CN109231228B - High-expansion-rate expanded vermiculite based on low-hydration phlogopite intercalation and preparation method thereof - Google Patents
High-expansion-rate expanded vermiculite based on low-hydration phlogopite intercalation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-expansion-rate expanded vermiculite based on a weakly hydrated phlogopite intercalation and a preparation method thereof, and the preparation method comprises the following steps: grinding and stripping, impurity removal and grading are carried out on the raw ore of the low-hydration phlogopite to obtain low-hydration phlogopite fine pieces; adding the raw materials of the composite intercalator into an acid-resistant reaction vessel according to the proportion, and uniformly mixing to obtain a composite intercalator solution; placing the low-hydration phlogopite flakes into an acid-resistant reaction container filled with a composite intercalator to be stirred until the low-hydration phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging to ensure that the intercalator is fully inserted into the interlamination region of the vermiculite crystal layer and part of the phlogopite crystal layer to obtain the composite intercalated low-hydration phlogopite flakes; and heating the obtained compound intercalated weakly hydrated phlogopite flakes to obtain the high-expansion-rate expanded vermiculite product. The method is green and environment-friendly, and the prepared expanded vermiculite has high expansion rate and low density, and is beneficial to further development and utilization of the weakly hydrated phlogopite.
Description
Technical Field
The invention belongs to the technical field of inorganic nonmetal functional materials and mineral functional materials, and particularly relates to a high-expansion-rate expanded vermiculite based on a weakly hydrated phlogopite intercalation and a preparation method thereof.
Background
Phlogopite is a trioctahedral layered silicate mineral. It can be hydrated and changed into vermiculite under the action of hydrothermal liquid or surface water. Vermiculite has good thermal expansibility, and when heated sharply, the volume of the vermiculite can expand by tens of times rapidly to form expanded vermiculite. The expanded vermiculite has the characteristics of small density, large specific surface area, stable chemical property, heat preservation, heat insulation, sound absorption and sound insulation, good fireproof effect and the like, and is widely applied to the fields of buildings, agriculture, forestry, environmental protection, gardens, chemical industry and the like. Industrial vermiculite includes vermiculite and hydrated phlogopite (or hydrated biotite) with expansion ratio meeting the industrial requirements. Phlogopite has no rapid thermal expansion property, and weakly hydrated phlogopite is difficult to industrially use as an industrial vermiculite raw material for producing expanded vermiculite due to low expansion rate.
The defects of small expansion rate, insufficient delamination, low strength, large brittleness and the like generally exist in the field of processing and producing the expanded vermiculite by the current industrial vermiculite, the performance of the produced expanded vermiculite product has not been greatly broken through, and particularly, the preparation of the expanded vermiculite with high expansion rate is difficult to break through the limit of 40 times of the expansion rate of the aggregate under the condition of not damaging the structural layer attribute, so that the application field of the expanded vermiculite product is greatly limited.
The existing preparation method of expanded vermiculite mainly comprises a direct heating expansion method, a chemical auxiliary heating expansion method, an ultrasonic heating expansion method and the like. The chemical auxiliary agents used in the chemical auxiliary heating expansion method comprise potassium nitrate, potassium chloride, magnesium nitrate, magnesium chloride, hydrogen peroxide, oxalic acid and the like, and the heating mode comprises a roasting method, a microwave method, a burning method and the like. Qianyitong and the like adopt a chemical auxiliary heating expansion method to prepare expanded vermiculite on a vermiculite sample in a composite method for preparing expanded vermiculite (silicate report, 2017, 36(9):2875-2879), hydrogen peroxide with the concentration of 25% and the solid-to-liquid ratio of 1:4 is adopted to soak the vermiculite, the vermiculite is roasted at the temperature of 300 ℃, when the particle size of the vermiculite is 1.4-4 mm, the expansion rate is 37.8, and the method has large consumption on the hydrogen peroxide and high production cost. In the vermiculite expansion process (application number: 00101332.7, application date: 2000-01-06, publication number: 1302778A, publication date: 2001-07-11), 2-10% of vegetable oil, potassium nitrate and the like are added into vermiculite to be soaked for 12-24 h, and then the mixture is heated to 300-400 ℃ to obtain an expanded vermiculite product, wherein the maximum expansion multiple of the product is 14 times, and the defects of poor vermiculite expansion effect, low expansion multiple and the like still exist. A vermiculite modified expansion preparation method (application number: CN201610907607.7, application date: 20161018, publication number: CN106431046A, publication date: 20170222) comprises the steps of soaking vermiculite in a chemical reagent (potassium nitrate or potassium chloride, magnesium nitrate or magnesium chloride, hydrogen peroxide, oxalic acid and the like) with a certain concentration for 4-24 hours, and heating at 90-550 ℃ for 3-10 minutes to obtain an expanded vermiculite product. The vermiculite treated by the method has an excessively poor expansion effect, and the expansion multiple is only 3-6 times.
