阅读说明：本技术 一种高韧高柔氧化铜煤气脱硫剂的制备方法 (Preparation method of high-toughness high-flexibility copper oxide gas desulfurizer ) 是由 张曼 冯宇 卢建军 米杰 王建成 于 2020-06-08 设计创作，主要内容包括：本发明公开了一种高韧高柔氧化铜煤气脱硫剂的制备方法,包括以下步骤：A.三维正交结构预制件的制备：采用三维机织技术将纤维长丝织造成三维正交结构预制件；B.浸渍液的制备：将1.9-7.6g草酸铜粉末溶于20mL水中得到浸渍液；C.等体积浸渍：将步骤A中得到的三维正交结构预制件等体积浸渍于步骤B中得到的浸渍液中浸泡24h；D.高韧高柔脱硫剂的制备：将步骤C中得到的浸渍后的三维正交结构预制件通过高温焙烧处理后即可得到高韧高柔氧化铜煤气脱硫剂。本发明工艺简单,可实现脱硫剂的工业化生产；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 high-toughness and high-flexibility copper oxide gas desulfurizer, which comprises the following steps: A. preparing a three-dimensional orthogonal structure prefabricated member: weaving the fiber filaments into a three-dimensional orthogonal structure prefabricated member by adopting a three-dimensional weaving technology; B. preparation of the impregnation liquid: dissolving 1.9-7.6g of copper oxalate powder in 20mL of water to obtain an impregnation solution; C. and (3) soaking in equal volume: soaking the three-dimensional orthogonal structure prefabricated member obtained in the step A in the soaking solution obtained in the step B for 24 hours in an equal volume; D. preparing a high-toughness high-flexibility desulfurizing agent: and D, performing high-temperature roasting treatment on the impregnated three-dimensional orthogonal structure prefabricated member obtained in the step C to obtain the high-toughness high-flexibility copper oxide gas desulfurizer. The method has simple process and can realize the industrial production of the desulfurizer; and the desulfurizer adopts fiber materials with high flexibility and rich porosity as carriers to construct a multistage microscopic pore structure of the desulfurizer, so that the adsorption capacity and desulfurization reaction activity of the desulfurizer can be improved.)

1. The preparation method of the high-toughness and high-flexibility copper oxide gas desulfurizer is characterized by comprising the following steps:

A. preparing a three-dimensional orthogonal structure prefabricated member: weaving the fiber filaments into a three-dimensional orthogonal structure prefabricated member by adopting a three-dimensional weaving technology;

B. preparation of the impregnation liquid: dissolving 1.9-7.6g of copper oxalate powder in 20mL of water to obtain an impregnation solution;

C. and (3) soaking in equal volume: soaking the three-dimensional orthogonal structure prefabricated member obtained in the step A in the soaking solution obtained in the step B for 24 hours in an equal volume;

D. preparing a high-toughness high-flexibility desulfurizing agent: and D, performing high-temperature roasting treatment on the impregnated three-dimensional orthogonal structure prefabricated member obtained in the step C to obtain the high-toughness high-flexibility copper oxide gas desulfurizer.

2. The method for preparing the high-toughness high-flexibility copper oxide gas desulfurizer as claimed in claim 1, wherein in step A, the fiber filament used for the warp and weft in the three-dimensional orthogonal structure preform 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 binding yarn is one of high silica glass fiber filament, silicon dioxide fiber filament or corundum fiber filament.

3. The preparation method of the high-toughness high-flexibility copper oxide gas desulfurizer as claimed in claim 2, wherein the fiber filaments used for the warp and weft in the three-dimensional orthogonal structure preform are preferably carbon fiber filaments; the fiber filaments used in the binder yarns are preferably high silica glass fiber filaments.

4. The preparation method of the high-toughness high-flexibility copper oxide gas desulfurizer according to any one of claims 1 to 3, wherein the density of warp yarns in the three-dimensional orthogonal structure preform is 600 yarns/10 cm, the density of binder yarns is 150 yarns/10 cm, and the density of weft yarns is 300 yarns/10 cm.

