Desulfurizer for high-sulfur liquefied gas and method of making and using same

Abstract

The present application relates to liquefied gas desulfurization technical field, it is a kind of high sulfur-containing liquefied gas desulfurizer and its preparation and use method, the raw material of the high sulfur-containing liquefied gas desulfurizer includes sulfone compound 1% to 10%, antioxidant 0.5% to 2%, emulsifier 0.001% to 0.02%, water-soluble base 0.01% to 10%, organic ester 1% to 10%, the balance is water according to mass fraction.The high sulfur-containing liquefied gas desulfurizer and its preparation and use method provided by the present application, desulfurizer raw material is conventional, easy to obtain, preparation process is simple, removal effect is good, energy consumption is low, easy to realize industrial production.The desulfurization method using the desulfurizer, operation method is simple, energy consumption is small, does not produce three wastes, and economic efficiency is good.

Description

Technical Field

[0001] This invention relates to the field of desulfurization technology for liquefied petroleum gas (LPG), specifically a desulfurizing agent for high-sulfur LPG and its preparation and application methods. Background Technology

[0002] Liquefied petroleum gas (LPG) desulfurization is a process that removes sulfur-containing gases from LPG through solvent dissolution and reaction. The main components of desulfurizing agents are not a single type of compound, but rather a variety of compounds with different compositions, molecular structures, and performance characteristics, comprising several solvent components. It not only possesses excellent performance in removing organic sulfur, but also has long regeneration and service life. Under certain harsh conditions, desulfurizing agents can meet the requirements of refineries using LPG with high concentrations of sulfur-containing gases; secondly, they are required to be able to be stored or used at low temperatures (<35℃) without freezing; the increasingly stringent environmental protection requirements worldwide have also spurred continuous research and development of such additives. Furthermore, the increasing demands for stable operation of upstream and downstream units in refineries and the need to process high-sulfur crude oil have also led to an increase in the application of high-performance desulfurization additives. LPG desulfurization additives (referred to as desulfurizers) should exhibit significant stability and substitutability in the existing Mirox process system, thus becoming an important area of ​​research and development both domestically and internationally. The main components of these desulfurization aids generally include organic amines, alcohols, and inorganic bases, among which organic amine components are the most widely studied and used.

[0003] Liquefied gas desulfurization aids are among the earliest developed and applied types of blended gas desulfurizers, exhibiting good desulfurization performance. Currently, the world's gas desulfurizer systems are mainly divided into two categories: sulfonated titanium cobalt cyanide and composite organic amines. Sulfonated titanium cobalt cyanide organic desulfurizers currently face numerous environmental problems, such as the difficulty in treating wastewater, and many domestic refineries are gradually phasing out this method. In contrast, the wastewater from composite organic amine organic sulfur removal agents after adsorbing sulfur-containing gases is not only easily regenerated and reused, but the small amount of amine substances carried to downstream units can be degraded and treated by hydrogenation units.

[0004] With the methods and related processes for deep C4 desulfurization in refineries becoming relatively mature, desulfurization technologies are continuously developing. Hydrogenation reactions can cause olefin saturation in the C4 fraction, reducing its utilization value; therefore, hydrogenation is not suitable for removing organic sulfur from the C4 fraction. Industrially, adsorption and absorption methods are mainly used.

[0005] Adsorption method: Commonly used adsorbents for this method include molecular sieves, activated carbon, modified activated carbon fibers, and metal oxide compounds.

[0006] Molecular sieves, after treatment, can adsorb and remove organic sulfur from C4 hydrocarbons; this method is widely used abroad. Combining molecular sieves with activated carbon, silica gel, and activated alumina can effectively remove not only organic sulfur from C4 hydrocarbons but also water, inorganic sulfur, and other impurities. Wlidt Thomas et al. proposed a cation-modified molecular sieve, which can only handle low-sulfur feed gases with relatively small sulfur content. Jieun Lee et al. used Ag(I) and Cu(I) ion-exchange zeolites to remove DMDS (dimethyl disulfide) from C4 hydrocarbon mixtures. The adsorption capacity of Ag(I)-exchanged β-zeolite was 7.06 mg / g, and that of Cu(I)-exchanged β-zeolite was 8.7 mg / g. Molecular sieve desulfurization does not require pre-alkali washing, can be performed at room temperature, and has minimal environmental impact. However, its disadvantages include high regeneration temperatures, high regeneration gas treatment costs, and large initial investment in the equipment, thus limiting its application.

[0007] Activated carbon itself has the ability to adsorb organic sulfur. Zhang Jinchang et al. obtained type 3018 modified activated carbon using carbonates and other active components, which showed a very high COS conversion efficiency. Therefore, altering the surface chemical environment of activated carbon fibers is an effective method to increase the sulfur content of activated carbon fibers. Organic sulfur mainly adsorbs onto activated carbon fibers (ACFs), but adsorption, as a means, only transfers organic sulfur to the adsorbent; it does not truly eliminate it. This can easily cause secondary pollution during post-treatment processes.

[0008] Zinc oxide (ZnO) is recognized worldwide as the most precise desulfurizing agent. Furthermore, ZnO is frequently used as a follow-up desulfurizing agent in reduction and hydrolysis methods. When ZnO is used for desulfurization and purification of raw gas, organic sulfur can not only be adsorbed into the internal cavities and on the surface of ZnO solid particles, but can also penetrate into the interior of the crystals to react. Although ZnO has a good desulfurization effect, it generally requires high temperatures and is not easily regenerated, which increases equipment investment and operating costs. At the same time, the high price of ZnO is also a major factor restricting its widespread application.

[0009] Absorption methods: Absorption methods mainly include chemical absorption, physical absorption, and physicochemical absorption. Chemical absorption removes organic sulfur mainly by utilizing the chemical reaction between the solvent and organic sulfur; physical absorption removes organic sulfur based on the different solubilities of organic sulfur in solution under different conditions; physicochemical absorption combines the advantages of the above two methods.

[0010] Chemical absorption method: This method utilizes a reversible chemical reaction to complete the desulfurization and solvent regeneration process. This method is suitable for C4 desulfurization in refineries with low partial pressure of acidic gases, especially high CO2 content and low H2S content. However, it is not particularly suitable for removing organic sulfur from C4, for example, a 20% aqueous solution of MDEA (methyldiethanolamine) has a removal rate of less than 40% for organic sulfur, and it is difficult to regenerate. Among chemical absorption methods, the organic amine absorption method is the most representative.

