CN103013558A - Production method of SBS rubber filling oil - Google Patents
Production method of SBS rubber filling oil Download PDFInfo
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Abstract
The invention relates to a production method of SBS rubber filling oil. According to the invention, under a hydrogenation treatment reaction condition, raw oil and a hydrogenation treatment catalyst are subjected to a contact reaction, and product oil is obtained through stripping. The method is characterized in that the hydrogenation treatment catalyst comprises a catalyst Ia and a catalyst Ib which form a layered arrangement. Calculated according to volume and with the catalyst Ia as a standard, the content of the catalyst Ib is 3-40%. The content of hydrogenation active metal component of the catalyst Ib is 10-30% of that of the hydrogenation active metal component of Ia. With the layered arrangement, the raw oil sequentially contacts the catalyst Ib and the catalyst Ia in a hydrogenation treatment reaction unit. Compared with prior art, when the method provided by the invention is used for producing SBS rubber filling oil, a yield is high.
Description
Invention field
The present invention relates to the production method of thermoplastic elastomer SBS's rubber filling oil, particularly utilize intermediate base low-viscosity index base oil to produce the method for general SBS rubber filling oil and the SBS of anti-xanthochromia rubber filling oil.
Technical background
The SBS synthetic rubber is styrene-butadiene-styrene block copolymer, is mainly used in the industries such as shoemaking, glue tube belt, modifying plastics, sizing agent and asphalt modification.Thereby usually can add a certain amount of oily components in the pressing of SBS rubber and the course of processing of extruded product and improve its moldability, extrusion performance so that processing; the physical and mechanical properties of the preparation that also can optimize simultaneously and reduction product cost etc., this part oily components is called rubber filling oil or treated oil.Rubber filling oil is generally made by processing mineral oil, and is different according to the kind of petroleum, generally is divided into naphthenic rubber extending oil and intermediate base rubber filling oil.In addition, rubber clone not simultaneously, the character such as the quality grade of the rubber filling oil that needs and hydrocarbon composition also have very large difference.The extending oil that needs the high aromaticity content of aromatic hydrocarbons such as styrene-butadiene rubber(SBR), SBS rubber then needs the base oil of low arene content.Therefore the production of rubber filling oil is different different with rubber clone according to product summary, and its production method also has very large difference.
US5504135 discloses a kind of rubber filling oil and has contained the rubber of this extending oil, has wherein related to the production method of rubber filling oil.The method is take vacuum residuum as raw material, production kinematic viscosity (100 ℃) 32-50mm
2/ s, aromaticity content 30-55%, but polycyclic aromatic hydrocarbons is lower than 3% RUBBER PROCESS OIL, and this RUBBER PROCESS OIL is the aromatic hydrocarbons type, is used for the processing of styrene-butadiene rubber(SBR).Concrete steps are the step that comprises propane deasphalting, solvent dewaxing and reclaim RUBBER PROCESS OIL from the disengaging edible vegetable oil of dewaxing.
CN1752182 discloses a kind of production method of aromatic hydrocarbon rubber filling oil, it is characterized in that being comprised of following steps: A. coal tar fraction and hydrogen enter hydrogenator after mixing, with Mo-Ni-P catalyst for hydro-upgrading contact reacts, remove sulphur, nitrogen impurity and colloid, bituminous matter in the coal tar fraction, reaction conditions is: hydrogen dividing potential drop 8.0～14.0MPa, 370～390 ℃ of temperature of reaction, volume space velocity 0.6～1.0h-1, hydrogen to oil volume ratio 1000～1200, reaction afterreaction product is derived hydrogenator; Described Mo-Ni-P catalyst for hydro-upgrading, in oxide dry basis, MoO3 accounts for 15～25w% of total catalyst weight, and NiO accounts for 2～6w% of total catalyst weight, and P2O5 accounts for 3～8w% of total catalyst weight, and all the other are the amorphous silicic acid alumina supporter; B. the reaction product that obtains of steps A enters gas delivery and stable system after heat exchange, cooling, isolate hydrogen, dry gas, hydrogen sulfide and ammonia and liquefied gas after, obtain product liquid; C. the product liquid that step B is obtained carries out fractionation, cutting in separation column, obtain cut more than 360 ℃, and this cut is the aromatic hydrocarbon rubber filling oil product.
