CN112717931B - Iron-based composite desulfurizer, preparation method thereof and application thereof in removing hydrogen sulfide in gas - Google Patents
Iron-based composite desulfurizer, preparation method thereof and application thereof in removing hydrogen sulfide in gas Download PDFInfo
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- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
Abstract
The invention provides an iron-based composite desulfurizer, a preparation method thereof and application thereof in removing hydrogen sulfide in gas, wherein the iron-based composite desulfurizer comprises carbon nano tubes and hydrated ferric oxide loaded on the carbon nano tubes, and the mass percentage of the hydrated ferric oxide in the desulfurizer is 50-90%. According to the invention, the carbon nano tube which is a strong conductive material is introduced into the desulfurizer for modification for the first time, and the strong interaction between the carbon nano tube and the hydrated ferric oxide is utilized, so that abundant point defects and surface hydroxyl groups are formed on the surface of the hydrated ferric oxide, the dispersibility of the hydrated ferric oxide is increased, and the desulfurization activity and the sulfur capacity are improved. The Fe-O-C chemical bond formed between the hydrated iron oxide and the carbon nano tube promotes the electron mobility during the desulfurization reaction. The desulfurizer has mild preparation conditions and low production cost, and is very suitable for industrial large-scale production. In addition, the desulfurizer of the invention has good low-temperature desulfurization performance, so that the desulfurizer of the invention can be used for high-concentration CO2The method has the characteristics of wide universality for removing trace hydrogen sulfide in the gas.
Description
Technical Field
The invention belongs to the technical field of hydrogen sulfide removal, and particularly relates to an iron-based composite desulfurizer, a preparation method thereof and application thereof in removing hydrogen sulfide in gas.
Background
Hydrogen sulfide (H)2S) is a corrosive, malodorous toxic gas found in air, water, natural gas, crude oil, industrial production, and municipal and agricultural sewage. Hydrogen sulfide is a great hazard to human health and can be distinguished by human smell when a few ppm of hydrogen sulfide exists in the air. Exposure to 20-50ppm hydrogen sulfide for one hour can cause damage to the eyes and respiratory system of humans. Prolonged exposure to 250ppm hydrogen sulfide can cause pulmonary edema and may also lead to death. One inhalation of hydrogen sulfide at a concentration of 1000ppm is fatal. Further, H contained in the raw material gas2S also causes many industrial problems (e.g., catalyst poisoning, corrosion of pipes) and environmental pollution (e.g., acid rain). Thus, H is removed2S is necessary and has important significance for environmental protection and eco-friendly industrial manufacturing.
H at home and abroad2Removal of S has been studied for many years, dating back to the 19 th century at the earliest. The desulfurization method can be divided into two main categories of wet desulfurization and dry desulfurization according to the form of the desulfurizer, and the dry desulfurization technology is widely applied in the actual industrial production in consideration of various factors such as desulfurization precision, energy consumption, purification cost and the like. The basic principle of dry desulfurization is to utilize gas-solid phase contact reaction to remove H by solid desulfurizing agent2S is adsorbed or reacted into solid sulfur or sulfide. Common desulfurizing agents include single-component desulfurizing agents such as activated carbon, iron oxide, zinc oxide and the like, and composite desulfurizing agents such as composite metal oxides, supported organic amines and the like. Among them, iron oxide is the most classical desulfurizing agent, and compared with other types of desulfurizing agents, it has large specific surface area, high sulfur capacity, simple preparation and low cost, however, the desulfurizing precision of this type of desulfurizing agent is not high, and it can remove H2A large amount of reaction heat is released in the S process. Therefore, it is very important to develop a desulfurizing agent which has a large sulfur capacity at low temperature, high accuracy, reproducibility and low cost.
For example, chinese patent document CN1868572A discloses an iron-based composite metal oxide catalyst, which is prepared by a coprecipitation method and contains iron oxide, aluminum oxide, titanium oxide, zinc oxide, and vanadium oxide in different mass fractions. In addition, chinese patent document CN103691300A discloses a preparation method of a normal temperature iron-based desulfurizing agent, which comprises the following steps: preparing a mixed solution of soluble cobalt salt and ferric salt with a certain molar ratio, adding urea with a certain proportion, and using NaHCO3Regulating the pH value of the solution to be neutral, reacting in a high-pressure kettle at a certain temperature and pressure to prepare cobalt-containing iron oxyhydroxide particles, and finally roasting in an oxygen-containing atmosphere to prepare the desulfurizer product.
