阅读说明：本技术 组合脱硫剂的制备方法、组合脱硫剂及脱硫方法 (Preparation method of combined desulfurizer, combined desulfurizer and desulfurization method ) 是由 陈斌 蒋汪洋 覃春平 周英 徐沾 倪龙军 于 2021-10-08 设计创作，主要内容包括：本发明涉及一种组合脱硫剂的制备方法、组合脱硫剂及脱硫方法,制备方法包括步骤S1,制备DHS-1脱硫剂,具体包括：步骤S11,选择活性氧化铝作为载体；步骤S12,配置成混合溶液a,并将混合溶液a喷淋至步骤S1的载体,得到半成品；步骤S13,对步骤S12得到的半成品进行活化处理,得到DHS-1脱硫剂；步骤S2,制备DHS-2脱硫剂,具体包括：步骤S21,配置混合溶液b,并配合氧化铝粉A,得到粉料B；步骤S22,利用粉料B制成颗粒,并进行焙烧处理,得到半成品；步骤S23,将焙烧后的半成品还原；步骤S24,将加热温度升温至150～200℃,通入零级空气,当反应管后的温度不再增加时,保持零级空气量不变,继续通气,并自然冷却至室温,关闭空气,取出脱硫剂,得到成品的DHS-2脱硫剂。(The invention relates to a preparation method of a combined desulfurizer, the combined desulfurizer and a desulfurization method, wherein the preparation method comprises the step of S1, and the preparation method comprises the following steps: step S11, selecting active alumina as a carrier; step S12, preparing a mixed solution a, and spraying the mixed solution a to the carrier in the step S1 to obtain a semi-finished product; step S13, activating the semi-finished product obtained in the step S12 to obtain a DHS-1 desulfurizer; step S2, preparing the DHS-2 desulfurizing agent, which specifically comprises the following steps: step S21, preparing a mixed solution B, and matching with the alumina powder A to obtain powder B; step S22, preparing the powder B into particles, and roasting to obtain a semi-finished product; step S23, reducing the roasted semi-finished product; and step S24, heating the temperature to 150-200 ℃, introducing zero-order air, keeping the zero-order air amount unchanged when the temperature after the reaction tube is not increased any more, continuously introducing air, naturally cooling to room temperature, closing the air, and taking out the desulfurizer to obtain the finished DHS-2 desulfurizer.)

1. The preparation method of the combined desulfurizer is characterized by comprising the following steps:

step S1, preparing the DHS-1 desulfurizing agent, which specifically comprises the following steps:

step S11, selecting active alumina as a carrier;

step S12, preparing a mixed solution a, and spraying the mixed solution a to step S1

The carrier is subjected to standing, drying and roasting to obtain a semi-finished product;

step S13, activating the semi-finished product obtained in the step S12 to obtain a DHS-1 desulfurizer;

step S2, preparing the DHS-2 desulfurizing agent, which specifically comprises the following steps:

step S21, preparing a mixed solution B, adding the alumina powder A into the mixed solution B, and performing impregnation, filtration, washing, drying and roasting to obtain powder B;

step S22, filling the powder B into a container, adding calcium stearate or magnesium stearate or stearic acid, then adding deionized water, then adding sesbania powder and/or water glass and/or methyl cellulose, uniformly mixing, covering the container opening with a film, standing for a period of time, performing compression molding, and roasting the molded particles to obtain a semi-finished product;

step S23, the baked semi-finished product is put into a reaction tube,with hydrogen containing H₂Reducing the nitrogen for 8 hours at the temperature of 300-400 ℃, then cooling to room temperature, and introducing nitrogen for protection;

and step S24, heating the temperature to 150-200 ℃, introducing zero-level air, slowly increasing the air flow, observing the temperature detection after the reaction tube, keeping the zero-level air amount unchanged when the temperature after the reaction tube is not increased any more, continuously introducing air for 30-60 min, naturally cooling to room temperature, closing the air, and taking out the desulfurizer to obtain the finished DHS-2 desulfurizer.

2. The method of claim 1, wherein the mixed solution a in step S12 is prepared from palladium nitrate or chloride.

3. The method of claim 1, wherein the mixed solution a in step S12 is prepared from nitric acid or chloride of ruthenium.