[0011] Commonly used chemical solvents are various alkanolamine solutions, which can remove components of sulfides with significant acidity, but are less effective for neutral organic sulfur compounds. Organic amine absorption methods suffer from a series of problems, including low acid gas load under low-temperature conditions, large solution circulation volume, high energy consumption, easy degradation and corrosion, and a strong tendency for solution foaming. Alkyl alcoholamines are basic organic amine compounds that can be used to treat refinery gases containing both H2S and COS, but their COS removal rate is not high. Using conventional alkanolamine solutions for refinery C4 desulfurization and purification is generally only an initial treatment; subsequent treatments are required to ensure that the total sulfur content of the purified gas does not exceed the standard. If the desulfurization effect is unsatisfactory at any stage, sulfides will affect catalyst activity. The selefining method can significantly reduce the circulation volume of the absorbent solution and is suitable for feed gases with higher H2S content. The disadvantage of this method is that hydrocarbon co-absorption is significant, and it cannot completely remove organic sulfur compounds.

[0012] Currently, most of the liquefied petroleum gas (LPG) used by domestic refineries to produce polypropylene is obtained by removing hydrogen sulfide and organic sulfur from catalytic cracking gas and then cryogenically concentrating it. LPG produced from refinery coking units also contains a large amount of propylene gas, but due to the complex composition of coking LPG and its high content of organic sulfur, especially carbonyl sulfur, domestic refineries rarely use it for propylene production. If catalytic cracking gas is mixed with coking LPG, the concentration of organic sulfur gas in the LPG can reach 1000 mg / m³. 3 Up to 2000 mg / m 3 Even more so, it is difficult for general desulfurization aids to remove sulfides from these two gas mixtures to the concentration range suitable for polypropylene production.

[0013] Because the catalyst system in downstream polypropylene plants using liquefied petroleum gas (LPG) has very strict requirements regarding the organic sulfur content in the LPG, the LPG and its sulfur-containing gases, after cryogenic treatment, will be concentrated into the propylene at a concentration 3 to 5 times higher. High concentrations of propylene gas will significantly reduce the production capacity of the polypropylene plant and waste expensive polypropylene catalysts. In extreme cases, it can even cause the polypropylene plant to become completely viscous, resulting in substantial losses. Therefore, the ability to produce high-quality LPG with low organic sulfur content has become a key focus for research institutions and manufacturing companies.

[0014] Blended organic amine desulfurizers are usually products obtained by blending various inorganic bases, organic amines, alcohols, esters, water, and sulfone compounds at a certain temperature. Organic amine components can be divided into monoamines, polyenes and polyamines, and specifically synthesized amines. The main mechanisms of desulfurization reaction are: (1) dissolution of organic sulfur in water, such as the dissolution of carbonyl sulfur in water. (2) hydrolysis of carbonyl sulfur in water under the catalysis of organic amines and inorganic bases.

[0015] Studies have shown that amines and inorganic bases have good hydrolysis effects on most hydrogen sulfide and large molecular organic sulfur, while the hydrolysis of carbonyl sulfide is more difficult. Factors such as hydrolysis efficiency and auxiliary agent cost must be considered comprehensively. Inorganic bases, organic bases, and esters each have different desulfurization advantages. When desulfurization reactions use desulfurizing agents (such as organic amines and esters), the formation of organic sulfur into thiols, sodium sulfides, and thioesters is accelerated and promoted under the action of trace amounts of organic antioxidants and other catalysts. The adsorbed compounds contain a certain amount of sulfur, transforming the organic sulfur in liquefied petroleum gas into inorganic sulfur, small-molecule water-soluble sulfides, and large-molecule oil-soluble organic sulfur. The first two types of sulfur can usually be removed by water washing, alkali washing, or a combination thereof. Large-molecule organic sulfur is easily hydrolyzed in the desulfurizing agent system and is therefore easier to remove. The challenge lies in the compounding of various amines, esters, alcohols, and sulfones to effectively remove carbonyl sulfide.

[0016] Chinese patent document CN111701411A discloses a syngas desulfurizing agent, its preparation method, and its application. The syngas desulfurizing agent of this invention is prepared by modifying a conventional zinc oxide desulfurizing agent with metal oxides and non-metal oxides. The resulting desulfurizing agent has good structural stability and still has a high ability to remove sulfides under high water vapor partial pressure and high temperature oxidation conditions. The above-mentioned syngas desulfurizing agent is a solid desulfurizing agent for removing hydrogen sulfide and organic sulfur from syngas that is suitable for fluidized bed high temperature desulfurization processes. It can remove hydrogen sulfide and organic sulfur from syngas and save energy and reduce consumption. However, this invention is not applicable to the desulfurization of high sulfur content liquefied gas.

[0017] Chinese patent document CN107754582A discloses a method for desulfurizing dry gas and liquefied petroleum gas (LPG). The sulfur-containing dry gas, at 40°C and 1.3 MPa, enters a dry gas separator to remove carried droplets and mechanical impurities. It then enters the lower part of a dry gas desulfurization tower, where it comes into countercurrent contact with lean amine solution pumped into the tower by an amine circulation pump. The H2S in the dry gas is absorbed by the lean amine solution. The desulfurized dry gas then passes through a gravity settling section and a wire mesh demister within the tower to remove carried solvents. It then enters a settling tank for further settling and solvent separation. After passing through a pressure regulating valve, it goes to a hydrogen enrichment device. The dry gas after the hydrogen enrichment device then enters the plant's high-pressure gas system. This process can effectively remove inorganic sulfur components from dry gas and LPG, yielding high-purity dry gas and LPG. However, this invention is not applicable to the desulfurization of high-sulfur LPG.

[0018] Chinese patent document CN107029537A discloses a complexed iron desulfurizing agent for desulfurization of liquefied petroleum gas (LPG). The complexed iron desulfurizing agent comprises a water-soluble ferrous salt, an inorganic alkali, a water-soluble manganese salt, an organic complexing agent, and water. The iron ion content is 0.5 wt% to 6 wt% by weight. The molar ratio of metal ions to iron ions in the inorganic alkali is 0.8 to 1.2, the molar ratio of manganese ions to iron ions is 0.01 to 0.1, and the molar ratio of the organic complexing agent to the sum of the molar numbers of manganese and iron ions is 1.2 to 3.0. The complexed iron desulfurizing agent also includes piperazine and an organic solvent. The piperazine content in the mixture is 1 wt% to 5 wt%, and the organic solvent content is 1 wt% to 10 wt%. However, this invention is not applicable to the desulfurization of high-sulfur LPG.

[0019] Chinese patent document CN108084980A discloses a high-efficiency sulfur dissolving agent and its preparation method. The sulfur dissolving agent is composed of the following components in the indicated mass percentages: 15% to 20% primary amines, 75% to 80% dimethyl sulfoxide, 0.5% to 1.5% polyethylenepolyamine, and 5% to 10% Lewis base. The preparation method of this high-efficiency sulfur dissolving agent includes: adding a primary amine solvent and dimethyl sulfoxide to a reaction vessel at room temperature and pressure, and stirring thoroughly until homogeneous; then adding polyethylenepolyamine and stirring thoroughly until homogeneous; finally adding a Lewis base and stirring thoroughly until homogeneous to obtain the high-efficiency sulfur dissolving agent. Under room temperature conditions, the sulfur solubility can reach over 90%. This invention is applicable to natural gas desulfurization, but not to the desulfurization of high-sulfur liquefied petroleum gas in refineries.