Although the desulfurization performance of the desulfurizing agent is greatly improved in the above-mentioned technology, there are still many problems, such as low sulfur capacity when used at low temperature, difficult regeneration, or complicated preparation process, high production cost, and difficulty in industrial production, especially in high concentration CO2When fine desulfurization is carried out in the atmosphere, the sulfur capacity of the desulfurizer is large due to the problem of competitive adsorptionThe degree is reduced and the industrial desulfurization requirement cannot be met.
Disclosure of Invention
The invention solves the problem that the iron-based desulfurizer in the prior art contains a large amount of CO at low temperature2The desulfurization activity of the industrial gas is still low, and the method for removing the hydrogen sulfide in the gas at low temperature by using the iron-based composite desulfurizer is further provided, the used iron-based composite desulfurizer has the advantages of simple preparation process, low production cost, excellent desulfurization activity and suitability for high-concentration CO2And (4) desulfurizing in the atmosphere.
The technical scheme of the invention is as follows:
the iron-based composite desulfurizer comprises carbon nanotubes and hydrated iron oxide loaded on the carbon nanotubes, wherein Fe-O-C chemical bonds beneficial to desulfurization are formed between the hydrated iron oxide and the carbon nanotubes, and the mass percent of the hydrated iron oxide in the iron-based composite desulfurizer is 50-90%.
The invention also provides a preparation method of the iron-based composite desulfurizer, which is a physical mixing or coprecipitation method.
The preparation method of the iron-based composite desulfurizer is a coprecipitation method, and specifically comprises the following steps:
(1) completely dissolving iron salt in deionized water to form an iron salt solution;
(2) adding carbon nano tubes into the ferric salt solution, and uniformly stirring to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution, and then transferring the mixed solution into a water bath for heating;
(3) under the condition of continuously stirring, dropwise adding a precipitant aqueous solution, and adjusting the pH to 3-11 to form a suspension; aging the suspension while maintaining continuous stirring;
(4) after the aging is finished, carrying out suction filtration, and collecting precipitates; washing the obtained precipitate with deionized water, drying, grinding, tabletting and screening to obtain the iron-based composite desulfurizer.
In the step (1), the concentration of iron ions in the iron salt solution is 0.1-5mol/L, and the type of iron salt is Fe2(SO4)3、Fe(NO3)3·9H2O and FeCl3·6H2One or more of OAnd (4) seed preparation.
In the step (2), the carbon nanotubes are multi-walled carbon nanotubes.
In the step (2), the ultrasonic time of the mixed solution is 1-3 hours; the heating temperature of the water bath is 25-100 ℃.
In the step (3), the precipitant is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and urea; the concentration of the precipitant in the precipitant aqueous solution is 0.1-5 mol/L.
The suspension is aged for 0.5 to 6 hours; the suspension ageing temperature is 25-100 ℃.
In the step (4), the drying temperature is 90-120 ℃, and the drying time is 2-4 hours; the granules after tabletting and screening are 40-60 meshes.
The invention also provides application of the iron-based composite desulfurizer in removing hydrogen sulfide in gas. Specifically, the raw material gas containing hydrogen sulfide passes through a fixed bed layer of the iron-based composite desulfurizer to remove the hydrogen sulfide.
The desulfurization temperature is 10-100 ℃.
The airspeed is 2000-8000 h-1The raw material gas also comprises carbon dioxide, and the volume percentage of the hydrogen sulfide in the raw material gas is 0.1-5%.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the carbon nano tube is introduced into the desulfurizer for the first time, and due to the strong interaction between the hydrated iron oxide and the carbon nano tube, the hydrated iron oxide particles with small particle size grow on the surface of the carbon nano tube, so that the dispersity of the hydrated iron oxide desulfurizer is improved, more adsorption sites are exposed, and the activity and the capacity of the composite desulfurizer are improved. Fe-O-C chemical bonds are formed between the hydrated ferric oxide and the carbon nano tubes, and the electron mobility of the iron-based composite desulfurizer is promoted during the desulfurization reaction, so that the desulfurization activity, the penetration sulfur capacity and the desulfurization precision of the desulfurizer are improved.
