CN115193391B - Nano rod-shaped zinc oxide desulfurizing agent and preparation method and application thereof - Google Patents
Nano rod-shaped zinc oxide desulfurizing agent and preparation method and application thereof Download PDFInfo
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- CN115193391B CN115193391B CN202210993859.1A CN202210993859A CN115193391B CN 115193391 B CN115193391 B CN 115193391B CN 202210993859 A CN202210993859 A CN 202210993859A CN 115193391 B CN115193391 B CN 115193391B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
Abstract
The invention discloses a nano rod-shaped zinc oxide desulfurizer, a preparation method and application thereof, which comprises the following components by weight of the total mass of the desulfurizer: 55-90 parts of nano rod-shaped zinc oxide, 0.1-10 parts of metal oxide, 0.1-8 parts of binder, 0.1-5 parts of pore-forming agent and 0.1-5 parts of solvent; the sulfur capacity of the desulfurizing agent is 23-36 wt% at 200-500 ℃; the total specific surface area of the nano rod-shaped zinc oxide is 100-225 m 2 And/g, the grain diameter is 30-60 nm, and the compressive strength is 80-88N/cm; the desulfurization performance is good, and the removal effect on organic sulfur and hydrogen sulfide is good.
Description
Technical Field
The invention relates to the technical field of desulfurization, in particular to a nano rod-shaped zinc oxide desulfurizing agent and a preparation method and application thereof.
Background
With the development of chemical technology, people gradually grasp a method for deeply utilizing natural energy substances. The raw materials of coal, petroleum, natural gas and the like all contain a certain amount of sulfur compounds, and after the raw materials are processed, the sulfur compounds exist in downstream products in different forms, for example, gas coke oven gas prepared from coal, refinery gas generated in the oil refining process and the like all contain various sulfur impurity gases. The hazard of sulfur-containing impurity gases is manifested in many ways: they can interact with the active components of the noble metal catalyst to deactivate the catalyst. Sulfur-containing impurities can also accelerate the depreciation of chemical equipment and pipelines, and can cause serious environmental problems when they are discharged into nature, and when the amount of these sulfur-containing gases inhaled by the human body is accumulated to some extent, irreparable damage is caused to the respiratory and nervous systems of the human body. Thus, desulfurization technology is an important guarantee for the utilization of many gas resources.
The sulfur-containing substances mainly existing in the industrial raw materials are hydrogen sulfide and organic sulfur, and the desulfurizing agents commonly used in the market at present comprise ferric oxide desulfurizing agents, copper oxide desulfurizing agents, zinc oxide desulfurizing agents and the like; among them, zinc oxide and hydrogen sulfide have better thermodynamic performance and high desulfurization precision, so that the zinc oxide and hydrogen sulfide become a common fine desulfurizing agent and have a relevant role in the desulfurization process.
However, the existing zinc oxide desulfurizer mainly has the problems of low sulfur capacity, low desulfurization precision, insufficient low-temperature activity of the desulfurizer, incapability of simultaneously removing hydrogen sulfide and organic sulfur and the like, and the defects seriously limit the industrialized application of the zinc oxide desulfurizer.
Disclosure of Invention
Aiming at the problems that the existing zinc oxide desulfurizer has low sulfur capacity, low desulfurization precision, insufficient low-temperature activity of the desulfurizer and can not realize the removal of hydrogen sulfide and organic sulfur at the same time, the invention provides a nano rod-shaped zinc oxide desulfurizer and a preparation method thereof. The invention controls the zinc oxide crystal face to grow along the specific direction, and the prepared nano rod ZnO can be S 2- The catalyst provides more reactive sites, has large specific surface area, can adsorb more hydrogen sulfide and organic sulfur, and has excellent desulfurization performance; meanwhile, metal is doped in the process of preparing the desulfurizing agent, so that the bimetal synergistic effect can be achieved, the dispersity of ZnO is improved, the surface alkalinity of the desulfurizing agent is increased, and the sulfur capacity and the desulfurizing precision of the desulfurizing agent are improved.
