CN108516565A - A method of preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag - Google Patents
A method of preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag Download PDFInfo
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- CN108516565A CN108516565A CN201810472833.6A CN201810472833A CN108516565A CN 108516565 A CN108516565 A CN 108516565A CN 201810472833 A CN201810472833 A CN 201810472833A CN 108516565 A CN108516565 A CN 108516565A
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- calcium powder
- molecular sieve
- type zeolite
- zeolite molecular
- aluminium calcium
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- 239000002893 slag Substances 0.000 title claims abstract description 91
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 72
- 239000010457 zeolite Substances 0.000 title claims abstract description 72
- 239000000843 powder Substances 0.000 title claims abstract description 69
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 56
- 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 56
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 96
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 72
- 238000002386 leaching Methods 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004411 aluminium Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 abstract description 36
- 230000008025 crystallization Effects 0.000 abstract description 36
- 150000003839 salts Chemical class 0.000 abstract description 25
- 239000002253 acid Substances 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract 1
- 238000007725 thermal activation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052605 nesosilicate Inorganic materials 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 125000002370 organoaluminium group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 metals ion Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of methods preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag, the present invention is to react slag as raw material using the aluminium calcium powder generated during aluminium calcium powder production aluminium polychloride, it is leached through persalt, leachate return prepares aluminium polychloride, salt acid leaching slag obtains product of roasting by roasting, and product of roasting is mixed with sodium hydroxide solution, stirred evenly, crystallization is carried out after ageing, is filtered after crystallization, drying obtains P type zeolite molecular sieve.It is characteristic of the invention that making aluminium calcium powder reaction slag structure change using salt Ore Leaching, the impurity that Fe, Ti, Ca etc. influence zeolite crystal growth is effectively removed, make fired slags that can directly prepare P type zeolite molecular sieve, and crystallization time is short, hydrochloric acid leachate is used to prepare aluminium polychloride simultaneously, resource is fully utilized, and is environmentally friendly production technology.P type zeolite molecular sieve by the way of 850 DEG C of thermal activations after crystallization has compared with little crystal grain, and crystallinity is up to 92.20%.
Description
Technical field
The present invention relates to a kind of methods preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag, belong to solid waste
Utilization technology field.
Background technology
Part calcium aluminate powder is had in the dissolving of aluminium calcium powder production aluminium polychloride, polymerization process and other mineral cannot be molten
Solution is press-filtered out the aluminium calcium powder reaction slag generated every year in Chinese aluminium polychloride production process to become industrial residue about
There are 150,000 t.And these aluminium calcium powders reaction slag can only be used as solid waste at present and transfer to correlation after paying certain processing cost
Environmentally friendly processed in units.Processing is not only added significantly to the burden of enterprise in this way, but also there are still the risks of environmental pollution, separately
Outside since these aluminium calcium powders reaction slag also contains a large amount of Al, there is good Al reuses value, if as solid waste
Processing, causes the prodigious wasting of resources.
P type zeolite molecular sieve is a kind of zeolite molecular sieve more early synthesized, has octatomic ring pore passage structure.Its structure size
RespectivelyWithIts unique pore structure provides space restriction effect for the Selective adsorption of gas, together
When due to balancing charge cation presence so that the effective aperture of P type zeolite molecular sieve existsH is removed in left and right2O、NH3Deng
The smaller gas of kinetic diameter, does not adsorb other components, and P type zeolite molecular sieve is to the Ca in aqueous solution in addition2+、Mg2+Deng from
Son has preferable selectivity, these characteristics make P type zeolite molecular sieve have in fields such as washing assisant, water process and adsorbing separations
More wide application.
Silicon ash, sodium aluminate, sodium hydroxide and water are pressed nNa by Ibraheem O.Ali etc.2O：nSiO2：nAl2O3：nH2O=
(1.4~1.6)：(1.4~5.7)：1：125 mixing obtain p-type boiling after being aged 30min at 25 DEG C at 100 DEG C after crystallization 4d
Stone molecular sieve.This method can effectively prepare high-crystallinity P type zeolite, but crystallization time is long, and efficiency of energy utilization is low.
[Ibraheem O.Ali,Said M.El-Sheikh,Tarek M.Salama,et al.Controllable synthesis
of NaP zeolite and its application in calcium adsorption[J].Science China
Materials,2015,58(8):621-633.]
