CN111439782B - Synchronous protection NH 3 /SO 2 Preparation method of zirconium hydroxide protective material - Google Patents
Synchronous protection NH 3 /SO 2 Preparation method of zirconium hydroxide protective material Download PDFInfo
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- C01G25/00—Compounds of zirconium
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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- C—CHEMISTRY; METALLURGY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
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 in the 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 protection capability.
Description
Technical Field
The invention relates to the technical field of zirconium hydroxide protective materials, in particular to a method for synchronously and efficiently protecting NH 3 /SO 2 The 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 shielding effect against sulfur dioxide due to its high content of effective basic hydroxyl-terminated functional groups, for example, Gregory et al, which prepares zirconium hydroxide powder into 12X 30 mesh particles, shows a shielding time of 89min against sulfur dioxide gas, a breakthrough capacity of 70.78 mg/g. (Gregory W. Peterson, Christopher J. Karwacki, William B. Feaver. Zirconium Hydroxide as a Reactive Substrate for the Removal of Sulfur Dioxide [ J ]. Industrial & Engineering Chemistry Research, 2009, 48(4): 1694 to 1698).
Although zirconium hydroxide has excellent protection performance on acid gas sulfur dioxide, the protection effect on alkaline gas ammonia is poor, and the zirconium hydroxide needs to be modified to have excellent ammonia protection 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 treatment 2 /g。（T. Grant Glover,*,† Gregory W. Peterson,‡ Jared B. DeCoste,‡ and Matthew A. Browe‡.Adsorption of Ammonia by Sulfuric Acid Treated Zirconium Hydroxide [J]Langmuir, 2012, 28, 10478-10487). Peterson showed a saturated adsorption capacity of 4.4mol/kg for ammonia 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,. lambda.,. † Joseph A. Rossin,. § Jared B. Decoste,. DELTA.Kato L. Killops, † Matthew Browe, † Erica valves, † and Paulette J. zirconia Hydroxide-Metal-Organic Framework components for Toxic Chemical Removal [ J ]. Industrial & Engineering Chemistry Research, 2013, 52(15), 5462～5469）。
Despite the aboveThe literature prepares the zirconium hydroxide preparation material for effectively protecting ammonia gas by treating zirconium hydroxide with acid and physically mixing the zirconium hydroxide with a metal organic framework material for preventing alkaline toxic gas, but the defects of obvious reduction of the specific surface area of the zirconium hydroxide material, serious loss of alkaline active sites and the like exist, and the requirement for synchronous high-efficiency protection of NH is difficult to meet 3 /SO 2 The requirements of (2).
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 NH 3 /SO 2 The preparation method of the zirconium hydroxide protective material comprises the following steps:
(1) Weighing ZrOC1 2 ·8H 2 Adding 20-30 g of deionized water into O (11.28 g, 0.035 mol), magnetically stirring for 0.5h for dissolving, and then adding 40-60 g of ammonia water (25 wt%) (the adding speed is 0.05-1.5 mL/s) 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 + SO 2 → Zr(OH) 2 (SO 3 ) + H 2 O （1）
Zr(OH) 2 (SO 3 ) + SO 2 → Zr(SO 3 ) 2 + H 2 O （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:
2NH 3 + CuSO 4 → Cu(NH 3 ) 2 SO 4 （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.
Example 1
A preparation method of a zirconium hydroxide adsorbing material with high specific surface area and high-efficiency protection of sulfur dioxide and ammonia gas comprises the following steps:
1) Weighing 11.28g of ZrOCl 2 ·8H 2 O, adding 20g of deionized water, magnetically stirring for 0.5h until the deionized water is dissolved, and then adding 50g of ammonia water (25 wt%) (the adding speed is 1mL s) under the action of magnetic stirring (1300 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 3h at 150 ℃, airing the reaction kettle to room temperature, filtering, washing and drying the product at 80 ℃ to obtain zirconium hydroxide powder;
3) repeating the step 1) and the step 2) to prepare a certain amount of zirconium hydroxide, grinding the prepared zirconium hydroxide powder, sieving the zirconium hydroxide powder with a 230-mesh sieve, weighing 100g of zirconium hydroxide powder, adding 150g of deionized water, and carrying out ultrasonic treatment at 80Hz for 2 hours to form uniformly dispersed suspension;
4) weighing 5g of copper sulfate and 3g of potassium chloride, adding 20g of deionized water, and stirring at 25 ℃ for 0.5h until the copper sulfate and the potassium chloride are dissolved;
5) adding the solution obtained in the step 4) into the suspension solution obtained in the step 3), and stirring for 2 hours at 25 ℃ 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 12h, and then drying in an oven at 60 ℃ for 3h to obtain a light blue powder zirconium-based material;
7) Pressing the powder zirconium-based material obtained in the step 6) into a sheet-shaped molding material with the diameter of 1.1cm and the thickness of 0.3cm, and then crushing and screening the sheet-shaped molding material to obtain a particle material with the diameter of 0.6-1.2 mm.
