Adsorbent for removing organic sulfide, and preparation method therefor and use thereof

Abstract

An adsorbent for removing organic sulfide, and a preparation method therefor and a use thereof, relating to the technical field of desulfurization adsorbents. The adsorbent for removing organic sulfide comprises a high-pore-volume core and a coating layer attached to the high-pore-volume core; the high-pore-volume core is obtained by mixing a nonionic surfactant, an alkali metal precursor and / or an alkaline-earth metal precursor, and an aluminum-containing compound and then carrying out forming and drying on same; and the coating layer is formed by an Ag and Ce co-modified high-silicon molecular sieve and a composition Al2(OH)nCl6-n (n=1-5). The adsorbent has the characteristics of high desulfurization efficiency, wide desulfurization range, high desulfurization precision, mild use conditions, long service life and the like, can achieve deep removal of organic sulfur under normal-temperature and normal-pressure conditions, can remove the organic sulfur in raw materials to 10 ppb or below, and is particularly suitable for desulfurization and purification of liquefied petroleum gas or natural gas.

Description

An adsorbent for removing organic sulfides, and its preparation method and application Technical Field

[0001] The present invention relates to the technical field of desulfurization adsorbents, and in particular to an adsorbent for removing organic sulfides, a preparation method thereof, and applications thereof. Background Art

[0002] Petrochemical products, such as liquefied petroleum gas (LPG), natural gas, gasoline, and diesel, contain a wide variety of organic sulfides, including polysulfides such as mercaptans, sulfides, carbonyl sulfide, and thiophene. Upon combustion, these organic sulfides form SO₂ and SO₃, which then combine with atmospheric water to form acid mist or acid rain, severely impacting the ecological environment and people's daily lives. Furthermore, demands for the quality of petroleum products are becoming increasingly stringent, and sulfides in fossil fuels can deactivate catalysts such as precious metals commonly used in chemical processes. Therefore, it is necessary to deeply remove organic sulfides from petroleum products to obtain higher-purity and higher-quality petroleum products.

[0003] Currently, the commonly used desulfurization methods are divided into two categories: wet desulfurization and dry desulfurization. Compared with wet desulfurization, dry desulfurization is mainly suitable for the deep removal of chemically stable organic sulfur. In addition to the advantages of low operating costs and simple process flow, its most prominent advantage is high desulfurization accuracy. Currently, the commonly used dry desulfurization methods mainly include hydrodesulfurization, oxidative desulfurization, and adsorption desulfurization. Among them, adsorption desulfurization fixes the sulfur element of organic sulfide in the adsorbent through the appropriate pore structure of the adsorbent and the interaction between the active metal in the adsorbent and the organic sulfur. This method has the advantages of simple operation, low operating cost and high adsorption capacity. No H2S is generated during the reaction to form secondary pollution, and it can achieve efficient and deep removal of organic sulfide.

[0004] Currently, the commonly used adsorption desulfurization adsorbents mainly include activated carbon adsorbents, copper-based adsorbents, nickel-based adsorbents and molecular sieve adsorbents. The details are as follows:

[0005] Activated carbon adsorbents are widely used for flue gas and liquefied petroleum gas desulfurization. Chinese patents CN96118013.7 and CN98113750.4 both use activated carbon as a carrier and prepare desulfurizers through an alkali solution impregnation method. While these desulfurizers have achieved some success in desulfurization, particularly in removing organic sulfur, they exhibit relatively low sulfur capacity and rapid degradation. Chinese patent CN00114588.6 discloses a desulfurizer prepared through an impregnation method using activated carbon as a carrier. Water-soluble compounds of sodium, copper, and silicon are added to the activated carbon before forming to enhance its desulfurization performance. Chinese patent CN200410042864.6 discloses a desulfurizer prepared by extruding an alkali metal compound or alkaline earth metal compound into strips after mixing with activated carbon powder. This desulfurizer suffers from the disadvantage of being fragile during use and potentially clogging the adsorbent bed.

[0006] Copper-based adsorbents are primarily copper-zinc-aluminum composite oxides, with copper oxide and zinc oxide as active components and aluminum oxide as a carrier. These adsorbents are simple to prepare, have high mechanical strength, and offer high desulfurization accuracy. However, they suffer from low active component utilization, performance that is affected by various factors, and non-renewability. Chinese patent CN112138625A discloses an adsorption desulfurizer for ultra-deep removal of thiophene from coke oven gas and its preparation method. This adsorption desulfurizer incorporates an Al2O3 carrier and NiO and ZrO2 additives into a Cu / ZnO composite to enhance its mechanical strength and increase its pore structure. The synergistic effect of the metal additives on copper and zinc increases the surface area of ​​the adsorption desulfurizer, enhancing its activity and further improving its desulfurization efficiency. Chinese patent CN104707565A discloses an ultra-deep desulfurization and olefin reduction adsorbent for gasoline, as well as its preparation method and application. It is prepared by co-precipitation reaction of transition metal salt, metal salt and precipitant, and evenly mixed with modified molecular sieve and adhesive, and extruded into strips by adding peptizing agent, and dried and roasted to obtain a desulfurization adsorbent. This adsorbent can remove most sulfides, but the preparation process is complicated and the cost is high. The adsorbent contains a large amount of heavy metal elements, which is easy to pollute the environment. Chinese patent CN115254006A discloses a desulfurization adsorbent for ultra-deep thiophene removal from coke oven gas and its preparation method. It uses copper oxide and zinc oxide as active components. By regulating the content of the carrier and the metal additive, the active component utilization rate and desulfurization performance of the desulfurization adsorbent are improved.

