CN111943223A - Method for preparing X-type zeolite by utilizing coal gangue and rice hulls - Google Patents
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Abstract
The invention discloses a method for preparing X-type zeolite by utilizing coal gangue and rice hulls, which comprises the steps of drying, mixing, grinding, sieving and burning the rice hulls and the coal gangue in sequence to obtain mixed burning ash of the coal gangue and the rice hulls; the method not only utilizes the rice hulls as biomass fuel to improve the combustion performance of the coal gangue, provides heat for promoting the conversion of kaolin in the coal gangue to metakaolin, reduces the energy consumption required by the calcination of zeolite prepared from the traditional coal gangue, but also can fully utilize active silicon in rice hull ash to adjust the silicon-aluminum ratio of the obtained X-type zeolite.
Description
Technical Field
The invention relates to a preparation method of zeolite, in particular to a method for preparing X-type zeolite with higher added value by utilizing bulk industrial solid waste coal gangue and biomass rice hulls, belonging to the technical field of solid waste recycling.
Background
The X-type zeolite is a substance with a Faujasite (FAU) framework structure, has a silicon-aluminum molar ratio (n (Si)/n (Al)) of 1-1.5, and plays an important role in the fields of catalysis and adsorption. The synthesis of zeolite requires the use of chemical reagents such as sodium silicate, sodium aluminate, etc., and the process of producing these chemicals is also energy consuming, so it is important to find inexpensive and readily available raw materials for the synthesis of zeolite molecules.
The coal gangue is a rock with low carbon content discharged in the coal mining process, and the stockpiling amount is large, thereby influencing the environment. The kaolin coal gangue has good silicon-aluminum elements, and a plurality of researchers improve the process conditions and routes, promote the preparation of zeolite by using the coal gangue as a raw material, and synthesize NaA, NaX, NaY zeolite and the like. The main preparation method comprises the following steps: hydrothermal synthesis, alkali fusion, and the like. Most of the existing documents activate coal gangue through calcination, and kaolin in the coal gangue can be converted into more active metakaolin at a certain temperature, so that the time for forming zeolite is greatly shortened. However, the calorific value of the coal gangue is about 1300kcal/kg, and the calorific value of the coal gangue is not fully utilized in the prior art. The rice husk is agricultural waste, has huge annual output, is not easy to decompose quickly, is easy to cause air pollution by open-air combustion, and is used as fuel in the most direct utilization mode, and the combustion product of the rice husk is mainly SiO2Generally, the content is more than 80%. At present, no relevant report of utilizing silicon source in rice hull ash for zeolite synthesis exists.
Disclosure of Invention
In order to solve the problems of zeolite preparation from coal gangue in the prior art, the invention aims to provide a method for preparing X-type zeolite with high purity and good crystallinity by using coal gangue and rice husk as raw materials through the process steps of mixed combustion, caustic soda excitation activation and the like.
In order to achieve the technical purpose, the invention provides a method for preparing X-type zeolite by utilizing coal gangue and rice hulls, which comprises the following steps:
1) drying, mixing, grinding and sieving the rice hulls and the coal gangue in sequence to obtain a mixed powder raw material;
2) burning the mixed powder raw material to obtain coal gangue and rice hull mixed burning ash;
3) mixing and reacting the coal gangue and rice hull mixed burning ash with a sodium hydroxide solution, and then aging and crystallizing to obtain the coal gangue and rice hull mixed burning ash.
The key point of the technical scheme of the invention is that a large amount of industrial solid waste coal gangue and biomass rice hulls are matched and subjected to synergistic treatment to obtain the X-type zeolite with high utilization value and economic value. The introduction of the rice hulls plays an important role in improving the heat value of the coal gangue and the utilization rate of silicon-aluminum components, on one hand, the rice hulls are used as biomass fuel to improve the combustion performance of the coal gangue, the heat value of the coal gangue can be fully released, heat is provided for promoting the conversion of kaolin in the coal gangue to metakaolin, and the energy consumption required by the calcination of zeolite prepared from the traditional coal gangue is reduced.