Example 2
A preparation method of a zirconium hydroxide adsorbing material with high specific surface area and high-efficiency protection of sulfur dioxide and ammonia gas comprises the following steps:
1) weighing 11.28g of ZrOCl 2 ·8H 2 O, adding 22g of deionized water, magnetically stirring for 0.5h until the deionized water is dissolved, and then adding 50g of ammonia water (25 wt%) (the adding speed is 1mL s) under the action of magnetic stirring (1300 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 3h at 150 ℃, airing the reaction kettle to room temperature, filtering, washing and drying the product at 80 ℃ to obtain zirconium hydroxide powder;
3) repeating the step 1) and the step 2) to prepare a certain amount of zirconium hydroxide, grinding the prepared zirconium hydroxide, sieving the zirconium hydroxide with a 230-mesh sieve, weighing 100g of zirconium hydroxide powder, adding 150g of deionized water, and performing ultrasonic treatment at 80Hz for 2h to form uniformly dispersed suspension;
4) weighing 3g of copper sulfate and 3g of potassium chloride, adding 20g of deionized water, and stirring at 25 ℃ for 0.5h until the copper sulfate and the potassium chloride are dissolved;
5) Adding the solution obtained in the step 4) into the suspension solution obtained in the step 3), and stirring for 2 hours at 25 ℃ 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 12h, and then drying in an oven at 60 ℃ for 3h to obtain a light blue powder zirconium-based material;
7) pressing the powder zirconium-based material obtained in the step 6) into a sheet-shaped molding material with the diameter of 1.1cm and the thickness of 0.3cm, and then crushing and screening the sheet-shaped molding material to obtain a particle material with the diameter of 0.6-1.2 mm.
Example 3
A preparation method of a zirconium hydroxide adsorbing material with high specific surface area and high-efficiency protection of sulfur dioxide and ammonia gas comprises the following steps:
1) weighing 11.28g of ZrOCl 2 ·8H 2 O, adding 20g of deionized water, magnetically stirring for 0.5h until the deionized water is dissolved, and then adding 50g of ammonia water (25 wt%) (the adding speed is 1mL s) under the action of magnetic stirring (1300 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 3h at 150 ℃, airing the reaction kettle to room temperature, filtering, washing and drying the product at 80 ℃ to obtain zirconium hydroxide powder;
3) repeating the step 1) and the step 2) to prepare a certain amount of zirconium hydroxide, grinding the prepared zirconium hydroxide, sieving the zirconium hydroxide with a 230-mesh sieve, weighing 100g of zirconium hydroxide powder, adding 150g of deionized water, and performing ultrasonic treatment at 80Hz for 2h to form uniformly dispersed suspension;
4) Weighing 3g of copper sulfate and 1g of potassium chloride, adding 20g of deionized water, and stirring at 25 ℃ for 0.5h until the copper sulfate and the potassium chloride are dissolved;
5) adding the solution obtained in the step 4) into the suspension solution obtained in the step 3), and stirring for 2 hours at 25 ℃ 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 12h, and then drying in an oven at 60 ℃ for 3h to obtain a light blue powder zirconium-based material;
7) pressing the powder zirconium-based material obtained in the step 6) into a sheet-shaped molding material with the diameter of 1.1cm and the thickness of 0.3cm, and then crushing and screening the sheet-shaped molding material to obtain a particle material with the diameter of 0.6-1.2 mm.
