Organic vulcanizing agents, their stepwise preparation methods, and applications

Abstract

This invention relates to the field of sulfurizing agent preparation technology, and discloses an organic sulfurizing agent and its stepwise preparation method and application. The method includes: dissolving a first sulfur in a solvent to obtain a mixed sulfurized oil; contacting the mixed sulfurized oil with a second sulfur, olefin oil, and a solid catalyst under primary heating and reflux; then contacting the resulting mixture I with an optional additive under secondary heating and reflux, wherein the temperature of the primary heating and reflux is lower than the temperature of the secondary heating and reflux; distilling the resulting mixture II; and then separating the solid-liquid mixture to obtain the liquid phase as the organic sulfurizing agent; or, after separating the solid-liquid mixture II, distilling the resulting liquid mixture to obtain the heavy fraction as the organic sulfurizing agent. This method eliminates the need for hydrogen sulfide, and the resulting organic sulfurizing agent has a higher sulfur content, up to 65% by weight. Preferably, no hydrogen sulfide is released during the preparation process, making it more environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of sulfurizing agent preparation technology, specifically to organic sulfurizing agents and stepwise preparation methods of such organic sulfurizing agents, as well as the application of such organic sulfurizing agents in the pre-sulfurization of hydrogenation catalysts. Background Technology

[0002] Hydrogenation catalysts are mainly used in reaction processes such as hydroremoval, hydrorefining, hydrocracking, hydromodification, and water-gas shift reaction. Most of these catalysts utilize Group VIB and Group VIII metals such as molybdenum, cobalt, nickel, and tungsten. Typically, sulfide-state catalysts, due to the electronic effects of the ortho-position environment, allow low-valence transition metals to possess certain empty orbitals. Furthermore, the synergistic effect of polymetallic sulfides gives them hydrogenation activity similar to that of noble metals, while avoiding the drawbacks of hydrogen sulfide and ammonia poisoning. This makes them widely used in industrial plants.

[0003] In the initial stages of catalyst use, during the processing of low-sulfur feedstocks, the catalyst typically needs to be converted to a sulfidized state through sulfidation. This process usually uses hydrogen sulfide for sulfidation; however, hydrogen sulfide is a highly toxic gas and is corrosive to equipment. Industrial catalysts are pre-sulfided by reacting sulfur-containing sulfiding agents such as carbon disulfide (CS2), dimethyl disulfide (DMDS), and SZ-54 in the system to generate hydrogen sulfide. The manufacturing process of these sulfiding agents is relatively complex, and although they have low flash points, they still pose certain hazards. Therefore, sulfiding agents used for catalyst sulfidation have been extensively studied. Industrial sulfiding agents mainly include inorganic sulfiding agents, solid sulfiding agents, and organic sulfiding agents. Organic sulfiding agents have been widely studied due to their high sulfur content, low impurities, low price, and greater safety.

[0004] CN1417299A discloses a pre-sulfurization method for a hydrogenation catalyst. The method includes impregnating a hydrogenation catalyst with a solution containing sulfur-containing olefins, followed by heating the catalyst under an inert atmosphere. The solution containing sulfur-containing olefins is a solution of sulfur-containing olefins containing dissolved elemental sulfur at a temperature of room temperature to 220°C. The total sulfur content in the solution containing sulfur-containing olefins containing dissolved elemental sulfur is 4-40 wt%, wherein the weight ratio of sulfur present in elemental form to sulfur present in sulfur-containing olefins is 0.5-7. The impregnation temperature is room temperature to 220°C, and the impregnation time is 0.5-5 hours. Based on the sulfurized hydrogenation catalyst, the amount of the solution containing sulfur-containing olefins containing dissolved elemental sulfur used results in the sulfurized hydrogenation catalyst containing 1-7.5 wt% sulfur, calculated as elemental sulfur. The solution of sulfur-containing olefins containing elemental sulfur is prepared by the following method: (1) A component containing an olefin and elemental sulfur are mixed and heated at 100-220°C for 0.5-10 hours, wherein the molar ratio of elemental sulfur to olefin double bonds is 1-1.5, and the product is cooled or not cooled to room temperature, and the resulting liquid product is the solution of sulfur-containing olefins; (2) The obtained solution of sulfur-containing olefins is mixed with elemental sulfur and heated at 100-220°C to dissolve the elemental sulfur, thereby obtaining the product of sulfur-containing olefins containing elemental sulfur. The amount of elemental sulfur and the solution of sulfur-containing olefins is such that the total sulfur content in the final solution of sulfur-containing olefins containing elemental sulfur is 4-40 wt% based on elemental sulfur, and the weight ratio of sulfur in elemental state to sulfur in sulfur-containing olefins is 0.5-7. Although this method of pre-sulfurizing the hydrogenation catalyst can greatly reduce the catalyst breakage rate and improve the sulfur retention, it needs to be carried out under inert gas protection and the hydrogenation catalyst that is ultimately sulfided needs to be introduced during the preparation of sulfurized oil.