4. The method of claim 1, wherein the mixed solution a in step S12 is prepared from a nitric acid product of palladium and a nitric acid product of ruthenium, or from a chloride of palladium and a chloride of ruthenium.

5. The method of claim 1, wherein in step S21, the mixed solution b is prepared from chlorides, nitrates or acetates of at least two metals selected from copper, nickel and silver.

6. The method for preparing a combined desulfurizing agent according to claim 1, wherein the activating treatment in step S13 is as follows:

heating the mixture from room temperature to 150-180 ℃ at a heating rate of 1.5-3 ℃/min, placing the mixture in an environment of 150-180 ℃ for 2-3 h, heating the mixture to 250-300 ℃ at a heating rate of 2-4 ℃/min, placing the mixture in an environment of 250-300 ℃ for 4-6 h, and naturally cooling the mixture to room temperature.

7. The method for preparing a combined desulfurizing agent according to claim 1, wherein the activating treatment in step S13 is as follows:

and (3) treating by using an aqueous solution of sodium borohydride, wherein the concentration range of the aqueous solution of sodium borohydride is 5-250 g/L, the temperature range is 40-80 ℃, and the soaking time range is 0.5-2 h.

8. The method for preparing a combined desulfurizing agent according to claim 1, wherein the activating treatment in step S13 is as follows:

treating with a hydrazine hydrate solution, wherein the proportion of the hydrazine hydrate solution is that 10-100 ml of hydrazine hydrate is added into every 1 liter of water, the temperature of the hydrazine hydrate solution is 40-80 ℃, and the soaking time is 1-3 h.

9. A combined desulfurizing agent, which comprises DHS-1 desulfurizing agent and DHS-2 desulfurizing agent, and is prepared by the preparation method of any one of claims 1 to 8.

10. A desulfurization method using the combined desulfurization agent according to claim 9, comprising:

and (3) desulfurizing the feed gas by using a DHS-2 desulfurizing agent and a DHS-1 desulfurizing agent in sequence to obtain a product gas.

Technical Field

The invention relates to the field of a desulfurizing agent, and particularly relates to a preparation method of a combined desulfurizing agent, the combined desulfurizing agent and a desulfurizing method.

Background

Most of the existing desulfurizing agents in the market are used in the fields of converter smelting, environmental protection, flue gas purification and the like. These products have the following disadvantages:

(1) the desulfurization precision is not high, and the desulfurization precision range is as follows: 100ppm to 0.1 ppm.

(2) In the hydrogen environment, the metal oxide of the metal oxide desulfurizer is reduced into simple substances to cause the reduction of desulfurization performance.

Disclosure of Invention

In view of the above problems, the present invention has been made to provide a method for preparing a combined desulfurization agent, and a desulfurization method, which overcome the above problems or at least partially solve the above problems.

According to the first aspect of the present invention, a preparation method of a combined desulfurization agent is provided, including step S1, the preparation of DHS-1 desulfurization agent specifically includes: step S11, selecting active alumina as a carrier; step S12, preparing a mixed solution a, spraying the mixed solution a to the carrier in the step S1, standing, drying and roasting to obtain a semi-finished product; step S13, activating the semi-finished product obtained in the step S12 to obtain a DHS-1 desulfurizer; step S2, preparing the DHS-2 desulfurizing agent, which specifically comprises the following steps: step S21, preparing a mixed solution B, adding the alumina powder A into the mixed solution B, and performing impregnation, filtration, washing, drying and roasting to obtain powder B; step S22, filling the powder B into a container, adding calcium stearate or magnesium stearate or stearic acid, then adding deionized water, then adding sesbania powder and/or water glass and/or methyl cellulose, mixing uniformly, covering the container opening with a film, standing for a period of time, performing compression molding, and obtaining the finished productRoasting the obtained particles to obtain a semi-finished product; step S23, the semi-finished product after roasting is put into a reaction tube and is treated with H₂Reducing the nitrogen for 8 hours at the temperature of 300-400 ℃, then cooling to room temperature, and introducing nitrogen for protection; and step S24, heating the temperature to 150-200 ℃, introducing zero-level air, slowly increasing the air flow, observing the temperature detection after the reaction tube, keeping the zero-level air amount unchanged when the temperature after the reaction tube is not increased any more, continuously introducing air for 30-60 min, naturally cooling to room temperature, closing the air, and taking out the desulfurizer to obtain the finished DHS-2 desulfurizer.

