Potassium felspar sand is utilized to produce the method for molecular sieve
Technical field
The present invention relates to a kind of method producing molecular sieve, specifically, relate in a kind of industrial production and utilize potassium felspar sand to produce 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 produced 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 produce 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 produce molecular sieve, and preparation process comprises the following steps:
Step 1: potassium felspar sand and NH
4f reaction generates SiF
4gas and containing Al
3+, K
+and F
-residue;
Step 2: what generate in step 1 contains Al
3+, K
+and F
-residue in add Fluorspar Powder and H
2sO
4, after mixing, reaction generates SiF
4gas and containing Al
3+, K
+, SO
4 2-and CaSO
4residue;
Step 3: by the SiF generated in step 1-2
4gas passes in NaOH solution, obtains the Na containing NaF crystal
2siO
3solution;
Step 4: the resultant in step 3 is purified, from Na
2siO
3in solution, NaF crystal separation is gone out;
Step 5: contain Al by what generate in step 2
3+, K
+, SO
4 2-and CaSO
4residue pulverize after leach in the hot water, then press filtration obtains containing K
+, Al
3+, SO
4 2-leaching liquid;
Step 6: add ammoniacal liquor in leaching liquid described in step 5, reaction generates ammonium-potassium sulfate solution and Al (OH)
3precipitation;
Step 7: by the Al (OH) filtered out
3join in NaOH solution, reaction generates NaAlO
2solution, and to this NaAlO
2solution carries out filtration and purifies;
Step 8: by the Na after purification in step 4
2siO
3naAlO after purifying in solution and step 7
2solution mixes in water, through being obtained by reacting molecular sieve work in-process, described molecular sieve work in-process are washed successively, press filtration, drying, obtain molecular sieve finished product.
Based on above-mentioned, the reaction in described step 8 comprises aging and crystallization, and aging temperature is 70 DEG C-80 DEG C, and digestion time is 1-4 hour; Crystallization temperature is 93 DEG C-97 DEG C, and crystallization time is 3-4 hour; In described step 8, the silica alumina ratio of two kinds of reactants is 2:1.
Based on above-mentioned, the purification in described step 4 is comprised the centrifugation and condensing crystal successively carried out.
Based on above-mentioned, described centrifugation is from Na
2siO
3in solution, NaF crystal separation is gone out a part, then isolated NaF crystal is washed, dry, obtain NaF finished product.
Based on above-mentioned, described condensing crystal is from the Na after described centrifugation
2siO
3isolate NaF crystal in solution, then this NaF crystal is rejoined in the resultant of described step 3, again participate in described step 4; Through the Na of described condensing crystal
2siO
3solution is for participating in the reaction of described step 8.
Based on above-mentioned, also comprise ammonia in the resultant in described step 1, ammonia cold water carries out absorption and forms ammoniacal liquor, and this ammoniacal liquor is for participating in the reaction of step 6.
Based on above-mentioned, in described step 1, potassium felspar sand and NH
4the mass ratio of F is 1:(0.4-0.6), temperature of reaction is 300 DEG C-320 DEG C, 0.5 hour-2 hours reaction times.
Based on above-mentioned, in described step 2, containing Al
3+, K
+, F
-residue and the mass ratio of Fluorspar Powder and sulfuric acid be 1:(0.4-0.5): (0.7-1), temperature of reaction is 350 DEG C-390 DEG C, 0.5 hour-2 hours reaction times.
Based on above-mentioned, in described step 5, hot water with containing Al
3+, K
+, SO
4 2-and CaSO
4the ratio of mass of residue be (3-5): 1, temperature is 85 DEG C-95 DEG C, leaching time 1-3 hour.
Hinge structure of the present invention has outstanding substantive distinguishing features and significant progress, and specifically, the present invention utilizes potassium felspar sand and NH
4the SiF of F low-temperature decomposition gained
4gas, changes into Na in NaOH solution
2siO
3and NaF; Solid slag simultaneously after potassium feldspar decomposition obtains containing K through leaching
+, Al
3+, SO
4 2-leaching liquid, leaching liquid leads to ammonia can obtain Al (OH)
3precipitation and agricultural composite fertilizer ammonium-potassium sulfate.With NaOH process Al (OH)
3naAlO can be obtained
2, NaAlO
2with Na
2siO
3synthesis of molecular sieve under hydrothermal conditions.By control Na
2siO
3solution and NaAlO
2the proportioning of solution, realizes the adjustable of sial when crystal formation, to meet different customer demand, and by-product Agricultural Fertilizer ammonium-potassium sulfate and industrial goods Sodium Fluoride, 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 produce molecular sieve has design science, the sial advantage that when crystal formation is adjustable, element utilization ratio is high, good in economic efficiency.
Accompanying drawing explanation
Fig. 1 is preparation flow schematic diagram of the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
embodiment 1
As shown in Figure 1, a kind of method utilizing potassium felspar sand to produce molecular sieve, preparation process comprises the following steps:
Step 1: after converter temperature reaches 350 DEG C, proportionally by potassium felspar sand 60Kg and NH
4f(30-40) Kg mixes, and adds in converter feed bin in batches, opens batch mixing spiral, star-like blanking device charging successively, feldspar in powder and NH
4f reacts and generates SiF in converter
4gas and containing Al
3+, K
+and F
-residue.Wherein, potassium felspar sand and NH before reaction
4the mass ratio of F is 1:(0.4-0.6), temperature of reaction is 300 DEG C-320 DEG C, 0.5 hour-2 hours reaction times.After reacting half an hour, open discharging spiral, reacted material slag is discharged by stove tail.