Firstly, the invention provides a nano rod-shaped zinc oxide desulfurizer which comprises the following components by weight percent:
55-90 parts of nano rod-shaped zinc oxide, 0.1-10 parts of metal oxide, 0.1-8 parts of binder, 0.1-5 parts of pore-forming agent and 0.1-5 parts of solvent; the sulfur capacity of the desulfurizing agent is 23-36 wt% at 200-500 ℃; the total specific surface area of the nano rod-shaped zinc oxide is 160-225 m 2 And/g, the grain diameter is 30-60 nm, and the compressive strength is 80-88N/cm.
Further, the nano rod-shaped zinc oxide desulfurizer comprises the following components by weight of the total mass of the desulfurizer: 65-85 parts of nano rod-shaped zinc oxide, 3-5 parts of metal oxide, 0.1-8 parts of binder, 0.1-5 parts of pore-forming agent and 0.1-5 parts of solvent.
Further, the nanorod-shaped zinc oxide is prepared by the following method:
mixing zinc alkali solution with absolute ethyl alcohol to obtain mixed solution;
mixing the mixed solution with ethylenediamine, and performing hydrothermal reaction to obtain a suspension;
washing and drying the suspension liquid in sequence to obtain the nano rod-shaped zinc oxide;
wherein, zn in the zinc alkali solution 2+ And ethylenediamine in a molar ratio of 1:50 to 60, preferably 1:55.
Further, zn in the zinc alkali solution 2+ And OH (OH) - The molar ratio of (2) is 1:18-22, preferably 1:20.
Further, in the step of preparing the suspension, the temperature of the hydrothermal reaction is 120 to 220 ℃, preferably 160 to 200 ℃.
Further, the zinc alkali solution is mainly prepared by mixing a zinc source and an alkaline solution and then dissolving the mixture in a solvent.
Further, the zinc source comprises at least one of zinc nitrate, zinc acetate and zinc sulfate, preferably zinc nitrate; the alkaline solution comprises at least one of sodium hydroxide, urea and ammonia, preferably sodium hydroxide.
The invention has the beneficial effects that: 1. the invention controls the growth direction of the nano zinc oxide to enable the nano zinc oxide to grow along the crystal face favorable for reacting with hydrogen sulfide, and the prepared nano zinc oxide has the advantages of uniform nano size, more exposed crystal faces, more active sites, large specific surface area and high desulfurization efficiency. Simultaneously, the metal is doped, the concentration of ZnO lattice defects is increased by utilizing the synergistic effect of the metal, and S is promoted 2- The diffusion rate in ZnO improves the desulfurization performance to some extent.
2. Compared with the traditional zinc oxide desulfurizer, the nano zinc oxide desulfurizer of the invention not only can remove H 2 S, COS can be effectively removed. Secondly, the invention also discloses a preparation method of the desulfurizing agent, which comprises the steps of preparing the nano rodMixing zinc oxide, metal salt, binder and pore-forming agent, and dry-mixing.
The invention has the beneficial effects that: the preparation method of the desulfurizing agent disclosed by the invention has the advantages of simple process, convenience in operation and low production cost, and can meet market demands.
Drawings
FIGS. 1 and 2 are SEM results of a desulfurizing agent according to an embodiment of the present invention;
FIG. 3 shows the physical adsorption results of the desulfurizing agent prepared in example 1;
FIG. 4 shows the pore size distribution, specific surface area and pore volume of the desulfurizing agent prepared in example 1.
Detailed Description
The inventor of the present invention has found that when the conventional desulfurizing agent is used to remove industrial raw materials such as coal, petroleum, natural gas, etc., the desulfurizing agent is easily reduced to zinc simple substance during desulfurization at high temperature and under a strong reducing atmosphere, thereby causing volatilization of active components and reducing desulfurization efficiency.