[0020] Chinese patent document CN106978208A discloses a method for desulfurizing light hydrocarbons. This method is implemented in a system including an alkali washing unit. The method includes: introducing an alkali solution from the dispersed phase inlet of a two-phase mixing reactor into the reactor shell side; the alkali solution then enters a mixing channel through distribution holes to contact the light hydrocarbons introduced into the mixing channel sequentially through the reactor inlet and the mixing channel inlet; the flow direction of the alkali solution in the reactor shell side is opposite to its flow direction in the mixing channel; the mixture formed after the alkali solution contacts the light hydrocarbons is sequentially led out of the two-phase mixing reactor through the mixing channel outlet and the reactor outlet. In this invention, by using a two-phase mixing reactor, high-speed flow and vigorous mixing of sulfur-containing light hydrocarbons and alkali solution are achieved in the mixing channel, resulting in low mass transfer resistance. This allows for sufficient reaction between the acidic sulfur-containing substances in the sulfur-containing light hydrocarbons and the alkali solution, achieving deep desulfurization of the sulfur-containing light hydrocarbons, with an acidic sulfur-containing substance removal rate greater than 90%. This invention can be applied to natural gas desulfurization but is not suitable for desulfurization of high-sulfur liquefied petroleum gas (LPG) in refineries.

[0021] The SSH-1 desulfurizer described in Zhang Haifeng et al.'s article "Application of High-Efficiency Desulfurizer in Liquefied Petroleum Gas Desulfurization and Purification" (Chemical Engineering Design Communications) is mainly designed to meet the sulfur content requirements of civil liquefied petroleum gas standards. In the desulfurization and purification process of catalytic cracking liquefied petroleum gas, the high-efficiency desulfurizer was used to investigate its removal efficiency of sulfur compounds from the liquefied petroleum gas. The trial results showed that the hydrogen sulfide content in the desulfurized liquefied petroleum gas was 0.12 mg / m³. 3 The total sulfur content is 59.41 mg / m³. 3 The total organic sulfur removal rate is above 64%. Therefore, the SSH-1 desulfurizer described in this literature is only suitable for removing catalytic cracking liquefied gas at low concentrations and cannot be used for desulfurization of high-sulfur liquefied gas from refineries as described in this invention.

[0022] The paper "Research on High-Efficiency Purification Technology of High-Acidity Petroleum and Natural Gas—Development and Desulfurization Effect of UDS High-Efficiency Desulfurization Solvent" (8th National Conference on Oil and Gas Storage and Transportation of Universities) by Shen Benxian et al. introduces the design and development of UDS high-efficiency desulfurization solvent. Sulfur-containing heterocyclic compounds and cyclic amine compounds significantly improve the removal performance of UDS solvent for COS and thiols. Simulation and pilot-scale test results show that UDS solvent not only has good removal performance for high-content H2S, but also excellent organic sulfur removal performance, with a COS removal rate significantly higher than that of MDEA solvent. However, the UDS absorbent described in this paper is only suitable for removing low-concentration dry gas and liquefied petroleum gas, and cannot be used for the desulfurization of high-sulfur liquefied petroleum gas in refineries as described in this invention.

[0023] The paper "Preparation and Performance Study of Triazine Liquid Desulfurizer" by Tan Fuyuan et al. (Shandong Chemical Industry) introduces the desulfurization principle of triazine liquid desulfurizer. A triazine liquid desulfurizer was synthesized using formaldehyde and ethanolamine. The effects of process conditions such as H2S concentration, operating temperature, CO2 content, and pH value on the performance of the desulfurizer were investigated, providing methodological and technical support for the removal of H2S from natural gas. The triazine liquid desulfurizer described in this paper is only suitable for removing H2S from liquefied petroleum gas (LPG) and cannot be used for desulfurization of high-sulfur LPG in refineries.

[0024] In summary, the desulfurizing agents and methods described in the above patents and documents cannot meet the desulfurization requirements of refineries for high-concentration sulfur-containing liquefied petroleum gas, especially the desulfurization process requirements for high-concentration carbonyl organic sulfur. Summary of the Invention

[0025] This invention provides a desulfurizing agent for high-sulfur liquefied petroleum gas (LPG), overcoming the shortcomings of the prior art. It can effectively solve the problems that conventional desulfurization hydrogen sulfide removal, desulfurization alkaline washing, or their combinations cannot effectively reduce the sulfur content of high-sulfur LPG produced during crude oil processing in refineries, and that organic carbonyl sulfur in high-sulfur LPG is difficult to remove.

[0026] One of the technical solutions of the present invention is achieved by the following measures: a desulfurizing agent for high sulfur content liquefied gas, wherein the raw materials include, by mass percentage, 1% to 10% sulfone compounds, 0.5% to 2% antioxidants, 0.001% to 0.02% emulsifiers, 0.01% to 10% water-soluble alkalis, 1% to 10% organic esters, and the balance being water.

[0027] The following are further optimizations and / or improvements to one of the above-mentioned technical solutions:

[0028] The aforementioned sulfone compounds are one or more of dimethyl sulfoxide, dimethyl sulfone, and sulfolane.

[0029] The antioxidants mentioned above are one or more of antioxidant 168, antioxidant 1010, and antioxidant 1076.

[0030] The emulsifier mentioned above is one or more of OP-5, OP-7, OP-10, Tween 40, Tween 60, Tween 80, JFC penetrant, and ethylene glycol monobutyl ether emulsifier.

[0031] The water-soluble base mentioned above is one or more of sodium hydroxide, potassium hydroxide, ethylenediamine, diethanolamine, triethanolamine, diethylenetriamine, and triethylenetetramine.

[0032] The aforementioned organic esters are one or more of dioctyl phthalate (DOP), dibutyl phthalate (DBP), and dioctyl sebacate (DOS).

[0033] The above-mentioned desulfurizing agent for high-sulfur liquefied petroleum gas is prepared according to the following steps: after stirring and mixing the required amount of sulfone compound, water-soluble alkali and water at 20°C to 30°C, the required amount of antioxidant, emulsifier and organic ester are added, and the mixture is stirred for 30 min to 60 min to obtain the desulfurizing agent for high-sulfur liquefied petroleum gas.

