CN103013558B - Production method of SBS rubber filling oil - Google Patents

Abstract

A method for producing SBS rubber extension oil, comprising: under hydrotreating reaction conditions, contacting raw material oil and hydrogen with a hydrotreating catalyst for reaction, and stripping to obtain product oil, characterized in that the hydrotreating catalyst Including catalyst I _a and catalyst I _b , catalyst I _a and catalyst I _b layered arrangement, by volume and based on the catalyst I _a , the content of catalyst I _b is 3-40%, wherein, the catalyst I The content of the hydrogenation active metal component of _b is 10-30% of the content of the hydrogenation active metal component of catalyst I _a , and the described layered arrangement makes the described feedstock oil in the hydrogenation reaction unit sequence and catalyst I _b and Catalyst I _{a is} contacted. Compared with the prior art, when adopting the method provided by the invention to produce SBS rubber filler oil, its yield is improved.

Description

Production method of SBS rubber filler oil

field of invention

The invention relates to a production method of a thermoplastic elastomer SBS rubber extension oil, in particular to a method for producing a general-purpose SBS rubber extension oil and an anti-yellowing SBS rubber extension oil by using an intermediate base oil with a low viscosity index.

technical background

SBS synthetic rubber is a styrene-butadiene-styrene block copolymer, which is mainly used in industries such as shoemaking, hose tape, plastic modification, adhesive and asphalt modification. During the processing of molded and extruded products of SBS rubber, a certain amount of oily components are usually added to improve their molding performance and extrusion performance for easy processing, and at the same time optimize the physical and mechanical properties of the preparation and reduce product costs, etc. , This part of the oily component is called rubber filler oil or processing oil. Rubber filler oils are generally made from processed mineral oils. According to different types of petroleum raw materials, they are generally divided into naphthenic rubber filler oils and intermediate rubber filler oils. In addition, when the types of rubber are different, the quality grade and hydrocarbon composition of the rubber filler oil required are also very different. For example, styrene-butadiene rubber needs extender oil with high aromatic content, while SBS rubber needs base oil with low aromatic content. Therefore, the production of rubber filler oil varies greatly according to different product objectives and rubber varieties, and its production methods are also very different.

US5504135 discloses a rubber extender oil and rubber containing the extender oil, which relates to a production method of the rubber extender oil. The method uses vacuum residue as raw material to produce rubber processing oil with a kinematic viscosity (100°C) of 32-50 mm ² /s, an aromatic content of 30-55%, but a polycyclic aromatic hydrocarbon of less than 3%, and the rubber processing oil is an aromatic hydrocarbon Type, for the processing of styrene-butadiene rubber. The specific steps include the steps of propane deasphalting, solvent dewaxing and recovering rubber processing oil from dewaxed clear oil.

CN1752182 discloses a production method of aromatic hydrocarbon type rubber extension oil, which is characterized in that it consists of the following steps: A. Coal tar fraction and hydrogen are mixed and then enter the hydrogenation reactor, and react with Mo-Ni-P hydrogenation modification catalyst , to remove sulfur, nitrogen impurities, colloids, and asphaltenes in coal tar fractions. The reaction conditions are: hydrogen partial pressure 8.0-14.0MPa, reaction temperature 370-390°C, volume space velocity 0.6-1.0h-1, hydrogen oil The volume ratio is 1000-1200, and the reaction product after the reaction is exported to the hydrogenation reactor; the Mo-Ni-P hydrogenation modification catalyst is calculated on a dry basis of oxides, and MoO3 accounts for 15-25w% of the total weight of the catalyst, and NiO accounts for 15-25w% of the total weight of the catalyst. 2～6w% of the total weight, P2O5 accounts for 3～8w% of the total catalyst weight, and the rest is an amorphous aluminum silicate carrier; B. The reaction product obtained in step A enters the gas separation and stabilization system after heat exchange and cooling, and separates After hydrogen, dry gas, hydrogen sulfide, ammonia and liquefied gas are produced, a liquid product is obtained; C. The liquid product obtained in step B is fractionated and cut in a fractionating tower to obtain a fraction above 360°C, which is the aromatic hydrocarbon rubber Filler oil products.

Liu Guangyuan et al. (Hydrogenation application technology of SBS rubber extension oil, Liu Guangyuan et al., Petrochemical Technology, 2005, 12 (3), 59-62) commented on the existing hydrogenation method to produce SBS rubber extension oil technology, and respectively The production of rubber oil by medium-pressure hydrogenation treatment; the production of rubber oil by two-stage hydrogenation; the production of rubber extension oil by all-hydrogen process technology and the production of rubber extension oil by hydrogenation refining are introduced.

Among them, the two-stage hydrogenation method to produce rubber extender oil technology is to use MVI base oil as raw material, and produce rubber extender oil through two-stage hydrogenation refining. Its characteristic is that the raw material undergoes a stage of hydrogenation first, and the heterocyclic compounds are removed by using a sulfurized catalyst to saturate most of the aromatic hydrocarbons. Then, after the second stage of hydrogenation, a non-precious metal reduced catalyst is used to saturate the remaining aromatics, improve the oxidation stability, and make the product Saybolt colorimetric reach more than +30.