Publication No. CN102961959A discloses a zinc oxide fine desulfurizing agent prepared by mixing and extruding active zinc oxide, high alumina powder, bentonite, calcium hydroxide and sodium carboxymethyl cellulose. The catalyst is used for preparing H in liquid propylene at normal temperature 2 S removal can be as low as 0.03ppm, but the sulfur capacity is only 3.1%. Publication No. CN1094331A discloses a preparation method of a normal-temperature zinc oxide desulfurizer, which is mainly prepared by mixing ZnO and iron cement, and has a sulfur capacity of only about 8.6-11.7% at a temperature of 20-80 ℃, and is difficult to meet the requirement of industrialization.
Publication No. CN100384515A discloses a preparation method of a normal-temperature nano zinc oxide desulfurizer, the particle size of the desulfurizer is 12.4-14nm, the desulfurization reaction speed is high, but the sulfur capacity is only 10-16%. Publication No. CN101485954A discloses a desulfurizing agent, which is a mixture formed by mixing nano zinc oxide, copper oxide, a binder, a pore-forming agent and water, wherein the sulfur capacity of the catalyst reaches 24wt% at 200-250 ℃, but the sulfur capacity of the catalyst is only 15.5wt% below 30 ℃, and the use requirement of industrialized popularization cannot be met.
The inventor of the present invention has found that by controlling the molar ratio of zinc ions and ethylenediamine in the zinc alkali solution, the use of high alkaline conditions and alcoholic environment are key factors for ensuring the formation of ZnO, and then controlling the release from the alcohol-water mixed phase to form zinc oxide nanostructures, ethylenediamine can be used as an adsorption (chelating) ligand to Zn 2+ On cations (mainly on six prism side planes), inhibiting zinc oxide from increasing the growth direction of nano rod-shaped zinc oxide along the radial direction of the zinc oxide, so that the crystal face of the zinc oxide grows along a polar crystal face with negative charges to obtain the zinc oxide with the polar crystal face, which can be S 2- Provides more reactive sites and has good adsorption effect on polar hydrogen sulfide and organic sulfur.
The invention discloses a preparation method of nano rod-shaped zinc oxide, and the nano rod-shaped zinc oxide refers to zinc oxide with nano-scale particle size and radial size far smaller than longitudinal size, and single-particle zinc oxide is columnar in a mirror image.
The preparation method comprises the following steps:
s1, mixing a zinc alkali solution with absolute ethyl alcohol to obtain a mixed solution;
as used herein, the "zinc alkali solution" refers to a mixed solution that is alkaline and is formed by mixing a zinc source and an alkaline solution.
As used herein, the "zinc source" refers to a substance whose aqueous solution is capable of ionizing zinc ions, such as zinc nitrate, zinc acetate or zinc sulfate, suitably the zinc source includes, but is not limited to, at least one of zinc nitrate, zinc acetate and zinc sulfate, more suitably the zinc source is zinc nitrate.
As used herein, the "alkaline solution" means that hydroxide ions can be ionized and the solution is alkaline, such as sodium hydroxide, urea or ammonia, suitably the alkaline solution includes, but is not limited to, at least one of sodium hydroxide, urea and ammonia, more suitably the alkaline solution is sodium hydroxide.
In the present invention, the molar ratio of zinc ions to hydroxide ions in the zinc alkali solution is generally from 1:18 to 22, suitably 1:20.
As used herein, the term "absolute ethanol" refers to an aqueous ethanol solution having a concentration greater than 99.5wt% and is a mixture of ethanol and water.
In the present invention, the volumes of the zinc alkali solution and the absolute ethyl alcohol are generally 10 to 50:150 to 350, suitably 30:250 to 300.
In this step, water may be optionally added according to the uniformity of mixing of the zinc alkali solution and the absolute ethyl alcohol, and the water may be distilled water or deionized water, and the volume ratio of the water to the zinc alkali solution is generally 0-100:1-50, and suitably 0-50:30.
