A hydrogenation catalyst vulcanizing agent, its preparation method and application

Abstract

The application discloses a hydrogenation catalyst vulcanizing agent and a preparation method and application thereof. The hydrogenation catalyst vulcanizing agent is an organic polysulfide, the organic polysulfide is calcined at 100 DEG C-280 DEG C under a hydrogen atmosphere, and the weight loss of the hydrogenation catalyst vulcanizing agent is as follows: 25-40% at 100 DEG C-180 DEG C, 20-35% at greater than 180 DEG C to less than 215 DEG C, and 20-30% at 215 DEG C-270 DEG C, with the total weight of the hydrogenation catalyst vulcanizing agent as the basis. The preparation method of the hydrogenation catalyst vulcanizing agent mainly comprises the following steps: reacting elemental sulfur and unsaturated hydrocarbons in the presence of alkaline substances and C8 or above aliphatic hydrocarbons, and obtaining the hydrogenation catalyst vulcanizing agent through separation after the reaction is completed. The hydrogenation catalyst vulcanizing agent not only has a simple preparation method and is easy to control, but also can slowly decompose and release hydrogen sulfide in a hydrogen atmosphere.

Description

TECHNICAL FIELD

[0001] The present application relates to a hydrogenation catalyst vulcanizing agent and its preparation method and application, and in particular to an organic polysulfide hydrogenation catalyst vulcanizing agent and its preparation method and application. BACKGROUND

[0002] Organic polysulfide is a kind of substance with general formula R-S x x is between 2 and 20, R and R1 are alkyl, alkylaryl, aryl or aralkyl functional groups, which can be the same or different, and can be saturated or unsaturated hydrocarbons, or straight-chain, branched or naphthenic hydrocarbons. Organic polysulfide is often used for pre-sulfurization treatment of hydrogenation catalysts. Whether it is in-situ pre-sulfurization or ex-situ pre-sulfurization, the activation of the hydrogenation catalyst must be carried out in the presence of a vulcanizing agent.

[0003] There are many routes for the synthesis of organic polysulfide. The commonly used method at home and abroad is to use mercaptan and elemental sulfur as raw materials to prepare organic polysulfide in the presence of a catalyst. The development direction of this method is mainly to improve the traditional catalysts such as amines, alkyl amines, alkanol amines, inorganic bases, mercaptide salts and alcoholates. For example, US4876389 uses a composition with general formula RSH·x(C m H 2m O)·yMOH as a catalyst, US5068445 uses a basic resin as a catalyst, and US6051739 uses a traditional basic substance and a compound with general formula R2O[CH2CH·(R3)O] nThe surface active substance SO3M is combined together as a catalyst, the yield of the synthesis reaction product is improved, and the catalyst is easy to separate from the product. US4937385, US6472354, and US6544936 respectively provide a method for preparing organic polysulfide by using olefin, sulfur and hydrogen sulfide as raw materials in the presence of different catalysts. The reaction path is: first, hydrogen sulfide reacts with olefin to generate intermediate alkyl mercaptan compound in the presence of elemental sulfur, then the sulfur molecule is ring-opening under heat, and various organic polysulfides with different sulfur atom contents are generated in the presence of a basic catalyst. The above method uses mercaptan as a substrate, or has mercaptan as an intermediate during the reaction. Since most mercaptans are expensive, toxic and have a foul odor, the obtained organic polysulfide has a bad odor due to the dissolution of hydrogen sulfide and unreacted mercaptan, and has poor stability. US5135670, US5338468, US5849677, and CN200710098327.7 respectively disclose a method for preparing organic polysulfide containing polysulfide cross-linking bonds by using olefin and elemental sulfur as raw materials in the presence of different catalysts. This method has simple preparation process, cheap and easy-to-obtain raw materials, and does not introduce halogen, but the obtained product has many impurities, bad odor and low sulfur content. US4204969, US5410088, and CN1534019 respectively provide a method for preparing relatively pure polysulfide by using olefin and halogenated sulfur as raw materials, first generating sulfurated olefin containing halogen groups, and then dehalogenating. The obtained product has high sulfur content and mild conditions, but a large amount of waste water, waste gas (HCl, H2S gas), and waste residue (containing NaCl and sulfide) are generated in the reaction, which is difficult to treat.

