CN108946754A - SBA-15 mesopore molecular sieve and preparation method and application and flyash produce the method for aluminium oxide and SBA-15 mesopore molecular sieve - Google Patents
SBA-15 mesopore molecular sieve and preparation method and application and flyash produce the method for aluminium oxide and SBA-15 mesopore molecular sieve Download PDFInfo
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- CN108946754A CN108946754A CN201710373424.6A CN201710373424A CN108946754A CN 108946754 A CN108946754 A CN 108946754A CN 201710373424 A CN201710373424 A CN 201710373424A CN 108946754 A CN108946754 A CN 108946754A
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- molecular sieve
- mesopore molecular
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- flyash
- aluminum
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 164
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000010881 fly ash Substances 0.000 title claims abstract description 83
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 57
- 239000011148 porous material Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000003513 alkali Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- 238000003786 synthesis reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000001354 calcination Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000010883 coal ash Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000000547 structure data Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- 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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- C01P2004/01—Particle morphology depicted by an image
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
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Abstract
Field is utilized the present invention relates to flyash acid system residue of aluminum-extracted, the method for disclosing SBA-15 mesopore molecular sieve and its preparation method and application and flyash production aluminium oxide and SBA-15 mesopore molecular sieve.On the basis of the gross weight of the mesopore molecular sieve, which contains the Al of 10~20 weight %2O3, the SiO of 80~90 weight %2.Flyash acid system residue of aluminum-extracted may be implemented, SBA-15 mesopore molecular sieve is prepared, using flyash acid system residue of aluminum-extracted and obtains high added value material.Obtained SBA-15 mesopore molecular sieve also contains Al in composition, and has mesoporous, micropore double-pore structure.
Description
Technical field
Field is utilized the present invention relates to flyash acid system residue of aluminum-extracted, and in particular to flyash acid system residue of aluminum-extracted is made
SBA-15 mesopore molecular sieve, and the method for the SBA-15 mesopore molecular sieve and the application of the SBA-15 mesopore molecular sieve are prepared,
There are also the methods of flyash production aluminium oxide and SBA-15 mesopore molecular sieve.
Background technique
Flyash is one of maximum industrial solid castoff of China's current emissions amount, and annual emissions are up to 300,000,000 tons or more.
The bulk deposition of flyash not only land occupation resource and causes serious harm to natural ecological environment.In addition currently, I
State's energy consumption is still based on coal.With the development of economy, the discharge amount of flyash is in increase trend year by year.By fine coal
Ash is turned waste into wealth, and can not only alleviate influence of the flyash to environment, but also can be realized energy-saving and emission-reduction, is sent out society and harmonious economy
Exhibition is advantageous.
In the practical application of total utilization of PCA, one kind is to be applied to foundation engineering and agricultural as raw material
Field etc., such as the raw material as construction material, soil improvement etc.；Another kind of is by certain process, from flyash
The middle product for extracting high utility value.But flyash is applied in building trade, and the technology content of utility value is not high, without abundant
Available maximization is not achieved in the potential for excavating flyash, therefore, is with the development and application that high value added product is guiding
One direction of total utilization of PCA future development.
Currently, can be using aluminous fly-ash as raw material, using " one step acid extracting of joint removal of impurities " technique extraction and application fine coal
Aluminium oxide in ash, but generate the residue that acid system mentions aluminium again simultaneously, severe handling problems are equally also faced, if mishandling
It then will form new solid waste, form secondary pollution.
" white clay " is commonly called as using the residue that acid system proposes aluminium generation.Using aluminous fly-ash as raw material, 1,000,000 tons of Al of every production2O3
About 1,300,000 tons of white clay will be discharged.Regulation in " the aluminium industry access condition " newly revised for 2012 according to Ministry of Industry and Information, creates and utilizes
The solid waste comprehensive utilization ratio of aluminous fly-ash production alumina system must reach 96% or more.Therefore high-alumina fly is realized
The high-efficiency resource recycling of coal ash residue of aluminum-extracted --- white clay is most important.
But mesopore molecular sieve mostly is prepared by raw material of flyash disclosed in the prior art.And general mesopore molecular sieve is full Si
Molecular sieve, and the hole of only mesoporous scale.
CN103818920A discloses a kind of method for preparing Si-Al ordered mesoporous molecular sieve, wherein includes: with thermoelectricity
The discarded flyash of factory is that raw material abstraction obtains the solution containing silicon and aluminium, and using CTAB as template, second alcohol and water is added in room
The lower rapid synthesis basic products of temperature are placed in calcining in Muffle furnace and remove template, obtain product after cooling；Wherein, the CTAB, water,
The molar ratio of sial total amount is (0.4-0.6): (300-500): (50-60): 1 in ethyl alcohol and solution.It is further open: extraction silicon
Silicon source is that 550-600 DEG C of calcining 1-2h is carried out after mixing flyash and NaOH, grinds and mixes with water after cooling and isolates again
Supernatant is as silicon and aluminum source solution；Then silicon and aluminum source solution is added in CTAB, water, ethyl alcohol and obtains mixed solution, adopted and be adjusted with acid
The pH of mixed solution is 9-10, stirs to get white solid.The method of this method treated coal ash is alkali fusion, and high temperature is needed to forge
It burns, energy consumption is big, and technique is not green；And the method being adjusted with acid obtains mesopore molecular sieve, rather than the method for hydrothermal crystallizing.The hair
The bright structure type without the open mesopore molecular sieve obtained, does not also disclose the structure in the hole having.