In the prior art, methods including hydroprocessing can be used to produce SBS rubber filler oil. However, limited by the performance of the catalyst used, the yield of SBS rubber extender oil is still not ideal.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new method for producing SBS rubber filler oil with significantly improved yield and the like on the basis of the prior art.

The present invention relates to the following:

1. A method for producing SBS rubber extender oil, comprising: under hydrotreating reaction conditions, feedstock oil and hydrogen are contacted with a hydrotreating catalyst to react, and product oil is obtained through stripping, it is characterized in that the hydrogenation Catalyst treatment includes catalyst I _a and catalyst I _b , catalyst I _a and catalyst I _b are arranged in layers, by volume and based on catalyst I _a , the content of catalyst I _b is 3-40%, wherein, all The content of the hydrogenation active metal component of the catalyst _Ib is 10-30% of the content of the hydrogenation active metal component of the catalyst _Ia , and the layered arrangement makes the feedstock oil in the hydrogenation reaction unit sequence and the catalyst I _b is contacted with catalyst I _a .

2. according to the described method of 1, it is characterized in that, by volume and taking described catalyst I _a as a benchmark, the content of catalyst I _b is 5-30%

3. The method according to 2, characterized in that, based on the catalyst I _a , the content of the catalyst I _b is 6-20% by volume.

4. according to the method described in any one of 1, 2 or 3, it is characterized in that, the catalyst I _a contains a carrier selected from alumina and/or silicon oxide-alumina, selected from nickel and/or cobalt, molybdenum And/or tungsten's hydrogenation active metal component, with or without one or more auxiliary components selected from fluorine, boron and phosphorus, and with or without organic additives, based on the catalyst, based on the oxide The content of nickel and/or cobalt is 1 to 5% by weight, the content of molybdenum and/or tungsten is 12 to 35% by weight, and the content of one or more additives selected from fluorine, boron and phosphorus in terms of elements The content of the component is 0-9% by weight, and the molar ratio of the organic matter to the sum of hydrogenation active metal components calculated as oxides is 0-2.

5. according to the described method of 4, it is characterized in that, described catalyst is made of gamma-Al ₂ O ₃ carrying tungsten and nickel oxide and auxiliary agent fluorine, and its composition (weight): nickel oxide 1～5%, Tungsten oxide is 12-35%, fluorine is 1-9%, and the balance is γ-Al ₂ O ₃ .

6. according to the described method of 4, it is characterized in that, described catalyst is a kind of fluorine-containing, phosphorus hydrogenation catalyst that is carrier with silicon oxide-alumina, and the composition after this catalyst roasting is: nickel oxide 1-10 weight %, the sum of molybdenum oxide and tungsten oxide is greater than 10 to 50% by weight, 1-10% by weight of fluorine, 0.5-8% by weight of phosphorus oxide, and the balance is silicon oxide-alumina; A fluorine-containing hydrogenation catalyst as a carrier, the composition of the catalyst after calcination is: 1-10% by weight of nickel oxide, the sum of molybdenum oxide and tungsten oxide is greater than 10-50% by weight, 1-10% by weight of fluorine, and the balance is carrier or a phosphorus-containing hydrogenation catalyst with silicon oxide-alumina as a carrier and its preparation, the composition of the catalyst after roasting is: nickel oxide 1-10% by weight, the sum of molybdenum oxide and tungsten oxide greater than 10 to 50 % by weight, 1-9% by weight of phosphorus oxide, and the rest is silicon oxide-alumina, wherein the molar ratio of tungsten oxide to molybdenum oxide is greater than 2.6 to 30.

7. according to the described method of 6, it is characterized in that, described catalyzer, described catalyzer contains one or more selected from oxygen-containing or nitrogen-containing organic matter, and described organic matter and nickel, molybdenum in oxide form The molar ratio to the sum of tungsten is 0.03-2.

8. The catalyst according to claim 7, characterized in that, the oxygen-containing organic compound is selected from one or more of organic alcohols and organic acids, the nitrogen-containing organic compound is an organic amine, and the organic compound is oxidized with The molar ratio of the sum of nickel, molybdenum and tungsten in terms of material is 0.08-1.5.

9. according to the method described in 4, it is characterized in that, described catalyst is a kind of fluorine-containing, phosphorus hydrogenation catalyst that is carrier with alumina, and the composition after this catalyst roasting is: nickel oxide 1-10 weight %, oxidized The sum of molybdenum and tungsten oxide is greater than 10 to 50% by weight, phosphorus oxide is 0.5-8% by weight, fluorine is 1-10% by weight, and the balance is alumina; or a fluorine-containing hydrogenation catalyst with alumina as a carrier, The composition of the catalyst after roasting is: 1-10% by weight of nickel oxide, 10-50% by weight of the sum of molybdenum oxide and tungsten oxide, 1-10% by weight of fluorine, and the rest is alumina; A supported phosphorus-containing hydrogenation catalyst, the composition of the catalyst after calcination is 1-10% by weight of nickel oxide, the sum of molybdenum oxide and tungsten oxide is greater than 10-50% by weight, 1-9% by weight of phosphorus oxide, and the balance is aluminum oxide , wherein, in terms of oxides, the molar ratio of tungsten to molybdenum is greater than 2.6 to 30.

