CN104176744A - Method for preparing total potassium W type molecular sieve by activating potassium feldspar via KOH sub-molten salt - Google Patents
Method for preparing total potassium W type molecular sieve by activating potassium feldspar via KOH sub-molten salt Download PDFInfo
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- CN104176744A CN104176744A CN201410424180.6A CN201410424180A CN104176744A CN 104176744 A CN104176744 A CN 104176744A CN 201410424180 A CN201410424180 A CN 201410424180A CN 104176744 A CN104176744 A CN 104176744A
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- Prior art keywords
- potassium
- koh
- molecular sieve
- type molecular
- felspar sand
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Links
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000011591 potassium Substances 0.000 title claims abstract description 100
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 100
- 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
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000003839 salts Chemical class 0.000 title claims abstract description 16
- 230000003213 activating effect Effects 0.000 title abstract description 3
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 title abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 230000004913 activation Effects 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012452 mother liquor Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 10
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000004576 sand Substances 0.000 claims description 53
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 11
- 230000037452 priming Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 3
- 229910052682 stishovite Inorganic materials 0.000 abstract 3
- 229910052905 tridymite Inorganic materials 0.000 abstract 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910001679 gibbsite Inorganic materials 0.000 abstract 1
- 239000012265 solid product Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 123
- 101100041681 Takifugu rubripes sand gene Proteins 0.000 description 50
- 239000000047 product Substances 0.000 description 31
- 229910021536 Zeolite Inorganic materials 0.000 description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 18
- 239000010457 zeolite Substances 0.000 description 18
- 239000003513 alkali Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 238000004064 recycling Methods 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000010413 mother solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000003337 fertilizer Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 4A type Chemical compound 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 208000019025 Hypokalemia Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 208000007645 potassium deficiency Diseases 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for preparing a total potassium W type molecular sieve by activating potassium feldspar via KOH sub-molten salt. The method comprises the following steps of uniformly mixing KOH, potassium feldspar and water in a reactor and then placing in an oil bath pan at 140-175 DEG C to carry out reaction for 5-8h; replenishing one or several of Al(OH)3, white carbon black and water to the activated system to ensure that the components in the solution accord with the mole ratios that SiO2: Al2O3=(5-20): 1, K2O/SiO2=1-3.0. and H2O: SiO2=(40-120): 1; ageing at 25-70 DEG C for 2-15h; and crystallizing at 90-180 DEG C for 8-72h and then washing and drying the filter cake to obtain a solid product W type molecular sieve. According to the method, the problem that the potassium feldspar is high in activation temperature, large in energy consumption and complicated in operation, the W type molecular sieve with high application value is obtained and the cyclic utilization of the mother liquor is realized.
Description
Technical field
The present invention relates to the sub-fused salt activation of KOH potassium felspar sand and produce the method for full potassium W type molecular sieve, the mother liquor in the crystallization process of recycle and reuse simultaneously, products molecule sieve can be used as ion-exchanger, sorbent material and slow-release potassium fertilizer and uses.
Background technology
Potassium is one of necessary macroelement of crop growth, but not water-soluble potassium resource can not be absorbed and used by plants.China's potassium deficiency cultivated area increases day by day in recent years, due to economy, technical reason, all needs every year a large amount of potash fertilizer of import.China's water-soluble potassium resource is seriously deficient, and water-insoluble potassium resource reserves taking potassium felspar sand as representative are extremely abundant.Therefore, develop non-solubility potassium resource to make up the situation of China's water-soluble potassium shortage of resources, significant.China just starts potassium rich rock and proposes the research of potassium the latter stage fifties from twentieth century, successively carried out tens of kinds of technical studies, but due to technology and economic benefit reason, realized industrialization and still have limitation.
