CN103468303A - Method for selective hydrodesulfurization of gasoline - Google Patents

Abstract

A method for selective hydrodesulfurization of gasoline, comprising contacting and reacting gasoline distillate raw materials with a catalyst under gasoline hydrodesulfurization reaction conditions, wherein the catalyst contains a shaped carrier containing hydrated alumina, and at least One non-noble metal component selected from group VIII, at least one metal component selected from group VIB, based on the catalyst, the content of the metal component of group VIII in terms of oxide is 0.1-6% by weight, The content of the Group VIB metal component calculated as oxide is 1-25% by weight, and the content of the carrier is 69-98% by weight. Compared with the prior art, the gasoline hydrogenation desulfurization activity of the invention is obviously improved, and has very good hydrogenation desulfurization selectivity.

Description

A method for selective hydrodesulfurization of gasoline

technical field

The invention relates to a hydrodesulfurization method, in particular to a method for selective hydrodesulfurization of gasoline.

Background technique

Air pollution is a serious environmental problem, and a large amount of engine emissions is one of the important causes of air pollution. In recent years, in order to protect the environment, countries around the world have put forward stricter restrictions on the composition of engine fuel in order to reduce the emission of harmful substances.

At present, 90% to 99% of the sulfur in my country's finished gasoline comes from FCC gasoline. Therefore, reducing the sulfur content of FCC gasoline is the key to reducing the sulfur content of finished gasoline.

To reduce the sulfur content of FCC gasoline, there are usually two technical solutions: hydropretreatment of FCC feedstock (pre-hydrogenation) or hydrodesulfurization of FCC gasoline (post-hydrogenation). Among them, the pretreatment of catalytic cracking raw materials can greatly reduce the sulfur content of catalytic cracking gasoline, but it needs to be operated under very harsh conditions of temperature and pressure. At the same time, because of the large processing capacity of the device, the hydrogen consumption is also relatively large, all of which will increase the capacity of the device. investment or operating costs. However, due to the heavy crude oil in the world, more and more catalytic cracking units have begun to process inferior raw materials containing atmospheric and vacuum residues, so the number of hydrogenation units for catalytic cracking raw materials is also increasing year by year. At the same time, with the innovation of catalytic cracking technology and the gradual application of catalytic cracking desulfurization additives and/or olefin reduction additives, the sulfur content of catalytic cracking gasoline of some enterprises in my country can reach below 500 μg/g, or even below 150 μg/g. But if you want to further reduce the sulfur content of FCC gasoline, make it less than 50μg/g (meet the limit of gasoline sulfur content in Euro IV emission standard), or even less than 10μg/g (meet the limit of sulfur content in gasoline in Euro V emission standard) , it is still necessary to build a gasoline hydrogenation unit. Compared with pre-hydrogenation, FCC gasoline hydrodesulfurization is lower than FCC raw material hydrodesulfurization pretreatment in terms of equipment investment, production cost and hydrogen consumption. However, using traditional catalysts and processes, while hydrodesulfurization, large hydrogenation saturation of olefins will cause a large loss of product octane number. One of the effective ways to solve the above problems is to use selective hydrodesulfurization technology to treat FCC gasoline.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new method for gasoline hydrodesulfurization with better selectivity.

The content involved in the present invention includes:

1. A gasoline selective hydrodesulfurization method, comprising contacting the gasoline distillate raw material with a catalyst under the conditions of gasoline hydrodesulfurization reaction, wherein the catalyst contains a molded product carrier containing hydrated alumina, loaded on the carrier At least one non-noble metal component selected from Group VIII, at least one metal component selected from Group VIB, based on the catalyst, the content of the Group VIII metal component in terms of oxides is 0.1-6 % by weight, the content of Group VIB metal components calculated as oxides is 1-25% by weight, and the content of the carrier is 69-98% by weight.

2. The method according to 1, characterized in that, based on the catalyst, the content of the Group VIII metal component in terms of oxides in the hydrodesulfurization catalyst is 1-5% by weight, and the content of the group VIII metal components in terms of oxides The content of the VIB group metal component is 5-20% by weight, and the content of the carrier is 75-94% by weight.

3. The method according to 1, characterized in that the carrier of the shaped product containing alumina hydrate in the hydrodesulfurization catalyst contains hydrated alumina and cellulose ether, and the radial crushing strength of the shaped product is Greater than or equal to 12N/mm, the water absorption rate is 0.4-1.5, and the δ value is less than or equal to 10%; where, δ=((Q1-Q2)/Q1)×100%, Q1 is the radial crushing strength of the molding, and Q2 It is the radial crushing strength of the molded product after soaking in water for 30 minutes and heating and drying at 120°C for 4 hours.

4. The method according to 3, characterized in that the radial crushing strength of the molding is 15-30 N/mm, the water absorption is 0.6-1, and δ is less than or equal to 5%.

5. The method according to 3, characterized in that, based on the molded product, the mass fraction of the cellulose ether is 0.5-8%.

6. The method according to 5, characterized in that, based on the molded product, the mass fraction of the cellulose ether is 1-6%.

7. The method according to 6, characterized in that, based on the molded product, the mass fraction of the cellulose ether is 2-5%.

