An organic acid ball-milling activated analcime, a preparation method and application thereof

Abstract

The application provides a ball-milling activated analcime based on organic acid and a preparation method and application thereof; the preparation method of the analcime comprises the following steps: S1, providing lithium residue and mixed acid; the mixed acid comprises first organic acid and second organic acid, the first organic acid comprises citric acid, the second organic acid comprises oxalic acid, and the mass ratio of the first organic acid to the second organic acid is 0.8-3:1; S2, the lithium residue and the mixed acid are used as solid-state materials, and the solid-state materials and water are jointly ball-milled to obtain a ball-milling product; S3, the ball-milling product and an alkaline solution are mixed to obtain a to-be-treated liquid; the to-be-treated liquid is subjected to hydrothermal treatment to obtain a reaction liquid; S4, the reaction liquid is subjected to solid-liquid separation to obtain a solid separation product; the solid separation product comprises analcime. The analcime product with high crystallinity and high yield can be obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of preparing faujasite, and particularly relates to a faujasite based on organic acid ball milling activation and a preparation method and application thereof. BACKGROUND

[0002] Lithium residue is a waste residue produced in the process of extracting lithium from ore. It is an industrial silicon-aluminum waste residue produced in the process of producing lithium carbonate and other lithium salts after high-temperature calcination of lithium ore. It faces problems such as large stockpiling and difficult resource utilization. Faujasite is a common feldspar-like mineral belonging to the zeolite family, with special structure and performance. It has ion exchange, catalytic, thermal stability and acid resistance, and is widely used in building materials, environmental protection, daily light industry, petroleum and chemical industry and other fields. Therefore, converting lithium residue into faujasite can not only realize the treatment of solid waste, but also obtain a resourceful product, realizing the resource utilization of solid waste.

[0003] Chinese patent application for invention with publication number CN117643861A (applicant's prior case) discloses a sulfur-resistant and high-temperature-resistant gaseous arsenic adsorption material and its preparation method and application. Although it activates the lithium residue by mechanical ball milling to obtain a gaseous arsenic adsorption material, which has application value, it does not obtain a more stable structure of faujasite material from lithium residue, and does not study the yield of faujasite.

[0004] Therefore, it is necessary to provide a faujasite based on organic acid ball milling activation and a preparation method and application thereof to solve or at least alleviate the technical problem of how to prepare faujasite from lithium residue. SUMMARY

[0005] The main purpose of the present application is to provide a faujasite based on organic acid ball milling activation and a preparation method and application thereof, aiming to solve the above technical problem of how to prepare faujasite from lithium residue.

[0006] To achieve the above purpose, the present application provides a preparation method of a faujasite based on organic acid ball milling activation, comprising the following steps:

[0007] S1, providing lithium residue and mixed acid; the lithium residue contains Li element, Si element, Al element, Na element, K element, F element and Ca element; the mixed acid comprises a first organic acid and a second organic acid, the first organic acid comprises citric acid, the second organic acid comprises oxalic acid, and the mass ratio of the first organic acid to the second organic acid is 0.8-3:1;

[0008] S2, the lithium residue and the mixed acid are ball milled together as solid materials, to obtain a ball-milling product; the mass ratio of the mixed acid to the lithium residue is 1.5-5:5; the mass percentage of the water to the solid material is 20-60%; the rotation speed of the ball milling is 290-310 r / min or 450-800 r / min, and the ball milling time is not less than 120 min;

[0009] S3, the ball-milling product and an alkaline solution are mixed to obtain a to-be-treated liquid; the to-be-treated liquid is subjected to hydrothermal treatment to obtain a reaction liquid; the alkaline solution contains an alkaline substance, and the alkaline substance includes one or more of sodium hydroxide and potassium hydroxide; the hydrothermal treatment is performed at a temperature of 130-210℃ for a time period of 40-180 min;

[0010] S4, the reaction liquid is subjected to solid-liquid separation to obtain a solid separation product; the solid separation product contains analcime.

[0011] Further, the first organic acid is citric acid, the second organic acid is oxalic acid, and the mass ratio of the first organic acid to the second organic acid is 0.8-2:1; the mass ratio of the mixed acid to the lithium residue is 1.5-3.5:5.

[0012] Further, the rotation speed of the ball milling is 500-560 r / min, the ball milling time is 120-300 min, and the ball-to-material mass ratio used in the ball milling is 4-12:1.

[0013] Further, the concentration of the alkaline substance in the alkaline solution is 0.5-4 mol / L.

[0014] Further, the mass-to-volume ratio of the ball-milling product to the alkaline solution is 0.5-10 g:45 mL.

[0015] Further, the hydrothermal treatment is performed in a microwave hydrothermal manner; and the microwave hydrothermal treatment is performed in a microwave hydrothermal reactor.

[0016] Further, the mass percentage of the Li element in the lithium residue is 0.1-2%, the mass percentage of the Si element in the lithium residue is 10-15%, the mass percentage of the Al element in the lithium residue is 5-12%, the mass percentage of the Na element in the lithium residue is 5-10%, the mass percentage of the K element in the lithium residue is 5-10%, the mass percentage of the F element in the lithium residue is 2-8%, and the mass percentage of the Ca element in the lithium residue is 5-10%.