[0007] Nickel-based adsorbents are mainly prepared by mixing active components of nickel oxide, zinc oxide and silicon-aluminum composite carriers. They have high reactivity and excellent desulfurization performance, but their service life is greatly affected by reaction temperature, water vapor changes and carbon deposition. Chinese patent CN115646433A discloses a gasoline and diesel desulfurization adsorbent loaded with nickel sulfate and its preparation method. It uses ZnO-Al2O3-SiO2 as a carrier, loads nickel sulfate by impregnation, and obtains a desulfurization adsorbent after drying and roasting. This invention shows good adsorption desulfurization activity and stability when treating simulated gasoline and diesel feeds, and exhibits unique product selectivity; Chinese patent CN111195520A discloses a highly dispersed adsorption desulfurization catalyst and its preparation and application. It is composed of at least one +2-valent metal oxide, one +3-valent metal oxide, one IIA group metal oxide, at least one IVB group metal oxide and at least one VIII group metal oxide. The obtained catalyst active components have high dispersion, so the desulfurization activity and adsorption sulfur capacity are higher.

[0008] Molecular sieve adsorbents have attracted widespread attention in the field of adsorption desulfurization due to their advantages, including suitable pore structure, large specific surface area, good thermal stability, excellent ion exchangeability, and suitable surface acidity. Chinese patent CN114433003A discloses a desulfurization adsorbent, its preparation method, and application. The desulfurization adsorbent is a highly dispersed ruthenium oxide on a composite carrier of 13X molecular sieve and aluminum oxide, resulting in an adsorbent with high adsorption capacity and deep desulfurization. Chinese patent CN1330126A discloses a method for removing organic sulfur from liquefied gas. Specifically, it uses high-valent metal cations to modify X or Y molecular sieves. The resulting desulfurizer is regenerable and has a long service life. However, the adsorbent requires a high metal content and is subject to harsh operating conditions.

[0009] In summary, existing organic sulfide adsorbents suffer from low sulfur capacity, low desulfurization accuracy, demanding desulfurization conditions, short service life, and the inability to simultaneously remove large organic sulfur molecules and COS. To address these issues, the present invention provides an adsorbent for deep removal of organic sulfides and a method for preparing the same. Summary of the Invention

[0010] To address the above issues, the present invention provides an adsorbent for removing organic sulfides, as well as its preparation method and application. This adsorbent has the characteristics of high desulfurization accuracy, a wide desulfurization range, mild operating conditions, and a long service life. It can remove sulfides from liquefied petroleum gas or natural gas to below 10 ppb.

[0011] In a first aspect, the present invention provides an adsorbent for removing organic sulfides, the adsorbent for removing organic sulfides comprising a high pore volume core and a coating layer attached to the high pore volume core;

[0012] The high pore volume core is obtained by mixing a nonionic surfactant, an alkali metal precursor and / or an alkaline earth metal precursor and an aluminum-containing compound, followed by molding and drying;

[0013] The coating layer is composed of high silicon molecular sieve modified by Ag and Ce and Al2(OH) n Cl 6-n (n=1~5) composition is formed.

[0014] Furthermore, the adsorbent for removing organic sulfides comprises the following components in percentage by weight:

[0015] Ag2O 0.2~3wt%, CeO20.5~10wt%, CaO 0.1~5wt%, M2O 0.1~10wt%, Cl - 0.1~3wt%, SiO230~60wt%, the balance is Al2O3;

[0016] The M is an alkali metal.

[0017] Furthermore, the M2O includes at least one of Na2O and K2O.

[0018] Furthermore, the nonionic surfactant includes at least one of alkylolamide, polyethylene glycol and isopropanolamide; the alkali metal precursor includes at least one of Na2O and K2O; the alkaline earth metal precursor includes CaO; the aluminum-containing compound includes at least one of AlOOH and Al(OH)3; the high silicon molecular sieve includes at least one of Y molecular sieve, ZSM-5 molecular sieve, MOR molecular sieve and SiO2 / Al2O3>10-50:1 molecular sieve.

[0019] Furthermore, the pore volume of the adsorbent for removing organic sulfides is 0.1 to 0.9 ml / g.

[0020] In a second aspect, the present invention provides a method for preparing the adsorbent for removing organic sulfides according to any one of the first aspects, the preparation method comprising the following steps:

[0021] The nonionic surfactant, alkali metal precursor and / or alkaline earth metal precursor and aluminum-containing compound are uniformly mixed, and then formed and dried to obtain a spherical composite carrier core;

[0022] The high-silicon molecular sieve is modified with an acidified solution of a silver compound and a cerium composition by an impregnation or ion exchange method, and then dried to obtain a high-silicon molecular sieve co-modified with Ag and Ce;

[0023] The Ag and Ce co-modified high silicon molecular sieve and Al2(OH) n Cl 6-n (n=1-5) is coated on the surface of the core of the spherical composite carrier, and then dried to obtain an adsorbent precursor;

[0024] The adsorbent precursor is calcined to obtain the adsorbent for removing organic sulfides.