In potassium felspar sand, remove containing K
2outside O, still containing a certain amount of Al
2o
3, SiO
2, manufacture potash fertilizer research and show, although that potassium felspar sand is manufactured separately potash fertilizer is technical feasible, unreasonable economically.Reasonably utilizing silico-aluminate resource is wherein another important research topic, is wherein a comparatively desirable selection taking silico-aluminate as raw material synthesis zeolite.At present, the zeolite molecular sieves such as 4A type, MCM type, AlMCM-41 type, 13X have successfully been prepared both at home and abroad taking potassium felspar sand as raw material.Because potassium felspar sand is the potassium silicate that contains of a kind of shape structure, its structure is extremely stable, under normal temperature and pressure, except hydrofluoric acid, is not decomposed by any acid, alkali.Therefore, in synthesis zeolite technique, first potassium felspar sand will be activated, this step is most important.When potassium felspar sand to 1800 DEG C, could change the ore structure of potassium felspar sand and decomposite Element Potassium, the decomposition reaction of potassium felspar sand is only being added suitable auxiliary agents as CaCl conventionally
2-NaCl, K
2cO
3deng just can carry out, and activation temperature is high, power consumption is large.The present invention proposes to adopt sub-molten salt method activation potassium felspar sand thus, can effectively reduce activation temperature.
Chinese Academy Of Sciences Process Engineering Research Institute is devoted to the research and development of sub-fused salt platform technology for many years, and sub-fused-salt medium is applied to and processes the difficult mineral wealth of multiple low grade, has obtained impressive progress.Compare conventional reaction medium, sub-fused-salt medium has the character such as high reaction activity, low-steam pressure and good mobility.At present, sub-fused-salt medium success for the treatment of reason Bayer process red mud, leach Low-grade Refractory Tantalum-Niobium Ore, decompose vanadium in ilmenite, stripping v-bearing steel slag etc.With the potassium felspar sand of processing mineral wealth as low-grade refractory, adopt sub-fused-salt medium to be activated and also belong to feasible.
Potassium type molecular sieve is because potassium content is high, and the performance of its ion-exchange receives much concern, and for example potassium type zeolite has broad application prospects in slow-release potassium fertilizer; Potassium type zeolite has potassium ion memory function, after ion-exchanged, demonstrates good characteristic in potassium from sea water.Wherein W type molecular sieve has good adsorption selectivity to potassium ion.In recent years, the people such as Jin Hou and Jun sheng Yuan utilizes chemical feedstocks to successfully synthesize the W molecular sieve that loading capacity is 54.9mg/g.The people such as G.Belardi have studied the method by the synthetic W type molecular sieve containing potassium of flyash.Steven G.Thoma and Tina M.Nenoff are using organic cation and not using in organic cations situation respectively, taking organometallic silicon and aluminium as raw material, have successfully prepared W molecular sieve by hydrothermal method.The people such as the seat Big Dipper of China Environmental Science Research Institute successfully prepare w-type zeolite molecular sieve taking Hanggin 2# soil as raw material by several different methods.The people such as Du Cuihua utilize KOH alkali fusion activation potassium felspar sand successfully to prepare W molecular sieve.(article " KOH alkali fusion activation potassium felspar sand produce full potassium W type molecular sieve " article numbering: 1000-985X (2014) 01-0153-10 " artificial lens journal ") but still Shortcomings of its technique: potassium felspar sand activation temperature is up to 500 DEG C, energy consumption is large, increases process costs and operability difficulty.Simultaneous reactions is pure solid state reaction, and system poor fluidity is processed relative complex to the system after activation.As can be seen here, mainly still synthesize W molecular sieve with chemical feedstocks both at home and abroad at present, or realize synthetic taking mineral as raw material high temperature alkali fuse.To sum up the present invention proposes to adopt the sub-fused-salt medium activation of KOH potassium felspar sand to prepare full potassium W type molecular sieve.
The present invention will utilize the distinctive advantage of sub-fused-salt medium, effectively reduce potassium felspar sand activation temperature, and energy efficient, without generation of waste materials, realizes prepared using optimization.The full potassium W of product type molecular sieve is widely used simultaneously, can be used as the uses such as ion-exchanger, sorbent material, catalyzer, slow-release potassium fertilizer, has important value.
Summary of the invention
The present invention is successfully taking potassium felspar sand as raw material, the sub-fused salt of KOH is activated media, adopt the sub-fused salt technology activation of KOH potassium felspar sand, prepare full potassium type W molecular sieve, this technique has replaced traditional fused salt technology with the sub-fused salt technology of KOH, determined that the alkali ore deposit in reactivation process is than scope, activation temperature scope and various synthesis condition scope have realized Recycling Mother Solution simultaneously.Because sub-fused-salt medium has high reaction activity, low-steam pressure, the feature that boiling point is high, so can realize high dense high-temperature pressure in reactor in the time of activation potassium felspar sand, gets off activation temperature adjustment, saves the energy.It is wide that this invention has raw material sources, and synthesis technique is simple to operation, and process energy consumption is low, in the potassium resource while making full use of in potassium felspar sand, rationally utilized silicate wherein, without liquid and waste slag produced.
