 1.0g/mL, and unit volume water absorption rate is 280.2g/L.
Embodiment 3
(quality meter) is mixed by white clay, 45 parts of solid NaOH, the 200 parts of water that preparation example 3 obtains by 50 parts, in 20min is reacted at 100 DEG C, is filtered, is obtained element silicon with SiO2The content of meter is the Silicon-rich filtrate of 125g/L.It will be in preparation example 3 Liquor alumini chloridi progress crystallized at 140 DEG C, obtain Aluminium chloride hexahydrate；Then by the Aluminium chloride hexahydrate 350 20min is roasted at DEG C, is obtained rich aluminium and is consolidated product.
The Silicon-rich filtrate of 7.5 parts of the present embodiment is mixed with 51 parts of water, and 0.7 part of piece alkali is added, after mixing evenly, is added The rich aluminium of 1 part of the present embodiment consolidates product, is stirred to react 30min under 20, obtains silicon-aluminum sol, in gained silicon-aluminum sol respectively with Na2O、Al2O3And SiO2Na element, Al element and the Si element and H of meter2The molar ratio of O is 3.2:1:2.1:375；By institute Silicon-aluminum sol is obtained to continue to stir, the crystallization 12h at 90 DEG C is filtered, and is washed, and it is dry, obtain 4A molecular sieve Z3.
As a result: the XRD diagram and SEM of 4A molecular sieve Z3 schemes Fig. 1 and Fig. 2 with the 4A molecular sieve Z1 in embodiment 1 respectively It is similar, crystallinity 99.2%.0.08 part of byproduct sodium chloride is obtained when preparing 4A molecular sieve Z3 by the method for the present embodiment.The 4A The heap density of molecular sieve is 1.0g/mL, and unit volume water absorption rate is 279.3g/L.
Embodiment 4
The present embodiment is carried out using method similar to Example 1, except that:
The Silicon-rich filtrate of 4.3 parts of the present embodiment is mixed with 3 parts of water, and 0.01 part of piece alkali is added, after mixing evenly, is added The rich aluminium of 1 part of the present embodiment consolidates product, is stirred to react 25min at 25 DEG C, obtains silicon-aluminum sol, distinguishes in gained silicon-aluminum sol With Na2O、Al2O3And SiO2Na element, Al element and the Si element and H of meter2The molar ratio of O is 1.2:1:1.2:40；By institute Silicon-aluminum sol is obtained to continue to stir, the crystallization 10h at 95 DEG C is filtered, and is washed, and it is dry, obtain 4A molecular sieve Z4.
As a result: the XRD diagram and SEM of 4A molecular sieve Z4 schemes Fig. 1 and Fig. 2 with the 4A molecular sieve Z1 in embodiment 1 respectively It is similar, crystallinity 99.0%.0.08 part of byproduct sodium chloride is obtained when preparing 4A molecular sieve Z4 by the method for the present embodiment.The 4A The heap density of molecular sieve is 0.9g/mL, and unit volume water absorption rate is 252.4g/L.
The product of the present embodiment is compared with commercial goods it is found that the heap density of the product of the present embodiment is higher, and unit bodies Long-pending water absorption rate is higher.
Compare the product of the present embodiment and embodiment 1 it is found that byproduct sodium chloride yield close under the premise of, embodiment 1 Product it is higher compared with the heap density of the product of the present embodiment and unit volume water absorption rate.
Embodiment 5
The present embodiment is carried out using method similar to Example 2, except that:
In the present embodiment, by Aluminium chloride hexahydrate in 400 DEG C of roasting 60min.
Remaining is in the same manner as in Example 2.Obtain 4A molecular sieve Z5.
As a result: the XRD diagram and SEM of 4A molecular sieve Z5 schemes Fig. 1 and Fig. 2 with the 4A molecular sieve Z1 in embodiment 1 respectively It is similar, crystallinity 99.0%.0.11 part of byproduct sodium chloride is obtained when preparing 4A molecular sieve Z5 by the method for the present embodiment.The 4A The heap density of molecular sieve is 0.81g/mL, and unit volume water absorption rate is 241.75g/L.
