CN103922363A - Method for preparing 4A zeolite by taking ferrous sulfide tailings as raw materials - Google Patents
Method for preparing 4A zeolite by taking ferrous sulfide tailings as raw materials Download PDFInfo
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Abstract
The invention discloses a method for preparing 4A zeolite by taking ferrous sulfide tailings as raw materials, belonging to the field of chemical industry. The method comprises the steps of crushing ferrous sulfide tailings, and then, preparing 20-30% of slurry; respectively adding a CuSO4 solution, butyl xanthate and terpenic oil in the slurry, and then, filtering, drying and grinding; next, adding a mixed acid solution, sufficiently mixing the solution, then, cleaning by using clear water, drying and grinding; calcining at the temperature of 620-650 DEG C for 2-4h, then, adding a NaOH solution, and stirring at the constant temperature of 50-60 DEG C for 2-5h; reacting at the temperature of 90-95 DEG C for 2-5h, centrifuging and drying to obtain a 4A zeolite product. According to the invention, the 4A zeolite can be prepared by taking the ferrous sulfide tailings as raw materials, so that the ferrous sulfide tailings are effectively recycled, the pollution of the ferrous sulfide tailings to the environment is reduced, and meanwhile, the costs of the raw materials for preparing the 4A zeolite are reduced.
Description
Technical field
The present invention relates to chemical field, particularly a kind ofly take pyrite tailing and prepare the method for 4A zeolite as raw material.
Background technology
4A zeolite is a kind of hydrated aluminosilicate-sodium silicoaluminate crystal, and English Sodium Alumino-Silicate by name is the aluminosilicate crystal of synthetic, its chemical formula Na
12[AlO
2(SiO
2)]
1227H
2o, belongs to NaA type zeolite.Synthetic for 4A zeolite, prior synthesizing method is chemical method, take the method that water glass, aluminium hydroxide, caustic soda is raw water thermal synthesis, the method steady quality, but high cost.Utilize the synthetic `4A zeolite of raw mineral materials to reduce costs, have at present Activated, swelling local method, kaolin method and coal gangue method etc.Kaolin method wherein, to utilize kaolin silica alumina ratio and the basically identical feature of 4A zeolite, be translated into the metakaolinite with reactive behavior, and in the caustic soda aqueous solution, carry out hydrothermal crystallization conversion reaction and make zeolite, the method technique is simple, do not need to supplement He Lv source, silicon source, there is lower-cost feature.In the synthetic 4A zeolite of kaolin method, material choice is very important, strictly control existence and the content of impurity in kaolin, conventionally adopts high grade kaolinite.Because impurity can have a strong impact on structure (as crystalline structure, aperture etc.), physical properties (as color and luster, particle diameter etc.) and the chemical property (adsorptivity and ion exchangeable etc.) of the finished product, make the finished product can not reach the requirement of 4A zeolite.
Essential mineral pyrite (the FeS of sulfurous iron ore
2), be a kind of important minerals commonly used in chemical industry raw material, mainly for the manufacture of sulfuric acid.Part is used for industrial chemicals to produce sulphur and various sulfocompounds etc.The said pyrite tailing of this patent refers to kaolinite matter clay pit that exploit out and pyrite in exploitation sulfurous iron ore.Sulfurous iron ore is after selecting pyrite, and rest part just becomes mine tailing, is called pyrite tailing.The fluctuation of the mineral composition of pyrite tailing and chemical composition scope is larger, and essential mineral consists of kaolinite, also contains a small amount of nakrite, Wingdale, anatase octahedrite and the pyrite that is not selected etc.Typical case's chemistry of the said pyrite tailing of this patent consists of (weight percent) SiO
230 ~ 52%, Al
2o
325 ~ 40%, CaO 0.2 ~ 2.0%, Fe
2o
30.6 ~ 19%, TiO
20.5 ~ 7.0%, SO
30.5 ~ 4.5%, other impurity composition 1 ~ 5%.Although the essential mineral composition of visible pyrite tailing is kaolinite, but compare with general kaolinite, the chemical component fluctuation scope of pyrite tailing is large, titanium content is generally higher, add union dyeing and the oxidation of pyritous local surfaces of pyritous symbiosis, organic matter and fixed carbon, make in pyrite tailing that impurity is many and content is high, be difficult to directly be applied.Therefore, in China Pyrite Mine Area, pyrite tailing can not be utilized for a long time, is deposited in ground or gully, causes serious environmental pollution.
