Compound sulfur particle size regulator, preparation method and application thereof

Abstract

The application discloses a compound sulfur particle size regulator, a preparation method and application thereof, and can regulate the sulfur particle size, reduce the probability of generating oversized or undersized sulfur, and make the distribution of the sulfur particle size more concentrated. When the complex iron self-circulation reactor is operated under different loads, more sulfur can enter the reactor cone for sedimentation through the bubble wake vortex and liquid phase circulation, the deposition of the sulfur on the bottom plate of the complex iron self-circulation reactor is obviously relieved, and the compound sulfur particle size regulator can regulate the sulfur particle size, so that the distribution of the sulfur particle size is more concentrated.

Description

A compound sulfur particle size modifier, its preparation method and application Technical Field

[0001] This invention belongs to the field of hydrogen sulfide-containing acid gas purification, specifically relating to a compound sulfur particle size regulator, its preparation method, and its application. Background Technology

[0002] H2S, a toxic and harmful substance widely present in industrial gases and waste gases in the petrochemical industry, poses a threat to industrial production, the environment, and human health if not removed. Among various methods for H2S removal, industrial plants employing the complexed iron liquid-phase oxidation method are becoming increasingly common. The complexed iron self-circulating sulfur recovery process has attracted the most attention due to its elimination of the circulation pump, significantly reducing operating costs, and the non-toxic nature of the desulfurization liquid.

[0003] In the process of treating acidic gas using a complexed iron self-circulating sulfur recovery system, surfactants are added to rapidly wet the sulfur and cause the sulfur particles to grow quickly into particles of a certain size. As shown in Figure 1, the reactor chamber is divided into an ascending zone and a descending zone by a series of baffles and weirs. The reactor chamber and the reactor cone are separated by a bottom plate, with only one descending zone and one ascending zone directly connected to the reactor chamber. Sulfur particles generated in the reactor chamber are fluidized by the gas-liquid two-phase system, circulating in the reactor along with the bubble tail vortex or liquid phase, and finally entering the reactor cone through the descending zone connected to the cone. The desulfurization liquid containing sulfur has a certain residence time in the cone, ensuring that the sulfur settles completely under gravity. The clear liquid is then re-entered into the reactor chamber for circulation through the ascending zone connected to the reactor cone. In this way, the sulfur formed in the chamber continuously enters the cone with the desulfurization liquid to settle, achieving solid-liquid separation. To achieve the above effects, the particle size of sulfur particles needs to be kept within a certain range. If the sulfur particle size is too small, the sulfur settling rate is slow, and the sulfur is carried out of the settling zone before it has completely settled in the cone and re-enters the circulation, affecting the desulfurization effect. If the sulfur particle size is too large, its own gravity plays a dominant role in the flow, and the sulfur particles will not settle under their own gravity with the bubble tail vortex or liquid phase movement. As a result, this part of the sulfur cannot be carried into the cone, which leads to the sulfur depositing on the bottom plate of the reactor, causing reactor blockage and affecting the normal production of the equipment.

[0004] A Chinese invention patent application (publication number CN106139837A) published by Shaanxi Yanchang Petroleum (Group) Co., Ltd. on November 23, 2016, discloses a sulfur particle modifier for complexing iron desulfurization liquid and its application method. The addition amount of the sulfur particle modifier is 30-100 ppm, which can rapidly wet the sulfur and increase its diameter from tens of micrometers to over 120 micrometers, making the sulfur easier to settle. However, the generated sulfur particles are relatively large, easily causing sulfur to settle on the bottom plate of the reactor, resulting in reactor blockage. A Chinese invention patent application (publication number CN105194911A) published by North China University of Technology on December 30, 2015, discloses a sulfur particle flocculant for iron-based desulfurization liquid, which can rapidly increase the sulfur particle size to 69.9-176.1 μm, causing more than 90% of the sulfur to quickly settle out in the settling tank. However, in actual production, there are still problems with uneven particle size distribution, and some of the sulfur produced has a particle size that is too large or too small.

[0005] Therefore, the current issue to be addressed is the uneven sulfur particle size distribution in the desulfurization liquid used in the complexed iron self-circulating sulfur recovery process. Summary of the Invention

[0006] The purpose of this invention is to solve the problem of uneven sulfur particle size distribution in the desulfurization liquid of the complexed iron self-circulating sulfur recovery process. It provides a compound sulfur particle size regulator, its preparation method and application. When used in the desulfurization liquid of the complexed iron self-circulating sulfur recovery process, it enables more sulfur to enter the reactor cone and settle with the bubble tail vortex and liquid phase circulation when the complexed iron self-circulating reactor is running under different loads.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A method for preparing a compound sulfur particle size regulator involves adding polyoxyethylene ether surfactants, low-carbon alcohol wetting agents, organic polymer flocculants, and oligosaccharides to water and stirring until completely dissolved to obtain the compound sulfur particle size regulator.

