CN103013558B - Production method of SBS rubber filling oil - Google Patents
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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 color inhibition SBS rubber filling oil.
Technical background
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.Usually a certain amount of oily components be can add in the pressing of SBS rubber and the course of processing of extruded product thus its moldability, extrusion performance improved so that processing; the physical and mechanical properties of the preparation simultaneously also can optimized and reduction product cost etc., this part oily components is called rubber filling oil or treated oil.Rubber filling oil is generally obtained by processing mineral oil, different according to the kind of petroleum, is generally divided into naphthenic rubber extending oil and intermediate base rubber filling oil.In addition, when rubber clone is different, the character such as the quality grade of the rubber filling oil of needs and hydrocarbon composition also have very large difference.As styrene-butadiene rubber(SBR) needs the extending oil of aromatic hydrocarbons height aromaticity content, 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 the rubber containing this extending oil, has wherein related to the production method of rubber filling oil.The method take vacuum residuum as raw material, production kinematic viscosity (100 DEG C) 32-50mm
2/ s, aromaticity content 30-55%, but polycyclic aromatic hydrocarbons is lower than the RUBBER PROCESS OIL of 3%, and this RUBBER PROCESS OIL is aromatic hydrocarbons type, for the processing of styrene-butadiene rubber(SBR).Concrete steps are the step comprising 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 made up of following steps: after A. coal tar fraction and hydrogen mixing, enter hydrogenator, with Mo-Ni-P catalyst for hydro-upgrading contact reacts, remove the sulphur in coal tar fraction, nitrogen impurity and colloid, bituminous matter, reaction conditions is: hydrogen dividing potential drop 8.0 ~ 14.0MPa, temperature of reaction 370 ~ 390 DEG C, volume space velocity 0.6 ~ 1.0h-1, hydrogen to oil volume ratio 1000 ~ 1200, after reaction, reaction product derives 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 amorphous silicic acid alumina supporter; B. the reaction product that steps A obtains enters gas delivery and stable system after heat exchange, cooling, after isolating hydrogen, dry gas, hydrogen sulfide and ammonia and liquefied gas, obtains product liquid; C. the product liquid obtained by step B carries out fractionation, cutting in separation column, and obtain more than 360 DEG C cuts, this cut is 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) produce SBS rubber filling oil tech to existing hydrogenation method to comment, and right respectively: medium-pressure hydrocracking process for producing rubber oil technology; Two-stage hydrogenation method produces rubber oil technology; Perhydro type flow technologies produces rubber filling oil tech and hydrofining production rubber filling oil tech is introduced.
Wherein, it is utilize MVI base oil for raw material that two-stage hydrogenation method produces rubber filling oil tech, produces rubber filling oil through two-section hydrotreating.Be characterized in raw material first through one-stage hydrogenation, use sulphided state catalyst removal heterogeneous ring compound, saturated most of aromatic hydrocarbons.Then through second segment hydrogenation, use base metal reduction-state catalyzer, saturated residue aromatic hydrocarbons, improves oxidation stability, and product saybolt colorimeter is reached more than+30.
In prior art, the method comprising hydrotreatment can be adopted to produce SBS rubber filling oil.But by the restriction of used catalyst 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, provide a kind of newly, production SBS rubber filling oil method that yield etc. obviously improves.
The present invention relates to following content:
1. produce a method for SBS rubber filling oil, comprising: at hydrotreating reaction conditions, by 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, by volume and with described catalyst I
afor 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. the method according to 1, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%
3. the method according to 2, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 6-20%.
4. the method according to 1,2 or 3 any one, is characterized in that, described catalyst I
acontaining the carrier being 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, containing or not containing being selected from fluorine, in boron and phosphorus one or more adjuvant components and containing or not containing organic additive, take catalyzer as benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 12 ~ 35 % by weight, fluorine is selected from element, in boron and phosphorus, the content of one or more adjuvant components is 0 ~ 9 % by weight, described organism with the mol ratio of the hydrogenation active metals component sum of oxide basis for 0-2.