[0017] The lithium residue contains nepheline, muscovite, and orthoclase; and the lithium residue has a framework aluminosilicate structure.

[0018] The application further provides a chabazite prepared by the method.

[0019] The application further provides application of the chabazite in any of the above in arsenic removal or anti-sulfur arsenic removal.

[0020] The application further provides an arsenic removal method, comprising: adsorbing arsenic in arsenic-containing flue gas by the chabazite in any of the above, wherein the adsorption is performed at a temperature of 400-900 DEG C, and the adsorption time is 20-90 min; the arsenic-containing flue gas contains As2O3, or the arsenic-containing flue gas contains As2O3 and SO2.

[0021] When the arsenic-containing flue gas contains As2O3, the concentration of As2O3 in the arsenic-containing flue gas is not higher than 1 mg / L; when the arsenic-containing flue gas contains As2O3 and SO2, the concentration of As2O3 in the arsenic-containing flue gas is not higher than 1 mg / L, and the volume ratio of SO2 in the arsenic-containing flue gas is not higher than 15%.

[0022] Compared with the prior art, the application has at least the following advantages:

[0023] Based on citric acid and oxalic acid, the lithium slag is ball milled under a certain humidity to obtain a ball milling product, and then the ball milling product is hydrothermally synthesized in a specific alkaline solution to obtain a chabazite product with high crystallinity and high yield; and the chabazite in the application can still efficiently remove arsenic in the presence of sulfur at a high temperature of 800 DEG C, and the structure is stable. Therefore, the application realizes resource utilization of lithium leaching residue and provides a new way for lithium residue disposal, and realizes waste-to-resource; the preparation method of the chabazite provided by the application is suitable for large-scale preparation of enterprises and conforms to the actual production.

[0024] In the ball milling process, the hydrogen ions in the organic acid attack the aluminum silicate framework during ball milling; at the same time, citric acid and oxalic acid cooperatively attack Si-O and Al-O bonds, promote the release of silicon and aluminum elements, and enhance the reactivity of lithium slag for subsequent hydrothermal synthesis; in the hydrothermal synthesis process, citric acid is complexed with a plurality of divalent metal ions and does not preferentially adsorb calcium ions, and after the addition of oxalic acid, oxalic acid preferentially complexes with Ca 2+ , so that the concentration of Ca 2+ in the solution is low, thereby further inhibiting the pozzolanic reaction and improving the crystallinity and yield of the chabazite. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to make the technical solutions in the embodiments of the present application or the prior art clearer, the accompanying drawings needed in the embodiments or prior art description will be briefly introduced. Obviously, the accompanying drawings in the following description only only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained without creative labor based on the structures shown in the drawings.

[0026] Figure 1 XRD pattern of lithium slag in the analysis example 1 of the present application;

[0027] Figure 2 Activity index pattern of lithium slag after ball milling under different ball milling speeds in the embodiment 1 of the present application;

[0028] Figure 3 Activity index pattern of lithium slag after ball milling under different ball milling times in the embodiment 2 of the present application;

[0029] Figure 4 Activity index pattern of lithium slag after ball milling under different ball milling ratios in the embodiment 3 of the present application;

[0030] Figure 5 Activity index pattern of lithium slag after ball milling under different auxiliary materials (different ball milling auxiliary materials) in the embodiment 4 of the present application;

[0031] Figure 6 Activity index pattern of lithium slag after ball milling under different mixed acid ratios (mass ratio of citric acid and oxalic acid) in the embodiment 5 of the present application;

[0032] Figure 7 Activity index pattern of lithium slag after ball milling under different auxiliary material ratios (mass ratio of auxiliary material and main material lithium slag) in the embodiment 6 of the present application;

[0033] Figure 8 XRD pattern of the prepared product (zeolite) in the embodiment 7 of the present application; in the figure, citric acid + oxalic acid refers to the prepared product in the embodiment 7;

[0034] Figure 9 Adsorption effect pattern of the adsorbent on gaseous arsenic under different adsorption temperatures in the embodiment 8 of the present application;

[0035] Figure 10 Adsorption effect pattern of the adsorbent on gaseous arsenic under different sulfur dioxide concentrations in the embodiment 9 of the present application;

[0036] Figure 11 XRD pattern of the prepared product in the comparative example 1 of the present application;

[0037] Figure 12 XRD pattern of the prepared product in the comparative example 2 of the present application;

[0038] Figure 13XRD pattern of the product prepared in Inventive Example 3 of the present application;

[0039] Figure 14 XRD pattern of the product prepared in Inventive Example 4 of the present application;

[0040] Figure 15 XRD pattern of the product prepared in Inventive Example 5 of the present application.

[0041] The objectives, functional characteristics and advantages of the present application will be further described with reference to the accompanying drawings in conjunction with the embodiments. DETAILED DESCRIPTION

[0042] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. The embodiments described below are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without any creative work under the premise that the embodiments in the present application are within the scope of protection of the present application.

[0043] In addition, the technical solutions among the embodiments of the present application can be combined with each other, but it must be based on the premise that the technical solutions can be realized by those skilled in the art, and when the combination of the technical solutions appears contradictory or unachievable, it should be considered that the combination of the technical solutions does not exist, and is not within the scope of protection required by the present application.

