CN105439167A - Method for preparing 3A molecular sieve from potassium feldspar - Google Patents
Method for preparing 3A molecular sieve from potassium feldspar Download PDFInfo
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- CN105439167A CN105439167A CN201510842295.1A CN201510842295A CN105439167A CN 105439167 A CN105439167 A CN 105439167A CN 201510842295 A CN201510842295 A CN 201510842295A CN 105439167 A CN105439167 A CN 105439167A
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Abstract
The invention provides a method for preparing a 3A molecular sieve from potassium feldspar. The method is mainly characterized in that amorphous silica, aluminum hydroxide precipitate and a potassium silicate solution are prepared from products obtained through decomposition of the potassium feldspar and NH4F at a low temperature; then solid sodium hydroxide, solid potassium hydroxide, amorphous silica, the aluminum hydroxide precipitate and the potassium silicate solution in a certain proportion are mixed and react according to a predetermined sequence, the 3A molecular sieve is prepared and an industrial product potassium fluoride is obtained. Integrated utilization of K, Al and Si elements of the potassium feldspar is realized, and the economic benefit is remarkable. The method for preparing the 3A molecular sieve from the potassium feldspar has the advantages of scientific design, high element utilization ratio and good economic benefit.
Description
Technical field
The present invention relates to a kind of method preparing molecular sieve, specifically, relate in a kind of industrial production and utilize potassium felspar sand to prepare the method for molecular sieve.
Background technology
Molecular sieve, also known as zeolite, being a kind of aluminosilicate of crystal type, because limiting by natural resource, nearly all adopting synthetic now.The silicon source that synthesis of molecular sieve is used and aluminium source decide the quality of technique, product performance and economy.Potassium felspar sand provides silicon, aluminium two spike-type cultivars simultaneously, and molecular sieve prepared by exploitation potassium felspar sand is obviously good selection.Have a kind of method utilizing alkaline residue and potassium felspar sand molecular sieve in prior art, because multiplex fertilizer obtains, technological process is difficult to hold, and product performance are not high; Also have a kind of technology to be improve the former, adopt soda ash or caustic soda, but still be faced with the problem of the high and constant product quality difference of technology difficulty.If directly adopt purer industrial raw material to carry out large-scale molecular sieve production, obvious economy is bad.
In order to solve above Problems existing, people are seeking a kind of desirable technical solution always.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, thus provide a kind of design science, the sial potassium felspar sand that utilizes that when crystal formation is adjustable, element utilization ratio is high, good in economic efficiency to prepare the method for molecular sieve.
To achieve these goals, the technical solution adopted in the present invention is: a kind of method utilizing potassium felspar sand to prepare 3A molecular sieve, and it comprises the following steps:
(1) potassium feldspar decomposition: by potassium felspar sand, Neutral ammonium fluoride, 98% sulfuric acid fully mix according to the mass ratio of 1:1.5 ~ 2.6:1.6 ~ 1.8, react under 190 ~ 250 DEG C and autogenous pressure, obtain potassium feldspar decomposition residue and containing SiF
4decomposition gas;
(2) gas absorption: to described containing SiF
4decomposition gas carry out dust removal process, then adopt aqueous ethanolic solution to carry out absorption generation silicofluoric acid and precipitation of silica; Filtering separation, obtains soft silica and silicate fluoride solution;
(3) leaching of reaction residues: at 90 ~ 110 DEG C, leaches described potassium feldspar decomposition residue with the dilution heat of sulfuric acid that volume fraction is 8 ~ 10%, then carries out filtration to the solution after leaching and obtains leaching liquid;
(4) preparation of aluminium hydroxide: adopt ion exchange resin column to carry out cation-adsorption process to described leaching liquid, obtains potassium sulfate filtrate and adsorbs saturated ion exchange resin column; Then desorption and extraction treatment are carried out to the saturated ion exchange resin column of absorption; Afterwards, with the lower floor's aqueous phase after ammonia neutralization extracting and demixing to neutral, then carry out ageing, filtration, washing, dry obtained aluminium hydroxide, wherein, the extraction agent of the use in described extraction treatment process is volume be 1:1 P204 and sulfonated kerosene;