The people such as Liu Guangyuan (the hydrogenation utilisation technology of SBS rubber filling oil, Liu Guangyuan etc., petrochemical technology, 2005,12 (3), 59-62) existing hydrogenation method is produced SBS rubber filling oil tech and comment, and right respectively: medium-pressure hydrocracking process for producing rubber oil technology; The two-stage hydrogenation method is produced the rubber oil technology; Perhydro type flow process technology produces the rubber filling oil tech and hydrofining production rubber filling oil tech is introduced.
Wherein, it is to utilize the MVI base oil to be raw material that the two-stage hydrogenation method is produced the rubber filling oil tech, produces rubber filling oil through two-section hydrotreating.Be characterized in that raw material passes through first one-stage hydrogenation, use sulphided state catalyst removal heterogeneous ring compound, saturated most of aromatic hydrocarbons.Then pass through the second segment hydrogenation, use base metal reduction-state catalyzer, saturated residue aromatic hydrocarbons improves oxidation stability, make the product saybolt colorimeter reach+more than 30.
In the prior art, can adopt the method that comprises hydrotreatment to produce the SBS rubber filling oil.But be subjected to the restriction of catalyst system therefor performance, SBS rubber filling oil yield etc. are still desirable not to the utmost.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, the production SBS rubber filling oil method that provides a kind of new, yield etc. obviously to improve.
The present invention relates to following content:
1. method of producing the SBS rubber filling oil, comprising: under the hydrotreatment reaction conditions, with stock oil and hydrogen and hydrotreating catalyst contact reacts, obtain product oil through stripping, it is characterized in that, described hydrotreating catalyst is for comprising catalyst I
aAnd catalyst I
b, catalyst I
aAnd catalyst I
bLayered arrangement is by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 3-40%, wherein, described catalyst I
bThe content of hydrogenation active metals component be catalyst I
aThe 10-30% of hydrogenation active metals component concentration, described layered arrangement makes described stock oil in hydrotreatment reaction member order and catalyst I
bAnd catalyst I
aContact.
2. according to 1 described method, it is characterized in that, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 5-30%
3. according to 2 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 6-20%.
4. according to 1,2 or 3 each described methods, it is characterized in that described catalyst I
aContain the carrier that is selected from aluminum oxide and/or silica-alumina, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, contain or do not contain and be selected from fluorine, one or more adjuvant components and contain or do not contain organic additive in boron and the phosphorus, take catalyzer as benchmark, take the content of the nickel of oxide compound and/or cobalt as 1～5 % by weight, the content of molybdenum and/or tungsten is 12～35 % by weight, the fluorine that is selected from element, the content of one or more adjuvant components is 0～9 % by weight in boron and the phosphorus, described organism with take the mol ratio of the hydrogenation active metals component sum of oxide compound as 0-2.
5. according to 4 described methods, it is characterized in that, described catalyzer is by γ-Al
2O
3Support tungsten and nickel oxide and the auxiliary agent fluorine consists of, its composition (weight): nickel oxide 1～5%, Tungsten oxide 99.999 12～35%, fluorine are 1～9%, surplus is γ-Al
2O
3
6. according to 4 described methods, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus are silica-alumina; Or be a kind of hydrogenation catalyst of containing fluorin take silica-alumina as carrier, and consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, and fluorine 1-10 % by weight, surplus are carrier; Or be a kind of hydrogenation catalyst of containing phosphor and preparation thereof take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and wherein the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.
7. according to 6 described methods, it is characterized in that, described catalyzer, described catalyzer contain and are selected from one or more that contain in oxygen or the nitrogenous organism, described organism with take the mol ratio of nickel, molybdenum and the tungsten sum of oxide compound as 0.03-2.
8. catalyzer according to claim 7, it is characterized in that, described oxygen-containing organic compound is selected from one or more in Organic Alcohol, the organic acid, and organic compounds containing nitrogen is organic amine, described organism with take the mol ratio of nickel, molybdenum and the tungsten sum of oxide compound as 0.08-1.5.
9. according to 4 described methods, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst take aluminum oxide as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 0.5-8 % by weight, fluorine 1-10 % by weight, surplus are aluminum oxide; Or be a kind of hydrogenation catalyst of containing fluorin take aluminum oxide as carrier, and consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, and all the other are aluminum oxide; Or be a kind of hydrogenation catalyst of containing phosphor take aluminum oxide as carrier, consist of nickel oxide 1-10 % by weight after this catalyzer roasting, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
10. according to 9 described methods, it is characterized in that, described catalyzer contains and is selected from one or more that contain in oxygen or the nitrogenous organism, described organism with take the mol ratio of nickel, molybdenum and the tungsten sum of oxide compound as 0.03-2.