The patent flexible expanded vermiculite microwave continuous expansion method and special equipment (application number: CN201010244821.1, application date: 20100804, publication number: CN101893377A, publication date: 20101124) disclose that continuous microwave expansion equipment is used for carrying out continuous microwave expansion on raw vermiculite ore, and the vermiculite expansion temperature is not more than 300 ℃. Although the preparation method has the advantages of low energy consumption, difficult pulverization of the produced expanded vermiculite and high strength, the expansion multiple is only 20-30 times, the treatment effect on the vermiculite raw ore with poor quality is not ideal, and specific equipment is required. A method for preparing expanded vermiculite by utilizing an ultrasonic pretreatment mode (application number: CN201110053693.7, application date: 20110307, publication number: CN102167531A, publication date: 20110831) comprises the steps of screening and removing impurities from raw vermiculite, soaking the raw vermiculite in 5-30% hydrogen peroxide for 1-14 hours, performing ultrasonic pretreatment on the soaked vermiculite for 10-60 minutes, standing for 1-2 hours, and then placing the vermiculite into a microwave device for microwave expansion for 0.5-4 minutes to prepare the expanded vermiculite, wherein the minimum stacking density of the produced expanded vermiculite is 46kg/m3The maximum expansion factor still does not reach 40 times.
The patent relates to a vermiculite expansion production process (application number: CN201710813535.4, application date: 20170911, publication number: CN107500590A, publication date: 20171222), which comprises the following specific steps of coarse screening, lifting feeding, drying and preheating, high-temperature expansion, air separation, screening, feeding bin and bagging. The preheating temperature is about 500 ℃, the heating temperature of the high-temperature expansion furnace is about 1000 ℃, the expansion multiple of the prepared expanded vermiculite product is still low and is only 7-8 times, and the expanded vermiculite product needs to be heated twice, so that the energy consumption is high, and the process is complex.
In summary, in order to improve the expansion rate of vermiculite, chemical additives are usually selected to modify raw vermiculite ore in advance, and then the raw vermiculite ore is subjected to heating treatment by roasting or microwave and the like to obtain the expanded vermiculite. However, the existing production process has the defects of small expansion rate, large energy consumption, high water consumption, toxic and harmful chemical additives used, difficulty in treating generated wastewater and waste gas, damaged structural layers of prepared expanded vermiculite products, high brittleness, low strength, undesirable vermiculite expansion effect with poor quality and the like, and limits the utilization rate of vermiculite resources and the application range of expanded vermiculite, and the technology and the method for processing the weak hydration phlogopite which is usually discarded in the process of mining industrial vermiculite have no capability of reaching high expansion rate.
Disclosure of Invention
In view of the above, the present invention provides a high expansion rate expanded vermiculite based on low hydration phlogopite intercalation and a preparation method thereof, aiming at the problems of small expansion rate, damaged lamellar structure layer, low strength and high brittleness, high energy consumption and high water consumption of the production process, toxic and harmful chemical additives used, difficulty in treatment of generated wastewater, and unsatisfactory expansion effect of industrial vermiculite with poor quality or difficulty in utilization of low hydration phlogopite in the existing vermiculite expansion processing process and technology.