(5) preparation of potassium silicate: add the silicate fluoride solution from described step (2) according to stoichiometric relation in described potassium sulfate filtrate, generation potassium silicofluoride precipitates, silicate fluoride solution excessive 20% ~ 100%, after ageing, then through Filter Press, the obtained potassium silicofluoride of washing; According to stoichiometric relation, in described potassium silicofluoride, add hot potassium hydroxide solution, generate the potassium silicate solution containing Potassium monofluoride crystal; Potassium silicate solution containing Potassium monofluoride crystal is purified, isolates Potassium monofluoride, obtain the potassium silicate solution that massfraction is 28% ~ 32%;
(6) preparation of molecular sieve: take solid sodium hydroxide and potassium hydroxide respectively, and join in described potassium silicate solution and mix, obtain the first mixing solutions; In described first mixing solutions, add the aluminium hydroxide prepared by described step (4), stir, crystallization is carried out in heating; While crystallization, under stirring, add the soft silica that extra aluminium hydroxide and described step (2) are obtained, and carry out thermostatic crystallization; By crystallization product after filtration, dry nanometer 3A zeolite product; Wherein, in this first mixing solutions, the mol ratio of sodium hydroxide, potassium hydroxide and the potassium silicate prepared by described step (4) is 1:0.3 ~ 0.4:1 ~ 1.1; The add-on of described extra aluminium hydroxide and soft silica is be 1:0.6 ~ 0.7:0.5 ~ 0.6 according to the mol ratio of the sodium hydroxide in described first mixing solutions, aluminium hydroxide, soft silica.
Based on above-mentioned, described step (2) comprises described containing SiF
4decomposition gas introduce dedusting in dust removal filter, to pass into successively after dust removal and filtration in I and II absorption tower and to be absorbed by the aqueous ethanolic solution that volume fraction is 10% ~ 30%, generate white precipitate and silicate fluoride solution, through centrifugation, wash to obtain silicon-dioxide.
Based on above-mentioned, the crystallization temperature in described step (6) is 80 DEG C ~ 90 DEG C, and the thermostatic crystallization time is 2.5 ~ 4h.Wherein, in this step (6), when adding extra aluminium hydroxide and soft silica, add in mode equably in 0.5 ~ 1h.
Compared with prior art, the method utilizing potassium felspar sand to prepare 3A molecular sieve provided by the invention, mainly utilizes potassium felspar sand and NH
4f low-temperature decomposition obtains soft silica, aluminum hydroxide precipitation and potassium silicate solution; Then solid sodium hydroxide, solid potassium hydroxide, soft silica, aluminum hydroxide precipitation and potassium silicate solution are carried out mixing, reacting according to certain proportioning, predetermined order, obtained 3A zeolite product, and industrial goods Potassium monofluoride, realize the comprehensive utilization to K-feldspar K, Al, Si tri-kinds of elements, remarkable in economical benefits.This method utilizing potassium felspar sand to prepare molecular sieve has high, the good in economic efficiency advantage of design science, element utilization ratio.In addition, the nanometer 3A molecular sieve prepared by method of the present invention has product purity compared with advantages such as high, specific surface area are large, selective adsorption performance is good, and price is lower.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
The embodiment of the present invention 1 provides a kind of method utilizing potassium feldspar decomposition to prepare potassium silicate, and it comprises the following steps:
(1) potassium feldspar decomposition: by potassium felspar sand, Neutral ammonium fluoride, 98% sulfuric acid fully mix according to the mass ratio of 1:2:1.7, react under 220 DEG C and autogenous pressure, obtain potassium feldspar decomposition residue and containing SiF
4decomposition gas; Wherein, in this process, the main reaction occurred is:
NH
4F=HF+NH
3，
2K[AlSi
3O
8]+24HF+4H
2SO
4=K
2SO
4+Al
2(SO
4)
3+6SiF
4↑+16H
2O；
(2) gas absorption: to described containing SiF
4decomposition gas carry out dust removal process, then adopt aqueous ethanolic solution adsorb, filter, washing obtain silicon-dioxide; Particularly, SiF is contained by described
4decomposition gas introduce dedusting in dust removal filter, to pass into successively after dust removal and filtration in I and II absorption tower and to be absorbed by the aqueous ethanolic solution that volume fraction is 10% ~ 30%, generate white precipitate and silicate fluoride solution, through centrifugation, wash to obtain silicon-dioxide; Wherein, in this process, the main reaction occurred is:
