CN106082265A - A kind of method of brown coal solid phase synthesis ZSM 5 molecular sieve - Google Patents
A kind of method of brown coal solid phase synthesis ZSM 5 molecular sieve Download PDFInfo
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- CN106082265A CN106082265A CN201610464271.1A CN201610464271A CN106082265A CN 106082265 A CN106082265 A CN 106082265A CN 201610464271 A CN201610464271 A CN 201610464271A CN 106082265 A CN106082265 A CN 106082265A
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- brown coal
- molecular sieve
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- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- 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
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- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A kind of method that the invention discloses brown coal solid phase synthesis ZSM 5 molecular sieve, by brown coal, sodium silicate, template and alkali source ground and mixed, in 140 ~ 220 DEG C of crystallization 5 ~ 48h, product obtains final products through grinding, dissolve, filter, drying.The present invention directly utilizes brown coal as silicon and aluminum source, replace Si, Al chemical reagent synthesis of molecular sieve, need not to its carry out acid treatment except place ash also without taking sulfonation, nitrification etc. to process, not only reduce the synthesis cost of ZSM 5 molecular sieve, and achieve the higher value application of brown coal.Meanwhile, this synthetic route pertains only to the mixing of initial feed, does not uses any solvent, and synthesis technique is simple, and energy-saving and emission-reduction have huge prospects for commercial application.
Description
Technical field
The present invention relates to technical field of molecular sieve preparation, particularly relate to one brown coal silicon and aluminum source solid phase synthesis molecular sieve
Method.
Background technology
ZSM-5 molecular sieve is that Mobil company of the U.S. has two-dimensional channel system, Du Tejiao in what 20 century 70s were developed
The aluminosilicate zeolite molecular sieve of the high silicon/aluminum ratio of fork pore passage structure, structure cell composition can be expressed as: { Nan +(H2O)16
[AlnSi96-nO192], n < 27}, silica alumina ratio can change in a big way, can be from Silicon-rich until total silicon type.ZSM 5 molecular sieve
Basic structural unit be made up of 8 five-membered rings, this basic structural unit is coupled to chain structure by common limit, i.e.
Pentasil chain, surrounds skeleton structure of zeolite the most again.The skeleton of ZSM-5 molecular sieve contains two kinds of intersection ducts, and one is ten
Ring straight hole road, aperture is 0.51 × 0.55nm, and another kind is Zigzag shape ten-ring duct, aperture 0.53 ×
0.56nm.ZSM-5 framework of molecular sieve inner frame atom silicon leads to peroxide bridge and skeleton tetrahedral aluminium phase in tetrahedral coordination mode
Connection.
ZSM-5 molecular sieve oleophilic drainage, hydrothermal stability is high, has special duct geometric configuration and adjustable sial
Ratio, has good molecule shape selectivity energy, adjustable acid and stronger anti-carbon performance, and therefore it is widely used in stone
Oil chemical industry.The oil-refining chemical process of its application has: catalytic cracking, lube cut dewaxing, xylene isomerization, toluene discrimination
Change, methanol converts gasoline processed, methanol-to-olefins reaction etc..Applied research currently for ZSM-5 molecular sieve is still molecule
One of focus of sieve research field, its application gradually develops to the direction of fine chemistry industry, environmental conservation, continues to show huge
Big application potential.
Using Hydrothermal Synthesis crystallization method is commonplace a kind of synthetic method preparing zeolite, and main cause is former for synthesis
Material, building-up process are simple, and experimental temperature is the highest simultaneously, advantage that equipment is simple etc..But hydrothermal synthesis method needs organic formwork
Agent and water are as solvent.If adding solvent in an experiment, not only resulting in water and polluting, there is also great safety problem simultaneously.
If able to explore the synthetic method that low cost, less energy consumption, pollution are little, its using value will be more extensive.Thus, solid phase
Synthetic method is arisen at the historic moment, and because it merely relates to the ground and mixed of Solid raw materials, period need not add any solvent, and mixing completes
Just can be directly loadable in reactor and carry out crystallization.It is simple to operate, has greatly saved the use of clean water resource, high
Raw material availability and product yield, reduce the environmental pollution that brings of waste discharge.