[0025] Furthermore, the spherical composite carrier core comprises the following components in percentage by weight:

[0026] Nonionic surfactant 0.1~15wt%, alkali metal / alkaline earth metal: 0.1-15wt%, and the balance is aluminum compound.

[0027] Furthermore, the silver compound includes at least one of silver nitrate and silver sulfate; the cerium composition is a combination of one or more cerium salt precursors that can form CeO2; the drying working parameters include: drying temperature of 100~250℃, drying time of 0.5~12 hours; the roasting working parameters include: roasting temperature of 300~550℃, roasting time of 0.5~8 hours.

[0028] Furthermore, the adsorbent precursor comprises the following components in weight percentage:

[0029] Spherical composite carrier core 20-50wt%, Ag, Ce co-modified high silicon molecular sieve 50-80wt% and Al2(OH) n Cl 6-n (n=1~5)5-15wt%.

[0030] In a third aspect, the present invention provides the use of the adsorbent for removing organic sulfides described in any one of the first aspects, and / or the adsorbent prepared by the preparation method described in any one of the second aspects, in the desulfurization and purification of petrochemical products.

[0031] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0032] 1) The adsorbent for removing organic sulfides provided by the present invention uses a non-ionic surfactant and macroporous alumina impregnated and modified with an alkali metal and / or alkaline earth metal as a carrier, thereby improving the mass transfer rate. At the same time, it adopts molecular sieve deep adsorption and alkali high-capacity adsorption, thereby reducing the preparation cost while ensuring the desulfurization accuracy and desulfurization depth. It has the characteristics of high desulfurization efficiency and a wide desulfurization range. Moreover, it can deeply remove organic sulfur and can also adsorb other types of sulfides.

[0033] 2) The adsorbent provided by the present invention for removing organic sulfides uses high-silicon molecular sieves, which reduces the cationic sites in the molecular sieves and reduces the required maximum loading amount of the active components. At the same time, it improves the hydrophobicity of the molecular sieves in the adsorbent, increases the adsorbent's tolerance to water, and improves the life of the adsorbent, thereby realizing the adsorption capacity of the adsorbent for gases with high water content.

[0034] 3) The adsorbent for removing organic sulfides provided by the present invention uses Ag and Ce to co-modify the molecular sieve. The π coordination of Ag and the S-Ce bond between Ce and sulfide are utilized to change the electrostatic field strength within the adsorbent pores, polarizing the sulfide molecules, thereby improving the desulfurization capacity and thermal stability of the adsorbent. This allows for deep adsorption of sulfur under both high and low temperature conditions, with a desulfurization accuracy of less than 10 ppb.

[0035] 4) The adsorbent for removing organic sulfides provided by the present invention can achieve deep removal of organic sulfur at room temperature and pressure, has mild operating conditions, is regenerable, and has a long service life. At the same time, it has high desulfurization accuracy and can remove organic sulfur in the raw material to below 10 ppb. The water content in the raw material has little effect on the desulfurization ability of the adsorbent. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0038] FIG1 is a schematic flow chart of a method for preparing an adsorbent for removing organic sulfides provided in an embodiment of the present invention.

[0039] FIG2 shows the results of a desulfurization performance evaluation and post-regeneration evaluation for removing organic sulfides provided in Example 1 of the present invention. Modes for Carrying Out the Invention

[0040] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0041] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0042] In a first aspect, the present invention provides an adsorbent for removing organic sulfides, the adsorbent for removing organic sulfides comprising a high pore volume core and a coating layer attached to the high pore volume core;

[0043] The high pore volume core is obtained by mixing a nonionic surfactant, an alkali metal precursor and / or an alkaline earth metal precursor and an aluminum-containing compound, followed by molding and drying;

[0044] The coating layer is composed of high silicon molecular sieve modified by Ag and Ce and Al2(OH) n Cl 6-n(n=1~5) composition is formed.

[0045] The above technical solution provided by the embodiment of the present invention has at least the following advantages compared with the prior art:

[0046] 1) The adsorbent for removing organic sulfides provided by the present invention uses a non-ionic surfactant and macroporous alumina impregnated and modified with an alkali metal and / or alkaline earth metal as a carrier, thereby improving the mass transfer rate. At the same time, it adopts molecular sieve deep adsorption and alkali high-capacity adsorption, thereby reducing the preparation cost while ensuring the desulfurization accuracy and desulfurization depth. It has the characteristics of high desulfurization efficiency and a wide desulfurization range. Moreover, it can deeply remove organic sulfur and can also adsorb other types of sulfides.

[0047] 2) The adsorbent provided by the present invention for removing organic sulfides uses high-silicon molecular sieves, which reduces the cationic sites in the molecular sieves and reduces the required maximum loading amount of the active components. At the same time, it improves the hydrophobicity of the molecular sieves in the adsorbent, increases the adsorbent's tolerance to water, and improves the life of the adsorbent, thereby realizing the adsorption capacity of the adsorbent for gases with high water content.