[0044] When the embodiments give numerical ranges, it should be understood that, unless otherwise stated by the present application, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present application are consistent with the mastery of the prior art by those skilled in the art and the description of the present application, and any method, equipment and material of the prior art similar or equivalent to the method, equipment and material described in the embodiments of the present application can be used to realize the present application.

[0045] In the present application, when calculating the ball material ratio, the lithium slag, the alkaline auxiliary material and the water are all counted as the ball milling materials. In the embodiments and comparative examples of the present application, alumina grinding balls are used for ball milling, and the number ratio of the alumina grinding balls is big ball (diameter 15 mm) : medium ball (diameter 10 mm) : small ball (diameter 5 mm) = 15:9:6; in the present application, further, the number ratio of the grinding balls can be big ball (diameter 14-16 mm) : medium ball (diameter 9-11 mm) : small ball (diameter 4-6 mm) = 14-16:8-10:5-7. The microwave hydrothermal reaction kettle used in the embodiments and comparative examples of the present application is from Beijing Xianghu Science and Technology Development Co., Ltd., which is a multifunctional microwave hydrothermal parallel synthesis instrument, model XH-800SP, microwave frequency 2450 MHz.

[0046] In the application, the calculation formula of the activity index of the lithium slag after ball milling is: Wherein, a represents the activity index of the lithium slag after ball milling, m1 represents the content of active aluminum in the lithium slag after ball milling, and m0 represents the content of active aluminum in the lithium slag before ball milling.

[0047] In the application, the aluminum dissolved after alkali leaching is defined as active aluminum.

[0048] A 100 mL sodium hydroxide solution with a concentration of 1 mol / L is prepared and poured into a 250 mL beaker; the beaker is placed on a digital constant temperature magnetic stirrer and heated to 60 DEG C; 3 g of the measured substance (lithium slag after ball milling or lithium slag before ball milling) is added to the beaker, and the alkali leaching experiment is carried out, with a leaching time of 30 min and a stirring speed of 300 r / min; after the leaching is completed, hot filtration is carried out, the filtrate is acidified to pH < 2 with concentrated HNO3 and placed in a refrigerator for standby, and then ICP-OES is used to analyze and test the aluminum concentration; the higher the content of active aluminum, the greater the activity of the lithium slag.

[0049] The application provides a preparation method of offretite based on organic acid ball milling activation, comprising the following steps:

[0050] S1, providing lithium slag and mixed acid; the lithium slag contains Li element, Si element, Al element, Na element, K element, F element and Ca element; the mixed acid comprises first organic acid and second organic acid, the first organic acid comprises citric acid, the second organic acid comprises oxalic acid, and the mass ratio of the first organic acid to the second organic acid is 0.8-3:1; preferably, the first organic acid is citric acid, the second organic acid is oxalic acid, and the mass ratio of the first organic acid to the second organic acid is 0.8-2:1.

[0051] In the application, the mass proportion of the Li element in the lithium slag is 0.1-2%, the mass proportion of the Si element in the lithium slag is 10-15%, the mass proportion of the Al element in the lithium slag is 5-12%, the mass proportion of the Na element in the lithium slag is 5-10%, the mass proportion of the K element in the lithium slag is 5-10%, the mass proportion of the F element in the lithium slag is 2-8%, and the mass proportion of the Ca element in the lithium slag is 5-10%.

[0052] The lithium slag contains nepheline, muscovite and orthoclase phases; the lithium slag has aluminosilicate, especially has a framework aluminosilicate structure.

[0053] S2, the lithium slag and the mixed acid are used as solid materials, and the solid materials and water are jointly ball milled to obtain a ball milling product.

[0054] The application can promote the release of silicon and aluminum elements in the lithium residue, increase the amorphization degree of the lithium residue, and enhance the reaction activity of the lithium residue by performing the ball milling, and the operation is simple.

[0055] In the application, the mass ratio of the mixed acid to the lithium residue is 1.5-5:5, the mass percentage of the water and the solid material is 20-60%, the rotation speed of the ball milling is 290-310 r / min or 450-800 r / min, and the ball milling time is not less than 120 min.

[0056] Preferably, the mass ratio of the mixed acid to the lithium residue is 1.5-3.5:5 or 1.9-2.1:5, the mass percentage of the water and the solid material is 30-50%, the rotation speed of the ball milling is 500-560 r / min, the ball milling time is 120-300 min or 120-250 min, the ball-to-material mass ratio in the ball milling is 4-12:1, and further 7-9:1.

[0057] In the application, the ball milling is performed by sequentially performing forward rotation and reverse rotation, and the forward rotation and the reverse rotation have an interval time, wherein the set time of each forward rotation is 5-15 min (specifically 10 min), the set time of each reverse rotation is 5-15 min (specifically 10 min), and the interval time is set to 3-7 min (specifically 5 min); the ball milling is stopped when the ball milling time reaches the set time, and the interval time is included in the ball milling time.

[0058] S3, the ball milling product and the alkaline solution are mixed to obtain a to-be-treated liquid; the to-be-treated liquid is subjected to hydrothermal treatment (hydrothermal reaction) to obtain a reaction liquid.