CN101381086A discloses a kind of preparation method of Si-MCM-41 mesopore molecular sieve, comprising: 1) flyash is added
The concentrated sulfuric acid is stirred to react 2h at room temperature and obtains the first reaction system；2) be dissolved in water the first reaction system, solution temperature be 85~
90℃；First reaction system produces Al2(SO4)3And impurity, it is centrifugated out filtrate Al2(SO4)3With other impurities and wash residual
Then the NaOH solution of excess 4M is added in filtrate, reacts 30min under 120 DEG C of oil baths, obtains the second reaction system for slag；
3) the second reaction system is centrifugated, filter residue is discarded after washing, collected centrifugate and obtain Na2SiO3Solution；4) suitable template is taken
Agent, after adding ethanol in proper amount and water to dissolve, by Na2SiO3Solution is added thereto, and is stirred 10min, is obtained mixed solution；5) sulfuric acid is used
The pH value of mixed solution is adjusted, until white precipitate is generated in solution, containing the Si-MCM-41 with template points in the white precipitate
Son sieve then proceedes to stirring 1h, stands 1h；6) mixed solution is filtered, obtains the Si-MCM-41 molecule with template
Sieve, and dried under the conditions of 100 DEG C；7) the Si-MCM-41 molecular sieve with template is placed at 550 DEG C and burns up template,
Up to Si-MCM-41 mesopore molecular sieve.Step 1) is first passed through in this method and flyash processing 2) is separated into filtrate Al2
(SO4)3And residue, then filtrate addition NaOH solution is reacted and isolates Na therein again2SiO3Solution divides for synthesizing
Son sieve.And during synthesis of molecular sieve, this method is using sulphur acid for adjusting pH value until generating white precipitate in solution and obtaining
It is not the synthetic method of hydrothermal crystallizing to molecular sieve.As can be seen that this method is by step 1) and 2) obtained filtrate Al2
(SO4)3It is further utilized, without handling residue；And the method being adjusted with acid is made to obtain mesopore molecular sieve.
CN103172080A discloses the preparation method of mesopore molecular sieve MCM-48 a kind of, using single template CTAB, mentions
It takes the effective component in flyash as silicon source, under the action of Ethanol activation, MCM- is synthesized with hydro-thermal method under alkaline medium
48, comprising: 1) mixture that siliceous supernatant, template CAB, dehydrated alcohol and water form is placed in reactor, in 30-40
It is slowly stirred at DEG C until all dissolving, after reacting 2-3h, the pH that mixed liquor is adjusted with sulfuric acid solution is 10-11, continues to stir
2-3h obtains white gels；2) gained white gels are placed in a kettle, controlled at 100-110 DEG C, crystallization
60-72h, after reaction, filtration washing, drying obtain pulverulent solids, and 500 DEG C of roasting 5h obtain MCM-48 sample.The party
Method extract flyash in effective component as silicon source specific method as recorded in embodiment 1: first by flyash with 20%
HCl treatment, and wash to neutral, drying, it is then contacted with NaOH and siliceous supernatant is obtained by filtration.This only uses dilute salt
Acid cleans flyash, de-iron is removed, without reference to the processing method of acid system residue of aluminum-extracted.
CN103861556A discloses the preparation method of fly ash base SBA-15 a kind of, comprising: (1) mixes flyash and alkali
It is melted after conjunction, it is cooling, obtain mixture；(2) distilled water dissolution is added in mixture, it is stand-by to filter to take supernatant, wherein on
Clear liquid is aluminosilicate solution；(3) surfactant P123 is dissolved in distilled water, adjusting pH is acidity, is sufficiently stirred, so
Aging afterwards is filtered, washed, dries；(4) material calcination by step (3) after dry, obtains powdered mesoporous material powder after cooling
Coal ash base SBA-15.The Kong Rongwei 0.6-0.9cm of the mesoporous material disclosed3/ g, specific surface area are 370~810m3/ g,
Aperture is 5-8nm.Wherein flyash takes alkali fusion to handle, and needing high-temperature calcination, energy consumption is high without reference to acid system residue of aluminum-extracted
Processing, and describe in the preparation, do not have to the harsh conditions such as hydro-thermal.
The coal ash for manufacturing of the prior art needs the alkali fusion of high-temperature calcination to react for the method for mesoporous material, and energy consumption is high.For
How treated coal ash acid system residue of aluminum-extracted there is no providing methods for synthesising mesoporous molecular sieve.How flyash acid system is utilized
Residue of aluminum-extracted (" white clay ") produces the mesopore molecular sieve of high added value, and realizes that the waste material of " white clay " is eliminated, and needs suitable side
Method.
Summary of the invention
The problem of how preparing mesopore molecular sieve the purpose of the present invention is to solve flyash acid system residue of aluminum-extracted, provides
SBA-15 mesopore molecular sieve and its preparation method and application and flyash production aluminium oxide and SBA-15 mesopore molecular sieve
Method, containing there is micropore, mesoporous double-pore structure on aluminium oxide and structure in the composition of the SBA-15 mesopore molecular sieve.Jie
Porous molecular sieve can use the synthesis of flyash acid system residue of aluminum-extracted, not only reduce white clay stockpiling, but also realize production high added value
Mesopore molecular sieve improves the utility value of flyash acid system residue of aluminum-extracted or even flyash.
