阅读说明：本技术 一种磁性Na-P型沸石的合成方法 (Synthesis method of magnetic Na-P type zeolite ) 是由 张耀君 韩智超 贺攀阳 陈浩 张叶 刘礼才 于 2019-11-26 设计创作，主要内容包括：本发明公开了一种磁性Na-P型沸石的合成方法,该方法将锌渣、粉煤灰、氢氧化钠、去离子水放入高压釜中,经水热反应、洗涤、干燥,即得到Na-P型沸石,其中锌渣、粉煤灰、氢氧化钠、去离子水的质量比为0.25～1.5：1：0.73：15。本发明以工业固体废弃物锌渣及粉煤灰为原料,采用水热反应,一步法直接合成磁性Na-P型沸石。其合成工艺简单,成本低廉,符合循环经济发展原则,是工业固体废弃物锌渣及粉煤灰高附加值利用的新途径。(The invention discloses a synthesis method of magnetic Na-P type zeolite, which comprises the steps of putting zinc slag, fly ash, sodium hydroxide and deionized water into a high-pressure kettle, carrying out hydrothermal reaction, washing and drying to obtain the Na-P type zeolite, wherein the mass ratio of the zinc slag, the fly ash, the sodium hydroxide and the deionized water is 0.25-1.5: 1: 0.73: 15. the invention takes industrial solid waste zinc slag and fly ash as raw materials, adopts hydrothermal reaction, and directly synthesizes magnetic Na-P type zeolite by a one-step method. The synthetic process is simple, the cost is low, the principle of circular economy development is met, and the method is a new way for high-added-value utilization of industrial solid waste zinc slag and fly ash.)

1. A synthesis method of magnetic Na-P type zeolite is characterized by comprising the steps of putting zinc dross, fly ash, sodium hydroxide and deionized water into a high-pressure kettle, carrying out hydrothermal reaction, washing and drying to obtain the Na-P type zeolite, wherein the mass ratio of the zinc dross to the fly ash to the sodium hydroxide to the deionized water is 0.25-1.5: 1: 0.73: 15.

2. the method according to claim 1, characterized in that it is carried out in particular by the following steps:

(1) weighing zinc slag and fly ash according to the formula ratio, and uniformly mixing to obtain a mixture;

(2) weighing solid sodium hydroxide according to the formula ratio, and placing the solid sodium hydroxide into a beaker;

(3) weighing deionized water according to the formula amount, pouring the deionized water into the beaker in the step (2), and stirring to completely dissolve sodium hydroxide to form 45mL of 1-2 mol/L sodium hydroxide solution;

(4) and (3) placing the sodium hydroxide solution obtained in the step (3) and the mixture obtained in the step (1) into a high-pressure reaction kettle, sealing the kettle, reacting for 12-48 hours at 90-120 ℃, and naturally cooling, filtering, washing and drying after the reaction is finished to obtain the magnetic Na-P type zeolite.

3. The method of claim 1 or 2, wherein:

the zinc slag comprises the following main oxides in percentage by mass: fe₂O₃：39.68％，SiO₂：16.79％，Al₂O₃：8.49％，CaO：9.10％，K₂O：4.00％，MgO：2.32％，Na₂O：1.00％，SO₃：0.42％，LOI：18.20％；

The main oxides of the fly ash comprise the following components in percentage by mass: al (Al)₂O₃：42.24％，SiO₂：37.15％，CaO：2.97％，Fe₂O₃：3.01％，TiO₂：2.02％，Na₂O：0.41％，MgO：0.31％，K₂O：0.45％，P₂O₅：0.23％，SO₃：0.89％，LOI：10.32％。

4. A magnetic Na-P zeolite obtainable by a process according to any one of claims 1 to 3.

Technical Field

The invention belongs to the field of resource utilization of solid wastes and synthesis of zeolite, and relates to a method for synthesizing zeolite, in particular to a method for directly synthesizing magnetic Na-P type zeolite by using solid wastes, namely zinc slag and fly ash as raw materials through a one-step method.