[0005] CN101029012A discloses a method for synthesizing organic polysulfides. This method uses olefin-rich FCC distillate oil as raw material. Under the action of an alkaline catalyst, sulfur undergoes an addition reaction with the double bonds in the olefins to form an adduct. Unreacted elemental sulfur is then purified and separated to obtain a relatively pure mixture of organic polysulfides. This organic polysulfide is mainly used as a sulfiding agent for pre-sulfurization outside the hydrogenation catalyst. It has low production costs and a high sulfur content. Because it uses mixed olefins as raw material, it can alleviate the problem of excessively concentrated exothermic reactions during application. Although this organic polysulfide has many advantages, its sulfur content is still relatively low, not exceeding 25%.

[0006] US6544936B2 discloses a method for preparing sulfurized olefins. This method involves a one-step reaction of olefins, sulfur, and hydrogen sulfide using a solid catalyst to obtain sulfurized olefins. The molecular sieve has meso- and macroporous pores of 0.5-0.8 nm. One embodiment uses an LZY-52 molecular sieve as the catalyst, which is obtained by modifying a Y-type molecular sieve and contains 10.4% sodium oxide, 0.3% calcium oxide, 0.2% ferric oxide, 66.5% silicon, and 20.8% aluminum by mass, with a specific surface area of ​​820 m². 2 / g, after the reaction was completed and simply filtered, a yellow clear oily substance with a sulfur mass fraction of 37% was obtained. There was no elemental sulfur residue on the filtrate and the catalyst, indicating that the sulfur mass fraction in the product was still low, and hydrogen sulfide was introduced in the preparation process, which is not conducive to production safety.

[0007] CN103476833A discloses a method for preparing polysulfides of formula (I), the method comprising: HS-(CH2)nO-(CH2) m -O-(CH2) p -[SS-CH2) n -O-(CH2) m -O-(CH2) p ] q -SH(I), where m is an integer from 1 to 4, n and p are integers from 1 to 10, and q is an integer from 1 to 60, the method being carried out by oxidizing the dithiol diether compound of formula (II) with elemental sulfur in the presence of a base and a protic solvent: HS-(CH2) n -O-(CH2) m -O-(CH2) p -SH(II). This method has high selectivity for the formation of linear disulfides, but requires an oxidation step with a dithiol diether compound, and may produce solid polymers as the values ​​of m and n increase.

[0008] Current research on organosulfurizing agents mainly focuses on ring-opening reactions of water-soluble and / or oil-soluble bases in the S8 sulfur ring, resulting in physical dissolution or sulfur insertion into the double bond of olefins to form organic polysulfide compounds, thereby preparing organosulfurizing agents with high stability. However, the dispersed basic ring-opening promoters used in existing technologies may introduce alkali metals into the product, which is detrimental to maintaining the activity of the hydrogenation catalyst. Furthermore, existing technologies require the use of hydrogen sulfide or generate hydrogen sulfide during the reaction, which will lead to significant environmental hazards in the production of sulfurizing agents. Summary of the Invention

[0009] The purpose of this invention is to overcome the problem of low sulfur content in existing organic sulfurizing agents, and to provide an organic sulfurizing agent, a method for preparing the organic sulfurizing agent, and its application in the pre-sulfurization of hydrogenation catalysts. This organic sulfurizing agent has a higher sulfur content, up to 65% by weight.