To achieve the goals above, first aspect present invention provides a kind of SBA-15 mesopore molecular sieve, wherein mesoporous with this
On the basis of the gross weight of molecular sieve, which contains the Al of 10~20 weight %2O3, the SiO of 80~90 weight %2。
Preferably, the mesopore molecular sieve contains micropore, and micro pore volume accounts for the 10 of the total pore volume of the mesopore molecular sieve
~20 volume %.
Preferably, mesoporous 0.75~0.82cm of Kong Rongwei of the mesopore molecular sieve3/ g, the micropore of the mesopore molecular sieve
0.25~0.4cm of Kong Rongwei3/g。
Preferably, the specific surface area of the mesopore molecular sieve is 690~870m2/g；The aperture of the mesopore molecular sieve is 6
~10nm, the average particle size particle size of the mesopore molecular sieve are 12~18nm.
Preferably, the SBA-15 mesopore molecular sieve is made by flyash acid system residue of aluminum-extracted.
Second aspect of the present invention provides the preparation method of SBA-15 mesopore molecular sieve of the invention, this method comprises:
(1) flyash acid system residue of aluminum-extracted, alkali and water are mixed and carries out alkali soluble reaction, and obtained product is filtered
Obtain filtrate；
(2) filtrate progress pH is adjusted to acidity, and with polyethylene oxide-polypropylene oxide-polyethylene oxide three
Block copolymer is configured to synthesis mother liquid；
(3) synthesis mother liquid is put into autoclave, hydrothermal crystallizing reaction is carried out under heating, pressurized conditions, is obtained
SBA-15 mesopore molecular sieve.
Preferably, in step (3), hydrothermal crystallizing reaction temperature be 110~130 DEG C, hydrothermal crystallizing reaction pressure be 2~
6MPa, hydrothermal crystallizing time are 24~72h.
Third aspect present invention provides the application of SBA-15 mesopore molecular sieve of the invention in catalysis reaction and absorption.
Fourth aspect present invention provides the method for a kind of flyash production aluminium oxide and SBA-15 mesopore molecular sieve, this method
It include: that flyash progress acid system is mentioned aluminium to obtain flyash acid system residue of aluminum-extracted and aluminium oxide；By flyash acid system residue of aluminum-extracted
SBA-15 mesopore molecular sieve is prepared by means of the present invention.
Through the above technical solutions, the present invention uses flyash acid system residue of aluminum-extracted for raw material, with alkali soluble reaction and hydro-thermal
Crystallization combines, and flyash acid system residue of aluminum-extracted may be implemented, SBA-15 mesopore molecular sieve is prepared, to utilize powder
Coal ash acid system residue of aluminum-extracted simultaneously obtains high added value material.It is simultaneously total silicon group compared to conventional SBA-15 mesopore molecular sieve
At the SBA-15 mesopore molecular sieve that the present invention obtains also contains Al in composition, and has mesoporous, micropore double-pore structure, has
Good application prospect.
Detailed description of the invention
Fig. 1 is the small angle XRD spectra of SBA-15 mesopore molecular sieve provided by the invention；
Fig. 2 is nitrogen adsorption-desorption isotherm figure of SBA-15 mesopore molecular sieve provided by the invention；
Fig. 3 is the graph of pore diameter distribution of SBA-15 mesopore molecular sieve provided by the invention；
Fig. 4 is that the TEM of SBA-15 mesopore molecular sieve provided by the invention schemes；
Fig. 5 is the flow diagram that flyash acid system residue of aluminum-extracted of the invention prepares SBA-15 mesopore molecular sieve.
Specific embodiment
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.
One aspect of the present invention provides a kind of SBA-15 mesopore molecular sieve, wherein on the basis of the gross weight of the mesopore molecular sieve,
The mesopore molecular sieve contains the Al of 10~20 weight %2O3, the SiO of 80~90 weight %2。
For conventional SBA-15 mesopore molecular sieve using ethyl orthosilicate as Material synthesis, it is SiO that group, which is helped,2.Of the invention
Also contain the Al of above-mentioned content in the composition of SBA-15 mesopore molecular sieve2O3.SBA- of the invention can be determined by elemental analysis
The composition of 15 mesopore molecular sieves.Preferably, in SBA-15 mesopore molecular sieve of the invention, Al2O3: SiO2Weight ratio can be
1:(5~8.5).SBA-15 mesopore molecular sieve of the invention with this feature can have better application prospect.Furthermore originally
Also flyash acid system residue of aluminum-extracted is come from, can be containing a small amount of other substances in the SBA-15 mesopore molecular sieve of invention
TiO2、CaO、Fe2O3、K2O, SrO or SO3, but the performance of SBA-15 mesopore molecular sieve is not influenced.
SBA-15 mesopore molecular sieve of the invention can pass through small its crystal structure of angle XRD analysis.Such as the small angle XRD of Fig. 1
Shown in spectrogram, it is 0.8 ° of characteristic diffraction peak for the last one nearby occur in 2 θ, corresponds to (100) crystal face of molecular sieve SBA-15,
Occur two weaker characteristic diffraction peaks between 1.2 °~2 °, (110) and (200) for respectively corresponding molecular sieve SBA-15 are brilliant
Face is the characteristic diffraction peak of typical two-dimentional hexagonal hole road structure, thus proves that molecular sieve of the invention is with SBA-15 points
Son sieves the mesopore molecular sieve of typical framework characteristic, and the SBA-15 mesopore molecular sieve has preferable crystallinity and the degree of order.