[0059] In the application, the alkaline solution contains an alkaline substance, the alkaline substance includes one or more of sodium hydroxide and potassium hydroxide, the concentration of the alkaline substance in the alkaline solution is 0.5-4 mol / L, and further 0.7-1.3 mol / L or 0.9-1.1 mol / L, and the mass-to-volume ratio of the ball milling product to the alkaline solution is 0.5-10 g:45 mL, and further 1-5 g:45 mL.

[0060] In the application, the temperature of the hydrothermal treatment is 130-210℃, and further 140-160℃, the time of the hydrothermal treatment is 40-180 min, and further 110-130 min, the hydrothermal treatment is performed by microwave hydrothermal treatment, the microwave hydrothermal treatment is performed in a microwave hydrothermal reaction kettle, and by using the microwave hydrothermal treatment, microwave field energy can be applied to the materials in the reaction kettle in the synthesis stage, so that the zeolite crystallization rate is accelerated.

[0061] S4, performing solid-liquid separation on the reaction solution to obtain a solid separation product (separation residue); the solid separation product contains analcime.

[0062] The analcime preparation method provided in the present application is simple and low in cost, the prepared analcime has large adsorption capacity, analcime products can be obtained, gaseous arsenic emission of non-ferrous smelting enterprises can be effectively reduced in a high-temperature environment, the storage of lithium residue in the lithium carbonate industry is reduced, and resource utilization is realized.

[0063] Analcime is a new type of three-dimensional material and is widely used in the fields of environment, medical treatment and catalysis, and the main component of analcime is consistent with that of lithium residue, so the lithium residue has the potential to synthesize analcime; the present application synthesizes zeolite from lithium residue to adsorb gaseous arsenic in flue gas, which solves the problem of resource utilization of lithium residue and provides a simple and low-cost method for efficient treatment of gaseous arsenic.

[0064] The technical key of the present application mainly lies in that:

[0065] Firstly, the lithium residue is activated by mechanical ball milling under the joint action of the first organic acid (citric acid) and the second organic acid (oxalic acid), so as to enhance the activity of the lithium residue; the mechanical ball milling is to make the grinding balls and the materials collide, shear and rub in the tank body by rotating the drum, so as to achieve the effects of material crushing, mixing and surface activity enhancement.

[0066] In the ball milling process, the hydrogen ions in the auxiliary organic acid attack the aluminum silicate framework; the auxiliary organic acid root anions are adsorbed on the cation reaction sites in the mineral crystal, and the cations in the crystal lattice are dissolved out through polarization, so that the mineral crystal structure is destroyed; at the same time, the citric acid and the oxalic acid cooperatively attack the Si-O and Al-O bonds, promote the release of silicon and aluminum elements, and enhance the reaction activity of the lithium residue, so as to facilitate the subsequent hydrothermal synthesis; and in the ball milling process, the auxiliary material can also be used as a grinding aid.

[0067] Secondly, after the mixed acid ball milling, the ball-milled and activated lithium residue is subjected to hydrothermal synthesis; although the lithium residue is co-ball milled with citric acid and then subjected to hydrothermal synthesis, analcime with a certain crystallinity and yield can also be obtained, but in the process of hydrothermal synthesis, the citric acid is complexed with numerous divalent metal ions and does not preferentially adsorb calcium ions; after the addition of oxalic acid, the oxalic acid is preferentially complexed with Ca 2+ , so that the concentration of Ca 2+ in the solution is low, thereby inhibiting the pozzolanic reaction and further improving the crystallinity and yield of the analcime; the ball-milled and activated lithium residue is dissolved, diffused, monomer restructured and polycondensed in a microwave hydrothermal environment to form zeolite.

[0068] Thirdly, the application has specific requirements for humidity in the ball milling process, mainly because suitable moisture can cooperate with organic acid to destroy the structure of lithium slag, thereby promoting the release of Si and Al elements.

[0069] Fourthly, the application has specific requirements for the alkaline solution used in hydrothermal, mainly because OH - The concentration will affect the dissolution rate of silicon and aluminum and the crystallization rate of zeolite, so a suitable concentration needs to be used; and the introduction of Ca 2+ , Mg 2+ will promote the pozzolanic reaction, thereby inhibiting the generation of analcime.

[0070] Fifthly, the application can utilize F elements in lithium slag in situ, which plays the role of inorganic template during hydrothermal, and combines with Ca 2+ to generate CaF2 precipitate, thereby inhibiting the pozzolanic reaction and promoting the generation of analcime.

[0071] The application also provides an analcime, which is prepared by the analcime preparation method described in any of the above.

[0072] The application also provides an application of the analcime described in any of the above in arsenic removal or arsenic removal in the presence of sulfur.

[0073] As a specific way of the above application, the application also provides an arsenic removal method, which comprises: adsorbing arsenic in arsenic-containing flue gas by using the analcime described in any of the above, the adsorption being carried out at a temperature of 400-900 DEG C (preferably 750-850 DEG C or 750-800 DEG C), and the adsorption time being 20-90 min (preferably 25-35 min); the arsenic-containing flue gas has As2O3, or the arsenic-containing flue gas has As2O3 and SO2.

