CN105271313A - Novel method for comprehensively utilizing potassium feldspar - Google Patents
Novel method for comprehensively utilizing potassium feldspar Download PDFInfo
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Abstract
The invention discloses a novel method for comprehensively utilizing potassium feldspar. According to the method, NaOH-Na2CO3 is used for being mixed with sub-molten salt to decompose the potassium feldspar, and potassium feldspar decomposing mother liquid and kankrinite are obtained; the potassium feldspar decomposing mother liquid is subjected to carbonatation and filtration to obtain filter liquid containing potassium bicarbonate and salic filtering slag; filtering liquid is subjected to evaporation, crystallization and drying, and potassium carbonate can be obtained; meanwhile, the salic filtering slag is subjected to supplementing addition of KOH, Al(OH)3 and H2O for regulating the mixture ratio of the K2O/SiO2, the Al2O3/SiO2 and the H2O/SiO2; at a certain temperature, aging and crystallization are performed for a period of time; W molecular sieves are synthesized. The method has the characteristics that the decomposing temperature is low; the potassium ion dissolving rate is high; the decomposing mother liquid can be easily acidified; the product added value is high; the raw material utilization rate is high; no waste liquid and no waste slag are produced. The method conforms to the green production principle, and has good potential economic benefits.
Description
Technical field
The invention belongs to Mineral resources processing, inorganic metal compound preparation and silico-aluminate compound fabricating technology field, be specifically related to the utilization of potassium felspar sand, the preparation of salt of wormwood, cancrinite and W molecular sieve.
Background technology
China's soluble potassium ore resources is poor, Jin Zhan world total reserves about 0.4%, and along with steadily improving of the level of economic development, country increases year by year to the demand of water-soluble sylvite, and production capacity and demand differ greatly.And China's water-insoluble potassium resource reserve enriches, wherein potash feldspar ore is distributed widely in 23 provinces and regions, and proven reserve reach over ten billion ton.
Potassium felspar sand (KAlSi
3o
8) in theory containing K
2o16.9%, SiO
264.7%, Al
2o
318.4%, the full use of potassium felspar sand be realized, the potassium in potassium felspar sand, Silicified breccias resource will have been made full use of.For potassium resource contained in potassium felspar sand, water-soluble sylvite can be produced by potassium felspar sand deep processing, and the molecular sieve Silicified breccias in potassium felspar sand being made high added value is research tendency in recent years.
The method that potassium feldspar decomposition prepares sylvite is broadly divided into following a few class: lime burning method, middle temperature decomposition method, high temperature alkali fuse method, sintering process, low-temperature decomposition method, microbial method etc.Wherein sintering process and low-temperature decomposition method are two kinds of methods comparatively commonly used.Sintering process mainly utilizes composite additive and potassium felspar sand calcination, can reduce temperature of reaction to a certain extent, but reaction still need be carried out in the Reaktionsofen of 600 ~ 850 DEG C, and energy consumption is larger.Low-temperature decomposition rule mainly uses sulfuric acid and fluorine-containing auxiliary agent and potassium felspar sand to react under low temperature (90 ~ 150 DEG C), and the feature of this method to fully utilize potassium felspar sand, but Potassium leaching rate is lower, residue environmental pollution serious, is unfavorable for manufacture.All there is the shortcomings such as energy expenditure is large, cost is high, complex process, mine tailing residue are many technically and economically in additive method.And by Chinese Academy of Sciences's process open virtuous academician (ZhangY, LiZH, QiT.GreenChemistryofChromateCleanerProduction [J].
chineseJournalofChemistry.1999,17 (3): 258-266.) sub-molten salt method proposed successfully is applied to and refines containing insoluble mineral such as chromium, vanadium, titanium, aluminium, is characterized in that low temperature energy consumption is little, metal dissolving rate is high, just can solves the above problems.