8. The method according to 3, wherein the cellulose ether is selected from one or more of methylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.

9. The method according to 8, wherein the cellulose ether is methyl cellulose, hydroxyethyl methyl cellulose and mixtures thereof.

10. The method according to 1 or 3, wherein the hydrated alumina is selected from one or more of pseudoboehmite, boehmite, aluminum hydroxide, and aluminum hydroxide trihydrate.

11. The method according to 10, wherein the hydrated alumina is pseudo-boehmite.

12. The method according to 1, characterized in that the catalyst contains one or more organic substances selected from alcohols, organic acids and organic amines, and the molar ratio of the organic substances to the Group VIII metal component is 0.5-2.5.

13. The method according to 12, characterized in that the molar ratio of the organic matter to the Group VIII metal component is 1-2.

14. The method according to 1, characterized in that when the gasoline distillate feedstock and hydrogen are contacted with the hydrodesulfurization catalyst, it also includes introducing a heavy distillate to contact the catalyst, and the heavy distillate The initial boiling point of the oil is greater than the final boiling point of the gasoline distillate, and the introduction amount of the heavy distillate is 0.2h ^-1 -2h ^-1 in terms of liquid hourly volume space velocity,

15. The method according to 14, wherein the heavy distillate is selected from diesel distillate and/or lubricating oil distillate, and the initial boiling point of the heavy distillate is the same as the final boiling point of the gasoline distillate. The temperature difference of the distillation point is not less than 1°C, and the introduction amount of heavy distillate oil is 0.4h ^-1 -1.8h ^-1 in terms of liquid hourly volume space velocity.

16. The method according to 15, characterized in that the temperature difference between the initial boiling point of the heavy distillate and the final boiling point of the gasoline distillate is not less than 10°C, measured by liquid hourly volume space velocity, heavy The introduction amount of distillate is 0.6h ^-1 -1.8h ^-1 .

17. The method according to 15 or 16, characterized in that the temperature difference between the initial boiling point of the heavy distillate and the end boiling point of the gasoline distillate is not less than 20°C.

18. The method according to 17, characterized in that the temperature difference between the initial boiling point of the heavy distillate and the final boiling point of the gasoline distillate is not less than 40°C.

19. The method according to 15 or 16, wherein the heavy distillate oil is derived from one or more of petroleum and synthetic oil.

20. The method according to 19, wherein the synthetic oil is selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthetic oil and biosynthetic oil.

21. The method according to 1, wherein the gasoline distillate is selected from one or more of catalytic cracked gasoline, catalytic cracked gasoline, straight-run gasoline, coker gasoline, thermal cracked gasoline and thermal cracked gasoline.

22. The method according to 21, wherein the gasoline distillate has a distillation range of 30-220°C.

23. The method according to 1, characterized in that the gasoline hydrodesulfurization reaction conditions include: pressure 0.8MPa-3.2MPa, temperature 200°C-320°C, gasoline distillate oil liquid hourly volume space velocity 3h ^- 1-8h ^-1 . The hydrogen-to-oil ratio is 200Nm ³ /m ³ to 600Nm ³ /m ³ .

24. The method according to 23, characterized in that the gasoline hydrodesulfurization reaction conditions include: reaction pressure 1MPa-2.8MPa, reaction temperature 220°C-270°C, gasoline distillate oil liquid hourly volume space velocity 3h ^- 1-6h ^-1 . The hydrogen-to-oil ratio is 300Nm ³ /m ³ -500Nm ³ /m ³ .

25. The method according to 1 or 14, characterized in that, after the gasoline distillate raw material is contacted and reacted with the catalyst under the gasoline hydrodesulfurization reaction conditions, the step of separating the produced oil is further included.

26. The method according to 24, wherein said separation comprises the steps of stripping and fractionation.

Wherein, the preparation method of the water-containing and alumina molding includes mixing alumina hydrate and cellulose ether, molding and drying, wherein, the amount of each component and the molding and drying conditions make the radial crushing of the molding The strength is greater than or equal to 12N/mm, the water absorption rate is 0.4-1.5, and the δ value is less than or equal to 10%; where, δ=((Q1-Q2)/Q1)×100%, Q1 is the radial crushing strength of the molding, Q2 is the radial crushing strength of the molded product after soaking in water for 30 minutes and heating and drying at 120°C for 4 hours. The value of δ represents the change in radial crushing strength (or strength loss rate) of the hydrated alumina molding before and after soaking in water.

Preferably, the dosage of each component and the molding and drying conditions make the radial crushing strength of the molded product 15N/mm-30N/mm, the water absorption rate 0.6-1, and δ is less than or equal to 5%. Based on the molded product, the mass fraction of the cellulose ether is 0.5-8%, more preferably 1%-6%, more preferably 2%-5%; the drying conditions include: a temperature of 60°C to Less than 350°C, more preferably 80-150°C, more preferably 100-130°C; drying time is 1-48 hours, more preferably 2-14 hours, more preferably 3-10 hours. The cellulose ether is selected from one or more of methyl cellulose, hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose, more preferably methyl cellulose, hydroxyethyl methyl cellulose and their mixture.