5. the method according to 4, is characterized in that, described catalyzer is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine formed, it forms (weight): nickel oxide 1 ~ 5%, Tungsten oxide 99.999 12 ~ 35%, and fluorine is 1 ~ 9%, and surplus is γ-Al
2o
3.
6. the method according to 4, it is characterized in that, fluorine-containing, the phosphorus hydrogenation catalyst of described catalyzer to be a kind of with silica-alumina be 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 is silica-alumina; Or the hydrogenation catalyst of containing fluorin of to be a kind of with silica-alumina be 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, and surplus is carrier; Or hydrogenation catalyst of containing phosphor and the preparation thereof of to be a kind of with silica-alumina be 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. the method according to 6, is characterized in that, described catalyzer, and described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 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, organic acid, and organic compounds containing nitrogen is organic amine, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.08-1.5.
9. the method according to 4, it is characterized in that, fluorine-containing, the phosphorus hydrogenation catalyst of described catalyzer to be a kind of with aluminum oxide be 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 is aluminum oxide; Or the hydrogenation catalyst of containing fluorin of to be a kind of with aluminum oxide be 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; Or the hydrogenation catalyst of containing phosphor of to be a kind of with aluminum oxide be carrier, nickel oxide 1-10 % by weight is consisted of 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, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
10. the method according to 9, is characterized in that, described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 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, organic acid, and organic compounds containing nitrogen is organic amine, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.08-1.5.
12. methods according to 1, it is characterized in that, hydrotreatment reaction conditions comprises: pressure is 10-20MPa, temperature 280-380 DEG C, and volume space velocity is 0.2-2h
-1, hydrogen to oil volume ratio is 300-1200: 1.
13. methods according to 12, it is characterized in that, hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 300-360 DEG C, and volume space velocity is 0.4-1.5h
-1, hydrogen to oil volume ratio is 350-1000: 1.
14. methods according to 13, it is characterized in that, hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 330-360 DEG C, and volume space velocity is 0.4-1.2h
-1, hydrogen to oil volume ratio is 500-1000: 1.
15. methods according to 1, is characterized in that, described stock oil to be boiling range that viscosity index is less than 80 the be distillate of 350 DEG C-560 DEG C.
16. methods according to 15, is characterized in that, described stock oil to be viscosity index be-20 to 80 boiling range be the distillate of 350 DEG C-530 DEG C.
17. methods according to 1, is characterized in that, in described catalyst I
awith catalyst I
bbetween comprise catalyst I
c, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent for being greater than 0 to being 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 be greater than 30% to being less than or equal to 70%.
18. methods according to 17, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 5-40%.
19. methods according to 18, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 10-30%.
20. methods according to 1, it is characterized in that, after described hydrotreatment reaction before stripping, comprise at hydrotreating reaction conditions, oil and hydrogen secondary and the catalytic step of hydrotreating catalyst will be generated, wherein, secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 10-50 DEG C.
21. methods according to 20, it is characterized in that, described secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 20-30 DEG C.
22. methods according to 20 or 21, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-20MPa, temperature 250-360 DEG C, and volume space velocity is 0.5-6h
-1, hydrogen to oil volume ratio is 300-1200: 1.
23. methods according to 22, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 260-350 DEG C, and volume space velocity is 1-4h
-1, hydrogen to oil volume ratio is 350-1000: 1.
24. methods according to 23, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 280-330 DEG C, and volume space velocity is 1.5-3.5h
-1, hydrogen to oil volume ratio is 450-800: 1.
25. methods according to 1, is characterized in that, comprise and carry out hydrorefined step to stripped product after described stripping.
26. methods according to 25, is characterized in that, described hydrofining catalyzer is take as-reduced metal as the catalyzer of hydrogenation active component, and wherein, described as-reduced metal is selected from nickel, platinum and/or palladium.
27. methods according to 25, it is characterized in that, described hydrofining reaction condition comprises: pressure 10-20MPa, temperature 150-320 DEG C, and volume space velocity is 0.3-3h
-1, hydrogen to oil volume ratio is 100-3000: 1.