[0010] To achieve the above objectives, a first aspect of the present invention provides a method for preparing an organic sulfurizing agent, the method comprising the following steps:

[0011] (1) Dissolve the first sulfur in a solvent to obtain a mixed sulfurized oil;

[0012] (2) The mixed sulfurized oil is contacted with second sulfur, olefin oil and solid catalyst and subjected to primary heating and reflux to obtain mixture I;

[0013] (3) The mixture I is contacted with an optional additive and subjected to two-stage heating and reflux to obtain mixture II; wherein the temperature of the first-stage heating and reflux is lower than the temperature of the second-stage heating and reflux;

[0014] (4-a) The mixture II is subjected to a first distillation to remove the light components, and then the resulting solid-liquid mixture is subjected to a first solid-liquid separation, the resulting liquid phase being the organic sulfurizing agent; or

[0015] (4-b) The mixture II is subjected to a second solid-liquid separation, and then the resulting liquid mixture is subjected to a second distillation to remove the light components. The resulting heavy fraction is the organic sulfurizing agent.

[0016] A second aspect of the present invention provides an organic vulcanizing agent prepared by the method described in the first aspect.

[0017] The third aspect of this invention provides the application of the organic sulfurizing agent described in the second aspect in the presulfurization of hydrogenation catalysts.

[0018] The above technical solution eliminates the need for hydrogen sulfide in the method provided by this invention, and the resulting organic sulfurizing agent has a higher sulfur content, up to 65% by weight. In preferred cases, no hydrogen sulfide is released during the preparation process, making it more environmentally friendly. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] Unless otherwise expressly stated, the term "optional" as used in this invention means either performing or not performing the operation, or adding or not adding the material.

[0021] In this invention, unless otherwise specified, "first," "second," "primary," and "secondary" do not represent a sequential order, nor do they limit the various materials or operations. They are merely used to distinguish between different materials or operations. For example, "first" and "second" in "first sulfur" and "second sulfur" are only used to distinguish them to indicate that they are not the same sulfur; "first" and "second" in "first distillation" and "second distillation" are only used to distinguish them to indicate that they are not the same distillation operation.

[0022] The first aspect of this invention provides a method for preparing an organic sulfurizing agent, the method comprising the following steps:

[0023] (1) Dissolve the first sulfur in a solvent to obtain a mixed sulfurized oil;

[0024] (2) The mixed sulfurized oil is contacted with second sulfur, olefin oil and solid catalyst and subjected to primary heating and reflux to obtain mixture I;

[0025] (3) The mixture I is contacted with an optional additive and subjected to two-stage heating and reflux to obtain mixture II; wherein the temperature of the first-stage heating and reflux is lower than the temperature of the second-stage heating and reflux;

[0026] (4-a) The mixture II is subjected to a first distillation to remove the light components, and then the resulting solid-liquid mixture is subjected to a first solid-liquid separation, the resulting liquid phase being the organic sulfurizing agent; or

[0027] (4-b) The mixture II is subjected to a second solid-liquid separation, and then the resulting liquid mixture is subjected to a second distillation to remove the light components. The resulting heavy fraction is the organic sulfurizing agent.

[0028] According to some embodiments of the present invention, in step (1), the first sulfur is dissolved in a solvent to obtain a mixed sulfurized oil. This step is beneficial for promoting the dispersion of elemental sulfur. Preferably, the dissolution conditions include: a temperature of 30-95°C, more preferably 40-80°C; and / or a time of 1-4 hours, more preferably 2-4 hours. Dissolution conditions meeting the above ranges are beneficial for maximizing the solubility of sulfur.

[0029] According to some embodiments of the present invention, there are no particular limitations on the type of solvent, as long as it can dissolve sulfur, the inventive objective of the present invention can be achieved to a certain extent. Preferably, the solvent is carbon disulfide (CS2) and / or dimethyl disulfide DMDS. Using the above preferred embodiments, sulfur has high solubility in DMDS and CS2 solvents, which is beneficial for further promoting sulfur dissolution.

[0030] According to some embodiments of the present invention, preferably, the weight ratio of the first sulfur to the solvent is 1:0.8-1, more preferably 1:0.8-0.9. Using the above preferred embodiments is beneficial for further promoting sulfur dissolution.

[0031] According to some embodiments of the present invention, preferably, step (1) further includes cooling the product obtained from the dissolution to obtain a mixed sulfurized oil; the temperature of the mixed sulfurized oil is lower than the dissolution temperature; preferably, the temperature of the mixed sulfurized oil is 35-45°C. The purpose of cooling the product obtained from the dissolution is to allow insoluble sulfur to precipitate, which is beneficial to improving the stability of the sulfurized oil.