In order to solve the technical problem, the invention discloses a preparation method of expanded vermiculite with high expansion rate based on low hydration phlogopite intercalation,
the method comprises the following steps:
1) grinding and stripping, impurity removal and grading are carried out on the raw ore of the low-hydration phlogopite to obtain low-hydration phlogopite fine pieces;
2) mixing an oxidant and industrial water to prepare an oxidant solution, adding the oxidant solution and reductive organic acid into an acid-resistant reaction vessel, and uniformly mixing to obtain a composite intercalation agent;
3) pouring the low-hydration phlogopite flakes obtained in the step 1) into the acid-resistant reaction container filled with the composite intercalator in the step 2) for stirring until the low-hydration phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging to ensure that the intercalator is fully inserted into the interlamination region of the vermiculite crystal layer and part of the phlogopite crystal layer to obtain the composite intercalation low-hydration phlogopite flakes;
4) heating the composite intercalation weakly hydrated phlogopite flakes obtained in the step 3) to obtain an expanded vermiculite product with high expansion rate.
Optionally, the sheet diameter of the low-hydration phlogopite refined sheet in the step 1) is 3-10 mm.
Optionally, the oxidizing agent in step 2) is one of hydrogen peroxide or calcium peroxide; the reducing organic acid is one of malic acid, gluconic acid or citric acid.
Optionally, the concentration of the oxidant solution in the step 2) is 5-30 wt%; the volume-to-mass ratio (L/Kg) of the oxidant solution to the reducing organic acid is 15: 1-240: 1.
Optionally, the mass-to-volume ratio of the weakly hydrated phlogopite flakes and the composite intercalator placed in the acid-resistant reactor in the step 3) is 1: 1.2-1: 2.4(Kg/L), and the temperature is 10-30 ℃ and the time is 5-24 hours in the standing and aging process.
Optionally, the heating treatment in step 4) is a microwave heating treatment or an electric heating treatment.
Optionally, the heating temperature of the heating treatment in the step 4) is 200-750 ℃, and the heating time is 1-5 min.
The invention also discloses the expanded vermiculite with high expansion rate obtained by the preparation method.
Optionally, the high-expansion-rate expanded vermiculite has an aggregate expansion rate of 40-80 times and a density of 15-30 kg/m3。
Compared with the prior art, the invention can obtain the following technical effects:
1) after the intercalation pretreatment is carried out on the weakly hydrated phlogopite, the expanded vermiculite with high expansion rate is obtained, low-value resources are effectively utilized, and high-performance and high-value-added materials are processed;
2) the composite intercalation agent and related technical parameters are used, so that the consumption of water and chemical additives is reduced, and the production cost is reduced;
3) the stirring and standing aging process promotes the composite intercalator to be inserted into the interlamination domain of the vermiculite crystal layer and part of the phlogopite crystal layer, effectively improves the water absorption capacity of the interlamination domain, and lays a material foundation for the generation of high gas pressure required by the expansion of the interlamination domain and the peeling of the crystal layer;
4) no waste liquid and toxic and harmful gas are discharged in the process, the treatment cost of the waste liquid and the waste gas is avoided, and the method is a green processing technology;
5) the expanded vermiculite prepared by the technology has the maximum aggregate expansion rate of 80 times, thin expanded sheet, large specific surface area, undamaged structural layer, higher mechanical strength and lowest density of 15kg/m3Whereas the maximum collective expansion ratio of the exfoliated vermiculite material prepared according to the techniques in the prior documents and patents does not exceed 37.8;
6) the method aims at the problem that weakly hydrated phlogopite with poor quality is subjected to heat treatment after intercalation treatment by a composite intercalator, the set expansion rate and density of the weakly hydrated phlogopite can not only meet the high standard requirement of the high-quality industrial vermiculite expansion rate, but also improve the expansion rate to a higher level, so that the method has important technical significance for promoting the high-expansion-rate processing of the industrial vermiculite, can develop low-value weakly hydrated phlogopite and has important significance for resource protection and comprehensive utilization;
7) the high-expansion-rate expanded vermiculite product prepared by the method has uniform delamination effect, can be prepared into nano-scale slices through proper treatment, and lays a foundation for expanding the application field of the expanded vermiculite.