28. methods according to 27, it is characterized in that, described hydrofining reaction condition comprises: pressure 12-18MPa, temperature 180-300 DEG C, and 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, to remove for the purpose of sulphur, nitrogen compound and the aromatic saturation in raw material.Wherein, the reactor that can be used for hydrotreatment reaction that the reactor device of described hydrogenation reaction can provide for arbitrary prior art, such as fixed-bed reactor.Described catalyst I
afor be selected from containing heat-resistant inorganic oxide carrier and load hydrogenation active metals component on this carrier, containing or do not conform to be selected from one or more adjuvant components in fluorine, boron and phosphorus and containing or do not conform in the catalyzer of organic additive one or more.In a preferred embodiment, described catalyst I
abe selected from one or more in following catalyzer, comprise:
Catalyzer disclosed in CN85104438, it is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine formed, it forms (weight): nickel oxide 1 ~ 5%, Tungsten oxide 99.999 12 ~ 35%, and fluorine is 1 ~ 9%.
It take silica-alumina as fluorine-containing, phosphorus hydrogenation catalyst and the preparation thereof of carrier that CN1853780A discloses a kind of, 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 is silica-alumina.The method preparation of fluorine, phosphorus, molybdenum, nickel and tungsten introduced by this catalyzer to silicaalumina carrier by comprising, wherein, consisting of after the consumption of each component makes 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 is silica-alumina.
It take silica-alumina as hydrogenation catalyst of containing fluorin and the preparation thereof of carrier that CN1853779A discloses a kind of, 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, and surplus is carrier.The preparation method of this catalyzer comprises to silicaalumina carrier introducing fluorine, molybdenum, nickel and tungsten, wherein, consisting of after the consumption of each component makes 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, surplus is carrier.
It take silica-alumina as hydrogenation catalyst of containing phosphor and the preparation thereof of carrier that CN1853781A discloses a kind of, 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 silicaalumina carrier introducing phosphorus, molybdenum, nickel and tungsten, wherein, consisting of after the consumption of each component makes 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.
It take aluminum oxide as fluorine-containing, phosphorus hydrogenation catalyst and the preparation thereof of carrier that CN1853781A discloses a kind of, 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 is aluminum oxide.The method preparation of fluorine, phosphorus, molybdenum, nickel and tungsten introduced by this catalyzer to alumina supporter by comprising, wherein, consisting of after the consumption of each component makes 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 is aluminum oxide.
It take aluminum oxide as hydrogenation catalyst of containing fluorin and the preparation thereof of carrier that CN1872959A discloses a kind of, 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, consisting of after the consumption of each component makes 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 is aluminum oxide.
It take aluminum oxide as hydrogenation catalyst of containing phosphor and the preparation thereof of carrier that CN1872960A discloses a kind of, nickel oxide 1-10 % by weight is consisted of 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, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.This catalyzer introduces phosphorus, molybdenum, nickel and tungsten by comprising in alumina supporter, wherein, consisting of after the consumption of each component makes 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 aluminum oxide, wherein, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
In catalyzer disclosed in CN1853780A, CN1853779A, CN1853781A, CN1872959A and CN1872960A, preferably also containing organic additive, wherein, described organism with the mol ratio of the hydrogenation active metals component sum of oxide basis for 0.03-2 is preferably 0.08-1.5.
About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump their parts as content of the present invention are quoted here.
Described catalyst I
bthere is comparatively 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 arbitrary prior art to prepare.
In a specific embodiment, this type of catalyzer usually containing heat-resistant inorganic oxide carrier and load hydrogenation active metals component on this carrier, containing or do not conform to and be selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal.With catalyst I
bfor benchmark, described catalyst I
bwith the content of the nickel of oxide basis and/or cobalt for 0.5-4 % by weight, be preferably 1.0-3 % by weight, the content of molybdenum and/or tungsten is 2.5-9 % by weight, be preferably 3.5-6.5 % by weight, in the content being selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal of element for 0-5 % by weight, and the total amount meeting 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%.
Such as, the preparation method of catalyzer disclosed in CN1344781, CN1966616 and CN101134173A just can be used to prepare the catalyzer meeting application claims.Here in the lump their parts as content of the present invention are quoted.