[0074] When the arsenic-containing flue gas has As2O3, other components in the arsenic-containing flue gas can include or be oxygen, argon, carbon dioxide, and the concentration of As2O3 in the arsenic-containing flue gas is not higher than 1 mg / L (preferably 0.5-0.8 mg / L); when the arsenic-containing flue gas has As2O3 and SO2, other components in the arsenic-containing flue gas can include or be oxygen, argon, carbon dioxide, the concentration of As2O3 in the arsenic-containing flue gas is not higher than 1 mg / L (preferably 0.5-0.8 mg / L), and the volume ratio of SO2 in the arsenic-containing flue gas is not higher than 15% (preferably 4-6% or 5-10%).

[0075] The following are specific examples of the present invention:

[0076] Analysis Example 1

[0077] The lithium slag is taken from a lithium carbonate production company in Jiangxi.

[0078] 1、In this analysis example, the partial elemental composition of the lithium residue is shown in Table 1; in Table 1, Rb* and Cs* are tested by digestion-ICP, and the rest of the elements are tested by XRF.

[0079] Table 1 Elemental composition of lithium residue (mass percentage)

[0080]

[0081] 2、In this analysis example, the lithium residue has nepheline, muscovite, and orthoclase; the XRD analysis of the lithium residue is shown in Figure 1 ; through analysis, the lithium residue has a framework aluminosilicate structure.

[0082] Example 1

[0083] Take the lithium residue in Analysis Example 1, and ball mill under the condition that the ball mill rotation speed is 300, 350, 400, 450, 500, 550, 600, 650, 700 r / min, respectively, to obtain the ball mill products under different ball mill rotation speeds; the ball-to-material ratio used in ball milling is 6:1, and the ball milling time is 25 min (set the ball mill to rotate forward for 10 min, interval 5 min, reverse for 10 min).

[0084] Detect the activity index of the ball mill products (lithium residue after ball milling) under different ball mill rotation speeds; as shown in Figure 2 , when the ball mill rotation speed is 550 r / min, the activity index of the lithium residue after ball milling reaches 9.1.

[0085] Example 2

[0086] Take the lithium residue in Analysis Example 1, and ball mill under the condition that the ball milling time is 25, 50, 75, 100, 125, 150, 200, 250 min, respectively (set the ball mill to rotate forward for 10 min, interval 5 min, reverse for 10 min, interval 5 min), to obtain the ball mill products under different ball milling times; the ball-to-material ratio used in ball milling is 6:1, and the ball mill rotation speed is 550 r / min.

[0087] Detect the activity index of the ball mill products (lithium residue after ball milling) under different ball milling times; as shown in Figure 3 , when the ball milling time reaches 125 min, the activity index of the lithium residue after ball milling basically no longer improves, and the activity index reaches 15.2.

[0088] Example 3

[0089] The lithium slag from Analytical Example 1 was taken and ball-milled at ball-to-material ratios of 4:1, 6:1, 8:1, and 10:1 to obtain ball-milled products with different ball-to-material ratios. The ball-milling time was 125 min for all ball mills (the ball mill was set to rotate forward for 10 min, with a 5 min interval, then rotate in reverse for 10 min, with a 5 min interval), and the ball milling speed was 550 r / min for all ball mills.

[0090] The activity index of the ball-milled products (lithium slag after ball milling) under different ball-to-material ratios was tested; such as Figure 4 As shown, when the ball-to-material ratio is 8:1, the activity index of the lithium slag after ball milling reaches 20; when the ball-to-material ratio is 10:1, the activity index of the lithium slag after ball milling drops rapidly. It is speculated that the insufficient material may cause some lithium slag to stick to the ball mill jar and grinding balls, resulting in systematic error and making the measured value too small.

[0091] Example 4

[0092] The lithium slag from Analytical Example 1 was used as a solid material, and the auxiliary materials and lithium slag were mixed at a mass ratio of 3:5. The solid material and water were then ball-milled together to obtain ball-milled products with different auxiliary materials. In this embodiment, ball milling was performed under the conditions that the auxiliary materials were sodium hydroxide, citric acid, oxalic acid, sodium citrate, and mixed acid (citric acid and oxalic acid were mixed at a mass ratio of 1:1). In this embodiment, the mass percentage of water and solid material was 40% (equivalent to moisture content) during ball milling, the ball-to-material ratio was 8:1, the ball milling time was 125 min (the ball mill was set to rotate forward for 10 min, with a 5 min interval, then reverse for 10 min, with a 5 min interval), and the ball milling speed was 550 r / min.

[0093] The activity index of the ball milling products (lithium slag after ball milling) under different auxiliary materials was tested; such as Figure 5 As shown, the activity index of the lithium slag after ball milling corresponding to the mixed acid reached 34.8. It is speculated that citric acid and oxalic acid have a preferred orientation for dissolving Si and Al. This allows citric acid and oxalic acid to synergistically attack Si-O and Al-O bonds under the action of mixed acid, destroying the aluminosilicate framework of the mineral. On the other hand, organic acid anions are adsorbed on the cationic reaction sites in the mineral crystal, and dissolve the cations in the crystal lattice through polarization, resulting in the destruction of the mineral crystal structure.