Also just because of the compositing characteristic of above-mentioned pyrite tailing, when the synthetic 4A zeolite of traditional kaolin method, pyrite tailing is not meet as the requirement of raw material to carry out 4A zeolite synthesis, and pyrite tailing adopts the existing technique can not be for the synthesis of 4A zeolite.
Summary of the invention
For the problems referred to above, the object of this invention is to provide a kind of pyrite tailing that adopts is the method that raw material is prepared 4A zeolite, to recycle pyrite tailing.
To achieve these goals, the present invention adopts following technical scheme: a kind ofly take pyrite tailing and prepare the method for 4A zeolite as raw material, comprise the following steps:
(1) pulverize after pyrite tailing, be mixed with solid masses percentage composition and be 20～30% slip;
(2) described slip step (1) being obtained regulates pH value to 8 ~ 9, and after stirring, in slip per ton, adding 4～5L mass concentration is 5% CuSO
4solution after stirring, adds 150～250 grams of butyl xanthates in slip per ton, after stirring, then in slip per ton, adds 120～200 grams of pine camphor oils, after stirring, scrapes filtering drying after foam-expelling, and levigate to crossing 200 mesh sieves, obtains powder one time;
(3) in the powder obtaining in step (2), add acid solution, the ratio adding is that a powder adds 3.3～3.8 L acid solutions described in per kilogram, heat to 58～62 ℃, after fully stirring, with clear water, be washed till pH to 5～6, dry and levigate 200～500 mesh sieves of extremely crossing, obtain secondary powder;
(4) secondary powder that will obtain through step (3) is after 620 ~ 650 ℃ of temperature lower calcination 2～4h, adding volumetric molar concentration is the NaOH solution of 2.8～4.0mol/L, the ratio adding is in per kilogram secondary powder, to add NaOH solution described in 5L, and constant temperature stirs 2～5h at 50 ~ 60 ℃, product in the middle of obtaining;
(5) will at 90 ~ 95 ℃, react 2～5h by product in the middle of step (4) gained, obtain work in-process;
(6) will be centrifugal by step (5) gained work in-process, dry, obtain 4A zeolite product.
Present method be take impurity component complexity and the high pyrite tailing of foreign matter content and is prepared 4A zeolite as raw material, in order to prepare the 4A zeolite of qualified even high-quality, above-mentioned steps (1)-(3) are that pyrite tailing is carried out to composition adjustment, comprise and reduce the content of impurity and adjust the silica alumina ratio in raw material, concrete:
In step (1), by after pyrite tailing fragmentation, be beneficial to the removal of follow-up impurity;
In step (2), because pyrite surface electric charge is for just, easily by xanthate anionoid adsorption of collector, and pine camphor oil is as pore forming material, is conducive to reduce the surface tension of the aqueous solution, makes to be filled with air in water and is easy to disperse and becomes bubble stabilise bubbles.Pine camphor oil and xanthate gang are adsorbed in mineral grain surface, make ore particle floating, thereby effectively remove the impurity such as pyrite, and the existence of copper sulfate can suppress unsulfided and are adsorbed;
In step (3), the iron cpd that adopts acid solution to make ferric ion generate solubility enters solution, thus further deironing, and can remove portion titanium and adjustment silica alumina ratio.
