阅读说明：本技术 同步防护nh3/so2的氢氧化锆防护材料的制备方法 (Synchronous protection NH3/SO2Preparation method of zirconium hydroxide protective material ) 是由 武越 赵婷 崔洪 齐嘉豪 金彦任 孙晓敏 李若梅 温宇慧 于 2020-03-04 设计创作，主要内容包括：本发明公开了一种同步防护NH<Sub>3</Sub>/SO<Sub>2</Sub>的氢氧化锆防护材料的制备方法,包括如下步骤：(1)、称取ZrOC1<Sub>2</Sub>·8H<Sub>2</Sub>O,加入去离子水磁力搅拌0.5h至溶解,然后在磁力搅拌的作用下,加入氨水,将得到的混合物再搅拌0.5h；(2)、将步骤(1)的混合物转移到聚四氟乙烯内衬反应釜中,在110～170℃下水热反应3～8h,反应釜晾至室温后,将生成物过滤、洗涤、40～100℃干燥。本发明采用微量金属活性组分原位担载到氢氧化锆悬浮液中,制成的氢氧化锆改性材料活性位点均匀分散,同时具有高的彼表面积、优异的酸碱有毒工业气体防护能力。(The invention discloses a synchronous protection NH 3 /SO 2 The preparation method of the zirconium hydroxide protective material comprises the following steps: (1) weighing ZrOC1 2 ·8H 2 Adding deionized water, magnetically stirring for 0.5h until the deionized water is dissolved, then adding ammonia water under the action of magnetic stirring, and stirring the obtained mixture for 0.5 h; (2) transferring the mixture obtained in the step (1) into a polytetrafluoroethylene lining reaction kettle, carrying out hydrothermal reaction for 3-8 h at 110-170 ℃, airing the reaction kettle to room temperature, filtering and washing a product, and drying at 40-100 ℃. The invention adopts trace metal active components to be loaded in situ into zirconium hydroxide suspension, and the prepared zirconium hydroxide modified material has uniformly dispersed active sites, high specific surface area and excellent acid-base toxic industrial gas preventionAnd (4) protecting the ability.)

1. Synchronous protection NH₃/SO₂The preparation method of the zirconium hydroxide protective material is characterized by comprising the following steps: the method comprises the following steps:

(1) weighing ZrOC1₂·8H₂Adding deionized water, magnetically stirring for 0.5h until the deionized water is dissolved, then adding ammonia water under the action of magnetic stirring, and stirring the obtained mixture for 0.5 h;

(2) transferring the mixture obtained in the step (1) into a polytetrafluoroethylene lining reaction kettle, carrying out hydrothermal reaction for 3-8 h at 110-170 ℃, airing the reaction kettle to room temperature, filtering and washing a product, and drying at 40-100 ℃ to obtain zirconium hydroxide powder;

(3) grinding the prepared zirconium hydroxide powder, sieving the zirconium hydroxide powder with a 170-400-mesh sieve, weighing the zirconium hydroxide powder, adding 150-300 g of deionized water, and carrying out ultrasonic treatment at 50-85 Hz for 2-4 h to form uniformly dispersed suspension;

(4) weighing 1-6 g of copper sulfate and 0.5-5 g of potassium chloride per 100g of zirconium hydroxide powder, adding 10-40 g of deionized water, and stirring for 0.5-2 h at 25-40 ℃ until the materials are dissolved;

(5) adding the solution obtained in the step (4) into the suspension solution obtained in the step (3), and stirring for 1-3 hours at 25-40 ℃ to obtain light blue suspension liquid;

(6) filtering the light blue suspension liquid obtained in the step (5) by using filter paper to obtain a light blue solid, airing at room temperature for 9-18 h, and drying in an oven at the temperature of 40-120 ℃ for 3-8 h to obtain a light blue powder zirconium-based material;

(7) and (3) pressing the powder zirconium-based material obtained in the step (6) into a sheet-shaped molding material with the diameter of 0.9-1.4 cm and the thickness of 0.2-0.4 cm, and then crushing and screening to obtain a particle material with the diameter of 0.6-1.2 mm.