[0009] Furthermore, the polyoxyethylene ether surfactant is any one or two of isotridecyl alcohol polyoxyethylene ether, isodecyl alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and dodecylphenol polyoxyethylene ether.

[0010] Furthermore, the mass concentration of the polyoxyethylene ether surfactant added to the water is 10-15 g / L.

[0011] Furthermore, the low-carbon alcohol wetting agent is any one or two of n-octanol, isopropanol, propylene glycol, and glycerin.

[0012] Furthermore, the mass concentration of the low-carbon alcohol wetting agent added to the water is 3-10 g / L.

[0013] Furthermore, the organic polymeric flocculant is any one or two of polyvinylpyrrolidone, polyacrylamide, and sodium polystyrene sulfonate.

[0014] Furthermore, the organic polymer flocculant is added to water at a mass concentration of 4–6 g / L.

[0015] Furthermore, the oligosaccharide is any one or two of pentose, hexose and sucrose, and the mass concentration of the oligosaccharide added to the water is 8-12 g / L.

[0016] A compound sulfur particle size modifier is prepared using the preparation method described above.

[0017] An application of a compound sulfur particle size modifier in a complexed iron self-circulating sulfur recovery process involves adding the aforementioned compound sulfur particle size modifier to the desulfurization liquid in a complexed iron self-circulating reactor. Self-circulation ensures the compound sulfur particle size modifier is uniformly dispersed in the desulfurization liquid of the complexed iron self-circulating sulfur recovery process. The pH of the compound sulfur particle size modifier is 8–8.9, and the amount added is 10–30 ppm.

[0018] Compared with the prior art, the present invention has the following beneficial technical effects:

[0019] This invention provides a compound sulfur particle size regulator that can adjust sulfur particle size, reduce the probability of producing excessively large or small sulfur particles, and make the sulfur particle size distribution more concentrated. This allows more sulfur to settle into the reactor cone along with the bubble tail vortex and liquid phase circulation during operation of the complexed iron self-circulating reactor under different loads.

[0020] The compound sulfur particle size regulator provided by this invention can be used in the self-circulating complex iron-sulfur recovery process. It can adjust the sulfur particle size so that the majority (≥80%) of the sulfur particles are distributed between 23 and 148 μm. The deposition of sulfur on the bottom plate of the complex iron self-circulating reactor is significantly alleviated. The compound sulfur particle size regulator can adjust the sulfur particle size, making the sulfur particle size distribution more concentrated. Attached Figure Description

[0021] The accompanying drawings are provided to further understand the invention and constitute a part of this invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0022] Figure 1 is a schematic diagram of the structure of the existing complexed iron self-circulating reactor and the flow direction of the desulfurization liquid. Detailed Implementation

[0023] The present invention will be further explained in detail below with reference to the accompanying drawings:

[0024] A compound sulfur particle size regulator is composed of an aqueous solution of polyoxyethylene ether surfactants, low-carbon alcohol wetting agents, organic polymer flocculants, and oligosaccharides.

[0025] The polyoxyethylene ether surfactant is any one or two of isotridecyl alcohol polyoxyethylene ether, isodecyl alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and dodecylphenol polyoxyethylene ether, and the mass concentration added to water is 10-15 g / L.

[0026] The low-carbon alcohol wetting agent is any one or two of n-octanol, isopropanol, propylene glycol and glycerin, and the mass concentration added to water is 3 to 10 g / L.

[0027] The organic polymeric flocculant is any one or two of polyvinylpyrrolidone, polyacrylamide, and sodium polystyrene sulfonate, and the mass concentration added to the water is 4-6 g / L.

[0028] Oligosaccharides are any one or two of pentoses, hexoses and sucroses, and the mass concentration added to water is 8-12 g / L.

[0029] A method for preparing a compound sulfur particle size regulator is as follows: the above-mentioned polyoxyethylene ether surfactant, low carbon alcohol wetting agent, organic polymer flocculant and oligosaccharide are added to an aqueous solution and stirred until the solid is completely dissolved. The resulting sulfur particle size regulator should be a slightly yellow transparent solution.

[0030] An application of a compound sulfur particle size modifier in a complexed iron self-circulating sulfur recovery process involves directly adding the compound sulfur particle size modifier to the desulfurization liquid within the complexed iron self-circulating reactor, as shown in Figure 1. Self-circulation ensures the compound sulfur particle size modifier is uniformly dispersed in the desulfurization liquid of the complexed iron self-circulating sulfur recovery process. The optimal pH for use of this compound sulfur particle size modifier is 8–8.9, and the addition amount is 10–30 ppm.

[0031] Example 1

[0032] Dissolve 10 g / L of isotridecyl alcohol polyoxyethylene ether, 5 g / L of isopropanol, 6 g / L of polyacrylamide and 8 g / L of hexose in water and stir until the solid is completely dissolved to obtain a compound sulfur particle size regulator.