On the other hand, that reports at present prepares in the method for molecular sieve by potassium felspar sand, major part adopts roasting method decomposing of potassium feldspar, as (Du Cuihua such as Du Cuihua, Zhao Bin, full potassium W type molecular sieve [J] produced by the .KOH alkali fusion activation potassium felspar sands such as Guo Hongfei. artificial lens journal, 2014,43 (1): 1-10.) and utilize KOH alkali fusion activation potassium felspar sand at 500 DEG C to synthesize W molecular sieve; Zhang Jieqing etc. (Zhang Qingjie, Cao Jilin, Liu Xiuwu etc. potassium felspar sand alkali fusion activation synthesis 4A zeolite research [J]. artificial lens journal, 2013,42 (5): 953-958.) utilize Na
2cO
3at 780 DEG C, Roasting Decomposition potassium felspar sand has synthesized 4A molecular sieve; ShidingMiao etc. (MiaoSD, LiuZM, MaHW, etal.SynthesisandCharacterizationofMesoporousAluminosili cateMolecularSievefromK-feldspar [J].
microporousandMesoporousMaterial2005,83:277-282.), Wang Jingjie etc. (Wang Jingjie, Zhao Bin, Li Lin etc. potassium felspar sand Hydrothermal Synthesis K-ZSM-5 molecular sieve [J]. silicate journal, 2014,42 (3): 340-348.) and Li Xianzhou etc. (Li Xianzhou, Yuan Lin, Ning Weikun etc. the experimental study [J] of X-type molecular sieve prepared by potassium felspar sand. International Geology, 2008,27 (4): 454-458.) K is utilized
2cO
3more than 800 DEG C, Roasting Decomposition potassium felspar sand has synthesized mesoporous Si-Al molecular sieve, K-ZSM-5 molecular sieve and mesoporous X-type molecular sieve respectively.Aforesaid method has 2 deficiencies on the whole: one, and the temperature of reaction of Roasting Decomposition potassium felspar sand is all more than 500 DEG C, and the energy consumption of process is larger; Its two, above reported method take mainly synthesis of molecular sieve as target, less demanding to Potassium leaching rate, causes the waste of potassium resource to a certain extent.
Therefore, for solving by extracting potassium from potash feldspar and the problem prepared in molecular sieve process simultaneously, the present invention proposes with NaOH-Na
2cO
3mixing sub-molten salt is dielectric breakdown potassium felspar sand and synthesizes cancrinite and W molecular sieve, obtains K in addition
2cO
3, by-product Na
2cO
3, a new operational path is explored in the comprehensive utilization for potassium felspar sand.The program, except can keeping advantage that the low and metal dissolving rate of sub-molten salt method decomposition temperature is high, can also reduce the difficulty of follow-up acidifying.The Na of by-product
2cO
3can be recycled, improve raw material availability, there is good potential economic benefit.
Summary of the invention
The object of the invention is to utilize NaOH-Na
2cO
3mixing sub-molten salt decomposing of potassium feldspar, the potassium contained by utilizing in potassium felspar sand, silicon, aluminium source prepare salt of wormwood, cancrinite and W molecular sieve, realize the comprehensive utilization of potassium felspar sand resource.
for achieving the above object, the present invention is by the following technical solutions:
The novel method of a kind of potassium felspar sand comprehensive utilization of the present invention, comprises the steps:
(1) by potassium felspar sand breeze and NaOH-Na
2cO
3mixing sub-molten salt solution, by proportioning mixing, is put in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into autoclave, and be fixed in homogeneous phase stirred reactor, is heated to potassium felspar sand breeze decomposition temperature, reaction for some time; Filtered by reacted grog, wash, filter residue is dried and is cancrinite, and filtrate is potassium feldspar decomposition mother liquor;
(2) in potassium feldspar decomposition mother liquor, CO is passed into
2carry out carbonating, regulate pH to be 8 ~ 10, make silicon and aluminum precipitation get off to be formed sal filter residue, filtering separation acquisition filtrate, filtrate is by adding NaOH Posterior circle to the decomposition of step (1) for potassium felspar sand;
(3) when after the circulation at least twice from step (1) to step (2), by the pH regulator of the potassium feldspar decomposition mother liquor of acquisition to 5 ~ 8, the sodium in guarantee potassium feldspar decomposition mother liquor and potassium are with NaHCO
3and KHCO
3form exist, then filters potassium feldspar decomposition mother liquor and obtain filtrate, then filtrate filtering separation obtained is by least three evaporations, crystallizations be separated, and obtains NaHCO
3and KHCO
3, at 200 DEG C, dry decomposition obtains Na
2cO
3and K
2cO
3, Na
2cO
3solid can be cycled to used in the potassium feldspar decomposition of step (1);
(4) the sal filter residue that precipitates of step (2), by adding KOH, Al (OH)
3and H
2o, regulation system K
2o/SiO
2, Al
2o
3/ SiO
2and H
2o/SiO
2proportioning, at a certain temperature aging and crystallization for some time, filtered by product, wash, filter cake is W molecular sieve, and filtrate is W molecular sieve mother liquor, can be cycled to used in the synthesis of W molecular sieve.