(2) According to the preparation method of the iron-based composite desulfurizer, the mixed solution of the ferric salt and the carbon nano tube is subjected to ultrasonic treatment for 1-3 hours, so that iron ions are effectively promoted to enter the inside of the pore channel of the carbon nano tube, hydrated ferric oxide and the carbon nano tube are combined more tightly, the dispersion degree of the hydrated ferric oxide on the carbon nano tube is improved, the agglomeration phenomenon of the desulfurizer is effectively reduced, and the desulfurization performance is improved.
(3) The invention relates to a preparation method of an iron-based composite desulfurizer, wherein iron salt is Fe2(SO4)3、Fe(NO3)3·9H2O and FeCl3·6H2And O, the precipitator adopts sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and urea, and has wide sources and low price.
(4) The preparation method of the iron-based composite desulfurizer does not need high-temperature and high-pressure conditions in all reactions, so that the preparation method is simple in preparation process, low in production cost and suitable for industrial production.
(5) The iron-based composite desulfurizer of the invention is suitable for high-concentration CO2Trace H in gas2Removal of S at low temperature: (<Has excellent low-temperature desulfurization performance at 100 ℃, and the penetrating adsorption capacity can reach 144.2 mg.g-1The desulfurization precision can reach 0.1ppm, and the application range is wide.
Drawings
FIG. 1 shows (a) SEM and (b) TEM images of the iron-based composite desulfurizing agent obtained in example 1 of the present invention.
Detailed Description
The iron-based composite desulfurizing agent and the preparation method thereof provided by the present invention are explained in detail below with reference to specific examples under different parameters, which are provided for the purpose of explanation and not limitation.
Comparative example 1
(1) FeCl is added3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) respectively adding activated carbon, a 13X molecular sieve, an MCM-41 molecular sieve, an SBA-15 molecular sieve, a ZSM-22 molecular sieve, a ZSM-35 molecular sieve, activated alumina, silica and artificial zeolite into the ferric salt solution, and uniformly stirring to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 1 hour, and then transferring the mixed solution into a water bath to heat to 25 ℃;
(3) under the condition of continuous stirring, adding a potassium hydroxide aqueous solution with the concentration of 1mol/L into the mixed solution as a precipitator, and adjusting the pH value to 7 to form a suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 25 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh particles to obtain the iron-based composite desulfurizer, wherein the mass ratio of hydrated iron oxide to porous material is 1: 0.3.
comparative example 2
(1) FeCl is added3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) carrying out ultrasonic treatment on the iron salt solution for 1 hour, and then transferring the solution into a water bath to heat the solution to 60 ℃;
(3) under the condition of continuous stirring, adding 1mol/L potassium hydroxide aqueous solution as a precipitator into the ferric salt solution, and adjusting the pH value to 7 to form suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 60 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh granules to obtain the iron-based desulfurizer.
Example 1
(1) FeCl is added3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) adding multi-walled carbon nanotubes into the ferric salt solution, uniformly stirring to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 1 hour, and then transferring the mixed solution into a water bath to heat to 25 ℃;
(3) under the condition of continuous stirring, adding a potassium hydroxide solution with the concentration of 1mol/L into the mixed solution as a precipitator, and adjusting the pH value to 7 to form a suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 25 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh particles to obtain the iron-based composite desulfurizer, wherein the mass ratio of hydrated iron oxide to multi-walled carbon nanotubes is 1: 0.3.
the test method comprises the following steps:
the desulfurization performance of the desulfurizing agents of comparative example 1 and example 1 was tested by using a fixed bed dynamic adsorption apparatus, and 1g of the desulfurizing agent was charged into a reaction tube, and the temperature of an adsorption column was controlled by a temperature controller and a heating furnace. When the temperature of the adsorption column reaches 40 ℃, the feed gas enters the adsorption column to react with a desulfurizer, and H in the feed gas2S content 1000ppm (balance gas CO)2) Gas space velocity of 2000h-1At normal pressure, outlet H2Detecting the concentration of S by gas chromatograph while discharging H2When the S concentration reached 0.1ppm, the aeration was stopped, and the desulfurizing agent was considered to have penetrated.