The product of comparison the present embodiment is with commercial goods it is found that the heap density of the product of the present embodiment is higher.
Compare the product of the present embodiment and embodiment 2 it is found that embodiment 2 product compared with the present embodiment product heap density It is higher, and byproduct sodium chloride yield is lower.
Embodiment 6
The present embodiment is carried out using method similar to Example 5, except that:
In the present embodiment, by Aluminium chloride hexahydrate in 400 DEG C of roasting 20min.
Remaining is in the same manner as in Example 5.Obtain 4A molecular sieve Z6.
As a result: the XRD diagram and SEM of 4A molecular sieve Z6 schemes Fig. 1 and Fig. 2 with the 4A molecular sieve Z1 in embodiment 1 respectively It is similar, crystallinity 99.0%.0.11 part of byproduct sodium chloride is obtained when preparing 4A molecular sieve Z6 by the method for the present embodiment.The 4A The heap density of molecular sieve is 0.8g/mL, and unit volume water absorption rate is 241.38g/L.
The product of comparison the present embodiment is with commercial goods it is found that the heap density of the product of the present embodiment is higher.
Compare the product of the present embodiment and embodiment 2 it is found that embodiment 2 product compared with the present embodiment product heap density It is higher, and the byproduct sodium chloride yield of the product of embodiment 2 is lower.
The product of the present embodiment and embodiment 5 is compared it is found that the unit volume water absorption rate and byproduct sodium chloride of the two produce It measures suitable.
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that:
The Silicon-rich filtrate of 9.5 parts of embodiments 1 and the Aluminium chloride hexahydrate (not being fired) of 4.8 parts of embodiments 1 are stirred Mix reaction.
Remaining is in the same manner as in Example 1.Obtain 4A molecular sieve D-Z1.
As a result: the XRD diagram and SEM of 4A molecular sieve D-Z1 schemes Fig. 1 and figure with the 4A molecular sieve Z1 in embodiment 1 respectively 2 is similar, crystallinity 99.0%.3.5 parts of byproduct sodium chloride are obtained when preparing 4A molecular sieve D-Z1 by the method for this comparative example.It should The heap density of 4A molecular sieve is 0.72g/mL, and unit volume water absorption rate is 198.0g/L.
Comparative example 2
This comparative example is carried out using method similar to Example 1, except that:
The Silicon-rich filtrate of 9.5 parts of embodiments 1 and the Aluminium chloride hexahydrate (not being fired) of 3.2 parts of embodiments 1 are stirred Reaction.
Remaining is in the same manner as in Example 1.Obtain 4A molecular sieve D-Z2.
As a result: the XRD diagram and SEM of 4A molecular sieve D-Z2 schemes Fig. 1 and figure with the 4A molecular sieve Z1 in embodiment 1 respectively 2 is similar, crystallinity 99.0%.3.5 parts of byproduct sodium chloride are obtained when preparing 4A molecular sieve D-Z2 by the method for this comparative example.It should The heap density of 4A molecular sieve is 0.46g/mL, and unit volume water absorption rate is 112.7g/L.
4A points be prepared it can be seen from the result of above-described embodiment and comparative example using method provided by the invention The condition of son sieve is preferable, and heap density is compared with prior art height；And obtained when using method of the invention preparing 4A molecular sieve Sodium chloride by-product is obviously lower compared with the prior art；Moreover, method of the invention is by during using aluminium is mentioned by flyash acid system By-product and avoid additional sodium metaaluminate, to further save production cost.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (22)