10. The method according to 9, characterized in that, the catalyst contains one or more selected from oxygen-containing or nitrogen-containing organic matter, the sum of the organic matter and nickel, molybdenum and tungsten in terms of oxides The molar ratio is 0.03-2.

11. The catalyst according to claim 10, characterized in that, the oxygen-containing organic compound is selected from one or more of organic alcohols and organic acids, the nitrogen-containing organic compound is an organic amine, and the organic compound is oxidized with The molar ratio of the sum of nickel, molybdenum and tungsten in terms of material is 0.08-1.5.

12. The method according to 1, wherein the hydrotreating reaction conditions include: pressure 10-20MPa, temperature 280-380°C, volume space velocity 0.2-2h ^-1 , hydrogen-oil volume ratio 300-1200 : 1.

13. The method according to 12, wherein the hydroprocessing reaction conditions include: pressure 12-18MPa, temperature 300-360°C, volume space velocity 0.4-1.5h ^-1 , hydrogen-oil volume ratio 350-1000 : 1.

14. The method according to 13, characterized in that the hydroprocessing reaction conditions include: pressure 14-18MPa, temperature 330-360°C, volume space velocity 0.4-1.2h ^-1 , hydrogen-oil volume ratio 500-1000 : 1.

15. The method according to 1, wherein the feedstock oil is a distillate with a viscosity index less than 80 and a distillation range of 350°C-560°C.

16. The method according to 15, characterized in that the feedstock oil is distillate oil with a viscosity index of -20 to 80 and a distillation range of 350°C to 530°C.

17. The method according to 1, wherein the catalyst _Ic is included between the catalyst _Ia and the catalyst _Ib , by volume and based on the catalyst _Ia , the content of the catalyst _Ic is greater than 0 to less than or equal to 80%, wherein the content of the hydrogenation active metal component of the catalyst _Ic is greater than 30% to less than or equal to 70% of the content of the hydrogenation active metal component of the catalyst _Ia .

18. The method according to 17, characterized in that, based on the catalyst _Ia , the content of the catalyst _Ic is 5-40% by volume.

19. The method according to 18, characterized in that the content of the catalyst _Ic is 10-30% by volume and based on the catalyst _Ia .

20. The method according to 1, characterized in that, before the stripping after the hydrotreating reaction, including under the conditions of the hydrotreating reaction, the process of contacting the generated oil and hydrogen with the hydrotreating catalyst for the second time Step, wherein, the reaction temperature of the second hydrogenation treatment is lower than the reaction temperature of the first hydrogenation treatment by 10-50°C.

21. The method according to 20, characterized in that the reaction temperature of the secondary hydrotreatment is 20-30° C. lower than the reaction temperature of the primary hydrotreatment.

22. The method according to 20 or 21, characterized in that the reaction conditions for the secondary hydrogenation treatment include: pressure 12-20MPa, temperature 250-360°C, volume space velocity 0.5-6h ^-1 , hydrogen oil volume The ratio is 300-1200:1.

23. The method according to 22, characterized in that the reaction conditions for the secondary hydrotreating include: pressure 12-18MPa, temperature 260-350°C, volume space velocity 1-4h ^-1 , hydrogen-oil volume ratio of 350-1000:1.

24. The method according to 23, characterized in that the reaction conditions for the secondary hydrotreating include: pressure 14-18MPa, temperature 280-330°C, volume space velocity 1.5-3.5h ^-1 , hydrogen-to-oil volume ratio It is 450-800:1.

25. The method according to 1, characterized in that, after the stripping, a step of hydrotreating the stripped product is included.

26. The method according to 25, characterized in that, the catalyst for hydrofinishing is a catalyst with a reduced metal as a hydrogenation active component, wherein the reduced metal is selected from nickel, platinum and/or palladium .

27. The method according to 25, characterized in that the hydrofining reaction conditions include: pressure 10-20MPa, temperature 150-320°C, volume space velocity 0.3-3h ^-1 , hydrogen-oil volume ratio 100- 3000:1.

28. The method according to 27, wherein the hydrofining reaction conditions include: pressure 12-18MPa, temperature 180-300°C, volume space velocity 0.5-1.5h ^-1 , hydrogen-oil volume ratio 200 -1000:1.

According to the method provided by the present invention, the purpose of the hydrotreating reaction is to remove sulfur, nitrogen compounds and aromatic hydrocarbon saturation in the raw material. Wherein, the reactor used for the hydrogenation reaction may be any reactor provided by the prior art that can be used for the hydrogenation reaction, such as a fixed-bed reactor. The catalyst I _a is selected from a heat-resistant inorganic oxide carrier and a hydrogenation active metal component supported on the carrier, containing or not containing one or more auxiliary components selected from fluorine, boron and phosphorus, and One or more catalysts with or without organic additives. In a preferred embodiment, the catalyst _Ia is selected from one or more of the following catalysts, including:

The catalyst disclosed in CN85104438 is made of gamma-Al ₂ O ₃ loaded tungsten, nickel oxide and auxiliary agent fluorine, and its composition (weight): nickel oxide 1～5%, tungsten oxide 12～35%, fluorine is 1-9%.