TABLE 1 penetration adsorption capacity of iron-based composite desulfurizer with different porous materials
As can be seen from Table 1, the iron-based composite desulfurizer prepared by using the carbon nano tube has the best desulfurization effect, and the penetrating adsorption capacity reaches 91.3mg g-1. The dispersibility of the desulfurizer is improved due to the strong interaction between the carbon nano tube and the hydrated ferric oxide, as shown in figure 1, and Fe-O-C chemical bonds are formed between the hydrated ferric oxide and the carbon nano tube, so that the mobility of electrons during the desulfurization reaction is promoted, and the desulfurization performance is improved.
Example 2
(1) FeCl is added3·6H2Dissolving O in deionized water to form iron salt solution with iron ion concentrationIs 0.1 mol/L;
(2) adding multi-walled carbon nanotubes into the ferric salt solution, uniformly stirring to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 1 hour, and then transferring the mixed solution into a water bath to be respectively heated to 25 ℃, 40 ℃, 60 ℃, 80 and 100 ℃;
(3) under the condition of continuous stirring, adding a potassium hydroxide aqueous solution with the concentration of 1mol/L into the mixed solution as a precipitator, and adjusting the pH value to 7 to form a suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 25 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh particles to obtain the iron-based composite desulfurizer, wherein the mass ratio of hydrated iron oxide to multi-walled carbon nanotubes is 1: 0.3.
the test method is the same as above.
TABLE 2 penetration adsorption capacity of iron-based composite desulfurizing agent synthesized at different temperatures
As can be seen from Table 2, the iron-based composite desulfurizing agent synthesized at 60 ℃ has the best desulfurizing performance, which is 136.6mg g-1。
Example 3
(1) FeCl is added3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) adding multi-wall carbon nano tubes into the ferric salt solution, and uniformly stirring to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 1 hour, and then transferring the mixed solution into a water bath to heat to 60 ℃ respectively;
(3) under the condition of continuous stirring, adding 1mol/L potassium hydroxide aqueous solution as a precipitator into the mixed solution, and respectively adjusting the pH value to 3, 5, 7, 9 and 11 to form suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 60 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh particles to obtain the iron-based composite desulfurizer, wherein the mass ratio of hydrated iron oxide to multi-walled carbon nanotubes is 1: 0.3.
the test method is the same as above.
TABLE 3 penetration adsorption capacity of iron-based composite desulfurizer synthesized at different pH values
As can be seen from Table 3, the composite desulfurizing agent needs to be carried out in a neutral environment, and the activity of the synthesized desulfurizing agent is not favorable when the pH is too high or too low. The iron-based composite desulfurizing agent synthesized at the pH value of 7 has the best desulfurizing performance, and is 136.6mg g-1。
Example 4
(1) FeCl is added3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) adding multi-wall carbon nano tubes into the ferric salt solution, and uniformly stirring to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 1 hour, and then transferring the mixed solution into a water bath to heat to 60 ℃ respectively;
(3) under the condition of continuous stirring, adding a potassium hydroxide aqueous solution with the concentration of 1mol/L into the mixed solution as a precipitator, and adjusting the pH value to 7 to form a suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 60 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh particles to obtain the iron-based composite desulfurizer, wherein the mass ratio of hydrated iron oxide to multi-walled carbon nanotubes is 1: 0.1-0.5.
the test method is the same as above.