[0048] 3) The adsorbent for removing organic sulfides provided by the present invention uses Ag and Ce to co-modify the molecular sieve, and utilizes the π coordination of Ag and the S-Ce bond between Ce and sulfide to change the electrostatic field strength in the adsorbent pores, polarize the sulfide molecules, improve the desulfurization ability and thermal stability of the adsorbent, and achieve deep adsorption of sulfur under high and low temperature conditions. It is used to remove sulfides from natural gas, and can remove total sulfur to below 10ppb, with a breakthrough sulfur capacity greater than 1wt%.

[0049] 4) The adsorbent for removing organic sulfides provided by the present invention can achieve deep removal of organic sulfur at room temperature and pressure, has mild operating conditions, is regenerable, and has a long service life. At the same time, it has high desulfurization accuracy and can remove organic sulfur in the raw material to below 10 ppb. The water content in the raw material has little effect on the desulfurization ability of the adsorbent.

[0050] In some specific embodiments, the adsorbent for removing organic sulfides comprises the following components, measured by weight percentage:

[0051] Ag2O 0.2~3wt%, CeO20.5~10wt%, CaO 0.1~5wt%, M2O 0.1~10wt%, Cl - 0.1~3wt%, SiO230~60wt%, the balance is Al2O3;

[0052] The M is an alkali metal.

[0053] In some specific embodiments, the M2O includes at least one of Na2O and K2O.

[0054] In some specific embodiments, the nonionic surfactant includes at least one of alkyl alcohol amide, polyethylene glycol and isopropyl alcohol amide; the alkali metal precursor includes at least one of Na2O and K2O; the alkaline earth metal precursor includes CaO; the aluminum-containing compound includes at least one of AlOOH and Al(OH)3; the high silicon molecular sieve includes at least one of Y molecular sieve, ZSM-5 molecular sieve, MOR molecular sieve and SiO2 / Al2O3>10-50:1 molecular sieve.

[0055] In some specific embodiments, the pore volume of the adsorbent for removing organic sulfides is 0.1 to 0.9 ml / g.

[0056] In some specific embodiments, the Al2(OH) n Cl 6-n (n=1~5) is also called aluminum sol. Its composition is closely related to the bonding performance and has a great influence on the mechanical strength of the adsorbent. The preferred range of n is 3-5.

[0057] In a second aspect, based on a general inventive concept, the present invention provides a method for preparing an adsorbent for removing organic sulfides according to any one of the first aspects, as shown in FIG1 , the preparation method comprising the following steps:

[0058] The preparation method comprises the following steps:

[0059] The nonionic surfactant, alkali metal precursor and / or alkaline earth metal precursor and aluminum-containing compound are uniformly mixed, and then formed and dried to obtain a spherical composite carrier core;

[0060] The high-silicon molecular sieve is modified with an acidified solution of a silver compound and a cerium composition by an impregnation or ion exchange method, and then dried to obtain a high-silicon molecular sieve co-modified with Ag and Ce;

[0061] The Ag and Ce co-modified high silicon molecular sieve and Al2(OH) n Cl 6-n (n=1-5) is coated on the surface of the core of the spherical composite carrier, and then dried to obtain an adsorbent precursor;

[0062] The adsorbent precursor is calcined to obtain the adsorbent for removing organic sulfides.

[0063] The preparation method of the adsorbent for removing organic sulfides provided by the present invention is simple, does not require additional specialized equipment, and is suitable for industrial production. Furthermore, this preparation method is based on the adsorbent for removing organic sulfides described in any one of the first aspects, and thus exhibits at least the beneficial effects of the adsorbent for removing organic sulfides described in any one of the first aspects, and thus will not be further elaborated herein.

[0064] In some specific embodiments, the spherical composite carrier core comprises the following components, calculated by weight percentage:

[0065] Nonionic surfactant 0.1~15wt%, alkali metal / alkaline earth metal: 0.1-15wt%, and the balance is aluminum compound.

[0066] Preferably, the inner core of the spherical composite carrier comprises the following components in weight percentage: 1-10 wt% of nonionic surfactant, 2-8 wt% of alkali metal / alkaline earth metal, and the rest of AlOOH and / or Al(OH)3.

[0067] In some specific embodiments, the silver compound comprises at least one of silver nitrate and silver sulfate; the cerium composition comprises a combination of one or more cerium salt precursors capable of forming CeO2; the drying parameters include a drying temperature of 100-250°C and a drying time of 0.5-12 hours; and the calcination parameters include a calcination temperature of 300-550°C and a calcination time of 0.5-8 hours. Preferably, the silver compound is silver nitrate; and the cerium composition comprises at least one of cerium nitrate, cerium oxalate, and cerium hydroxide, more preferably cerium nitrate.

[0068] In some specific embodiments, the adsorbent precursor comprises the following components in weight percentage:

[0069] Spherical composite carrier core 20-50wt%, Ag, Ce co-modified high silicon molecular sieve 50-80wt% and Al2(OH) n Cl 6-n (n=1~5)5-15wt%.