[0034] The second technical solution of the present invention is achieved through the following measures: a method for preparing a desulfurizing agent for high sulfur content liquefied gas, comprising the following steps: mixing the required amount of sulfone compound, water-soluble alkali and water at 20°C to 30°C until uniform, then adding the required amount of antioxidant, emulsifier and organic ester, and stirring for 30 min to 60 min to obtain the desulfurizing agent for high sulfur content liquefied gas.

[0035] The third technical solution of the present invention is achieved through the following measures: a method for using a desulfurizing agent for high-sulfur liquefied petroleum gas, comprising the following steps: mixing the desulfurizing agent for high-sulfur liquefied petroleum gas with a sodium hydroxide solution to obtain a desulfurization solution; adding the desulfurization solution to a desulfurization reactor; maintaining the temperature of the desulfurization solution at 20°C to 60°C; introducing high-sulfur liquefied petroleum gas into the desulfurization reactor; and stirring at a speed of 500 r / min to 1000 r / min for 10 min to 60 min to carry out the reaction and desulfurization; wherein the mass percentage of the desulfurizing agent for high-sulfur liquefied petroleum gas in the desulfurization solution is 15% to 20%.

[0036] The following are further optimizations and / or improvements to the third technical solution of the above invention:

[0037] The aforementioned desulfurization reactor is one of the following: a batch reactor, a packed absorber reactor, or a gravity reactor.

[0038] The aforementioned high-sulfur liquefied petroleum gas was produced by a refinery with a sulfur content of 20 mg / m³. 3 Up to 3000 mg / m 3 liquefied gas.

[0039] The present invention provides a desulfurizing agent for high-sulfur liquefied petroleum gas, as well as its preparation and application methods. The raw materials for the desulfurizing agent are conventional and readily available, the preparation process is simple, the desulfurization effect is good, the energy consumption is low, and it is easy to realize industrial production. The desulfurization method using this desulfurizing agent is simple to operate, consumes little energy, does not generate waste, and is economical. Attached Figure Description

[0040] Appendix Figure 1 This is a schematic diagram of the process flow for the desulfurization of high-sulfur liquefied petroleum gas in a batch reactor in Embodiment 11 of the present invention.

[0041] Appendix Figure 2 This is a schematic diagram of the process flow for the desulfurization of high-sulfur liquefied petroleum gas in a packed absorption tower reactor in Embodiment 20 of the present invention.

[0042] Appendix Figure 3 This is a schematic diagram of the process flow for the desulfurization of high-sulfur liquefied petroleum gas in a supergravity reactor in Embodiment 32 of the present invention. Detailed Implementation

[0043] This invention is not limited to the following embodiments, and specific implementation methods can be determined according to the technical solutions and actual conditions of this invention. Unless otherwise specified, all chemical reagents and chemicals mentioned in this invention are well-known and commonly used chemical reagents and chemicals in the prior art; unless otherwise specified, all percentages in this invention are mass percentages; unless otherwise specified, all solutions in this invention are aqueous solutions with water as the solvent, for example, hydrochloric acid solution is an aqueous solution of hydrochloric acid; room temperature in this invention generally refers to a temperature between 15°C and 25°C, generally defined as 25°C.

[0044] The present invention will be further described below with reference to embodiments:

[0045] Example 1: The desulfurizing agent for high sulfur content liquefied petroleum gas contains, by mass percentage, 1% to 10% sulfone compounds, 0.5% to 2% antioxidants, 0.001% to 0.02% emulsifiers, 0.01% to 20% water-soluble alkalis, 1% to 10% organic esters, and the balance being water.

[0046] Example 2: The desulfurizing agent for high sulfur content liquefied petroleum gas contains, by mass percentage, 1% or 10% sulfone compounds, 0.5% or 2% antioxidants, 0.001% or 0.02% emulsifiers, 0.01% or 20% water-soluble alkalis, 1% or 10% organic esters, with the balance being water.

[0047] Example 3: As an optimization of the above examples, the sulfone compound is one or more of dimethyl sulfoxide, dimethyl sulfone, and sulfolane.

[0048] Example 4: As an optimization of the above example, the antioxidant is one or more of antioxidant 168, antioxidant 1010, and antioxidant 1076.

[0049] Example 5: As an optimization of the above examples, the emulsifier is one or more of OP-5 (polyethylene glycol nonylphenyl ether), OP-7, OP-10, Tween 40, Tween 60, Tween 80, JFC penetrant, and ethylene glycol monobutyl ether emulsifier.

[0050] Example 6: As an optimization of the above examples, the water-soluble base is one or more of sodium hydroxide, potassium hydroxide, ethylenediamine, diethanolamine, triethanolamine, diethylenetriamine, and triethylenetetramine.

[0051] Example 7: As an optimization of the above examples, the organic ester is one or more of dioctyl phthalate (DOP), dibutyl phthalate (DBP), and dioctyl sebacate (DOS).

[0052] Example 8: The desulfurizing agent for high sulfur content liquefied petroleum gas is prepared according to the following steps: the required amount of sulfone compound, water-soluble alkali and water are stirred and mixed evenly at 20°C to 30°C, and then the required amount of antioxidant, emulsifier and organic ester are added, and stirred for 30 min to 60 min to obtain the desulfurizing agent for high sulfur content liquefied petroleum gas.

[0053] Example 9: The method of using the desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) is as follows: The desulfurizing agent for high-sulfur LPG is mixed with a sodium hydroxide solution to obtain a desulfurization solution. This solution is then added to a desulfurization reactor, maintaining the temperature at 20°C to 60°C. High-sulfur LPG is then introduced into the reactor, and the mixture is stirred at 500 rpm to 1000 rpm for 10 to 60 minutes to carry out the desulfurization reaction. The mass percentage of the desulfurizing agent for high-sulfur LPG in the desulfurization solution is 15% to 20%. After treatment with the desulfurizing agent of this invention, the sulfur content of the high-sulfur LPG can reach less than 20 mg / m³. 3 The requirements are as follows: the concentration of the sodium hydroxide solution is 20wt% to 40wt%.

[0054] Example 10: As an optimization of Example 8 above, the desulfurization reactor is one of the following: a batch reactor, a packed absorber reactor, or a gravity reactor.

[0055] Example 11: As an optimization of Examples 8 and 9 above, the high-sulfur liquefied petroleum gas produced by the refinery has a sulfur content of 20 mg / m³. 3 Up to 3000 mg / m 3 liquefied gas.