[0094] Example 5

[0095] Take the lithium slag in analysis example 1, citric acid and oxalic acid are matched into mixed acid with mass ratio of 1:3, 1:2, 1:1, 2:1, 3:1, and each ratio of mixed acid is matched with lithium slag with mass ratio of 3:5 to form solid material, then each solid material is ball milled with water to obtain ball milled product under different mixed acid ratios. In this embodiment, the mass percentage of water and solid material is 40% (equivalent to water content) during ball milling, the ball-to-material ratio is 8:1, the ball milling time is 125 min (set the ball mill to rotate forward for 10 min, interval 5 min, reverse for 10 min, interval 5 min), and the ball milling speed is 550 r / min.

[0096] The ball milled products (lithium slag after ball milling) under different mixed acid ratios are detected for activity index; from Figure 6 It can be seen that when the mass ratio of citric acid and oxalic acid is 1:1, the activity index of lithium slag after ball milling reaches 34.8, because citric acid and oxalic acid can attack Si-O bond and Al-O bond synergistically under the action of mixed acid, and destroy the aluminosilicate framework of minerals.

[0097] Example 6

[0098] Take the lithium slag in analysis example 1, citric acid and oxalic acid are matched into mixed acid with mass ratio of 1:1, and the mixed acid and lithium slag are matched into solid material with mass ratio of 0, 1:5, 2:5, 3:5, 4:5, 1:1 (equivalent to different auxiliary material ratio, mass ratio of 0 represents no mixed acid) respectively, then each solid material is ball milled with water to obtain ball milled product under different auxiliary material ratio. In this embodiment, the mass percentage of water and solid material is 40% (equivalent to water content) during ball milling, the ball-to-material ratio is 8:1, the ball milling time is 125 min (set the ball mill to rotate forward for 10 min, interval 5 min, reverse for 10 min, interval 5 min), and the ball milling speed is 550 r / min.

[0099] The ball milled products (lithium slag after ball milling) under different auxiliary material ratios are detected for activity index; from Figure 7 It can be seen that when the mass ratio of citric acid and oxalic acid is 1:1, the activity index of lithium slag after ball milling reaches 34.8, because citric acid and oxalic acid can attack Si-O bond and Al-O bond synergistically under the action of mixed acid, and destroy the aluminosilicate framework of minerals.

[0100] Example 7

[0101] Take the lithium slag in analysis example 1, mix the citric acid and oxalic acid in a mass ratio of 1:1 to form mixed acid, and then mix the mixed acid and lithium slag in a mass ratio of 2:5 to form solid-state material. Then, the solid-state material and water are ball milled together to obtain a ball-milled product (lithium slag after ball milling). In this example, the amount of lithium slag used in ball milling is 7.8 g, the mass percentage of water and solid-state material is 40% (equivalent to the water content), the ball-to-material ratio used in ball milling is 8:1, the ball milling time is 125 min (set the ball mill to rotate forward for 10 min, interval 5 min, reverse for 10 min, interval 5 min), and the ball milling speed is 550 r / min.

[0102] Take 3 g of the ball-milled product and place it in a microwave hydrothermal reactor. Add 45 mL of a 1 mol / L NaOH solution and perform a hydrothermal reaction (microwave hydrothermal reaction). The hydrothermal reaction temperature is 150°C, and the hydrothermal reaction time is 120 min. After the hydrothermal reaction is complete, a reaction solution is obtained.

[0103] Centrifuge the reaction solution at room temperature at a speed of 8000 r / min for 10 min, and perform vacuum filtration to separate the solid and liquid phases. Dry the separated solid to obtain a prepared product.

[0104] Measure the prepared product using XRD to determine whether it is analcime. Use jade software to calculate the crystallinity of the prepared product. Measure the aluminum content in the separated liquid using ICP. Calculate the analcime yield based on the proportion of consumed aluminum in the total aluminum (aluminum in the lithium slag). The aluminum in the separated liquid is defined as unspent aluminum, and the aluminum in the separated solid is defined as consumed aluminum.

[0105] As shown in Figure 8 , the prepared product in this example is analcime. The crystallinity is 54.9%, and the analcime yield is 47.7%.

[0106] Example 8

[0107] Take 0.1 g of the prepared product (analcime) in example 7 as an adsorbent and place it in a gaseous arsenic adsorption system for arsenic adsorption experiments. The adsorption time is 30 min.

[0108] In this example, the system of the gaseous arsenic adsorption system consists of a hydrogen arsenide generator, an adsorption reactor, and a tail gas treatment system. The hydrogen arsenide generator produces hydrogen arsenide, which enters the adsorption reactor along with simulated flue gas. The adsorption reactor consists of two-stage reaction furnaces. The hydrogen arsenide is oxidized to arsenic trioxide in the first-stage reaction furnace, and the arsenic trioxide enters the second-stage reaction furnace for adsorption reaction. The tail gas is discharged through the tail gas treatment system.

[0109] In this embodiment, the atmosphere used by the simulated flue gas is O2 5%, Ar 87%, SO2 5%, CO2 3% by volume ratio, and the flue gas flow rate is 400 mL / min; the concentration of As2O3 in the simulated flue gas is 0.6 mg / L.

[0110] The arsenic adsorption experiment is performed at an adsorption temperature of 400, 500, 600, 700, and 800°C, respectively.