CN1853780A discloses a fluorine-containing and phosphorus hydrogenation catalyst with silicon oxide-alumina as a carrier and its preparation. The composition of the catalyst after roasting is: nickel oxide 1-10% by weight, the sum of molybdenum oxide and tungsten oxide greater than 10 To 50% by weight, 1-10% by weight of fluorine, 0.5-8% by weight of phosphorus oxide, and the balance is silicon oxide-alumina. The catalyst is prepared by a method including introducing fluorine, phosphorus, molybdenum, nickel and tungsten into a silica-alumina carrier, wherein the amount of each component is such that the composition of the catalyst after calcination is: nickel oxide 1-10% by weight, molybdenum oxide The sum of tungsten oxide and tungsten oxide is greater than 10 to 50% by weight, 1-10% by weight of fluorine, 0.5-8% by weight of phosphorus oxide, and the balance is silicon oxide-alumina.

CN1853779A discloses a fluorine-containing hydrogenation catalyst supported by silica-alumina and its preparation. The composition of the catalyst after roasting is: nickel oxide 1-10% by weight, the sum of molybdenum oxide and tungsten oxide greater than 10 to 50 % by weight, 1-10% by weight of fluorine, and the rest is carrier. The preparation method of the catalyst comprises introducing fluorine, molybdenum, nickel and tungsten into the silicon oxide-alumina carrier, wherein, the consumption of each component makes the composition after the catalyst is calcined: nickel oxide 1-10% by weight, molybdenum oxide and tungsten oxide The sum is more than 10 to 50% by weight, 1-10% by weight of fluorine, and the rest is carrier.

CN1853781A discloses a phosphorus-containing hydrogenation catalyst supported by silicon oxide-alumina and its preparation. The composition of the catalyst after roasting is: nickel oxide 1-10% by weight, the sum of molybdenum oxide and tungsten oxide greater than 10 to 50 % by weight, 1-9% by weight of phosphorus oxide, and the rest is silicon oxide-alumina, wherein the molar ratio of tungsten oxide to molybdenum oxide is greater than 2.6 to 30. The preparation method of the catalyst comprises introducing phosphorus, molybdenum, nickel and tungsten into the silicon oxide-alumina carrier, wherein, the consumption of each component makes the composition after the catalyst is calcined: nickel oxide 1-10% by weight, molybdenum oxide and tungsten oxide The sum is greater than 10 to 50% by weight, phosphorus oxide is 1-9% by weight, and the balance is silicon oxide-alumina, and the molar ratio of tungsten oxide and molybdenum oxide is greater than 2.6 to 30.

CN1853781A discloses a fluorine-containing and phosphorus hydrogenation catalyst with alumina as a carrier and its preparation. The composition of the catalyst after roasting is: 1-10% by weight of nickel oxide, and the sum of molybdenum oxide and tungsten oxide is greater than 10 to 50% by weight %, 0.5-8% by weight of phosphorus oxide, 1-10% by weight of fluorine, and the balance is aluminum oxide. The catalyst is prepared by introducing fluorine, phosphorus, molybdenum, nickel and tungsten into the alumina carrier, wherein the amount of each component makes the composition of the catalyst after calcination: nickel oxide 1-10% by weight, molybdenum oxide and tungsten oxide The sum is greater than 10 to 50% by weight, 1-10% by weight of fluorine, 0.5-8% by weight of phosphorus oxide, and the balance is aluminum oxide.

CN1872959A discloses a fluorine-containing hydrogenation catalyst with alumina as a carrier and its preparation. The composition of the catalyst after roasting is: nickel oxide 1-10% by weight, molybdenum oxide and tungsten oxide the sum of 10-50% by weight, Fluorine is 1-10% by weight, and the rest is alumina. The preparation method of the catalyst comprises introducing fluorine, molybdenum, nickel and tungsten into the alumina carrier, wherein, the consumption of each component makes the composition of the catalyst after roasting: 1-10% by weight of nickel oxide, and the sum of molybdenum oxide and tungsten oxide is 10 to 50% by weight, 1-10% by weight of fluorine, and the balance is alumina.

CN1872960A discloses a phosphorus-containing hydrogenation catalyst with alumina as a carrier and its preparation. The composition of the catalyst after roasting is 1-10% by weight of nickel oxide, the sum of molybdenum oxide and tungsten oxide is greater than 10 to 50% by weight, and the oxidized Phosphorus is 1-9% by weight, and the balance is aluminum oxide, wherein, in terms of oxides, the molar ratio of tungsten and molybdenum is greater than 2.6 to 30. The catalyst consists of introducing phosphorus, molybdenum, nickel and tungsten into the alumina carrier, wherein the amount of each component makes the composition of the catalyst after roasting: 1-10% by weight of nickel oxide, and the sum of molybdenum oxide and tungsten oxide is greater than 10% to 50% by weight, 1-9% by weight of phosphorus oxide, and the balance is aluminum oxide, wherein, in terms of oxides, the molar ratio of tungsten to molybdenum is greater than 2.6 to 30.