In the present invention, the measuring method of the radial crushing strength of the molding is carried out according to the RIPP 25-90 catalyst compressive strength test method, and the specific steps for measuring the radial crushing strength of the molding are introduced in detail in RIPP 25-90, I won't go into details here.

The water absorption rate is measured by the following specific method: first, the sample to be tested is dried at 120° C. for 4 hours. Take out the sample, place it in a desiccator to cool to room temperature, sieve it with a 40-mesh standard sieve, weigh 20g of the sieve (code: w1) of the sample to be tested, add 50g of deionized water, soak for 30min, filter, and solid-phase leach Dry for 5 minutes, weigh the weight of the solid phase (code: w2), transfer the solid phase to an oven, heat and dry at 120°C for 4 hours, and place it in a desiccator to cool to room temperature. Water absorption = (w2-w1)/w1

The hydrated alumina moldings provided by the present invention may contain auxiliary components that do not affect or are beneficial to improve the radial crushing strength, water absorption and δ value of the moldings. For example, it contains a starch addition component, and the starch can be any powder obtained by crushing plant seeds, such as kale powder.

The hydrated alumina is selected from any hydrated alumina that can be used as an adsorbent and a catalyst carrier precursor, for example, it can be pseudo-boehmite, boehmite, aluminum hydroxide, aluminum hydroxide trihydrate, Pseudoboehmite is preferred.

In the present invention, the preparation method of the hydrated alumina molded article may be any prior art. For example, the forming method may be extrusion, spheronization, sheeting and a combination thereof. In order to ensure the smooth progress of molding, additives and water can be introduced into the material (here, a mixture of alumina hydrate and cellulose ether) during molding. For example, when molding by extrusion method, including the Alumina hydrate and cellulose ether are mixed with water, with or without extrusion aid, and then extruded to obtain a wet strip, and then dried to obtain the molded product of the present invention. The auxiliary agent is selected from starch, and the starch can be any powder obtained by pulverizing plant seeds, such as kale powder. The preferred molding method is extrusion molding.

Support at least one metal component selected from non-noble metals of Group VIII and at least one metal component selected from Group VIB on the formed water and alumina carrier, and the catalyst contains alcohols, organic acids When and organic amine, the method that is selected from alcohol, organic acid and organic amine is preferably impregnated on the water of shaping and alumina carrier, and described impregnating method is conventional method, for example pore saturation method impregnation, excess liquid impregnation and spray dipping etc. Wherein, preparation of impregnation solution is included, for example, the compound containing at least one metal component selected from Group VIB, the compound containing at least one metal component of Group VIII, or the organic substance is respectively prepared impregnation solution ( When containing organic matter), and impregnating the carrier with these impregnating solutions; or by the compound containing at least one metal component selected from Group VIB, the metal component containing at least one Group VIII and the Two or three of the organics (when organics are contained) are prepared to mix impregnation solutions and impregnate the support with these impregnation solutions. When the impregnation is a stepwise impregnation, there is no limitation on the order in which the impregnation solution impregnates the support. Although not required, a drying step is preferably included after each impregnation. The drying conditions include: a drying temperature of 100-210°C, preferably 150-190°C, and a drying time of 1-6 hours, preferably 2-4 hours.

The compound containing the non-noble metal component of Group VIII is selected from one or more of their soluble salts and complexes, for example, nitrates, chlorides, acetates, basic carbonic acid salts of Group VIII metals One or more in the salt, take cobalt salt as an example and be selected from one or more in the solubility of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt.

The compound containing VIB group metal components is selected from one or more of their soluble compounds, for example, molybdenum oxide, molybdate (for example, ammonium molybdate, ammonium paramolybdate, ammonium phosphomolybdate), One or more of tungstates (for example, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate).

Described alcohol can be selected from one or more in ethylene glycol, glycerol, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, and described acid is selected from acetic acid , maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, malic acid, the organic amine is selected from ethylenediamine or EDTA and its ammonium salt. Wherein, the introduction amount selected from alcohols, organic acids and organic amines satisfies the molar ratio of the organic matter to the Group VIII metal component, preferably 0.5-2.5, more preferably 1-2.

According to the method provided by the present invention, the catalyst may contain any substance that does not affect the catalytic performance of the catalyst provided by the present invention or that can improve the catalytic performance of the catalyst provided by the present invention. If phosphorus can be contained, the content of the above-mentioned additives is not more than 10% by weight, preferably 0.5-5% by weight, in terms of elements and based on the catalyst.

When the catalyst also contains components selected from phosphorus and the like, the introduction method of the components selected from phosphorus can be any method, such as combining the compound containing the auxiliary agent with the non- The metal salt of the noble metal and the metal salt selected from the VIB group are formulated into a mixed solution and then introduced by impregnating the carrier.

Before the catalyst provided by the invention is used, it is usually preferred to carry out presulfurization with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370 ° C in the presence of hydrogen, and this presulfurization can be carried out outside the device or in the device. In situ vulcanization converts it to the sulfide form.