Technical scheme of the present invention is:
The sub-fused salt activation of KOH potassium felspar sand is produced a method for full potassium W type molecular sieve, comprises the steps:
KOH, potassium felspar sand and water are mixed in reactor, wherein, taking KOH mass concentration in the system of water and KOH as 70～80%, mass ratio KOH: potassium felspar sand=3:1; Be placed in again 140-175 DEG C of oil bath pan, stir condensing reflux and carry out sub-fused salt priming reaction 5-8h; System after activation is by adding Al (OH)
3, one or more in white carbon black and water, the composition and ratio in solution is met: mol ratio SiO
2: Al
2o
3=5-20:1, K
2o/SiO
2=1-3.0, H
2o:SiO
2=40-120:1; Wherein, when KOH calculates, need be converted into K
2the molar weight meter of O; Then aging 2-15h at 25-70 DEG C; System after aging is put into airtight crystallizing kettle, crystallization 8-72h at 90-180 DEG C, and the crystallization mother liquor after crystallization mixture filters is that next cycle recycles, filter cake is through washing, the dry solid phase prod W molecular sieve that obtains.
Beneficial effect of the present invention:
The present invention is taking sub-fused salt as activated media, alleviated that potassium felspar sand activation temperature is high for a long time, and power consumption is large, the problem of complex operation.Previously for the use of large, the widespread potassium felspar sand resource of China's reserves has been opened up new road.The costly W type molecular sieve that is simultaneously applied, has realized mother liquid recycling.
Above-mentioned beneficial effect is embodied in:
(1) taking potassium felspar sand as raw material, it is with low cost, and the comprehensive utilization of potassium felspar sand resource fully, has been realized in source.
(2) with the sub-fused-salt medium activation of KOH potassium felspar sand, because sub-fused-salt medium has high reaction activity, low-steam pressure, the feature that boiling point is high, so can realize high dense high-temperature pressure in reactor in the time of activation potassium felspar sand, activation temperature adjustment is got off, save the energy.In the activation potassium felspar sand technique of previous report, activation temperature is all higher than 500 DEG C, and the present invention can be reduced to activation temperature 160 DEG C, cost-saving in the time realizing technique industrialization in the future.
(3) when adopting sub-fused-salt medium activation potassium felspar sand, solid-solid reaction state when roasting alkali is melted to technique is changed into solid-liquid state, and adopts stirring to promote reaction, the good fluidity of whole system, the operation of being more convenient for.And KOH contacts more fully with potassium felspar sand, activate more complete.
(3) mother liquid recycling after crystallization, realizes resources effective utilization, zero release.The molecular sieve crystallite simultaneously existing in mother liquor can play the effect of crystal seed, improves the relative crystallinity of synthesis of molecular sieve.
(4) obtain product W type molecular sieve, pattern becomes clavate bunch shape, and impurity is less, becomes brilliant complete rule.Product application is worth high.The slow-release potassium fertilizer can be used as in ion exchange absorbent and the agriculture production of potassium from sea water uses.
Brief description of the drawings
Fig. 1 is the XRD figure of potassium felspar sand breeze.
Fig. 2 is the XRD figure of the synthetic potassium type molecular sieve W of embodiment 1.Determine that by the contrast at the characteristic peak of this figure and the XRD standard feature peak of W molecular sieve synthetic product is W molecular sieve.
Fig. 3 is the SEM figure of the zeolite product produced of embodiment 1.
Fig. 4 is the XRD figure of the synthetic potassium type molecular sieve W of embodiment 2.
Fig. 5 is the SEM figure of the synthetic potassium type molecular sieve W of embodiment 2.
Fig. 6 is the XRD figure of the synthetic potassium type molecular sieve W of embodiment 3.
Fig. 7 is the SEM figure of the synthetic potassium type molecular sieve W of embodiment 3.
Fig. 8 is the XRD figure of the synthetic potassium type molecular sieve W of embodiment 4.
Fig. 9 is the SEM figure of the synthetic potassium type molecular sieve W of embodiment 4.
Figure 10 is the XRD figure of the synthetic potassium type molecular sieve W of embodiment 5.
Figure 11 is the SEM figure of the synthetic potassium type molecular sieve W of embodiment 5.