NaOH-Na in described step (1)
2cO
3the concentration of mixing sub-molten salt solution is 50wt% ~ 80wt%.
Na in described step (1)
2cO
3account for NaOH-Na
2cO
3mix 30 ~ 50% of the total alkali content of sub-molten salt.
Described step (1) potash feldspar ore and NaOH-Na
2cO
3mixing sub-molten salt weight ratio is 1:3.0 ~ 6.0.
In described step (1), potassium feldspar decomposition temperature is 190 ~ 210 DEG C, and the resolving time is 2 ~ 5h.
In described step (2), potassium feldspar decomposition mother liquor passes into CO
2when carrying out carbonating, the SiO in potassium feldspar decomposition mother liquor
3 2-it is 0.3 ~ 0.6mol/L, CO that concentration controls
2flow velocity be 0.2 ~ 0.4L/min, adopt mechanical stirring in carbonation, rotating speed is 400 ~ 600r/min.
In described step (4), W Zeolite synthesis system weight of material proportion optimization is K
2o/SiO
2=0.5 ~ 1.5, Al
2o
3/ SiO
2=0.02 ~ 0.15, H
2o/SiO
2=35 ~ 55.
In described step (4) synthesis W molecular sieve need at 25 ~ 50 DEG C aging 2 ~ 5h, crystallization 12 ~ 48h at 140 ~ 170 DEG C.
specifically,the above-mentioned potassium felspar sand used of the present invention is a kind of aluminium silicate mineral containing potassium, has stable sial, silicon-oxy tetrahedron structure.Potash feldspar ore will start melting usually more than 1150 DEG C, close to complete melting when 1400 DEG C.Therefore, in order to reduce energy consumption, the general method of adding auxiliary agent that adopts carrys out decomposing of potassium feldspar, as conventional alkali fusion, sintering process etc.For potassium felspar sand-sodium carbonate system, the decomposition temperature of potassium felspar sand can be down to 750 ~ 850 DEG C.On the one hand because adding of sodium carbonate forms the melt temperature that eutectic can reduce system, sodium carbonate participates in reaction on the other hand, and namely potassium felspar sand and sodium carbonate generation solid decompose reaction cause stable silicon (aluminium) oxide structure to destroy.Previously we adopted sodium hydroxide sub-molten salt system decomposing of potassium feldspar, can carry out under low temperature (lower than 200 DEG C) normal pressure.Alkaline solution produces highly reactive form of oxygen negative ion and hydroxide ion in sub-molten salt region, at interface, O occurs with potassium felspar sand lattice
2-mutual metalepsy, causes lattice distortion.Simultaneously, sub-molten salt is that whole reaction provides good flowing environment as the non-conventional media of the aqueous solution and fused salt intermediate state, all there is certain dissolving power to reactant and product, good dispersion, transmission effect are played to reaction system, improves speed of reaction.K under good flowing environment in potassium felspar sand crystalline network
+rapidly to the diffusion of lattice outside, thus decomposing potash feldspar ore realizes putting forward potassium object.But sodium hydroxide sub-molten salt also exists limitation, as high in NaOH concentration, follow-up acidization needs a large amount of acid and longer acidificatoin time, and NaOH cannot recycle, and Financial cost is higher; And the residue that reaction generates is sodalite, very stable, be difficult to utilize, cause the waste of resource.The present invention adopts NaOH-Na
2cO
3mixing sub-molten salt system decomposing of potassium feldspar, with Na
2cO
3replace part NaOH, but still ensure that whole reaction system has the characteristic of sub-molten salt medium.Due to Na
2cO
3introducing do not reduce the concentration of total salt, so sodium hydroxide still can produce highly reactive form of oxygen negative ion O
2-with the O in potash feldspar ore lattice
2-there is mutual metalepsy, simultaneously CO
3 2-also can participate in reaction, while the two, effect makes the three-dimensional rack-like of potassium felspar sand destructurized, realizes the decomposition of potassium felspar sand.Due to Na