[0004] CN103937540A and CN108097333A disclose a sulfiding agent for hydrogenation catalyst and a preparation method thereof. The sulfur content of the sulfiding agent is 40wt%-80wt%, and the sulfiding agent comprises linear polysulfide and cyclic sulfide. The method overcomes the problems of existing sulfiding agents, such as high toxicity and high production cost. However, the proportion of cyclic polysulfide in the prepared sulfiding agent needs to be further improved, the length of the sulfur chain in the cyclic polysulfide is generally below 2, and 4A molecular sieves need to be added during the preparation process. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a hydrogenation catalyst sulfiding agent, a preparation method and application thereof. The sulfiding agent not only has a simple preparation method and is easy to control, but also can slowly decompose and release hydrogen sulfide in a hydrogen atmosphere.

[0006] A hydrogenation catalyst vulcanizing agent, which is an organic polysulfide, is calcined under a hydrogen atmosphere at 100-280 DEG C, and the weight loss is as follows, based on the total weight of the hydrogenation catalyst vulcanizing agent: 25-40% at 100-180 DEG C, 20-35% at greater than 180 DEG C to less than 215 DEG C, and 20-30% at 215-270 DEG C, preferably 28-35% at 100-180 DEG C, 25-30% at greater than 180 DEG C to less than 215 DEG C, and 22-28% at 215-270 DEG C.

[0007] In the hydrogenation catalyst vulcanizing agent, the mass content of disulfides in the hydrogenation catalyst vulcanizing agent is 8-20%, preferably 10-18%; the mass content of trisulfides is 25-50%, preferably 30-40%; and the mass content of tetrasulfides is 30-60%, preferably 40-50%.

[0008] In the hydrogenation catalyst vulcanizing agent, the sulfur content of the hydrogenation catalyst vulcanizing agent is 45 wt% or more, preferably 50-70 wt%.

[0009] In the hydrogenation catalyst vulcanizing agent, the hydrogenation catalyst vulcanizing agent contains cyclic trisulfides CnR2nS3, wherein R is any group that can be connected to a carbon atom, and is generally a hydrogen atom or an alkyl group (preferably a methyl group); and is further preferably C3H6S3.

[0010] In the hydrogenation catalyst vulcanizing agent, the cyclic trisulfides CnR2nS3 contained in the hydrogenation catalyst vulcanizing agent account for 2-15%, preferably 4-10%, of the total mass of the organic polysulfide. n R 2n S3.

[0011] A method for preparing a hydrogenation catalyst vulcanizing agent, which mainly comprises the following steps: reacting sulfur, an unsaturated hydrocarbon and a C8 or higher aliphatic hydrocarbon in the presence of an alkaline substance, and obtaining the hydrogenation catalyst vulcanizing agent after separation.

[0012] In the method, the C8 or higher aliphatic hydrocarbon can be a straight-chain alkane or an alkane with branches, and is preferably a straight-chain alkane with a chain length of C 10 -C 15 The addition amount of the aliphatic hydrocarbon is 1-10%, preferably 2-5%, of the mass of the sulfur.

[0013] In the method, the reaction temperature is controlled by heating the material system containing elemental sulfur, monitoring the viscosity coefficient of the material system, and when the viscosity coefficient of the material system changes from gradually decreasing to increasing, the temperature of the material system at this time is recorded as T, and the temperature of the material system is controlled to be higher than T by 0-15°C, preferably higher than 3-10°C, and after a period of reaction, the temperature is lowered, and the liquid material is separated to obtain a sulfur-containing composition.

[0014] In the method, the basic substance and / or alkane are added to the material system at least before the viscosity coefficient of the material system changes from gradually decreasing to increasing, and can be added before heating the material system or during heating the material system.

[0015] In the method, the unsaturated hydrocarbon can be added to the material system at one time and then heated, or can be introduced during heating, or can be introduced during the reaction, and the introduction can be continuous or intermittent.

[0016] In the method, the composition of the gas phase in the material system is detected during the continuous reaction, and when the volume content of hydrogen sulfide in the gas phase reaches 1-5%, preferably 2-4%, the reaction is stopped.