[0056] This invention provides a desulfurizing agent for high-sulfur liquefied petroleum gas (LPG). Based on the sulfur composition of high-sulfur LPG in refineries, the chemical composition and structure of its main substances were clarified through infrared and mass spectrometry analysis. A corresponding desulfurization solvent formulation was designed, fundamentally solving the technical problem of desulfurization of high-sulfur LPG in refineries. By introducing the high-sulfur LPG into the desulfurizing agent of this invention under certain conditions in a reactor, and carrying out desulfurization according to the technical scheme, the purpose of effective desulfurization is ultimately achieved. Its mechanism of action is as follows: when the high-sulfur LPG reacts with the desulfurizing agent of this invention at a certain rate, the desulfurization solvent rapidly forms gas-encapsulated microspheres around the sulfur-containing LPG. Water-soluble alkalis, sulfones, and esters at the interface of the microspheres adsorb sulfur-containing double bonds in the organic sulfur molecules through polar adsorption. The water-soluble alkali in the microspheres, through its strong alkalinity, hydrolyzes and breaks the sulfur bonds in the aforementioned substances. The sulfur released after bond breakage forms sulfide anions, which are then absorbed by the alkali solution to form water-soluble salts. Simultaneously, inorganic sulfur in the liquefied petroleum gas is also neutralized into water-soluble salts. The antioxidant in the desulfurizing agent formulation of this invention can further hydrolyze organic carbonyl sulfur to form small-molecule water-soluble sulfate esters, ammonium sulfates, etc. At the same time, the antioxidant ensures that the desulfurizing agent is not easily oxidized and deteriorated during regeneration under oxygen-containing conditions, thereby preventing acidification and degradation.

[0057] Taking the water-soluble base triethanolamine as an example, the reaction mechanism of triethanolamine in hydrolyzing organic carbonyl sulfides containing S=O bonds into easily removable H2S is as follows:

[0058] COS + r3N + H2O → HCO2S - +r3NH + First step hydrolysis

[0059] HCO2S- + r3N + H2O → HCO3- - +r3NH + + HS - Control steps

[0060] COS + OH - → CO2+ HS - Inorganic hydrolysis reaction

[0061] The overall reaction is: COS + H2O → CO2 + H2S

[0062] In the presence of water, some organic carbonyl sulfides in the liquefied petroleum gas react with alcoholic amines to generate carbonyl sulfide anions. These anions then react with alcoholic amines to generate hydrosulfite ions, which are finally neutralized by NaOH to form water-soluble salts and removed, thus effectively desulfurizing the gas.

[0063] Example 12:

[0064] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfoxide, 0.5% type 168 antioxidant, 1% OP-10, 2% Tween-40, 0.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 5% diethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed thoroughly at 20°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0065] like Figure 1 As shown, a desulfurization solution is obtained by mixing a desulfurizing agent and a sodium hydroxide solution with high-sulfur liquefied petroleum gas (LPG). The desulfurization solution is then added to a batch reactor, and the temperature of the desulfurizing agent is maintained at 40°C. The organic sulfur content is 20 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. The reactor was stirred at 500 r / min for 20 min to perform one desulfurization operation. The overflowing LPG was collected and the sulfur content was measured to be 1.0 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 200g, and the dosage of desulfurizing solution is 1200g.

[0066] Example 13:

[0067] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 10% dimethyl sulfoxide, 2% type 1010 antioxidant, 1% OP-5, 2% Tween-60, 0.5% JFC penetrant, 0.02% ethylene glycol monobutyl ether emulsifier, 0.01% potassium hydroxide, 5% sodium hydroxide, 5% triethanolamine, 2% dibutyl phthalate (DBP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed thoroughly at 25°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 40 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0068] A desulfurization solution is obtained by mixing a desulfurizing agent and a sodium hydroxide solution with high-sulfur liquefied petroleum gas (LPG). This solution is then added to a batch reactor, maintaining the temperature of the desulfurizing agent at 40°C, to achieve a sulfur content of 1000 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. A single desulfurization process was performed with a stirring speed of 600 r / min for 20 min. The overflowing LPG was collected and its sulfur content was measured to be 4.55 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 200g, and the dosage of desulfurizing solution is 1200g.

[0069] Example 14:

[0070] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 5% dimethyl sulfone, 1% type 1076 antioxidant, 1% OP-5, 1% Tween-80, 1% JFC penetrant, 0.001% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 1% diethylenetriamine, 1% dioctyl sebacate (DOS), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed thoroughly at 20°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 40 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0071] A desulfurization solution is obtained by mixing a desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) with a sodium hydroxide solution. This solution is then added to a batch reactor, maintaining the temperature of the desulfurizing agent at 40°C, to achieve an organic sulfur content of 1500 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. The reactor was stirred at 800 r / min for 30 min to perform a single desulfurization operation. The overflowing LPG was collected and its sulfur content was measured to be 6.76 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 300g, and the dosage of desulfurizing solution is 1500g.

[0072] Example 15:

[0073] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfoxide, 0.5% sulfolane, 0.5% type 1010 antioxidant, 2.5% OP-10, 2% Tween-40, 1.5% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% triethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed thoroughly at 25°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 40 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0074] A desulfurization solution is obtained by mixing a desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) with a sodium hydroxide solution. This solution is then added to a batch reactor, maintaining the temperature of the desulfurizing agent at 20°C. The organic sulfur content is 3000 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min, and stirred at a speed of 500 r / min for 60 min to perform one desulfurization operation. The overflowing LPG was collected and the sulfur content was measured to be 16.22 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 200g, and the dosage of desulfurizing solution is 1000g.

[0075] Example 16:

[0076] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfone, 0.5% sulfolane, 0.5% type 168 antioxidant, 2.5% OP-7, 2% Tween-60, 1.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 10% diethylenetriamine, 2% dioctyl sebacate (DOS), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 40 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0077] A desulfurization solution is obtained by mixing a desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) with a sodium hydroxide solution. This solution is then added to a batch reactor, maintaining the temperature of the desulfurizing agent at 20°C and the sulfur content at 2500 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. The reactor was stirred at 800 r / min for 30 min to perform a single desulfurization operation. The overflowing LPG was collected and its sulfur content was measured to be 15.56 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 300g, and the dosage of desulfurizing solution is 1500g.

[0078] Example 17:

[0079] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfone, 0.5% sulfolane, 0.5% type 1010 antioxidant, 2.5% OP-10, 2% Tween-80, 1.5% JFC penetrant, 0.02% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% ethylenediamine, 10% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 40 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0080] A desulfurization solution is obtained by mixing a desulfurizing agent and sodium hydroxide solution with high-sulfur liquefied petroleum gas (LPG). This solution is then added to a batch reactor, maintaining the temperature of the desulfurizing agent at 20°C, to achieve an organic sulfur content of 2000 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. The reactor was stirred at 1000 r / min for 10 min to perform one desulfurization operation. The overflowing LPG was collected and its sulfur content was measured to be 12.39 mg / m³. 3The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 300g, and the dosage of desulfurizing solution is 1500g.