Technical Field

The invention relates to the technical field of zirconium hydroxide protective materials, in particular to a method for synchronously and efficiently protecting NH₃/SO₂The preparation method of the zirconium hydroxide protective material.

Background

Zirconium hydroxide is an amphoteric adsorbing material simultaneously having an acidic bridging hydroxyl functional group and an alkaline terminal hydroxyl functional group, has a high specific surface and a developed pore structure, and has a certain protective property for various toxic gases (sulfur dioxide, chlorine, phosgene, hydrogen chloride) and the like, so that the zirconium hydroxide is concerned by scholars in the field of domestic and foreign protection.

Zirconium Hydroxide itself has excellent protective effects against Sulfur Dioxide due to its high content of effective basic terminal hydroxyl functional groups, for example, Gregory et al, which prepares Zirconium Hydroxide powder into particles of 12 × 30 mesh, shows a protective time of 89min against Sulfur Dioxide gas, a penetration capacity of 70.78mg/g (Gregory W. Peterson, Christopher J. Karwacki, William B. Feaver. Zirconium Hydroxide a Reactive Substrate for the Removal of Sulfur Dioxide [ J ]. Industrial & Engineering chemical research, 2009, 48(4): 1694-1698).

Although zirconium hydroxide has excellent protective performance for acid gas sulfur dioxide, the protective effect for alkaline gas ammonia is poor, and the zirconium hydroxide needs to be modified to have excellent ammonia protective capability. For example, Glover sulfuric acid treatment of zirconium hydroxide powder showed 3.9mol/kg penetration capacity for ammonia gas, but did not give sulfur dioxide protection, and had a specific surface area of only 67m after acid treatment²/g。（T. Grant Glover,*,† Gregory W. Peterson,‡Jared B. DeCoste,‡ and Matthew A. Browe‡.Adsorption of Ammonia by SulfuricAcid Treated Zirconium Hydroxide [J]L angmuir, 2012, 28, 10478-10487) Peterson shows a saturated adsorption capacity of 4.4mol/kg for ammonia gas and only 0.4mol/kg for sulfur dioxide by physically mixing Zirconium Hydroxide powder with Cu-BTC powder in a ratio of 1:1 (Gregory W.Peterson,. † Joseph A. Rossin,. Jared B. Decaste,. l TtT transition = & "&/T & &Kato L. llkiops, † Matthew Browe, † Erica valves, † and Paulette Jones. Zironium Hydroxide-Metal-organic frameworks compositions for Toxico J]. Industrial&EngineeringChemistry Research, 2013, 52(15), 5462～5469）。

Although the above documents use acid treatment for zirconium hydroxide and physically mix with metal organic framework material for preventing alkaline toxic gas to prepare zirconium hydroxide preparation material for effectively protecting ammonia gas, the disadvantages of obvious reduction of specific surface area of zirconium hydroxide material, serious loss of alkaline active sites and the like exist, and it is difficult to satisfy synchronous high-efficiency protection of NH₃/SO₂The requirements of (1).

Disclosure of Invention

The traditional zirconium hydroxide adsorbing material has rich alkaline active sites, but has low content of acid sites and poor protection performance on alkaline gas. Although the zirconium hydroxide modified material can have excellent alkaline gas protection capability by mixing and modifying the zirconium hydroxide with the later-stage acid or alkaline gas prevention material, the acid gas protection capability is poor, the loss of the specific surface area is serious, and the zirconium hydroxide modified material cannot have excellent protection capability for acid and alkaline gases at the same time.

The invention aims to solve the problem of the capability of zirconium hydroxide for protecting alkaline gas, keep the excellent capability of protecting acid gas and simultaneously have high specific surface area.

