阅读说明：本技术 一种氧化锌煤气脱硫剂的制备方法 (Preparation method of zinc oxide gas desulfurizer ) 是由 张曼 冯宇 米杰 卢建军 王建成 于 2020-06-08 设计创作，主要内容包括：本发明公开了一种氧化锌煤气脱硫剂的制备方法,包括如下步骤：采用四步法三维编织技术将纤维长丝编织成带轴纱的三维全五向编织件；将浓度为0.10-0.25mol/L的Zn(NO<Sub>3</Sub>)<Sub>2</Sub>·6H<Sub>2</Sub>O溶液和体积分数为25％的NH<Sub>3</Sub>·H<Sub>2</Sub>O溶液按照任意比例混合,得到水热溶液；将得到的三维全五向编织件放置水热溶液中,在室温环境下进行水热反应,生成氧化锌纳米结构；将生成的氧化锌纳米结构通过高温焙烧处理即可得到氧化锌煤气脱硫剂。本发明脱硫材料工艺路线简单、易于实施,可以满足脱硫剂工业化的性能要求；且脱硫剂采用柔韧性高、孔隙率丰富的纤维材料作为载体构筑脱硫剂多级微观孔隙结构,可提高脱硫剂的吸附能力和脱硫反应活性。(The invention discloses a preparation method of a zinc oxide gas desulfurizer, which comprises the following steps: weaving the fiber filaments into a three-dimensional full five-way woven piece with axial yarns by adopting a four-step three-dimensional weaving technology; zn (NO) with the concentration of 0.10-0.25mol/L 3 ) 2 ·6H 2 O solution and NH with volume fraction of 25% 3 ·H 2 Mixing the O solution according to any proportion to obtain a hydrothermal solution; placing the obtained three-dimensional full-five-direction woven piece into a hydrothermal solution, and carrying out hydrothermal reaction at room temperature to generate a zinc oxide nano structure; and (3) carrying out high-temperature roasting treatment on the generated zinc oxide nano structure to obtain the zinc oxide gas desulfurizer. The desulfurization material has simple process route and easy implementation, and can meet the performance requirement of industrialization of the desulfurizer; the desulfurizer adopts fiber with high flexibility and rich porosityThe material is used as a carrier to construct a multi-level micro-pore structure of the desulfurizer, and the adsorption capacity and the desulfurization reaction activity of the desulfurizer can be improved.)

1. The preparation method of the zinc oxide gas desulfurizer is characterized by comprising the following steps:

A. preparing a three-dimensional full-five-direction woven piece: weaving the fiber filaments into a three-dimensional full five-way woven piece with axial yarns by adopting a four-step three-dimensional weaving technology;

B. hydrothermal solution preparation: zn (NO) with the concentration of 0.10-0.25mol/L₃)₂·6H₂O solution and NH with volume fraction of 25%₃·H₂Mixing the O solution according to any proportion to obtain a hydrothermal solution;

C. placing the three-dimensional all-five-direction woven piece obtained in the step A into the hydrothermal solution obtained in the step B, and carrying out hydrothermal reaction at room temperature to generate a zinc oxide nano structure;

D. preparation of zinc oxide desulfurizer: and C, carrying out high-temperature roasting treatment on the zinc oxide nano structure generated in the step C to obtain the zinc oxide gas desulfurizer.

2. The method for preparing the zinc oxide gas desulfurizer according to claim 1, wherein in the step A, the fiber filament used by the axial yarn in the three-dimensional all-five-direction weaving member is one of carbon fiber filament, polyacrylonitrile filament, polyester filament, polyamide filament, Kevlar filament, nylon filament or polypropylene filament; the fiber filament used by the weaving yarn is one of high silica glass fiber filament, silicon dioxide fiber filament or corundum fiber filament.

3. The method for preparing zinc oxide gas desulfurizer according to claim 1, wherein in step a, the length, width and height of the three-dimensional all-five-direction woven fabric are all in the range of 10-100 mm.

4. The preparation method of the zinc oxide gas desulfurizer as claimed in claim 3, wherein the length, width and height of the three-dimensional all-five-direction woven piece are preferably 10mm, 10mm and 20mm respectively.

