CN106082265B - A kind of method with lignite synthesis in solid state ZSM-5 molecular sieve - Google Patents
A kind of method with lignite synthesis in solid state ZSM-5 molecular sieve Download PDFInfo
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- CN106082265B CN106082265B CN201610464271.1A CN201610464271A CN106082265B CN 106082265 B CN106082265 B CN 106082265B CN 201610464271 A CN201610464271 A CN 201610464271A CN 106082265 B CN106082265 B CN 106082265B
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- lignite
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- 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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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of method with 5 molecular sieves of lignite synthesis in solid state ZSM, and by lignite, sodium metasilicate, template and alkali source ground and mixed, in 140 ~ 220 DEG C of 5 ~ 48h of crystallization, reaction product obtains final products by grinding, dissolving, filtering, drying.The present invention is directly used as silicon and aluminum source by the use of lignite, instead of Si, Al chemical reagent synthesis of molecular sieve, acid treatment need not be carried out to it except place's ash content is also without taking sulfonation, nitrification etc. to handle, not only reduces the synthesis cost of 5 molecular sieves of ZSM, and realize the higher value application of lignite.Meanwhile the synthetic route pertains only to the mixing of initial feed, any solvent is not used, synthesis technique is simple, energy-saving and emission-reduction, there is huge prospects for commercial application.
Description
Technical field
The present invention relates to technical field of molecular sieve preparation, and lignite silicon and aluminum source synthesis in solid state molecular sieve is used more particularly to one kind
Method.
Background technology
ZSM-5 molecular sieve be Mobil companies of the U.S. developed the 1970s have two-dimensional channel system, Du Tejiao
Pitch pore passage structure high silicon/aluminium than aluminosilicate zeolite molecular sieve, structure cell composition can be expressed as:{Nan +（H2O）16
[AlnSi96-nO192], n<27 }, silica alumina ratio can be in interior change in a big way, can be from Silicon-rich until total silicon type.ZSM-5 molecular sieve
Basic structural unit be made of 8 five-membered rings, this basic structural unit is coupled to chain structure by common side, i.e.,
Pentasil chains, then surround skeleton structure of zeolite again.The skeleton of ZSM-5 molecular sieve contains two kinds of intersection ducts, and one kind is ten
Yuan of rings straight hole road, aperture are 0.51 × 0.55nm, and another kind is Zigzag shape ten-rings duct, aperture 0.53 ×
0.56nm.ZSM-5 framework of molecular sieve inner frame atom silicon passes through oxygen bridge and skeleton tetrahedral aluminium phase in a manner of tetrahedral coordination
Connection.
ZSM-5 molecular sieve oleophilic drainage, hydrothermal stability is high, has special duct geometric configuration and adjustable sial
Than there is good molecule shape selectivity energy, adjustable acid and stronger anti-carbon performance, therefore it is widely used in stone
Oily chemical industry.Its oil-refining chemical process applied has：Catalytic cracking, lube cut dewaxing, xylene isomerization, toluene discrimination
Change, methanol conversion gasoline processed, methanol-to-olefins reaction etc..At present, the application study for ZSM-5 molecular sieve is still molecule
One of hot spot of research field is sieved, its application field gradually develops to the direction of fine chemistry industry, environmental protection, continues to show huge
Big application potential.
It is a kind of commonplace synthetic method for preparing zeolite using Hydrothermal Synthesiss crystallization method, main cause is former for synthesis
The advantages that material, building-up process are simple, while experimental temperature is not high, and equipment simply waits.But hydrothermal synthesis method needs organic formwork
Agent and water are as solvent.If adding solvent in an experiment, water pollution is not only resulted in, while also there are great safety problem.
If can explore low cost, less energy consumption, pollute small synthetic method, its application value will be more extensive.Thus, solid phase
Synthetic method is come into being, and because it merely relates to the ground and mixed of Solid raw materials, during which need not add any solvent, mixing is completed
It can be directly loadable into reaction kettle and carry out crystallization.Its is easy 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 solution of synthesis in solid state ZSM-5 type zeolite molecular sieves.For example, patent application
Publication No. is CN102627287A, discloses Xiao Fengshou et al. and uses sodium metasilicate, silica gel or amorphous silicon oxide powder as silicon source,
It is ground and mixes with silicon source, source of metal atoms, organic formwork agent and alkalinity regulator, in 80 ~ 180 DEG C of crystallization 1 ~ 8 day, reaction
After product is fully washed with a large amount of deionized waters, in 80 DEG C of dry 12h ZSM-5 molecular sieves derived above, Beta molecular sieves, ZSM-
39 molecular sieves and SOD molecular sieves.Similarly, when 120 ~ 200 DEG C of crystallization at least 4 are small after the additional activated carbon mixing of CN104891520A
Obtained multi-stage porous molecular sieve has the MFI structure of micro porous molecular sieve ZSM-5.But these synthesis in solid state ZSM-5 types zeolite point
The technical solution of son sieve does not utilize method of the raw material containing SiO2 by synthesis in solid state molecular sieve directly.
Through retrieval, synthesis in solid state molecular sieve is directly directly ground as silicon and aluminum source by the use of lignite, it is standby to reduce system with molecular sieve for preparing
The technical solution of cost is not open.