Further, SBA-15 mesopore molecular sieve of the invention has micropore, mesoporous double-pore structure.SBA-15 of the invention
Mesopore molecular sieve is through N2Absorption/desorption test, obtained N2Absorption/desorption isothermal curve is as shown in Fig. 2, the hole that BJH is calculated
Diameter distribution map is as shown in Figure 3.Show that this molecular sieve has typical IV type isothermal curve in IUPAC classification from Fig. 2, is mesoporous knot
The characteristic feature of structure.The curve is in relative pressure p/p0There is apparent mutation between=0.4~0.8, be in H1 type hysteresis loop, this is existing
As if as caused by capillary condensation.It can be seen that from the graph of pore diameter distribution of Fig. 3, SBA-15 mesopore molecular sieve of the invention has
The meso-hole structure of high-sequential, uniform pore-size distribution and regular duct.Preferably, the mesopore molecular sieve contains micropore,
Micro pore volume accounts for 10~20 volume % of the total pore volume of the mesopore molecular sieve.It is highly preferred that Jie of the mesopore molecular sieve
Kong Kongrong is 0.75~0.82cm3/ g, the Micropore volume of the mesopore molecular sieve are 0.25~0.4cm3/g.Further preferably,
The specific surface area of the mesopore molecular sieve is 690~870m2/g.According to the classification of IUPAC, hole of the aperture less than 2nm is micropore,
Aperture is mesoporous between 2nm and 50nm.
SBA-15 mesopore molecular sieve of the invention can be with further progress tem observation.As shown in Fig. 4 a, 4b, observe
The channel pore array structure of SBA-15 mesopore molecular sieve.Fig. 4 c, 4d show SBA-15 mesopore molecular sieve of the invention in (100) side
To six side's images and striated image, show SBA-15 mesopore molecular sieve of the invention have typical high-sequential two
Hexagonal phase structure is tieed up, the mesoporous pore size and average particle size particle size of SBA-15 mesopore molecular sieve of the invention can be obtained by TEM figure.It is preferred that
Ground, the aperture of the mesopore molecular sieve are 6~10nm, and the average particle size particle size of the mesopore molecular sieve is 12~17nm.
Preferably, the SBA-15 mesopore molecular sieve is made by flyash acid system residue of aluminum-extracted.
Second aspect of the present invention provides the preparation method of SBA-15 mesopore molecular sieve of the invention, as shown in figure 5, this method
Include:
(1) flyash acid system residue of aluminum-extracted, alkali and water are mixed and carries out alkali soluble reaction, and obtained product is filtered
Obtain filtrate；
(2) filtrate progress pH is adjusted to acidity, and with polyethylene oxide-polypropylene oxide-polyethylene oxide three
Block copolymer is configured to synthesis mother liquid；
(3) synthesis mother liquid is put into autoclave, hydrothermal crystallizing reaction is carried out under heating, pressurized conditions, is obtained
SBA-15 mesopore molecular sieve.
In the present invention, using flyash acid system residue of aluminum-extracted as raw material.The flyash acid system residue of aluminum-extracted, which can be, to be come from
Residue of the flyash of coal-burning power plant after acidity extraction aluminium oxide therein, general composition may include: 12~15 weights
Measure the Al of %2O3, 70~80 weight % SiO2, 0~0.5 weight % SO3, 0~0.5 weight % K2O, 0~0.6 weight %
CaO, 2~6 weight % TiO2, 0~1 weight % Fe2O3, 0~0.1 weight % SrO and 0~5 weight % other
Substance.
In the present invention, the flyash acid system residue of aluminum-extracted passes through XRD analysis, it can be seen that described compared to flyash
The low activities component such as mullite, quartz, anatase is further enriched in flyash acid system residue of aluminum-extracted, and Fe, Ca etc. are acid-soluble miscellaneous
Matter is reduced.
According to the present invention, step (1) by add alkali alkali soluble react can in activating fly ash acid system residue of aluminum-extracted silicon,
Aluminium element, treated coal ash acid system residue of aluminum-extracted obtain the filtrate for being suitble to synthesis SBA-15 mesopore molecular sieve.The flyash acid
As long as each plant demand of method residue of aluminum-extracted, alkali and water is able to satisfy the needs of the alkali soluble reaction, it is preferable that in step (1)
In, the mass ratio of the flyash acid system residue of aluminum-extracted, alkali and water is 100:(60~84): (40~60).
According to the present invention, the condition that alkali soluble is reacted in step (1), which meets to obtain, is suitble to synthesis SBA-15 mesopore molecular sieve
Filtrate.Preferably, alkali soluble reaction temperature is 80~100 DEG C, and the alkali soluble reaction time is 20~40min.
According to the present invention, in step (1) preferably, in the filtrate, the SiO containing 35~55g/L2, 6~10g/L's
Al2O3。
According to the present invention, in step (1) preferably, the alkali is highly basic, preferably sodium hydroxide and/or potassium hydroxide.
According to the present invention, synthesis mother liquid needed for hydrothermal crystallizing reaction of the step (2) for further preparation steps (3).
Preferably, in step (2), the pH adjusts pH=3~5 for making the filtrate.It is preferred that adjust can be by institute by the pH
Show and hydrochloric acid, sulfuric acid or nitric acid are added in filtrate.
In the present invention, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in step (2) (P123,
PEO-PPO-PEO) it is used as the template of synthesis SBA-15 mesopore molecular sieve, can be commercially available, as BASF Corp. of Germany produces
P123.Preferably, relative to 100 parts by weight SiO in the filtrate2, polyethylene oxide-polypropylene oxide-polycyclic oxygen second
The additional amount of alkane triblock copolymer is 95~120 parts by weight.