[0017] In the method, the preparation method of the hydrogenation catalyst sulfiding agent specifically comprises the following steps:

[0018] (1) heating the material system containing elemental sulfur, a basic substance, and a C8 or higher aliphatic hydrocarbon to liquefy the elemental sulfur;

[0019] (2) measuring the viscosity coefficient of the material system, when the viscosity coefficient of the material system changes from gradually decreasing to increasing, the temperature of the material system at this time is recorded as T, and then unsaturated hydrocarbon is introduced for reaction, and the temperature of the material system is controlled to be higher than T by 0-15°C, preferably higher than 5-10°C;

[0020] (3) detecting the composition of the gas phase in the material system, and when the volume content of hydrogen sulfide in the gas phase reaches 1-5%, preferably 2-4%, the reaction is stopped;

[0021] (4) after the reaction in step (2) is completed, the temperature is lowered, and after the liquid material is separated, a hydrogenation catalyst sulfiding agent is obtained.

[0022] According to the method, the elemental sulfur in step (1) is sulfur, which is a solid at room temperature and exists in the form of S8. The sulfur can be a commercially available product or prepared according to the prior art, and the purity of the sulfur is not strictly limited, and the sulfur can contain an appropriate amount of impurities.

[0023] According to the method of the present application, the basic substance in step (1) can be an organic basic substance and / or an inorganic basic substance. The basic substance can be one or more of methylamine, urea, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, 1,3-propanediamine, 1,2-propanediamine, tripropylamine, triethanolamine, butylamine, isobutylamine, tert-butylamine, hexylamine, octylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, aqueous ammonia, preferably one or more of dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, 1,3-propanediamine, 1,2-propanediamine, tripropylamine, triethanolamine.

[0024] According to the method of the present application, the basic substance in step (1) can also be a solid base, which can be a commercially available product or prepared according to the prior art.

[0025] According to the method of the present application, the mass ratio of the basic catalyst to the sulfur source in step (1) is 0.005-0.15, preferably 0.01-0.1.

[0026] According to the method of the present application, in step (1), the elemental sulfur, the basic substance and the C8+ aliphatic hydrocarbon are first put into a reaction device, for example, a reaction kettle; then the air is replaced with nitrogen gas and heated. The reaction device is equipped with a stirring device, a heat exchange device (heating or heat removal), a viscosity measuring device, a pressure measuring device, a temperature measuring device, etc.

[0027] According to the method of the present application, the heating rate in step (1) is not particularly limited, but in order to facilitate monitoring of the change in viscosity of the system, the heating rate is generally 0.5-5°C / min, preferably 1-3°C / min.

[0028] According to the method of the present application, the unsaturated hydrocarbon in step (2) is a low-carbon olefin, preferably a C2-C5 olefin. The olefin can be a pure olefin or a mixed olefin. The pure olefin can be any one of ethylene, propylene, 1-butene, 2-butene, isobutylene, n-pentene, isopentene, preferably propylene or isobutylene; the mixed olefin can be any mixture of the above pure olefins, or one or more of liquefied petroleum gas, ether front carbon four, ether rear carbon four mainly containing mixed olefins.

[0029] According to the method of the present application, the unsaturated hydrocarbon compound can be introduced in one time or continuously in step (2). When the unsaturated hydrocarbon compound is introduced in one time, the molar ratio of the total amount of the unsaturated hydrocarbon compound to the elemental sulfur is generally 1:1-1:5, preferably 1:2-1:4. When the unsaturated hydrocarbon compound is introduced continuously, the pressure of the reaction system is generally controlled at 20-40 kg / cm 2 , preferably 25-35 kg / cm 2 . 2 2 .

[0030] According to the method of the present application, the viscosity of the material system in step (2) is gradually reduced and then increased. The specific viscosity at the time when the viscosity is increased is different for different material systems. Generally, the viscosity is 3-40 Pa·s, preferably 5-30 Pa·s.

[0031] According to the method of the present application, the cooling process in step (4) can be carried out by using a conventional cooling method. The gaseous material after cooling can be recovered and reused. The liquid material can be separated by flash evaporation or distillation to obtain a sulfur-containing composition. For example, the flash evaporation is generally carried out at 30-70 °C and 1000-20000 pa for 1-2 h.

[0032] In the method of the present application, the length of the sulfur chain in the organic polysulfide vulcanizing agent is a key factor determining the sulfur content and properties of the organic polysulfide. Moreover, the proportion of linear organic polysulfide and cyclic organic polysulfide in the organic polysulfide has an important influence on the vulcanization properties. Taking the sulfurized hydrogenation catalyst as an example, the different decomposition temperatures of the organic polysulfide and the cyclic organic polysulfide can be used to achieve continuous and slow vulcanization of the catalyst, thereby inhibiting the adverse effects of concentrated vulcanization heat release on the active metals of the hydrogenation catalyst. However, it is difficult to prepare long-chain organic polysulfides.