TABLE 4 penetration adsorption capacity of iron-based composite desulfurizer synthesized by different mass ratios of iron oxide hydrate to carbon nanotube
As can be seen from Table 4, the penetrating adsorption capacity of the iron-based composite desulfurizer is obviously improved after the carbon nano tube is added, and when the mass ratio of the hydrated iron oxide to the carbon nano tube is 1:0.2, the prepared iron-based composite desulfurizer has the highest penetrating adsorption capacity of 144.2mg g-1。
Example 5
(1) Mixing Fe2(SO4)3、Fe(NO3)3·9H2O and FeCl3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) respectively adding multi-wall carbon nano tubes into the ferric salt solution, and uniformly stirring to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 1 hour, and then transferring the mixed solution into a water bath to heat to 60 ℃ respectively;
(3) under the condition of continuous stirring, adding a potassium hydroxide aqueous solution with the concentration of 1mol/L into the mixed solution as a precipitator, and adjusting the pH value to 7 to form a suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 60 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh particles to obtain the iron-based composite desulfurizer, wherein the mass ratio of hydrated iron oxide to multi-walled carbon nanotubes is 1: 0.2.
the test method is the same as above.
TABLE 5 penetration adsorption capacity of iron-based composite desulfurizer synthesized from different iron salts
As can be seen from Table 5, the iron-based composite desulfurizer synthesized by three iron salts has excellent desulfurization performance, wherein the best performance is FeCl3·6H2O is used as a desulfurizer for iron salt synthesis, and the breakthrough adsorption capacity is 136.6mg g-1
Example 6
(1) FeCl is added3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) adding multi-wall carbon nano tubes into the ferric salt solution, and uniformly stirring to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 1 hour, and then transferring the mixed solution into a water bath to heat to 60 ℃ respectively;
(3) under the condition of continuously stirring, respectively adding sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and urea aqueous solution with the concentration of 1mol/L into the mixed solution as precipitating agents, and adjusting the pH value to 7 to form suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 60 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, drying at 100 ℃ for 4 hours, and finally grinding, tabletting and screening to obtain 40-60-mesh particles to obtain the iron-based composite desulfurizer, wherein the mass ratio of hydrated iron oxide to multi-walled carbon nanotubes is 1: 0.2.
the test method is the same as above.
TABLE 6 penetration adsorption capacity of iron-based composite desulfurizer synthesized by different precipitants
As can be seen from Table 6, the iron-based composite desulfurizer synthesized by using sodium hydroxide, potassium hydroxide and ammonia water as precipitating agents has excellent desulfurization performance, while the desulfurizer synthesized by using sodium carbonate, sodium bicarbonate and urea with weak alkalinity as precipitating agents has relatively weak desulfurization performance.
Example 7
(1) FeCl is added3·6H2Completely dissolving O in deionized water to form an iron salt solution, wherein the concentration of iron ions in the iron salt solution is 0.1 mol/L;
(2) adding multi-wall carbon nano tubes into the ferric salt solution, and uniformly stirring to obtain a mixed solution; the mass ratio of the ferric salt to the multi-walled carbon nano-tube is 1:0 and 1: 0.08; carrying out ultrasonic treatment on the two solutions for 1 hour, and then transferring the two solutions into a water bath to heat the two solutions to 60 ℃ respectively;
(3) under the condition of continuous stirring, respectively adding 1mol/L potassium hydroxide aqueous solution as a precipitator into the mixed solution, and adjusting the pH value to 7 to form suspension; the suspension was aged in the mother liquor for 3 hours at an aging temperature of 60 ℃ while maintaining continuous stirring.
(4) Carrying out suction filtration treatment on the suspension, and collecting precipitates; washing the obtained precipitate with deionized water, and drying at 100 deg.C for 4 hr to obtain two kinds of precipitates of pure iron oxide hydrate and hydrated iron oxide composite carbon nanotube (wherein the mass ratio of hydrated iron oxide to multi-walled carbon nanotube is 1: 0.2).
(5) Taking the pure hydrated ferric oxide precipitate, adding the solid multi-walled carbon nano-tube, and physically and uniformly mixing, wherein the mass ratio of the hydrated ferric oxide to the carbon nano-tube is 1: 0.2; the last two samples were ground, tabletted and sieved to 40-60 mesh particles.
The test method is the same as above.
TABLE 7 penetration adsorption capacity of iron-based composite desulfurizer synthesized by different synthesis methods
As can be seen from Table 7, the physical mixing of hydrated iron oxide with carbon nanotubes also significantly improved the desulfurization performance, indicating that there was a strong interaction between the two.