In the catalysts disclosed by CN1853780A, CN1853779A, CN1853781A, CN1872959A and CN1872960A, preferably also contain organic additives, wherein, the molar ratio of the sum of the organic matter and the hydrogenation active metal components calculated as oxides is 0.03-2, preferably 0.08-1.5.

The more detailed preparation methods of the above-mentioned catalysts are all described in the above-mentioned patent documents, which are hereby cited as a part of the content of the present invention.

The catalyst _Ib has a lower hydrogenation active metal component content than the catalyst _Ia , and the hydrogenation active metal component content of the catalyst _Ib is 10-30% of the hydrogenation active metal component content of the catalyst _Ia . %, preferably 12-25%. On this premise, the present invention has no special limitation on the catalyst I _b , which can be commercially available or can be prepared by any prior art.

In a specific embodiment, this type of catalyst usually contains a heat-resistant inorganic oxide carrier and a hydrogenation active metal component supported on the carrier, containing or not containing one or more of fluorine, boron, phosphorus and alkaline earth metal Auxiliary components. Based on the catalyst _Ib , the catalyst _Ib has a nickel and/or cobalt content of 0.5-4% by weight, preferably 1.0-3% by weight, and a molybdenum and/or tungsten content of 2.5-9% by weight. % by weight, preferably 3.5-6.5% by weight, the content of one or more auxiliary components selected from fluorine, boron, phosphorus and alkaline earth metals in terms of elements is 0-5% by weight, and meets the requirements of nickel and/or The total amount of cobalt and molybdenum and/or tungsten content is 10-30%, preferably 12-25%, of the content of _the hydrogenation active metal component of catalyst Ia.

For example, the catalyst preparation methods disclosed in CN1344781, CN1966616 and CN101134173A can be used to prepare catalysts meeting the requirements of the present invention. They are hereby cited together as a part of the summary of the present invention.

When the catalyst _Ic is further included between the catalyst _Ia and the catalyst _Ib , the content of the hydrogenation active metal component of the catalyst _Ic is greater than that of the catalyst _Ib and less than that of the catalyst _Ia . The hydrogenation active metal component content of the catalyst _Ic is greater than 30 to less than or equal to 70% by weight, preferably 40-60% of the hydrogenation active metal component content of the catalyst _Ia . On this premise, the present invention has no special limitation on the catalyst I _b , which can be commercially available or can be prepared by any prior art.

In a specific embodiment, this type of catalyst usually contains a heat-resistant inorganic oxide carrier and a hydrogenation active metal component supported on the carrier, containing or not containing one or more of fluorine, boron, phosphorus and alkaline earth metal Auxiliary components. Based on the catalyst _Ic , the content of nickel and/or cobalt in the catalyst _Ic as an oxide is 0.3-8% by weight, preferably 0.5-7.5% by weight, and the content of molybdenum and/or tungsten is 0.5-15% by weight. % by weight, preferably 0.8-12% by weight, and satisfying that the total amount of nickel and/or cobalt and molybdenum and/or tungsten content is 30-70% of the content of catalyst _Ia hydrogenation active metal component, preferably 40- 60%.

For example, the catalyst preparation methods disclosed in CN1626625A, CN1690172A, CN1782031A and CN1782033A can be used to prepare catalysts meeting the requirements of the present invention. They are hereby cited together as a part of the summary of the present invention.

The purpose of the stripping is to remove the heteroatom compounds such as hydrogen sulfide and the small molecular hydrocarbon compounds that may be generated through hydrogenation treatment. and conditions are not particularly limited. For example, high-pressure stripping or atmospheric stripping using steam as the stripping medium. The method and operating conditions about the stripping are the methods and conditions commonly used in the art, and will not be repeated here.

When after the hydroprocessing reaction and before the stripping, it also includes under the hydroprocessing reaction conditions, the step of contacting the generated oil and hydrogen with the hydroprocessing catalyst for the second time, the catalyst used for the secondary hydroprocessing reaction It can be the same as the catalyst used for the primary hydroprocessing reaction, for example, one or more catalysts selected from the hydroprocessing catalyst _Ia . In the preferred embodiment. The catalyst for the secondary hydroprocessing reaction is selected from hydrorefining catalysts that do not contain fluorine and/or molecular sieves. They can be commercially available or prepared by any existing method.

Such catalysts usually contain a heat-resistant inorganic oxide support, a hydrogenation-active metal component, with or without additive phosphorus and with or without organic additives. Wherein, the heat-resistant inorganic oxide support is selected from one or more of various heat-resistant inorganic oxides commonly used as catalyst supports and/or substrates. For example, may be selected from alumina, silica, titania, magnesia, silica-alumina, alumina-magnesia, silica-magnesia, silica-zirconia, silica-thoria, silica- Beryllium oxide, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica - Alumina - one or more of zirconia, natural zeolite, clay, preferably alumina. The organic additive is selected from one or more organic compounds in oxygen-containing or nitrogen-containing organic compounds, and the preferred oxygen-containing organic compound is selected from one or more of organic alcohols and organic acids; the preferred nitrogen-containing organic compounds The compound is selected from one or several kinds of organic amines. For example, the oxygen-containing organic compound can include ethylene glycol, glycerol, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, One or more of 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, malic acid, nitrogen-containing organic compounds include ethylenediamine, EDTA and ammonium salts thereof.