The gasoline hydrodesulfurization reaction conditions are conventional gasoline selective hydrodesulfurization reaction conditions, and the preferred operating conditions include: reaction pressure 0.8MPa-3.2MPa, reaction temperature 200°C-320°C, gasoline distillate oil liquid hourly volume space velocity 3h ^-1 -8h ^-1 , hydrogen oil ratio 200Nm ³ /m ³ -600Nm ³ /m ³ , further preferred reaction conditions include: reaction pressure 1MPa-2.4MPa, reaction temperature 220°C-270°C, gasoline distillate oil The volume space velocity is 3h ^-1 -6h ^-1 , the hydrogen-oil ratio is 300Nm ³ /m ³ -500Nm ³ /m ³ .

According to the method provided by the present invention, the gasoline raw material to be hydrogenated may be one or more of catalytic cracking gasoline, catalytic cracking gasoline, straight-run gasoline, coker gasoline, pyrolysis gasoline and thermal cracking gasoline. The gasoline raw material to be hydrogenated is a whole distillate gasoline raw material, and the distillation range is the conventional distillation range of gasoline distillate, for example: 30-220°C.

In the present invention, the heavy distillate oil is selected from diesel distillate oil and/or lubricating oil distillate oil, and the temperature difference between the initial boiling point of the heavy distillate oil and the final boiling point of the gasoline distillate oil is not less than 1°C, Preferably not less than 10°C, more preferably not less than 20°C, more preferably not less than 40°C. The amount of heavy distillate introduced is preferably 0.4h ^-1 -1.8h ^-1 , more preferably 0.6h ^-1 -1.8h ^-1 .

The heavy distillate oil is derived from one or more of petroleum and synthetic oil (for example: selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthetic oil and biosynthetic oil). Under the reaction conditions of the present invention, at least part of the heavy distillate exists in the form of liquid.

The method of introducing the heavy distillate in the present invention is not limited as long as the conditions are sufficient to introduce the heavy distillate into contact with the catalyst. For example, the heavy distillate can be mixed with gasoline distillate at first, and then introduced into the reactor to contact with the catalyst under gasoline hydrodesulfurization reaction conditions; device, and then contact the catalyst under gasoline selective hydrodesulfurization reaction conditions. In this regard, the present invention is not particularly limited. The reactor may be any reactor suitable for hydrogenation of gasoline distillates in the prior art, such as a fixed-bed hydrogenation reactor.

According to the method provided by the present invention, it also includes any separation steps required to obtain the target product, and the separation methods and devices are commonly used methods and devices in the art. For example, the resulting oil is stripped using conventional devices and methods in the art to remove gaseous impurities such as hydrogen sulfide contained in the resulting oil, followed by distillation and separation. Gasoline distillates obtained by separation are recovered as products, and when heavy distillates are introduced, heavy distillates are recovered after separation, and the oil may be partially or fully recycled

Compared with the prior art, the gasoline hydrogenation desulfurization activity of the invention is obviously improved, and has very good hydrogenation desulfurization selectivity.

Detailed ways

The following examples will further illustrate the method provided by the present invention, but do not limit the present invention thereby.

Examples 1-6 illustrate shaped supports comprising hydrated alumina and their preparation.

Example 1

Take 100g of pseudo-boehmite powder produced by Catalyst Changling Branch, add 4.0g of methyl cellulose, 3.0g of scallop powder and 95mL of deionized water, fully stir and mix evenly, after kneading evenly by an extruder, extrude to form A wet form of aluminum hydroxide is obtained. Place the wet aluminum hydroxide molding in an oven at 150°C for 12 hours to dry. The molded carrier Z1 was obtained, and the radial crushing strength, water absorption rate and δ value (strength loss rate) of Z1 were measured, and the results are listed in Table 1.

Example 2

Take 50g of pseudo-boehmite powder produced by Catalyst Changling Branch, 50g of self-made amorphous aluminum hydroxide powder, add 2.0g of methylcellulose, 3.0g of hydroxyethylmethylcellulose and 95mL of deionized water, fully stir and mix Uniform, after being kneaded evenly by extruder, extruded to obtain wet molding of aluminum hydroxide. Place the wet aluminum hydroxide molding in an oven at 220°C to dry for 6 hours. The molded carrier Z2 was obtained, and the radial crushing strength, water absorption rate and δ value of Z2 were measured, and the results are listed in Table 1.

Example 3

Get 60g of pseudo-boehmite powder produced by Catalyst Changling Branch, 40g of aluminum hydroxide trihydrate, add 1.0g of methylcellulose, 2.0g of hydroxypropylmethylcellulose, 3.0g of kale powder and 95mL of deionized water , fully stirred and mixed evenly, after being kneaded evenly by an extruder, extruded to obtain a wet molded product of aluminum hydroxide. Place the wet aluminum hydroxide molding in an oven at 80°C for 12 hours to dry. The molded carrier Z3 was obtained, and the radial crushing strength, water absorption rate and δ value of Z3 were measured, and the results are listed in Table 1.

Example 4

Take 100 g of pseudo-boehmite SB powder produced by Sasol Company, add 3.0 g of hydroxyethyl methylcellulose and 90 mL of deionized water, fully stir and mix evenly, after kneading evenly by an extruder, extrude to obtain a shaped bar. The aluminum hydroxide shaped strips were dried in an oven at 150°C for 12 hours. The molded carrier Z4 was obtained, and the radial crushing strength, water absorption rate and δ value of Z4 were measured, and the results are listed in Table 1.