2cO
3alkalescence weak compared with NaOH, be conducive to the total alkalinity reducing reaction, the Na simultaneously produced in carbonating and evaporation and crystal process
2cO
3raw material as reaction capable of circulation, improves the economic benefit of whole production technique.Secondly the new negatively charged ion CO owing to introducing
3 2-reaction can be participated in, make reaction residues by sodalite (molecular formula Na
8si
6al
6o
24(OH)
2(H
2o)
2) change cancrinite (molecular formula Na into
8(Si6Al
6o
24) (H
0.88(CO
3)
1.44) (H
2o)
2).Cancrinite is a kind of silicon aluminate crystal with the one-dimensional channels of twelve-ring, and the amount existed at nature is little.Cancrinite is in building-up process, and because fault can cause the obstruction in defect and ion pair duct, this makes it be different from general molecular sieve, does not substantially have ion-exchange capacity.But this structure makes it as the material of main part of Subjective and Objective structure, can apply to some extent in the one dimension oriented growth of guest molecule.Simultaneously because the special structure of cancrinite, it can be fixed in their passage by having the anion radical of electrical and optical properties, unstable molecule and atomic group, to meet the requirement of the aspect application such as optical, electrical.
The present invention's research shows, total alkali concn, Na
2cO
3accounting for the per-cent of total alkali content, alkali ore deposit ratio, temperature of reaction and reaction times has larger impact to the decomposition of potash feldspar ore and the generation of cancrinite.In the present invention, preferably total alkali concn is 50 ~ 80wt%NaOH-Na
2cO
3mixing solutions, its concentration is sub-molten salt field normal concentration.Na
2cO
3account for NaOH-Na
2cO
3when mixing 30 ~ 50% of the total alkali content of sub-molten salt, reaction system has the characteristic of sub-molten salt medium, and reaction activity is large, and potassium feldspar decomposition is respond well, and can ensure that reacting the filter residue generated is cancrinite.Potash feldspar ore and NaOH-Na
2cO
3when mixing sub-molten salt weight ratio is 1:3.0 ~ 6.0, whole reaction system good fluidity, when weight ratio is lower than 1:3.0, reaction system poor fluidity, reaction medium can not fully contact with potassium felspar sand, and decomposition course efficiency is low; When weight ratio is higher than 1:6.0, potassium ion solubility rate, close to the limit, continues ratio of gaining in weight, and the change of potassium ion solubility rate is little.Temperature of reaction is preferably 190 ~ 210 DEG C, and temperature of reaction raises, and sub-molten salt dielectric viscosity reduces, and mobility increases, and the activity of sub-molten salt medium is increased, and active oxygen anion increases, and potash feldspar ore decomposes acceleration; This temperature range is also applicable to the generation of cancrinite simultaneously.When temperature of reaction is lower than 190 DEG C, potassium feldspar decomposition effect is general, and the filter residue cancrinite simultaneously now generated is impure more; When temperature of reaction is higher than 210 DEG C, on the decomposition of potash feldspar ore and generation almost no impact of cancrinite.Reaction times is preferably 2 ~ 5h, this is because sub-molten salt fully need contact with potassium felspar sand, destroy potassium felspar sand structure gradually and make potassium ion stripping, certain reaction times also can be decomposed lower than potassium felspar sand during 2h, but discomposing effect is not good; When being when reacted 2 ~ 5h, not only the discomposing effect of potassium felspar sand is significantly improved, and also can compare pure cancrinite by resultant simultaneously.