For example, CN1085934 discloses a hydrogenation refining catalyst, which contains magnesium oxide, nickel oxide, tungsten oxide and aluminum oxide, and consists of: magnesium oxide 0.1-1.9%, nickel oxide 2.5-6%, tungsten oxide 24- 34% and the balance alumina.

CN1872960A discloses a phosphorus-containing hydrogenation catalyst with alumina as a carrier. The composition of the catalyst after roasting is 1-10% by weight of nickel oxide, the sum of molybdenum oxide and tungsten oxide is greater than 10 to 50% by weight, and phosphorus oxide is 1-10% by weight. 9% by weight, and the balance is aluminum oxide, wherein, in terms of oxides, the molar ratio of tungsten and molybdenum is greater than 2.6 to 30.

CN1840618A A hydrogenation catalyst with silica-alumina as the carrier and its preparation, the composition of the catalyst after roasting is: 1-10% by weight of nickel oxide, the sum of molybdenum oxide and tungsten oxide is greater than 10-50% by weight, and the rest The amount is the carrier.

The catalysts disclosed in CN1872960A and CN1840618A preferably also contain organic additives, wherein the molar ratio of the organic matter to the sum of hydrogenation active metal components calculated as oxides is 0.03-2, preferably 0.08-1.5.

These catalysts can all be used in the present invention as the hydrorefining catalyst. The more detailed preparation methods of the above-mentioned catalysts are all described in the above-mentioned patent documents, which are hereby cited as a part of the content of the present invention.

When the reaction step of secondary hydrogenation treatment is included, any existing heat exchange technology can be used to make the temperature of the material flow from the primary hydrogenation reactor when it enters the secondary hydrogenation reactor meet the stated requirements. The secondary hydrogenation reactor can be any reactor available in the prior art that can be used for hydrogenation reactions, such as a fixed-bed reactor.

The purpose of the hydrofinishing is to further saturate hydrogenated aromatics, and the hydrofinishing catalyst used contains a carrier and at least one metal component selected from Group VIII of nickel, platinum and/or palladium supported on the carrier. The carrier may be selected from alumina, silica, titania, magnesia, silica-alumina, alumina-magnesia, silica-magnesia, silica-zirconia, silica-thoria, silica - beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia, silica-alumina-magnesia, One or more of silicon-alumina-zirconia, natural zeolite, and clay. The content of the Group VIII metal is preferably 0.1-10% by weight, more preferably 0.1-5% by weight, calculated as metal and based on the catalyst. For example, CN1510112A discloses a metal-type hydrogenation catalyst, and CN1245204 discloses a bimetallic hydrogenation catalyst, etc., all of which have good hydrofining performance and can be used as hydrofining catalysts in the present invention. They are hereby cited together as a part of the summary of the present invention.

According to the method provided by the present invention, the raw oil can be a distillate oil from any source with a viscosity index of 0-80, preferably a viscosity index of 20-80, and a distillation range of 350°C-560°C, preferably 350°C-530°C. Distillate oil at °C (the distillation range in the present invention refers to the distillation temperature corresponding to the distillate with a distillate volume greater than or equal to 5% to less than or equal to 95%). On the premise of meeting the above requirements, there is no special restriction on the source of the raw material oil. For example, the by-product low viscosity index dewaxed oil in the process of paraffin wax production can meet this requirement and can be directly used as raw material for the production of SBS rubber filler oil.

Compared with the prior art, when adopting the method provided by the invention to produce SBS rubber filler oil, its yield is improved.

Detailed ways

The following examples will further illustrate the present invention.

Example 1

The raw material oil is a kind of oil obtained by refining furfural and dewaxing ketonebenzene from the distillate oil derived from intermediate base crude oil, and its properties are shown in raw material 1 in Table 1.

The hydroprocessing reaction is carried out in a fixed-bed reactor, and the reaction conditions include: temperature 330°C, pressure 14MPa, space velocity 0.8h ^-1 , hydrogen-oil volume ratio 450:1.

Catalyst is catalyst I _a and catalyst I _b of layered packing, respectively:

Catalyst _Ia is prepared according to the method disclosed in CN85104438, and its composition is: 3% by weight of nickel oxide, 25% by weight of tungsten oxide, 4% by weight of fluorine, and the balance is γ-Al ₂ O ₃ .

Catalyst _Ib is prepared according to Example 6 in CN1966616A, wherein the hydrogenation active metal components are molybdenum and nickel, calculated as oxides and based on the catalyst, the content of molybdenum is 4.5% by weight, and the content of nickel is 1.5% by weight.

Wherein, in terms of volume, the amount of _Ib is 12% of the amount of _Ia .

Stripping: stripping is carried out in a vacuum stripping device, and the stripping medium is water vapor.

The product oil was obtained by stripping, and the yield and properties of the product oil are shown in Table 2.

Comparative example 1

Raw material oil is the same with embodiment 1. The catalyst is the single catalyst I _a in Example 1; the reaction conditions include: temperature 330°C, pressure 14MPa, space velocity 0.8h ^-1 , hydrogen-oil volume ratio 450:1; others are the same as Example 1.