Background

The zinc slag is an industrial solid waste discharged in the process of smelting metal zinc. In the zinc smelting process flow, according to the report of the national statistical bureau and the data center of the Chinese report hall^[1]568.1 million tons of zinc are produced by zinc smelting enterprises in 2018, 0.96 ton of zinc dross is discharged when 1 ton of metal zinc is produced, and according to the estimation, the discharge amount of the zinc dross in China is about 545 million tons only in 2018, and the historical stock of the zinc dross exceeds hundred million tons^[2]. The stacking of a large amount of zinc slag not only pollutes the environment, but also contains metal zinc, iron, manganese, lead, cadmium, nickel, copper and the like, and if the zinc slag is not used, valuable metals are wasted.

The fly ash is the main solid waste discharged by coal-fired power plants, and the discharge amount of the fly ash is increased year by year along with the continuous development of the electric power industry in China. The annual discharge amount of fly ash in China exceeds five hundred million tons^[3,4]. When a large amount of fly ash is stacked, the fly ash is blown by wind and rain, dust is raised, the atmosphere is polluted, and silting of a drainage system and underground water quality pollution are caused.

Fly ash has been widely used in the art as a primary raw material for zeolite production.

Glittering and translucent^[5]Etc. magnetic Fe₃O₄The nano particles are loaded on the surface of the fly ash, then alkali and an aluminum source are added to synthesize the magnetic fly ash zeolite by hydrothermal method, and NaOH and NaAlO are investigated₂The addition amount has influence on the synthesis of magnetic fly ash zeolite, which is a mixture of A-type zeolite, sodalite, analcite, etc. and magnetic Fe₃O₄A composite of nanoparticles.

Wangkai^[6]Using fly ash as main raw material, acidifying fly ash by hydrochloric acid to load magnetic Fe₃O₄Then the magnetic fly ash is obtained. The magnetic fly ash solid and 2mol/L NaOH solution are stirred vigorously for 1h, the mixture is placed in a metal reaction kettle, then the mixture is aged for 1h at 50 ℃, then the temperature is raised to 110 ℃, and then the mixture is crystallized for 24h, and finally the magnetic fly ash zeolite is obtained after washing and drying.

Wenxing Qingqing^[7]Taking fly ash as a raw material, and carrying out acidification treatment on the fly ash by adopting hydrochloric acid under the water bath heating condition of 80 ℃; then mixing and grinding the pretreated fly ash and solid NaOH according to the ratio of 1:1.2, carrying out melt calcination at 550 ℃ for 1h, and cooling to room temperature; with magnetic Fe₃O₄@TiO₂Taking nano particles, fly ash and a sample which is fused and calcined at 550 ℃ by solid NaOH as raw materials, adding sodium stearate and distilled water, and synthesizing the loaded Fe through high-pressure reaction₃O₄@TiO₂The magnetic Na-P type zeolite composite material of (1).

Sun Qi^[8]Taking kaolin as a raw material, preparing 4A zeolite by adopting a hydrothermal method, and then loading magnetic Fe₃O₄Magnetic 4A zeolite was prepared.

Sun Qi et al^[9]The patent reports that P-type zeolite is prepared by taking fly ash calcined at 500-800 ℃ as a raw material and adopting a hydrothermal method, and then Fe₃O₄The magnetic P-type zeolite is obtained by loading the P-type zeolite.

Periapical peak and the like^[10]Mixing fly ash and solid NaOH according to the mass ratio of 1.2: 1 of alkali ash, and weighing a certain amount of SiO₂Adding the powder into the mixture to enable the Si/Al molar ratio to be 1.0, grinding, uniformly mixing, placing into a crucible, adding a small amount of deionized water, and placing into a high-temperature furnace to roast for 2 hours at 600 ℃ to obtain the fly ash clinker. Mixing Fe₃O₄Fine particles dissolved in a small amount of deionized water to produce Fe₃O₄And (3) dispersing the mixture. Weighing a certain amount of fly ash clinker and Fe₃O₄Mixing the dispersion liquid, mixing the dispersion liquid with 6 times of deionized water, stirring at room temperature for 24h to achieve the purpose of aging, taking supernatant liquid, placing in a high-temperature high-pressure reaction kettle, and crystallizing at 100 ℃ for 4 h. The A-type zeolite can be prepared.

Yamaura et al^[11,12]Taking fly ash as a raw material, preparing hydroxysodalite through hydrothermal reaction, and then mixing the hydroxysodalite with magnetic Fe₃O₄And mixing and stirring the mixture in the aqueous solution according to the mass ratio of 3:1 to obtain the magnetic hydroxyl sodalite.