With aluminium oxide, aluminum soluble salt, aluminate in a kind of preparation method of p-zeolite (CN103274427A) patent
With in organo-aluminium alcoholate compound it is one or more be used as silicon source, in Ludox, waterglass and organosilicon acid esters one kind or
It is a variety of to be used as silicon source.Silicon source, silicon source, sodium hydroxide and water are pressed into nNa2O：nSiO2：nAl2O3：nH2O=(3~7)：(2~5)：
1：(50~250) are mixed to form presoma, the Si-Al molecular sieve for having GIS structures are added as crystal seed, the addition of crystal seed is
Al contained by crystal seed2O3Substance amount be presoma in Al2O3The 2~50% of the amount of substance, at 70~190 DEG C, crystallization 4~
168h obtains P type zeolite molecular sieve.This method is prepared for the P type zeolite that relative crystallinity is 99.7%, but to silicon source, silicon source
Quality requirements are high and need to add crystal seed in preparation process, and production cost is higher.
With aluminium oxide, aluminum soluble salt, aluminium in a kind of microwave preparation of p-zeolite (CN106745058A) patent
It is one or more as silicon source in hydrochlorate and organo-aluminium alcoholate compound, with one in Ludox, waterglass and organosilicon acid esters
Kind is a variety of as silicon source.Silicon source, silicon source, sodium hydroxide and water are pressed into nNa2O：nSiO2：nAl2O3：nH2O=(5~20)：(2
~8)：1：(1000~2500) it mixes, 10~120min is stirred at 20~60 DEG C and obtains p-zeolite mother liquor；By p-type molecule
Sieve mother liquor is transferred in microwave reaction kettle, first in 80~140 DEG C of 0.1~12h of crystallization next time, then at 150~200 DEG C it is secondary
Crystallization 0.5~obtain p-zeolite for 24 hours.For this method with microwave heating, it is uniform to be prepared for Lens capsule, opposite to tie
Brilliant high P type zeolite.But it needing secondary synthesis and second of crystallization temperature is higher, energy consumption is larger, and silicon source, silicon source quality requirements are high,
Production cost is higher.
Invention content
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of preparing high-crystallinity p-type using aluminium calcium powder reaction slag
The method of zeolite molecular sieve, this method simple process and low cost, non-secondary pollution.
To achieve the goals above, the present invention provides the following technical solutions：
Aluminium calcium powder reaction slag is added into the hydrochloric acid of a concentration of 6~10mol/L and is leached, is separated by solid-liquid separation, obtains leached mud
And leachate, leached mud is subjected to roasting and obtains product of roasting, product of roasting is added in sodium hydroxide solution and obtains slurries, it is right
Slurries carry out hydro-thermal reaction after being aged, acquisition hydrothermal product is washed, is drying to obtain P type zeolite molecular sieve.
Aluminium calcium powder with nesosilicate structure is reacted slag by technical scheme of the present invention by the way of salt Ore Leaching
It is converted into the silicate mineral with layer structure, then using phyllosilicate as raw material, zeolite point is prepared using hydrothermal synthesis method
Son sieve.
In the inventive solutions, aluminium calcium powder reacts SiO of the slag after salt Ore Leaching in the leached mud of gained2With
Al2O3Molar ratio be 6：1~9:1.SiO in leached mud2With Al2O3Molar ratio in the proportional region, can be obtained after crystallization
To ideal P type zeolite molecular sieve.
Inventor has found that the concentration of hydrochloric acid prepares P type zeolite molecular sieve to the present invention and has a great impact, concentration of hydrochloric acid mistake
Low, aluminium leaching rate is low, product of roasting SiO2With Al2O3The ratio between amount of substance is unable to reach 6:1~9:1, bauxite resource cannot be had
Effect recycles, and ideal P type zeolite molecular sieve is unable to get after crystallization.Concentration of hydrochloric acid is excessively high, also results in the SiO in leached mud2
With Al2O3The ratio between the amount of substance can not be in 6:1~9:Within 1, in addition concentration of hydrochloric acid is excessively high, and it is tight to also result in hydrochloric acid volatilization
Weight, hydrochloric acid loss is high, and equipment corrosion is severe.
Preferred scheme, a concentration of 7~10mol/L of the hydrochloric acid.
As further preferred, a concentration of 8~9mol/L of the hydrochloric acid.
Preferred scheme, the liquid-solid ratio that the hydrochloric acid reacts slag with aluminium calcium powder are 3:1~6:1(mL:g).
Preferred scheme, the hydrochloric acid leachate are returned for the original in aluminium calcium powder production aluminium polychloride technical process
Material.