[0033] Based on years of in-depth research on the preparation of organic polysulfides, the inventors found that there are two main reasons: first, the generation of sulfur free radicals in the reaction stage, long-chain free radicals with more than 2 sulfur atoms are unstable and tend to further crack, resulting in a low content of long-chain sulfur free radicals in the reaction system; second, due to factors such as reaction temperature and concentration of each material affecting the reaction equilibrium in the later stage of the reaction, the generated long-chain organic polysulfides are further decomposed.

[0034] ​Under the guidance of the above theory, the inventors innovatively propose adding an appropriate amount of C8 or more aliphatic hydrocarbon to the reaction system, using the phase transfer principle, and the long-chain organic polysulfide produced in the reaction process can be quickly transferred to the C8 aliphatic hydrocarbon. The long-chain organic polysulfide diffused in the aliphatic hydrocarbon can avoid the secondary cracking of monosulfide or disulfide caused by the high local temperature due to the sulfur chain breakage in the reaction process, thereby effectively adjusting the distribution of polysulfide in the sulfiding agent of the hydrogenation catalyst, and making the decomposition temperature of the produced sulfiding agent wide and slow, which is beneficial to the sulfuration of the hydrogenation catalyst.

[0035] In addition, the present application controls the end time by the content of the gas phase pressure change, avoids the decomposition of long-chain organic polysulfide, and controls the reaction temperature by monitoring the viscosity of the material system, thereby strengthening the concentration of sulfur tri-radicals in the reaction process and promoting the formation of long-chain organic polysulfide. The inventors surprisingly found that by the above control method, not only the sulfur content in the organic polysulfide is greatly improved, but also a cyclic trisulfide is found in the organic polysulfide. DETAILED DESCRIPTION

[0036] The effects and advantages of the method of the present application will be further illustrated by the following examples and comparative examples, but the following examples do not constitute a limitation on the present application. In the context of the present application, unless otherwise specified, all are mass percentages. In the method of the present application, the composition and sulfur content of the prepared organic polysulfide are determined by GC-MAS. In the method of the present application, the reaction equipment is a reaction kettle, which is equipped with stirring device, heat exchange device (heating or heat removal), viscosity measuring device, pressure measuring device, temperature measuring device, etc. as needed.

[0037] Example 1

[0038] Take 200g of elemental sulfur, 10g of diethylamine and 6g of n-dodecane into the reactor, then close the reactor and heat it at a rate of 2℃ / min, while monitoring the viscosity of the reaction material. When the viscosity coefficient of the material system changes from gradual decrease to increase, and the viscosity is 20Pa·s, the temperature at this time is 163℃. Then continuously introduce propylene, measure the total mass of propylene by mass flow meter, control the reaction temperature to be not higher than 171℃, and the pressure in the reactor to be 30kg / cm 2 At the same time, detect the content of hydrogen sulfide in the gas phase. When the volume content of hydrogen sulfide reaches 3%, stop the reaction. After the reaction is completed, cool the reactor to room temperature, take out the crude sulfiding agent product in the reactor, flash evaporate it at 50℃ and 10000pa for 1h to obtain the sulfiding agent product. The unreacted olefins are cooled and recycled for reuse. The analysis results of the obtained sulfiding agent product are shown in Table 1.

[0039] Example 2

[0040] Take 200g of elemental sulfur, 2g of dimethylamine and 6g of n-decane into the reactor, then seal the reactor and heat it up at a rate of 1°C / min while monitoring the viscosity of the reaction material. When the viscosity coefficient of the material system gradually decreases and then increases, and the viscosity is 5 Pa·s, the temperature is 159°C at this time. Continue to introduce ethylene, measure the total mass of ethylene by mass flow meter, control the reaction temperature to be no higher than 169°C, and the pressure in the reactor to be 20 kg / cm 2 At the same time, detect the content of hydrogen sulfide in the released gas. When the volume content of hydrogen sulfide reaches 2%, stop the reaction. After the reaction is completed, cool the reactor to room temperature, take out the crude vulcanizing agent product in the reactor, and flash evaporate it at 30°C and 20,000 Pa for 2h to obtain the vulcanizing agent product. The unreacted olefins are cooled and recycled for reuse. The analysis results of the obtained vulcanizing agent product are shown in Table 1.