In addition, research also finds, the pH value of potassium feldspar decomposition mother liquor acidifying is preferably 8 ~ 10, and now in decomposition nut liquid, the Silicified breccias of the overwhelming majority can exist with the form of precipitation.SiO in decomposition nut liquid
3 2-concentration is 0.3 ~ 0.6mol/L, CO
2flow velocity be 0.2 ~ 0.4L/min, in acidization, adopt mechanical stirring, rotating speed is 400 ~ 600r/min, now homogeneous sized by gained sal filter residue particulate state, and reactive behavior is high, is suitable as the silicon and aluminum source of synthesis W molecular sieve.If SiO in decomposition nut liquid
3 2-concentration is excessive, CO
2flow velocity too high, revolution is too low or adopt magnetic agitation, and now gained sial filter residue is gel, not easily dries, and easily produces hard aggregation, and for the preparation of also needing during molecular sieve through grinding and drying and processing again, integrated operation is comparatively complicated.
Meanwhile, research also finds, in the process of preparation W molecular sieve, requires that system consists of K
2o/SiO
2=0.5 ~ 1.5, Al
2o
3/ SiO
2=0.02 ~ 0.15, H
2o/SiO
2=35 ~ 55, then aging 2 ~ 5h at 25 ~ 50 DEG C, crystallization 12 ~ 48h at 140 ~ 170 DEG C.The W molecular sieve performance be now synthesized is best.W molecular sieve due to potassium content high, good to potassium ion selective, except can be used as slow-release potassium fertilizer and directly using, also can be used for potassium from sea water, 50-60mgK be about to the potassium ion exchange capacity of seawater
+/ g, has a extensive future.
beneficial effect of the present invention is embodied in:
1. with potassium felspar sand cheap and easy to get for raw material, the potassium in potassium felspar sand, Silicified breccias resource can be made full use of, avoid problem of resource waste.
2. utilize NaOH-Na
2cO
3mixing sub-molten salt just can decomposing of potassium feldspar at about 200 DEG C, and potassium ion solubility rate, up to 98.96wt%, compared with the method for Roasting Decomposition, has temperature of reaction low, and potassium ion solubility rate is high, simple to operate, and plant and instrument requires low feature; Simultaneously compared with other hydrothermal method decomposing of potassium feldspar, whole reaction system basicity is lower, decreases the use of souring agent, cost-saving.
3. the filter residue generated after potassium feldspar decomposition is cancrinite, and cancrinite has certain application in guest molecule, light and electricity etc.
4. with CO
2as the souring agent of potassium feldspar decomposition mother liquor, there is technique comparatively simple, be easy to the advantage of recycle.Obtain after acidifying containing NaHCO
3and KHCO
3mixing solutions, carry out evaporative crystallization, isolate NaHCO
3and KHCO
3, then obtain Na dry decomposition
2cO
3and K
2cO
3, to realize in potassium felspar sand insoluble potassium resource to the transformation of soluble potassium resource.The simultaneously acidified filtrate decomposition for potassium felspar sand capable of circulation, not only energy-saving and emission-reduction, and can improve potassium content in filtrate, disposablely obtain more purer K
2cO
3, there is good potential economic benefit.
5. the preparation sal filter residue obtained after potassium feldspar decomposition being used for molecular sieve is research tendency in recent years, and W molecular sieve is due to good to potassium ion selective, can be used for potassium from sea water, is 50-60mgK to the potassium ion exchange capacity of seawater
+/ g, can alleviate the present situation of China's soluble potassium shortage of resources further.Also can be used as slow-release potassium fertilizer directly to use, the value added of product is high simultaneously.
6. prepare the mother liquor after W molecular sieve by adding KOH, sal filter residue and Al (OH)
3, realize the recycle of mother liquor, avoid waste liquid and waste sludge discharge.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the XRD contrast spectrogram that example 1,3,5 and 6 potash feldspar ore decomposes the filter residue cancrinite of gained.
Fig. 3 is the SEM contrast spectrogram that example 1,3,5 and 6 potash feldspar ore decomposes the filter residue cancrinite of gained.
Fig. 4 for example 1,10,11,12 and 16 utilize the W molecular sieve obtained by sal filter residue XRD contrast spectrogram.
Fig. 5 for example 1,10,11,12 and 16 utilize the W molecular sieve obtained by sal filter residue SEM contrast spectrogram.