As a preferred scheme, the coal gangue and the rice hull comprise the following components in percentage by mass: 20-30 percent and 70-80 percent. In order to fully utilize the silicon-aluminum components in the coal gangue and the heat value contained in the coal gangue, the ratio of the coal gangue to the rice hulls is preferably controlled within a proper range. If the mass ratio of the coal gangue is too high, the calorific value is reduced, the combustion performance is poor, the X-type zeolite with higher purity cannot be obtained due to improper silica-alumina ratio, if the mass ratio of the coal gangue is too low, the effect of fully utilizing the silica-alumina components in the coal gangue cannot be achieved, and meanwhile, the change of the silica-alumina ratio is also caused to be unfavorable for generating the X-type zeolite with higher purity.
As a preferable scheme, the combustion control temperature is 580-620 ℃, and the time is 2-3 h. If the temperature is lower than the interval, the kaolin phase in the coal gangue is difficult to convert to the metakaolin phase, the alkali liquor in the zeolite synthesis process is difficult to destroy the relation between the silicon-oxygen tetrahedron and the aluminum-oxygen tetrahedron, the zeolite synthesis reaction speed is slow, and if the temperature is higher than the interval, amorphous SiO in the rice hull ash can be caused2Is easy to be converted into quartz crystal, which is not beneficial to later-stage zeolite synthesis.
As a preferable scheme, the solid-to-liquid ratio of the coal gangue and rice hull mixed burning ash to the sodium hydroxide solution is 1g: 8-10 mL, and the concentration of the sodium hydroxide solution is 3.8-4.2 mol/L. Too high liquid-solid ratio or too high concentration of the alkali liquor can increase the consumption of the alkali liquor and reduce the utilization rate of the alkali liquor, but too low concentration of the sodium hydroxide solution or too low liquid-solid ratio can influence the reaction speed.
As a preferable scheme, the aging process is aging for 1.5-2 hours at the temperature of 80-85 ℃. Below this aging time and temperature, the mixed burning ash and the sodium hydroxide aqueous solution can not fully react, the later crystallization speed and trend are influenced, and above this aging time and temperature, the requirements for equipment can be raised.
As a preferable scheme, the crystallization process is crystallization for 8-9 hours at the temperature of 80-85 ℃. Below this crystallization temperature and time, the zeolite crystals in the blended ash do not crystallize completely, and above this crystallization temperature and time, the type of crystals in the product may change.
The method for preparing the zeolite by utilizing the coal gangue and the stone rice hulls comprises the following specific steps:
1) drying a certain amount of coal gangue and rice hulls at 105 ℃, wherein the mass ratio of the coal gangue to the rice hulls is 1: 5, mixing, grinding in a planetary mill, and sieving with a 40-mesh sieve to obtain a rice hull and coal gangue mixed raw material;
2) burning the mixed raw materials in a muffle furnace at 600 ℃ to obtain coal gangue and rice hull mixed burning ash;
3) mixing the mixed burning ash with 4mol/L sodium hydroxide aqueous solution according to the proportion of 1g: mixing 10 ml;
4) carrying out water bath on the mixed solution in the step 3), and aging for 2h at 80 ℃;
5) crystallizing the aged liquid at 80 ℃ for 8 h;
6) and transferring the crystallized liquid into a centrifuge tube for centrifugation, pouring out supernatant, washing with distilled water, centrifuging again, reciprocating until the solution is neutral, and drying the final solid to obtain the X-type zeolite.
Compared with the prior art, the technical scheme of the invention has the following advantages and effects:
1. according to the scheme, the X-type zeolite with high utilization value can be obtained by using the coal gangue and the rice hull as raw materials, meanwhile, the comprehensive utilization of the coal gangue and the rice hull is realized, the environmental problem in the stockpiling of the two solid wastes is solved, and meanwhile, the high economic value is brought;
2. according to the scheme of the invention, the rice hulls and the coal gangue are mixed and ground, and the coal gangue can be used as a grinding aid to improve the grinding efficiency and reduce the power consumption in the rice hull grinding process;
3. according to the scheme, the combustion performance of the coal gangue can be improved by using the rice hulls, and the energy consumption in the traditional process of calcining the coal gangue is reduced;
4. according to the scheme, the rice hull ash can be used as a silicon source, and the condition that the silicon source or the aluminum source is needed to be added to adjust the silicon-aluminum ratio in the prior art is reduced by adjusting the silicon-aluminum ratio;
5. according to the scheme of the invention, under the condition of no organic template agent, the ageing temperature and the crystallization temperature are both lower, and the steps are simple, so that the method has popularization and application values.