[0033] The aforementioned compound sulfur particle size modifier was added to a self-made complexed iron solution with an iron ion concentration of 1500 ppm and a complexing agent concentration of 1000 ppm, and the pH was adjusted to 8. The compound sulfur particle size modifier was added at a concentration of 10 ppm. Experiments were conducted on a complexed iron desulfurization and regeneration experimental device. After hydrogen sulfide was introduced for a period of time, sulfur particles were formed. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0034] Example 2

[0035] Dissolve 5 g / L of nonylphenol polyoxyethylene ether, 10 g / L of isomeric decayl alcohol polyoxyethylene ether, 10 g / L of n-octanol, 4 g / L of polyacrylamide, and 10 g / L of hexose in water and stir until the solid is completely dissolved to obtain a compound sulfur particle size regulator.

[0036] The aforementioned compound sulfur particle size modifier was added to a self-made complexed iron solution, with an iron ion concentration of 1500 ppm and a complexing agent concentration of 1000 ppm. The pH of the solution was adjusted to 8.5. The sulfur particle size modifier concentration was 20 ppm. Experiments were conducted on a complexed iron desulfurization and regeneration experimental device. After hydrogen sulfide was introduced for a period of time, sulfur particles were formed. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0037] Example 3

[0038] Dissolve 15 g / L of isomeric decayl alcohol polyoxyethylene ether, 5 g / L of isopropanol, 3 g / L of glycerol, 2 g / L of polyvinylpyrrolidone, 4 g / L of polyacrylamide, and 12 g / L of sucrose in water and stir until the solid is completely dissolved to obtain a compound sulfur particle size regulator.

[0039] The aforementioned compound sulfur particle size modifier was added to a self-made complexed iron solution, with an iron ion concentration of 1500 ppm and a complexing agent concentration of 1000 ppm. The pH was adjusted to 8.9. The sulfur particle size modifier concentration was 15 ppm. Experiments were conducted on a complexed iron desulfurization and regeneration experimental device. After hydrogen sulfide was introduced for a period of time, sulfur particles were formed. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0040] Example 4

[0041] Dissolve 10 g / L dodecylphenol polyoxyethylene ether, 3 g / L n-octanol, 5 g / L sodium polystyrene sulfonate, 5 g / L pentose, and 6 g / L sucrose in water and stir until the solid is completely dissolved to obtain a compound sulfur particle size regulator.

[0042] The aforementioned compound sulfur particle size modifier was added to a self-made complexed iron solution, with an iron ion concentration of 1500 ppm and a complexing agent concentration of 1000 ppm. The pH was adjusted to 8.3. The sulfur particle size modifier concentration was 30 ppm. Experiments were conducted on a complexed iron desulfurization and regeneration experimental device. After hydrogen sulfide was introduced for a period of time, sulfur particles were formed. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0043] Example 5

[0044] Add 12 g / L of isotridecyl alcohol polyoxyethylene ether, 3 g / L of isopropanol, 5 g / L of sodium polystyrene sulfonate, and 12 g / L of sucrose to water and stir until completely dissolved to obtain a compound sulfur particle size regulator.

[0045] The aforementioned compound sulfur particle size modifier was added to a complexed iron self-circulating reactor in a natural gas purification plant. The iron ion concentration in the complexed iron solution was approximately 450 ppm, the complexing agent concentration was 300 ppm, and the pH of the complexed iron solution was 8.3. The compound sulfur particle size modifier was added at a rate of 7.4 L / h, and the concentration of the sulfur particle size modifier in the complexed iron solution was approximately 10 ppm. The sulfur particle size of the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0046] Example 6

[0047] Add 10 g / L of dodecylphenol polyoxyethylene ether, 8 g / L of isopropanol, 5 g / L of sodium polystyrene sulfonate, and 10 g / L of sucrose to water and stir until completely dissolved to obtain a compound sulfur particle size regulator.

[0048] The aforementioned compound sulfur particle size modifier was added to a complexed iron self-circulating reactor in a natural gas purification plant. The iron ion concentration in the complexed iron solution was approximately 450 ppm, the complexing agent concentration was 300 ppm, and the pH of the complexed iron solution was 8.2. The compound sulfur particle size modifier was added at a rate of 18.5 L / h, and the concentration of the compound sulfur particle size modifier in the complexed iron solution was approximately 25 ppm. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0049] Example 7

[0050] Add 5 g / L of isomeric decayl alcohol polyoxyethylene ether, 8 g / L of nonylphenol polyoxyethylene ether, 5 g / L of n-octanol, 3 g / L of propylene glycol, 5 g / L of polyvinylpyrrolidone, 6 g / L of pentose, and 5 g / L of hexose to water and stir until the solids are completely dissolved to obtain a compound sulfur particle size regulator.