Inventor has found that liquid-solid ratio is larger to the influence of extraction of foreign metal ion, and liquid-solid ratio is too low, Ca2+、Ti4+、Fe3+
Leaching rate is small, reduces the purity of zeolite molecular sieve, and liquid-solid ratio is excessive, and aluminium mass percent reduces in hydrochloric acid leachate, is unfavorable for
Hydrochloric acid leachate is returned for being used as raw material in aluminium calcium powder production aluminium polychloride technical process；Aluminium polychloride is prepared again,
As a further preference, the liquid-solid ratio that the hydrochloric acid reacts slag with aluminium calcium powder is 4:1:6:1(mL:g).
As further preferably, the liquid-solid ratio that the hydrochloric acid reacts slag with aluminium calcium powder is 5:1(mL:g).
Inventor has found that hydrochloric acid reacts the liquid-solid ratio of slag with aluminium calcium powder 5:Foreign metal ion leaching rate is larger when 1, leaching
Go out liquid to be most suitable for preparing aluminium polychloride.
The present invention uses hydrochloric acid extract technology, first, aluminium calcium powder can be reacted to the nesosilicate thaumatropy stratiform of slag
Structure, second is that part metals ion (mainly Ca2+、Ti4+、Fe3+Deng) it is leached a large amount of active site of generation, be conducive to follow-up
The progress of crystallization in hydrothermal reaction process, and the purity of zeolite is promoted, third, extract technology through the invention, gained leached mud
In SiO2With Al2O3Molar ratio be 6.0~9.0, silica alumina ratio in the range can ensure finally to obtain crystallinity high
P type zeolite molecular sieve, while can also ensure only to form p-zeolite.Fourth, it is of the invention using hydrochloric acid as leachate, so
Leachate can realize that the closed circuit of resource follows as the raw material produced directly as aluminium calcium powder in aluminium polychloride technical process
Loopback is received, and zero-emission is realized！
The temperature of preferred scheme, the leaching is 60~95 DEG C, and the time of the leaching is 2~4h.
The temperature of preferred scheme, the roasting is 600~900 DEG C, and the time of roasting is 2~4h.
As further preferably, the temperature of the roasting is 800~850 DEG C.Inventor's discovery, the temperature of roasting,
Have an impact to the crystallinity of p-zeolite, in the preferred range, the crystallinity highest of gained p-zeolite.
Preferred scheme, the concentration of sodium hydroxide solution are 2~6mol/L.
As a further preference, the concentration of sodium hydroxide solution is 3~4mol/L.
Preferred scheme, the sodium hydroxide solution are 2 with fired slags liquid-solid ratio:1~6:1(L:kg).
As a further preference, the sodium hydroxide solution and fired slags liquid-solid ratio are 3:1~5:1(L:kg).
Preferred scheme, the temperature of the ageing are 20~80 DEG C, time of ageing is 2~for 24 hours.
As a further preference, the temperature of the ageing is 40~60 DEG C, and the time of ageing is 2~6h.
The temperature of preferred scheme, the hydro-thermal reaction is 90~130 DEG C, and the time of hydro-thermal reaction is 12~20h.
As a further preference, the temperature of the hydro-thermal reaction is 100~120 DEG C, time of hydro-thermal reaction is 14~
18h。
In the present invention, crystallinity >=80% of gained P type zeolite molecular sieve.
In the preferred embodiment of the present invention, the crystallinity of gained P type zeolite molecular sieve is 89.42%~92.20%.
Calculate molecular sieve crystallinity according to the following formula in the present invention：
In formula：
Xc- crystallinity
IcThe sum of the intensity of-sample zeolite crystal diffraction maximum
IaThe sum of-zeolite crystal characteristic peak diffracted intensity
It is zeolite molecular sieve crystal characteristic diffraction peak that choose 2 θ, which be 12.5 °, 17.7 °, 21.6 °, 28.2 °, 33.4 °, relatively
Crystallinity is five feature peak intensity the sum of of the sum of the five feature peak intensities of sample than upper zeolite crystal base peak.
Beneficial effects of the present invention are as follows：
The disadvantage long for existing P type zeolite molecular sieve generated time, synthetic method is complicated, synthesis cost is high, the present invention
Slag is reacted as raw material, using salt Ore Leaching, roasting, hydro-thermal crystalline substance using the aluminium calcium powder generated during aluminium calcium powder production aluminium polychloride
Change method prepares P type zeolite molecular sieve.The present invention will be only capable of the aluminium calcium powder reaction slag conversion as Solid state fermentation for high price originally
The product P type zeolite molecular sieve of value, realizing turns waste into wealth, while zero-emission is realized in whole process, has important warp
Agent value and the value of environmental protection.