S2, mixing the mixed solution with ethylenediamine, and performing hydrothermal reaction to obtain a suspension;
as used herein, the english language "Ethylenediamine" is fully known as ethyleneimine, abbreviated as EDA, and is a typical aliphatic diamine.
In the invention, ethylenediamine is generally added into the mixed solution, and after the addition is finished, the mixed solution can be placed in a water bath for ultrasonic treatment to shorten the mixing time and make the mixing more uniform, and the ultrasonic process can be properly carried out with stirring, wherein the stirring time is generally 10-60 min, and properly 20-40 min.
As used herein, the term "hydrothermal reaction" refers to a general term for chemical reactions carried out in a fluid such as water, aqueous solution or steam at a certain temperature and pressure, and in the present invention, the temperature of the hydrothermal reaction is generally 120 to 220 ℃, suitably 160 to 200 ℃; the hydrothermal reaction is generally carried out for a period of from 16 to 26 hours, suitably from 18 to 24 hours, and may be carried out in conventional hydrothermal equipment such as a polytetrafluoroethylene autoclave.
In the present invention, zn in the zinc alkali solution is suitably 2+ And ethylenediamine in a molar ratio of 1:50 to 60, more suitably 1:55.
S3, washing and drying the suspension liquid in sequence to obtain the nano rod-shaped zinc oxide;
in the present invention, the suspension may be cooled and centrifuged before being washed, and the suspension may be centrifuged, washed and dried after being cooled to normal temperature, and the centrifugation, washing and drying may be performed in a conventional apparatus and at a conventional temperature or rotation speed, which are not described in detail herein.
The total specific surface area of the zinc oxide prepared by the preparation method is 100-225 m 2 /g, capable of exposing more active sites and therefore S 2- Provides more reactive sites and has good adsorption effect on polar hydrogen sulfide and organic sulfur; the zinc oxide prepared by the method has the particle size of 30-60 nm and the compressive strength of 80-88N/cm, and has good industrial application value.
The invention also discloses a desulfurizing agent which comprises the following components in percentage by mass: 55-90 parts of nano rod-shaped zinc oxide, 0.1-10 parts of metal oxide, 0.1-8 parts of binder, 0.1-5 parts of pore-forming agent and 0.1-5 parts of solvent; the sulfur capacity of the desulfurizing agent is 23-36 wt% at 200-500 ℃.
In the present invention, the metal oxide includes, but is not limited to, at least one of copper oxide, cobalt oxide, and nickel oxide, and suitably the metal oxide is a mixture of copper oxide, cobalt oxide, and nickel oxide.
In the present invention, the copper oxide may be derived from copper salts including, but not limited to, at least one of copper nitrate, copper chloride, and copper sulfate, suitably copper nitrate; in the present invention, the cobalt oxide may be derived from cobalt salts including, but not limited to, at least one of cobalt nitrate, cobalt chloride and cobalt sulfate, suitably cobalt nitrate; in the present invention, the nickel oxide may be derived from a nickel salt including, but not limited to, at least one of nickel nitrate, nickel chloride and nickel sulfate, suitably nickel nitrate.
In the present invention, the binder includes, but is not limited to, at least one of attapulgite, bentonite, carboxymethyl cellulose, and kaolin, suitably carboxymethyl cellulose.
As used herein, the "pore-forming agent" refers to a substance that can be burned to generate carbon dioxide gas and water vapor under calcination, and the gas generated after combustion of the pore-forming agent volatilizes to leave individual pores in the desulfurizing agent, thereby increasing the specific surface area and the adsorption capacity for sulfur; in the present invention, the pore-forming agent includes, but is not limited to, at least one of starch, ammonium bicarbonate, and sesbania powder, suitably sesbania powder.
In the invention, the mass fraction of the nano rod-shaped zinc oxide in the desulfurizing agent is more suitably 65-85 parts, and the mass fraction of the metal oxide in the desulfurizing agent is more suitably 3-5 parts.