The invention is realized by adopting the following technical scheme:

synchronous protection NH₃/SO₂The preparation method of the zirconium hydroxide protective material comprises the following steps:

(1) weighing ZrOC1₂·8H₂O (11.28 g, 0.035 mol), 20-30 g deionizationStirring water for 0.5h until the water is dissolved, and then adding 40-60 g (the adding speed is 0.05-1.5 m L & s) of ammonia water (25 wt%) under the action of magnetic stirring (400-1800 rpm)^-1) Stirring the obtained mixture for 0.5 h;

(2) transferring the mixture obtained in the step (1) into a polytetrafluoroethylene lining reaction kettle, carrying out hydrothermal reaction for 3-8 h at 110-170 ℃, airing the reaction kettle to room temperature, filtering and washing a product, and drying at 40-100 ℃ to obtain zirconium hydroxide powder;

(3) repeating the step 1) and the step 2) to prepare a certain amount of zirconium hydroxide powder, then grinding the prepared zirconium hydroxide powder, sieving the ground zirconium hydroxide powder with a 170-400-mesh sieve, weighing the zirconium hydroxide powder, adding 150-300 g of deionized water, and carrying out ultrasonic treatment at 50-85 Hz for 2-4 hours to form uniformly dispersed suspension;

(4) weighing 1-6 g of copper sulfate and 0.5-5 g of potassium chloride per 100g of zirconium hydroxide powder, adding 10-40 g of deionized water, and stirring for 0.5-2 h at 25-40 ℃ until the materials are dissolved;

the types of the metal active components mainly use copper sulfate and potassium chloride, but are not limited to adding or using other metal active components on the basis, and the copper sulfate can be replaced by inorganic, organic copper or ferric chloride such as copper nitrate, copper chloride and the like; the potassium chloride can be replaced by active additives such as potassium sulfate, potassium nitrate, potassium iodide and the like;

the non-metal active component is supported, the metal active component is supported in the invention, but the invention is not limited to the supporting of components such as amino acid, organic alkali and the like on the basis;

(5) adding the solution obtained in the step (4) into the suspension solution obtained in the step (3), and stirring for 1-3 hours at 25-40 ℃ to obtain light blue suspension liquid;

(6) filtering the light blue suspension liquid obtained in the step (5) by using filter paper to obtain a light blue solid, airing at room temperature for 9-18 h, and drying in an oven at the temperature of 40-120 ℃ for 3-8 h to obtain a light blue powder zirconium-based material;

(7) and (3) pressing the powder zirconium-based material obtained in the step (6) into a sheet-shaped molding material with the diameter of 0.9-1.4 cm and the thickness of 0.2-0.4 cm, and then crushing and screening to obtain a particle material with the diameter of 0.6-1.2 mm.

According to the scheme, trace metal active components are carried on the zirconium hydroxide base material to prepare the novel modified zirconium-based adsorbing material, and the prepared modified zirconium-based material has excellent protection capability on ammonia gas through the addition of the metal active components while ensuring the high specific surface area, the high adsorption capacity and the high sulfur dioxide protection capability of the zirconium hydroxide base material. The novel modified zirconium-based adsorption material prepared by the invention can protect sulfur dioxide mainly through a hydroxyl-terminated functional group, and the mechanism is as follows:

Zr(OH)₄+ SO₂→ Zr(OH)₂(SO₃) + H₂O （1）

Zr(OH)₂(SO₃) + SO₂→ Zr(SO₃)₂+ H₂O （2）

zirconium hydroxide substrate material itself can carry out certain protection to the ammonia through bridging hydroxyl, but its effective bridging functional group content is low, and is poor to ammonia protective capability, through carrying out trace metal active ingredient to substrate material and carrying the back, through ammonia and copper reaction center complex, adsorb through weakening chemistry and form coordination compound, reach the purpose of protection ammonia, this in-process potassium chloride is as catalytic assistant, strengthens the dynamic protection effect of novel modified zirconium base adsorbing material to the ammonia, and the reaction formula is as follows:

2NH₃+ CuSO₄→ Cu(NH₃)₂SO₄（3）

the invention adopts a method of loading trace metal active components into zirconium hydroxide in situ to prepare the zirconium-based material for efficiently protecting acid-base toxic industrial gas. The zirconium-based material prepared by the method has the advantages of high specific surface area, uniform dispersion of active components, high sulfur dioxide and ammonia gas protection time (77 min sulfur dioxide and 45min ammonia gas), simple process, easy realization of large-scale production and good popularization and application values.

Detailed Description

The following provides a detailed description of specific embodiments of the present invention.