[0081] Example 18:

[0082] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfoxide, 0.6% sulfolane, 0.5% T501 antioxidant, 3% OP-10, 2.5% Tween-40, 2% Tween-80, 2% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 50 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0083] A desulfurization solution is obtained by mixing a desulfurizing agent and sodium hydroxide solution with high-sulfur liquefied petroleum gas (LPG). This solution is then added to a batch reactor, maintaining the temperature of the desulfurizing agent at 40°C, to achieve an organic sulfur content of 500 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. The reactor was stirred at 800 r / min for 10 min, and desulfurization was performed twice. The overflowing LPG was collected and the sulfur content was measured to be 8.58 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 400g, and the dosage of desulfurizing solution is 2000g.

[0084] Example 19:

[0085] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfone, 0.5% sulfolane, 0.5% type 1010 antioxidant, 3% OP-10, 1% Tween-60, 5% Tween-80, 1% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 10% triethylenetetramine, 1% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 50 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0086] A desulfurization solution is obtained by mixing a desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) with a sodium hydroxide solution. This solution is then added to a batch reactor, and the temperature of the desulfurizing agent for the high-sulfur LPG is maintained at 60°C. The organic sulfur content is 2000 mg / m³. 3Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. The reactor was stirred at 1000 r / min for 10 min, and desulfurization was performed twice. The overflowing LPG was collected and the sulfur content was measured to be 18.27 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 400g, and the dosage of desulfurizing solution is 2000g.

[0087] Example 20:

[0088] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfoxide, 0.5% sulfolane, 0.5% type 168 antioxidant, 3% OP-5, 2.5% Tween-60, 2% Tween-80, 2% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 25°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0089] A desulfurization solution is obtained by mixing a desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) with a sodium hydroxide solution. This solution is then added to a batch reactor, and the temperature of the desulfurizing agent for the high-sulfur LPG is maintained at 60°C. The organic sulfur content is 2000 mg / m³. 3 Liquefied petroleum gas (LPG) was introduced into a stirred tank reactor at a rate of 50 mL / min. The reactor was stirred at 800 r / min for 10 min, and desulfurization was performed twice. The overflowing LPG was collected and the sulfur content was measured to be 16.85 mg / m³. 3 The dosage of desulfurizing agent for high-sulfur liquefied petroleum gas is 400g, and the dosage of desulfurizing solution is 2000g.

[0090] Example 21:

[0091] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfoxide, 0.5% type 168 antioxidant, 1% OP-10, 2% Tween-40, 0.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 5% diethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0092] like Figure 2As shown, a desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate to 1 m³ / s. 3 / h, then the sulfur content is 1000mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 40°C at a rate of 100 mL / min, with the reflux ratio controlled at 1. The overflowing LPG was collected and its sulfur content was measured to be 8.74 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0093] Example 22:

[0094] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfoxide, 0.5% type 1076 antioxidant, 1% OP-10, 2% Tween-60, 0.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 5% ethylenediamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0095] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1.5 m³ / s. 3 / h, then the sulfur content is 1000mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 40°C at a rate of 120 mL / min, with the reflux ratio controlled at 1.2. The overflowing LPG was collected and its sulfur content was measured to be 10.97 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0096] Example 23:

[0097] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfoxide, 0.5% type 168 antioxidant, 1% OP-10, 2% Tween-40, 0.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed thoroughly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0098] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1.25 m³ / min. 3 / h, then the sulfur content is 1000mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 40°C at a rate of 110 mL / min, with the reflux ratio controlled at 1.1. The overflowing LPG was collected and its sulfur content was measured to be 11.65 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0099] Example 24:

[0100] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfone, 0.5% sulfolane, 0.5% type 168 antioxidant, 2.5% OP-7, 2% Tween-80, 1.5% JFC penetrant, 0.02% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% diethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0101] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1 m³ / s. 3 / h, then the sulfur content is 1500mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 60°C at a rate of 150 mL / min, with the reflux ratio controlled at 1. The overflowing LPG was collected and the sulfur content was measured to be 10.52 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0102] Example 25:

[0103] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfoxide, 0.6% sulfolane, 0.5% type 1010 antioxidant, 2.5% OP-10, 2% Tween-40, 1.5% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% triethanolamine, 2% dioctyl sebacate (DOS), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed thoroughly at 20°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0104] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1.5 m³ / s. 3 / h, then the sulfur content is 2000mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 20°C at a rate of 250 mL / min, with the reflux ratio controlled at 1.2. The overflowing LPG was collected and its sulfur content was measured to be 15.35 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0105] Example 26:

[0106] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfone, 0.6% sulfolane, 0.5% type 168 antioxidant, 2.5% OP-7, 2% Tween-80, 1.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% ethylenediamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0107] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1.25 m³ / min. 3 / h, then the sulfur content is 2000mg / m 3Liquefied petroleum gas (LPG) was introduced into the absorption system at 40°C at a rate of 200 mL / min, with the reflux ratio controlled at 1.1. The overflowing LPG was collected and its sulfur content was measured to be 13.58 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0108] Example 27:

[0109] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfoxide, 0.6% sulfolane, 0.5% T501 antioxidant, 3% OP-10, 2.5% Tween-40, 2% Tween-80, 2% JFC penetrant, 50 μg / g ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0110] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 50 kg of this solution is then added to the countercurrent absorption tower reactor to establish a circulation process between the absorption tower, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1.5 m³ / s. 3 / h, then the organic sulfur content is 2000 mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 40°C at a rate of 200 mL / min, with the reflux ratio controlled at 1.2. The overflowing LPG was collected and its sulfur content was measured to be 14.84 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 10 kg.

[0111] Example 28:

[0112] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfoxide, 0.6% sulfolane, 0.5% type 168 antioxidant, 3% OP-5, 2.5% Tween-40, 2% Tween-60, 2% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0113] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 50 kg of the desulfurization solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 2 m³ / s. 3 / h, then the organic sulfur content is 2000 mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 60°C at a rate of 300 mL / min, with the reflux ratio controlled at 1.5. The overflowing LPG was collected and its sulfur content was measured to be 13.38 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 10 kg.

[0114] Example 29:

[0115] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfone, 0.6% sulfolane, 0.5% T501 antioxidant, 3% OP-10, 2.5% Tween-40, 2% Tween-80, 2% JFC penetrant, 0.02% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 4% diethanolamine, 6% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0116] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 50 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1.75 m³ / h. 3 / h, then the organic sulfur content is 1500 mg / m 3 Liquefied petroleum gas (LPG) was introduced into the absorption system at 20°C at a rate of 260 mL / min, with the reflux ratio controlled at 1.25. The overflowing LPG was collected and its sulfur content was measured to be 13.64 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 10 kg.