[0032] According to some embodiments of the present invention, in step (2), the mixed sulfurized oil is contacted with a second sulfur, an olefin oil, and a solid catalyst and subjected to primary heating under reflux to obtain mixture I. In the above steps, the dissolved sulfur and the olefins in the olefin oil undergo an addition reaction under the action of a solid catalyst, and the resulting mixture I contains polysulfides, dissolved sulfur, and a solid catalyst.

[0033] According to some embodiments of the present invention, preferably, the conditions for the primary heating reflux include: a temperature of 80-130°C, preferably 90-120°C; and / or a time of 1-10 hours, preferably 2-10 hours. Meeting the above ranges for the primary heating reflux conditions is beneficial for fully dissolving sulfur and further increasing the sulfur content in the organic sulfurizing agent.

[0034] According to some embodiments of the present invention, preferably, the weight ratio of the mixed sulfurized oil, the second sulfur, the solid catalyst, and the olefin oil is 1:0.9-1.1:0.2-0.4:0.9-1.1. Using the above preferred embodiments is beneficial for further increasing the sulfur content in the organic sulfurizing agent.

[0035] According to some embodiments of the present invention, preferably, in step (2), the olefin oil contains 30-100% by weight of olefins; preferably, the olefins are C5-C10 olefins; preferably, the olefin oil is selected from the full or partial fraction of catalytic gasoline or vapor-cracked gasoline. Using the above preferred embodiments is beneficial for further increasing the sulfur content in the organic sulfurizing agent.

[0036] According to some embodiments of the present invention, compared with the dispersed alkaline ring-opening additives used in the prior art, the present invention uses a solid catalyst in conjunction with specific preparation steps and conditions, which is beneficial for achieving the separation of sulfurized oil and catalyst and increasing the sulfur content in the organic sulfurizing agent. In order to better separate from the organic sulfurizing agent and further increase the sulfur content in the organic sulfurizing agent, preferably, in step (2), the solid catalyst includes NaY molecular sieve, alkaline metal oxide and heat-resistant inorganic oxide.

[0037] According to some embodiments of the present invention, preferably, on a dry basis, the weight ratio of NaY molecular sieve, alkali metal oxide and heat-resistant inorganic oxide in the solid catalyst is (0.1-20):(0.1-20):1.

[0038] According to some embodiments of the present invention, preferably, the NaY molecular sieve has a cell constant of 2.460-2.469 nm and a specific surface area of ​​600-800 m². 2 / g, pore volume is 0.2-0.38mL / g, Na2O content is 10-14% by weight.

[0039] According to some embodiments of the present invention, preferably, the alkaline metal oxide is selected from potassium oxide and / or sodium oxide.

[0040] According to some embodiments of the present invention, preferably, the heat-resistant inorganic oxide is selected from at least one of alumina, silicon oxide, titanium oxide, zirconium oxide and magnesium oxide, and preferably alumina.

[0041] According to some embodiments of the present invention, there are no particular limitations on the preparation method of the solid catalyst, and it can be prepared with reference to existing technologies, as long as a solid catalyst that meets the above-mentioned requirements can be obtained. To better separate from the organic sulfurizing agent and further increase the sulfur content in the organic sulfurizing agent, preferably, the preparation method of the solid catalyst includes: mixing and extruding NaY molecular sieve, an alkaline metal oxide precursor, and a heat-resistant inorganic oxide precursor, followed by sequential drying and calcination. The NaY molecular sieve can be selected as described above and will not be repeated here. The alkaline metal oxide precursor can be selected from any compound containing the alkaline metal oxide or from any compound that can be converted into the alkaline metal oxide after mixing, extrusion, drying, and calcination, for example, it can be selected from KOH and / or NaOH. The heat-resistant inorganic oxide precursor can be selected from any compound containing the heat-resistant inorganic oxide or from any compound that can be converted into the heat-resistant inorganic oxide after mixing, extrusion, drying, and calcination, for example, the alumina precursor can be selected from boehmite. The mixing, extrusion, drying, and calcination can all be carried out with reference to existing technologies. For example, the drying temperature can be 110-130℃; the calcination conditions can include a calcination temperature of 550-650℃ and a calcination time of 2-4 hours. There are no particular restrictions on the amount of NaY molecular sieve, alkali metal oxide precursor, and heat-resistant inorganic oxide precursor used, as long as the weight ratio of NaY molecular sieve, alkali metal oxide, and heat-resistant inorganic oxide in the obtained solid catalyst is (0.1-20):(0.1-20):1 on a dry basis.