In addition, the magnetic zeolite can be prepared by ion exchange, electrostatic adsorption, or the like. Horikawa et al^[13]Selecting Ni⁺The ions react with Na in Na-A, Na-Y zeolite⁺The ions are ion exchanged to form Ni-A, Ni-Y two kinds of magnetic zeolite.

Anunziata, etc^[14]Passing Na-ZSM-11 through NH₄ ⁺Exchange preparation of ammonium ion exchanged NH₄-ZSM-11 zeolite, followed by FeSO₄·7H₂O and Fe (NO)₃)₃·9H₂Soaking solution of O salt in NH₄-ZSM-11 zeolite, N₂Roasting at 500 ℃ for 10h in an air atmosphere, and continuously roasting a sample at 500 ℃ for 12h in an air atmosphere to obtain the loaded Fe₃O₄The magnetic H-ZSM-11 zeolite composite material.

Tao et al^[15]Dispersing fly ash in 95% ethanol, screening floating beads with the diameter of 200-300 microns, then chemically plating nickel on the surface of the floating beads, then adsorbing ZSM-5 zeolite seed crystals with the average particle size of 180nm on the surface of the nickel-plated floating beads (Ni/floating beads) through static electricity, mixing the seed crystals with a surfactant (tetraethylammonium bromide), NaOH, aluminum foil, tetraethyl orthosilicate and deionized water in a certain proportion, carrying out hydrothermal reaction at 180 ℃ for 12-24h, and roasting at 550 ℃ for 5h to prepare the ZSM-5/Ni/fly ash floating bead magnetic composite material.

In summary, applicants have systematically consulted a large amount of domestic and foreign literature, and the existing literature reports mainly through Fe₃O₄The magnetic zeolite is formed by compounding a magnetic substance with A-type, P-type and ZSM-5 zeolite through a plurality of steps of loading, ion exchange, electrostatic adsorption and the like. However, no relevant literature report is found that solid wastes, namely the zinc dross and the fly ash, are used as raw materials, magnetic components in the zinc dross and the fly ash are fully utilized, and no magnetic substance is added, so that the magnetic zeolite is directly synthesized by a one-step method.

The following are references given by the inventors:

[1]http://www.chinabgao.com/chanliang/284778.html。

[2] hawaiping, Han dynasty, Gaoyanqiang, etc. comprehensive utilization of zinc smelting slag [ J ] inorganic salt industry, 2017,49(7): 57-60.

[3] Physical property and resource utilization of Zhuwanxin fly ash [ J ] colored equipment, 2016,4: 44-47.

[4] Jin dawn, guoping, zana et al research on fly ash synthetic zeolites advanced [ J ] environmental chemistry, 2015, 34 (11): 2025-2038.

[5]Preparation of magnetic fly ash zeolite and its application in Cu²⁺Study of adsorption [ J]Nonmetallic mine, 2014,37(6): 62-65.

[6] Wangkai, Li Xiuhua, Berger et al, preparation of magnetic fly ash based zeolite and its adsorption study on methylene blue [ J ]. Chifeng college bulletin (Nature edition), 2016,32(21): 12-14.

[7]Load Fe under the condition of mild weather₃O₄@TiO₂Preparation of Zeolite composite and oil absorption study thereof [ D]Master academic thesis, tianjin university, 2016.

[8] Sunzhi, Kaolin and fly ash, Zeolite synthesis and magnetic particle loading research [ D ]. doctor academic thesis, geological university of China, 2015.

[9] Grand, royal, liu and bin, etc. a preparation method of a magnetic P-type zeolite molecular sieve, chinese patent publication no: CN 109336186a, 2019.

[10] Zhou Lifeng, anyao, Guyue, etc. the research on the synthesis and adsorption performance of the fly ash-based magnetic A-type zeolite, metallurgical energy, 2018, 37(6): 54-58.