After adopting the method for step (1)-(3) to process, composition and the high grade kaolinite of the secondary powder obtaining are similar, then adopt to be similar to kaolin method and to carry out synthesizing of 4A zeolite, concrete:
In step (4), the object that mine tailing is after treatment calcined is that activation of kaoline is become to metakaolin, and its reaction formula is: Al
2si
2o
5(OH)
4→ Al
2si
2o
7+ 2H
2o.Active metakaolin after calcining under optimal temperature with NaOH ageing of solution, its objective is and make it be transformed into gradually uniform Edge by Aluminosilicate Sol-gel, form to transform molecular sieve presoma, for follow-up crystallization process lays the foundation.The reaction formula of this process is:
6(Al
2O
3·2SiO
2)+12NaOH+21H
2O→Na
12[(AlO
2)(SiO
2)]
12·27H
2O。
In step (4), adopted with conventional kaolin method and compared, 620 ~ 650 ℃ of lower calcining temperatures, the calcining temperature of conventional kaolin method is generally 750-850 ℃, and this all has benefited from the pretreatment process that has adopted the distinctive removal of impurities of the present invention and composition to adjust; Lower calcining temperature, on the one hand can save energy, can extend on the other hand the duration of service of calciner.
As preferred technical scheme: in step (1), pulverize pyrite tailing to crossing 200～500 mesh sieves.Synthetic 4A zeolite whiteness is relevant with the granularity of calcium ion-exchanged amount and raw material, and general raw material pulverizing fine size, is conducive to improve whiteness and calcium ion-exchanged amount.
As preferred technical scheme: in step (2), adopting mass percentage concentration while regulating pH value is 10% Na
2cO
3solution.
As preferred technical scheme: in step (3), described acid solution is mixed acid solution, described mixed acid solution is that to take sulfuric acid and the hydrochloric acid soln that mass concentration is 25%～35% be component, and 1:1 is formulated by volume.If only use salt acid treatment pyrite tailing, de-ferrous effect is better, but for the higher mine tailing of titaniferous, but can not effectively improve whiteness; Use vitriolization pyrite tailing can when removing a part of iron, remove a part of titanium.Adopt " sulfuric acid+hydrochloric acid " to process pyrite tailing, can change insoluble compound wherein into soluble compounds, and separated with kaolin, effectively remove iron contamination, and can partly remove titanium contained in kaolin, improve kaolin whiteness.In addition, the stability of kaolin in mineral acid is better, through persalt or vitriolization, only has Al seldom
2o
3be dissolved, use mixing acid to process kaolin and be more conducive to adjust kaolinic silica alumina ratio.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows: adopt method of the present invention, can adopt pyrite tailing to prepare 4A zeolite as raw material, thereby pyrite tailing has been carried out to effective recycling, when having reduced pyrite tailing to environment, reduced the cost of 4A zeolite raw materials; And the crystalline structure of the 4A zeolite preparing, aperture, physical properties (as color and luster, particle diameter etc.) and chemical property (adsorptivity and ion exchangeable etc.), can reach the requirement of 4A zeolite.If color and luster is white, whiteness is 85-90%, and calcium ion-exchanged amount reaches 300-340mgCaCO
3/ g.The pH value of 4A zeolite is 10-11.2.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the 4A zeolite that makes of the embodiment of the present invention 1;
Fig. 2 is the XRD figure of the 4A zeolite that makes of the embodiment of the present invention 2;
Fig. 3 is the XRD figure of the 4A zeolite that makes of the embodiment of the present invention 3;
In Fig. 1-3, X-coordinate is diffraction angle " 2-theta ", and unit is " degree "; Ordinate zou is " intensity ", and unit is " a.u ".