Preferably, the mixed solution a in step S12 is prepared using a nitrate or chloride of palladium.

Preferably, the mixed solution a in step S12 is prepared using nitric acid or chloride of ruthenium.

Preferably, the mixed solution a in step S12 is prepared using a nitric acid product of palladium and a nitric acid product of ruthenium, or a chloride of palladium and a chloride of ruthenium.

Preferably, in step S21, the mixed solution b is prepared by using chlorides, nitrates or acetates of at least two metals selected from copper, nickel and silver.

Preferably, the activation processing method in step S13 is as follows: heating the mixture from room temperature to 150-180 ℃ at a heating rate of 1.5-3 ℃/min, placing the mixture in an environment of 150-180 ℃ for 2-3 h, heating the mixture to 250-300 ℃ at a heating rate of 2-4 ℃/min, placing the mixture in an environment of 250-300 ℃ for 4-6 h, and naturally cooling the mixture to room temperature.

Preferably, the activation processing method in step S13 is as follows: and (3) treating by using an aqueous solution of sodium borohydride, wherein the concentration range of the aqueous solution of sodium borohydride is 5-250 g/L, the temperature range is 40-80 ℃, and the soaking time range is 0.5-2 h.

Preferably, the activation processing method in step S13 is as follows: treating with a hydrazine hydrate solution, wherein the proportion of the hydrazine hydrate solution is that 10-100 ml of hydrazine hydrate is added into every 1 liter of water, the temperature of the hydrazine hydrate solution is 40-80 ℃, and the soaking time is 1-3 h.

According to a second aspect of the present invention, there is provided a combined desulfurization agent, comprising DHS-1 desulfurization agent and DHS-2 desulfurization agent, prepared by the preparation method according to the first aspect.

According to a third aspect of the present invention, there is provided a desulfurization method using the combined desulfurization agent of the second aspect, specifically comprising: and (3) desulfurizing the feed gas by using a DHS-2 desulfurizing agent and a DHS-1 desulfurizing agent in sequence to obtain a product gas.

The invention can remove the sulfides such as hydrogen sulfide in the raw material gas to less than or equal to 1ppb by using the combined bed desulfurizer.

The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a schematic diagram of the use of the combined desulfurizing agent provided by the embodiment of the present invention.

Detailed Description

Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.

The terms "comprises" and "comprising," and any variations thereof, in the present description and claims and drawings are intended to cover a non-exclusive inclusion, such as a list of steps or elements.

The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.

The invention provides a preparation method of a combined desulfurizer, which comprises the following steps:

step S1, preparing the DHS-1 desulfurizing agent, which specifically comprises the following steps:

step S11, selecting active alumina as a carrier;

step S12, preparing a mixed solution a, spraying the mixed solution a to the carrier in the step S1, standing, drying and roasting to obtain a semi-finished product;

step S13, activating the semi-finished product obtained in the step S12 to obtain a DHS-1 desulfurizer;

step S2, preparing the DHS-2 desulfurizing agent, which specifically comprises the following steps:

step S21, preparing a mixed solution B, adding the alumina powder A into the mixed solution B, and performing impregnation, filtration, washing, drying and roasting to obtain powder B;

step S22, filling the powder B into a container, adding calcium stearate or magnesium stearate or stearic acid, then adding deionized water, then adding sesbania powder and/or water glass and/or methyl cellulose, uniformly mixing, covering the container opening with a film, standing for a period of time, performing compression molding, and roasting the molded particles to obtain a semi-finished product;

step S23, the semi-finished product after roasting is put into a reaction tube and is treated with H₂Reducing the nitrogen for 8 hours at the temperature of 300-400 ℃, then cooling to room temperature, and introducing nitrogen for protection;

and step S24, heating the temperature to 150-200 ℃, introducing zero-level air, slowly increasing the air flow, observing the temperature detection after the reaction tube, keeping the zero-level air amount unchanged when the temperature after the reaction tube is not increased any more, continuously introducing air for 30-60 min, naturally cooling to room temperature, closing the air, and taking out the desulfurizer to obtain the finished DHS-2 desulfurizer.