[0070] In some embodiments, the diameter of the inner core of the spherical composite carrier is in the range of 0.3-1 mm.

[0071] In a third aspect, based on a general inventive concept, the present invention provides an adsorbent for removing organic sulfides as described in any one of the first aspects, and / or an adsorbent prepared by the preparation method as described in any one of the second aspects, and their use in the desulfurization and purification of petrochemical products.

[0072] The adsorbent for removing organic sulfides provided by the present invention has the characteristics of high desulfurization accuracy, wide desulfurization range, mild operating conditions and long service life. It can remove sulfides in petrochemical products such as liquefied petroleum gas or natural gas to below 10ppb, thereby obtaining petroleum products with higher purity and better product quality, and has wide practical application value.

[0073] It should be noted that the raw material components involved in the adsorbent for removing organic sulfides, its preparation method, and its application provided by the present invention, unless otherwise specified or specified, can be directly purchased as commercial products or prepared in-house according to existing preparation processes. Furthermore, the process steps involved, unless otherwise specified or specified, can be carried out according to actual needs and existing processes, and will not be detailed in this application document.

[0074] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples where specific conditions are not specified are generally measured in accordance with national standards. If there are no corresponding national standards, then the methods are carried out in accordance with general international standards, conventional conditions, or the conditions recommended by the manufacturer.

[0075] Example 1

[0076] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0077] 11.6 g of sodium hydroxide, 4 g of calcium hydroxide and 15 g of polyethylene glycol were dissolved in 135 g of deionized water, stirred until clear, and then added to a mixture of 200 g of pseudo-thin and 100 g of Bayer stone to prepare a dry glue, which was formed into small balls on a ball rolling machine. The formed small balls were dried at 150°C for 5 hours to prepare a composite carrier core, which was recorded as A1; 26 g of silver nitrate, 82 g of cerium nitrate and 650 g of USY molecular sieve (industrial product, Shandong Hefa Environmental Protection Technology Co., Ltd., molecular silicon-aluminum ratio of 15) were added to 6.5 kg of deionized water, ion exchanged at 80°C for 5 hours under stirring, filtered, washed, and dried at 150°C for 5 hours, which was recorded as B1.

[0078] 280 g of A1, 630 g of B1, 50 g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20 wt%), and 420 g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the mixture was calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-A1 of Example 1.

[0079] Example 2

[0080] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0081] 11.6 g of sodium hydroxide, 4 g of calcium hydroxide, and 15 g of polyethylene glycol were dissolved in 135 g of deionized water, stirred until clear, and then added to a mixture of 200 g of pseudo-thin and 100 g of Bayer stone to prepare a dry glue. The mixture was formed into small balls on a ball rolling machine, and the formed small balls were dried at 150°C for 5 hours to prepare a composite carrier core, which was recorded as A2. 26 g of silver nitrate and 82 g of cerium nitrate were added to 33 g of deionized water, stirred until clear, and then added dropwise to 650 g of USY molecular sieve (industrial product, Shandong Hefa Environmental Protection Technology Co., Ltd., molecular silicon-aluminum ratio of 35), stirred evenly, and dried at 150°C for 5 hours, which was recorded as B2.

[0082] 280 g of A2, 630 g of B2, 50 g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20 wt%) and 420 g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the mixture was calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-A2 of Example 2.

[0083] Example 3

[0084] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0085] 16 g of potassium hydroxide, 4 g of calcium hydroxide and 18 g of isopropyl alcohol amide were dissolved in 135 g of deionized water, stirred until clear, and then added to a mixture of 250 g of pseudo-thin and 50 g of Bayer stone to prepare a dry glue, which was formed into small balls on a ball rolling machine. The formed small balls were dried at 150°C for 5 hours to prepare a composite carrier core, which was recorded as A3; 30 g of silver nitrate, 77 g of cerium nitrate and 650 g of ZSM-5 molecular sieve (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., molecular silicon-aluminum ratio of 30) were added to 6.5 kg of deionized water, ion exchanged at 80°C for 5 hours while stirring, filtered, washed, and dried at 150°C for 5 hours, which was recorded as B3.

[0086] 280 g of A3, 630 g of B3, 50 g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20 wt%) and 420 g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the spheres were calcined in a muffle furnace at 500°C for 2 hours to prepare the desulfurization adsorbent DRS-A3 of Example 3.

[0087] Example 4

[0088] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0089] 16 g of potassium hydroxide, 4 g of calcium hydroxide and 18 g of isopropyl alcohol amide were dissolved in 135 g of deionized water, stirred until clear, and then added to a mixture of 250 g of pseudo-thin and 50 g of Bayer stone to prepare a dry glue, which was formed into small balls on a ball rolling machine. The formed small balls were dried at 150°C for 5 hours to prepare a composite carrier core, which was recorded as A4; 30 g of silver nitrate, 77 g of cerium nitrate and 650 g of MOR molecular sieve (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., molecular silicon-aluminum ratio of 10) were added to 6.5 kg of deionized water, and ion exchange was carried out at 80°C for 5 hours while stirring. After filtering and washing, it was dried at 150°C for 5 hours, which was recorded as B4.

[0090] 280 g of A4, 630 g of B4, 50 g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20 wt%) and 420 g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the mixture was calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-A4 of Example 3.