6. The scheme of the invention can obtain the X-type zeolite with large grain diameter and polyhedral crystal structure.
Drawings
FIG. 1 is an SEM image of zeolite X prepared in example 1;
figure 2 is an XRD pattern of zeolite X prepared in example 1;
FIG. 3 is an SEM image of zeolite type A prepared in comparative example 1;
figure 4 is an XRD pattern of zeolite type a prepared in comparative example 1;
FIG. 5 is an XRD pattern of the product prepared in comparative example 2;
FIG. 6 is an XRD pattern of the product prepared in comparative example 3;
FIG. 7 is an XRD pattern of the product prepared in comparative example 4;
FIG. 8 is an XRD pattern of the product prepared in comparative example 5;
FIG. 9 is an XRD pattern of the product prepared in comparative example 6;
fig. 10 is an XRD pattern of the product prepared in comparative example 7.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
The coal gangue in the following examples is from the Yangquan coal industry group of Shanxi province, and the main mineral phase components are kaolinite and quartz, and the silica-alumina ratio is 1.74. And crushing the obtained coal gangue blocks to a particle size of less than 10mm by using a crusher for later use.
Example 1
1) Drying the coal gangue and the rice hulls at 105 ℃, wherein the mass ratio of the coal gangue to the rice hulls is 1: 5, mixing, grinding for 5min in a high-speed planetary mill at the rotating speed of 300r/min, and sieving by a 40-mesh sieve to obtain a rice hull and coal gangue mixed raw material;
2) burning the mixed raw materials in a muffle furnace at 600 ℃ to obtain coal gangue and rice hull mixed burning ash, wherein the silicon-aluminum ratio of the mixed burning ash is 4.71;
3) mixing 5g of mixed burning ash with 50ml of 4mol/L sodium hydroxide aqueous solution;
4) carrying out water bath on the mixed solution in the step 3) at the temperature of 80 ℃, and aging for 2 h;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing for 8 hours at the temperature of 80 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
The SEM image of the prepared X-type zeolite is shown in figure 1, and the SEM image can clearly see that the zeolite product has clear and uniform structure, good crystal growth and micron-sized particle size.
The XRD pattern of the prepared X-type zeolite is shown in figure 2, wherein the peaks of the product are highly fitted with X zeolite cards, especially the peaks within 10 degrees, and a small amount of SiO is also contained in the product2The existence of the quartz phase indicates that the mixed burning ash of coal gangue and rice husk can be used for preparing the zeolite.
Comparative example 1
1) Drying the coal gangue at 105 ℃, grinding the coal gangue in a high-speed planetary mill for 5min at the rotating speed of 300r/min, and sieving the coal gangue by a 40-mesh sieve to obtain coal gangue powder;
2) burning the coal gangue powder in a muffle furnace at 600 ℃ to obtain calcined coal gangue powder with the silicon-aluminum ratio of 1.74;
3) mixing 5g of calcined coal gangue powder with 50ml of 4mol/L sodium hydroxide aqueous solution;
4) carrying out water bath on the mixed solution in the step 3) at the temperature of 80 ℃, and aging for 2 h;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing for 8 hours at the temperature of 80 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
For example 1, the SEM and XRD patterns of the zeolite product obtained in comparative example 1 are shown in fig. 3 and 4, respectively. It can be seen that the zeolite product type in comparative example 1 is quite different from that in example 1. The crystal sizes of the two crystals were different, with the crystal diameter of comparative example 1 being about 3 to 4 microns and the crystal diameter of example 1 being about 40 microns. The crystal shapes are different, namely polyhedral zeolite in example 1 and cubic crystal zeolite in comparative example 1, which are supposed to be added as silicon sources in rice hulls, and influence the growth condition of the zeolite.
Comparative example 2
1) Drying the coal gangue and the rice hulls at 105 ℃, wherein the mass ratio of the coal gangue to the rice hulls is 1: 5, mixing, grinding for 5min in a high-speed planetary mill at the rotating speed of 300r/min, and sieving by a 40-mesh sieve to obtain a rice hull and coal gangue mixed raw material;
2) burning the mixed raw materials in a muffle furnace at 600 ℃ to obtain coal gangue and rice hull mixed burning ash, wherein the silicon-aluminum ratio of the mixed burning ash is 4.71;
3) taking 4 parts of 5g of mixed burning ash to be mixed with 50ml of 2mol/L sodium hydroxide aqueous solution in turn;
4) carrying out water bath on the mixed solution in the step 3) at the temperature of 80 ℃, and aging for 2 h;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and respectively crystallizing for 4h, 6h, 8h and 10h at the temperature of 80 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
In comparative example 2, no zeolite was formed and XRD of the product showed the presence of a quartz phase, indicating that basicity also affected the synthesis of the zeolite. When the alkalinity is low, soluble silica-alumina is not polymerized to form zeolite molecules, so that a quartz phase which does not participate in the reaction in the coal gangue is displayed in the washed solid.