In an exemplary embodiment, at step S11,the specific surface area of the activated alumina is more than or equal to 250m²Per g, pore volume is more than or equal to 0.56cm³(ii) in terms of/g. Soaking the carrier in an acidic solution (with the pH value of 3-5) for 2-4 hours, filtering, washing and drying at 100-120 ℃ to constant weight.

In an exemplary embodiment, the mixed solution a in step S12 is prepared using a nitrate or chloride of palladium.

In an exemplary embodiment, the mixed solution a in step S12 is prepared using nitric acid or chloride of ruthenium.

In an exemplary embodiment, the mixed solution a in step S12 is prepared using a nitric acid product of palladium and a nitric acid product of ruthenium.

In an exemplary embodiment, the mixed solution a in step S12 is prepared using a chloride of palladium and a chloride of ruthenium.

In an exemplary embodiment, in the preparation of the mixed solution a, nitric acid or chloride of iron and/or cobalt may also be added as an auxiliary, depending on ruthenium or palladium, as to whether nitric acid or chloride, if ruthenium or palladium is selected from nitric acid, iron and/or cobalt is also selected from nitric acid, and if ruthenium or palladium is selected from chloride, iron and/or cobalt is also selected from chloride.

In an exemplary embodiment, the content of the metal in the mixed solution a ranges from 0.1% to 5% by weight.

In an exemplary embodiment, in step S12, a pH slow-release agent is used to adjust the pH value of the solution, the solution is uniformly sprayed onto the carrier in step S11 by a sprayer, the carrier is kept still for 15-30 min after spraying is finished, the carrier is dried at 80-120 ℃, and then the carrier is baked at 250-500 ℃ for 2-8 hours to obtain a semi-finished product.

In an exemplary embodiment, the activation process of the semi-finished product obtained in step S12 in step S13 may be performed in any one of the following three ways:

the first method is as follows: hydrogen gas is adopted: 3% -6%, nitrogen: the mixed gas of the balance gas is treated, and the treatment procedure is as follows:

heating the mixture from room temperature to 150-180 ℃ at a heating rate of 1.5-3 ℃/min, placing the mixture in an environment of 150-180 ℃ for 2-3 h, heating the mixture to 250-300 ℃ at a heating rate of 2-4 ℃/min, placing the mixture in an environment of 250-300 ℃ for 4-6 h, and naturally cooling the mixture to room temperature.

The second method comprises the following steps: and (3) treating by using an aqueous solution of sodium borohydride, wherein the concentration range of the aqueous solution of sodium borohydride is 5-250 g/L, the temperature range is 40-80 ℃, and the soaking time range is 0.5-2 h.

The third method comprises the following steps: treating with hydrazine hydrate solution, wherein the proportion of the hydrazine hydrate solution is that 10-100 ml of hydrazine hydrate is added into every 1 liter of water, the temperature is 40-80 ℃, and the soaking time is 1-3 h.

And obtaining the DHS-1 desulfurizer after the activation is finished.

In an exemplary embodiment, the mixed solution b in step S21 is prepared using a chloride, nitrate or acetate of copper and a chloride, nitrate or acetate of nickel.

In an exemplary embodiment, the mixed solution b in step S21 is prepared using a chloride, nitrate, or acetate of copper and a chloride, nitrate, or acetate of silver.

In an exemplary embodiment, the mixed solution b in step S21 is prepared using a chloride, nitrate, or acetate of nickel and a chloride, nitrate, or acetate of silver.

In an exemplary embodiment, the mixed solution b in step S21 is prepared using a chloride, nitrate or acetate of copper, a chloride, nitrate or acetate of nickel, and a chloride, nitrate or acetate of silver.

In an exemplary embodiment, the metal content of the mixed solution b ranges from 1% to 50% by weight.

In an exemplary embodiment, in step S21, 20 to 60 mesh alumina powder a is added to the solution B, dipped for 4 to 12 hours, filtered, washed, dried at 100 to 120 ℃, and then calcined at 350 to 550 ℃ for 3 to 8 hours to obtain powder B.

In an exemplary embodiment, in step S22, powder B is filled into a container, calcium stearate or magnesium stearate or stearic acid in an amount of 0.3% to 2% by weight of powder B is added, then deionized water in an amount of 3.7% to 5.6% by weight of powder B is added, sesbania powder and/or water glass and/or methyl cellulose in an amount of 0.5% to 10% by weight of powder B is added, after mixing uniformly, the container is covered with a film, and after standing for 12 to 24 hours, compression molding is performed, and the molded particles are subjected to a baking treatment at 450 to 570 ℃ to obtain a semi-finished product.