The present invention uses the nesosilicate thaumatropy layer structure that hydrochloric acid extract technology makes aluminium calcium powder react slag first,
Foreign metal ion (mainly Ca in the slag of aluminium calcium powder reaction simultaneously2+、Ti4+、Fe3+Deng) be leached, generate a large amount of activity
Point, and can make that fired slags directly prepare P type zeolite molecular sieve and crystallization time is short.Additionally by the extract technology of the present invention, institute
Obtain the SiO in leached mud2With Al2O3Molar ratio be 6:1~9:1, silica alumina ratio in the range can ensure finally to obtain
The high P type zeolite molecular sieve of crystallinity, while can also ensure only to form p-zeolite.
Through the layered silicate structure obtained by acid leaching process of the present invention at the SiO obtained in aluminium calcium powder reaction slag2And Al2O3It is past
Into also in crystal structure, it is difficult to be reacted with acid or alkali, the sial species with high reaction activity are converted to after fired.
In crystallization process, hydro-thermal method is still used, this method is simple for process and can quickly prepare the P type zeolite of high-crystallinity point
Son sieve.
Generated leachate in the present invention can be used as and produce aluminium polychloride technical process directly as aluminium calcium powder
In raw material, so that resource is fully used so that whole process realize zero-emission, non-secondary pollution.
In conclusion present invention process is simply controllable, at low cost, flow is short, non-secondary pollution, realizes the reaction of aluminium calcium powder
The recycling of slag has great economic implications and environment protection significance.
Figure of description：
Fig. 1 is the XRD spectrum of 1 gained P type zeolite molecular sieve of embodiment.
Fig. 2 is the XRD spectrum of 2 gained P type zeolite molecular sieve of embodiment.
Fig. 3 is the XRD spectrum of 3 gained P type zeolite molecular sieve of embodiment.
Fig. 4 is the XRD spectrum of 4 gained P type zeolite molecular sieve of embodiment.
Fig. 5 is the XRD spectrum of 1 products therefrom of comparative example.
Fig. 6 is the XRD spectrum of 2 products therefrom of comparative example.
Specific implementation mode：
The preparation method of aluminium calcium powder reaction slag used in following embodiment of the present invention is as follows：It is by 900L mass concentrations
In 31% hydrochloric acid injection reaction tank, 265kg aluminium hydrate powders are added, start stirring, at 100 DEG C, are added after reacting 4h
1300L water adds 350kg aluminium calcium powders, at 85 DEG C, react 2h after filter 135kg moisture content be 26.6% aluminium calcium powder
Slag is reacted, drying aluminium calcium powder reaction dreg chemistry ingredient is as shown in table 1.
Table 1 dries aluminium calcium powder reaction dreg chemistry ingredient (%)
Embodiment 1
It weighs aluminium calcium powder reaction slag 20kg to be placed in reactor, reacts slag liquid-solid ratio (L with aluminium calcium powder by hydrochloric acid:kg)4:1
The hydrochloric acid of a concentration of 10mol/L of 58.72L is added, starts stirring, at 85 DEG C, is filtered, washed after leaching 3h, dries to obtain 10kg
Salt acid leaching slag and 77.6L hydrochloric acid leachates, drying salt acid leaching slag chemical composition are as shown in table 2.Hydrochloric acid leachate is mainly changed
It studies point as shown in table 3.SiO in salt acid leaching slag2With Al2O3The ratio between the amount of substance be 8.9.
Table 2 dries salt acid leaching slag chemical composition (%)
3 hydrochloric acid leachate main chemical compositions (g/L) of table
It weighs salt acid leaching slag 2.2kg to be put into Muffle furnace, controls 630 DEG C of calcination temperature, fired slags are obtained after roasting 2h,
2kg fired slags are placed in reactor, by sodium hydroxide solution and fired slags liquid-solid ratio (L:kg)4:1 addition 8L is a concentration of
The sodium hydroxide solution of 2mol/L, stirs evenly, and at 50 DEG C, is transferred in reaction kettle after being aged 4h, crystallization is carried out, 100
At DEG C, crystallization 16h.It is filtered after crystallization, drying obtains 1.1kgP type zeolite molecular sieves.Such as through X-ray diffraction its XRD spectrum
Shown in Fig. 1, the relative crystallinity for measuring P type zeolite molecular sieve is 80.46%.