[0051] The aforementioned compound sulfur particle size modifier was added to a complexed iron self-circulating reactor in a natural gas purification plant. The iron ion concentration in the complexed iron solution was approximately 550 ppm, the complexing agent concentration was 600 ppm, and the pH of the complexed iron solution was 8.4. The compound sulfur particle size modifier was added at a rate of 21.5 L / h, and the concentration of the compound sulfur particle size modifier in the complexed iron solution was approximately 25 ppm. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0052] Comparative Example 1

[0053] The iron ion concentration in the complexed iron solution was 1500 ppm, and the complexing agent concentration was 1000 ppm. A commercially available surfactant, 1, was used as the sulfur particle size modifier at a concentration of 20 ppm. Experiments were conducted on a complexed iron desulfurization and regeneration experimental device. After hydrogen sulfide was introduced for a period of time, sulfur particles were formed. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0054] Comparative Example 2

[0055] The iron ion concentration in the complexed iron solution was 1500 ppm, and the complexing agent concentration was 1000 ppm. A commercially available surfactant, 2, was used as the sulfur particle size modifier at a concentration of 30 ppm. Experiments were conducted on a complexed iron desulfurization and regeneration experimental device. After hydrogen sulfide was introduced for a period of time, sulfur particles were formed. The sulfur particle size in the complexed iron solution was obtained using a laser particle size analyzer, as shown in Table 1.

[0056] The sulfur particle size distribution of Examples 1-7 and Comparative Examples 1-2 is shown in Table 1:

[0057] Table 1. Statistical table of sulfur particle size distribution in Examples 1-7 and Comparative Examples 1-2

[0058]

[0059]

[0060] As shown in Table 1, the compound sulfur particle size regulators for desulfurization liquid in the self-circulating complexing iron-sulfur recovery process provided in Examples 1-4 of the present invention can significantly improve the particle size distribution of sulfur particles, making the particle size distribution of sulfur particles more concentrated. Comparing Examples 1-4 with Comparative Examples 1-2, the compound sulfur particle size regulators for desulfurization liquid in the complexing iron process provided by the present invention can make more than 80% of sulfur particles distributed between 23 and 148 μm, while Comparative Example 1 has more than 80% of the particles distributed between 6 and 230 μm, and Comparative Example 2 has more than 80% of the particles distributed between 15 and 197 μm. The compound sulfur particle size regulators provided by the present invention significantly improve the particle size distribution of sulfur particles, making the sulfur particle size distribution more concentrated and reducing the distribution of sulfur particles in excessively large or small particle size ranges. In conjunction with Examples 5-7, the deposition of sulfur on the bottom plate of the reactor was significantly alleviated. The compound sulfur particle size regulator can adjust the particle size of sulfur particles, making the sulfur particle size distribution more concentrated.

[0061] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit its scope of protection. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that after reading the present invention, they can still make various changes, modifications or equivalent substitutions to the specific implementation of the invention, but these changes, modifications or equivalent substitutions are all within the scope of protection of the pending claims of the invention.

Claims

1. A method for preparing a compound sulfur particle size modifier, characterized in that, A compound sulfur particle size regulator is obtained by adding polyoxyethylene ether surfactants, low-carbon alcohol wetting agents, organic polymeric flocculants, and oligosaccharides to water and stirring until completely dissolved. The polyoxyethylene ether surfactants are any one or two of isotridecyl alcohol polyoxyethylene ether, isodecyl alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and dodecylphenol polyoxyethylene ether; the mass concentration of the polyoxyethylene ether surfactants in water is 10–15 g / L. The low-carbon alcohol wetting agents are any one or two of n-octanol, isopropanol, propylene glycol, and glycerol; the mass concentration of the low-carbon alcohol wetting agents in water is 3–10 g / L. The organic polymeric flocculants are any one or two of polyvinylpyrrolidone, polyacrylamide, and sodium polystyrene sulfonate; the mass concentration of the organic polymeric flocculants in water is 4–6 g / L. The oligosaccharides are any one or two of pentose, hexose, and sucrose; the mass concentration of the oligosaccharides in water is 8–12 g / L.

2. A compound sulfur particle size regulator, characterized in that, It was prepared using the preparation method described in claim 1.

3. The application of a compound sulfur particle size modifier in a complexed iron self-circulating sulfur recovery process, characterized in that, The compound sulfur particle size regulator of claim 2 is added to the desulfurization liquid in the complexed iron self-circulating reactor. The compound sulfur particle size regulator is uniformly dispersed in the desulfurization liquid of the complexed iron self-circulating sulfur recovery process by utilizing self-circulation. The pH of the compound sulfur particle size regulator is 8 to 8.9, and the amount of compound sulfur particle size regulator added is 10 to 30 ppm.

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