According to the present invention, the process of preparation described in step (2) can be polyethylene oxide-polypropylene oxide-polycyclic
Oxidative ethane triblock copolymer is added in the filtrate after pH is adjusted, and is stirred 8~12h at 30~40 DEG C, then obtains
The synthesis mother liquid being configured to.
According to the present invention, step (3) carries out hydrothermal crystallizing reaction, prepares SBA-15 by the synthesis mother liquid that step (2) obtains
Molecular sieve.The synthesis mother liquid can be put into closed autoclave, such as be poured into the stainless steel of polytetrafluoroethyllining lining
The hydrothermal crystallizing reaction is carried out in reaction kettle.Under preferable case, hydrothermal crystallizing reaction temperature is 110~130 DEG C, hydrothermal crystallizing
Reaction pressure is 2~6MPa, and the hydrothermal crystallizing time is 24~72h.
In the present invention, the hydrothermal crystallizing can also include that the product that will be obtained successively is filtered, washes after reaction
It washs, drying and calcination, obtains SBA-15 mesopore molecular sieve powder.Wherein colloid deionization can will be obtained by filtration in washing
It is washed to neutrality.Drying can carry out 2~4h in an oven at 90~100 DEG C.Calcining can carry out 4 at 500~600 DEG C
~8h, wherein heating rate can be 3~6 DEG C/min.
In the present invention, combined using alkali soluble reaction-hydrothermal crystallizing reaction, flyash is prepared with above-mentioned for realization
The SBA-15 mesopore molecular sieve of the Nomenclature Composition and Structure of Complexes feature.
Third aspect present invention provides the application of SBA-15 mesopore molecular sieve of the invention in catalysis reaction and absorption.It can
To have broad application prospects in fields such as catalysis, separation, biology and nano materials.
Fourth aspect present invention provides the method for a kind of flyash production aluminium oxide and SBA-15 mesopore molecular sieve, this method
It include: that flyash progress acid system is mentioned aluminium to obtain flyash acid system residue of aluminum-extracted and aluminium oxide；By flyash acid system residue of aluminum-extracted
SBA-15 mesopore molecular sieve is prepared by means of the present invention.
It may be implemented to utilize flyash by above-mentioned process, production obtains aluminium oxide and mesoporous point of SBA-15
Son sieve.
The present invention will be described in detail by way of examples below.
In following embodiment, the crystal structure of molecular sieve obtained is measured by small angle XRD analysis, uses German Bruker
The D8ADVANCE of company, test sweep speed are 0.5 ° -5 °/min；
The pore structure of molecular sieve obtained passes through N2Adsorption method measurement, uses Micromeritics company of the U.S.
2020 physical adsorption appearance of ASAP, adsorbing medium N2；
The mesoporous pore size and average particle size particle size of molecular sieve obtained are measured by TEM, use the JEM of Japanese JEOL company
ARM200F spherical aberration corrects transmission electron microscope, observes after sample is placed on copper mesh ultrasonic disperse in ethanol；
The composition of molecular sieve obtained is measured by X-fluorescence elemental analysis, uses the ZSX of Japanese Rigaku company
PrimusX ray fluorescence spectrometer.
The flyash acid system residue of aluminum-extracted that above embodiments use is changed from Shenhua Zhungeer Energy Co., Ltd
It is as shown in table 1 to learn composition:
Table 1
Embodiment 1
(1) by flyash acid system residue of aluminum-extracted, NaOH and water, it is that 100:60:40 is mixed according to mass ratio, then exists
Alkali soluble is carried out at 95 DEG C and reacts 30min, and the product then obtained is filtered, and is obtained filtrate, is contained in analysis measurement filtrate
The SiO of 35g/L2, the Al of 6g/L2O3；
(2) HCl of 2mol/L is added into filtrate, carries out pH and adjust the pH of filtrate to be 3；Then it is added according to 1L filtrate
The P123 of 33g, continuously stirs 10h at 35 DEG C, and preparation obtains synthesis mother liquid；
(3) synthesis mother liquid is put into the stainless steel cauldron of polytetrafluoroethyllining lining, hydrothermal crystallizing is carried out at 110 DEG C
React 48h；Then product is filtered to obtain colloid, spends ion-cleaning to neutrality, 3h then is dried at 95 DEG C；
It places into and is warming up to 550 DEG C in calcining furnace with 5 DEG C/min and carries out calcining 6h, obtain molecular sieve powder.
Obtained molecular sieve powder is subjected to small angle XRD test, obtained spectrogram is as shown in Figure 1, be wherein 0.8 ° in 2 θ
Nearby there is the characteristic diffraction peak of the last one, correspond to (100) crystal face of molecular sieve SBA-15, occurs two between 1.2 °~2 °
Weaker characteristic diffraction peak respectively corresponds (110) and (200) crystal face of molecular sieve SBA-15, is typical two-dimentional hexagonal hole
The characteristic diffraction peak of road structure shows that the molecular sieve has the material framework characteristic of SBA-15 molecular sieve.
Obtained molecular sieve powder is subjected to N2Absorption/desorption test, obtained N2Absorption/desorption isothermal curve such as Fig. 2 institute
Show, the graph of pore diameter distribution that BJH is calculated is as shown in Figure 3.Obtained pore structure data are shown in Table 2.