Figure 12 is the XRD figure of the synthetic potassium type molecular sieve W of embodiment 6 Recycling Mother Solution.
Figure 13 is the SEM figure of the synthetic potassium type molecular sieve W of embodiment 6 Recycling Mother Solution.
Figure 14 is the process flow sheet that the sub-fused salt activation of KOH potassium felspar sand is produced full potassium W type molecular sieve.
Embodiment:
The potassium felspar sand breeze that the present invention uses derives from Sha County, Fujian Province, pulverizes 200 mesh sieve before use, and its chemical constitution is shown in Table 1,
Table 1
XRD spectra is shown in shown in accompanying drawing Fig. 1.
The potassium hydroxide that the KOH purity that the present invention uses is is 85% containing mass percent.
Embodiment 1
(1) activation is got the raw materials ready
KOH (purity is 85%) 35.2943g, water 7.5ml join in there-necked flask and mix, making initial alkali concn is that KOH mass concentration is 70%, again potassium felspar sand breeze 9.9998g is joined in there-necked flask and mixed with KOH and water, make ore deposit alkali quality than potassium felspar sand: KOH=1:3.Mixed system is placed in to 160 DEG C of oil bath pans and stirs condensing reflux priming reaction 5h.
(2) aging
SiO in system after activation
2and Al
2o
3content be SiO in potassium felspar sand
2and Al
2o
3content, K
2the content of O is K in potassium felspar sand
2stripping quantity and the KOH of O are converted into K
2after O, (reduction formula is
) content sum.After activating, system is according to a mole proportioning SiO
2/ Al
2o
3=12, K
2o/SiO
2=1.6, H
2o/SiO
2=51, add silicon source (white carbon black-be SiO
2, (composition of described White Carbon black is gas-phase silica, and main component is SiO
2, purity is 99%)) 3.3284g, aluminium hydroxide 0.1012g (be converted into Al
2o
3calculate, reduction formula is
) and 147.70ml water, and stir.By mixture mechanical stirring 3h at 25 DEG C.
(3) crystallization
The mixed solution that step (2) is obtained is put into airtight crystallizing kettle, crystallization 48h at 150 DEG C.
(4) product treatment
The mixed solution filtering separation that (3) are obtained obtains zeolite product 8.66g and corresponding mother liquor 195.26mL, and wherein zeolite product is also dried to neutral with deionized water wash.The XRD standard feature peak of the XRD characteristic peak of accompanying drawing Fig. 2 and W molecular sieve is compared, can determine that synthetic product is W type molecular sieve.Can find out that by accompanying drawing 3 W type molecular sieve is dumbbell bar-shaped, inside is that cluster is fibrous scatters.So the material proportion of embodiment 1 and synthesis condition can successfully synthesize W type molecular sieve.
(5) mother liquor reclaims
Analysis records each component concentration mother liquid obtained in (4), contains K in the mother liquor obtaining
2o 0.8624mol/L, SiO
20.0950mol/L, Al
2o
39.72 × 10
-4mol/L.Mother liquor is used for to recycle.The visible embodiment 6 of mother liquid recycling.
Embodiment 2
(1) activation is got the raw materials ready
KOH (purity is 85%) 35.2943g, water 4.7ml join in there-necked flask and mix, making initial alkali concn is that KOH mass concentration is 75%, again potassium felspar sand breeze 10.0006g is joined in there-necked flask and mixed with KOH and water, make ore deposit alkali quality than potassium felspar sand: KOH=1:3.Mixed system is placed in to 160 DEG C of oil bath pans and stirs condensing reflux priming reaction 5h.
(2) aging
To in (1), activate rear system according to proportioning SiO
2/ Al
2o
3=12, K
2o/SiO
2=1.6, H
2o/SiO
2=51, add silicon source (white carbon black) 3.3156g, aluminium hydroxide 0.0982g and 143.56ml water, and stir.By mixture mechanical stirring 3h at 25 DEG C.
(3) crystallization
The mixed solution that step (2) is obtained is put into airtight crystallizing kettle, crystallization 48h at 150 DEG C.