11. catalyzer according to claim 10, it is characterized in that, described oxygen-containing organic compound is selected from one or more in Organic Alcohol, the organic acid, and organic compounds containing nitrogen is organic amine, described organism with take the mol ratio of nickel, molybdenum and the tungsten sum of oxide compound as 0.08-1.5.
12. according to 1 described method, it is characterized in that, the hydrotreatment reaction conditions comprises: pressure is 10-20MPa, and temperature 280-380 ℃, volume space velocity is 0.2-2h
-1, hydrogen to oil volume ratio is 300-1200: 1.
13. according to 12 described methods, it is characterized in that, the hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 300-360 ℃, volume space velocity is 0.4-1.5h
-1, hydrogen to oil volume ratio is 350-1000: 1.
14. according to 13 described methods, it is characterized in that, the hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 330-360 ℃, volume space velocity is 0.4-1.2h
-1, hydrogen to oil volume ratio is 500-1000: 1.
15. according to 1 described method, it is characterized in that, described stock oil is viscosity index less than 80 boiling range is 350 ℃-560 ℃ distillate.
16. according to 15 described methods, it is characterized in that, described stock oil is that viscosity index is that-20 to 80 boiling range is 350 ℃-530 ℃ distillate.
17. according to 1 described method, it is characterized in that, in described catalyst I
aWith catalyst I
bBetween comprise catalyst I
c, by volume and with described catalyst I
aBe benchmark, described catalyst I
cContent be greater than 0 to less than or equal to 80%, wherein, described catalyst I
cThe content of hydrogenation active metals component be catalyst I
aThe content of hydrogenation active metals component greater than 30% to less than or equal to 70%.
18. according to 17 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, described catalyst I
cContent be 5-40%.
19. according to 18 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, described catalyst I
cContent be 10-30%.
20. according to 1 described method, it is characterized in that, before stripping after the described hydrotreatment reaction, be included under the hydrotreatment reaction conditions, to generate oil and hydrogen secondary and the catalytic step of hydrotreating catalyst, wherein, secondary hydrotreatment temperature of reaction is lower than 10-50 ℃ of hydrotreatment temperature of reaction.
21. according to 20 described methods, it is characterized in that, described secondary hydrotreatment temperature of reaction is lower than 20-30 ℃ of hydrotreatment temperature of reaction.
22. according to 20 or 21 described methods, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-20MPa, temperature 250-360 ℃, volume space velocity is 0.5-6h
-1, hydrogen to oil volume ratio is 300-1200: 1.
23. according to 22 described methods, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 260-350 ℃, volume space velocity is 1-4h
-1, hydrogen to oil volume ratio is 350-1000: 1.
24. according to 23 described methods, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 280-330 ℃, volume space velocity is 1.5-3.5h
-1, hydrogen to oil volume ratio is 450-800: 1.
25. according to 1 described method, it is characterized in that, after described stripping, comprise stripped product is carried out hydrorefined step.
26. according to 25 described methods, it is characterized in that, described hydrofining catalyzer is for to be the catalyzer of hydrogenation activity component take the as-reduced metal, wherein, described as-reduced metal is selected from nickel, platinum and/or palladium.
27. according to 25 described methods, it is characterized in that, described hydrofining reaction condition comprises: pressure 10-20MPa, temperature 150-320 ℃, volume space velocity is 0.3-3h
-1, hydrogen to oil volume ratio is 100-3000: 1.
28. according to 27 described methods, it is characterized in that, described hydrofining reaction condition comprises: pressure 12-18MPa, temperature 180-300 ℃, volume space velocity is 0.5-1.5h
-1, hydrogen to oil volume ratio is 200-1000: 1.
According to method provided by the invention, described hydrotreatment reaction is to remove sulphur, nitrogen compound and aromatic saturation in the raw material as purpose.Wherein, the reactor that can be used for the hydrotreatment reaction that the reactor device that described hydrogenation reaction is used can provide for prior art arbitrarily, for example fixed-bed reactor.Described catalyst I
aContain heat-resistant inorganic oxide carrier and load on hydrogenation active metals component on this carrier, contain or do not conform to one or more in the catalyzer that is selected from one or more adjuvant components in fluorine, boron and the phosphorus and contains or do not conform to organic additive for being selected from.In preferred embodiment, described catalyst I
aBe selected from one or more in the following catalyzer, comprise:
The disclosed catalyzer of CN85104438, it is by γ-Al
2O
3Support tungsten and nickel oxide and the auxiliary agent fluorine consists of, its composition (weight): nickel oxide 1～5%, Tungsten oxide 99.999 12～35%, fluorine are 1～9%.