[0042] According to some embodiments of the present invention, in step (3), the mixture I is contacted with an optional additive and subjected to a two-stage reflux heating to obtain mixture II. The temperature of the first-stage reflux heating is lower than the temperature of the second-stage reflux heating. The above steps facilitate further dissolution of sulfur, facilitate the dispersion of sulfur in the sulfurized oil that is not bound in the organosulfur compounds, and promote the further progress of the addition reaction between sulfur and olefins under the solid catalyst; the resulting mixture II contains polysulfides, sulfur, and a solid catalyst.

[0043] According to some embodiments of the present invention, preferably, the conditions for the secondary heating reflux include: a temperature of 130-180°C, more preferably 135-170°C; and / or a time of 1-10 hours, more preferably 2-10 hours. Meeting the above ranges for the secondary heating reflux conditions is beneficial for further promoting the reaction and increasing the sulfur content in the organic sulfurizing agent.

[0044] According to some embodiments of the present invention, preferably, the additive is an alkaline amine and / or alcohol compound, preferably at least one selected from methanol, monoethanolamine, diethanolamine, and triethanolamine, more preferably methanol and / or diethanolamine, and even more preferably a mixture of methanol and diethanolamine, wherein the content of diethanolamine is 5-20% by weight, and the content of methanol is 80-95% by weight. Preferably, the weight ratio of the mixed sulfurized oil to the additive is 1:0.2-0.3.

[0045] According to some embodiments of the present invention, steps (1) to (3) facilitate the further increase of sulfur content in the organic sulfurizing agent while preventing the release of hydrogen sulfide during the preparation process.

[0046] According to some embodiments of the present invention, in step (4-a), the mixture II is subjected to a first distillation to separate and remove the dissolved components, sulfur-free low-molecular-weight gasoline components, and other light components from the solution, thereby purifying and enriching the sulfurized oil. Then, the resulting solid-liquid mixture undergoes a first solid-liquid separation, and the resulting liquid phase is the organic sulfurizing agent. The heavy distillate liquid phase of the solid-liquid mixture is the organic sulfurizing agent, and the solid phase is the solid catalyst. The first solid-liquid separation can be performed using conventional methods in the art, without particular limitations; for example, filtration can be used to separate the solid catalyst from the organic sulfurizing agent.

[0047] According to some embodiments of the present invention, preferably, in step (4-a), the temperature of mixture II is higher than the temperature of the first distillation; preferably, the temperature of mixture II is 130-180°C; and / or, the temperature of the first distillation is 80-120°C. Using the above preferred embodiments is beneficial for further increasing the sulfur content in the organic sulfurizing agent.

[0048] According to some embodiments of the present invention, in step (4-b), the mixture II is subjected to a second solid-liquid separation to separate the solid catalyst from the liquid mixture. The resulting liquid mixture is then subjected to a second distillation to remove light components, and the resulting heavy fraction is the organic sulfurizing agent. The second solid-liquid separation can be performed using conventional methods in the art, and there are no particular limitations. For example, filtration can be used to separate the solid catalyst from the liquid mixture.

[0049] According to some embodiments of the present invention, preferably, in step (4-b), the temperature of the mixture II is lower than the temperature of the second distillation; and / or, the temperature of the second distillation is 80-120°C.

[0050] The above-described preferred embodiments are beneficial for further improving the yield of organic sulfurizing agents.

[0051] According to a particularly preferred embodiment of the present invention, the method for preparing the organic sulfurizing agent includes:

[0052] S1-1. Dissolve the first sulfur in a solvent to obtain a mixed sulfurized oil; wherein the dissolution temperature is 30-95℃ and the time is 1-4h; the solvent is carbon disulfide and / or dimethyl disulfide; the weight ratio of the first sulfur to the solvent is 1:0.8-1;

[0053] S2-1. The mixed sulfurized oil is contacted with second sulfur, olefin oil and solid catalyst and subjected to primary heating and reflux to obtain mixture I; the temperature of the primary heating and reflux is 80-130℃ and the time is 1-10h; the weight ratio of the mixed sulfurized oil, second sulfur, solid catalyst and olefin oil is 1:0.9-1.1:0.2-0.4:0.9-1.1; the olefin content in the olefin oil is 30-100% by weight; the solid catalyst includes NaY molecular sieve, alkaline metal oxide and heat-resistant inorganic oxide; on a dry basis, the weight ratio of NaY molecular sieve, alkaline metal oxide and heat-resistant inorganic oxide is (0.1-20):(0.1-20):1;