Step 2: after converter temperature reaches 370 DEG C, add Fluorspar Powder, Fluorspar Powder opens sulfuric acid charging ball valve after adding two minutes, start sulfuric acid volume pump, according to 48Kg/h:(40-50) ratio of Kg/h adds H
2sO
4react.Containing Al
3+, K
+, F
-residue mix with Fluorspar Powder and sulfuric acid after react and generate SiF
4gas and containing Al
3+, K
+, SO
4 2-and CaSO
4residue; Containing Al
3+, K
+, F
-residue and the mass ratio of Fluorspar Powder and sulfuric acid be 1:(0.4-0.5): (0.7-1), temperature of reaction is 350 DEG C-390 DEG C, 0.5 hour-2 hours reaction times.
Step 3: by the SiF generated in step 1-2
4gas passes in the NaOH solution of 1000 liters of 2mol/L, obtains the Na containing NaF crystal
2siO
3solution; The NH generated in step 1-2
3absorb with water.
Step 4: the resultant in step 3 is purified, from Na
2siO
3in solution, NaF crystal separation is gone out.NaF crystal finished product is important industrial goods raw material, improves the economic benefit that potassium feldspar decomposition produces.
Step 5: contain Al by what generate in step 2
3+, K
+, SO
4 2-and CaSO
4residue pulverizer pulverize after leach in the hot water, in plate-and-frame filter press, then carry out press filtration obtain containing K
+, Al
3+, SO
4 2-leaching liquid; Hot water with containing Al
3+, K
+, SO
4 2-and CaSO
4the ratio of mass of residue be (3-5): 1, temperature is 85 DEG C-95 DEG C, leaching time 1-3 hour, then naturally cooling.
Step 6: open and stir, add ammoniacal liquor in leaching liquid described in 1000L in step 5, reaction generates ammonium-potassium sulfate solution and Al (OH)
3precipitation; Equal 8 to pH, filter and obtain 25Kg Al (OH)
3precipitation.Institute adds ammonia and Al
3+mol ratio be 3.5:1.Ammonium-potassium sulfate, as by product, is important Agricultural Fertilizer raw material, significantly improves the economic benefit that potassium feldspar decomposition produces.
Step 7: by Al (OH)
3join in NaOH solution, reaction generates NaAlO
2solution.NaOH and Al (OH)
3mol ratio be 1.2:1.According to Na
2o/Al
2o
3ratio-dependent NaOH, Al (OH) of=1.34
3, H
2the consumption of O, the concentration of NaOH is 30%(massfraction).Al (OH) is added in the NaOH solution of heating
3, 115 DEG C of continuous stirrings make it fully react, and obtain NaAlO
2solution, chemical examination sodium aluminate content and to this NaAlO
2solution carries out filtration and purifies.
Step 8: by the Na after purification in water, mother liquor, step 4
2siO
3naAlO after purifying in solution and step 7
2solution joins in crystallizing kettle successively, adds 10 grams of crystal seeds, if produce 13X type molecular sieve, needs to be warming up to 80 DEG C, aging 1 hour, then continues to be warmed up to 95 DEG C, crystallization 4 hours; If produce 4A type molecular sieve, aging temperature is needed to be 70 degree, digestion time 4 hours, crystallization temperature 95 degree, 4 hours time.After open kettle cover naturally cooling, obtain molecular sieve work in-process, described molecular sieve work in-process washed successively, press filtration, drying, obtain molecular sieve finished product.Initial wash equipment is belt filter press, degree of depth washing plate-and-frame filter press, and drying plant is cyclone drying machine.In this step 8, the silica alumina ratio of two kinds of reactants is 2:1.
Silica alumina ratio in molecular sieve and crystal formation can be different according to different customer demand, and natural mineral composition has been fixed, and cannot complete this adjustment, so by the step 8 in the present invention, and can control Na
2siO
3solution and NaAlO
2the proportioning of solution, realizes the sial object that when crystal formation is adjustable with this.Adjustment Na
2o, Al
2o
3, SiO
2, H
2the ratio of O can obtain dissimilar product.
embodiment 2
Embodiment 2 is with the difference of embodiment 1: the purification in described step 4 comprises the centrifugation and condensing crystal successively carried out.
Described centrifugation is from Na in tripod pendulum type batch centrifugal
2siO
3in solution, NaF crystal separation is gone out a part, then isolated NaF crystal is washed, dry, obtain NaF crystal finished product.NaF crystal finished product is important industrial goods raw material, improves the economic benefit that potassium feldspar decomposition produces.
Described condensing crystal be vacuum tightness be-0.08Mpa, temperature is in the crystallization kettle of 70 DEG C, from the Na after described centrifugation
2siO
3isolate NaF crystal crude product in solution, because the NaF crystal crude product through condensing crystal is pure not as centrifugalled NaF crystal finished product, so rejoin in the resultant of described step 3 by this NaF crystal crude product, again participate in described step 4; Through the Na of described condensing crystal
2siO
3solution is for participating in the reaction of described step 8.
embodiment 3
Embodiment 3 is with the difference of embodiment 2: also comprise ammonia in the resultant in described step 1, and ammonia cold water carries out absorption and forms ammoniacal liquor, and this ammoniacal liquor is for participating in the reaction of step 6.After centrifugation washed NaF crystal water in containing NaF, may be used for preparing NaOH solution, this NaOH solution can be used for the reaction participating in step 3 and step 7.As can be seen from above 2, waste gas and waste water are recycled by the present invention, participate in production process, improve the utilization ratio of product in potassium feldspar decomposition technique while energy-saving and emission-reduction.
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.