5. The method for preparing the high-toughness high-flexibility copper oxide gas desulfurizer as claimed in claim 1, wherein in the step A, the length and width of the three-dimensional orthogonal structure preform are both in the range of 20-100mm, and the thickness is in the range of 5-15 mm.

6. The method for preparing the high-toughness and high-flexibility copper oxide gas desulfurizer as claimed in claim 1, wherein in step C, the three-dimensional orthogonal structure preform can completely absorb the impregnation liquid during the equal volume impregnation process.

7. The preparation method of the high-toughness and high-flexibility copper oxide gas desulfurizer as claimed in claim 1, wherein in the step D, the parameters of the high-temperature roasting process are as follows: the oxygen concentration is 5-20%, the roasting temperature is 500-.

8. The preparation method of the high-toughness and high-flexibility copper oxide gas desulfurizer as claimed in claim 7, wherein the parameters of the high-temperature roasting process are preferably: the oxygen concentration is 5-10%, the roasting temperature is 500-.

9. The preparation method of the high-toughness high-flexibility copper oxide gas desulfurizer according to claim 1, which is characterized by comprising the following steps: the sulfur capacity of the prepared high-toughness and high-flexibility copper oxide gas desulfurizer can reach 19.99% after single desulfurization, and can reach 19.93% after ten times of vulcanization/regeneration recycling.

10. The preparation method of the high-toughness high-flexibility copper oxide gas desulfurizer according to claim 1, which is characterized by comprising the following steps: the single active component utilization rate of the prepared high-toughness and high-flexibility copper oxide gas desulfurizer is kept above 99.9 percent, and after ten times of vulcanization-regeneration cycle use, the active component utilization rate is still 99.0 percent.

Technical Field

The invention belongs to the technical field of preparation of coal chemical industry desulfurizing agents, and particularly relates to a preparation method of a high-toughness high-flexibility copper oxide gas desulfurizing agent.

Background

The coal gas is used as a power and raw material source in the IGCC technology, and contains a large amount of sulfide, wherein over 90 percent of the sulfide is hydrogen sulfide gas. Hydrogen sulfide not only corrodes industrial equipment and poisons catalysts, but also threatens the ecological environment and human health after being discharged into the atmosphere. Therefore, the hydrogen sulfide in the coal gas must be removed before the coal gas is used.

The coal gas desulfurization technology comprises a wet desulfurization method and a dry desulfurization method. The wet desulphurization technology has large treatment capacity and relatively mature technology, but the technology has the defects of low utilization efficiency of sensible heat of coal gas, large water consumption, low desulphurization efficiency and the like. The medium-high temperature dry method gas desulfurization can obviously improve the utilization rate of sensible heat of the gas, has the advantage of high desulfurization efficiency, and is suitable for H₂And (4) fine removal of S. The medium-high temperature gas desulfurizer mainly takes single metal oxide and composite metal oxide as main materials, and in the reaction process of the gas desulfurizer, as the metal sulfide of a vulcanization product occupies larger space than the metal oxide, the desulfurizer taking a traditional rigid material as a carrier is easy to cause the internal volume expansion of the desulfurizer due to oxygen-sulfur displacement, so that the internal structure collapses and the pores are blocked, the restriction on the reaction rate, the micro mass transfer and the ion diffusion is large, and the desulfurization activity of the desulfurizer is seriously influenced; some desulfurizing agents have the problems of uneven distribution of active components, relatively small specific surface area and pore volume, insufficiently developed pore structures and the like.