CN1853780A discloses a kind of fluorine-containing, phosphorus hydrogenation catalyst and preparation thereof take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus are silica-alumina.This catalyzer is by comprising method preparation from tungsten to the silica-alumina carrier that introduce fluorine, phosphorus, molybdenum, nickel and, wherein, the consumption of each component makes consisting of after the catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus are silica-alumina.
CN1853779A discloses a kind of hydrogenation catalyst of containing fluorin and preparation thereof take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, and fluorine 1-10 % by weight, surplus are carrier.The preparation method of this catalyzer comprises to silica-alumina carrier introducing fluorine, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after the catalyzer roasting: nickel oxide 1-10 % by weight, and molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, surplus are carrier.
CN1853781A discloses a kind of hydrogenation catalyst of containing phosphor and preparation thereof take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and wherein the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.The preparation method of this catalyzer comprises to silica-alumina carrier introducing phosphorus, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after the catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and the mol ratio of described Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.
CN1853781A discloses a kind of fluorine-containing, phosphorus hydrogenation catalyst and preparation thereof take aluminum oxide as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 0.5-8 % by weight, fluorine 1-10 % by weight, surplus are aluminum oxide.This catalyzer is by comprising method preparation from tungsten to alumina supporter that introduce fluorine, phosphorus, molybdenum, nickel and, wherein, the consumption of each component makes consisting of after the catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus are aluminum oxide.
CN1872959A discloses a kind of hydrogenation catalyst of containing fluorin and preparation thereof take aluminum oxide as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, and all the other are aluminum oxide.The preparation method of this catalyzer comprises to alumina supporter introducing fluorine, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after the catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, surplus are aluminum oxide.
CN1872960A discloses a kind of hydrogenation catalyst of containing phosphor and preparation thereof take aluminum oxide as carrier, consist of nickel oxide 1-10 % by weight after this catalyzer roasting, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.This catalyzer is introduced phosphorus, molybdenum, nickel and tungsten by comprising in alumina supporter, wherein, the consumption of each component makes consisting of after the catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus are aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
In the disclosed catalyzer of CN1853780A, CN1853779A, CN1853781A, CN1872959A and CN1872960A, preferably also contain organic additive, wherein, described organism be preferably 0.08-1.5 take the mol ratio of the hydrogenation active metals component sum of oxide compound as 0.03-2.
About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump they are quoted as the part of content of the present invention here.
Described catalyst I
bHave than catalyst I
aLow hydrogenation active metals component concentration, described catalyst I
bThe content of hydrogenation active metals component be catalyst I
aThe 10-30% of the content of hydrogenation active metals component is preferably 12-25%.Putting before this, the present invention is to described catalyst I
bBe not particularly limited, they can be that commercially available commodity also can adopt arbitrarily prior art preparation.
In embodiment, this type of catalyzer usually contains heat-resistant inorganic oxide carrier and loads on hydrogenation active metals component on this carrier, contains or do not conform to and be selected from one or more adjuvant components in fluorine, boron, phosphorus and the alkaline-earth metal.With catalyst I
bBe benchmark, described catalyst I
bTake the content of the nickel of oxide compound and/or cobalt as the 0.5-4 % by weight, be preferably the 1.0-3 % by weight, the content of molybdenum and/or tungsten is the 2.5-9 % by weight, be preferably the 3.5-6.5 % by weight, take the content that is selected from one or more adjuvant components in fluorine, boron, phosphorus and the alkaline-earth metal of element as the 0-5 % by weight, and the total amount that satisfies nickel and/or cobalt and molybdenum and/or W content is catalyst I
aThe 10-30% of the content of hydrogenation active metals component is preferably 12-25%.
For example, the preparation method of disclosed catalyzer just can be used to prepare and satisfies the catalyzer that the present invention requires among CN1344781, CN1966616 and the CN101134173A.Here in the lump they are quoted as the part of content of the present invention.
When in described catalyst I
aWith catalyst I
bBetween also comprise catalyst I
cThe time, described catalyst I
cThe content of hydrogenation active metals component greater than catalyst I
b, less than catalyst I
aDescribed catalyst I
cThe content of hydrogenation active metals component be catalyst I
aThe hydrogenation active metals component concentration greater than 30 to less than or equal to 70 % by weight, be preferably 40-60%.Putting before this, the present invention is to described catalyst I
bBe not particularly limited, they can be that commercially available commodity also can adopt arbitrarily prior art preparation.
