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CN-117551013-B - Organic vulcanizing agent and stepwise preparation method and application thereof

CN117551013BCN 117551013 BCN117551013 BCN 117551013BCN-117551013-B

Abstract

The invention relates to the technical field of vulcanizing agent preparation, and discloses an organic vulcanizing agent, a stepwise preparation method and application thereof. The method comprises the steps of dissolving first sulfur in a solvent to obtain mixed vulcanized oil, contacting the mixed vulcanized oil with second sulfur, olefin oil and a solid catalyst to perform primary heating reflux, contacting the obtained mixture I with an optional auxiliary agent to perform secondary heating reflux, wherein the temperature of the primary heating reflux is lower than that of the secondary heating reflux, distilling the obtained mixture II, performing solid-liquid separation on the obtained solid-liquid mixture to obtain a liquid phase which is an organic vulcanizing agent, or performing solid-liquid separation on the obtained liquid mixture II, and distilling the obtained liquid mixture to obtain a heavy fraction which is the organic vulcanizing agent. The method does not need hydrogen sulfide, and the prepared organic vulcanizing agent has higher sulfur content which can reach 65 weight percent, preferably has no hydrogen sulfide release in the preparation process, and is more environment-friendly.

Inventors

  • MAO YICHAO
  • ZHAO XINQIANG
  • YANG QINGHE
  • ZHAO YANG
  • ZHANG RUNQIANG
  • ZHU MEI
  • ZHU LI

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260505
Application Date
20220803

Claims (16)

  1. 1. A method of preparing an organic vulcanizing agent, the method comprising the steps of: (1) Dissolving first sulfur in a solvent to obtain mixed vulcanized oil; (2) Contacting the mixed vulcanized oil with second sulfur, olefin oil and a solid catalyst to perform primary heating reflux to obtain a mixture I; (3) Contacting the mixture I with an optional auxiliary agent to perform secondary heating reflux to obtain a mixture II, wherein the temperature of the primary heating reflux is lower than that of the secondary heating reflux; (4-a) subjecting the mixture II to a first distillation to remove light components, and subjecting the resulting solid-liquid mixture to a first solid-liquid separation to obtain a liquid phase which is the organic vulcanizing agent, or (4-B) subjecting the mixture II to a second solid-liquid separation, and then subjecting the obtained liquid mixture to a second distillation to remove light components, wherein the obtained heavy fraction is the organic vulcanizing agent; in step (2), the solid catalyst comprises NaY molecular sieve, basic metal oxide and refractory inorganic oxide.
  2. 2. The method according to claim 1, wherein in the step (1), the conditions of dissolution include a temperature of 30-95 ℃ and/or a time of 1-4 hours; And/or the solvent is carbon disulphide and/or dimethyl disulphide; and/or the dosage weight ratio of the first sulfur to the solvent is 1:0.8-1.
  3. 3. The method of claim 1, wherein step (1) further comprises cooling the dissolved product to obtain a mixed vulcanized oil, wherein the temperature of the mixed vulcanized oil is lower than the dissolution temperature.
  4. 4. The method according to claim 2, wherein in the step (1), the conditions of dissolution include a temperature of 40-80 ℃ and/or a time of 2-4 hours; And/or the solvent is carbon disulphide and/or dimethyl disulphide; and/or the dosage weight ratio of the first sulfur to the solvent is 1:0.8-0.9; and/or the temperature of the mixed vulcanized oil is 35-45 ℃.
  5. 5. The process of claim 1, wherein in step (2), the primary heating reflux conditions comprise a temperature of 80-130 ℃ and/or a time of 1-10 hours; And/or the weight ratio of the mixed vulcanized oil to the second sulfur to the solid catalyst to the olefin oil is 1:0.9-1.1:0.2-0.4:0.9-1.1.
  6. 6. The method according to claim 5, wherein in the step (2), the condition of the primary heating reflux comprises a temperature of 90-120 ℃ and/or a time of 2-10h.
  7. 7. The method according to claim 1, wherein in step (2), the content of olefin in the olefin oil is 30 to 100% by weight.
  8. 8. The process of claim 7, wherein the olefin is a C5-C10 olefin.
  9. 9. The method of claim 7, wherein the olefin oil is selected from a full fraction or a partial fraction of a catalytic gasoline or a steam cracking gasoline.
  10. 10. The method of claim 1, wherein, In the solid catalyst, the weight ratio of NaY molecular sieve to alkali metal oxide to heat-resistant inorganic oxide is (0.1-20): 1; And/or the unit cell constant of the NaY molecular sieve is 2.460-2.469nm, the specific surface area is 600-800m 2 /g, the pore volume is 0.2-0.38mL/g, and the Na 2 O content is 10-14 wt%; And/or the basic 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, silica, titania, zirconia, and magnesia.
  11. 11. The method of claim 10, wherein the refractory inorganic oxide is alumina.
  12. 12. The process according to any one of claims 1 to 11, wherein in step (3), the conditions of the secondary heating reflux comprise a temperature of 130 to 180 ℃ and/or a time of 1 to 10 hours; and/or the auxiliary agent is an amine and/or alcohol compound with alkalinity.
  13. 13. The method according to claim 12, wherein in the step (3), the condition of the secondary heating reflux comprises a temperature of 135-170 ℃ and/or a time of 2-10h; and/or the auxiliary agent is at least one of methanol, monoethanolamine, diethanolamine and triethanolamine.
  14. 14. The method of claim 13, wherein the auxiliary is methanol and/or diethanolamine.
  15. 15. The process according to any one of claims 1-11, wherein in step (4-a) the temperature of the mixture II is higher than the temperature of the first distillation; and/or in step (4-b), the temperature of the mixture II is lower than the temperature of the second distillation.
  16. 16. The process according to claim 15, wherein the temperature of mixture II is 130-180 ℃; and/or the temperature of the first distillation is 80-120 ℃; and/or the temperature of the second distillation is 80-120 ℃.