When in described catalyst I
awith catalyst I
bbetween also comprise catalyst I
ctime, described catalyst I
cthe content of hydrogenation active metals component be greater than catalyst I
b, be less than catalyst I
a.Described catalyst I
cthe content of hydrogenation active metals component be catalyst I
ahydrogenation active metals component concentration be greater than 30 to being 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 arbitrary prior art to prepare.
In a specific embodiment, this type of catalyzer usually containing heat-resistant inorganic oxide carrier and load hydrogenation active metals component on this carrier, containing or do not conform to and be selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal.With catalyst I
cfor benchmark, described catalyst I
cwith the content of the nickel of oxide basis and/or cobalt for 0.3-8 % by weight, be preferably 0.5-7.5 % by weight, the content of molybdenum and/or tungsten is 0.5-15 % by weight, be preferably 0.8-12 % by weight, and the total amount meeting 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%.
Such as, the preparation method of catalyzer disclosed in CN1626625A, CN1690172A, CN1782031A and CN1782033A just can be used to prepare the catalyzer meeting application claims.Here in the lump their parts as content of the present invention are quoted.
Described stripping is to remove comprising for the purpose of the heteroatomic compounds such as hydrogen sulfide and the small molecule hydrocarbon compounds that may generate of producing through hydrotreatment, and be enough under the prerequisite realizing this object, the present invention is not particularly limited described steam stripped method and condition.Such as, take water vapour as high pressure stripping or the atmospheric stripping of stripping fluid.Be ability customary way and condition about described steam stripped method and operational condition, do not repeat here.
Before stripping after described hydrotreatment reaction, also comprise at hydrotreating reaction conditions, when will generate oil and hydrogen secondary and the catalytic step of hydrotreating catalyst, secondary hydrotreatment reaction used catalyst can be identical with a described anti-applications catalyst of hydrotreatment, such as, being selected from hydrotreating catalyst is I
ain one or more catalyzer.In a preferred embodiment.The anti-applications catalyst of described secondary hydrotreatment is selected from Hydrobon catalyst that is not fluorine-containing and/or molecular sieve.They can be commercially available commodity or adopt any 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 contain 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 being commonly used for support of the catalyst and/or matrix.Such as, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia, natural zeolite, clay, are preferably aluminum oxide.Described organic additive is selected from the organic compound containing one or more in oxygen or organic compounds containing nitrogen, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine.Such as, oxygen-containing organic compound can enumerate ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartrate, oxysuccinic acid, organic compounds containing nitrogen can enumerate quadrol, EDTA and ammonium salt thereof.
Such as, a kind of Hydrobon catalyst disclosed in 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 remainder alumina.
A kind of disclosed in CN1872960A take aluminum oxide as the hydrogenation catalyst of containing phosphor of carrier, nickel oxide 1-10 % by weight is consisted of 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, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
CN1840618A mono-kind take silica-alumina as hydrogenation catalyst and the preparation thereof of carrier, consisting of after this 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, and surplus is carrier.
In catalyzer disclosed in CN1872960A and CN1840618A, preferably also containing organic additive, wherein, described organism with the mol ratio of the hydrogenation active metals component sum of oxide basis for 0.03-2 is preferably 0.08-1.5.
These catalyzer all can be used as described Hydrobon catalyst 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 their parts as content of the present invention are quoted here.
When comprising the reactions steps of secondary hydrotreatment, any existing heat transfer technology can be adopted to make the temperature of streams when entering secondary hydrogenator being derived from a hydrogenator meet described requirement.The reactor that can be used for hydrotreatment reaction that described secondary hydrogenator can provide for arbitrary prior art, such as fixed-bed reactor.
Described hydrofining is for the purpose of further hydrogenation aromatic saturation, and Hydrobon catalyst used contains carrier and load at least one on this carrier and is selected from the nickel of group VIII, platinum and/or metallic palladium component.One or more in the optional self-alumina of described carrier, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia, natural zeolite, clay.Be benchmark in metal and with catalyzer, the content of described group VIII metal is preferably 0.1-10 % by weight, is more preferably 0.1-5 % by weight.Such as, 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 for the present invention.Here in the lump their parts as content of the present invention are quoted.