It should be noted that the above-mentioned embodiments are merely preferred examples of the present invention, and those skilled in the art may make other variations or modifications based on the above-mentioned description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications can be made without departing from the scope of the invention.
Claims (9)
1. The application of the iron-based compound desulfurizer in removing hydrogen sulfide in gas is characterized in that: the iron-based composite desulfurizer comprises carbon nano tubes and hydrated ferric oxide loaded on the carbon nano tubes, wherein Fe-O-C chemical bonds are formed between the hydrated ferric oxide and the carbon nano tubes, and the mass percent of the hydrated ferric oxide in the iron-based composite desulfurizer is 50-90%.
2. The application of the iron-based composite desulfurizing agent of claim 1 in removing hydrogen sulfide in gas, which is characterized in that: the iron-based composite desulfurizer is prepared by physical mixing.
3. The application of the iron-based composite desulfurizing agent of claim 2 in removing hydrogen sulfide in gas, which is characterized in that: the iron-based composite desulfurizer is prepared by a coprecipitation method, and specifically comprises the following steps:
(1) completely dissolving iron salt in deionized water to form an iron salt solution;
(2) adding carbon nano tubes into the ferric salt solution, and uniformly stirring to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution, and then transferring the mixed solution into a water bath for heating;
(3) under the condition of continuously stirring, dropwise adding a precipitant aqueous solution, and adjusting the pH to 3-11 to form a suspension; aging the suspension while maintaining continuous stirring;
(4) after the aging is finished, carrying out suction filtration, and collecting precipitates; washing the obtained precipitate with deionized water, drying, grinding, tabletting and screening to obtain the iron-based composite desulfurizer.
4. The application of the iron-based composite desulfurizing agent of claim 3 in removing hydrogen sulfide in gas, which is characterized in that: in the step (2), the carbon nanotubes are multi-walled carbon nanotubes.
5. The application of the iron-based composite desulfurizing agent of claim 3 in removing hydrogen sulfide in gas, which is characterized in that: in the step (2), the ultrasonic time of the mixed solution is 1-3 hours; the heating temperature of the water bath is 25-100 ℃.
6. The application of the iron-based composite desulfurizing agent of claim 3 in removing hydrogen sulfide in gas, which is characterized in that: in the step (1), the concentration of iron ions in the iron salt solution is 0.1-5 mol/L; in the step (3), the precipitant is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and urea; the concentration of the precipitant in the precipitant aqueous solution is 0.1-5mol/L, and the suspension aging time is 0.5-6 hours; the suspension ageing temperature is 25-100 ℃.
7. The application of the iron-based composite desulfurizing agent of claim 1 in removing hydrogen sulfide in gas, which is characterized in that: and (3) passing the raw material gas containing hydrogen sulfide through a fixed bed layer of the iron-based composite desulfurizer to remove the hydrogen sulfide.
8. The application of the iron-based composite desulfurizing agent of claim 7 in removing hydrogen sulfide in gas, which is characterized in that: the desulfurization temperature is 10-100 ℃.
9. The application of the iron-based composite desulfurizing agent of claim 7 or 8 in removing hydrogen sulfide in gas, which is characterized in that: the airspeed is 2000-8000 h-1The raw material gas also comprises carbon dioxide, and the volume percentage of the hydrogen sulfide in the raw material gas is 0.1-5%.
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| CN105056719A (en) * | 2015-07-30 | 2015-11-18 | 福州大学化肥催化剂国家工程研究中心 | Preparation method of FeOOH low-temperature desulfurizer and desulfurizer prepared through same |
| CN106621797A (en) * | 2016-12-09 | 2017-05-10 | 武汉纺织大学 | Efficient composite oxide desulfurizing agent preparation method |
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| CN105056719A (en) * | 2015-07-30 | 2015-11-18 | 福州大学化肥催化剂国家工程研究中心 | Preparation method of FeOOH low-temperature desulfurizer and desulfurizer prepared through same |
| CN106621797A (en) * | 2016-12-09 | 2017-05-10 | 武汉纺织大学 | Efficient composite oxide desulfurizing agent preparation method |
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