Description

Organic vulcanizing agent and stepwise preparation method and application thereof Technical Field The invention relates to the technical field of preparation of vulcanizing agents, in particular to an organic vulcanizing agent, a stepwise preparation method of the organic vulcanizing agent and application of the organic vulcanizing agent in presulfiding of hydrogenation catalysts. Background The hydrogenation catalyst is mainly used in the reaction processes of hydrodeimpurity, hydrofining, hydrocracking, hydro-upgrading, water gas shift and the like. Among them, metals of group VIB and group VIII metals such as molybdenum, cobalt, nickel and tungsten are mostly used, and in general, a sulfided catalyst has a certain empty orbit of a low-valence transition metal due to an electron effect of an ortho-position environment, and exhibits hydrogenation activity similar to that of a noble metal due to a synergistic effect of multi-metal sulfides, thereby avoiding disadvantages of hydrogen sulfide and ammonia poisoning thereof, which makes it widely used in industrial devices. In the initial stage of catalyst use, in the process of processing raw oil with low sulfur content, etc., the catalyst is usually required to be converted into a vulcanized state by using a vulcanization method, and the process is usually carried out by using hydrogen sulfide, however, the hydrogen sulfide is a toxic gas and has a certain corrosion type to equipment. Industrial catalysts are presulfided by reacting sulfur-containing sulfiding agents such as carbon disulfide (CS 2), dimethyl disulfide (DMDS), SZ-54, etc. in a system to produce hydrogen sulfide. The preparation process of the vulcanizing agents is complex, the flash point is low, and the vulcanizing agents still have certain hazard, so that the vulcanizing agents for catalyst vulcanization are widely researched, and the industrial vulcanizing agents mainly comprise inorganic vulcanizing agents, solid vulcanizing agents and organic vulcanizing agents. The organic vulcanizing agent has the characteristics of high sulfur content, less impurities, low price, safety and the like, and is widely researched. CN1417299a discloses a process for presulfiding a hydrogenation catalyst which comprises impregnating a hydrogenation catalyst with an olefin sulfide-containing solution at a temperature of from room temperature to 220 ℃ in which elemental sulfur is dissolved, and then heating the catalyst under an inert atmosphere. The total content of sulfur in the solution containing the sulfide olefin in which elemental sulfur is dissolved is 4 to 40% by weight, wherein the weight ratio of sulfur present in the elemental state to sulfur present in the sulfide olefin is 0.5 to 7, the impregnation temperature is room temperature to 220 ℃, and the impregnation time is 0.5 to 5 hours. The amount of the solution containing the sulfur-containing olefin in which elemental sulfur is dissolved is such that the sulfided hydrogenation catalyst contains from 1 to 7.5% by weight of sulfur, based on elemental sulfur, based on the sulfided hydrogenation catalyst. The solution containing the sulfur-containing olefin dissolved therein is prepared by (1) mixing an olefin-containing component with elemental sulfur, heating the mixture at a temperature of 100-220 ℃ for 0.5-10 hours, wherein the molar ratio of elemental sulfur to olefin double bonds is 1-1.5, cooling or not cooling the product to room temperature to obtain a liquid product, namely the solution containing the sulfur-containing olefin, (2) mixing the obtained solution containing the sulfur-containing olefin with elemental sulfur, heating the mixture at a temperature of 100-220 ℃ to dissolve the elemental sulfur to obtain a product containing the sulfur-containing olefin dissolved therein, and the amounts of elemental sulfur and the solution containing the sulfur-containing olefin to be used are such that the total content of sulfur in the final solution containing the sulfur-containing olefin dissolved therein is, calculated as elemental sulfur, 4-40% by weight, and the weight ratio of sulfur present in elemental state to sulfur present in the vulcanized olefin is 0.5-7. Although the method is adopted to presulfide the hydrogenation catalyst, the breakage rate of the catalyst can be greatly reduced, and the retention degree of sulfur can be improved, the method is carried out under the protection of inert gas, and the final sulfided hydrogenation catalyst needs to be introduced in the preparation process of the sulfided oil. CN101029012a discloses a method for synthesizing organic polysulfide, which uses FCC distillate oil rich in olefin as raw material, under the action of alkaline catalyst, sulfur and double bond in olefin produce an adduct, and unreacted elemental sulfur is separated by purification, so as to obtain purer mixture of organic polysulfide. The organic polysulfide is mainly used as a vulcanizing agent for pre-vulcanizing outside a hy