According to method provided by the invention, described stock oil can be viscosity index is 0-80, preferred viscosities index is 20-80's, boiling range is the distillate in any source of 350 DEG C-560 DEG C, is preferably the distillate (boiling range described in the present invention refer to be more than or equal to 5% to distillation temperature corresponding to the overhead product that be less than or equal to 95% with distillation yield) of 350 DEG C-530 DEG C.Under the prerequisite meeting described requirement, the source of described stock oil is not particularly limited.Such as, in paraffin production process, the low-viscosity index pressed oil of by-product can meet this requirement, can directly use as the raw material producing SBS rubber filling oil.
Compared with prior art, when adopting the method that the invention provides to produce SBS rubber filling oil, its yield improves.
Embodiment
The present invention is described further for the following examples.
Embodiment 1
Stock oil be a kind of come from intermediate base crude oil subtract the oil that two distillates obtain through furfural treatment and benzol-kentone dewaxing, its character is in the raw material 1 in table 1.
Hydrotreatment reaction is carried out in fixed-bed reactor, and reaction conditions comprises: temperature 330 DEG C, 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, Tungsten oxide 99.999 25 % by weight, and fluorine is weight 4%, and surplus is γ-Al
2o
3.
Catalyst I
bprepare according to the embodiment 6 in CN1966616A, wherein hydrogenation active metals component is molybdenum and nickel, is benchmark with oxide basis and with catalyzer, and 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 steam stripping at reduced pressure device, stripping fluid is water vapour.
Obtain product oil through stripping, product oil yield and character thereof are in table 2.
Comparative example 1
Stock oil and embodiment 1 are together.Catalyzer is catalyst I single in embodiment 1
a; Reaction conditions comprises: temperature 330 DEG C, 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 obtained through stripping and character thereof are in table 2.
Embodiment 2
Stock oil is with embodiment 1.
Catalyzer is the catalyst I of layering filling
a, catalyst I
band catalyst I
c.Wherein, catalyst I
a, catalyst I
bidentical with embodiment 1, catalyst I
cprepare according to the embodiment 15 of CN1782033A, wherein hydrogenation active metals component is molybdenum and nickel, is benchmark with oxide basis and with catalyzer, and 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%, I of consumption
cconsumption is I
a50% of consumption.
Reaction conditions comprises: temperature 330 DEG C, pressure 14MPa, cumulative volume air speed 0.8h
-1, hydrogen to oil volume ratio is 450: 1.
Stripping: stripping carries out in steam stripping at reduced pressure device, stripping fluid is water vapour.
The product oil yield obtained through steam stripping at reduced pressure and character thereof are in table 2.
Embodiment 3
Hydrofining step is increased after the stripping of embodiment 2.
Hydrofining reaction carries out in fixed-bed reactor, and reaction conditions comprises: temperature 220 DEG C, pressure 16MPa, air speed 0.8h
-1, hydrogen to oil volume ratio is 350: 1.
Hydrobon catalyst is prepared according to the example 11 in 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 are in table 2.
The standard of rubber filling oil is in table 3.
Embodiment 4
Stock oil be a kind of come from intermediate base crude oil subtract the oil that three distillates obtain through furfural treatment and benzol-kentone dewaxing, its character is in the raw material 2 in table 1.
Hydrotreatment reaction is carried out in the fixed-bed reactor of two series connection, is configured with interchanger between two reactors.Wherein, the reaction conditions of hydrotreatment reaction comprises: temperature 345 DEG C, pressure 14MPa, total air speed 0.87h
-1, hydrogen to oil volume ratio is 500: 1.The reaction conditions of secondary hydrotreatment reaction comprises: temperature 330 DEG C, pressure 14MPa, air speed 1.90h
-1, hydrogen to oil volume ratio is 500: 1, and 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
b.Wherein, 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 remainder alumina.
Stripping: stripping carries out in steam stripping at reduced pressure device, stripping fluid is water vapour.