[0054] S3-1. The mixture I is contacted with an additive and subjected to a two-stage heating reflux to obtain mixture II; wherein the temperature of the two-stage heating reflux is 130-180℃ and the time is 1-10h; the additive is methanol and / or diethanolamine;

[0055] S4-1. The mixture II is subjected to a first distillation to remove light components. The temperature of the first distillation is 80-120°C. Then, the resulting solid-liquid mixture is subjected to a first solid-liquid separation. The resulting liquid phase is the organic sulfurizing agent. The temperature of the mixture II is 130-180°C.

[0056] The above-described preferred embodiments are particularly advantageous in increasing the sulfur content in the organic sulfurizing agent while preventing the release of hydrogen sulfide during the preparation process.

[0057] According to another particularly preferred embodiment of the present invention, the method for preparing the organic sulfurizing agent includes:

[0058] S1-2. Dissolve the first sulfur in a solvent to obtain a mixed sulfurized oil; wherein the dissolution temperature is 30-95℃ and the time is 1-4h; the solvent is carbon disulfide and / or dimethyl disulfide; the weight ratio of the first sulfur to the solvent is 1:0.8-1;

[0059] S2-2. The mixed sulfurized oil is contacted with the second sulfur, olefin oil, and solid catalyst and subjected to primary heating and reflux to obtain mixture I; the temperature of the primary heating and reflux is 80-130℃, and the time is 1-10h; the weight ratio of the mixed sulfurized oil, the second sulfur, the solid catalyst, and the olefin oil is 1:0.9-1.1:0.2-0.4:0.9-1.1; the olefin content in the olefin oil is 30-100% by weight; the solid catalyst includes NaY molecular sieve, alkaline metal oxide, and heat-resistant inorganic oxide; on a dry basis, the weight ratio of NaY molecular sieve, alkaline metal oxide, and heat-resistant inorganic oxide is (0.1-20):(0.1-20):1;

[0060] S3-2. The mixture I is contacted with an additive and subjected to a two-stage heating reflux to obtain mixture II; wherein the temperature of the two-stage heating reflux is 130-180℃ and the time is 1-10h; the additive is methanol and / or diethanolamine;

[0061] S4-2. The mixture II is subjected to a second solid-liquid separation, and then the resulting liquid mixture is subjected to a second distillation to remove the light components. The heavy fraction obtained is the organic sulfurizing agent. The temperature of the mixture II is lower than the temperature of the second distillation. The temperature of the second distillation is 80-120°C.

[0062] A second aspect of the present invention provides an organic vulcanizing agent prepared by the method described in the first aspect.

[0063] According to some embodiments of the present invention, preferably, the sulfur content of the organic vulcanizing agent is 45-70% by weight, more preferably 45-65% by weight. A higher sulfur content in the organic vulcanizing agent is beneficial for reducing costs.

[0064] The third aspect of this invention provides the application of the organic sulfurizing agent described in the second aspect in the presulfurization of hydrogenation catalysts.

[0065] The present invention will be described in detail below through embodiments.

[0066] Unless otherwise specified, all raw materials used in the following examples and comparative examples are commercially available products.

[0067] Preparation Examples 1-2 illustrate the preparation method of the solid catalyst used in this invention.

[0068] Preparation Example 1

[0069] Take 100g of NaY molecular sieve (produced by Sinopec Catalyst Changling Branch, with a unit cell constant of 2.470nm and a specific surface area of ​​732m²). 2The following ingredients were mixed evenly: 30g KOH and 30g boehmite (produced by Sinopec Catalyst Changling Branch, trade name PB90, Al2O3 content 71% by weight, dry basis 0.71%), extruded into cylindrical strips with an outer diameter of 2.5 mm, dried at 120℃, and calcined at 600℃ for 3 hours to obtain solid catalyst A. In this catalyst, the weight ratio of NaY molecular sieve, KO (alkaline metal oxide) and Al2O3 (heat-resistant inorganic oxide) is 3.6:1.4:1.