[0111] Referring to Figure 9 As shown in FIG. 7, the gaseous arsenic (referring to As2O3) adsorption capacity of the prepared product (cubic zeolite) in Example 7 can reach 22.26 mg / g at an adsorption temperature of 800°C, which has excellent gaseous arsenic adsorption capacity.

[0112] Example 9

[0113] 0.1 g of the prepared product (cubic zeolite) in Example 7 is taken as the adsorbent, and the adsorbent is placed in the gaseous arsenic adsorption system to perform the arsenic adsorption experiment, and the adsorption temperature is 400°C and the adsorption time is 30 min.

[0114] In this embodiment, the gaseous arsenic adsorption system is composed of a hydrogen arsenide generator, an adsorption reactor, and a tail gas treatment system. The hydrogen arsenide generator generates hydrogen arsenide, which enters the adsorption reactor together with the simulated flue gas. The adsorption reactor is composed of two-stage reaction furnaces. The hydrogen arsenide enters the first-stage reaction furnace to be oxidized into arsenic trioxide, which enters the second-stage reaction furnace to perform the adsorption reaction, and the tail gas is discharged through the tail gas treatment system.

[0115] In this embodiment, the arsenic adsorption experiment is performed on different simulated flue gases, and the compositions of the simulated flue gases are as follows:

[0116] The atmosphere used by the simulated flue gas (corresponding to 0%) is O2 5%, Ar 92%, SO2 0%, CO2 3% by volume ratio, and the flue gas flow rate is 400 mL / min; the concentration of As2O3 in the simulated flue gas is 0.6 mg / L.

[0117] The atmosphere used by the simulated flue gas (corresponding to 5%) is O2 5%, Ar 87%, SO2 5%, CO2 3% by volume ratio, and the flue gas flow rate is 400 mL / min; the concentration of As2O3 in the simulated flue gas is 0.6 mg / L.

[0118] The atmosphere used by the simulated flue gas (corresponding to 10%) is O2 5%, Ar 82%, SO2 10%, CO2 3% by volume ratio, and the flue gas flow rate is 400 mL / min; the concentration of As2O3 in the simulated flue gas is 0.6 mg / L.

[0119] Referring toFigure 10 As shown in the figure, when the SO2 concentration is 5%, the gaseous arsenic (referring to As2O3) adsorption capacity of the product (chabazite) prepared in Example 7 can reach 16.63 mg / g, which has excellent gaseous arsenic adsorption capacity.

[0120] Comparative Example 1

[0121] I. Preparation of the product:

[0122] In the preparation of the product, the mixed acid in the solid material of the present comparative example is adjusted to citric acid compared with Example 7, and other conditions remain unchanged.

[0123] In the present comparative example, referring to Figure 11 As shown in the figure, the product is chabazite, the crystallinity is 47.1%, and the chabazite yield is 42.5%.

[0124] II. Arsenic adsorption experiment:

[0125] In the arsenic adsorption experiment, the adsorbent of the present comparative example is adjusted to the product of the present comparative example compared with Example 8, and the adsorption temperature is limited to 800°C, and other conditions remain unchanged.

[0126] In the present comparative example, the gaseous arsenic (referring to As2O3) adsorption capacity of the adsorbent is 20.7 mg / g.

[0127] Comparative Example 2

[0128] I. Preparation of the product:

[0129] In the preparation of the product, the mixed acid in the solid material of the present comparative example is adjusted to oxalic acid compared with Example 7, and other conditions remain unchanged.

[0130] In the present comparative example, referring to Figure 12 As shown in the figure, the product is chabazite, the crystallinity is 31.4%, and the chabazite yield is 29.6%.

[0131] II. Arsenic adsorption experiment:

[0132] In the arsenic adsorption experiment, the adsorbent of the present comparative example is adjusted to the product of the present comparative example compared with Example 8, and the adsorption temperature is limited to 800°C, and other conditions remain unchanged.

[0133] In the present comparative example, the gaseous arsenic (referring to As2O3) adsorption capacity of the adsorbent is 20.7 mg / g.

[0134] Comparative Example 3

[0135] I. Preparation of the product:

[0136] In obtaining the prepared product, compared with Example 7, the oxalic acid in the mixed acid was changed to hydrochloric acid (citric acid was retained in the mixed acid and the proportion remained unchanged), while other conditions remained unchanged.

[0137] In this comparative example, see Figure 13 As shown, no anthocyanins were formed in the product.

[0138] II. Arsenic Adsorption Experiment:

[0139] In the arsenic adsorption experiment, compared with Example 8, the adsorbent in this comparative example was adjusted to the prepared product in this comparative example, and the adsorption temperature was limited to 800°C, while other conditions remained unchanged.

[0140] In this comparative example, the adsorption capacity of the adsorbent for gaseous arsenic (referring to As2O3) was 4.3 mg / g.

[0141] Comparative Example 4

[0142] I. Obtaining the preparation product:

[0143] In obtaining the prepared product, compared with Example 7, the alkaline solution used in the hydrothermal process in this comparative example was changed to pure water, while other conditions remained unchanged.

[0144] In this comparative example, see Figure 14 As shown, analcime was formed in the prepared product, but the crystallinity was only 12.5%, and the yield of analcime was 10.7%.