Fig. 6 is the XRD spectra of gained sal filter residue after the acidifying of example 1 potash feldspar ore decomposition nut liquid.
Fig. 7 is the SEM spectrogram of gained sal filter residue after the acidifying of example 1 potash feldspar ore decomposition nut liquid.
Fig. 8 be example 1 acidified mother liquor circulate different number of times decomposing of potassium feldspar gained filter residue cancrinite XRD contrast spectrogram.
Fig. 9 is the W Molecular Sieve Comparative spectrogram synthesized before and after example 1W molecular sieve Recycling Mother Solution.
Embodiment
As shown in Figure 1, the invention discloses the novel method of a kind of potassium felspar sand comprehensive utilization, utilize NaOH-Na
2cO
3mixing sub-molten salt decomposing of potassium feldspar, obtains potassium feldspar decomposition mother liquor and cancrinite.Potassium feldspar decomposition mother liquor is through carbonating, and filter and obtain containing saleratus filtrate and sal filter residue, filtrate, through evaporation, crystallization and drying, can obtain salt of wormwood; Sal filter residue simultaneously, by adding KOH, Al (OH)
3and H
2o, regulation system K
2o/SiO
2, Al
2o
3/ SiO
2and H
2o/SiO
2proportioning, at a certain temperature, aging, crystallization for some time, synthesis W molecular sieve.
example 1
(1) by 7.50gNaOH and 7.50gNa
2cO
3with 15.00gH
2join in the polytetrafluoroethyllining lining of 100ml after O mixes, then add 10.00gK
2o content is the potassium felspar sand breeze of mistake 150 mesh sieve of 8.61%, autoclave is put it into after stirring, and be fixed in homogeneous phase stirred reactor (HZ-6), reactor is warming up to 200 DEG C, start timing, stop heating after reaction 4h, take out liner after the cooling of question response still, sample filtration, to wash to filter cake without CO
3 2-after, at 105 DEG C, dry 2h.Gained filtrate is for being potassium feldspar decomposition mother liquor containing potassium filtrate, and recording Potassium in K Feldspar Ion release rate is 95.33wt%.
(2) CO is passed into toward the potassium filtrate that contains in step (1)
2carry out acidifying, control SiO in filtrate
3 2-concentration be about 0.5mol/L, CO
2flow velocity be 0.3L/min, stir in acidization, rotating speed is 500r/min simultaneously.When solution ph is adjusted to 10 after reaction 2h, silicon and aluminum precipitation are got off, after filtering separation, containing a large amount of CO in filtrate
3 2-and HCO
3 -, filtrate is by volume divided into 2 parts, and every part is evaporated to volume when being about 20ml, then adds 7.50gNaOH, and being evaporated to volume is 20ml, is recycled to step (1), is respectively used to the decomposition of potassium felspar sand.
(3) after repeating above-mentioned steps (1) and step (2) 4 times, by the acidification of filtrate that finally obtains to pH=8, by evaporate for 4 times, crystallization and being separated, NaHCO is obtained
3and KHCO
3, at 200 DEG C, dry decomposition obtains Na
2cO
3and K
2cO
3, Na
2cO
3solid still can be used for potassium feldspar decomposition.
(4) according to mol ratio K
2o/SiO
2=1.0, Al
2o
3/ SiO
2=0.067, H
2o/SiO
2=45, get the sal filter residue 2.83g obtained in step (2), by adding KOH (purity is 85%) 6.23g, Al (OH)
30.44g and H
2o37.2ml, aging 2h at 30 DEG C, be then transferred in stainless steel crystallizing kettle, crystallization 24h at 150 DEG C.After product filtration, washing, drying, obtain W molecular sieve.By supplementing KOH0.42g to molecular sieve mother liquor, sal filter residue 1.14g and Al (OH)
30.46g, the preparation for W molecular sieve capable of circulation.
Example 2 ~ 6:
In the step (1) of example 2 ~ 6, each condition change is as shown in table 1, and under different condition, Potassium in K Feldspar Ion release rate is different, XRD and the SEM spectrogram of potassium feldspar decomposition filter residue respectively as shown in the figure; The step (2) of example 2 ~ 6, (3) and (4) are with example 1.