[0041] Example 3

[0042] Take 200g of elemental sulfur, 20g of propylamine and 4g of n-pentadecane into the reactor, then seal the reactor and heat it up at a rate of 3°C / min while monitoring the viscosity of the reaction material. When the viscosity coefficient of the material system gradually decreases and then increases, and the viscosity is 5 Pa·s, the temperature is 167°C at this time. Introduce propylene, measure the total mass of propylene by mass flow meter, control the reaction temperature to be no higher than 172°C, and the pressure in the reactor to be 40 kg / cm 2 At the same time, detect the content of hydrogen sulfide in the released gas. When the volume content of hydrogen sulfide reaches 4%, stop the reaction. After the reaction is completed, cool the reactor to room temperature, take out the crude vulcanizing agent product in the reactor, and flash evaporate it at 70°C and 1,000 Pa for 1.5h to obtain the vulcanizing agent product. The unreacted olefins are cooled and recycled for reuse. The analysis results of the obtained vulcanizing agent product are shown in Table 1.

[0043] Example 4

[0044] Take 300g of elemental sulfur, 7g of trimethylamine, 8g of triethylamine and 6g of n-dodecane into the reactor, then seal the reactor and heat it up at a rate of 2°C / min while monitoring the viscosity of the reaction material. When the viscosity coefficient of the material system gradually decreases and then increases, and the viscosity is 20 Pa·s, the temperature is 160°C at this time. Continuously introduce isobutylene, measure the total mass of isobutylene by mass flow meter, control the reaction temperature to be no higher than 169°C, and the pressure in the reactor to be 30 kg / cm 2 At the same time, detect the content of hydrogen sulfide in the released gas. When the volume content of hydrogen sulfide reaches 3%, stop the reaction. After the reaction is completed, cool the reactor to room temperature, take out the crude vulcanizing agent product in the reactor, and flash evaporate it at 50°C and 10,000 Pa for 1h to obtain the vulcanizing agent product. The unreacted olefins are cooled and recycled for reuse. The analysis results of the obtained vulcanizing agent product are shown in Table 1.

[0045] Example 5

[0046] Take 300g of elemental sulfur, 5g of triethanolamine and 10g of n-decane into the reactor, then seal the reactor and heat it at a rate of 1°C / min while monitoring the viscosity of the reaction material. When the viscosity coefficient of the material system changes from gradual decrease to increase and the viscosity is 20 Pa-s, the temperature is 161°C. At this time, a mixture of propylene and isobutylene (mass ratio 1:2) is introduced, the total mass of the mixture is measured by a mass flow meter, the reaction temperature is controlled to be no higher than 169°C, and the pressure in the reactor is 25 kg / cm 2 At the same time, the content of hydrogen sulfide in the released gas is detected. When the volume content of hydrogen sulfide reaches 3%, the reaction is stopped. After the reaction is completed, the reactor is cooled to room temperature, the vulcanizing agent crude product in the reactor is taken out, and the vulcanizing agent product is obtained by flashing at 50°C and 10,000 Pa for 1 h. The unreacted olefins are recovered after cooling and reused. The analysis results of the obtained vulcanizing agent product are shown in Table 1.

[0047] Example 6

[0048] Take 300g of elemental sulfur, 10g of 1,3-propanediamine and 8g of n-dodecane into the reactor, then seal the reactor and heat it at a rate of 2°C / min while monitoring the viscosity of the reaction material. When the viscosity coefficient of the material system changes from gradual decrease to increase and the viscosity is 21 Pa-s, a mixture of propylene and 2-butene (mass ratio 1:1) is introduced, the total mass of the mixture is measured by a mass flow meter, the reaction temperature is controlled to be no higher than 169°C, and the pressure in the reactor is 30 kg / cm 2 At the same time, the content of hydrogen sulfide in the released gas is detected. When the volume content of hydrogen sulfide reaches 3%, the reaction is stopped. After the reaction is completed, the reactor is cooled to room temperature, the vulcanizing agent crude product in the reactor is taken out, and the vulcanizing agent product is obtained by flashing at 50°C and 10,000 Pa for 1 h. The unreacted olefins are recovered after cooling and reused. The analysis results of the obtained vulcanizing agent product are shown in Table 1.