[0145] II. Arsenic Adsorption Experiment:

[0146] In the arsenic adsorption experiment, compared with Example 8, the adsorbent in this comparative example was adjusted to the prepared product in this comparative example, and the adsorption temperature was limited to 800°C, while other conditions remained unchanged.

[0147] In this comparative example, the adsorption capacity of the adsorbent for gaseous arsenic (referring to As2O3) was 8.9 mg / g.

[0148] Comparative Example 5

[0149] I. Obtaining the preparation product:

[0150] In obtaining the prepared product, compared with Example 7, the lithium slag was directly ball-milled (without adding mixed acid and water), while other conditions remained unchanged.

[0151] In this comparative example, see Figure 15 As shown, analcime was formed in the prepared product, but the crystallinity was only 13.1% and the yield was 8.1%.

[0152] II. Arsenic Adsorption Experiment:

[0153] In the arsenic adsorption experiment, compared with Example 8, the adsorbent is adjusted to the preparation product in the present example, and the adsorption temperature is limited to 800 DEG C, and other conditions remain unchanged.

[0154] In the present example, the gaseous arsenic (referring to As2O3) adsorption capacity of the adsorbent is 13.69 mg / g.

[0155] In the above technical solutions of the present application, the above is only the preferred embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structural transformation made under the technical concept of the present application, using the content of the present application specification and drawings, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present application.

Claims

1. A method for preparing analcime based on organic acid ball milling activation, characterized in that, Including the following steps: S1 provides lithium slag and mixed acid; the lithium slag contains Li, Si, Al, Na, K, F and Ca elements; the mixed acid includes a first organic acid and a second organic acid, the first organic acid includes citric acid and the second organic acid includes oxalic acid, and the mass ratio of the first organic acid to the second organic acid is 0.8-3:

1. S2, the lithium slag and the mixed acid are used as solid materials, and the solid materials and water are ball-milled together to obtain a ball-milled product; the mass ratio of the mixed acid to the lithium slag is 1.5-5:5; the mass percentage of water to the solid material is 20-60%; the ball milling speed is 290-310 r / min or 450-800 r / min, and the ball milling time is not less than 120 min; S3, the ball-milled product is mixed with an alkaline solution to obtain a solution to be treated; the solution to be treated is subjected to hydrothermal treatment to obtain a reaction solution; The alkaline solution contains an alkaline substance, which includes one or more of sodium hydroxide and potassium hydroxide; the hydrothermal treatment temperature is 130-210℃, and the hydrothermal treatment duration is 40-180 min; S4, the reaction solution is subjected to solid-liquid separation to obtain a solid separator; the solid separator contains analcime.

2. The method for preparing analcime according to claim 1, characterized in that, The first organic acid is citric acid, the second organic acid is oxalic acid, and the mass ratio of the first organic acid to the second organic acid is 0.8-2:1; the mass ratio of the mixed acid to the lithium slag is 1.5-3.5:

5.

3. The method for preparing analcime according to claim 1, characterized in that, The ball mill operates at a rotation speed of 500-560 r / min, and the milling time is 120-300 min. The ball-to-material mass ratio used in the ball mill is 4-12:

1.

4. The method for preparing analcime according to claim 1, characterized in that, The concentration of the alkaline substance in the alkaline solution is 0.5-4 mol / L.

5. The method for preparing analcime according to claim 1, characterized in that, The mass-to-volume ratio of the ball-milled product to the alkaline solution is 0.5-10 g: 45 mL.

6. The method for preparing analcime according to claim 1, characterized in that, The hydrothermal treatment method is microwave hydrothermal; the microwave hydrothermal treatment is carried out in a microwave hydrothermal reactor.

7. The method for preparing analcime according to claim 1, characterized in that, The mass percentage of Li in the lithium slag is 0.1-2%, the mass percentage of Si in the lithium slag is 10-15%, the mass percentage of Al in the lithium slag is 5-12%, the mass percentage of Na in the lithium slag is 5-10%, the mass percentage of K in the lithium slag is 5-10%, the mass percentage of F in the lithium slag is 2-8%, and the mass percentage of Ca in the lithium slag is 5-10%. The lithium slag contains nepheline, muscovite, and orthoclase; the lithium slag has a framework aluminosilicate structure.

8. A type of analcime, characterized in that, include: The analcime was prepared using the method described in any one of claims 1-7.

9. The application of the analcime as described in claim 8 in arsenic removal or sulfur-resistant arsenic removal.

10. A method for removing arsenic, characterized in that, include: Arsenic in arsenic-containing flue gas is adsorbed using the zeolite as described in claim 8, wherein the adsorption is carried out at a temperature of 400-900℃ and the adsorption time is 20-90 min; wherein the arsenic-containing flue gas contains As2O3, or wherein the arsenic-containing flue gas contains As2O3 and SO2. When the arsenic-containing flue gas contains As2O3, the concentration of As2O3 in the arsenic-containing flue gas is not higher than 1 mg / L; when the arsenic-containing flue gas contains both As2O3 and SO2, the concentration of As2O3 in the arsenic-containing flue gas is not higher than 1 mg / L, and the volume percentage of SO2 in the arsenic-containing flue gas is not higher than 15%.

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