The yield and properties of the product oil obtained by stripping are shown in Table 2.

Example 2

Raw material oil is with embodiment 1.

The catalysts are catalyst I _a , catalyst I _b and catalyst I _c packed in layers. Wherein, catalyst I _a , catalyst I _b are identical with embodiment 1, and catalyst I _c is prepared according to the embodiment 15 of CN1782033A, and wherein hydrogenation active metal component is molybdenum and nickel, is based on oxide and is based on catalyst, molybdenum The content is 13.7% by weight, and the content of nickel is 3% by weight. On a volume basis, the amount of _Ib is 12% of that of _Ia , and the amount of _Ic is 50% of that of _Ia .

The reaction conditions include: temperature 330°C, pressure 14MPa, total volume space velocity 0.8h ^-1 , hydrogen-oil volume ratio 450:1.

Stripping: stripping is carried out in a vacuum stripping device, and the stripping medium is water vapor.

The yield and properties of the product oil obtained by vacuum stripping are shown in Table 2.

Example 3

A hydrofinishing step was added after the stripping of Example 2.

The hydrofining reaction is carried out in a fixed-bed reactor, and the reaction conditions include: temperature 220°C, pressure 16MPa, space velocity 0.8h ^-1 , volume ratio of hydrogen to oil 350:1.

The hydrorefining catalyst was prepared according to Example 11 in CN1510112A, wherein the content of platinum metal was 0.22% by weight, and the content of palladium metal was 0.43% by weight.

The product oil yield and its properties are shown in Table 2.

The standard of rubber filling oil is shown in Table 3.

Example 4

The raw material oil is a kind of oil obtained from the subtractive three-distillate oil derived from intermediate base crude oil through furfural refining and ketone-benzene dewaxing, and its properties are shown in raw material 2 in Table 1.

The hydrotreating reaction is carried out in two fixed-bed reactors connected in series, and a heat exchanger is arranged between the two reactors. Among them, the reaction conditions of the primary hydrotreating reaction include: temperature 345°C, pressure 14MPa, total space velocity 0.87h ^-1 , hydrogen-oil volume ratio 500:1. The reaction conditions for the secondary hydroprocessing reaction include: temperature 330°C, pressure 14MPa, space velocity 1.90h ^-1 , hydrogen oil volume ratio 500:1, total volume space velocity 0.6h ^-1 .

The catalysts in the reactor of the primary hydroprocessing reaction are catalyst I _a and catalyst I _b packed in layers. Wherein, catalyst _Ia and catalyst _Ib are identical with embodiment 1, and by volume, _Ib consumption is also identical with embodiment 1.

The catalyst in the reactor of the secondary hydroprocessing reaction is prepared according to the disclosed method of CN1085934, and its composition is: 1% by weight of magnesium oxide, 4% by weight of nickel oxide, 29% by weight of tungsten oxide and the balance of aluminum oxide.

Stripping: stripping is carried out in a vacuum stripping device, and the stripping medium is water vapor.

The yield and properties of the product oil obtained by vacuum stripping are shown in Table 2.

Table 1

raw material 1 Raw material 2 Density/(kg/m ³ ) 873.2 903.1 Kinematic viscosity/(mm ² /s) 100℃ 4.72 10.56 40℃ 28.30 128.0 Viscosity index 74 47 Sulfur content/(mg/kg) 3200 2800 Nitrogen content/(mg/kg) 324 393 5% distillation temperature/℃ 345 416 95% distillation temperature/℃ 446 486

Table 2

Example 1 Comparative example 1 2 3 4 Product oil yield, wt% 93.1 86.2 95.4 95.2 88.6 Density/(kg/m ³ ) 883.6 881.2 884.2 883.9 880.3 Kinematic viscosity(100℃)/(mm ² /s) 4.56 4.42 4.58 4.57 9.54 Saybolt color/number ＞+30 ＞+30 ＞+30 ＞+30 ＞+30 Sulfur content/(mg/kg) 3.5 3.2 3.1 0.06 2.2 Nitrogen content/(mg/kg) 1.6 4.1 2.1 0.02 1.8 UV absorbance (260nm) - - - ＜0.1 - Carbon type distribution/% CA 0.60 0.55 0.32 0.0 0.63 CN 39.20 38.42 41.06 42.62 42.59 Cp 60.74 61.03 58.62 57.38 56.78

table 3

General purpose rubber oil Anti-yellowing rubber filling oil Density/(kg/m ³ ) Report Report Kinematic viscosity(100℃)/(mm ² /s) Report Report Saybolt color/number ≮+26 ≮+30 Sulfur content/(mg/kg) ≯5 ≯2 Nitrogen content/(mg/kg) ≯2 ≯1 UV absorption (260nm) - ≯0.1 Carbon type distribution/% CA ≯1 0 CN ≮30 ≮30 Cp Report Report

Claims (19)