[0070] Preparation Example 2

[0071] Take 66g of NaY molecular sieve (produced by Sinopec Catalyst Changling Branch, with a unit cell constant of 2.463nm and a specific surface area of ​​712m²). 2 / g, pore volume of 0.33mL / g, Na2O content of 12.3 wt%, dry basis 0.76), 71g NaOH, 141g pseudoboehmite (produced by Sinopec Catalyst Changling Branch, trade name PB90, Al2O3 content of 71 wt%, dry basis 0.71) were mixed evenly, extruded into cylindrical strips with an outer circle diameter of 2.5 mm, dried at 120℃, and calcined at 600℃ for 3 hours to obtain solid catalyst B. In this catalyst, the weight ratio of NaY molecular sieve, Na2O (alkaline metal oxide) and Al2O3 (heat-resistant inorganic oxide) is 0.5:0.5:1.

[0072] Examples 1-3 illustrate the preparation method of the organic sulfurizing agent provided by the present invention.

[0073] Example 1

[0074] (1) Take 100g of sulfur, add 80g of DMDS, stir and heat to 60°C, keep reflux during the process, until the sulfur is completely dissolved, keep for 2 hours, and cool down to 40°C to obtain mixed sulfurized oil;

[0075] (2) Take 100g of mixed sulfurized oil, 100g of sulfur, 30g of solid catalyst A, and 100g of Guangshihua full-fraction catalyst gasoline (olefin content is 39% by weight) and mix them evenly. Heat the mixture to 110℃ and reflux for 3h to obtain mixture I.

[0076] (3) Add 20g of methanol to mixture I, heat to 160℃, and reflux for 3h to obtain mixture II;

[0077] (4) Cool the mixture II to 100°C and distill it to remove the light components. Then cool the resulting solid-liquid mixture to room temperature and filter it. The resulting liquid phase is the organic sulfurizing agent, denoted as SS-1.

[0078] Example 2

[0079] The method of Example 1 is followed, except that in step (3), methanol is replaced with a mixture of methanol and diethanolamine (wherein the content of diethanolamine is 10% by weight), and the rest is the same as in Example 1, to obtain an organic sulfurizing agent, denoted as SS-2.

[0080] Example 3

[0081] (1) Take 100g of sulfur, add 90g of CS2, stir and heat to 70℃, keep reflux during the process, until the sulfur is completely dissolved, keep for 3 hours, and cool down to 40℃ to obtain mixed sulfurized oil.

[0082] (2) Take 100g of mixed sulfurized oil, 90g of sulfur, 35g of solid catalyst B, and 95g of Guangshihua full-fraction catalyst gasoline (olefin content is 39% by weight) and mix them evenly. Heat the mixture to 120℃ and reflux for 2.5h to obtain mixture I.

[0083] (3) Add 25g of methanol to mixture I, heat to 170℃, and reflux for 2h to obtain mixture II;

[0084] (4) Cool the mixture II to 110°C and distill it to remove the light components. Then cool the resulting solid-liquid mixture to room temperature and filter it. The resulting liquid phase is the organic sulfurizing agent, denoted as SS-3.

[0085] Comparative Example 1

[0086] The method of Example 1 is followed, except that step (1) is omitted and the amount of sulfur used in step (2) is 200g. The rest is the same as in Example 1, and an organic sulfurizing agent is obtained, which is denoted as RSS-1.

[0087] Comparative Example 2

[0088] The method of Example 1 is followed, except that no solid catalyst is added in step (2), and the rest is the same as in Example 1, to obtain an organic sulfurizing agent, denoted as RSS-2.

[0089] The sulfur content in the organic vulcanizing agents prepared in Examples 1-3 and Comparative Examples 1-2 was tested respectively, and the results are shown in Table 1. The specific testing methods are as follows:

[0090] First, the organic sulfurizing agent was diluted 30 times with a mixed solvent of decahydronaphthalene and n-decane (mass ratio 1:1) to obtain a diluted solution. Then, the sulfur content in the diluted solution was determined by energy dispersive X-ray fluorescence spectrometry according to GBT 17040-2019, which is denoted as n. Thus, the sulfur content of the organic sulfurizing agent was 30*n.

[0091] Table 1

[0092]

[0093] The results above show that the method of the present invention does not require the use of hydrogen sulfide, and the resulting organic sulfurizing agent has a higher sulfur content, up to 65% by weight.