Obtained molecular sieve powder is subjected to tem observation, as shown in Figure 4.As shown in Fig. 4 a, 4b, observe that SBA-15 is situated between
The channel pore array structure of porous molecular sieve.Fig. 4 c, 4d show SBA-15 mesopore molecular sieve of the invention in six sides in (100) direction
Image and striated image show that SBA-15 mesopore molecular sieve of the invention has the two-dimentional hexagonal phase of typical high-sequential
Structure can be obtained the mesoporous pore size and average particle size particle size of SBA-15 mesopore molecular sieve by TEM figure, the results are shown in Table 2.
Embodiment 2
(1) by flyash acid system residue of aluminum-extracted, KOH and water, it is that 100:84:40 is mixed according to mass ratio, then exists
Alkali soluble is carried out at 100 DEG C and reacts 40min, and the product then obtained is filtered, and is obtained filtrate, is contained in analysis measurement filtrate
The SiO of 45g/L2, the Al of 10g/L2O3；
(2) HNO of 2mol/L is added into filtrate3, carry out pH and adjust the pH of filtrate to be 5；Then it is added according to 1L filtrate
The P123 of 43g, continuously stirs 10h at 35 DEG C, and preparation obtains synthesis mother liquid；
(3) synthesis mother liquid is put into the stainless steel cauldron of polytetrafluoroethyllining lining, hydrothermal crystallizing is carried out at 110 DEG C
React 48h；Then product is filtered to obtain colloid, spends ion-cleaning to neutrality, 3h then is dried at 95 DEG C；
It places into and is warming up to 550 DEG C in calcining furnace with 5 DEG C/min and carries out calcining 6h, obtain molecular sieve powder.
Obtained molecular sieve powder is subjected to small angle XRD test, shows that the molecular sieve has the material of SBA-15 molecular sieve
Framework characteristic.
Obtained molecular sieve powder is subjected to N2Absorption/desorption test, obtained pore structure data are shown in Table 2.
Obtained molecular sieve powder is subjected to tem observation, the mesoporous pore size and average grain ruler of SBA-15 mesopore molecular sieve
It is very little to the results are shown in Table 2.
Embodiment 3
(1) by flyash acid system residue of aluminum-extracted, NaOH and water, it is that 100:60:40 is mixed according to mass ratio, then exists
Alkali soluble is carried out at 95 DEG C and reacts 30min, and the product then obtained is filtered, and is obtained filtrate, is contained in analysis measurement filtrate
The SiO of 40g/L2, the Al of 8g/L2O3；
(2) H of 2mol/L is added into filtrate2SO4, carry out pH and adjust the pH of filtrate to be 2.4；Then add according to 1L filtrate
The P123 for entering 38g, continuously stirs 10h at 35 DEG C, and preparation obtains synthesis mother liquid；
(3) synthesis mother liquid is put into the stainless steel cauldron of polytetrafluoroethyllining lining, hydrothermal crystallizing is carried out at 110 DEG C
React 48h；Then product is filtered to obtain colloid, spends ion-cleaning to neutrality, 3h then is dried at 95 DEG C；
It places into and is warming up to 550 DEG C in calcining furnace with 5 DEG C/min and carries out calcining 6h, obtain molecular sieve powder.
Obtained molecular sieve powder is subjected to small angle XRD test, shows that the molecular sieve has the material of SBA-15 molecular sieve
Framework characteristic.
Obtained molecular sieve powder is subjected to N2Absorption/desorption test, obtained pore structure data are shown in Table 2.
Obtained molecular sieve powder is subjected to tem observation, the mesoporous pore size and average grain ruler of SBA-15 mesopore molecular sieve
It is very little to the results are shown in Table 2.
Comparative example 1
(1) by flyash acid system residue of aluminum-extracted, NaOH and water, it is that 100:60:40 is mixed according to mass ratio, then exists
Alkali soluble is carried out at 95 DEG C and reacts 30min, and the product then obtained is filtered, and is obtained filtrate, is contained in analysis measurement filtrate
The SiO of 35g/L2, the Al of 6g/L2O3；
(2) P123 of 33g is added according to 1L filtrate, obtains mixed solution；Mixed solution is added in the HCl of 2mol/L to adjust
PH is 10, is unable to get synthesis colloid, can not produce molecular sieve.
Comparative example 2
(1) by flyash acid system residue of aluminum-extracted, NaOH and water, it is that 100:60:40 is mixed according to mass ratio, then exists
Alkali soluble is carried out at 95 DEG C and reacts 30min, and the product then obtained is filtered, and is obtained filtrate, is contained in analysis measurement filtrate
The SiO of 35g/L2, the Al of 6g/L2O3；
(2) P123 of 33g is added according to 1L filtrate, obtains mixed solution；Mixed solution is added in the HCl of 2mol/L to adjust
PH is 3, is sufficiently stirred at 35~40 DEG C, after standing aging for 24 hours in 95 DEG C of baking ovens, is filtered, washed to neutrality, then 95
3h is dried at DEG C；It places into and is warming up to 550 DEG C in calcining furnace with 5 DEG C/min and carries out calcining 6h, obtain molecular sieve powder.
Obtained molecular sieve powder is analyzed, the results are shown in Table 2.