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Pyrite tailing that the present embodiment is used is taken from certain enterprise's pyrite tailing storehouse, area, south, river, is the mine tailing that enterprise piles up in decades for a long time, and because production technology level was low originally, so in this mine tailing, iron, titanium, sulphur content are all very high.Its chemical component weight per-cent is: SiO
240.89%, A1
2o
333.87%, CaO 3.97%, TiO
25.01%, Fe
2o
36.09%, K
2o 0.18%, SO
39.55%, other are 0.43% years old.Use this pyrite tailing to prepare the processing step of 4A zeolite as follows:
(1) with ball mill, pyrite tailing is levigate to crossing after 325 mesh sieves, to become solid masses percentage composition be 25% slip and be placed in certain container to take 300g preparation of powder;
(2) in the slip obtaining by step (1), adding mass concentration is 10% Na
2cO
3solution, regulates pH value to 8 ~ 9, stirs after 3min, adds the CuSO that 5 mass per liter concentration are 5% in slip per ton
4solution, stirs after 3min, adds 250 grams of butyl xanthates in slip per ton, stirs after 3min, then in slip per ton, adds 200 grams of pine camphor oils; Stir after 180 seconds, start to scrape bubble; This operation repeats to do after 3 road flotation, and suction filtration is dried, and levigate to crossing 200 mesh sieves, obtains powder one time;
(3) preparing respectively mass concentration is that 30% sulfuric acid and mass concentration are 30% hydrochloric acid soln;
(4) sulfuric acid that use is prepared by step (3) and hydrochloric acid soln by volume 1:1 are mixed with mixed acid solution;
(5) will press 3.5L/kg by the mixed acid solution of step (4) preparation
powderratio join in the powder obtaining by step (2), heat to 58 ℃, fully stir after 1 hour, with clear water, be washed till pH to 5-6, dry and levigately cross mesh sieves to 325, obtain secondary powder;
(6) secondary powder that will obtain through step (5) is after 620 ℃ of temperature lower calcination 4h, by 5L/kg
powderratio add the NaOH solution of volumetric molar concentration 2.8mol/L, and at 55 ℃, constant temperature stirs 4h, product in the middle of obtaining;
(7) will put into reactor by product in the middle of step (6) gained, at 90 ℃, react 2h, obtain work in-process;
(8) will, by step (7) gained work in-process centrifugal drying, obtain 4A zeolite product.
Prepared product is 4A zeolite, is white cube crystal, nontoxic, tasteless, non-corrosiveness.Water insoluble and organic solvent, can be dissolved in strong acid and highly basic, and pH value is 10, and its stable range is 5 ~ 12; Median size is 1.48 μ m, and size-grade distribution≤4 μ m accounts for 85.6%.X ray powder crystal diffraction (XRD) material phase analysis as shown in Figure 1, in the XRD spectra of synthetic product except there is the dephasign diffraction peak of a small amount of the unknown, the standard diagram of other diffraction peak and 4A zeolite is in full accord, shows that through example 1 technique synthesized used product crystalline phase be 4A zeolite.Its calcium ion-exchanged amount is 300.48mgCaCO
3/ g, whiteness is 87%.
Embodiment 2
Pyrite tailing that the present embodiment is used is taken from certain enterprise's pyrite tailing storehouse, area, south, river, and its chemical component weight per-cent is: SiO
245.90%, A1
2o
337.05%, CaO 1.98%, TiO
25.03%, Fe
2o
33.91%, K
2o 0.56%, SO
31.27%, other are 4.29% years old.Use this pyrite tailing to prepare the processing step of 4A zeolite as follows:
(1) with ball mill, pyrite tailing is levigate to crossing after 325 mesh sieves, to become solid masses percentage composition be 30% slip and be placed in certain container to take 300g preparation of powder;
(2) in the slip obtaining by step (1), adding mass concentration is 10% Na
2cO
3solution, regulates pH value to 8 ~ 9, stirs after 2.5min, adds the CuSO that 4.5 mass per liter concentration are 5% in slip per ton
4solution, stirs after 2.5min, adds 150 grams of butyl xanthates in slip per ton, stirs after 1min, then in slip per ton, adds 160 grams of pine camphor oils; Stir after 90 seconds, start to scrape bubble; This operation repeats to do after 3 road flotation, and suction filtration is dried, and levigate to crossing 200 mesh sieves, obtains powder one time;
(3) preparing respectively mass concentration is that 35% sulfuric acid and mass concentration are 35% hydrochloric acid soln;
(4) sulfuric acid that use is prepared by step (3) and hydrochloric acid soln by volume 1:1 are mixed with mixed acid solution;
(5) will press 3.8L/kg by the mixed acid solution of step (4) preparation
powderratio join in the powder obtaining by step (2), heat to 62 ℃, fully stir after 1 hour, with clear water, be washed till pH to 5-6, dry and levigately cross mesh sieves to 200, obtain secondary powder;
(6) secondary powder that will obtain through step (5) is after 650 ℃ of temperature lower calcination 4h, by 5L/kg
powderratio add the NaOH solution of volumetric molar concentration 4.0mol/L, and at 60 ℃, constant temperature stirs 5h, product in the middle of obtaining;
(7) will put into reactor by product in the middle of step (6) gained, at 95 ℃, react 5h, obtain work in-process;
(8) will, by step (7) gained work in-process centrifugal drying, obtain 4A zeolite product.