5. The method for preparing zinc oxide gas desulfurizer as claimed in claim 1, wherein the method comprises the step of adding zinc oxide gas desulfurizer to the gasIn the step B, it is preferable that: using Zn (NO) with a concentration of 0.10-0.25mol/L₃)₂·6H₂O and 8mL of NH with a volume fraction of 25%₃·H₂O make up 80mL of the hydrothermal solution.

6. The method for preparing the zinc oxide gas desulfurizing agent according to claim 1, wherein in the step C, the reaction time of the hydrothermal reaction is 8-20 h.

7. The method as claimed in claim 1, wherein in the step C, the parameters of the high temperature calcination process are set to 5-20% of oxygen concentration, 500-800 ℃ of calcination temperature and 1-4h of calcination time.

Technical Field

The invention belongs to the technical field of preparation of coal chemical industry desulfurizer, and particularly relates to a preparation method of a zinc oxide gas desulfurizer.

Background

Coal gasification is that coal after selective washing is sent into a gasification furnace reactor, organic matters in the coal are converted into CO and H through gasification agents such as air, steam, oxygen and the like under certain temperature and pressure₂、CH₄Isocombustible gas and CO₂、N₂And the like. In addition to these conventional components, the heavy metal components of coal form solid waste with the coal slag during coal gasification, and most of the sulfur in coal is converted into hydrogen sulfide and exists in coal gas. The use of gas that has not been desulfurized can be detrimental to subsequent processes. Firstly, hydrogen sulfide is a corrosive acidic gas, and if hydrogen sulfide in coal gas is not removed, equipment in the process of coal gas transportation and storage is corroded, so that potential safety hazards are formed, and meanwhile, the maintenance cost in the use process of the equipment is increased, and the service life of the equipment is prolonged. Secondly, hydrogen sulfide has strong adsorptivity and reactivity and has certain acidity. When the coal gas containing hydrogen sulfide enters a downstream synthesis process, the coal gas is easily adsorbed on the surface of a catalyst used in the synthesis process or reacts with a catalyst with stronger alkalinity, so that the catalyst is poisoned. In many fuel cells, the presence of hydrogen sulfide can cause catalyst deactivation, resulting in a drop in cell voltage. The presence of hydrogen sulfide can have serious impact and harm on downstream processes, resulting in increased production costs. Thirdly, the coal gas containing hydrogen sulfide can cause product pollution of downstream synthesis process, so that the purity of the product is reduced, and the product performance is influenced. Fourth, hydrogen sulfide is a very toxic gas, a strong neurotoxin, and a strong irritant to the mucosa. By combining the analysis, in order to meet the requirements of the production process, simultaneously reduce the environmental pollution and avoid the hidden danger of production, the hydrogen sulfide in the coal gas must be removed.

In the past decades, numerous research results with innovative and instructive significance have emerged in the field of metal oxide high-temperature gas desulfurization agents, but high-temperature gas desulfurization is still difficult to implement in large-scale application due to the very high requirements for high-temperature gas desulfurization technology in industrial production. The requirements for the high-temperature gas desulfurizer mainly comprise the following points:

(1) the adsorbent has strong adsorbability to hydrogen sulfide, can realize high-precision adsorption to the hydrogen sulfide under the use condition, and does not generate side reaction; (2) the desulfurizer has larger adsorption capacity on hydrogen sulfide and stronger reaction capacity with the hydrogen sulfide, and can reduce the dosage of the desulfurizer; (3) the desulfurizer has higher mechanical strength, maintains the structural performance of the desulfurizer in the vulcanization-regeneration process, and avoids the pulverization phenomenon of the desulfurizer; (4) the preparation process is simple and the cost is low; (5) the method has strong regenerability, can be repeatedly utilized for many times, can keep higher performance stability in the process of vulcanizing and regenerating for many times, and reduces the cost of the desulfurizer, which is an important index for realizing industrialization of the desulfurizer.

Patents CN201710151684.9, CN201510187119.9, CN201710151683.4 and CN201410671737.6 disclose methods for preparing different metal oxide desulfurizing agents, respectively. Although the technology of the method is mature, the method has the environmental problems of high energy consumption, serious pollution and the like. Some desulfurizing agents have the problems of uneven distribution of active components and the like, and are difficult to meet the industrial requirements.