Comparative example 3
(1) flyash acid system residue of aluminum-extracted and NaOH are mixed according to mass ratio for 100:60, is then calcined at 550 DEG C
2h grinds after cooling and mixes with water (flyash acid system residue of aluminum-extracted: mass ratio=100:40 of water).Since to mention aluminium residual for acid system
Slag will form a large amount of hydration SiO during adding the leaching of alkaline sintering pulp water2Gel precipitation not will form supernatant, can only obtain suspension
Liquid；
(2) HCl of 2mol/L is added into suspension, adjusting pH value is 3；Then the P123 of 33g is added according to 1L filtrate,
10h is continuously stirred at 35 DEG C, preparation obtains synthesis mother liquid；
(3) synthesis mother liquid is put into the stainless steel cauldron of polytetrafluoroethyllining lining, hydrothermal crystallizing is carried out at 110 DEG C
React 48h；Then product is filtered to obtain colloid, spends ion-cleaning to neutrality, 3h then is dried at 95 DEG C；
It places into and is warming up to 550 DEG C in calcining furnace with 5 DEG C/min and carries out calcining 6h, obtain molecular sieve powder.
Obtained molecular sieve powder is analyzed, the results are shown in Table 2.
Table 2
| Number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 2 | Comparative example 3 |
| Al2O3, weight % | 10.2 | 13.5 | 15.7 | 9.2 | 0 |
| SiO2, weight % | 85.9 | 82.4 | 80.2 | 84.2 | 82.6 |
| Specific surface area, m2/g | 694.7 | 865.4 | 744.9 | 644.4 | 420.6 |
| Total pore volume, cm3/g | 0.76 | 0.75 | 0.78 | 0.53 | 0.76 |
| Micropore volume, cm3/g | 0.25 | 0.32 | 0.4 | 0.03 | 0.5 |
| Mesoporous Kong Rong, cm3/g | 0.75 | 0.78 | 0.82 | 0.89 | 0.78 |
| Micro pore volume accounting, v% | 12 | 14 | 18 | 10 | 9 |
| Aperture, nm | 6 | 8 | 10 | 8 | 7 |
| Particle size, nm | 12.5 | 15.6 | 16.8 | 57.4 | 89.7 |
Can be seen that the present invention from the data of embodiment and table 2 may be implemented to synthesize using flyash acid system residue of aluminum-extracted
SBA-15 mesopore molecular sieve, SBA-15 mesopore molecular sieve composition contains aluminium oxide, and has mesoporous, micropore diplopore in pore structure
Structure.
The preparation process shown from embodiment can be seen that flyash acid system residue of aluminum-extracted preparation SBA- provided by the invention
Flyash acid system residue of aluminum-extracted is handled to obtain and is suitble to mesoporous point by the method for 15 mesopore molecular sieves using alkali soluble reaction first
The filtrate of son sieve synthesis, then adjusts and is configured to synthesis mother liquid, it is mesoporous to obtain SBA-15 finally by the method for hydrothermal crystallizing
Molecular sieve, alkali soluble reaction and hydrothermal crystallizing reaction, which are combined to realize to obtain, has above-mentioned composition characteristic and double-pore structure
SBA-15 mesopore molecular sieve.
It the use of alkali soluble reaction bonded prior art tune filtrate is alkalinity in comparative example 1, rather than hydrothermal crystallizing reacts, no
Mesopore molecular sieve can be synthesized.
The use of alkali soluble reaction bonded prior art tune filtrate is acidity, but stand aging at 95 DEG C in comparative example 2, closes
Do not have the pore structure of SBA-15 mesopore molecular sieve of the invention at the mesopore molecular sieve gone out.
It in comparative example 3, is reacted using alkali fusion reaction bonded hydrothermal crystallizing, composition is without aerobic in obtained mesopore molecular sieve
Change aluminium, and cannot also have the SBA-15 mesopore molecular sieve of pore structure of the invention.
Further, using method provided by the invention, it can handle flyash and utilized to obtain aluminium oxide and SBA-
15 mesopore molecular sieves.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of SBA-15 mesopore molecular sieve, which is characterized in that on the basis of the gross weight of the mesopore molecular sieve, the mesopore molecular sieve
Al containing 10~20 weight %2O3, the SiO of 80~90 weight %2。
2. SBA-15 mesopore molecular sieve according to claim 1, wherein the mesopore molecular sieve contains micropore, porous body
Product accounts for 10~20 volume % of the total pore volume of the mesopore molecular sieve.
3. SBA-15 mesopore molecular sieve according to claim 1 or 2, wherein the mesoporous Kong Rongwei of the mesopore molecular sieve
0.75~0.82cm3/ g, the Micropore volume of the mesopore molecular sieve are 0.25~0.4cm3/g。
4. SBA-15 mesopore molecular sieve described in any one of -3 according to claim 1, wherein the ratio of the mesopore molecular sieve
Surface area is 690~870m2/g；The aperture of the mesopore molecular sieve is 6~10nm, the average grain ruler of the mesopore molecular sieve
Very little is 12~18nm.
5. SBA-15 mesopore molecular sieve described in any one of -4 according to claim 1, wherein the SBA-15 mesoporous molecular
Sieve is made by flyash acid system residue of aluminum-extracted.
6. the preparation method of SBA-15 mesopore molecular sieve described in any one of claim 1-5, this method comprises:
(1) flyash acid system residue of aluminum-extracted, alkali and water are mixed and carries out alkali soluble reaction, and obtained product is filtered to obtain
Filtrate；
(2) filtrate progress pH is adjusted to acidity, and with polyethylene oxide-polypropylene oxide-polyethylene oxide three block
Copolymer is configured to synthesis mother liquid；
(3) synthesis mother liquid is put into autoclave, hydrothermal crystallizing reaction is carried out under heating, pressurized conditions, obtains SBA-
15 mesopore molecular sieves.