Prepared product is 4A zeolite, is white cube crystal, nontoxic, tasteless, non-corrosiveness.Water insoluble and organic solvent, can be dissolved in strong acid and highly basic, and pH value is 11, and its stable range is 5-12; Median size 2.24 μ m, size-grade distribution≤4 μ m accounts for 85.48%.X ray powder crystal diffraction (XRD) material phase analysis as shown in Figure 2, in the XRD spectra of synthetic product except there is the dephasign diffraction peak of a small amount of the unknown, the standard diagram of other diffraction peak and 4A zeolite is in full accord, show that through example 2 technique synthesized used product crystalline phase be 4A zeolite, and because Synthesis of 4 A-type Zeolite by Hydrothermal crystallization time is longer, crystal growth is perfect.This synthetic product whiteness is 87%, and its calcium ion-exchanged amount is 320.64mgCaCO
3/ g.
Embodiment 3
Pyrite tailing that the present embodiment is used is taken from the flotation cell of the small-sized heavy floating choosing of south, river certain enterprise of area, and its chemical component weight per-cent is: SiO
238.41%, A1
2o
332.40%, CaO 3.02%, TiO
24.01%, MgO 0.76%, Fe
2o
31.91%, Na
2o 0.16%, K
2o 0.35%, SO
30.92%, other are 0.80% years old.Use this pyrite tailing to prepare the processing step of 4A zeolite as follows:
(1) with ball mill, pyrite tailing is levigate to crossing after 200 mesh sieves, to become solid masses percentage composition be 20% slip and be placed in certain container to take 300g preparation of powder;
(2) in the slip obtaining by step (1), adding mass concentration is 10% Na
2cO
3solution, regulates pH value to 8 ~ 9, stirs after 2min, adds the CuSO that 4 mass per liter concentration are 5% in slip per ton
4solution, stirs after 2min, adds 200 grams of butyl xanthates in slip per ton, stirs after 1.5min, then in slip per ton, adds 120 grams of pine camphor oils; Stir after 30 seconds, start to scrape bubble; This operation repeats to do after 3 road flotation, and suction filtration is dried, and levigate to crossing 200 mesh sieves, obtains powder one time;
(3) preparing respectively mass concentration is that 25% sulfuric acid and mass concentration are 25% hydrochloric acid soln;
(4) sulfuric acid that use is prepared by step (3) and hydrochloric acid soln by volume 1:1 are mixed with mixed acid solution;
(5) will press 3.36L/kg by the mixed acid solution of step (4) preparation
powderratio join in the powder obtaining by step (2), heat to 60 ℃, fully stir after 1 hour, with clear water, be washed till pH to 5-6, dry and levigately cross mesh sieves to 325, obtain secondary powder;
(6) secondary powder that will obtain through step (5) is after 630 ℃ of temperature lower calcination 3h, by 5L/kg
powderratio add the NaOH solution of volumetric molar concentration 3.0mol/L, and at 50 ℃, constant temperature stirs 3h, product in the middle of obtaining;
(7) will put into reactor by product in the middle of step (6) gained, at 92 ℃, react 3h, obtain work in-process;
(8) will, by step (7) gained work in-process centrifugal drying, obtain 4A zeolite product.
Prepared product is 4A zeolite, is white cube crystal, nontoxic, tasteless, non-corrosiveness.Water insoluble and organic solvent, can be dissolved in strong acid and highly basic, and pH value is 11.2, and its stable range is 6-13, and median size is 2.11 μ m, and size-grade distribution≤4 μ m accounts for 89.84%.X ray powder crystal diffraction (XRD) material phase analysis as shown in Figure 3, in the XRD spectra of synthetic product except there is the dephasign diffraction peak of a small amount of the unknown, the standard diagram of other diffraction peak and 4A zeolite is in full accord, shows that through example 3 technique synthesized used product crystalline phase be 4A zeolite.This synthetic product whiteness is 90%, and calcium ion-exchanged amount is 330.68mgCaCO
3/ g.