In the invention, the desulfurizing agent not only can remove inorganic sulfur, but also can remove organic sulfur, and the principle of removing organic sulfur is as follows:
COS+H 2 →CO+H 2 S；CS 2 +2H 2 →C+2H 2 S。
therefore, compared with the traditional desulfurizing agent (only inorganic sulfur can be removed), the desulfurizing agent disclosed by the invention has the advantages that the types of sulfur which can be removed are obviously increased, and the industrial popularization and the use are facilitated.
In the invention, the sulfur capacity of the desulfurizing agent can reach 23-36 wt% at 200-500 ℃, and the desulfurizing precision can be obviously improved.
According to the invention, the metal oxide is added, and the dispersion degree of the nano rod-shaped zinc oxide is improved by utilizing the synergistic effect of the metal, so that the surface alkalinity of the desulfurizing agent is increased, and the organic sulfur can be converted and absorbed, so that the desulfurizing efficiency is improved.
In the present invention, compared with the conventional desulfurizing agent (the low temperature performance is insufficient, the desulfurizing effect cannot be satisfied, because the conventional desulfurizing agent is subject to sulfate poisoning at low temperature, resulting in reduced activity of the desulfurizing agent), the desulfurizing agent disclosed by the present invention has good low temperature performance, and because of its large specific surface area, high sulfur capacity and synergistic effect of metals, the desulfurizing effect can be satisfied at low temperature, and as used herein, the "low temperature" means that the temperature is 20 ℃ to 120 ℃.
The invention also discloses a preparation method of the desulfurizing agent, which comprises the steps of mixing the raw materials, preparing the desulfurizing agent by adopting a dry mixing method, wherein the dry mixing method is to take water as a solvent to dissolve the raw materials, and then sequentially shaping, drying and roasting to obtain corresponding products; the calcination temperature of the calcination is generally 200 to 500 ℃, suitably 300 to 450 ℃, and the calcination time is generally 0.5 to 10 hours, suitably 2 to 4 hours.
Examples
Example 1
148.7g of zinc nitrate and 400g of sodium hydroxide were dissolved in deionized water to prepare 1L of a zinc alkali solution ([ Zn) 2+ ]:[OH - ]=1:20). Mixing 30mL of zinc alkali solution, 25mL of deionized water and 300mL of absolute ethyl alcohol, and adding 550mL of ethylenediamine (weighing error [ Zn 2+ ]Eda=1:50-60), ultrasonic stirring in water bath for 30min, transferring into a polytetrafluoroethylene autoclave for hydrothermal reaction, preserving heat at 180 ℃ for 20h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain white nano ZnO.
110g of nano ZnO, 12.08g of copper nitrate, 14.6g of cobalt nitrate, 14.5g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, shaping and extruding are carried out, drying is carried out for 4 hours at 100 ℃, and calcining is carried out for 2 hours at 450 ℃, thus obtaining the desulfurizing agent DS-A1 of the example 1.
Comparative example 1
110g of commercial ZnO, 12.08g of copper nitrate, 14.6g of cobalt nitrate, 14.5g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, the mixture is shaped and extruded, dried for 4 hours at 100 ℃, and calcined for 2 hours at 450 ℃, and the desulfurizing agent DS-B1 of the comparative example 1 is obtained.
Comparative example 2
110g of commercial nano ZnO, 12.08g of copper nitrate, 14.6g of cobalt nitrate, 14.5g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, the mixture is shaped and extruded, dried for 4 hours at 100 ℃, and calcined for 2 hours at 450 ℃, and the desulfurizing agent DS-B2 of the comparative example 2 is obtained.
Comparative example 3
110g of commercial active nano ZnO, 12.08g of copper nitrate, 14.6g of cobalt nitrate, 14.5g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, the mixture is shaped and extruded, dried for 4 hours at 100 ℃, and calcined for 2 hours at 450 ℃, and the desulfurizing agent DS-B3 of the comparative example 3 is obtained.