Lignite, also known as bavin coal, how brown or brown-black, is a kind of high-volatile (50% or so), (30% is left for high moisture content
It is right), ash-rich (30% or so), low heat value (3200 kilocalories/kilogram), low ash smelting point, easy-weathering fragmentation, oxidizable spontaneous combustion it is bad
Matter fuel, is the minimum pit coal of degree of coalification.10,753,900,000,000 tons of worldwide coal gross reserves, wherein 2,622,900,000,000 tons of lignite, account for
The 24.4% of world's coal gross reserves.China's lignite resource enriches, and explored lignite reserves is up to 130,000,000,000 tons, accounts for
The 13% of national coal reserves, is mainly distributed on east Inner Mongolia, Central-western Yunnan and Eastern of Heilongjiang Province area.China is to brown
The occupation mode of coal is mostly directly to burn, without the utility value for playing lignite completely, due to natural quality and technical matters
Limitation, in exploitation, included using main problem existing for lignite process：Calorific value is low, and purposes is limited；It is not easy storage transport, pin
It is limited to sell radius；Heat utilization efficiency is low when lignite burns, and dust discharge amount is big, and environmental pollution is serious.How rationally effective use
Simultaneously the problem of its added value becomes current urgent need to resolve is continuously improved in lignite.
Then, the invention discloses a kind of method using lignite synthesis in solid state ZSM-5 zeolite, lignite is made to obtain abundant profit
With.Be conducive to energy-saving and emission-reduction and sustainable development, while utilize lignite synthesis in solid state ZSM-5 molecular sieve, there is larger economy
Interests.
The content of the invention
For the existing technical deficiency for synthesizing ZSM-5 molecular sieve and lignite resource enriches, service efficiency is low, seriously polluted
The problem of, it is described it is an object of the present invention to providing a kind of method for directly utilizing lignite synthesis in solid state ZSM-5 molecular sieve
Method synthesis cost is low, treatment process is simple, crystallization time is short, and reaction speed is fast；Single-autoclave yield rate is high, and production efficiency is high；And make
Standby obtained ZSM-5 molecular sieve crystallinity is high, and physical and chemical performance is excellent.
In order to realize object above and other purposes, the present invention including following technical scheme by realizing：
The invention discloses a kind of method of synthesis in solid state ZSM-5 molecular sieve, by lignite, sodium metasilicate, template and alkali source
Ground and mixed is uniform, in a kettle 140 ~ 220 DEG C of 5 ~ 48h of crystallization, and reaction product is ground, dissolves, filters, drying
To final products.
Brief description of the drawings
Fig. 1 is the XRD spectra of 1 product of example.
Fig. 2 is the XRD spectra of 2 product of example.
Fig. 3 is the XRD spectra of 3 product of example.
Embodiment
Presently preferred embodiments of the present invention is described in detail below in conjunction with the accompanying drawings, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, so as to make a clearer definition of the protection scope of the present invention.
Embodiment 1
1.315g sodium metasilicate is weighed, 0.43g ammonium chlorides, 0.24gTPABr, 1.0g lignite, pours into mortar, grinding mixing two
After ten minutes, which is put into the steel bomb of polytetrafluoroethyllining lining, in 160 DEG C of crystallization 24h, after cooling, instead
Ground thing, dissolving are answered, filters and can obtain final product in 60 DEG C of air dry oven 12 hours of drying.
Attached drawing 1 is the characterization result of the XRD of product, it can be seen that product is typical MFI structure, has preferable crystallization
Degree.
Embodiment 2
1.315g sodium metasilicate is weighed, 0.43g ammonium chlorides, 0.24gTPABr, 1.0g lignite, pours into mortar, grinding mixed 20
After minute, which is put into the steel bomb of polytetrafluoroethyllining lining, in 160 DEG C of crystallization 48h, after cooling, reaction
Thing is ground, dissolve, filter and can obtain final product in 60 DEG C of 12 hours of air dry oven drying.
Attached drawing 2 is the characterization result of the XRD of product, it can be seen that product is typical MFI structure, has preferable crystallization
Degree.
Embodiment 3
1.315g sodium metasilicate is weighed, 0.43g ammonium chlorides, 0.24gTPABr, 0.5g lignite, pours into mortar, grinding mixing two
After ten minutes, which is put into the steel bomb of polytetrafluoroethyllining lining, in 160 DEG C of crystallization 24h, after cooling, instead
Ground thing, dissolving are answered, filters and can obtain final product in 60 DEG C of air dry oven 12 hours of drying.
Attached drawing 3 is the characterization result of the XRD of product, it can be seen that product is typical MFI structure, has preferable crystallization
Degree.
The foregoing is merely the embodiment of the present invention, is not intended to limit the scope of the invention, every to utilize this hair
The equivalent structure or equivalent flow shift that bright specification and accompanying drawing content are made, is directly or indirectly used in other relevant skills
Art field, is included within the scope of the present invention.
Claims (3)
1. a kind of method of synthesis in solid state ZSM-5 molecular sieve, uniform by lignite, sodium metasilicate, template and alkali source ground and mixed,
In 140~220 DEG C of 5~48h of crystallization in reaction kettle, reaction product is ground, dissolves, filter, drying obtains final products；
The lignite needs not move through oxidation, nitrification, sulfonation activation process, it is not required that is handled by deliming；
Lignite, sodium metasilicate, the mass ratio of template and alkali source are 0.38~1：1：0.18：0.32~0.5.
2. method as claimed in claim 1, it is characterised in that the template is 4-propyl bromide, and the alkali source is selected from chlorine
Change ammonium, ammonium fluoride one of which.
3. method as claimed in claim 1, it is characterised in that lignite, sodium metasilicate, template and alkali source milling time are 5~25
Minute.
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| Application Number | Priority Date | Filing Date | Title |
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| 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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| 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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| CN106082265A CN106082265A (en) | 2016-11-09 |
| CN106082265B true 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 |
|---|
| Synthesis of ZSM-5 zeolite from lignite fly ash and rice husk ash;Metta Chareonpanich et al;;《Fuel Processing Technology》;20041231;第85卷;第1623–1634页 * |
| 松木屑与褐煤催化共气化特性实验研究;李少华等;《热力发电》;20150131;第44卷(第1期);第44-48页，第53页 * |
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