Comparative example 3
1) Drying the coal gangue and the rice hulls at 105 ℃, wherein the mass ratio of the coal gangue to the rice hulls is 1: 5, mixing, grinding for 5min in a high-speed planetary mill at the rotating speed of 300r/min, and sieving by a 40-mesh sieve to obtain a rice hull and coal gangue mixed raw material;
2) burning the mixed raw materials in a muffle furnace at 500 ℃ to obtain coal gangue and rice hull mixed burning ash, wherein the silicon-aluminum ratio of the mixed burning ash is 4.71;
3) mixing a plurality of 5g of mixed burning ash with 50ml of 2mol/L and 4mol/L sodium hydroxide aqueous solution in turn;
4) carrying out water bath on the mixed solution in the step 3) at the temperature of 80 ℃, and aging for 2 h;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing for 4 hours, 8 hours and 12 hours at the temperature of 80 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
In comparative example 3, no zeolite was produced. The XRD of the product showed mainly the quartz phase, probably because the kaolin phase in the calcined ash did not reach the conversion temperature, at which point the lye was acting mainly on the dissolution of the aluminosilicates in the calcined ash and did not reach the process of zeolite reformation.
Comparative example 4
1) Drying the coal gangue and the rice hulls at 105 ℃, wherein the mass ratio of the coal gangue to the rice hulls is 1: 5, mixing, grinding for 5min in a high-speed planetary mill at the rotating speed of 300r/min, and sieving by a 40-mesh sieve to obtain a rice hull and coal gangue mixed raw material;
2) burning the mixed raw materials in a muffle furnace at 600 ℃ to obtain coal gangue and rice hull mixed burning ash, wherein the silicon-aluminum ratio of the mixed burning ash is 4.71;
3) mixing a plurality of 5g of mixed burning ash with 50ml of 2mol/L and 4mol/L sodium hydroxide aqueous solution;
4) carrying out water bath on the mixed solution in the step 3) at the temperature of 80 ℃, and aging for 2 h;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing for 4 hours, 6 hours, 8 hours and 10 hours at the temperature of 120 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
From XRD analysis of the product, zeolite is generated at 4mol/L aqueous solution of sodium hydroxide and crystallization time of 8h and 10h, and the zeolite types in the product are two types: analcime and P-type zeolite. This indicates that the crystallization temperature has an influence on the synthesis of zeolite, and the crystallization temperature is different, and the type of zeolite produced is also different, and therefore the crystallization temperature of zeolite X is as listed in the preferred embodiment.
Comparative example 5
1) Drying the coal gangue and the rice hulls at 105 ℃, wherein the mass ratio of the coal gangue to the rice hulls is 1: 5, mixing, grinding for 5min in a high-speed planetary mill at the rotating speed of 300r/min, and sieving by a 40-mesh sieve to obtain a rice hull and coal gangue mixed raw material;
2) burning the mixed raw materials in a muffle furnace at 600 ℃ to obtain coal gangue and rice hull mixed burning ash, wherein the silicon-aluminum ratio of the mixed burning ash is 4.71;
3) mixing 5g of mixed burning ash with 50ml of 4mol/L sodium hydroxide aqueous solution;
4) aging the mixed solution in the step 3) for 2 hours at room temperature;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing for 10 hours at the temperature of 80 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
From the XRD pattern, no zeolite is generated under room-temperature aging, the peaks are numerous and complex, and it can be seen that the aluminosilicate in the mixed burning ash is recombined to generate muscovite minerals, a silicate with a layered structure, and no zeolite is generated, so the aging condition influences the generation of the zeolite.