[0094] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing an organic vulcanizing agent, characterized in that, The method includes the following steps: (1) Dissolve the first sulfur in a solvent to obtain a mixed sulfurized oil; (2) The mixed sulfurized oil is contacted with second sulfur, olefin oil and solid catalyst and subjected to primary heating and reflux to obtain mixture I; (3) The mixture I is contacted with an optional additive and subjected to two-stage heating and reflux to obtain mixture II; wherein the temperature of the first-stage heating and reflux is lower than the temperature of the second-stage heating and reflux; (4-a) The mixture II is subjected to a first distillation to remove the light components, and then the resulting solid-liquid mixture is subjected to a first solid-liquid separation, the resulting liquid phase being the organic sulfurizing agent; or (4-b) The mixture II is subjected to a second solid-liquid separation, and then the resulting liquid mixture is subjected to a second distillation to remove the light components. The heavy fraction obtained is the organic sulfurizing agent. In step (2), the solid catalyst includes NaY molecular sieve, alkaline metal oxide and heat-resistant inorganic oxide.

2. The method according to claim 1, wherein, In step (1), the dissolution conditions include: a temperature of 30-95℃; and / or a time of 1-4h; And / or, the solvent is carbon disulfide and / or dimethyl disulfide; And / or, the weight ratio of the first sulfur to the solvent is 1:0.8-1.

3. The method according to claim 1, wherein, Step (1) further includes cooling the product obtained from the dissolution to obtain a mixed sulfurized oil; the temperature of the mixed sulfurized oil is lower than the dissolution temperature.

4. The method according to claim 2, wherein, In step (1), the dissolution conditions include: a temperature of 40-80℃; and / or a time of 2-4 hours. And / or, the solvent is carbon disulfide and / or dimethyl disulfide; And / or, the weight ratio of the first sulfur to the solvent is 1:0.8-0.9; And / or, the temperature of the mixed sulfurized oil is 35-45°C.

5. The method according to claim 1, wherein, In step (2), the conditions for the first-stage heating reflux include: a temperature of 80-130℃; and / or a time of 1-10h; And / or, the weight ratio of the mixed sulfurized oil, second sulfur, solid catalyst and olefin oil is 1:0.9-1.1:0.2-0.4:0.9-1.

1.

6. The method according to claim 5, wherein, In step (2), the conditions for the first-stage heating reflux include: a temperature of 90-120℃; and / or a time of 2-10h.

7. The method according to claim 1, wherein, In step (2), the olefin content in the olefin oil is 30-100% by weight.

8. The method according to claim 7, wherein, The olefin is a C5-C10 olefin.

9. The method according to claim 7, wherein, The olefin oil is selected from the full or partial fraction of catalytic gasoline or vapor-cracked gasoline.

10. The method according to claim 1, wherein, On a dry basis, the weight ratio of NaY molecular sieve, alkali metal oxide and heat-resistant inorganic oxide in the solid catalyst is (0.1-20):(0.1-20):

1. And / or, the NaY molecular sieve has a cell constant of 2.460-2.469 nm and a specific surface area of ​​600-800 m². 2 / g, pore volume is 0.2-0.38mL / g, Na2O content is 10-14% by weight% And / or, the alkaline metal oxide is selected from potassium oxide and / or sodium oxide; And / or, the heat-resistant inorganic oxide is selected from at least one of alumina, silicon oxide, titanium oxide, zirconium oxide and magnesium oxide.

11. The method according to claim 10, wherein, The heat-resistant inorganic oxide is aluminum oxide.

12. The method according to any one of claims 1-11, wherein, In step (3), the conditions for the secondary heating reflux include: a temperature of 130-180℃; and / or a time of 1-10h; And / or, the adjuvant is an amine and / or alcohol compound that is basic.

13. The method according to claim 12, wherein, In step (3), the conditions for the secondary heating reflux include: a temperature of 135-170℃; and / or a time of 2-10h; And / or, the adjuvant is at least one of methanol, monoethanolamine, diethanolamine and triethanolamine.

14. The method according to claim 13, wherein, The additive is methanol and / or diethanolamine.

15. The method according to any one of claims 1-11, wherein, In step (4-a), the temperature of mixture II is higher than the temperature of the first distillation; And / or, in step (4-b), the temperature of mixture II is lower than the temperature of the second distillation.

16. The method according to claim 15, wherein, The temperature of mixture II is 130-180°C; And / or, the temperature of the first distillation is 80-120°C; And / or, the temperature of the second distillation is 80-120°C.

Images