7. according to the method described in claim 6, wherein, in step (1), the flyash acid system residue of aluminum-extracted, alkali and water
Mass ratio be 100:(60~84): (40~60)；
Preferably, the alkali is highly basic, preferably sodium hydroxide and/or potassium hydroxide；
Preferably, alkali soluble reaction temperature is 80~100 DEG C, and the alkali soluble reaction time is 20~40min；
Preferably, in the filtrate, the SiO containing 35~55g/L2, the Al of 6~10g/L2O3。
8. method according to claim 6 or 7, wherein in step (2), the pH adjusts the pH=3 for making the filtrate
~5；
Preferably, relative to 100 parts by weight SiO in the filtrate2, polyethylene oxide-polypropylene oxide-polyethylene oxide three
The additional amount of block copolymer is 95~120 parts by weight.
9. method according to claim 6 or 7, wherein in step (3), hydrothermal crystallizing reaction temperature is 110~130
DEG C, hydrothermal crystallizing reaction pressure is 2~6MPa, and the hydrothermal crystallizing time is 24~72h.
10. application of the SBA-15 mesopore molecular sieve described in any one of claim 1-5 in catalysis reaction and absorption.
11. a kind of method of flyash production aluminium oxide and SBA-15 mesopore molecular sieve, this method comprises: flyash is carried out acid
Method mentions aluminium and obtains flyash acid system residue of aluminum-extracted and aluminium oxide；By flyash acid system residue of aluminum-extracted by appointing in claim 6-9
SBA-15 mesopore molecular sieve is prepared in method described in meaning one.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021014513A1 (en) * | 2019-07-19 | 2021-01-28 | 株式会社環境浄化センター | Production method relating to industrial mass-production of high-purity artificial zeolite |
| WO2021129760A1 (en) | 2019-12-25 | 2021-07-01 | 中国石油化工股份有限公司 | Dlm-1 molecular sieve, manufacturing method therefor, and use thereof |
| CN114130363A (en) * | 2021-11-08 | 2022-03-04 | 中国科学院山西煤炭化学研究所 | Preparation of mesoporous SiO from coal ash and aluminium extraction slag2Process for foam-based solid amine adsorbents |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503202A (en) * | 2009-02-11 | 2009-08-12 | 陕西理工学院 | Technique for hydro-thermal synthesis of high purity zeolite and fly ash zeolite adsorbing agent from fly ash |
| CN102963903A (en) * | 2012-11-30 | 2013-03-13 | 北京交通大学 | Method for preparing P1-type zeolite |
| CN103861556A (en) * | 2012-12-18 | 2014-06-18 | 同济大学 | Mesoporous material preparation method using fly ash |
| CN104030311A (en) * | 2014-06-27 | 2014-09-10 | 周青 | Method for preparing micron-scaled analcite |
| CN105967201A (en) * | 2016-06-23 | 2016-09-28 | 中国神华能源股份有限公司 | Method for producing P-type zeolite from fly ash acid sludge |
| CN106587099A (en) * | 2016-12-01 | 2017-04-26 | 神华集团有限责任公司 | Method for preparing sodalite and ZSM-5 molecular sieve from fly ash acid process aluminum extraction residue and fly ash utilization method |
-
2017
- 2017-05-24 CN CN201710373424.6A patent/CN108946754B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503202A (en) * | 2009-02-11 | 2009-08-12 | 陕西理工学院 | Technique for hydro-thermal synthesis of high purity zeolite and fly ash zeolite adsorbing agent from fly ash |
| CN102963903A (en) * | 2012-11-30 | 2013-03-13 | 北京交通大学 | Method for preparing P1-type zeolite |
| CN103861556A (en) * | 2012-12-18 | 2014-06-18 | 同济大学 | Mesoporous material preparation method using fly ash |
| CN104030311A (en) * | 2014-06-27 | 2014-09-10 | 周青 | Method for preparing micron-scaled analcite |
| CN105967201A (en) * | 2016-06-23 | 2016-09-28 | 中国神华能源股份有限公司 | Method for producing P-type zeolite from fly ash acid sludge |
| CN106587099A (en) * | 2016-12-01 | 2017-04-26 | 神华集团有限责任公司 | Method for preparing sodalite and ZSM-5 molecular sieve from fly ash acid process aluminum extraction residue and fly ash utilization method |
Non-Patent Citations (4)
| Title |
|---|
| C.G. SONWANE ET AL.: "A note on micro- and mesopores in the walls of SBA-15 and hysteresis of adsorption isotherms", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| G. MUTHU KUMARAN ET AL.: "Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| PALLAVI BHANGE ET AL.: "Direct synthesis of well-ordered mesoporous Al-SBA-15 and its correlation with the catalytic activity", 《APPLIED CATALYSIS A: GENERAL》 * |
| 孙尧等: "Al-Z-SBA-15复合分子筛的制备及催化性能", 《硅酸盐学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021014513A1 (en) * | 2019-07-19 | 2021-01-28 | 株式会社環境浄化センター | Production method relating to industrial mass-production of high-purity artificial zeolite |
| JP6866004B1 (en) * | 2019-07-19 | 2021-04-28 | 満 久保田 | Manufacturing method for industrial mass production of high-purity artificial zeolite |
| WO2021129760A1 (en) | 2019-12-25 | 2021-07-01 | 中国石油化工股份有限公司 | Dlm-1 molecular sieve, manufacturing method therefor, and use thereof |
| CN114130363A (en) * | 2021-11-08 | 2022-03-04 | 中国科学院山西煤炭化学研究所 | Preparation of mesoporous SiO from coal ash and aluminium extraction slag2Process for foam-based solid amine adsorbents |
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