In an exemplary embodiment, in step S23, the calcined semi-finished product is charged into a reaction tube and is treated with H-containing gas₂Reducing the nitrogen for 8 hours at the temperature of 300-400 ℃, then cooling to room temperature, and introducing nitrogen for protection, wherein H in the nitrogen₂The volume content of (A) is 5-10%.

In an exemplary embodiment, step S24 specifically includes: heating to 150-200 deg.C, introducing zero-order air, and slowly increasing air flow from 10ml/min to 5ml/min every 30 min. And (3) observing the temperature detection after the reaction tube, keeping the zero-level air amount unchanged when the temperature after the reaction tube is not increased any more, continuously ventilating for 30-60 min, naturally cooling to room temperature, closing the air, and taking out the desulfurizer to obtain the finished DHS-2 desulfurizer.

The invention provides a combined desulfurizer, which comprises DHS-1 desulfurizer and DHS-2 desulfurizer and is prepared by the preparation method.

The invention provides a desulfurization method, which uses the combined desulfurizer to carry out desulfurization and specifically comprises the following steps:

the invention adopts the use mode of two desulfurizer combination beds to remove trace sulfur in the feed gas of the hydrogen energy industry to less than or equal to 1 ppb. The scheme can effectively increase the desulfurization precision and ensure the desulfurization effect.

As shown in a schematic diagram of the use of the product gas, DHS-2 desulfurizer and DHS-1 desulfurizer are put into a combined bed, an inlet of the combined bed is connected with a preheater, when the product gas is used, raw gas passes through the preheater and then is input into the combined bed, and the raw gas is desulfurized by the DHS-2 desulfurizer and the DHS-1 desulfurizer in sequence to obtain the product gas.

Note that:

(1) in the scheme, a DHS-2 desulfurizer is used at the inlet end of raw material gas, and a DHS-1 desulfurizer is used at the outlet end;

(2) in order to ensure the desulfurization effect, gas distribution should be done.

Test results

The combined bed desulfurizer can be used for removing 4.7-100 ppm of H in hydrogen fuel at room temperature of 25-300 DEG C₂S is removed to be less than 1ppb (0.001ppm), and the sulfur capacity can reach 3 x 103-2.27 x 105 mg/Kg.

Test data:

1. the raw material gas comprises the following components: h₂: balancing gas; h₂S：4.7ppm

Testing an instrument: KaPlus8000 enhanced plasma chromatograph, detection precision: 1ppb

Temperature/. degree.C	25	100	150	200	250	300
							H2S content/ppb	0.00	0.00	0.00	0.00	0.00	0.00

The combined desulfurizer can be used for removing 4.7ppm of H in hydrogen-rich gas at 25-300 DEG C₂S is removed to below 1 ppb.

2. The raw material gas comprises the following components: h₂: balancing gas; h₂S：100ppm

Testing an instrument: ka Plus8000 enhanced plasma chromatograph, detection precision: 1ppb

Temperature/. degree.C	25	100	150	200	250	300
							H2S content/ppb	0.79	0.93	0.00	0.00	0.00	0.00

The combined desulfurizer can be used for removing 100ppm H in hydrogen-rich gas at 25-300 DEG C₂S is removed to below 1 ppb. More preferably, the reaction conditions are 150-300 ℃.

3. When the feed gas contains CO, the removal effect of H2S can be influenced when the temperature is higher than 250 ℃;

the raw material gas comprises the following components: h₂: balancing gas; h₂S：4.7ppm；CO；20ppm

Testing an instrument: ka Plus8000 enhanced plasma chromatograph, detection precision: 1ppb

Temperature/. degree.C	25	100	150	200	250	300
							H2S content/ppb	0.00	0.00	0.00	0.00	3.26	8.16

If the feed gas contains CO, the desulfurization effect of the combined desulfurizer is influenced. When the hydrogen-rich gas contains 4.7ppm of H2S and 20ppm of CO, the using temperature is 25-200 ℃, and when the temperature is higher than 250 ℃, the desulfurization effect is reduced along with the temperature increase.

The above embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, it should be understood that the above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.