Example 5

Get 100g of pseudo-boehmite SB powder produced by Sasol Company, add 3.0g of hydroxyethyl methylcellulose, 2g of hydroxypropylmethylcellulose, 3.0g of turnip powder and 90mL of deionized water, fully stir and mix, After being uniformly kneaded by an extruder, the extruded bar is formed to obtain a shaped bar. The aluminum hydroxide shaped strips were dried in an oven at 250°C for 4 hours. The molded carrier Z5 was obtained, and the radial crushing strength, water absorption rate and δ value of Z5 were measured, and the results are listed in Table 1.

Example 6

Take 100g of pseudo-boehmite powder produced by Shandong Yantai Henghui Chemical Co., Ltd., add 5.0g of hydroxypropyl methylcellulose, 3.0g of scallop powder and 90mL of deionized water, stir and mix evenly, and knead evenly through an extruder Finally, extruded strips are formed to obtain shaped strips. The formed strips were dried in an oven at 120°C for 4 hours. The molded carrier Z6 was obtained, and the radial crushing strength, water absorption rate and δ value of Z6 were measured, and the results are listed in Table 1.

Comparative Examples 1-4 illustrate reference shaped supports and their preparation.

Comparative example 1

Take 100g of pseudo-boehmite powder produced by Catalyst Changling Branch, add 2.5mL of concentrated nitric acid, 3.0g of scallop powder and 95mL of deionized water, fully stir and mix evenly, after kneading evenly through an extruder, extrude into a shape strip. The formed strips were dried in an oven at 80°C for 4 hours. The molded carrier DZ1 was obtained, and the radial crushing strength, water absorption rate and δ value of DZ1 were measured, and the results are listed in Table 1.

Comparative example 2

Take 100g of pseudo-boehmite SB powder produced by Condea Company, add 20ml of aluminum sol, 3.0g of scallop powder and 90mL of deionized water, stir well and mix evenly. The formed strips were dried in an oven at 150°C for 4 hours. The molded carrier DZ2 was obtained, and the radial crushing strength, water absorption rate and δ value of DZ2 were measured, and the results are listed in Table 1.

Comparative example 3

Take 100g of pseudo-boehmite powder produced by Shandong Yantai Henghui Chemical Co., Ltd., add 5.0mL of acetic acid, 3.0g of scallop powder and 90mL of deionized water, fully stir and mix evenly, after kneading evenly by an extruder, extrude to obtain Molded strips. The formed strips were dried in an oven at 180°C for 4 hours. The molded carrier DZ3 was obtained, and the radial crushing strength, water absorption rate and δ value of DZ3 were measured, and the results are listed in Table 1.

Comparative example 4

Take 100g of pseudo-boehmite powder produced by Catalyst Changling Branch, add 2.5mL of concentrated nitric acid, 3.0g of scallop powder and 95mL of deionized water, fully stir and mix evenly, after kneading evenly through an extruder, extrude into a shape strip. The formed strips were dried in an oven at 80°C for 4 hours. The dry bar was baked at 600°C for 4 hours. The molded carrier DZ4 was obtained, and the radial crushing strength, water absorption rate and δ value of DZ4 were measured, and the results are listed in Table 1.

Table 1

Examples 7-11 and Comparative Examples 5-6 illustrate the preparation of catalysts using shaped supports containing hydrated alumina and the catalysts prepared with comparative examples of supports, respectively.

Example 7

Take 100 grams of carrier Z1.

Molybdenum, cobalt and organic matter are introduced into the carrier Z1 by means of co-impregnation. First, weigh 11.5 grams of citric acid, dissolve it in deionized water until it becomes clear and transparent, then continue heating to the solution temperature of 50°C, slowly add 12.9 grams of molybdenum trioxide and 7.1 grams of basic cobalt carbonate, and continue to dissolve to a total solution of 84 milliliters. Heating during the dissolution process and keeping the temperature at 50°C, impregnated 100g of carrier Z1 with this solution, and dried at 170°C for 4 hours to obtain catalyst C1. The molar ratio of citric acid to Group VIII metal components in catalyst C1 is 1.0, and the contents of cobalt and molybdenum oxides in C1 are listed in Table 2.

Example 8

Take 100 grams of carrier Z1.

Molybdenum and cobalt were introduced into the carrier Z1 by co-impregnation. First, weigh 12.7 grams of ammonium paramolybdate, weigh 11.3 grams of cobalt nitrate, and 12.6 grams of citric acid, and dissolve ammonium paramolybdate, citric acid and cobalt nitrate in turn with deionized water to a total solution of 84 milliliters, heat, and the dissolution temperature remains The carrier Z1 was impregnated with this solution at 50°C and dried at 170°C for 4 hours to obtain catalyst C2. The molar ratio of citric acid to Group VIII metal components in catalyst C2 is 1.6, and the contents of cobalt and molybdenum oxides in C2 are listed in Table 2.

Example 9

Take 100 grams of carrier Z1.