[0117] Example 30:

[0118] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfoxide, 0.6% sulfolane, 0.5% T501 antioxidant, 3% OP-10, 2.5% Tween-40, 2% Tween-80, 2% JFC penetrant, 0.002% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0119] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 150 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 15 m³ / s. 3 / h, then the organic sulfur content is 2000 mg / m 3 liquefied gas at 2m 3 The gas was fed into the absorption system at a rate of [value] / h at a temperature of 40℃, with the reflux ratio controlled at 1.2. The overflowing liquefied gas was collected and its sulfur content was measured to be 14.61 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 30 kg.

[0120] Example 31;

[0121] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfoxide, 0.5% sulfolane, 0.5% type 1010 antioxidant, 3% OP-7, 2.5% Tween-60, 2% Tween-80, 2% JFC penetrant, 0.02% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0122] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 150 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 20 m³ / s. 3 / h, then the organic sulfur content is 2000 mg / m 3 liquefied gas at 3m 3The gas was fed into the absorption system at a rate of [value] / h at a temperature of 60℃, with the reflux ratio controlled at 1.5. The overflowing liquefied gas was collected and its sulfur content was measured to be 17.84 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 30 kg.

[0123] Example 32:

[0124] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfone, 0.6% sulfolane, 0.5% T501 antioxidant, 3% OP-10, 2.5% Tween-40, 2% Tween-60, 2% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl sebacate (DOS), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0125] A desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 150 kg of this solution is added to the packed absorber reactor to establish a circulation process between the absorber, the bottom circulation pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 18 m³ / s. 3 / h, then the organic sulfur content is 2000 mg / m 3 The liquefied gas at 2.5m 3 The gas was fed into the absorption system at a rate of [value] / h at a temperature of 40℃, with the reflux ratio controlled at 1.25. The overflowing liquefied gas was collected and its sulfur content was measured to be 16.18 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 30 kg.

[0126] Example 33:

[0127] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfoxide, 0.5% type 168 antioxidant, 1% OP-10, 2% Tween-40, 0.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 5% diethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0128] like Figure 3As shown, a desulfurization solution is obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution is added to a centrifugal reactor, establishing a circulation process between the centrifugal reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1 m³ / s. 3 / h, then the sulfur content is 1000mg / m 3 Liquefied petroleum gas is introduced into the absorption system at 20°C at a rate of 100 mL / min for one-time desulfurization, while the gravity level of the hypergravity reactor is controlled at 10 m / s. 2 The sulfur content of the overflowing liquefied gas was measured to be 2.34 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0129] Example 34:

[0130] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 2% dimethyl sulfoxide, 0.5% type 1010 antioxidant, 1% OP-7, 2% Tween-40, 0.5% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 5% triethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0131] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas (LPG) with a desulfurizing agent and sodium hydroxide solution. 25 kg of this solution was added to a centrifugal reactor, establishing a circulation process between the reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 1.5 m³ / s. 3 / h, then the sulfur content is 1000mg / m 3 Liquefied petroleum gas was introduced into the absorption system at 40°C at a rate of 150 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2 The sulfur content of the overflowing liquefied gas was measured to be 4.42 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0132] Example 35:

[0133] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 1% dimethyl sulfone, 0.5% type 168 antioxidant, 1% OP-5, 2% Tween-80, 1% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 5% sodium hydroxide, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), and the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0134] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution was added to a centrifugal reactor, establishing a circulation process between the centrifugal reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 2 m³ / s. 3 / h, then the sulfur content is 1000mg / m 3 Liquefied petroleum gas was introduced into the absorption system at 60°C at a rate of 200 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2 The sulfur content of the overflowing liquefied gas was measured to be 5.28 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0135] Example 36:

[0136] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfoxide, 0.5% sulfolane, 0.5% type 1010 antioxidant, 2.5% OP-10, 2% Tween-40, 1.5% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% triethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0137] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution was added to a centrifugal reactor, establishing a circulation process between the centrifugal reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 2 m³ / s. 3 / h, then the sulfur content is 1500mg / m 3 Liquefied petroleum gas was introduced into the absorption system at 20°C at a rate of 200 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2The sulfur content of the overflowing liquefied gas was measured to be 4.95 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0138] Example 37:

[0139] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfoxide, 0.6% sulfolane, 0.5% type 168 antioxidant, 2.5% OP-10, 2% Tween-60, 1.5% JFC penetrant, 0.02% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% triethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed thoroughly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0140] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas (LPG) with a desulfurizing agent and sodium hydroxide solution. 25 kg of this solution was added to a centrifugal reactor, establishing a circulation process between the reactor, the circulating pump, and the desulfurizing agent storage tank, with the circulation flow rate controlled at 3.5 m³ / s. 3 / h, then the sulfur content is 1500mg / m 3 Liquefied petroleum gas was introduced into the absorption system at 40°C at a rate of 300 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2 The sulfur content of the overflowing liquefied gas was measured to be 6.57 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0141] Example 38:

[0142] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfone, 0.5% sulfolane, 0.5% type 1010 antioxidant, 2.5% OP-10, 2% Tween-80, 1.5% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 10% sodium hydroxide, 5% diethanolamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0143] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution was added to a centrifugal reactor, establishing a circulation process between the centrifugal reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 5 m³ / s. 3 / h, then the sulfur content is 2000mg / m 3 Liquefied petroleum gas was introduced into the absorption system at 60°C at a rate of 400 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2 The sulfur content of the overflowing liquefied gas was measured to be 10.77 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0144] Example 39:

[0145] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfoxide, 0.6% sulfolane, 0.5% T501 antioxidant, 3% OP-10, 2.5% Tween-40, 2% Tween-80, 2% JFC penetrant, 0.015% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0146] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution was added to a centrifugal reactor, establishing a circulation process between the centrifugal reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 5 m³ / s. 3 / h, then the sulfur content is 2000mg / m 3 Liquefied petroleum gas was introduced into the absorption system at 40°C at a rate of 300 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2 The sulfur content of the overflowing liquefied gas was measured to be 9.33 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0147] Example 40:

[0148] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.5% dimethyl sulfoxide, 0.5% sulfolane, 0.5% type 1010 antioxidant, 3% OP-5, 2.5% Tween-60, 2% Tween-80, 2% JFC penetrant, 0.01% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% triethylenetetramine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0149] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution was added to a centrifugal reactor, establishing a circulation process between the centrifugal reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 10 m³ / s. 3 / h, then the sulfur content is 2000mg / m 3 Liquefied petroleum gas was introduced into the absorption system at 40°C at a rate of 400 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2 The sulfur content of the overflowing liquefied gas was measured to be 12.75 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0150] Example 41:

[0151] This desulfurizing agent for high-sulfur liquefied petroleum gas (LPG) comprises, by mass percentage: 0.4% dimethyl sulfone, 0.6% sulfolane, 0.5% T501 antioxidant, 3% OP-7, 2.5% Tween-40, 2% Tween-60, 2% JFC penetrant, 0.02% ethylene glycol monobutyl ether emulsifier, 20% sodium hydroxide, 5% triethanolamine, 5% diethylenetriamine, 2% dioctyl phthalate (DOP), with the balance being water. The required amounts of sulfone compounds, water-soluble alkali, and water are stirred and mixed evenly at 20°C to 30°C. Then, the required amounts of antioxidant, emulsifier, and organic ester are added, and the mixture is stirred for 30 minutes until homogeneous, thus obtaining the desulfurizing agent for high-sulfur LPG.