Example 2
109.8g of zinc acetate and 600g of urea (carbamide) were dissolved in deionized water to prepare 1L of zinc base mixed solution ([ Zn) 2+ ]:[OH - ]=1:20). Mixing 30mL of zinc alkali solution, 25mL of deionized water and 300mL of absolute ethyl alcohol, and adding 550mL of ethylenediamine (Zn) 2+ Eda=1:50-60), ultrasonic stirring in water bath for 30min, transferring into a polytetrafluoroethylene autoclave for hydrothermal reaction, preserving heat at 180 ℃ for 20h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain white nano ZnO.
110g of nano ZnO, 12.08g of copper nitrate, 14.6g of cobalt nitrate, 14.5g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, shaping and extruding are carried out, drying is carried out for 4 hours at 100 ℃, and calcining is carried out for 2 hours at 450 ℃, thus obtaining the desulfurizing agent DS-A2 of the example 2.
Example 3
80.73g of zinc sulfate and 590g of potassium hydroxide were dissolved in deionized water to prepare 1L of a zinc base mixed solution ([ Zn) 2 + ]:[OH - ]=1:20). Mixing 30mL of zinc alkali solution, 25mL of deionized water and 300mL of absolute ethyl alcohol, and adding 550mL of ethylenediamine (Zn) 2+ Eda=1:50-60), ultrasonic stirring in water bath for 30min, transferring into a polytetrafluoroethylene autoclave for hydrothermal reaction, preserving heat at 180 ℃ for 20h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain white nano ZnO.
110g of nano ZnO, 12.08g of copper nitrate, 14.6g of cobalt nitrate, 14.5g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, shaping and extruding are carried out, drying is carried out for 4 hours at 100 ℃, and calcining is carried out for 2 hours at 450 ℃, thus obtaining the desulfurizing agent DS-A3 of the example 3.
Example 4
148.7g of zinc nitrate and 400g of sodium hydroxide were dissolved in deionized water to prepare 1L of zinc base mixed solution ([ Zn) 2 + ]:[OH - ]=1:20). Mixing 30mL of zinc alkali solution, 25mL of deionized water and 300mL of absolute ethyl alcohol, and adding 550mL of ethylenediamine (Zn) 2+ Eda=1:50-60), ultrasonic stirring in water bath for 30min, transferring into a polytetrafluoroethylene autoclave for hydrothermal reaction, preserving heat at 180 ℃ for 20h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain white nano ZnO.
110g of nano ZnO, 18.12g of copper nitrate, 21.83g of cobalt nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, the mixture is shaped and extruded, dried for 4 hours at 100 ℃, and calcined for 2 hours at 450 ℃, so that the desulfurizing agent DS-A4 of the example 4 is obtained.
Example 5
148.7g of zinc nitrate and 400g of sodium hydroxide were dissolved in deionized water to prepare 1L of zinc base mixed solution ([ Zn) 2 + ]:[OH - ]=1:20). Mixing 30mL of zinc alkali solution, 25mL of deionized water and 300mL of absolute ethyl alcohol, and adding 550mL of ethylenediamine (Zn) 2+ Eda=1:50-60), ultrasonic stirring in water bath for 30min, transferring into a polytetrafluoroethylene autoclave for hydrothermal reaction, preserving heat at 180 ℃ for 20h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain white nano ZnO.
110g of nano ZnO, 21.83g of cobalt nitrate, 21.8g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, shaping and extruding are carried out, drying is carried out for 4 hours at 100 ℃, and calcining is carried out for 2 hours at 450 ℃, thus obtaining the desulfurizing agent DS-A5 of the example 5.
Example 6
148.7g of zinc nitrate and 400g of sodium hydroxide were dissolved in deionized water to prepare 1L of zinc base mixed solution ([ Zn) 2 + ]:[OH - ]=1:20). Mixing 30mL of zinc alkali solution, 25mL of deionized water and 300mL of absolute ethyl alcohol, and adding 550mL of ethylenediamine (Zn) 2+ :EDA＝1:50-60), carrying out ultrasonic stirring in a water bath for 30min, transferring into a polytetrafluoroethylene autoclave for hydrothermal reaction, preserving heat at 180 ℃ for 20h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain white nano ZnO.