Of course, it is not necessary for any one product in which the invention is practiced to achieve all of the above-described technical effects simultaneously.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow diagram illustrating the production of a high expansion expanded vermiculite in accordance with the present invention;
FIG. 2 is a diagram of a sample of weakly hydrated phlogopite flakes of the present invention;
FIG. 3 is an X-ray diffraction pattern of a weakly hydrated phlogopite tablet of the present invention;
FIG. 4 is an X-ray diffraction pattern of a high expansion expanded vermiculite product of the present invention;
FIG. 5 is a graph of an exfoliated vermiculite product of example 1 of this invention;
FIG. 6 is a graph of a single exfoliated vermiculite product of example 1 of this invention;
FIG. 7 is a graph of an exfoliated vermiculite product of example 2 of this invention;
FIG. 8 is a graph of an exfoliated vermiculite product of example 3 of this invention;
FIG. 9 is a graph of an exfoliated vermiculite product of example 4 of this invention;
FIG. 10 is a graph of a single exfoliated vermiculite product of example 4 of this invention;
FIG. 11 is a graph of an exfoliated vermiculite product of example 5 of this invention;
FIG. 12 is a scanning electron microscope image (300X) of a high expansion ratio exfoliated vermiculite product of the present invention;
FIG. 13 is a scanning electron microscope image (50000 times) of a high expansion rate exfoliated vermiculite product of the present invention.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.
The invention discloses a preparation method of expanded vermiculite with high expansion rate based on weak hydration phlogopite intercalation, the production process of the process is shown in figure 1, and the method comprises the following steps:
1) grinding and stripping, impurity removal and grading are carried out on the raw ore of the weakly hydrated phlogopite to obtain weakly hydrated phlogopite flakes (shown in figure 2) with the flake diameter of 3-10 mm and the flake thickness of 0.3-1.2 mm, wherein the weakly hydrated phlogopite flakes have weak glass luster to glass luster, and part of particles have grease luster;
the relative intensity of the diffraction peak of the vermiculite crystal layer or the hydrophlogopite interstrate mineral in the weakly hydrated phlogopite raw material is not more than 3/10 (shown in figure 3) of phlogopite; i.e. diffraction peaks of mainly phlogopite in the X-ray diffraction pattern of the weakly hydrated phlogopite raw material
Diffraction peaks of Muscovitum interstrata mineral
Diffraction peaks of vermiculite
Each presents only one strongest peak and the intensity is very weak. The screening size fraction is 3-5 mm, 5-8 mm and 8-10 mm respectively; the crushing equipment can be selected from a jaw crusher, a cone crusher, a double-roll crusher and the like; the impurity removing equipment can be a winnowing machine, a color sorter and the like; various high-frequency vibrating screens can be selected as the screening equipment;
2) mixing an oxidant and industrial water to prepare an oxidant solution with the weight percent of 5-30, and adding the oxidant solution and reducing organic acid into an acid-resistant reaction vessel according to the volume mass ratio of 15: 1-240: 1(L/Kg) to be uniformly mixed to obtain a composite intercalation agent;
wherein, the oxidant in the composite intercalation agent is one of hydrogen peroxide or calcium peroxide; the reducing organic acid comprises one of malic acid, gluconic acid and citric acid.
3) Pouring the weakly hydrated phlogopite tablets obtained in the step 1) into the acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1: 1.2-1: 2.4(Kg/L) for stirring until the weakly hydrated phlogopite tablets uniformly absorb the composite intercalator without residual solution, standing and aging for 5-24 h at 10-30 ℃ to ensure that the intercalator is fully inserted into the interlamination region of the vermiculite crystal layer and part of the phlogopite crystal layer to obtain the composite intercalated weakly hydrated phlogopite tablets;
4) and (3) carrying out microwave or electric heating treatment on the composite intercalated weakly hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 200-750 ℃, and the heating time is 1-5 min, so as to obtain the expanded vermiculite product with high expansion rate. The heating equipment can be selected from a vertical kiln, a rotary kiln, a tubular kiln or other industrial microwave ovens;
the X-ray diffraction pattern of the expanded vermiculite product with high expansion rate is shown in figure 4, and the scanning electron microscope image is shown in figures 12 and 13. FIG. 4 shows that the expanded vermiculite product has only phlogopite phase in the X-ray diffraction pattern, has sharp diffraction peak and perfect structure, and has the following main diffraction peaks:
and so on. FIG. 12 shows that the original parallel structural sheets expand radially after expansion, and the expanded structural sheets have smooth surfaces and no cracking phenomenon; FIG. 13 shows that after swelling and peeling, the structural sheet is fully decomposed, the thickness of the single layer can reach about 20nm, the structural sheet is loose and porous, the cross section of the hole is in a willow leaf shape with different widths, and the micro-size width is 50 nm-200 nm.