In embodiment, this type of catalyzer usually contains heat-resistant inorganic oxide carrier and loads on hydrogenation active metals component on this carrier, contains or do not conform to and be selected from one or more adjuvant components in fluorine, boron, phosphorus and the alkaline-earth metal.With catalyst I
cBe benchmark, described catalyst I
cTake the content of the nickel of oxide compound and/or cobalt as the 0.3-8 % by weight, be preferably the 0.5-7.5 % by weight, the content of molybdenum and/or tungsten is the 0.5-15 % by weight, is preferably the 0.8-12 % by weight, and the total amount that satisfies nickel and/or cobalt and molybdenum and/or W content is catalyst I
aThe 30-70% of the content of hydrogenation active metals component is preferably 40-60%.
For example, the preparation method of disclosed catalyzer just can be used to prepare and satisfies the catalyzer that the present invention requires among CN1626625A, CN1690172A, CN1782031A and the CN1782033A.Here in the lump they are quoted as the part of content of the present invention.
Described stripping to be removing the small molecule hydrocarbon compounds that comprises the heteroatomic compound such as hydrogen sulfide and may generate that produces through hydrotreatment as purpose, realizes under the prerequisite of this purpose being enough to, and the present invention is not particularly limited described steam stripped method and condition.For example, high pressure stripping or the atmospheric stripping take water vapour as the stripping medium.Be ability customary way and condition about described steam stripped method and operational condition, do not give unnecessary details here.
When before stripping after the described hydrotreatment reaction, also be included under the hydrotreatment reaction conditions, in the time of will generating oil and hydrogen secondary and the catalytic step of hydrotreating catalyst, secondary hydrotreatment reaction catalyst system therefor can be identical with catalyzer with described hydrotreatment reaction, for example, being selected from hydrotreating catalyst is I
aIn one or more catalyzer.In preferred embodiment.Described secondary hydrotreatment reaction is selected from the Hydrobon catalyst of not fluorine-containing and/or molecular sieve with catalyzer.They can be commercially available commodity or adopt arbitrarily existing method preparation.
This type of catalyzer usually contains heat-resistant inorganic oxide carrier, hydrogenation active metals component, contains or do not conform to auxiliary agent phosphorus and contains or do not conform to organic additive.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay one or more are preferably aluminum oxide.Described organic additive is selected from one or more the organic compound that contains in oxygen or the organic compounds containing nitrogen, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in the organic amine.For example, oxygen-containing organic compound can be enumerated ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, citric acid, tartrate, the oxysuccinic acid one or more, organic compounds containing nitrogen can be enumerated quadrol, EDTA and ammonium salt thereof.
For example, the disclosed a kind of Hydrobon catalyst of CN1085934, this catalyzer contains by magnesium oxide, nickel oxide, Tungsten oxide 99.999 and aluminum oxide, and it consists of: magnesium oxide 0.1～1.9%, nickel oxide 2.5～6%, Tungsten oxide 99.999 24～34% and surplus aluminum oxide.
The disclosed a kind of hydrogenation catalyst of containing phosphor take aluminum oxide as carrier of CN1872960A, consist of nickel oxide 1-10 % by weight after this catalyzer roasting, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
CN1840618A hydrogenation catalyst and preparation thereof take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, and surplus is carrier.
In CN1872960A and the disclosed catalyzer of CN1840618A, preferably also contain organic additive, wherein, described organism be preferably 0.08-1.5 take the mol ratio of the hydrogenation active metals component sum of oxide compound as 0.03-2.
These catalyzer all can be used as described Hydrobon catalyst and are used for the present invention.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump they are quoted as the part of content of the present invention here.
When comprising the reactions steps of secondary hydrotreatment, the temperature of streams when entering the secondary hydrogenator that can adopt any existing heat transfer technology to make to be derived from a hydrogenator satisfies described requirement.The reactor that can be used for the hydrotreatment reaction that described secondary hydrogenator can provide for prior art arbitrarily, for example fixed-bed reactor.
Described hydrofining is take further hydrogenation aromatic saturation as purpose, and used Hydrobon catalyst contains carrier and at least a nickel, platinum and/or the metallic palladium component that is selected from group VIII that loads on this carrier.In the optional self-alumina of described carrier, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay one or more.In metal and take catalyzer as benchmark, the content of described group VIII metal is preferably the 0.1-10 % by weight, more is preferably the 0.1-5 % by weight.For example, CN1510112A discloses a kind of metal mold hydrogenation catalyst, and CN1245204 discloses a kind of bimetal hydrogenation catalyst etc., all has good hydrofining performance, all can be used as Hydrobon catalyst and is used for the present invention.Here in the lump they are quoted as the part of content of the present invention.