110g of nano ZnO, 18.12g of copper nitrate, 21.8g of nickel nitrate, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, the mixture is shaped and extruded, dried for 4 hours at 100 ℃, and calcined for 2 hours at 450 ℃, so that the desulfurizing agent DS-A6 of the example 6 is obtained.
Comparative example 4
110g of commercial ZnO, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, the mixture is shaped and extruded, dried for 4 hours at 100 ℃, and calcined for 2 hours at 450 ℃, and the desulfurizing agent DS-B4 of the comparative example 4 is obtained.
Comparative example 5
148.7g of zinc nitrate and 400g of sodium hydroxide were dissolved in deionized water to prepare 1L of zinc base mixed solution ([ Zn) 2 + ]:[OH - ]=1:20). Mixing 30mL of zinc alkali solution, 25mL of deionized water and 300mL of absolute ethyl alcohol, and adding 550mL of ethylenediamine (Zn) 2+ Eda=1:50-60), ultrasonic stirring in water bath for 30min, transferring into a polytetrafluoroethylene autoclave for hydrothermal reaction, preserving heat at 180 ℃ for 20h, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain white nano ZnO.
110g of nano rod-shaped ZnO, 3.02g of carboxymethyl cellulose and 4.53g of sesbania powder are placed in a mortar, ground and mixed uniformly, 10g of deionized water is added, the mixture is shaped and extruded, dried for 4 hours at 100 ℃, and calcined for 2 hours at 450 ℃, and the desulfurizing agent DS-B5 of comparative example 5 is obtained.
The desulfurizing agents prepared in examples 1 to 6 and comparative examples 1 to 5 were subjected to particle size distribution, strength and physical adsorption test, and the results are shown in Table 1.
TABLE 1 physical Properties of desulfurizing Agents prepared in examples 1-6 and comparative examples 1-5
As can be seen from Table 1, the desulfurizing agents prepared in examples 1 to 6 have a higher specific surface area and have good wear resistance as compared with the comparative examples.
The desulfurizing agents prepared in examples 1 to 6 and comparative examples 1 to 5 were subjected to adsorption performance test under the following conditions: 5mL of desulfurizing agent was charged into a normal pressure desulfurizing apparatus at a reaction temperature of 50℃and a raw material gas was fed with 100ppm of hydrogen sulfide and 50ppm of carbonyl sulfide (the remainder being high-purity N 2 ) The end point of the desulfurization reaction is the sulfur content of the outlet tail gas<The contents of hydrogen sulfide and carbonyl sulfide in the gas were measured by gas chromatography, and the breakthrough sulfur capacity was calculated by chemical analysis, and the results are shown in table 2.
TABLE 2 preparation of desulfurization results for desulfurizing agents examples 1-6 and comparative examples 1-5
As can be seen from Table 2, the desulfurization rate of the desulfurization agent prepared from the nano rod-shaped zinc oxide prepared in examples 1-6 can reach more than 98%, and the desulfurization agent not only can remove inorganic sulfur but also can remove organic sulfur (carbonyl sulfur), has good desulfurization performance, and has a sulfur capacity obviously higher than that of comparative examples 1-4 under the low temperature condition of 100 ℃, so that the desulfurization agent prepared in examples 1-6 has good low temperature desulfurization effect, and is worthy of industrial popularization and use.
As is clear from comparison of comparative example 5 with examples 1 to 6, the co-metal doping of copper, cobalt and nickel can significantly improve the sulfur capacity of the desulfurizing agent, and thus is also worth industrial popularization and use.
FIGS. 1-2 are SEM results of the preparation of zinc oxide of example 1. It can be seen that the zinc oxide prepared is in a rod-like structure, the nanorods are arranged in a jungle-like assembly, the diameter is about 200nm, the end faces protrude, and each nanorod has a uniform diameter along the whole length thereof. The desulfurizing agent which takes the nano rod-shaped zinc oxide as an active component is successfully prepared.