Example 1
The specific preparation method of the high-expansion-rate expanded vermiculite based on the low-hydration phlogopite intercalation comprises the following steps:
1) grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 3-5 mm;
2) mixing hydrogen peroxide and industrial water to prepare 15 wt% hydrogen peroxide solution, adding the hydrogen peroxide solution and malic acid into an acid-resistant reaction vessel according to the volume mass ratio of 15:1(L/Kg), and uniformly mixing to obtain a composite intercalation agent;
3) pouring the weakly hydrated phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1:2.4(Kg/L) for stirring until the weakly hydrated phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging for 24 hours at the temperature of 20 ℃, and fully inserting the intercalator into the interlamination of a vermiculite crystal layer and a part of phlogopite crystal layers to obtain the composite intercalated weakly hydrated phlogopite flakes;
4) and (3) carrying out electric heating treatment on the compound intercalation weakly-hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 700 ℃, and the heating time is 3min, so as to obtain the high-expansion-rate expanded vermiculite product.
The density is tested according to the technical specification of the national building material industry standard expanded vermiculite (JCT 441-2009). The collective expansion ratio K (K ═ density of the weakly hydrated phlogopite raw material/density after swelling of the weakly hydrated phlogopite) was measured by the change in density. The density of the expanded vermiculite was measured to be 16kg/m3The collective expansion ratio was 75 times. Meets the requirement of density in the national building material standard expanded vermiculite (JCT 441-2009). See fig. 5, 6 for details.
FIGS. 5 and 6 show that the expanded vermiculite product prepared by the method of example 1 is in a beige strip worm shape, mostly in a bent state, loose and porous, and uniform in pore distribution; the length of the expanded vermiculite after single expansion reaches about 40 mm.
Example 2
1) Grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 3-5 mm;
2) mixing calcium peroxide and industrial water to prepare 15 wt% of calcium peroxide solution, adding the calcium peroxide solution and malic acid into an acid-resistant reaction vessel according to the volume mass ratio of 15:1(L/Kg), and uniformly mixing to obtain a composite intercalation agent;
3) pouring the weakly hydrated phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1:2.4(Kg/L) for stirring until the weakly hydrated phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging for 24 hours at the temperature of 20 ℃, and fully inserting the intercalator into the interlamination of a vermiculite crystal layer and a part of phlogopite crystal layers to obtain the composite intercalated weakly hydrated phlogopite flakes;
4) and (3) carrying out electric heating treatment on the compound intercalation weakly-hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 700 ℃, and the heating time is 3min, so as to obtain the high-expansion-rate expanded vermiculite product.
The expanded vermiculite prepared by the method is subjected toThe performance test is basically the same as that of embodiment 1, and is not repeated here, but the difference is as follows: the density of the expanded vermiculite obtained was determined to be 23kg/m3The collective expansion ratio was 53 times. Meets the requirement of density in the national building material standard expanded vermiculite (JCT 441-2009). See figure 7 for details.
FIG. 7 shows that the expanded vermiculite product prepared by the method of example 2 is golden yellow and has long-strip worm shape, most of which are in a bent state, loose and porous, and uniform pore distribution.
Example 3
1) Grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 3-5 mm;
2) mixing hydrogen peroxide and industrial water to prepare 15 wt% hydrogen peroxide solution, adding the hydrogen peroxide solution and citric acid into an acid-resistant reaction container according to the volume mass ratio of 15:1(L/Kg), and uniformly mixing to obtain a composite intercalation agent;
3) pouring the weakly hydrated phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1:2.4(Kg/L) for stirring until the weakly hydrated phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging for 24 hours at the temperature of 20 ℃, and fully inserting the intercalator into the interlamination of a vermiculite crystal layer and a part of phlogopite crystal layers to obtain the composite intercalated weakly hydrated phlogopite flakes;
4) and (3) carrying out electric heating treatment on the compound intercalation weakly-hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 700 ℃, and the heating time is 3min, so as to obtain the high-expansion-rate expanded vermiculite product.