[0049] Table 1 Experimental results

[0050]

[0051] *: The synthesized product was analyzed by thermal gravimetric analysis using a Q600 type simultaneous thermal analyzer (Simultaneous DSC-TGA) produced by TA Company, USA. The thermal gravimetric analysis was carried out in a H2 atmosphere with a fixed flow rate of 30 mL / min; the temperature was increased from room temperature to 400°C at a fixed rate of 10°C / min.

Claims

1. A hydrogenation catalyst sulfiding agent, characterized in that: The hydrogenation catalyst sulfiding agent is an organic polysulfide, wherein the mass content of disulfide in the hydrogenation catalyst sulfiding agent is 8-20%, the mass content of trisulfide is 25-50%, and the mass content of tetrasulfide is 30-60%; the hydrogenation catalyst sulfiding agent contains cyclic trisulfide C. n R 2n S3, where R is any group attached to the same carbon atom, and the cyclic trisulfide C n R 2n S3 accounts for 2-15% of the total mass of the organic polysulfide; the organic polysulfide is calcined at 100℃-280℃ in a hydrogen atmosphere, and the weight loss is as follows based on the total weight of the hydrogenation catalyst and sulfiding agent: 25-40% weight loss at 100℃-180℃, 20-35% weight loss at temperatures above 180℃ to below 215℃, and 20-30% weight loss at 215℃-270℃.

2. The hydrogenation catalyst sulfiding agent according to claim 1, characterized in that: Based on the total weight of the hydrogenation catalyst sulfiding agent, the weight loss is as follows: 28-35% at 100℃-180℃, 25-30% at temperatures above 180℃ to below 215℃, and 22-28% at 215℃-270℃.

3. The hydrogenation catalyst sulfiding agent according to claim 1, characterized in that: The hydrogenation catalyst sulfiding agent contains 10-18% disulfide, 30%-40% trisulfide, and 40-50% tetrasulfide by mass.

4. The hydrogenation catalyst sulfiding agent according to claim 1, characterized in that: The sulfur content of the hydrogenation catalyst sulfiding agent is above 45 wt%.

5. The hydrogenation catalyst sulfiding agent according to claim 4, characterized in that: The sulfur content of the hydrogenation catalyst sulfiding agent is 50wt%-70wt%.

6. The hydrogenation catalyst sulfiding agent according to claim 1, characterized in that: Cyclic trisulfides are C3H6S3.

7. The hydrogenation catalyst sulfiding agent according to claim 1, characterized in that: The hydrogenation catalyst sulfiding agent contains cyclic trisulfide C n R 2n S3 accounts for 4-10% of the total mass of organic polysulfides.

8. A method for preparing the hydrogenation catalyst sulfiding agent according to any one of claims 1 to 7, characterized in that: The process includes the following: Elemental sulfur and unsaturated hydrocarbons react in the presence of alkaline substances and aliphatic hydrocarbons with 8 or more carbon atoms. After the reaction, a hydrogenation catalyst (sulfiding agent) is obtained through separation. The aliphatic hydrocarbons with 8 or more carbon atoms are C64-C ... 10 -C 15 Straight-chain alkanes; the amount of the C8 or higher aliphatic hydrocarbons added is 1%-10% of the mass of elemental sulfur; The reaction temperature is controlled as follows: the material system containing sulfur is heated, the viscosity coefficient of the material system is monitored, and when the viscosity coefficient of the material system changes from gradually decreasing to increasing, the temperature of the material system at this time is recorded as T. The temperature of the material system is controlled to be 0-15℃ higher than T. After the reaction is continued for a period of time, the temperature is lowered and the liquid material is separated to obtain the sulfur-containing composition. The gas phase composition of the material system is monitored during the continuous reaction process, and the reaction is stopped when the volume content of hydrogen sulfide in the gas phase reaches 1-5%.

9. The method according to claim 8, characterized in that: The amount of C8 or higher aliphatic hydrocarbons added is 2%-5% of the mass of elemental sulfur.

10. The method according to claim 8, characterized in that: The reaction temperature is controlled as follows: the material system containing elemental sulfur is heated, the viscosity coefficient of the material system is monitored, and when the viscosity coefficient of the material system changes from gradually decreasing to increasing, the temperature of the material system at this time is recorded as T. The temperature of the material system is controlled to be 3-10℃ higher than T. After the reaction is continued for a period of time, the temperature is lowered and the liquid material is separated to obtain the sulfur-containing composition.

11. The method according to claim 8, characterized in that: The alkaline substance and / or aliphatic hydrocarbons of C8 or above shall be added to the material system at least before the viscosity coefficient of the material system changes from gradually decreasing to increasing, or before the material system is heated, or during the heating process of the material system.