1. a kind of method for preparing 4A molecular sieve, which is characterized in that this method comprises: white clay is reacted with lye, obtain Silicon-rich filtrate；And liquor alumini chloridi is successively crystallized and roasted, it obtains rich aluminium and consolidates product；Then in hydrothermal synthesis reaction Under the conditions of, the Silicon-rich filtrate is consolidated into product with the rich aluminium and is contacted, and by the product obtained after the contact successively into Row crystallization and filtering, wherein the liquor alumini chloridi and the white clay respectively successively carry out acid by the material containing flyash Method mentions the filtrate obtained after aluminium and filtering and filter residue.
2. according to the method described in claim 1, including: that temperature is by the condition that the liquor alumini chloridi crystallizes wherein 100-160℃。
3. according to the method described in claim 1, including: 120-140 by the condition that the liquor alumini chloridi crystallizes wherein ℃。
4. according to the method described in claim 1, wherein, products therefrom roasts after the liquor alumini chloridi is crystallized Condition include: temperature be 150-400 DEG C, time 10-100min.
5. according to the method described in claim 1, wherein, products therefrom roasts after the liquor alumini chloridi is crystallized Condition include: temperature be 200-350 DEG C, time 20-60min.
6. method described in any one of -5 according to claim 1, wherein in the hydrothermal synthesis reaction, the Silicon-rich The dosage that filtrate and the rich aluminium consolidate product makes in the product obtained after the contact containing respectively with Na2O、Al2O3And SiO2 The molar ratio of meter is Na element, Al element and the Si element of 1.2-7:1:1.2-2.5；And
In the product obtained after the contact, with Al2O3The Al element and H of meter2The molar ratio of O is 1:40-420.
7. method described in any one of -5 according to claim 1, wherein in the hydrothermal synthesis reaction, the Silicon-rich The dosage that filtrate and the rich aluminium consolidate product makes in the product obtained after the contact containing respectively with Na2O、Al2O3And SiO2 The molar ratio of meter is Na element, Al element and the Si element of 2.4-3.2:1:1.8-2.1；And
In the product obtained after the contact, with Al2O3The Al element and H of meter2The molar ratio of O is 1:190-375.
8. method described in any one of -5 according to claim 1, wherein the Silicon-rich filtrate and the rich aluminium are consolidated product The condition contacted includes: that temperature is 0-50 DEG C, time 2-60min.
9. method described in any one of -5 according to claim 1, wherein the Silicon-rich filtrate and the rich aluminium are consolidated product The condition contacted includes: that temperature is 15-40 DEG C, time 15-30min.
10. method described in -5 kinds of any one according to claim 1, wherein carry out the product obtained after the contact brilliant The condition of change includes: that temperature is 80-120 DEG C, time 6-24h.
11. according to the method described in claim 1, wherein, the step of acid system mentions aluminium includes: by the material containing flyash It is mixed in acid condition.
12. according to the method for claim 11, wherein the acid condition is formed by the presence of acid solution, and the acid Property condition in hydrogen ion concentration be 1-12mol/L.
13. according to the method for claim 11, wherein mix the material containing flyash in acid condition Condition includes: that temperature is 60-200 DEG C, time 0.2-2h.
14. method described in any one of -5 according to claim 1, wherein the condition packet for reacting white clay with lye Include: temperature is 40-200 DEG C, time 5-150min.
15. method described in any one of -5 according to claim 1, wherein the condition packet for reacting white clay with lye Include: temperature is 80-120 DEG C, time 15-60min.
16. method described in any one of -5 according to claim 1, wherein what the dosage of the lye to be prepared Element silicon is in Silicon-rich filtrate with SiO2The content of meter is 80-160g/L.
17. according to the method described in claim 1, wherein, this method further comprises: before carrying out hydrothermal synthesis reaction, The basicity for adjusting the Silicon-rich filtrate is 1-5mol/L.
18. according to the method for claim 17, wherein the basicity for adjusting the Silicon-rich filtrate is 2.9-3.3mol/L.
19. according to the method described in claim 1, wherein, containing in the white clay with the 15-45 weight % of white clay total weight Al2O3, 40-70 weight % SiO2, 0-5 weight % P2O5, 0-3 weight % K2O, CaO, 0-5 weight of 0-4 weight % Measure the TiO of %2, 0-3 weight % Fe2O3, 0-2 weight % SrO, 0-2 weight % ZrO2, 0-3 weight % Na2O and The C of 0.01-8 weight %.
20. according to the method described in claim 1, wherein, the 20-55 weight with flyash total weight is contained in the flyash Measure the Al of %2O3, 10-45 weight % SiO2, 0-5 weight % P2O5, 0-3 weight % K2O, CaO, 0- of 0-10 weight % The TiO of 5 weight %2, 0-5 weight % Fe2O3, 0-2 weight % SrO, 0-1 weight % ZrO2, 0-2 weight % Na2O and The C of 0.01-30 weight %.
21. the 4A molecular sieve that the method as described in any one of claim 1-20 is prepared.
22. 4A molecular sieve according to claim 21, wherein the unit volume water absorption rate of the 4A molecular sieve is 230- 290g/L, heap density are 0.8-1.0g/mL, and the unit volume water absorption rate by 6287 molecular sieve Static Water of GB/T by being adsorbed The static water absorption that measuring method measures is calculated.
CN201610228003.XA 2016-04-13 2016-04-13 A kind of 4A molecular sieve and preparation method thereof Active CN107285337B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610228003.XA CN107285337B (en) 2016-04-13 2016-04-13 A kind of 4A molecular sieve and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610228003.XA CN107285337B (en) 2016-04-13 2016-04-13 A kind of 4A molecular sieve and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107285337A CN107285337A (en) 2017-10-24
CN107285337B true CN107285337B (en) 2019-10-11