Comparative example 6
1) Drying the coal gangue and the rice hulls at 105 ℃, wherein the mass ratio of the coal gangue to the rice hulls is 1: 5, mixing, grinding for 5min in a high-speed planetary mill at the rotating speed of 300r/min, and sieving by a 40-mesh sieve to obtain a rice hull and coal gangue mixed raw material;
2) burning the mixed raw materials in a muffle furnace at 600 ℃ to obtain coal gangue and rice hull mixed burning ash, wherein the silicon-aluminum ratio of the mixed burning ash is 4.71;
3) mixing 5g of mixed burning ash with 25ml of 4mol/L sodium hydroxide aqueous solution;
4) carrying out water bath on the mixed solution in the step 3) at the temperature of 80 ℃, and aging for 2 h;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing for 10 hours at the temperature of 80 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
As can be seen from the product XRD, at a liquid-solid ratio of 1: in the case of 5, the product also produced muscovite minerals, which indicates that the liquid-solid ratio in the recombination of aluminosilicate is very important, and the low liquid-solid ratio is not favorable for producing zeolite.
Comparative example 7
1) Drying the rice hulls at 105 ℃, grinding the rice hulls in a high-speed planetary mill for 5min at the rotating speed of 300r/min, and sieving the rice hulls by a 40-mesh sieve to obtain rice hull powder;
2) burning the mixed raw materials in a muffle furnace at 600 ℃ to obtain rice hull ash, wherein SiO is2The content of (A) is 87%;
3) 5g of rice hull ash is mixed with 50ml of 4mol/L sodium hydroxide aqueous solution;
4) carrying out water bath on the mixed solution in the step 3) at the temperature of 80 ℃, and aging for 2 h;
5) transferring the aged gelatinous mixture into a stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing for 8 hours at the temperature of 80 ℃;
6) and transferring the crystallized mixed solution into a centrifugal tube, centrifuging for 2min at the rotating speed of 3000r/min, pouring out the supernatant, adding a proper amount of clear water, centrifuging again until the pH value of the supernatant is neutral, and drying to obtain the product.
The product is flocculent in black color, XRD shows that no zeolite phase is generated, which may be caused by other impurities contained in the rice hull ash and serious unbalance of the ratio of silicon to aluminum. Only amorphous SiO was detected relative to rice hull ash2In particular, rice hull ash undergoing hydrothermal reaction generates many miscellaneous peaks including characteristic peaks containing calcium silicate hydrate, which indicates amorphous SiO in rice hull ash2To form a soluble silicon source, which can participate in the prior zeolite synthesis.
Claims (6)
1. A method for preparing X-type zeolite by utilizing coal gangue and rice hulls is characterized by comprising the following steps: the method comprises the following steps:
1) drying, mixing, grinding and sieving the rice hulls and the coal gangue in sequence to obtain a mixed powder raw material;
2) burning the mixed powder raw material to obtain coal gangue and rice hull mixed burning ash;
3) mixing and reacting the coal gangue and rice hull mixed burning ash with a sodium hydroxide solution, and then aging and crystallizing to obtain the coal gangue and rice hull mixed burning ash.
2. The method for preparing the X-type zeolite by using the coal gangue and the rice hulls as claimed in claim 1, wherein the method comprises the following steps: the coal gangue and the rice hull comprise the following components in percentage by mass: 20-30 percent and 70-80 percent.
3. The method for preparing the X-type zeolite by using the coal gangue and the rice hulls as claimed in claim 1, wherein the method comprises the following steps: the combustion temperature is controlled to be 580-620 ℃, and the time is 2-3 hours.
4. The method for preparing the X-type zeolite by using the coal gangue and the rice hulls as claimed in claim 1, wherein the method comprises the following steps: the solid-liquid ratio of the coal gangue and rice hull mixed burning ash to the sodium hydroxide solution is 1g: 8-10 mL, and the concentration of the sodium hydroxide solution is 3.8-4.2 mol/L.
5. The method for preparing the X-type zeolite by using the coal gangue and the rice hulls as claimed in claim 1, wherein the method comprises the following steps: the aging process is aging for 1.5-2 h at the temperature of 80-85 ℃.
6. The method for preparing the X-type zeolite by using the coal gangue and the rice hulls as claimed in claim 1, wherein the method comprises the following steps: the crystallization process is crystallization for 8-9 hours at the temperature of 80-85 ℃.
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| 田震等: "以煤矸石为原料合成13X型沸石", 《非金属矿》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735475A (en) * | 2021-09-03 | 2021-12-03 | 天津水泥工业设计研究院有限公司 | Light ceramsite and preparation method thereof |
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