3SiF
4+2H
2O=2H
2SiF
6+SiO
2↓；
(3) leaching of reaction residues: described potassium feldspar decomposition residue is placed in leaching groove, at 90 DEG C, add in described leaching groove volume fraction be 8% dilution heat of sulfuric acid leach described potassium feldspar decomposition residue, then the solution after leaching is carried out to filtration and obtains leaching liquid; Wherein, mainly unreacted potassium felspar sand is separated with the vitriol of solubility in this step;
(4) preparation of aluminium hydroxide: prepare the filtrate after potassium silicofluoride through cation-adsorption post absorption Al
3+and Fe
3+, the fluid sulphuric acid potassium filtrate after absorption is returned leaching groove by pump and is carried out circulation leaching; With dilution heat of sulfuric acid, desorption is carried out to the saturated ion exchange resin column of absorption, desorption solution is got in extraction kettle by pump and is extracted, layering is carried out again through extraction separator, lower layer of water to be passed in aluminium hydroxide neutralization reaction still with ammonia neutralization to pH ≈ 7 mutually, carries out after ageing by Filter Press, washing, dry obtained aluminium hydroxide; Extraction separator upper oil phase is got in reextraction still by pump, and strip with sulphuric acid soln, solution leads to layering in reextraction separator, and lower floor's aqueous phase goes to prepare ferric sulfate, and upper oil phase returns extraction kettle and continues extraction;
(5) preparation of potassium silicate: described potassium sulfate filtrate is got in potassium silicofluoride reactor through pump, the silicate fluoride solution added from described step (2) according to stoichiometric relation generates potassium silicofluoride precipitation, silicofluoric acid excessive 20%, after ageing, then through Filter Press, washing, dry obtained potassium silicofluoride; According to stoichiometric relation, in described potassium silicofluoride, add hot potassium hydroxide solution, generate the potassium silicate solution containing Potassium monofluoride crystal; Potassium silicate solution containing Potassium monofluoride crystal is purified, isolates Potassium monofluoride, obtain the potassium silicate solution that massfraction is 28%;
(6) preparation of molecular sieve: take solid sodium hydroxide and potassium hydroxide respectively, and join in described potassium silicate solution and mix, obtain the first mixing solutions; In described first mixing solutions, add aluminium hydroxide prepared by described step (4), stir, 80 DEG C time, carry out crystallization; While crystallization, under stirring, slowly add the obtained soft silica of extra aluminium hydroxide and described step (2) equably with 0.5h, and carry out thermostatic crystallization 4h; By crystallization product after filtration, dry nanometer 3A zeolite product; Wherein, in this first mixing solutions, the mol ratio of sodium hydroxide, potassium hydroxide and potassium silicate is 1:0.3:1; The add-on of described extra aluminium hydroxide and soft silica is 1:0.6:0.5 according to the mol ratio of the sodium hydroxide in described first mixing solutions, aluminium hydroxide, soft silica.
Embodiment 2
The embodiment of the present invention 2 provides a kind of method utilizing potassium feldspar decomposition to prepare potassium silicate, and the method that the method embodiment 1 provides is substantially identical, and difference is:
(1) potassium feldspar decomposition: the potassium felspar sand in this step, Neutral ammonium fluoride, 98% the mass ratio of sulfuric acid be that the mass ratio of 1:1.5:1.8 fully mixes, temperature of reaction is 190 DEG C;
(2) gas absorption: this step is identical with the step (2) of embodiment 1;
(3) leaching of reaction residues: the leaching temperature of this step is at 100 DEG C, the volume fraction of dilute sulphuric acid is 9%;
(4) preparation of aluminium hydroxide: this step is identical with the step (4) of embodiment 1;
(5) preparation of potassium silicate: silicofluoric acid excessive 60% in this step, the massfraction of the potassium silicate solution finally obtained is 30%;
(6) preparation of molecular sieve: in this step, the mol ratio of sodium hydroxide, potassium hydroxide and potassium silicate is 1:0.35:1.05, the mol ratio of sodium hydroxide, the aluminium hydroxide additionally added, soft silica is 1:0.65:0.6, the aluminium hydroxide additionally added and the joining day of soft silica are 0.8h, crystallization temperature is 85 DEG C, and the thermostatic crystallization time is 3h.