Family

ID=60095917

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610228003.XA Active CN107285337B (en) 2016-04-13 2016-04-13 A kind of 4A molecular sieve and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107285337B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109437223A (en) * 2018-11-06 2019-03-08 中国神华能源股份有限公司 It is a kind of to utilize Al-SBA-15 molecular sieve made from white clay and preparation method thereof
CN113144818B (en) * 2021-04-29 2023-05-02 华电宁夏灵武发电有限公司 Fly ash-based carbon dioxide absorption system and fly ash recycling method for absorbing carbon dioxide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101367529A (en) * 2008-09-28 2009-02-18 西安建筑科技大学 Method for synthesis of 4A molecular sieve with coal ash alkali melting method
CN101406825A (en) * 2008-11-07 2009-04-15 中南大学 Method for synthesizing 4A molecular sieve drier using kaoline
CN101445254A (en) * 2008-12-31 2009-06-03 平朔煤炭工业公司 Method for producing 4A molecular sieve

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101367529A (en) * 2008-09-28 2009-02-18 西安建筑科技大学 Method for synthesis of 4A molecular sieve with coal ash alkali melting method
CN101406825A (en) * 2008-11-07 2009-04-15 中南大学 Method for synthesizing 4A molecular sieve drier using kaoline
CN101445254A (en) * 2008-12-31 2009-06-03 平朔煤炭工业公司 Method for producing 4A molecular sieve

Also Published As

Publication number Publication date
CN107285337A (en) 2017-10-24

Similar Documents

Publication Publication Date Title
CN103240050B (en) For the adsorbent of carbon dioxide, its preparation method and carbon dioxide capture module
US6537348B1 (en) Method of adsorptive separation of carbon dioxide
JP6664631B2 (en) Phosphorus adsorbent, method for producing adsorbent, and adsorption method using adsorbent
CN104876253B (en) The processing method of calcium in high-calcium fly ass
CN109207716A (en) A kind of bone coal adds calcium sodium roasting vanadium-extracting method
CN110272299A (en) Coal ash for manufacturing for siliceous fertilizer method
JP5424562B2 (en) Method for producing cesium hydroxide solution
CN104254493A (en) Aluminum silicate and method for producing same
CN106119555B (en) A method of extracting scandium from flyash
WO2013143335A1 (en) Method for extracting aluminium oxide in fly ash by alkaline process
KR102132779B1 (en) Adsorbent for carbon dioxide, method preparing the same and capure module for carbon dioxide
CN111039303B (en) Application of modified M-SAPO-RHO type zeolite molecular sieve as ethylene selective adsorbent
WO2012083677A1 (en) Dust free lithium hydroxide monohydrate and preparation method therefor
CN107285337B (en) A kind of 4A molecular sieve and preparation method thereof
CN102649588A (en) Method for producing iron oxide red by using ferrous sulfate as titanium dioxide byproduct
CN104891549B (en) A kind of be raw material production barium chloride with witherite technique
CN106241873B (en) The preparation method of high-purity vanadium pentoxide
CN108754191A (en) A method of processing bone coal pickle liquor
CN111592014A (en) Method and system device for preparing potassium sulfate, calcium carbonate and ammonium chloride from phosphogypsum
CN109485058A (en) Preparation method of binder-free LSX molecular sieve
CN106215911A (en) A kind of for high-efficiency adsorbent separating CO and preparation method thereof
CN108276246A (en) A kind of method that hexachlorobutadiene is refined
CN113845128A (en) MOR zeolite molecular sieve and preparation method thereof
CN104136372A (en) Process for preparing sodium bicarbonate particles
CN108163871A (en) A kind of low silica-alumina ratio chabasie method of preparation and use

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
CP03 Change of name, title or address

Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22

Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd.

Patentee after: Beijing low carbon clean energy research institute

Address before: 100011 Shenhua building, 22 West Binhe Road, Dongcheng District, Beijing

Patentee before: SHENHUA GROUP Corp.,Ltd.

Patentee before: Beijing low carbon clean energy research institute

CP03 Change of name, title or address