The performance test of the expanded vermiculite prepared by the method is basically the same as that of the embodiment 1, and is not repeated herein, and the difference is as follows: the density of the expanded vermiculite obtained was determined to be 15kg/m3The collective expansion ratio was 80 times. Meets the requirement of density in the national building material standard expanded vermiculite (JCT 441-2009). See figure 8 for details.
FIG. 8 shows that the expanded vermiculite prepared by the method of example 3 is golden yellow and has long strip worm shape, most of which are in a bent state, loose and porous, and uniform pore distribution.
Example 4
1) Grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 5-8 mm;
2) mixing calcium peroxide and industrial water to prepare 15 wt% of calcium peroxide solution, adding the calcium peroxide solution and gluconic acid into an acid-resistant reaction container according to the volume mass ratio of 240:1(L/Kg), and uniformly mixing to obtain a composite intercalation agent;
3) pouring the weakly hydrated phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1:2.4(Kg/L) for stirring until the weakly hydrated phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging for 5 hours at the temperature of 20 ℃, and fully inserting the intercalator into the interlamination of a vermiculite crystal layer and a part of phlogopite crystal layers to obtain the composite intercalated weakly hydrated phlogopite flakes;
4) and 3) carrying out microwave heating treatment on the composite intercalated weakly hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 200 ℃, and the heating time is 4min, so as to obtain the expanded vermiculite product with high expansion rate.
The performance test of the expanded vermiculite prepared by the method is basically the same as that of the embodiment 1, and is not repeated herein, and the difference is as follows: the density of the expanded vermiculite was determined to be 30kg/m3The collective expansion ratio was 40 times. Meets the requirement of density in the national building material standard expanded vermiculite (JCT 441-2009). See fig. 9, 10 for details.
FIG. 9 shows that the expanded vermiculite product prepared by the method of example 4 is in the form of short yellow vermicular worms, mostly in a curved state, loose and porous, and has uniform pore distribution; as can be seen in FIG. 10, the expanded vermiculite product is in a curled long strip shape, has the length of about 50mm, and is easy to break into short strips after being expanded and curled.
Example 5
1) Grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 5-8 mm;
2) mixing hydrogen peroxide and industrial water to prepare 15 wt% hydrogen peroxide solution, adding the hydrogen peroxide solution and citric acid into an acid-resistant reaction container according to the volume mass ratio of 15:1(L/Kg), and uniformly mixing to obtain a composite intercalation agent;
3) pouring the weakly hydrated phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1:2.4(Kg/L) for stirring until the weakly hydrated phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging for 24 hours at the temperature of 20 ℃, and fully inserting the intercalator into the interlamination of a vermiculite crystal layer and a part of phlogopite crystal layers to obtain the composite intercalated weakly hydrated phlogopite flakes;
4) and 3) carrying out microwave heating treatment on the composite intercalated weakly hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 300 ℃, and the heating time is 3min, so as to obtain the expanded vermiculite product with high expansion rate.
The performance test of the expanded vermiculite prepared by the method is basically the same as that of the embodiment 1, and is not repeated herein, and the difference is as follows: the density of the expanded vermiculite obtained was determined to be 21kg/m3The collective expansion ratio was 58 times. Meets the requirement of density in the national building material standard expanded vermiculite (JCT 441-2009). See figure 11 for details.
FIG. 11 shows that the expanded vermiculite product prepared by the method of example 5 is in the shape of yellow gray short worms, mostly in a curved state, loose and porous, and has a relatively uniform pore distribution.
Example 6
1) Grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 8-10 mm;
2) mixing hydrogen peroxide and industrial water to prepare 5 wt% hydrogen peroxide solution, adding the hydrogen peroxide solution and gluconic acid into an acid-resistant reaction container according to the volume mass ratio of 150:1(L/Kg), and uniformly mixing to obtain a composite intercalation agent;
3) pouring the weakly hydrated phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1:1.2(Kg/L) for stirring until the weakly hydrated phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging for 15 hours at 10 ℃ to ensure that the intercalator is fully inserted into the interlamination of a vermiculite crystal layer and a part of phlogopite crystal layers to obtain the composite intercalated weakly hydrated phlogopite flakes;
4) carrying out microwave treatment on the composite intercalated weakly hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 750 ℃, and the heating time is 1min, so as to obtain the expanded vermiculite product with high expansion rate.