Claims (4)
1. the pyrite tailing of take is prepared the method for 4A zeolite as raw material, it is characterized in that, comprises the following steps:
(1) pulverize after pyrite tailing, be mixed with solid masses percentage composition and be 20～30% slip;
(2) described slip step (1) being obtained regulates pH value to 8 ~ 9, and after stirring, in slip per ton, adding 4～5L mass concentration is 5% CuSO
4solution after stirring, adds 150～250 grams of butyl xanthates in slip per ton, after stirring, then in slip per ton, adds 120～200 grams of pine camphor oils, after stirring, scrapes filtering drying after foam-expelling, and levigate to crossing 200 mesh sieves, obtains powder one time;
(3) in the powder obtaining in step (2), add acid solution, the ratio adding is that a powder adds 3.3～3.8 L acid solutions described in per kilogram, heat to 58～62 ℃, after fully stirring, with clear water, be washed till pH to 5～6, dry and levigate 200～500 mesh sieves of extremely crossing, obtain secondary powder;
(4) secondary powder that will obtain through step (3) is after 620 ~ 650 ℃ of temperature lower calcination 2～4h, adding volumetric molar concentration is the NaOH solution of 2.8～4.0mol/L, the ratio adding is in per kilogram secondary powder, to add NaOH solution described in 5L, and constant temperature stirs 2～5h at 50 ~ 60 ℃, product in the middle of obtaining;
(5) will at 90 ~ 95 ℃, react 2～5h by product in the middle of step (4) gained, obtain work in-process;
(6) will be centrifugal by step (5) gained work in-process, dry, obtain 4A zeolite product.
2. a kind ofly according to claim 1 take pyrite tailing and prepare the method for 4A zeolite as raw material, it is characterized in that: in step (1), pulverize pyrite tailing to crossing 200～500 mesh sieves.
3. a kind ofly according to claim 1 take pyrite tailing and prepare the method for 4A zeolite as raw material, it is characterized in that: in step (2), while regulating pH value, adopting mass percentage concentration is 10% Na
2cO
3solution.
4. a kind ofly according to claim 1 take pyrite tailing and prepare the method for 4A zeolite as raw material, it is characterized in that: in step (3), described acid solution is mixed acid solution, described mixed acid solution is that to take sulfuric acid and the hydrochloric acid soln that mass concentration is 25%～35% be component, and 1:1 is formulated by volume.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313695A (en) * | 2014-10-31 | 2015-01-28 | 成都理工大学 | Mullite nano-whisker prepared by using pyrite tailing as raw material and preparation method of mullite nano-whisker |
Citations (2)
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|---|---|---|---|---|
| JP2004203732A (en) * | 2002-12-10 | 2004-07-22 | Toshio Shimoda | Method for producing single crystal highly functional zeolite which is made mainly from sewerage sludge incineration ash, and device for producing it |
| CN101462739A (en) * | 2009-01-09 | 2009-06-24 | 桂林工学院 | Method for preparing 4A zeolite molecular sieve from red desmine |
-
2014
- 2014-04-30 CN CN201410178446.3A patent/CN103922363B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004203732A (en) * | 2002-12-10 | 2004-07-22 | Toshio Shimoda | Method for producing single crystal highly functional zeolite which is made mainly from sewerage sludge incineration ash, and device for producing it |
| CN101462739A (en) * | 2009-01-09 | 2009-06-24 | 桂林工学院 | Method for preparing 4A zeolite molecular sieve from red desmine |
Non-Patent Citations (1)
| Title |
|---|
| 王德清 等: "高岭石型硫铁矿烧渣合成磁性4A沸石及其表征", 《材料导报B:研究篇》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313695A (en) * | 2014-10-31 | 2015-01-28 | 成都理工大学 | Mullite nano-whisker prepared by using pyrite tailing as raw material and preparation method of mullite nano-whisker |
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