[11]Yamaura M，Fungaro D A.Synthesis and characterization of magneticadsorbent preparedby magnetite nanoparticles and zeolite from coal fly ash,Journal of Material Science,2013，48:5093-5101。

[12]Fungaro D A，Yamaura M，Craesmeyer G R.Removal from aqueoussolution by zeolitefrom fly ash-iron oxide magnetic nanocomposite，International Review of Chemical Engineering，2012，4(3):353-358。

[13]Horikawa Y，Ohnishi N，Hiraga K.Structures and magneticsusceptibility of Ni-ion-introduced zeolite A and X[J].Materials Science andEngineering A，1996，217/218:139-141。

[14]Anunziata O A，Costa M G,Beltramone A R.Fe-ZSM-11magneticproperties:Its relation with the catalytic activity for NOx SCR withisobutane and O₂[J].Applied Catalysis A General，2006，307(2):263-269。

[15]Tao H，Yao J，Zhang L，et al.Preparation of magnetic ZSM-5/Ni/fly-ash hollow microspheres using fly-ash cenospheres as the template[J].Materials Letters，2009，63(2):203-205。

Disclosure of Invention

In order to accord with the principle of circular economy development and further utilize industrial solid waste with high added value, the invention aims to provide a method for synthesizing magnetic Na-P type zeolite.

In order to realize the task, the invention adopts the following technical solution:

a synthesis method of magnetic Na-P type zeolite is characterized by comprising the steps of putting zinc dross, fly ash, sodium hydroxide and deionized water into a high-pressure kettle, carrying out hydrothermal reaction, washing and drying to obtain the Na-P type zeolite, wherein the mass ratio of the zinc dross to the fly ash to the sodium hydroxide to the deionized water is 0.25-1.5: 1: 0.73: 15.

the method specifically comprises the following steps:

(1) weighing zinc slag and fly ash according to the formula ratio, and uniformly mixing to obtain a mixture;

(2) weighing solid sodium hydroxide according to the formula ratio, and placing the solid sodium hydroxide into a beaker;

(3) weighing deionized water according to the formula amount, pouring the deionized water into the beaker in the step (2), and stirring to completely dissolve sodium hydroxide to form 45mL of 1-2 mol/L sodium hydroxide solution;

(4) and (3) placing the sodium hydroxide solution obtained in the step (3) and the mixture obtained in the step (1) into a high-pressure reaction kettle, sealing the kettle, reacting for 12-48 hours at 90-120 ℃, and naturally cooling, filtering, washing and drying after the reaction is finished to obtain the magnetic Na-P type zeolite.

The synthesis method of the magnetic Na-P type zeolite has the innovation points that: the pure magnetic Na-P type zeolite is directly synthesized by a one-step method by taking solid wastes of zinc dross and fly ash as raw materials and adopting a hydrothermal reaction. The method not only realizes the high added value utilization of the zinc slag and the fly ash, but also simplifies the synthesis process of the magnetic zeolite and reduces the synthesis cost of the magnetic zeolite.

Drawings

FIG. 1 is the XRD pattern of example 1;

FIG. 2 is a hysteresis loop in example 1;

FIG. 3 is a photograph showing a magnetic separation experiment of the magnetic Na-P type zeolite in example 1;

FIG. 4 is XRD patterns of comparative Experimental example 1 and comparative Experimental example 2;

the present invention will be described in further detail with reference to the following drawings and examples.

Detailed Description

It should be noted that the following examples are only for better illustrating the present invention and the present invention is not limited to these examples.

In the following embodiment, the raw materials of the prepared magnetic Na-P type zeolite comprise zinc dross, fly ash, sodium hydroxide and deionized water, wherein the mass ratio of the zinc dross to the fly ash to the sodium hydroxide to the deionized water is 0.25-1.5: 1: 0.73: 15.

(1) zinc slag: from a commercial zinc plant.

The main oxide composition (mass percent) of the zinc slag is as follows: fe₂O₃(39.68％)，SiO₂(16.79％)，Al₂O₃(8.49％)，CaO(9.10％)，K₂O(4.00％)，MgO(2.32％)，Na₂O(1.00％)，SO₃(0.42％)，LOI(18.20％)。

(2) Fly ash from inner Mongolia thermal power plants.

The main oxide composition (mass percent) of the fly ash is as follows: al (Al)₂O₃(42.24％)，SiO₂(37.15％)，CaO(2.97％)，Fe₂O₃(3.01％)，TiO₂(2.02％)，Na₂O(0.41％)，MgO(0.31％)，K₂O(0.45％)，P₂O₅(0.23％)，SO₃(0.89％)，LOI(10.32％)。

(3) Sodium hydroxide (anhydrous), purchased from Shanghai Michelin Biochemical technology Ltd, analytical grade reagent, molecular weight: 39.996.

(4) deionized water, self-made in laboratories.

The following are specific examples given by the inventors and comparative experimental examples.