The expanded vermiculite prepared by the method is subjected to performance test, and the density of the expanded vermiculite is 27kg/m3The collective expansion ratio was 44 times. Meets the requirement of density in the national building material standard expanded vermiculite (JCT441-2009), and has the same other characteristics as the embodiment 2.
Example 7
1) Grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 8-10 mm;
2) mixing calcium peroxide and industrial water to prepare a 30wt% calcium peroxide solution, adding the calcium peroxide solution and citric acid into an acid-resistant reaction container according to the volume mass ratio of 100:1(L/Kg), and uniformly mixing to obtain a composite intercalation agent;
3) pouring the weakly hydrated phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) according to the mass-to-volume ratio of 1:1.8(Kg/L) for stirring until the weakly hydrated phlogopite flakes uniformly absorb the composite intercalator without residual solution, standing and aging for 20 hours at the temperature of 30 ℃, and fully inserting the intercalator into the interlamination of a vermiculite crystal layer and a part of phlogopite crystal layers to obtain the composite intercalated weakly hydrated phlogopite flakes;
4) and (3) carrying out electric heating treatment on the compound intercalation weakly-hydrated phlogopite flakes obtained in the step 3), wherein the heating temperature is 500 ℃, and the heating time is 5min, so as to obtain the high-expansion-rate expanded vermiculite product.
The expanded vermiculite prepared by the method is subjected to performance test, and the density of the expanded vermiculite is 24kg/m3The collective expansion ratio was 50 times. Meets the requirement of density in the national building material standard expanded vermiculite (JCT441-2009), and has the same other characteristics as the embodiment 2.
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A preparation method of high-expansion-rate expanded vermiculite based on weak hydration phlogopite intercalation is characterized by comprising the following steps:
1) grinding and stripping, impurity removal and classification are carried out on the raw ore of the weakly hydrated phlogopite to obtain a weakly hydrated phlogopite fine sheet with the sheet diameter of 3-10 mm and the sheet thickness of 0.3-1.2 mm;
2) mixing an oxidant and industrial water to prepare an oxidant solution with the concentration of 5-30 wt%, and adding the oxidant solution and reductive organic acid into an acid-resistant reaction container to be uniformly mixed to obtain a composite intercalation agent, wherein the oxidant is one of hydrogen peroxide or calcium peroxide; the reducing organic acid is one of malic acid, gluconic acid or citric acid, and the L/Kg (volume to mass ratio) of the oxidant solution to the reducing organic acid is 15: 1-240: 1;
3) pouring the low-hydration phlogopite flakes obtained in the step 1) into an acid-resistant reaction container filled with the composite intercalator in the step 2) for stirring, wherein the mass-to-volume ratio Kg/L of the low-hydration phlogopite flakes to the composite intercalator is 1: 1.2-1: 2.4, standing and aging after the low-hydration phlogopite flakes uniformly absorb the composite intercalator without residual solution, wherein the aging temperature is 10-30 ℃, and the aging time is 5-24 hours, so that the intercalator is fully inserted into the interlamination region of the vermiculite crystal layer and part of the phlogopite crystal layer to obtain the composite intercalated low-hydration phlogopite flakes;
4) and (3) heating the compound intercalation weak hydration phlogopite flakes obtained in the step 3), wherein the heating temperature of the heating treatment is 200-750 ℃, and the heating time is 1-5 min, so that a high-expansion-rate expanded vermiculite product with a phlogopite phase is obtained.
2. The method for preparing the low-hydration phlogopite flakes according to claim 1), wherein the low-hydration phlogopite flakes in the step 1) have a low to glass luster, and the main minerals of the contained phases are phlogopite and contain small amounts of vermiculite and hydrophlogopite.
3. The production method according to claim 1, wherein the heating treatment in step 4) is a microwave heating treatment or an electric heating treatment.
4. A high expansion expanded vermiculite prepared by the method of any one of claims 1 to 3.
5. The high expansion rate expanded vermiculite according to claim 4, wherein the high expansion rate expanded vermiculite has an aggregate expansion rate of 40 to 80 times and a density of 15 to 30kg/m3。
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