1. A method for producing SBS rubber extender oil, comprising: under hydrotreating reaction conditions, feedstock oil and hydrogen are contacted with a hydrotreating catalyst to react, and product oil is obtained through stripping, it is characterized in that the hydrogenation Treating the catalyst includes catalyst _Ia and catalyst _Ib , catalyst _Ia and catalyst _Ib are arranged in layers, by volume and based on the catalyst _Ia , the content of catalyst _Ib is 3-40%, wherein, the The raw material oil is distillate oil with a viscosity index less than 80 and a distillation range of 350°C-560°C, and the content of the hydrogenation active metal component of the catalyst Ib is 10-30% of the content of _the hydrogenation active _metal component of the catalyst Ia , the layered arrangement makes the feed oil contact with catalyst I _b and catalyst I _a sequentially in the hydrotreating reaction unit, including catalyst I _c between the catalyst I _a and catalyst I _b , by volume and Based on the catalyst _Ia , the content of the catalyst _Ic is greater than 0 to less than or equal to 80%, wherein, the content of the hydrogenation active metal component of the catalyst _Ic is the catalyst _Ia hydrogenation active metal group The content of fennel is greater than 30% to less than or equal to 70%. 2. The method according to claim 1, characterized in that the catalyst _Ib is present in an amount of 5-30% by volume and based on the catalyst _Ia . 3. The method according to claim 2, characterized in that the catalyst _Ib is present in an amount of 6-20% by volume and based on the catalyst _Ia . 4. according to the described method of any one of claim 1,2 or 3, it is characterized in that, described catalyst 1 _a contains the carrier that is selected from alumina and/or silica-alumina, is selected from nickel and/or cobalt , molybdenum and/or tungsten hydrogenation active metal components, containing or not containing one or more auxiliary components selected from fluorine, boron and phosphorus, and containing or not containing organic additives, based on the catalyst, to The content of nickel and/or cobalt in terms of oxides is 1 to 5% by weight, the content of molybdenum and/or tungsten is 12 to 35% by weight, and one or more assistants selected from fluorine, boron and phosphorus in terms of elements The content of the additive component is 0-9% by weight, and the molar ratio of the organic additive to the sum of hydrogenation active metal components calculated as oxides is 0-2. 5. The method according to claim 1, wherein the hydroprocessing reaction conditions include: a pressure of 10-20 MPa, a temperature of 280-380°C, a volume space velocity of 0.2-2h ^-1 , and a hydrogen-to-oil volume ratio of 300 -1200. 6. The method according to claim 5, wherein the hydroprocessing reaction conditions include: pressure 12-18MPa, temperature 300-360°C, volume space velocity 0.4-1.5h ^-1 , hydrogen-oil volume ratio 350 -1000:1. 7. The method according to claim 6, wherein the hydroprocessing reaction conditions include: pressure 14-18MPa, temperature 330-360°C, volume space velocity 0.4-1.2h ^-1 , hydrogen-oil volume ratio 500 -1000:1. 8 . The method according to claim 1 , wherein the feedstock oil is a distillate oil with a viscosity index of -20 to 80 and a distillation range of 350° C. to 530° C. 8 . 9. The method according to claim 1, characterized in that, by volume and based on the catalyst _Ia , the content of the catalyst _Ic is 5-40%. 10. The method according to claim 9, characterized in that, based on the catalyst _Ia , the content of the catalyst _Ic is 10-30% by volume. 11. The method according to claim 1, characterized in that, before the stripping after the hydrotreating reaction, including under the hydrotreating reaction conditions, the generated oil and hydrogen are contacted with the hydrotreating catalyst for the second time The step of reacting, wherein the reaction temperature of the second hydrogenation treatment is 10-50°C lower than the reaction temperature of the first hydrogenation treatment. 12 . The method according to claim 11 , characterized in that, the reaction temperature of the second hydrogenation treatment is 20-30° C. lower than the reaction temperature of the first hydrogenation treatment. 13 . 13. The method according to claim 11 or 12, characterized in that the reaction conditions for the secondary hydrogenation treatment include: pressure 12-20MPa, temperature 250-360°C, volume space velocity 0.5-6h ^-1 , hydrogen The oil volume ratio is 300-1200:1. 14. The method according to claim 13, wherein the reaction conditions for the secondary hydrotreating include: pressure 12-18MPa, temperature 260-350°C, volume space velocity 1-4h ^-1 , hydrogen oil volume The ratio is 350-1000:1. 15. The method according to claim 14, wherein the reaction conditions for the secondary hydrotreating include: pressure 14-18MPa, temperature 280-330°C, volume space velocity 1.5-3.5h ^-1 , hydrogen oil The volume ratio is 450-800:1. 16. The method according to claim 1, characterized in that, after the stripping, a step of hydrotreating the stripped product is included. 17. The method according to claim 16, characterized in that, the hydrorefining catalyst is a catalyst with a reduced metal as a hydrogenation active component, wherein the reduced metal is selected from nickel, platinum and/or or palladium. 18. The method according to claim 16, characterized in that the hydrofining reaction conditions include: pressure 10-20MPa, temperature 150-320°C, volume space velocity 0.3-3h ^-1 , hydrogen-oil volume ratio of 100-3000:1. 19. The method according to claim 18, wherein the hydrofining reaction conditions include: pressure 12-18MPa, temperature 180-300°C, volume space velocity 0.5-1.5h ^-1 , hydrogen-to-oil volume ratio It is 200-1000:1.