Embodiment 3
The embodiment of the present invention 3 provides a kind of method utilizing potassium feldspar decomposition to prepare potassium silicate, and the method that the method embodiment 1 provides is substantially identical, and difference is:
(1) potassium feldspar decomposition: the potassium felspar sand in this step, Neutral ammonium fluoride, 98% the mass ratio of sulfuric acid be that the mass ratio of 1:2.6:1.6 fully mixes, temperature of reaction is 250 DEG C;
(2) gas absorption: this step is identical with the step (2) of embodiment 1;
(3) leaching of reaction residues: the leaching temperature of this step is at 110 DEG C, the volume fraction of dilute sulphuric acid is 10%;
(4) preparation of aluminium hydroxide: this step is identical with the step (4) of embodiment 1;
(5) preparation of potassium silicate: silicofluoric acid excessive 100% in this step, the massfraction of the potassium silicate solution finally obtained is 32%;
(6) preparation of molecular sieve: in this step, the mol ratio of sodium hydroxide, potassium hydroxide and potassium silicate is 1:0.4:1.1, the mol ratio of sodium hydroxide, the aluminium hydroxide additionally added, soft silica is 1:0.7:0.5, the aluminium hydroxide additionally added and the joining day of soft silica are 1h, crystallization temperature is 90 DEG C, and the thermostatic crystallization time is 4h.
Embodiment 4
The embodiment of the present invention 4 provides a kind of method utilizing potassium feldspar decomposition to prepare potassium silicate, and the method that the method embodiment 1 provides is substantially identical, and difference is:
(1) potassium feldspar decomposition: this step is identical with the step (1) of embodiment 2;
(2) gas absorption: this step is identical with the step (2) of embodiment 1;
(3) leaching of reaction residues: the leaching temperature of this step is at 95 DEG C, the volume fraction of dilute sulphuric acid is 10%;
(4) preparation of aluminium hydroxide: this step is identical with the step (4) of embodiment 1;
(5) preparation of potassium silicate: silicofluoric acid excessive 90% in this step, the massfraction of the potassium silicate solution finally obtained is 31%;
(6) preparation of molecular sieve: in this step, the mol ratio of sodium hydroxide, potassium hydroxide and potassium silicate is 1:0.4:1, the aluminium hydroxide additionally added and the joining day of soft silica are 0.7h, and crystallization temperature is 85 DEG C, and the thermostatic crystallization time is 3.5h.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the field are to be understood that: still can modify to the specific embodiment of the present invention or carry out equivalent replacement to portion of techniques feature; And not departing from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope of request of the present invention protection.