[0091] Example 5

[0092] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0093] 10 g of potassium hydroxide, 4 g of calcium hydroxide and 15 g of polyethylene glycol were dissolved in 140 g of deionized water, stirred until clear, and then added to 300 g of pseudo-thin to prepare a dry glue, which was formed into small balls on a ball rolling machine. The formed small balls were dried at 120°C for 8 hours to prepare a composite carrier core, which was recorded as A5; 12 g of silver nitrate, 93 g of cerium nitrate and 650 g of USY molecular sieve (industrial product, Shandong Hefa Environmental Protection Technology Co., Ltd., molecular silicon-aluminum ratio of 50) were added to 6.5 kg of deionized water, stirred, ion exchanged at 60°C for 12 hours, filtered, washed, and dried at 120°C for 8 hours, which was recorded as B5.

[0094] 280 g of A5, 630 g of B5, 50 g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20 wt%) and 420 g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 150°C for 5 hours, the mixture was calcined in a muffle furnace at 550°C for 2 hours to prepare the desulfurization adsorbent DRS-A5 of Example 5.

[0095] Comparative Example 1

[0096] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0097] 300 g of pseudo-thin and 135 g of deionized water were mixed into a dry glue, which was then formed into small balls on a ball rolling machine. The formed small balls were dried at 150° C. for 5 hours to prepare the carrier core, which was recorded as C1.

[0098] 280g of C1, 630g of USY molecular sieve (industrial product, Shandong Hefa Environmental Protection Technology Co., Ltd., molecular silicon-aluminum ratio of 15), 50g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20m%) and 420g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the mixture was calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-C1 of Comparative Example 1.

[0099] Comparative Example 2

[0100] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0101] 300 g of pseudo-thin and 135 g of deionized water were mixed into a dry glue, which was then formed into small balls on a ball rolling machine. The formed small balls were dried at 150°C for 5 hours to prepare the carrier core, which was recorded as C2. 26 g of silver nitrate, 82 g of cerium nitrate and 650 g of USY molecular sieve (industrial product, Shandong Hefa Environmental Protection Technology Co., Ltd., molecular silicon-aluminum ratio of 15) were added to 6.5 kg of deionized water, and ion exchange was carried out at 80°C for 5 hours while stirring. After filtration and washing, the mixture was dried at 150°C for 5 hours, which was recorded as D2.

[0102] 280g of C2, 630g of D2, 50g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20m%) and 420g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the spheres were calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-C2 of Comparative Example 2.

[0103] Comparative Example 3

[0104] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0105] 11.6 g of sodium hydroxide, 4 g of calcium hydroxide and 15 g of polyethylene glycol were dissolved in 135 g of deionized water, stirred until clear, and then added to a mixture of 200 g of pseudo-thin and 100 g of Bayer stone to prepare a dry glue. The dry glue was formed into small balls on a ball rolling machine, and the formed small balls were dried at 150°C for 5 hours to prepare a composite carrier core, which was recorded as C3.

[0106] 280g of C3, 630g of USY molecular sieve (industrial product, Shandong Hefa Environmental Protection Technology Co., Ltd., molecular silicon-aluminum ratio of 15), 50g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20m%) and 420g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the mixture was calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-C3 of Comparative Example 3.

[0107] Comparative Example 4

[0108] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0109] 11.6 g of sodium hydroxide, 4 g of calcium hydroxide and 15 g of polyethylene glycol were dissolved in 135 g of deionized water, stirred until clear, and then added to a mixture of 200 g of pseudo-thin and 100 g of Bayer stone to prepare a dry glue, which was formed into small balls on a ball rolling machine. The formed small balls were dried at 150°C for 5 hours to prepare a composite carrier core, which was recorded as C4; 26 g of silver nitrate, 82 g of cerium nitrate and 650 g of 13X molecular sieve (industrial product, Shanghai Jiuzhou Chemical Co., Ltd., molecular silicon-aluminum ratio of 2.6) were added to 6.5 kg of deionized water, ion exchanged at 80°C for 5 hours under stirring, filtered, washed, and dried at 150°C for 5 hours, which was recorded as D4.

[0110] 280g of C4, 630g of D4, 50g of aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20m%) and 420g of deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the spheres were calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-C4 of Comparative Example 4.

[0111] Comparative Example 5

[0112] This example provides an adsorbent for removing organic sulfides, and the preparation method thereof comprises the following steps:

[0113] 11.6 g of sodium hydroxide, 4 g of calcium hydroxide and 15 g of polyethylene glycol were dissolved in 135 g of deionized water, stirred until clear, and then added to a mixture of 200 g of pseudo-thin and 100 g of Bayer stone to prepare a dry glue, which was formed into small balls on a ball rolling machine. The formed small balls were dried at 150°C for 5 hours to prepare a composite carrier core, which was recorded as C5; 26 g of silver nitrate and 650 g of USY molecular sieve (industrial product, Shandong Hefa Environmental Protection Technology Co., Ltd., molecular silicon-aluminum ratio of 15) were added to 6.5 kg of deionized water, stirred, ion exchanged at 80°C for 5 hours, filtered, washed, and dried at 150°C for 5 hours, which was recorded as D5.