77.6L hydrochloric acid leachates obtained by the present embodiment are placed in reactor, by hydrochloric acid leachate and aluminium powder liquid-solid ratio
(L:kg)5:1 is added 15.5kg aluminium powders, and hydrochloric acid leachate and calcium powder liquid-solid ratio (L are pressed after 4h is reacted at 100 DEG C:Kg it is) 5:1
It is added after 15.5kg calcium powders react 2h at 85 DEG C and filters, obtain 83.6L aluminium polychlorides, Al2O3Content is 12.58%, salt
Base degree is 57.08%.Illustrate that the present embodiment gained hydrochloric acid leachate can directly react and is used to prepare aluminium polychloride technique.
Embodiment 2
It weighs aluminium calcium powder reaction slag 15kg to be placed in reactor, reacts slag liquid-solid ratio (L with aluminium calcium powder by hydrochloric acid:kg)5:1
The hydrochloric acid of a concentration of 8mol/L of 55.1L is added, starts stirring, at 85 DEG C, is filtered, washed after leaching 3h, dries to obtain 7.4kg salt
Acid leaching slag and 77.6L hydrochloric acid leachates.SiO in salt acid leaching slag2With Al2O3The ratio between the amount of substance be 8.0.
It takes salt acid leaching slag 3kg to be put into Muffle furnace, controls 800 DEG C of calcination temperature, fired slags are obtained after roasting 2h, it will
2.5kg fired slags are placed in reactor, by sodium hydroxide solution and fired slags liquid-solid ratio (L:kg)4:1 addition 10L is a concentration of
The sodium hydroxide solution of 3mol/L, stirs evenly, and at 50 DEG C, is transferred in reaction kettle after being aged 4h, crystallization is carried out, 100
At DEG C, crystallization 16h.It filtered after crystallization, dry and obtain 1.4kgP type zeolite molecular sieves, such as through X-ray diffraction its XRD spectrum
Shown in Fig. 2, the relative crystallinity for measuring P type zeolite molecular sieve is 89.42%.
Embodiment 3
It weighs aluminium calcium powder reaction slag 20kg to be placed in reactor, reacts slag liquid-solid ratio (L with aluminium calcium powder by hydrochloric acid:kg)5:1
The hydrochloric acid of a concentration of 9mol/L of 73.4L is added, starts stirring, at 85 DEG C, is filtered, washed after leaching 3h, dries to obtain 10.0kg
Salt acid leaching slag and 38.8L hydrochloric acid leachates.SiO in salt acid leaching slag2With Al2O3The ratio between the amount of substance be 8.0.
It takes salt acid leaching slag 2.5kg to be put into Muffle furnace, controls 850 DEG C of calcination temperature, fired slags are obtained after roasting 2h, it will
1.6kg fired slags are placed in reactor, by sodium hydroxide solution and fired slags liquid-solid ratio (L:Kg it is) 4:1 addition 6.4L is a concentration of
The sodium hydroxide solution of 4mol/L, stirs evenly, and at 50 DEG C, is transferred in reaction kettle after being aged 4h, crystallization is carried out, 100
At DEG C, crystallization 16h.It filtered after crystallization, dry and obtain 0.9kgP type zeolite molecular sieves, such as through X-ray diffraction its XRD spectrum
Shown in Fig. 3, the relative crystallinity for measuring P type zeolite molecular sieve is 92.20%.
Embodiment 4
It weighs aluminium calcium powder reaction slag 10kg to be placed in reactor, reacts slag liquid-solid ratio (L with aluminium calcium powder by hydrochloric acid:kg)6:1
The hydrochloric acid of a concentration of 7mol/L of 44.0L is added, starts stirring, at 85 DEG C, is filtered, washed after leaching 3h, dries to obtain 5.0kg salt
Acid leaching slag and 38.8L hydrochloric acid leachates.SiO in salt acid leaching slag2With Al2O3The ratio between the amount of substance be 7.4.
It takes salt acid leaching slag 2.5kg to be put into Muffle furnace, controls 850 DEG C of calcination temperature, fired slags are obtained after roasting 2h, it will
1.6kg fired slags are placed in reactor, by sodium hydroxide solution and fired slags liquid-solid ratio (L:Kg it is) 4:1 addition 6.4L is a concentration of
The sodium hydroxide solution of 6mol/L, stirs evenly, and at 50 DEG C, is transferred in reaction kettle after being aged 4h, crystallization is carried out, 130
At DEG C, crystallization 16h.It filtered after crystallization, dry and obtain 0.9kgP type zeolite molecular sieves, such as through X-ray diffraction its XRD spectrum
Shown in Fig. 4, the relative crystallinity for measuring P type zeolite molecular sieve is 82.35%.