Claims (3)
1. utilize potassium felspar sand to prepare a method for 3A molecular sieve, it comprises the following steps:
(1) potassium feldspar decomposition: by potassium felspar sand, Neutral ammonium fluoride, 98% sulfuric acid fully mix according to the mass ratio of 1:1.5 ~ 2.6:1.6 ~ 1.8, react under 190 ~ 250 DEG C and autogenous pressure, obtain potassium feldspar decomposition residue and containing SiF
4decomposition gas;
(2) gas absorption: to described containing SiF
4decomposition gas carry out dust removal process, then adopt aqueous ethanolic solution to carry out absorption generation silicofluoric acid and precipitation of silica; Filtering separation, obtains soft silica and silicate fluoride solution;
(3) leaching of reaction residues: at 90 ~ 110 DEG C, leaches described potassium feldspar decomposition residue with the dilution heat of sulfuric acid that volume fraction is 8 ~ 10%, then carries out filtration to the solution after leaching and obtains leaching liquid;
(4) preparation of aluminium hydroxide: adopt ion exchange resin column to carry out cation-adsorption process to described leaching liquid, obtains potassium sulfate filtrate and adsorbs saturated ion exchange resin column; Then desorption and extraction treatment are carried out to the saturated ion exchange resin column of absorption; Afterwards, with the lower floor's aqueous phase after ammonia neutralization extracting and demixing to neutral, then carry out ageing, filtration, washing, dry obtained aluminium hydroxide, wherein, the extraction agent of the use in described extraction treatment process is volume be 1:1 P204 and sulfonated kerosene;
(5) preparation of potassium silicate: add the silicate fluoride solution from described step (2) according to stoichiometric relation in described potassium sulfate filtrate, generation potassium silicofluoride precipitates, silicate fluoride solution excessive 20% ~ 100%, after ageing, then through Filter Press, the obtained potassium silicofluoride of washing; According to stoichiometric relation, in described potassium silicofluoride, add hot potassium hydroxide solution, generate the potassium silicate solution containing Potassium monofluoride crystal; Potassium silicate solution containing Potassium monofluoride crystal is purified, isolates Potassium monofluoride, obtain the potassium silicate solution that massfraction is 28% ~ 32%;
(6) preparation of molecular sieve: take solid sodium hydroxide and potassium hydroxide respectively, and join in described potassium silicate solution and mix, obtain the first mixing solutions; In described first mixing solutions, add the aluminium hydroxide prepared by described step (4), stir, crystallization is carried out in heating; While crystallization, under stirring, add the soft silica that extra aluminium hydroxide and described step (2) are obtained, and carry out thermostatic crystallization; By crystallization product after filtration, dry nanometer 3A zeolite product; Wherein, in this first mixing solutions, the mol ratio of sodium hydroxide, potassium hydroxide and the potassium silicate prepared by described step (4) is 1:0.3 ~ 0.4:1 ~ 1.1; The add-on of described extra aluminium hydroxide and soft silica is be 1:0.6 ~ 0.7:0.5 ~ 0.6 according to the mol ratio of the sodium hydroxide in described first mixing solutions, aluminium hydroxide, soft silica.
2. the method utilizing potassium felspar sand to prepare 3A molecular sieve according to claim 1, is characterized in that, described step (2) comprises described containing SiF
4decomposition gas introduce dedusting in dust removal filter, to pass into successively after dust removal and filtration in I and II absorption tower and to be absorbed by the aqueous ethanolic solution that volume fraction is 10% ~ 30%, generate white precipitate and silicate fluoride solution, through centrifugation, wash to obtain silicon-dioxide.
3. the method utilizing potassium felspar sand to prepare 3A molecular sieve according to claim 1 and 2, is characterized in that, the crystallization temperature in described step (6) is 80 DEG C ~ 90 DEG C, and the thermostatic crystallization time is 2.5 ~ 4h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887531A (en) * | 2012-10-15 | 2013-01-23 | 张军航 | Technique for producing potassium fluoride from potassium fluosilicate |
| CN103172074A (en) * | 2013-01-17 | 2013-06-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
| CN103539163A (en) * | 2013-10-31 | 2014-01-29 | 洛阳氟钾科技有限公司 | Technology for preparing potassium sulfate by use of potassium feldspar |
| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
-
2015
- 2015-11-29 CN CN201510842295.1A patent/CN105439167A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887531A (en) * | 2012-10-15 | 2013-01-23 | 张军航 | Technique for producing potassium fluoride from potassium fluosilicate |
| CN103172074A (en) * | 2013-01-17 | 2013-06-26 | 洛阳氟钾科技有限公司 | Process for decomposing potassium feldspar by adopting low-temperature semidry method for comprehensive utilization |
| CN103539163A (en) * | 2013-10-31 | 2014-01-29 | 洛阳氟钾科技有限公司 | Technology for preparing potassium sulfate by use of potassium feldspar |
| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
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| Title |
|---|
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| 魏成广: "《中国钾盐工业概览》", 30 July 2009 * |
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