[0114] 280g C5, 630g D5, 50g aluminum sol (industrial product, Sichuan Runhe Catalytic New Materials Co., Ltd., alumina ≮20m%) and 420g deionized water were mixed uniformly by a wet method, kneaded in a small kneader, and rolled into Φ4 mm spheres on a small rotary ball rolling machine. After drying at 120°C for 10 hours, the spheres were calcined at 500°C in a muffle furnace for 2 hours to prepare the desulfurization adsorbent DRS-C5 of Comparative Example 5.

[0115] Test Case

[0116] The adsorbents for removing organic sulfides obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were tested.

[0117] 1) The desulfurization adsorbents of Examples 1-5 and Comparative Examples 1-3 were subjected to adsorption desulfurization performance tests and pore structure characterization tests on a micro-evaluation device. The test conditions were normal temperature, normal pressure, and a space velocity of 200-300 h. -1 The desulfurizer loading is 1 kg, and the raw material is a type of natural gas from a chemical plant, with a sulfur content of 20 mg / m 3 , of which H2S is 1mg / m 3 The remaining sulfur was organic sulfur. The type and content of the sulfide at the outlet were determined by thermal desorption concentration and gas chromatography FPD detection. The adsorption reaction process was stopped when the total sulfur content at the outlet exceeded 10 ppb. This was considered a test cycle. The test results are listed in Tables 1 and 2 below.

[0118] 2) After the adsorbent of Example 1 was evaluated according to the adsorption desulfurization performance test evaluation method in 1) above, the adsorbent was removed and calcined in a muffle furnace at 550°C for 2 hours before regeneration. The regenerated sample was re-evaluated according to the evaluation method of Example 6; the above regeneration-evaluation experiment was repeated, and the evaluation results are shown in Figure 2.

[0119] 3) The desulfurization adsorbents of Example 1 and Comparative Example 4 were tested for adsorption desulfurization performance on a micro-evaluation device. The test conditions were normal temperature, normal pressure, and a space velocity of 200-300 h. -1The desulfurizer loading was 1 kg, and the feedstock was Class I natural gas mixed with 0.1% water vapor. The type and content of sulfides at the outlet were determined by thermal desorption concentration and gas chromatography using an FPD detector. The adsorption reaction was terminated when the total sulfur content at the outlet exceeded 10 ppb. This constituted one test cycle. The results are listed in Table 3 below.

[0120] 4) The desulfurization adsorbents of Example 1 and Comparative Example 5 were tested for adsorption desulfurization performance on a micro-evaluation device. The test conditions were 200°C, atmospheric pressure, and a space velocity of 200-300 hours. -1 The desulfurizer loading was 1 kg, and the raw material was Class I natural gas from a chemical plant. The type and content of sulfides at the outlet were determined by thermal desorption concentration and gas chromatography using an FPD detector. The adsorption reaction was terminated when the total sulfur content at the outlet exceeded 10 ppb. This constituted one test cycle. The results are listed in Table 4 below.

[0121] The test results are as follows:

[0122] Table 1 Comparison of pore structures of desulfurization adsorbents of Examples 1-5 and Comparative Examples 1-3

[0123] Item Total pore volume (cc / g) Macropore volume (cc / g) Alkali metal / alkaline earth metal content (%) Example 1 0.58 0.31 3.5 Example 2 0.59 0.31 3.5 Example 3 0.57 0.29 4.3 Example 4 0.57 0.30 4.3 Example 5 0.59 0.32 2.8 Comparative Example 1 0.38 / / Comparative Example 2 0.36 / / Comparative Example 3 0.55 0.30 3.5

[0124] Table 2 Comparison of desulfurization adsorbents of Examples 1-5 and Comparative Examples 1-3

[0125] Project Average desulfurization rate within 1 cycle (%) Average sulfur content at outlet within 1 cycle (ng / g) Sulfur capacity (m%) Example 1 99.95 1.43 1.5 Example 2 99.98 1.02 1.8 Example 3 99.96 1.36 1.7 Example 4 99.92 2.92 1.3 Example 5 99.95 1.37 1.4 Comparative Example 1 97.65 7.38 0.1 Comparative Example 2 98.7 94.24 0.8 Comparative Example 3 98.12 6.37 0.5

[0126] From the comparative data of Table 1 and Table 2, it can be seen that compared with Comparative Examples 1-2, Examples 1-5 all contain large pores of 0.3cc / g, which promote the rapid internal diffusion. At the same time, due to the high-capacity adsorption of alkali, the desulfurization efficiency is high and the sulfur capacity is large; compared with Comparative Example 3, Examples 1-5 all co-modify the molecular sieve, and the sulfur capacity is significantly higher than that of Comparative Example 3.

[0127] It can be seen from the results in FIG2 that the sample of the embodiment of the present invention still has good desulfurization performance after multiple regenerations.