According to method provided by the invention, described stock oil can be that viscosity index is 0-80, the preferred viscosities index is 20-80's, boiling range is the distillate in any source of 350 ℃-560 ℃, is preferably 350 ℃-530 ℃ distillate (boiling range described in the present invention refer to distillation yield more than or equal to 5% to less than or equal to distillation temperature corresponding to 95% overhead product).Satisfying under the prerequisite of described requirement, the source of described stock oil is being not particularly limited.For example, the low-viscosity index pressed oil of by-product can satisfy this requirement in the paraffin production process, can directly use as the raw material of producing the SBS rubber filling oil.
Compared with prior art, when adopting the method that the invention provides to produce the SBS rubber filling oil, its yield improves.
Embodiment
The present invention is described further for the following examples.
Embodiment 1
Stock oil is a kind of oil that two distillates obtain through furfural treatment and benzol-kentone dewaxing that subtracts that comes from intermediate base crude oil, and its character sees Table the raw material 1 in 1.
The hydrotreatment reaction is carried out in fixed-bed reactor, and reaction conditions comprises: 330 ℃ of temperature, pressure 14MPa, air speed 0.8h
-1, hydrogen to oil volume ratio is 450: 1.
Catalyzer is the catalyst I of layering filling
aAnd catalyst I
b, be respectively:
Catalyst I
aAccording to the open method preparation of CN85104438, it consists of: nickel oxide 3 % by weight, and Tungsten oxide 99.999 25 % by weight, fluorine is weight 4%, surplus is γ-Al
2O
3
Catalyst I
bAccording to embodiment 6 preparations among the CN1966616A, wherein the hydrogenation active metals component is molybdenum and nickel, and in oxide compound and take catalyzer as benchmark, the content of molybdenum is 4.5 % by weight, and the content of nickel is 1.5 % by weight.
Wherein, by volume, I
bConsumption is I
a12% of consumption.
Stripping: stripping carries out in the decompression stripper plant, and the stripping medium is water vapour.
Obtain product oil through stripping, product oil yield and character thereof see Table 2.
Comparative Examples 1
Stock oil and embodiment 1 are same.Catalyzer is catalyst I single among the embodiment 1
aReaction conditions comprises: 330 ℃ of temperature, pressure 14MPa, air speed 0.8h
-1, hydrogen to oil volume ratio is 450: 1; Other are identical with embodiment 1.
The product oil yield and the character thereof that obtain through stripping see Table 2.
Embodiment 2
Stock oil is with embodiment 1.
Catalyzer is the catalyst I of layering filling
a, catalyst I
bAnd catalyst I
cWherein, catalyst I
a, catalyst I
bIdentical with embodiment 1, catalyst I
cAccording to embodiment 15 preparations of CN1782033A, wherein the hydrogenation active metals component is molybdenum and nickel, and in oxide compound and take catalyzer as benchmark, the content of molybdenum is 13.7 % by weight, and the content of nickel is 3 % by weight.By volume, I
bConsumption is I
a12% of consumption, I
cConsumption is I
a50% of consumption.
Reaction conditions comprises: 330 ℃ of temperature, pressure 14MPa, cumulative volume air speed 0.8h
-1, hydrogen to oil volume ratio is 450: 1.
Stripping: stripping carries out in the decompression stripper plant, and the stripping medium is water vapour.
The product oil yield and the character thereof that obtain through the decompression stripping see Table 2.
Embodiment 3
After the stripping of embodiment 2, increase the hydrofining step.
Hydrofining reaction carries out in fixed-bed reactor, and reaction conditions comprises: 220 ℃ of temperature, pressure 16MPa, air speed 0.8h
-1, hydrogen to oil volume ratio is 350: 1.
Hydrobon catalyst is according to example 11 preparations among the CN1510112A, and wherein, the content of platinum is 0.22 % by weight, and the content of metallic palladium is 0.43 % by weight.
Product oil yield and character thereof see Table 2.
The standard of rubber filling oil sees Table 3.
Embodiment 4
Stock oil is a kind of oil that three distillates obtain through furfural treatment and benzol-kentone dewaxing that subtracts that comes from intermediate base crude oil, and its character sees Table the raw material 2 in 1.