Comparative example 1
This comparative example illustrates, with the experimentation and result of crystallization after the reaction slag roasting of aluminium calcium powder.
With embodiment 3, the difference is that this comparative example reacts slag roasting direct, crystallization with aluminium calcium powder.
It takes aluminium calcium powder reaction slag 2.5kg to be put into Muffle furnace, controls 850 DEG C of calcination temperature, fired slags are obtained after roasting 2h,
1.5kg fired slags are placed in reactor, by sodium hydroxide solution and fired slags liquid-solid ratio (L:Kg it is) 4:1 addition 6L is a concentration of
The sodium hydroxide solution of 4mol/L, stirs evenly, and at 50 DEG C, is transferred in reaction kettle after being aged 4h, crystallization is carried out, 100
At DEG C, crystallization 16h.After crystallization filter, dry obtain 1.2kg products, through its XRD spectrum of X-ray diffraction as shown in figure 5,
The relative crystallinity for measuring P type zeolite molecular sieve is 32.68%.
Comparative example 2
This comparative example illustrates, is roasted after using 3mol/L salt Ore Leachings in hydrochloric acid leaching process, the experimentation of crystallization
And result.
With embodiment 3, the difference is that this comparative example in hydrochloric acid leaching process with 3mol/L salt Ore Leachings.
It weighs aluminium calcium powder reaction slag 10kg to be placed in reactor, reacts slag liquid-solid ratio (L with aluminium calcium powder by hydrochloric acid:kg)5:1
The hydrochloric acid of a concentration of 3mol/L of 36.7L is added, starts stirring, at 85 DEG C, is filtered, washed after leaching 3h, dries to obtain 5.3kg salt
Acid leaching slag and 37.5L hydrochloric acid leachates.
It takes aluminium calcium powder reaction slag 2.5kg to be put into Muffle furnace, controls 850 DEG C of calcination temperature, fired slags are obtained after roasting 2h,
1.5kg fired slags are placed in reactor, by sodium hydroxide solution and fired slags liquid-solid ratio (L:Kg it is) 4:1 addition 6L is a concentration of
The sodium hydroxide solution of 4mol/L, stirs evenly, and at 50 DEG C, is transferred in reaction kettle after being aged 4h, crystallization is carried out, 100
At DEG C, crystallization 16h.After crystallization filter, dry obtain 1.0kg products, through its XRD spectrum of X-ray diffraction as shown in fig. 6,
The relative crystallinity for measuring P type zeolite molecular sieve is 36.42%.
Claims (10)
1. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag, it is characterised in that：Aluminium calcium powder reaction slag is added
Enter into the hydrochloric acid of a concentration of 6~10mol/L and leach, be separated by solid-liquid separation, obtains leached mud and leachate, leached mud is roasted
Product of roasting is obtained, product of roasting is added in sodium hydroxide solution and obtains slurries, it is anti-that hydro-thermal is carried out after being aged to slurries
It answers, acquisition hydrothermal product is washed, is drying to obtain P type zeolite molecular sieve.
2. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：The liquid-solid ratio that the hydrochloric acid reacts slag with aluminium calcium powder is 3:1~6:1(mL:g)；
A concentration of 7~10mol/L of the hydrochloric acid.
3. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：SiO in the leached mud2With Al2O3Molar ratio be 6:1~9:1.
4. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：The hydrochloric acid leachate is returned for the raw material in aluminium calcium powder production aluminium polychloride technical process.
5. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：The temperature of the leaching is 60~95 DEG C, and the time of the leaching is 2~4h.
6. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：The temperature of the roasting is 600~900 DEG C, and the time of roasting is 2~4h.
7. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：The concentration of sodium hydroxide solution is 2~6mol/L.
8. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：The sodium hydroxide solution is 2 with fired slags liquid-solid ratio:1~6:1(L:kg).
9. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature exist
In：The temperature of the ageing is 20~80 DEG C, time of ageing is 2~for 24 hours.
10. a kind of method preparing P type zeolite molecular sieve using aluminium calcium powder reaction slag according to claim 1, feature
It is：The temperature of the hydro-thermal reaction is 90~130 DEG C, and the time of hydro-thermal reaction is 12~20h.
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