Molybdenum and cobalt were introduced into the carrier Z1 by co-impregnation. First, take by weighing 18.0 grams of ammonium paramolybdate, and be dissolved in 70 milliliters of ammonia water with a concentration of 18% by weight until the solution is clear and transparent, then weigh 8.4 grams of basic cobalt carbonate, 22.2 grams of EDTA, add the above solution and continue to dissolve to The total solution is 84 ml. Heated during the dissolution process, and the temperature was kept at 50° C., impregnated 100 g of carrier Z3 with this solution, and dried at 170° C. for 4 hours to obtain catalyst C3. The molar ratio of EDTA to Group VIII metal components in catalyst C3 is 1.0, and the contents of cobalt and molybdenum oxides in C3 are listed in Table 2.

Example 10

Take 100 grams of carrier Z1.

Molybdenum and cobalt were introduced into the carrier Z1 by co-impregnation. First, take by weighing 8.9 grams of ammonium paramolybdate, and use a concentration of 18% by weight of ammonia to dissolve to 90 milliliters of the solution until it is clear and transparent, then weigh 3.6 grams of basic cobalt carbonate and 9.7 grams of EDTA, add the above solution and continue to dissolve to The total solution is 84 ml. Heating during the dissolution process, the temperature was kept at 50°C, impregnated 100g of carrier Z1 with this solution, and dried at 170°C for 4 hours to obtain catalyst C4. The molar ratio of EDTA to Group VIII metal components in catalyst C4 is 1.2, and the contents of cobalt and molybdenum oxides in C4 are listed in Table 2.

Example 11

Take 100 grams of carrier Z1.

Molybdenum and cobalt were introduced into the carrier Z1 by co-impregnation. First, weigh 21.9 grams of ammonium paramolybdate, weigh 18.6 grams of cobalt nitrate, dissolve ammonium paramolybdate and cobalt nitrate in turn with deconcentrated ammonia water until it is clear and transparent, then add dilute ammonia water to a total solution of 84 milliliters, heat the dissolution process, and keep the temperature The carrier Z1 was impregnated with this solution at 40°C, dried at 120°C for 4 hours, and calcined at 420°C for 3 hours to obtain catalyst C5. The contents of cobalt and molybdenum oxides in C5 are listed in Table 2.

Comparative example 5

Take 100 grams of carrier DZ4.

Molybdenum and cobalt were introduced into the carrier DZ4 by co-impregnation method. First, take by weighing 8.9 grams of ammonium paramolybdate, and use a concentration of 18% by weight of ammonia to dissolve to 90 milliliters of the solution until it is clear and transparent, then weigh 3.6 grams of basic cobalt carbonate and 9.7 grams of EDTA, add the above solution and continue to dissolve to The total solution is 95 ml. During the dissolution process, the temperature was kept at 50° C., and 100 g of carrier DZ4 was impregnated with this solution, and dried at 170° C. for 4 hours to obtain catalyst DB1. The molar ratio of EDTA to Group VIII metal components in catalyst DB1 is 1.2, and the contents of cobalt and molybdenum oxides in DB1 are listed in Table 2.

Comparative example 6

Take 100 grams of carrier DZ4.

Molybdenum and cobalt were introduced into the carrier DZ4 by co-impregnation method. First, 12.8 grams of ammonium paramolybdate was weighed and dissolved in 80 milliliters of ammonia water with a concentration of 18% by weight. After the solution was clear and transparent, 13.6 grams of cobalt nitrate was weighed, and the above solution was added to continue dissolving to 95 milliliters of the total solution. The dissolution process was slightly heated, and the temperature was kept at 30°C. This solution was used to impregnate 100g of carrier DZ4, dried at 170°C for 4 hours, and calcined at 350°C for 3 hours to obtain catalyst DB2. The contents of cobalt and molybdenum oxides in DB2 are listed in Table 2.

Table 2

Remarks: The amount of metal loading is the result of XRF analysis after the catalyst was calcined at 550°C for 4 hours.

Examples 12-16

Catalysts C1-C5 were evaluated for activity using model compounds containing 10% thiophene, 20% n-hexene and 70% n-heptane. The evaluation device is a fixed-bed hydrogenation microreactor, and the hydrogen is passed through once. Presulfidation was carried out before catalyst evaluation, and the sulfurized oil was cyclohexane containing 6% CS ₂ . The vulcanization conditions are: pressure 1.6MPa, hydrogen-oil volume ratio 3600:1, weight space velocity 6.0h ^-1 , temperature 320°C, time 2 hours.

After the vulcanization is completed, replace it with a model compound, change the reaction temperature at 230-320°C, conduct online chromatographic analysis, and draw the thiophene conversion rate-hydrogenation saturation rate curve, and then read the reaction curve when the thiophene conversion rate is 80%, the n-hexene Hydrogenation saturation rate HYD, the results are listed in Table 3.

Comparative example 7-8

The comparative catalysts DB1 and DB2 were evaluated in the same manner as in Examples 12-16, and the results are listed in Table 3.

table 3

Example Catalyst HYD,% 12 C1 43 13 C2 47 14 C3 40 15 C4 48 16 C5 45 Comparative example 7 DB1 63 Comparative example 8 DB2 58

Example 17

This example illustrates the method provided by the present invention and its effect.

The activity of catalyst C3 was evaluated by using high-sulfur FCC gasoline. The properties of raw oil are shown in Table 4.