[0152] A desulfurization solution was obtained by mixing high-sulfur liquefied petroleum gas with a desulfurizing agent and sodium hydroxide solution. 25 kg of the desulfurization solution was added to a centrifugal reactor, establishing a circulation process between the centrifugal reactor, the circulating pump, and the desulfurizing agent storage tank, controlling the circulation flow rate at 10 m³ / s. 3 / h, then the sulfur content is 2000mg / m 3Liquefied petroleum gas was introduced into the absorption system at a temperature of 60°C at a rate of 500 mL / min for a one-time desulfurization experiment, with the gravity level of the hypergravity reactor controlled at 10 m / s². 2 The sulfur content of the overflowing liquefied gas was measured to be 14.65 mg / m³. 3 The amount of desulfurizing agent used for high-sulfur liquefied petroleum gas is 5 kg.

[0153] The sulfur content detection method in Examples 12 to 41 above is SH / T 0689-2000. The results from Examples 12 to 41 show that the desulfurizing agent for high-sulfur liquefied petroleum gas of the present invention has a significant desulfurization effect on high-sulfur liquefied petroleum gas systems, is simple to operate, consumes little energy, does not generate waste, and has a high desulfurization rate.

[0154] This invention addresses the challenge of removing carbonyl sulfides from organic sulfur compounds through difficult hydrolysis. It utilizes water-soluble alkalis, sulfones, and esters to adsorb sulfur-containing double bonds in organic sulfur molecules via polar adsorption. Liquefied petroleum gas (LPG) with a high sulfur concentration is introduced into a desulfurizing agent system at a specific rate. After heating and stirring (or passing through a suitable reactor), the desulfurizing agent rapidly forms gas-encapsulated microspheres around the organic sulfur-containing gas. Organic amines and esters at the microsphere interface adsorb carbon-sulfur double bonds or carbonyl sulfides from the organic sulfur molecules through polar adsorption. The alkaline solvents, such as amines, within the microspheres hydrolyze and break these sulfur bonds due to their strong alkalinity. The resulting sulfur anions are absorbed by the alkaline solution to form salts. The antioxidants in the desulfurizing solvent ensure that the desulfurizing agent does not oxidize and deteriorate during regeneration under oxygen-containing conditions, and also have a certain degree of adsorption and hydrolysis-promoting effect on organic sulfur molecules, while preventing acidification and degradation of the desulfurizing agent system. In a desulfurization reactor, high-sulfur liquefied petroleum gas is purified and desulfurized through washing, stratification, and desorption. This process is simple, uses readily available raw materials, consumes little energy, and is economical. In summary, the desulfurizing agent described in this invention uses conventional and readily available raw materials, has a simple preparation process, achieves good removal efficiency, consumes little energy, and is easy to industrialize. The desulfurization method is simple to operate, consumes little energy, does not generate waste, and is economical.

[0155] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Unnecessary technical features can be added or removed according to actual needs to meet the needs of different situations.

Claims

1. A desulfurizing agent for high-sulfur liquefied petroleum gas, characterized in that... The raw materials, by mass percentage, include 1% to 10% sulfone compounds, 0.5% to 2% antioxidants, 0.001% to 0.02% emulsifiers, 0.01% to 10% water-soluble alkalis, 1% to 10% organic esters, and the balance being water; The sulfone compound is one or more of dimethyl sulfoxide, dimethyl sulfone, and sulfolane; The organic ester is one or more of dioctyl phthalate, dibutyl phthalate, and dioctyl sebacate. The antioxidant is one or more of antioxidant 168, antioxidant 1010, and antioxidant 1076; The water-soluble base is one or more of sodium hydroxide, potassium hydroxide, ethylenediamine, diethanolamine, triethanolamine, diethylenetriamine, and triethylenetetramine; The high-sulfur liquefied petroleum gas is produced by a refinery and has a sulfur content of 20 mg / m³. 3 Up to 3000 mg / m 3 liquefied gas.

2. The desulfurizing agent for high-sulfur liquefied petroleum gas according to claim 1, characterized in that... The emulsifier is one or more of OP-5, OP-7, OP-10, Tween 40, Tween 60, Tween 80, JFC penetrant, and ethylene glycol monobutyl ether emulsifier.

3. The desulfurizing agent for high-sulfur liquefied petroleum gas according to claim 1 or 2, characterized in that... The desulfurizing agent for high-sulfur liquefied petroleum gas is prepared by stirring and mixing the required amount of sulfone compound, water-soluble alkali and water at 20°C to 30°C until homogeneous. Then, the required amount of antioxidant, emulsifier and organic ester are added and stirred for 30 min to 60 min.

4. A method for preparing a desulfurizing agent for high-sulfur liquefied petroleum gas according to any one of claims 1 to 3, characterized in that... The process includes the following steps: mixing the required amount of sulfone compound, water-soluble alkali, and water at 20°C to 30°C until homogeneous, then adding the required amount of antioxidant, emulsifier, and organic ester, and stirring for 30 to 60 minutes to obtain a desulfurizing agent for high-sulfur liquefied petroleum gas. The high-sulfur liquefied petroleum gas is produced by a refinery and has a sulfur content of 20 mg / m³. 3 Up to 3000 mg / m 3 liquefied gas.

5. A method of using a desulfurizing agent for high-sulfur liquefied petroleum gas according to any one of claims 1 to 3, characterized in that... The following steps are performed: A desulfurization solution is obtained by mixing a desulfurizing agent and a sodium hydroxide solution with high-sulfur liquefied petroleum gas (LPG). The desulfurization solution is then added to a desulfurization reactor, maintaining the temperature at 20°C to 60°C. High-sulfur LPG is then introduced into the reactor, and the mixture is stirred at 500 rpm to 1000 rpm for 10 to 60 minutes to carry out the desulfurization reaction. The mass percentage of the desulfurizing agent in the desulfurization solution is 15% to 20%. The high-sulfur liquefied petroleum gas is produced by a refinery and has a sulfur content of 20 mg / m³. 3 Up to 3000 mg / m 3 liquefied gas.

6. The method of using the desulfurizing agent for high-sulfur liquefied petroleum gas according to claim 5, characterized in that... A desulfurization reactor is one of three types: a batch reactor, a packed absorption tower reactor, or a gravity reactor.

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