Disclosure of Invention

In view of the above, the present invention aims to provide a method for preparing a high-toughness and high-flexibility copper oxide gas desulfurizer, so as to solve the problems of low porosity and low utilization rate of active components and poor desulfurization-regeneration performance of the existing desulfurizer during the reaction process, 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 high-toughness and high-flexibility copper oxide gas desulfurizer comprises the following steps:

A. preparing a three-dimensional orthogonal structure prefabricated member: weaving the fiber filaments into a three-dimensional orthogonal structure prefabricated member by adopting a three-dimensional weaving technology;

B. preparation of the impregnation liquid: dissolving 1.9-7.6g of copper oxalate powder in 20mL of water to obtain an impregnation solution;

C. and (3) soaking in equal volume: soaking the three-dimensional orthogonal structure prefabricated member obtained in the step A in the soaking solution obtained in the step B for 24 hours in an equal volume;

D. preparing a high-toughness high-flexibility desulfurizing agent: and D, performing high-temperature roasting treatment on the impregnated three-dimensional orthogonal structure prefabricated member obtained in the step C to obtain the high-toughness high-flexibility copper oxide gas desulfurizer.

Preferably, in step a, the fiber filament used for the warp and weft in the three-dimensional orthogonal structure preform 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 binding yarn is one of high silica glass fiber filament, silicon dioxide fiber filament or corundum fiber filament.

More preferably, the fiber filaments used for the warp and weft in the three-dimensional orthogonal structure prefabricated member are carbon fiber filaments; the fiber filaments used in the binder yarns are preferably high silica glass fiber filaments.

Preferably, the density of warp yarns in the three-dimensional orthogonal structure prefabricated member is 600/10 cm, the density of binding yarns is 150/10 cm, and the density of weft yarns is 300/10 cm.

Preferably, in the step A, the length and the width of the three-dimensional orthogonal structure prefabricated member are both in the range of 20-100mm, and the thickness is in the range of 5-15 mm.

Preferably, in step C, the three-dimensional orthogonal structure preform may absorb all the impregnation liquid during the equal volume impregnation.

Preferably, in step D, the parameters of the high-temperature roasting process are as follows: the oxygen concentration is 5-20%, the roasting temperature is 500-.

More preferably, the parameters of the high-temperature roasting process are as follows: the oxygen concentration is 5-10%, the roasting temperature is 500-.

Preferably, the sulfur capacity of the prepared high-toughness and high-flexibility copper oxide gas desulfurizer can reach 19.99% after single desulfurization, and can reach 19.93% after ten times of vulcanization/regeneration recycling.

Preferably, the single active component utilization rate of the prepared high-toughness and high-flexibility copper oxide gas desulfurizer is kept above 99.9%, and after ten times of vulcanization-regeneration cycle use, the active component utilization rate is still 99.0%.

The invention has the beneficial effects that: the method firstly utilizes a three-dimensional weaving technology to prepare a three-dimensional orthogonal structure prefabricated part, and then prepares the desulfurizer by means of metal salt solution impregnation, high-temperature roasting and the like. During the calcination process, the conversion of the metal salt into the metal oxide (i.e. cupric oxalate CuC) is specifically designed₂O₄Converted into an active component CuO), and simultaneously polymer fibers or carbon fibers are removed, and the chemical compositions of warp yarns and weft yarns are replaced under the condition of not changing the structure of the three-dimensional woven fabric, so that the method has the following advantages:

(1) the desulfurizer is prepared by adopting the three-dimensional orthogonal structure prefabricated member, and by utilizing the characteristics of high flexibility and stable physical structure of the three-dimensional orthogonal structure prefabricated member and combining the advantages of high wear resistance, good heat resistance and stable physical and chemical structure of the high silica glass fiber, the stable physical structure and rich pore structure of the three-dimensional orthogonal structure prefabricated member can promote the absorption and reaction processes of the desulfurizer and keep the long-period cycle use performance of the desulfurizer while providing a supporting effect for the whole structure of the desulfurizer;

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

(3) in addition, 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 high-toughness and high-flexibility copper oxide gas desulfurizer prepared by the method not only keeps the utilization rate of single active components above 99.9%, but also has the utilization rate of 99.0% 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.