Disclosure of Invention

In view of this, the present invention aims to provide a preparation method of a zinc oxide gas desulfurizer, so as to solve the problems of low porosity and active component utilization rate and poor desulfurization-regeneration performance of the desulfurizer during the reaction process of the desulfurizer, and finally improve the desulfurization performance of the desulfurizer.

In order to achieve the purpose of the invention, the technical scheme is as follows:

a preparation method of a zinc oxide gas desulfurizer comprises the following steps:

A. preparing a three-dimensional full-five-direction woven piece: weaving the fiber filaments into a three-dimensional full five-way woven piece with axial yarns by adopting a four-step three-dimensional weaving technology;

B. hydrothermal solution preparation: zn (NO) with the concentration of 0.10-0.25mol/L₃)₂·6H₂O solution and NH with volume fraction of 25%₃·H₂Mixing the O solution according to any proportion to obtain a hydrothermal solution;

C. placing the three-dimensional all-five-direction woven piece obtained in the step A into the hydrothermal solution obtained in the step B, and carrying out hydrothermal reaction at room temperature to generate a zinc oxide nano structure;

D. preparation of zinc oxide desulfurizer: and C, carrying out high-temperature roasting treatment on the zinc oxide nano structure generated in the step C to obtain the zinc oxide gas desulfurizer.

Preferably, in step a, the fiber filament used for the axial yarn in the three-dimensional all-five-direction weaving element is one of a carbon fiber filament, a polyacrylonitrile filament, a polyester filament, a polyamide filament, a kevlar filament, a nylon filament or a polypropylene filament; the fiber filament used by the weaving yarn is one of high silica glass fiber filament, silicon dioxide fiber filament or corundum fiber filament.

Preferably, in the step A, the length, the width and the height of the three-dimensional all-five-direction braided piece are all in the range of 10-100 mm.

More preferably, the length, width and height of the three-dimensional all-five-direction knitting piece are 10mm, 10mm and 20mm respectively.

Preferably, the step B is: using Zn (NO) with a concentration of 0.10-0.25mol/L₃)₂·6H₂O and 8mL of NH with a volume fraction of 25%₃·H₂O make up 80mL of the hydrothermal solution.

Preferably, in step C, the reaction time of the hydrothermal reaction is 8-20 h.

Preferably, in the step C, the parameters of the high temperature roasting process are set to be 5-20% of oxygen concentration, 500-800 ℃ of roasting temperature and 1-4h of roasting time.

The invention has the beneficial effects that: the method comprises the steps of preparing a three-dimensional all-five-direction woven piece, and preparing the desulfurizer by means of hydrothermal synthesis of oxides, high-temperature roasting and the like. In the roasting process, polymer fibers or carbon fibers are specially designed to be burnt, the chemical composition of axial yarns is changed under the condition that the structure of the three-dimensional weaving piece is not changed, and the method has the following advantages:

(1) the desulfurizer is prepared by adopting a three-dimensional full-five-direction woven piece, the three-dimensional woven piece has the characteristics of high flexibility, stable physical structure and transverse isotropy, and high silica glass fiber with good wear resistance and heat resistance and stable physical and chemical structures is used as a woven structure framework to provide a supporting effect for the overall structure of the desulfurizer;

(2) the method has the advantages of simple process steps, strong controllability and convenient operation, can meet a large number of market demands, and the prepared hollow fiber membrane has good support property, high flexibility, toughness and strength, a unique nanofiber-shaped pore structure on the surface of the membrane, high porosity and large specific surface area, and can realize the cooperation of multi-component composite and multi-layer structures;

(3) the high silica glass fiber has excellent mechanical property and flexibility, can buffer the pore structure spalling caused by the volume increase of the desulfurization product, eliminates or weakens the adverse effect generated by the expansion-contraction of the microstructure in the desulfurizer in the reaction process, realizes the reinforcement of the gas-solid reaction rate and the mass transfer efficiency, reduces the structural property reduction of the desulfurizer, and improves the desulfurization efficiency of the unit desulfurizer. Tests prove that the zinc oxide gas desulfurizer prepared by the method not only keeps the utilization rate of single active components above 99.9 percent, but also has the utilization rate of active components of 98.9 percent after ten times of vulcanization-regeneration cycle use.

Detailed Description

The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.