The hydrotreatment reaction is carried out in the fixed-bed reactor of two series connection, disposes interchanger between two reactors.Wherein, the reaction conditions of hydrotreatment reaction comprises: 345 ℃ of temperature, pressure 14MPa, total air speed 0.87h
-1, hydrogen to oil volume ratio is 500: 1.The reaction conditions of secondary hydrotreatment reaction comprises: 330 ℃ of temperature, pressure 14MPa, air speed 1.90h
-1, hydrogen to oil volume ratio is 500: 1, the cumulative volume air speed is 0.6h
-1
Catalyzer in the reactor of hydrotreatment reaction is the catalyst I of layering filling
aAnd catalyst I
bWherein, catalyst I
aAnd catalyst I
bIdentical with embodiment 1, by volume, I
bConsumption is also identical with embodiment 1.
Catalyzer in the reactor of secondary hydrotreatment reaction is according to the open method preparation of CN1085934, and it consists of: magnesium oxide 1 % by weight, nickel oxide 4 % by weight, Tungsten oxide 99.999 29 % by weight and surplus aluminum oxide.
Stripping: stripping carries out in the decompression stripper plant, and the stripping medium is water vapour.
The product oil yield and the character thereof that obtain through the decompression stripping see 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 |
| Sulphur content/(mg/kg) | 3200 | 2800 |
| Nitrogen content/(mg/kg) | 324 | 393 |
| 5% recovered temperature/℃ | 345 | 416 |
| 95% recovered temperature/℃ | 446 | 486 |
Table 2
| Embodiment | 1 | Comparative Examples 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 colorimeter/number | ＞+30 | ＞+30 | ＞+30 | ＞+30 | ＞+30 |
| Sulphur 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 |
| Ultraviolet absorptivity (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
| Conventional rubber oil | The rubber filling oil of anti-the xanthochromia | |
| Density/(kg/m 3) | Report | Report |
| Kinematic viscosity (100 ℃)/(mm 2/s) | Report | Report |
| Saybolt colorimeter/number | ≮+26 | ≮+30 |
| Sulphur content/(mg/kg) | ≯5 | ≯2 |
| Nitrogen content/(mg/kg) | ≯2 | ≯1 |
| Ultraviolet light absorption (260nm) | - | ≯0.1 |
| Carbon type distribution/% | ||
| CA | ≯1 | 0 |
| CN | ≮30 | ≮30 |
| Cp | Report | Report |
Claims (26)
1. method of producing the SBS rubber filling oil, comprising: under the hydrotreatment reaction conditions, with stock oil and hydrogen and hydrotreating catalyst contact reacts, obtain product oil through stripping, it is characterized in that, described hydrotreating catalyst comprises catalyst I
aAnd catalyst I
b, catalyst I
aAnd catalyst I
bLayered arrangement is by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 3-40%, wherein, described catalyst I
bThe content of hydrogenation active metals component be catalyst I
aThe 10-30% of hydrogenation active metals component concentration, described layered arrangement makes described stock oil in hydrotreatment reaction member order and catalyst I
bAnd catalyst I
aContact.
2. according to 1 described method, it is characterized in that, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 5-30%
3. according to 2 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, catalyst I
bContent be 6-20%.
4. according to 1,2 or 3 each described methods, it is characterized in that described catalyst I
aContain the carrier that is selected from aluminum oxide and/or silica-alumina, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, contain or do not contain and be selected from fluorine, one or more adjuvant components and contain or do not contain organic additive in boron and the phosphorus, take catalyzer as benchmark, take the content of the nickel of oxide compound and/or cobalt as 1～5 % by weight, the content of molybdenum and/or tungsten is 12～35 % by weight, the fluorine that is selected from element, the content of one or more adjuvant components is 0～9 % by weight in boron and the phosphorus, described organism with take the mol ratio of the hydrogenation active metals component sum of oxide compound as 0-2.
5. according to 4 described methods, it is characterized in that, described catalyzer is by γ-Al
2O
3Support tungsten and nickel oxide and the auxiliary agent fluorine consists of, its composition (weight): nickel oxide 1～5%, Tungsten oxide 99.999 12～35%, fluorine are 1～9%, surplus is γ-Al
2O
3
6. according to 4 described methods, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus are silica-alumina; Or be a kind of hydrogenation catalyst of containing fluorin take silica-alumina as carrier, and consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, and fluorine 1-10 % by weight, surplus are carrier; Or be a kind of hydrogenation catalyst of containing phosphor and preparation thereof take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and wherein the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.