In recent years, it is disclosed by the technical scheme of solid phase synthesis ZSM-5 type zeolite molecular sieve.Such as, patent application
Publication No. is CN102627287A, discloses Xiao Fengshou et al. and uses sodium silicate, silica gel or amorphous silicon oxide powder to be silicon source,
It is ground mixing with aluminum source, source of metal atoms, organic formwork agent and alkalinity regulator, in 80 ~ 180 DEG C of crystallization 1 ~ 8 day, reaction
After product fully washs with a large amount of deionized waters, at 80 DEG C of dry 12h ZSM-5 molecular sieves derived above, Beta molecular sieve, ZSM-
39 molecular sieves and SOD molecular sieve.Similarly, 120 ~ 200 DEG C of crystallization at least 4 hours after the mixing of CN104891520A additional activated carbon
The multi-stage porous molecular sieve obtained has the MFI structure of micro porous molecular sieve ZSM-5.But, these solid phase synthesis ZSM-5 type zeolite divides
The technical scheme of son sieve does not the most directly utilize the method by solid phase synthesis molecular sieve of the raw material containing SiO2.
Through retrieval, directly utilize brown coal and directly grind solid phase synthesis molecular sieve as silicon and aluminum source, standby to reduce system with molecular sieve for preparing
The technical scheme of cost does not disclose.
Brown coal, have another name called bavin coal, how brown or brown-black, are a kind of high-volatile (about 50%), high moisture content (30% left side
Right), ash-rich (about 30%), low heat value (3200 kilocalories/kilogram), low ash smelting point, easy-weathering fragmentation, oxidizable spontaneous combustion bad
Matter fuel, is the pit coal that degree of coalification is minimum.Worldwide coal gross reserves 10,753,900,000,000 tons, wherein 2,622,900,000,000 tons of brown coal, account for
The 24.4% of world's coal gross reserves.China's lignite resource enriches, and explored brown coal reserves is up to 130,000,000,000 tons, accounts for
The 13% of whole nation coal reserves, is mainly distributed on east Inner Mongolia, Central-western Yunnan and Eastern of Heilongjiang Province area.China is to brown
Mostly the occupation mode of coal is directly burning, plays the value of brown coal the most completely, due to natural quality and technical matters
Restriction, include in exploitation, the subject matter that utilizes brown coal process to exist: calorific value is low, and purposes is limited；It is difficult to store transport, pin
Sell radius limited；During brown coal burning, heat utilization efficiency is low, and dust discharge amount is big, and environmental pollution is serious.The most effective use
Brown coal also improve constantly its added value and become the problem needing solution at present badly.
Then, the invention discloses a kind of method utilizing brown coal solid phase synthesis ZSM-5 zeolite, make brown coal obtain abundant profit
With.Be conducive to energy-saving and emission-reduction and sustainable development, utilize brown coal solid phase synthesis ZSM-5 molecular sieve simultaneously, there is bigger economy
Interests.
Summary of the invention
Abundant for the technical deficiency of existing synthesis ZSM-5 molecular sieve and lignite resource, service efficiency is low, seriously polluted
Problem, an object of the present invention is to provide a kind of method directly utilizing brown coal solid phase synthesis ZSM-5 molecular sieve, described
Method synthesizes low cost, technique is simple, crystallization time is short in process, and response speed is fast；Single-autoclave yield rate is high, and production efficiency is high；And system
The standby ZSM-5 molecular sieve degree of crystallinity obtained is high, and physical and chemical performance is excellent.
In order to realize object above and other purposes, the present invention is by including that techniques below scheme realizes:
A kind of method that the invention discloses solid phase synthesis ZSM-5 molecular sieve, grinds brown coal, sodium silicate, template and alkali source
Mix homogeneously, in a kettle. 140 ~ 220 DEG C of crystallization 5 ~ 48h, product is ground, dissolve, filter, dry and obtain
Finished product.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of example 1 product.
Fig. 2 is the XRD spectra of example 2 product.
Fig. 3 is the XRD spectra of example 3 product.
Detailed description of the invention
Below in conjunction with the accompanying drawings presently preferred embodiments of the present invention is described in detail, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, thus protection scope of the present invention is made apparent clear and definite defining.
Embodiment 1
Weigh 1.315g sodium silicate, 0.43g ammonium chloride, 0.24gTPABr, 1.0g brown coal, pour mortar into, grind mixing 20 points
Zhong Hou, puts into this mixture in teflon-lined steel bomb, in 160 DEG C of crystallization 24h, after cooling, reactant
Ground, dissolve, sucking filtration the air dry oven at 60 DEG C are dried 12 hours and i.e. can get final product.