The evaluation device is a fixed-bed hydrogenation reactor, and the hydrogen is passed through once. Before the reaction, the catalyst was firstly presulfurized, and the sulfurized oil was Daqing straight-run gasoline containing 2% CS ₂ . The vulcanization conditions are: pressure 1.6MPa, hydrogen-oil volume ratio 400:1, volume space velocity 2.0h ^-1 , temperature 320°C, time 3 hours. The feed was switched to Daqing straight-run gasoline. After 30 hours of stabilization, the feed was switched to high-sulfur FCC gasoline for reaction. The reaction conditions and results are listed in Table 5.

The antiknock index is (RON+MON)/2. The change of antiknock index refers to the difference between the antiknock index of the desulfurization product and the antiknock index of raw oil. If the antiknock index of the desulfurized product is lower than that of the raw oil, the antiknock index change is negative, otherwise it is positive.

Table 4

Test No. raw material Sulfur, μg/g 1500 Family composition, v% Saturated hydrocarbons 38.0 Olefins 22.9 Aromatics 39.1

table 5

Example 17 Reaction temperature, ℃ 280 LHSV, h ^-1 4 Reaction pressure, kg/ ^cm2 16 Hydrogen oil ratio, v/v 400:1 Sulfur, μg/g 38 Desulfurization rate, m% 97.47 Olefin saturation rate, v% 32.26

The results in Table 5 show that the catalysts prepared from hydrated alumina shaped supports have high desulfurization activity and low olefin saturation activity, and are more suitable for selective hydrodesulfurization of olefin-containing gasoline distillates.

Examples 18-22 illustrate the methods provided by the present invention and their effects.

Example 18

Hydrodesulfurization of a catalytically cracked gasoline as raw material oil A was carried out in a fixed-bed reactor with C3 as a catalyst.

The properties of the raw oil are shown in Table 6, and the reaction conditions are shown in Table 7. The reaction product was stripped to obtain a gasoline distillate product, and the properties of the product are listed in Table 7.

Comparative example 9

Hydrodesulfurization of a catalytically cracked gasoline as raw material oil A was carried out in a fixed-bed reactor with DB2 as a catalyst.

The properties of the raw oil are shown in Table 6, and the reaction conditions are shown in Table 7. The reaction product was stripped to obtain a gasoline distillate product, and the properties of the product are listed in Table 7.

Example 19

Hydrodesulfurization of raw oil C is carried out in a fixed-bed reactor using C3 as a catalyst. Raw oil C is a mixture of raw oil A and heavy distillate B (Fischer-Tropsch synthetic oil), and the content of B in the mixture is 30% by volume. The properties of the raw oil are shown in Table 6, and the reaction conditions are shown in Table 7. The reaction product was stripped and distilled to obtain gasoline distillate product and heavy distillate B. The properties of the products are listed in Table 7.

Comparative example 10

Hydrodesulfurization of raw oil I was carried out in a fixed-bed reactor with DB2 as a catalyst. Raw oil C is a mixture of raw oil A and heavy distillate B (Fischer-Tropsch synthetic oil), and the content of B in the mixture is 30% by volume. The properties of the raw oil are shown in Table 6, and the reaction conditions are shown in Table 7. The reaction product was stripped and distilled to obtain gasoline distillate product and heavy distillate B. The properties of the products are listed in Table 7.

Example 20

Hydrodesulfurization of raw oil E was carried out in a fixed bed reactor with C3 as catalyst. The raw material oil E is a mixture of the raw material oil A and heavy distillate D (white oil), and the content of D in the mixture is 30% by volume. The properties of the raw oil are shown in Table 6, and the reaction conditions are shown in Table 7. The reaction product was stripped and distilled to obtain gasoline distillate product and heavy distillate D. The properties of the products are listed in Table 7.

Example 21

Hydrodesulfurization of raw oil I was carried out in a fixed bed reactor with C5 as catalyst. The feedstock I is a mixture of feedstock A and heavy distillate H (PAO8), and the content of H in the mixture is 20% by volume. The properties of the raw oil are shown in Table 6, and the reaction conditions are shown in Table 7. The reaction product was stripped and distilled to obtain gasoline distillate product and heavy distillate H. The properties of the products are listed in Table 7.

Example 22

Hydrodesulfurization of raw oil K is carried out in a fixed bed reactor with C3 as catalyst. The raw material oil K is a mixture of the raw material oil A and heavy distillate oil J (VGO), and the content of J in the mixture is 20% by volume. The properties of the raw oil are shown in Table 6, and the reaction conditions are shown in Table 7. The reaction product was stripped and distilled to obtain gasoline distillate product and heavy distillate J. The properties of the products are listed in Table 7.