(4) product treatment
The mixed solution filtering separation that (3) are obtained obtains zeolite product and corresponding mother liquor, and wherein zeolite product is also dried to neutral with deionized water wash.The XRD standard feature peak of the XRD characteristic peak of accompanying drawing Fig. 4 and W molecular sieve is compared, can determine that synthetic product is W type molecular sieve, and accompanying drawing 4 is compared with accompanying drawing 3, goes out peak more complete, peak type is more sharp-pointed, illustrates that improving alkali concn is conducive to the synthetic of product.Can find out that by accompanying drawing 5 material proportion of example 2 and reaction conditions can successfully synthesize crystalline form complete, the W zeolite product being evenly distributed.
(5) mother liquor reclaims
Analysis records each component concentration mother liquid obtained in (4), i.e. potassium, silicon, aluminium plasma content.For recycle.Recycling Mother Solution method is referring to example 6.
Embodiment 3
(1) activation is got the raw materials ready
KOH (purity is 85%) 35.2943g, water 4.7ml join in there-necked flask and mix, making initial alkali concn is that KOH mass concentration is 75%, again potassium felspar sand breeze 10.0004g is joined in there-necked flask and mixed with KOH and water, make ore deposit alkali quality than potassium felspar sand: KOH=1:3.Mixed system is placed in to 140 DEG C of oil bath pans and stirs condensing reflux priming reaction 5h.
(2) aging
To in (1), activate rear system according to proportioning SiO
2/ Al
2o
3=12, K
2o/SiO
2=1.6, H
2o/SiO
2=51, add silicon source (white carbon black) 3.3423g, aluminium hydroxide 0.1370g and 143.54ml water, and stir.By mixture mechanical stirring 3h at 25 DEG C.
(3) crystallization
The mixed solution that step (2) is obtained is put into airtight crystallizing kettle, crystallization 48h at 150 DEG C.
(4) product treatment
The mixed solution filtering separation that (3) are obtained obtains zeolite product and corresponding mother liquor, and wherein zeolite product is also dried to neutral with deionized water wash.The XRD standard feature peak of the XRD characteristic peak of accompanying drawing Fig. 6 and W molecular sieve is compared, can determine that synthetic product is W type molecular sieve, but assorted peak is more, and collection of illustrative plates front end there is obvious bulge, illustrate that crystallization is incomplete.Can find out in synthetic product crystal, have a large amount of cluster things to exist under the condition of example 3 from accompanying drawing 7, crystal accumulation situation is serious.
(5) mother liquor reclaims
Analysis records each component concentration mother liquid obtained in (4), i.e. potassium, silicon, aluminium plasma content.For recycle.Recycling Mother Solution method is referring to example 6.
Embodiment 4
(1) activation is got the raw materials ready
KOH (purity is 85%) 35.2946g, water 4.7ml join in there-necked flask and mix, making initial alkali concn is that KOH mass concentration is 75%, again potassium felspar sand breeze 9.9997g is joined in there-necked flask and mixed with KOH and water, make ore deposit alkali quality than potassium felspar sand: KOH=1:3.Mixed system is placed in to 150 DEG C of oil bath pan stir-activating reaction 5h.
(2) aging
To in (1), activate rear system according to proportioning SiO
2/ Al
2o
3=12, K
2o/SiO
2=1.6, H
2o/SiO
2=51, add silicon source (white carbon black) 3.3306g, aluminium hydroxide 0.1315g and 143.54ml water, and stir.By mixture mechanical stirring 3h at 25 DEG C.
(3) crystallization
The mixed solution that step (2) is obtained is put into airtight crystallizing kettle, crystallization 48h at 150 DEG C.
(4) product treatment
The mixed solution filtering separation that (3) are obtained obtains zeolite product and corresponding mother liquor, and wherein zeolite product is also dried to neutral with deionized water wash.The XRD standard feature peak of the XRD characteristic peak of accompanying drawing Fig. 8 and W molecular sieve is compared, can determine that synthetic product is W type molecular sieve.Accompanying drawing 9 can find out, products molecule sieve pattern is compared with homogeneous, but not as product degree of crystallinity synthetic under example 2 conditions high, have a certain amount of impurity to exist.
(5) mother liquor reclaims
Analysis records each component concentration mother liquid obtained in (4), i.e. potassium, silicon, aluminium plasma content.For recycle.Recycling Mother Solution method is referring to example 6.