FIGS. 3 to 4 show adsorption/desorption isotherms and pore size distribution of the desulfurizing agent prepared in example 1, as measured by the physical adsorption method. It can be seen that the prepared desulfurizing agent has larger specific surface area and more mesopores, is favorable for the raw material gas to be rapidly diffused to the surface of the adsorbent, and is fully contacted and reacted with the adsorbent, so that the adsorption efficiency and the adsorption capacity of the adsorbent are high.
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The nano rod-shaped zinc oxide desulfurizing agent is characterized by comprising the following components in percentage by mass of the total mass of the desulfurizing agent:
65-85 parts of nano rod-shaped zinc oxide, 3-5 parts of metal oxide, 0.1-5 parts of binder, 0.1-5 parts of pore-forming agent and 0.1-5 parts of solvent; the sulfur capacity of the desulfurizing agent is 23-36wt% at 200-500 ℃; the total specific surface area of the nano rod-shaped zinc oxide is 100-225 m 2 Per gram, the grain diameter is 30-60 nm, and the compressive strength is 80-88N/cm;
the nano rod-shaped zinc oxide is prepared by the following steps:
mixing zinc alkali solution with absolute ethyl alcohol to obtain mixed solution;
mixing the mixed solution with ethylenediamine, and performing hydrothermal reaction to obtain a suspension;
washing and drying the suspension liquid in sequence to obtain the nano rod-shaped zinc oxide;
wherein, zn in the zinc alkali solution 2+ And ethylenediamine in a molar ratio of 1:50-60, wherein Zn in the zinc alkali solution is as follows 2+ And OH (OH) - The molar ratio of (2) is 1:18-22;
wherein, in the step of preparing the suspension, the temperature of the hydrothermal reaction is 120-220 ℃;
the zinc alkali solution is prepared by mixing a zinc source and an alkaline solution and dissolving the mixture in a solvent;
the zinc source comprises at least one of zinc nitrate, zinc acetate and zinc sulfate, and the alkaline solution comprises at least one of sodium hydroxide, urea and ammonia water;
wherein the metal oxide is a mixture of copper oxide, cobalt oxide and nickel oxide.
2. A method for preparing the nano rod-shaped zinc oxide desulfurizer according to claim 1, which is characterized in that the nano rod-shaped zinc oxide, the metal salt, the binder and the pore-forming agent are mixed and prepared by adopting a dry mixing method.
3. The method of preparing according to claim 2, wherein the metal salt comprises at least one of copper salt, cobalt salt and nickel salt;
the copper salt comprises at least one of copper nitrate, copper chloride and copper acetate;
the cobalt salt comprises at least one of cobalt nitrate, cobalt chloride and cobalt acetate;
the nickel salt comprises at least one of nickel nitrate, nickel chloride and nickel acetate;
the binder comprises at least one of attapulgite, bentonite, carboxymethyl cellulose and kaolin;
at least one of pore-forming agent starch, ammonium bicarbonate and sesbania powder.
4. Use of the desulfurizing agent according to claim 1 in the chemical industry.
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| CN101485954A (en) * | 2008-05-27 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Desulfurizing agent and preparation method thereof |
| CN103101962A (en) * | 2011-11-09 | 2013-05-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide/titanium dioxide composite nanorod |
| CN109126759A (en) * | 2018-08-17 | 2019-01-04 | 阿坝师范学院 | ZnO visible light catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101485954A (en) * | 2008-05-27 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Desulfurizing agent and preparation method thereof |
| CN103101962A (en) * | 2011-11-09 | 2013-05-15 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide/titanium dioxide composite nanorod |
| CN109126759A (en) * | 2018-08-17 | 2019-01-04 | 阿坝师范学院 | ZnO visible light catalyst and its preparation method and application |
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