Table 6

Table 7

Claims (26)

1. A method for selective hydrodesulfurization of gasoline, comprising contacting the gasoline distillate raw material with a catalyst under gasoline hydrodesulfurization reaction conditions, wherein the catalyst contains a molding carrier containing hydrated alumina, loaded on the carrier At least one non-noble metal component selected from Group VIII, at least one metal component selected from Group VIB, based on the catalyst, the content of the Group VIII metal component in terms of oxides is 0.1-6 % by weight, the content of Group VIB metal components calculated as oxides is 1-25% by weight, and the content of the carrier is 69-98% by weight. 2. The method according to 1, characterized in that, based on the catalyst, the content of the Group VIII metal component in terms of oxides in the hydrodesulfurization catalyst is 1-5% by weight, and the content of the group VIII metal components in terms of oxides The content of the VIB group metal component is 5-20% by weight, and the content of the carrier is 75-94% by weight. 3. The method according to 1, wherein the shaped product carrier containing alumina hydrate in the hydrodesulfurization catalyst contains hydrated alumina and cellulose ether, and the radial crushing strength of the shaped product is Greater than or equal to 12N/mm, the water absorption rate is 0.4-1.5, and the δ value is less than or equal to 10%; where, δ=((Q1-Q2)/Q1)×100%, Q1 is the radial crushing strength of the molding, and Q2 It is the radial crushing strength of the molded product after soaking in water for 30 minutes and heating and drying at 120°C for 4 hours. 4. The method according to 3, characterized in that the radial crushing strength of the molding is 15-30 N/mm, the water absorption is 0.6-1, and δ is less than or equal to 5%. 5. The method according to 3, characterized in that, based on the molded product, the mass fraction of the cellulose ether is 0.5-8%. 6. The method according to 5, characterized in that, based on the molded product, the mass fraction of the cellulose ether is 1-6%. 7. The method according to 6, characterized in that, based on the molded product, the mass fraction of the cellulose ether is 2-5%. 8. The method according to 3, wherein the cellulose ether is selected from one or more of methylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose. 9. The method according to 8, characterized in that the cellulose ether is methyl cellulose, hydroxyethyl methyl cellulose and mixtures thereof. 10. The method according to 1 or 3, wherein the hydrated alumina is selected from one or more of pseudo-boehmite, boehmite, aluminum hydroxide, and aluminum hydroxide trihydrate. 11. The method according to 10, wherein the hydrated alumina is pseudo-boehmite. the 12. The method according to 1, wherein the catalyst contains one or more organic substances selected from alcohols, organic acids and organic amines, and the molar ratio of the organic substances to the Group VIII metal component is 0.5-2.5. 13. The method according to 12, characterized in that the molar ratio of the organic matter to the Group VIII metal component is 1-2. 14. The method according to 1, characterized in that, when the gasoline distillate feedstock and hydrogen are in contact with the hydrodesulfurization catalyst, it also includes introducing a heavy distillate to contact the catalyst, and the heavy distillate The initial boiling point of the oil is greater than the final boiling point of the gasoline distillate, and the introduction amount of the heavy distillate is 0.2h ^-1 -2h ^-1 in terms of liquid hourly volume space velocity. 15. The method according to 14, wherein the heavy distillate is selected from diesel distillate and/or lube oil distillate, and the initial boiling point of the heavy distillate is the same as the end point of the gasoline distillate. The temperature difference of the distillation point is not less than 1°C, and the introduction amount of heavy distillate oil is 0.4h ^-1 -1.8h ^-1 in terms of liquid hourly volume space velocity. 16. The method according to 15, characterized in that, the temperature difference between the initial boiling point of the heavy distillate and the final boiling point of the gasoline distillate is not less than 10°C, measured by liquid hourly volume space velocity, heavy The introduction amount of distillate is 0.6h ^-1 -1.8h ^-1 . 17. The method according to 15 or 16, characterized in that the temperature difference between the initial boiling point of the heavy distillate and the end boiling point of the gasoline distillate is not less than 20°C. 18. The method according to 17, characterized in that the temperature difference between the initial boiling point of the heavy distillate and the final boiling point of the gasoline distillate is not less than 40°C. 19. The method according to 15 or 16, wherein the heavy distillate oil is derived from one or more of petroleum and synthetic oil. 20. The method according to 19, wherein the synthetic oil is selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthetic oil and biosynthetic oil. 21. The method according to 1, wherein the gasoline distillate is selected from one or more of catalytic cracking gasoline, catalytic cracking gasoline, straight-run gasoline, coker gasoline, thermal cracking gasoline and thermal cracking gasoline. 22. The method according to 21, wherein the distillation range of the gasoline distillate is 30-220°C. 23. The method according to 1, characterized in that the gasoline hydrodesulfurization reaction conditions include: pressure 0.8MPa-3.2MPa, temperature 200°C-320°C, volumetric space velocity of gasoline distillate oil ^3h -1-8h ^-1 . The hydrogen-to-oil ratio is 200Nm ³ /m ³ to 600Nm ³ /m ³ . 24. The method according to 23, characterized in that the gasoline hydrodesulfurization reaction conditions include: reaction pressure 1MPa-2.8MPa, reaction temperature 220°C-270°C, gasoline distillate oil liquid hourly volume space velocity 3h ^-1 - 6h ^-1 , hydrogen oil ratio 300Nm ³ /m ³ -500Nm ³ /m ³ . 25. The method according to 1 or 14, characterized in that, after the gasoline distillate raw material is contacted and reacted with the catalyst under the gasoline hydrodesulfurization reaction conditions, the step of separating the produced oil is also included. 26. The method according to 24, wherein said separation comprises the steps of stripping and fractionation. the