[0128] Table 3 Comparison of desulfurization adsorbents of Example 1 and Comparative Example 4

[0129] Project Average desulfurization rate within 1 cycle (%) Average sulfur content at the outlet within 1 cycle (ng / g) Sulfur capacity (m%) Example 1 99.9 31.4 31.4 Comparative example 4 97.3 28.0 40.3

[0130] As can be seen from Table 3, Example 1 uses high-silicon molecular sieve, the hydrophobicity of the adsorbent is enhanced, and the competitive adsorption of water is significantly reduced. Even when the water content of the raw material is high, the sulfur adsorption capacity is still greater than 1%. However, Comparative Example 4 reduces the sulfur capacity by 80% due to the preferential adsorption of water.

[0131] Table 4 Comparison of desulfurization adsorbents of Example 1 and Comparative Example 5

[0132] Project Average desulfurization rate within 1 cycle (%) Average sulfur content at the outlet within 1 cycle (ng / g) Sulfur capacity (m%) Example 199.931.681.5 Comparative Example 596.477.2940.5

[0133] As can be seen from Table 4, Example 1 uses Ag and Ce to co-modify the molecular sieve and can still achieve deep adsorption of sulfur when used under high temperature conditions, while Comparative Example 5 has a significantly reduced sulfur capacity when used under high temperature conditions.

[0134] Various embodiments of the present invention may be presented in the form of a range; it should be understood that the description in a range format is only for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; therefore, the range description should be considered to have specifically disclosed all possible subranges and single numerical values ​​within the range. For example, the description of a range from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is intended to include any cited numeral (fractional or integer) within the indicated range.

[0135] The foregoing description is intended only to provide specific embodiments of the present invention, which will enable those skilled in the art to understand and implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but is intended to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. An adsorbent for removing organic sulfides, characterized in that: The adsorbent for removing organic sulfide comprises a high pore volume core and a coating layer attached to the high pore volume core; The high pore volume inner core is obtained by mixing a nonionic surfactant, an alkali metal precursor and / or an alkaline earth metal precursor and an aluminum-containing compound, followed by molding and drying; The coating layer is a high silicon molecular sieve and Al2(OH) co-modified by Ag and Ce. n Cl 6-n (n=1~5) composition is formed.

2. The adsorbent for removing organic sulfides according to claim 1, characterized in that: The adsorbent for removing organic sulfide comprises the following components in weight percentage: Ag2O 0.2~3wt%, CeO20.5~10wt%, CaO 0.1~5wt%, M2O 0.1~10wt%, Cl - 0.1~3wt%, SiO230~60wt%, the balance is Al2O3; The M is an alkali metal.

3. The adsorbent for removing organic sulfides according to claim 2, characterized in that: The M2O includes at least one of Na2O and K2O.

4. The adsorbent for removing organic sulfides according to claim 1, characterized in that: The nonionic surfactant includes at least one of alkyl alcohol amide, polyethylene glycol and isopropanolamide; the alkali metal precursor includes at least one of Na2O and K2O; the alkaline earth metal precursor includes CaO; the aluminum-containing compound includes at least one of AlOOH and Al(OH)3; the high silicon molecular sieve includes at least one of Y molecular sieve, ZSM-5 molecular sieve, MOR molecular sieve and SiO2 / Al2O3>10-50:1 molecular sieve.

5. The adsorbent for removing organic sulfides according to claim 1, characterized in that: The pore volume of the adsorbent for removing organic sulfide is 0.1 to 0.9 ml / g.

6. A method for preparing an adsorbent for removing organic sulfides according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: The nonionic surfactant, the alkali metal precursor and / or the alkaline earth metal precursor and the aluminum-containing compound are uniformly mixed, and then molded and dried to obtain a spherical composite carrier core; The high-silicon molecular sieve is modified by an acidified solution of a silver compound and a cerium composition using an impregnation or ion exchange method, and then dried to obtain a high-silicon molecular sieve co-modified with Ag and Ce; The Ag and Ce co-modified high silicon molecular sieve and Al2(OH) n Cl 6-n (n=1-5) is coated on the inner core surface of the spherical composite carrier, and then dried to obtain an adsorbent precursor; The adsorbent precursor is calcined to obtain the adsorbent for removing organic sulfides.

7. The preparation method according to claim 6, characterized in that: The spherical composite carrier core comprises the following components in weight percentage: Nonionic surfactant 0.1~15wt%, alkali metal / alkaline earth metal: 0.1-15wt%, the balance is aluminum-containing compounds.

8. The preparation method according to claim 6, characterized in that: The silver compound includes at least one of silver nitrate and silver sulfate; the cerium composition is a combination of one or more cerium salt precursors capable of forming CeO2; The working parameters of the drying include: a drying temperature of 100-250° C. and a drying time of 0.5-12 hours; the working parameters of the roasting include: a roasting temperature of 300-550° C. and a roasting time of 0.5-8 hours.

9. The preparation method according to claim 6, characterized in that: The adsorbent precursor comprises the following components in weight percentage: Spherical composite carrier core 20-50wt%, Ag, Ce co-modified high silicon molecular sieve 50-80wt% and Al2(OH) n Cl 6-n (n=1~5)5-15wt%.

10. Use of the adsorbent for removing organic sulfides according to any one of claims 1 to 5, and / or the adsorbent prepared by the preparation method according to any one of claims 6 to 9 in desulfurization and purification of petrochemical products.

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