12. The method according to claim 8, characterized in that: Unsaturated hydrocarbons are added to the material system in one go, followed by heating, or introduced during heating or reaction, and the introduction can be continuous or intermittent.

13. The method according to claim 8, characterized in that: The gas phase composition of the material system is monitored during the continuous reaction process, and the reaction is stopped when the volume content of hydrogen sulfide in the gas phase reaches 2-4%.

14. The method according to claim 8, characterized in that: The preparation method of the hydrogenation catalyst sulfiding agent specifically includes the following steps: (1) Heating a material system containing elemental sulfur, alkaline substances, and aliphatic hydrocarbons with more than 8 carbon atoms to liquefy the elemental sulfur; (2) Measure the viscosity coefficient of the material system. When the viscosity coefficient of the material system changes from gradually decreasing to increasing, the temperature of the material system is recorded as T. Then, unsaturated hydrocarbons are introduced to react, and the temperature of the material system is controlled to be higher than T by 0-15℃. (3) Detect the gas phase composition in the material system, and stop the reaction when the volume content of hydrogen sulfide in the gas phase reaches 1-5%; (4) After the reaction in step (3) is completed, the temperature is lowered and the liquid material is separated to obtain the hydrogenation catalyst sulfiding agent.

15. The method according to claim 8, characterized in that: The preparation method of the hydrogenation catalyst sulfiding agent specifically includes the following steps: (1) Heating a material system containing elemental sulfur, alkaline substances, and aliphatic hydrocarbons with more than 8 carbon atoms to liquefy the elemental sulfur; (2) Measure the viscosity coefficient of the material system. When the viscosity coefficient of the material system changes from gradually decreasing to increasing, the temperature of the material system is recorded as T. Then, unsaturated hydrocarbons are introduced to react, and the temperature of the material system is controlled to be 5-10℃ higher than T. (3) Detect the gas phase composition in the material system. Stop the reaction when the volume content of hydrogen sulfide in the gas phase reaches 2-4%. (4) After the reaction in step (3) is completed, the temperature is lowered and the liquid material is separated to obtain the hydrogenation catalyst sulfiding agent.

16. The method according to claim 14 or 15, characterized in that: The elemental sulfur mentioned in step (1) is sulfur, which is a solid at room temperature and exists in the form of S8.

17. The method according to claim 14 or 15, characterized in that: The alkaline substance mentioned in step (1) is used as a catalyst, and the alkaline substance is an organic alkaline substance and / or an inorganic alkaline substance.

18. The method according to claim 14 or 15, characterized in that: The unsaturated hydrocarbons mentioned in step (2) are low-carbon olefins.

19. The method according to claim 18, characterized in that: The unsaturated hydrocarbons mentioned in step (2) are C2-C5 olefins.

20. The method according to claim 19, characterized in that: The unsaturated hydrocarbons mentioned in step (2) are propylene and / or isobutylene.

21. The method according to claim 14 or 15, characterized in that: In step (2), the required unsaturated hydrocarbons are introduced either all at once or continuously. When introducing unsaturated hydrocarbons all at once, the molar ratio of the total amount of unsaturated hydrocarbons to elemental sulfur is 1:1 to 1:

5. When introducing unsaturated hydrocarbons continuously, the pressure of the reaction system is controlled at 20 kg / cm². 2 -40kg / cm 2 .

22. The method according to claim 21, characterized in that: In step (2), the total amount of unsaturated hydrocarbons introduced at one time has a molar ratio of 1:2 to 1:4 to sulfur.

23. The method according to claim 21, characterized in that: In step (2), unsaturated hydrocarbons are continuously introduced to control the pressure of the reaction system at 25 kg / cm². 2 -35kg / cm 2 .

24. The method according to claim 14 or 15, characterized in that: In step (2), the viscosity of the material system changes from gradually decreasing to increasing, and the viscosity is 3-40 Pa·s.

25. The method according to claim 24, characterized in that: In step (2), the viscosity of the material system changes from gradually decreasing to increasing, and the viscosity is 5-30 Pa·s.

26. The method according to claim 14 or 15, characterized in that: In step (4), the cooling process adopts conventional cooling methods. The cooled gaseous material is recovered and reused, and the liquid material is separated by flash evaporation or distillation to obtain a sulfur-containing composition.

Images