Embodiment 5
(1) activation is got the raw materials ready
KOH (purity is 85%) 35.2945g, water 4.7ml join in there-necked flask and mix, making initial alkali concn is that KOH mass concentration is 75%, again potassium felspar sand breeze 10.0001g is joined in there-necked flask and mixed with KOH and water, make ore deposit alkali quality than potassium felspar sand: KOH=1:3.Mixed system is placed in to 170 DEG C of oil bath pan stir-activating reaction 5h.
(2) aging
To in (1), activate rear system according to proportioning SiO
2/ Al
2o
3=12, K
2o/SiO
2=1.6, H
2o/SiO
2=51, add silicon source (white carbon black) 3.3019g, aluminium hydroxide 0.0972g and 143.55ml water, and stir.By mixture mechanical stirring 3h at 25 DEG C.
(3) crystallization
The mixed solution that step (2) is obtained is put into airtight crystallizing kettle, crystallization 48h at 150 DEG C.
(4) product treatment
The mixed solution filtering separation that (3) are obtained obtains zeolite product and corresponding mother liquor, and wherein zeolite product is also dried to neutral with deionized water wash.The XRD standard feature peak of the XRD characteristic peak of accompanying drawing Figure 10 and W molecular sieve is compared, can determine that synthetic product is W type molecular sieve.And without assorted peak, peak shape is sharp-pointed substantially.It is high that accompanying drawing 11 can find out that example 5 can synthesize degree of crystallinity, the W molecular sieve being evenly distributed.
(5) mother liquor reclaims
Analysis records each component concentration mother liquid obtained in (4), i.e. potassium, silicon, aluminium plasma content.For recycle.Recycling Mother Solution method is referring to example 6.
Embodiment 6
The recycle of mother liquor is completed by following methods:
(1) according to embodiment (1) operation, obtain mixture after crystallization, filter to obtain mother liquor after crystallization;
(2) analyze each component concentration in mother liquor, in known mother liquor, contain K
2o 0.8624mol/L, SiO
20.0950mol/L, Al
2o
39.72 × 10
-4mol/L;
(3), according to each component concentration in mother liquor, add 13.1060gKOH, potassium felspar sand 10.0003g, in proportion SiO
2/ Al
2o
3=12, K
2o/SiO
2=1.6, H
2o/SiO
2=51, add silicon source (white carbon black) 2.2071g, Al (OH)
30.0716g, is made into the initial mixing liquid of synthesis of molecular sieve.
(4) the initial mixing solution obtaining in previous step is reacted to 5h at 160 DEG C;
(5) mixed solution in step (4) is repeated to (2)-(5) operation in embodiment 1;
(6) crystallization mother liquor in the every secondary response of recycle.
Can be found out by accompanying drawing 12,13, carry out Recycling Mother Solution and can successfully synthesize W molecular sieve.
Unaccomplished matter of the present invention is known technology.
Claims (1)
1. the sub-fused salt activation of KOH potassium felspar sand is produced a method for full potassium W type molecular sieve, it is characterized by and comprises the steps:
KOH, potassium felspar sand and water are mixed in reactor, wherein, taking KOH mass concentration in the system of water and KOH as 70 ~ 80%, mass ratio KOH: potassium felspar sand=3:1; Be placed in 140-175 DEG C of oil bath pan, stir condensing reflux and carry out sub-fused salt priming reaction 5-8h; System after activation is by adding Al (OH)
3, one or more in white carbon black and water, the composition and ratio in solution is met: mol ratio SiO
2: Al
2o
3=5-20:1, K
2o/SiO
2=1-3.0, H
2o:SiO
2=40-120:1; Wherein, when KOH calculates, need be converted into K
2the molar weight meter of O; Then aging 2-15h at 25-70 DEG C; System after aging is put into airtight crystallizing kettle, crystallization 8-72h at 90-180 DEG C, and the crystallization mother liquor after crystallization mixture filters is that next cycle recycles, filter cake is through washing, the dry solid phase prod W molecular sieve that obtains.
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| CN103553067A (en) * | 2013-11-19 | 2014-02-05 | 河北工业大学 | Method for producing total-potassium W-type molecular sieve by utilizing KOH alkali-activated potassium feldspar |
| CN103570036A (en) * | 2012-07-18 | 2014-02-12 | 中国石油大学(北京) | Synthesis method of Y type molecular sieve |
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| CN103553067A (en) * | 2013-11-19 | 2014-02-05 | 河北工业大学 | Method for producing total-potassium W-type molecular sieve by utilizing KOH alkali-activated potassium feldspar |
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