7. according to 4 described methods, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst take aluminum oxide as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 0.5-8 % by weight, fluorine 1-10 % by weight, surplus are aluminum oxide; Or be a kind of hydrogenation catalyst of containing fluorin take aluminum oxide as carrier, and consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, and all the other are aluminum oxide; Or be a kind of hydrogenation catalyst of containing phosphor take aluminum oxide as carrier, consist of nickel oxide 1-10 % by weight after this catalyzer roasting, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
8. according to 6 or 7 described methods, it is characterized in that, described catalyzer, described catalyzer contain and are selected from one or more that contain in oxygen or the nitrogenous organism, described organism with take the mol ratio of nickel, molybdenum and the tungsten sum of oxide compound as 0.03-2.
9. catalyzer according to claim 8, it is characterized in that, described oxygen-containing organic compound is selected from one or more in Organic Alcohol, the organic acid, and organic compounds containing nitrogen is organic amine, described organism with take the mol ratio of nickel, molybdenum and the tungsten sum of oxide compound as 0.08-1.5.
10. according to 1 described method, it is characterized in that, the hydrotreatment reaction conditions comprises: pressure is 10-20MPa, and temperature 280-380 ℃, volume space velocity is 0.2-2h
-1, hydrogen to oil volume ratio is 300-1200.
11. according to 10 described methods, it is characterized in that, the hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 300-360 ℃, volume space velocity is 0.4-1.5h
-1, hydrogen to oil volume ratio is 350-1000: 1.
12. according to 11 described methods, it is characterized in that, the hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 330-360 ℃, volume space velocity is 0.4-1.2h
-1, hydrogen to oil volume ratio is 500-1000: 1.
13. according to 1 described method, it is characterized in that, described stock oil is viscosity index less than 80 boiling range is 350 ℃-560 ℃ distillate.
14. according to 13 described methods, it is characterized in that, described stock oil is that viscosity index is that-20 to 80 boiling range is 350 ℃-530 ℃ distillate.
15. according to 1 described method, it is characterized in that, in described catalyst I
aWith catalyst I
bBetween comprise catalyst I
c, by volume and with described catalyst I
aBe benchmark, described catalyst I
cContent be greater than 0 to less than or equal to 80%, wherein, described catalyst I
cThe content of hydrogenation active metals component be catalyst I
aThe content of hydrogenation active metals component greater than 30% to less than or equal to 70%.
16. according to 15 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, described catalyst I
cContent be 5-40%.
17. according to 16 described methods, it is characterized in that, by volume and with described catalyst I
aBe benchmark, described catalyst I
cContent be 10-30%.
18. according to 1 described method, it is characterized in that, before stripping after the described hydrotreatment reaction, be included under the hydrotreatment reaction conditions, to generate oil and hydrogen secondary and the catalytic step of hydrotreating catalyst, wherein, secondary hydrotreatment temperature of reaction is lower than 10-50 ℃ of hydrotreatment temperature of reaction.
19. according to 18 described methods, it is characterized in that, described secondary hydrotreatment temperature of reaction is lower than 20-30 ℃ of hydrotreatment temperature of reaction.
20. according to 18 or 19 described methods, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-20MPa, temperature 250-360 ℃, volume space velocity is 0.5-6h
-1, hydrogen to oil volume ratio is 300-1200: 1.
21. according to 20 described methods, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 260-350 ℃, volume space velocity is 1-4h
-1, hydrogen to oil volume ratio is 350-1000: 1.
22. according to 21 described methods, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 280-330 ℃, volume space velocity is 1.5-3.5h
-1, hydrogen to oil volume ratio is 450-800: 1.
23. according to 1 described method, it is characterized in that, after described stripping, comprise stripped product is carried out hydrorefined step.
24. according to 23 described methods, it is characterized in that, described hydrofining catalyzer is for to be the catalyzer of hydrogenation activity component take the as-reduced metal, wherein, described as-reduced metal is selected from nickel, platinum and/or palladium.
25. according to 23 described methods, it is characterized in that, described hydrofining reaction condition comprises: pressure 10-20MPa, temperature 150-320 ℃, volume space velocity is 0.3-3h
-1, hydrogen to oil volume ratio is 100-3000: 1.
26. according to 25 described methods, it is characterized in that, described hydrofining reaction condition comprises: pressure 12-18MPa, temperature 180-300 ℃, volume space velocity is 0.5-1.5h
-1, hydrogen to oil volume ratio is 200-1000: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541248A (en) * | 2017-08-30 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of environmentally-frierubber rubber filling oil and preparation method thereof |
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| CN107541248A (en) * | 2017-08-30 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of environmentally-frierubber rubber filling oil and preparation method thereof |
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