Accompanying drawing 1 is the characterization result of the XRD of product, it can be seen that product is typical MFI structure, has preferably crystallization
Degree.
Embodiment 2
Weigh 1.315g sodium silicate, 0.43g ammonium chloride, 0.24gTPABr, 1.0g brown coal, pour mortar into, grind mixed 20 minutes
After, this mixture is put in teflon-lined steel bomb, in 160 DEG C of crystallization 48h, after cooling, reactant warp
Grinding, dissolving, sucking filtration the air dry oven at 60 DEG C are dried 12 hours and i.e. can get final product.
Accompanying drawing 2 is the characterization result of the XRD of product, it can be seen that product is typical MFI structure, has preferably crystallization
Degree.
Embodiment 3
Weigh 1.315g sodium silicate, 0.43g ammonium chloride, 0.24gTPABr, 0.5g brown coal, pour mortar into, grind mixing 20 points
Zhong Hou, puts into this mixture in teflon-lined steel bomb, in 160 DEG C of crystallization 24h, after cooling, reactant
Ground, dissolve, sucking filtration the air dry oven at 60 DEG C are dried 12 hours and i.e. can get final product.
Accompanying drawing 3 is the characterization result of the XRD of product, it can be seen that product is typical MFI structure, has preferably crystallization
Degree.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every utilize this
Equivalent structure or equivalence flow process that bright description and accompanying drawing content are made convert, or are directly or indirectly used in other relevant skills
Art field, is the most in like manner included in the scope of patent protection of the present invention.
Claims (6)
1. a method for solid phase synthesis ZSM-5 molecular sieve, brown coal, sodium silicate, template and alkali source ground and mixed is uniform,
In a kettle. in 140 ~ 220 DEG C of crystallization 5 ~ 48h, product is ground, dissolving, sucking filtration, drying obtain final products.
2. method as claimed in claim 1, it is characterised in that described brown coal need not move through at oxidation, nitrification, sulfonation activation
Reason, it is not required that process through deliming.
3. as claimed in claim 1 method, it is characterised in that the mass ratio of brown coal, sodium silicate, template and alkali source is 0.38 ~
1:1:0.18:0.32 ~ 0.5.
4. method as claimed in claim 1, it is characterised in that described template is 4-propyl bromide, and described alkali source is selected from chlorine
Change ammonium, ammonium fluoride one of which.
5. method as claimed in claim 1, it is characterised in that brown coal, sodium silicate, template and alkali source milling time are 5 ~ 25
Minute.
6. one kind as arbitrary in right 1 ~ 5 as described in method synthesis molecular sieve, it is characterised in that described molecular sieve has microporous molecular
The MFI structure of sieve ZSM-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610464271.1A CN106082265B (en) | 2016-06-24 | 2016-06-24 | A kind of method with lignite synthesis in solid state ZSM-5 molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610464271.1A CN106082265B (en) | 2016-06-24 | 2016-06-24 | A kind of method with lignite synthesis in solid state ZSM-5 molecular sieve |
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| Publication Number | Publication Date |
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| CN106082265A true CN106082265A (en) | 2016-11-09 |
| CN106082265B CN106082265B (en) | 2018-04-27 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN103979574A (en) * | 2014-06-05 | 2014-08-13 | 郑州大学 | Method for synthesizing molecular sieve by using solid phase |
| CN104891520A (en) * | 2015-06-02 | 2015-09-09 | 中国科学院上海高等研究院 | Method for synthesizing hierarchical-pore molecular sieve by solid phase |
-
2016
- 2016-06-24 CN CN201610464271.1A patent/CN106082265B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN103979574A (en) * | 2014-06-05 | 2014-08-13 | 郑州大学 | Method for synthesizing molecular sieve by using solid phase |
| CN104891520A (en) * | 2015-06-02 | 2015-09-09 | 中国科学院上海高等研究院 | Method for synthesizing hierarchical-pore molecular sieve by solid phase |
Non-Patent Citations (2)
| Title |
|---|
| METTA CHAREONPANICH ET AL;: "Synthesis of ZSM-5 zeolite from lignite fly ash and rice husk ash", 《FUEL PROCESSING TECHNOLOGY》 * |
| 李少华等: "松木屑与褐煤催化共气化特性实验研究", 《热力发电》 * |
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| CN106082265B (en) | 2018-04-27 |
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Granted publication date: 20180427 Termination date: 20190624 |