Example 4
A preparation method of a zirconium hydroxide adsorbing material with high specific surface area and high-efficiency protection of sulfur dioxide and ammonia gas comprises the following steps:
1) weighing 11.28g of ZrOCl 2 ·8H 2 O, adding 20g of deionized water, magnetically stirring for 0.5h until the deionized water is dissolved, and then adding 50g of ammonia water (25 wt%) (the adding speed is 1mL s) under the action of magnetic stirring (1300 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 3h at 150 ℃, airing the reaction kettle to room temperature, filtering, washing and drying the product at 80 ℃ to obtain zirconium hydroxide powder;
3) Repeating the step 1) and the step 2) to prepare a certain amount of zirconium hydroxide, grinding the prepared zirconium hydroxide, sieving the zirconium hydroxide with a 230-mesh sieve, weighing 100g of zirconium hydroxide powder, adding 150g of deionized water, and performing ultrasonic treatment at 80Hz for 2h to form uniformly dispersed suspension;
4) weighing 5g of copper sulfate and 1g of potassium chloride, adding 20g of deionized water, and stirring at 25 ℃ for 0.5h until the copper sulfate and the potassium chloride are dissolved;
5) adding the solution obtained in the step 4) into the suspension solution obtained in the step 3), and stirring for 2 hours at 25 ℃ 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 12h, and then drying in an oven at 60 ℃ for 3h to obtain a light blue powder zirconium-based material;
7) pressing the powder zirconium-based material obtained in the step 6) into a sheet-shaped molding material with the diameter of 1.1cm and the thickness of 0.3cm, and then crushing and screening the sheet-shaped molding material to obtain a particle material with the diameter of 0.6-1.2 mm.
Example 5
A preparation method of a zirconium hydroxide adsorbing material with high specific surface area and high-efficiency protection of sulfur dioxide and ammonia gas comprises the following steps:
1) weighing 11.28g of ZrOCl 2 ·8H 2 O, adding 21g of deionized water, magnetically stirring for 0.5h until the deionized water is dissolved, and then adding 50g of ammonia water (25 wt%) (the adding speed is 1mL s) under the action of magnetic stirring (1300 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 3h at 150 ℃, airing the reaction kettle to room temperature, filtering, washing and drying the product at 80 ℃ to obtain zirconium hydroxide powder;
3) repeating the step 1) and the step 2) to prepare a certain amount of zirconium hydroxide, grinding the prepared zirconium hydroxide, sieving the zirconium hydroxide with a 230-mesh sieve, weighing 100g of zirconium hydroxide powder, adding 150g of deionized water, and performing ultrasonic treatment at 80Hz for 2h to form uniformly dispersed suspension;
4) weighing 5g of copper sulfate and 2g of potassium chloride, adding 20g of deionized water, and stirring at 25 ℃ for 0.5h until the copper sulfate and the potassium chloride are dissolved;
5) adding the solution obtained in the step 4) into the suspension solution obtained in the step 3), and stirring for 2 hours at 25 ℃ 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 12h, and then drying in an oven at 60 ℃ for 3h to obtain a light blue powder zirconium-based material;
7) pressing the powder zirconium-based material obtained in the step 6) into a sheet-shaped molding material with the diameter of 1.1cm and the thickness of 0.3cm, and then crushing and screening the sheet-shaped molding material to obtain a particle material with the diameter of 0.6-1.2 mm.
The materials prepared in examples 1-5 were characterized for specific surface area, and tested for evaluation of the protection time of sulfur dioxide and ammonia. And compared with a zirconium hydroxide material not impregnated with an active component:
sulfur dioxide:specific speed of 0.346L/min.cm 2 Height 2.5cm, initial concentration of sulfur dioxide 4.3 mg/L.
Ammonia gas: specific speed of 0.346L/min.cm 2 Height 2.5cm, initial ammonia concentration 2.6 mg/L.
Table 1 specific surface area, sulfur dioxide, ammonia test data:
as can be seen from Table 1, the specific surface area of the zirconium hydroxide-based substrate material to which no active component was added was 464m 2 The content of effective end hydroxyl functional groups of the zirconium hydroxide substrate material is rich, so that the zirconium hydroxide substrate material has better protection capability on sulfur dioxide, but the content of effective bridging hydroxyl functional groups of the zirconium hydroxide substrate material is low, so that the protection capability on ammonia gas is poorer; this patent is through adding the active component of trace metal to zirconium hydroxide base material and preparing out novel zirconium base adsorbing material (embodiment 1-embodiment 5), and the novel zirconium base adsorbing material who sees out the preparation from table 1 can show the safeguard effect that promotes the ammonia when keeping zirconium hydroxide base material high specific surface area and sulfur dioxide protective capability, finally makes the novel zirconium base adsorbing material of preparation reach the purpose to the synchronous high-efficient protection of acid-base industrial gas (sulfur dioxide, ammonia).
The invention adopts trace metal active components to be loaded in situ into the 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 protection capability.
Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
Claims (1)
1. Synchronous protection NH 3 /SO 2 The preparation method of the zirconium hydroxide protective material is characterized by comprising the following steps: the method comprises the following steps:
(1) weighing ZrOC1 2 ·8H 2 O, adding deionized water, magnetically stirring for 0.5h until the mixture is dissolved, then adding ammonia water at the mass concentration of 25% and the adding speed of 1mL & s under the action of magnetic stirring at the rotating speed of 1300 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) 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.
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