Table 1
Example 7 ~ 9:
The step (1) of example 7 ~ 9, (3) and (4) are with example 1, and each condition change is as shown in table 2 in step (2), time under different condition needed for the acidifying of potassium feldspar decomposition mother liquor is different, and after acidifying, the pattern of the sal filter residue of filtering separation gained is also different.
table 2
Example 10 ~ 16:
The step (1) of example 10 ~ 16, (2) and (3) are with example 1, and in step (4), each condition change is as shown in table 3, and under different condition, XRD and the SEM spectrogram of the W molecular sieve of gained respectively as shown in the figure.
table 3
Claims (8)
1. a novel method for potassium felspar sand comprehensive utilization, is characterized in that, comprise the steps:
(1) by potassium felspar sand breeze and NaOH-Na
2cO
3mixing sub-molten salt solution, by proportioning mixing, is put in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into autoclave, and be fixed in homogeneous phase stirred reactor, is heated to potassium felspar sand breeze decomposition temperature, reaction for some time; Filtered by reacted grog, wash, filter residue is dried and is cancrinite, and filtrate is potassium feldspar decomposition mother liquor;
(2) in potassium feldspar decomposition mother liquor, CO is passed into
2carry out carbonating, regulate pH to be 8 ~ 10, make silicon and aluminum precipitation get off to be formed sal filter residue, filtering separation acquisition filtrate, filtrate is by adding NaOH Posterior circle to the decomposition of step (1) for potassium felspar sand;
(3) when after the circulation at least twice from step (1) to step (2), by the pH regulator of the potassium feldspar decomposition mother liquor of acquisition to 5 ~ 8, the sodium in guarantee potassium feldspar decomposition mother liquor and potassium are with NaHCO
3and KHCO
3form exist, then filters potassium feldspar decomposition mother liquor and obtain filtrate, then filtrate filtering separation obtained is by least three evaporations, crystallizations be separated, and obtains NaHCO
3and KHCO
3, at 200 DEG C, dry decomposition obtains Na
2cO
3and K
2cO
3, Na
2cO
3solid can be cycled to used in the potassium feldspar decomposition of step (1);
(4) the sal filter residue that precipitates of step (2), by adding KOH, Al (OH)
3and H
2o, regulation system K
2o/SiO
2, Al
2o
3/ SiO
2and H
2o/SiO
2proportioning, at a certain temperature aging and crystallization for some time, filtered by product, wash, filter cake is W molecular sieve, and filtrate is W molecular sieve mother liquor, can be cycled to used in the synthesis of W molecular sieve.
2. the novel method of a kind of potassium felspar sand comprehensive utilization according to claim 1, is characterized in that: NaOH-Na in described step (1)
2cO
3the concentration of mixing sub-molten salt solution is 50wt% ~ 80wt%.
3. the novel method of a kind of potassium felspar sand comprehensive utilization according to claim 1, is characterized in that: Na in described step (1)
2cO
3account for NaOH-Na
2cO
3mix 30 ~ 50% of the total alkali content of sub-molten salt.
4. the novel method of a kind of potassium felspar sand comprehensive utilization according to claim 1, is characterized in that: described step (1) potash feldspar ore and NaOH-Na
2cO
3mixing sub-molten salt weight ratio is 1:3.0 ~ 6.0.
5. the novel method of a kind of potassium felspar sand comprehensive utilization according to claim 1, is characterized in that: in described step (1), potassium feldspar decomposition temperature is 190 ~ 210 DEG C, and the resolving time is 2 ~ 5h.
6. the novel method of a kind of potassium felspar sand comprehensive utilization according to claim 1, is characterized in that: in described step (2), potassium feldspar decomposition mother liquor passes into CO
2when carrying out carbonating, the SiO in potassium feldspar decomposition mother liquor
3 2-it is 0.3 ~ 0.6mol/L, CO that concentration controls
2flow velocity be 0.2 ~ 0.4L/min, adopt mechanical stirring in carbonation, rotating speed is 400 ~ 600r/min.
7. the novel method of a kind of potassium felspar sand comprehensive utilization according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that: in described step (4), W Zeolite synthesis system weight of material proportion optimization is K
2o/SiO
2=0.5 ~ 1.5, Al
2o
3/ SiO
2=0.02 ~ 0.15, H
2o/SiO
2=35 ~ 55.
8. the novel method of a kind of potassium felspar sand comprehensive utilization according to claim 7, is characterized in that: in described step (4) synthesis W molecular sieve need at 25 ~ 50 DEG C aging 2 ~ 5h, crystallization 12 ~ 48h at 140 ~ 170 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276984A (en) * | 2016-07-22 | 2017-01-04 | 中国科学院青海盐湖研究所 | A kind of preparation method of potassium nitrate |
| CN106276975A (en) * | 2016-07-22 | 2017-01-04 | 中国科学院青海盐湖研究所 | A kind of preparation method of potassium hydroxide |
| CN106430233A (en) * | 2016-10-18 | 2017-02-22 | 河北工业大学 | Method for preparing low-silicon X-type molecular sieve by fusing and activating potassium-bearing rocks by Na2CO3-NaOH mixed alkali |
| CN106745028A (en) * | 2016-12-10 | 2017-05-31 | 福建师范大学 | The method that solid phase method is prepared W molecular sieves by potassium feldspar |
| CN107601525A (en) * | 2017-10-11 | 2018-01-19 | 许昌学院 | A kind of preparation method and applications of double hemispherical W zeolites |
| CN109850923A (en) * | 2018-12-13 | 2019-06-07 | 吉林大学 | A method of from the potassium sodium complex salt crystal extracted region sylvite of potassium-rich brine |
| CN111498870A (en) * | 2020-04-23 | 2020-08-07 | 苏州固利环保科技有限公司 | Method for treating sintering machine head ash in steel mill by using chemical production byproduct potassium carbonate |
| CN112299440A (en) * | 2019-07-29 | 2021-02-02 | 南京理工大学 | Method for preparing ZSM-5 molecular sieve by taking solid slag after potassium extraction as raw material without template |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276984A (en) * | 2016-07-22 | 2017-01-04 | 中国科学院青海盐湖研究所 | A kind of preparation method of potassium nitrate |
| CN106276975A (en) * | 2016-07-22 | 2017-01-04 | 中国科学院青海盐湖研究所 | A kind of preparation method of potassium hydroxide |
| CN106430233A (en) * | 2016-10-18 | 2017-02-22 | 河北工业大学 | Method for preparing low-silicon X-type molecular sieve by fusing and activating potassium-bearing rocks by Na2CO3-NaOH mixed alkali |
| CN106430233B (en) * | 2016-10-18 | 2019-01-25 | 河北工业大学 | A kind of Na2CO3The method that-NaOH mixing alkali fusion activation potassium bearing rock produces low-silicon X-shaped molecular screen |
| CN106745028A (en) * | 2016-12-10 | 2017-05-31 | 福建师范大学 | The method that solid phase method is prepared W molecular sieves by potassium feldspar |
| CN106745028B (en) * | 2016-12-10 | 2019-01-04 | 福建师范大学 | The method that solid phase method prepares W molecular sieve by potassium feldspar |
| CN107601525A (en) * | 2017-10-11 | 2018-01-19 | 许昌学院 | A kind of preparation method and applications of double hemispherical W zeolites |
| CN109850923A (en) * | 2018-12-13 | 2019-06-07 | 吉林大学 | A method of from the potassium sodium complex salt crystal extracted region sylvite of potassium-rich brine |
| CN112299440A (en) * | 2019-07-29 | 2021-02-02 | 南京理工大学 | Method for preparing ZSM-5 molecular sieve by taking solid slag after potassium extraction as raw material without template |
| CN112299440B (en) * | 2019-07-29 | 2023-10-31 | 南京理工大学 | Method for preparing ZSM-5 molecular sieve by taking solid slag after potassium extraction as raw material without template |
| CN111498870A (en) * | 2020-04-23 | 2020-08-07 | 苏州固利环保科技有限公司 | Method for treating sintering machine head ash in steel mill by using chemical production byproduct potassium carbonate |
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