The product oil yield obtained through steam stripping at reduced pressure and character thereof are 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 |
| Sulphur content/(mg/kg) | 3200 | 2800 |
| Nitrogen content/(mg/kg) | 324 | 393 |
| 5% recovered temperature/DEG C | 345 | 416 |
| 95% recovered temperature/DEG C | 446 | 486 |
Table 2
| Embodiment | 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 DEG C)/(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 | Color inhibition rubber filling oil | |
| Density/(kg/m 3) | Report | Report |
| Kinematic viscosity (100 DEG C)/(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 (19)
1. produce a method for SBS rubber filling oil, comprising: at hydrotreating reaction conditions, by 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, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 3-40%, wherein, described stock oil to be boiling range that viscosity index is less than 80 the be distillate of 350 DEG C-560 DEG C, 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, in described catalyst I
awith catalyst I
bbetween comprise catalyst I
c, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent for being greater than 0 to being 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 be greater than 30% to being less than or equal to 70%.
2. method according to claim 1, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%.
3. method according to claim 2, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 6-20%.
4. the method according to any one of claim 1,2 or 3, is characterized in that, described catalyst I
acontaining the carrier being 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, containing or not containing being selected from fluorine, in boron and phosphorus one or more adjuvant components and containing or not containing organic additive, take catalyzer as benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 12 ~ 35 % by weight, fluorine is selected from element, in boron and phosphorus, the content of one or more adjuvant components is 0 ~ 9 % by weight, described organic additive with the mol ratio of the hydrogenation active metals component sum of oxide basis for 0-2.
5. method according to claim 1, is characterized in that, hydrotreatment reaction conditions comprises: pressure is 10-20MPa, temperature 280-380 DEG C, and volume space velocity is 0.2-2h
-1, hydrogen to oil volume ratio is 300-1200.
6. method according to claim 5, is characterized in that, hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 300-360 DEG C, and volume space velocity is 0.4-1.5h
-1, hydrogen to oil volume ratio is 350-1000: 1.
7. method according to claim 6, is characterized in that, hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 330-360 DEG C, and volume space velocity is 0.4-1.2h
-1, hydrogen to oil volume ratio is 500-1000: 1.
8. method according to claim 1, is characterized in that, described stock oil to be viscosity index be-20 to 80 boiling range be the distillate of 350 DEG C-530 DEG C.
9. method according to claim 1, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 5-40%.
10. method according to claim 9, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 10-30%.
11. methods according to claim 1, it is characterized in that, after described hydrotreatment reaction before stripping, comprise at hydrotreating reaction conditions, oil and hydrogen secondary and the catalytic step of hydrotreating catalyst will be generated, wherein, secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 10-50 DEG C.
12. methods according to claim 11, is characterized in that, described secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 20-30 DEG C.
13. methods according to claim 11 or 12, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-20MPa, temperature 250-360 DEG C, and volume space velocity is 0.5-6h
-1, hydrogen to oil volume ratio is 300-1200: 1.
14. methods according to claim 13, is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 12-18MPa, temperature 260-350 DEG C, and volume space velocity is 1-4h
-1, hydrogen to oil volume ratio is 350-1000: 1.
15. methods according to claim 14, is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 14-18MPa, temperature 280-330 DEG C, and volume space velocity is 1.5-3.5h
-1, hydrogen to oil volume ratio is 450-800: 1.
16. methods according to claim 1, is characterized in that, comprise and carry out hydrorefined step to stripped product after described stripping.
17. methods according to claim 16, is characterized in that, described hydrofining catalyzer is take as-reduced metal as the catalyzer of hydrogenation active component, and wherein, described as-reduced metal is selected from nickel, platinum and/or palladium.
18. methods according to claim 16, is characterized in that, described hydrofining reaction condition comprises: pressure 10-20MPa, temperature 150-320 DEG C, and volume space velocity is 0.3-3h
-1, hydrogen to oil volume ratio is 100-3000: 1.
19. methods according to claim 18, is characterized in that, described hydrofining reaction condition comprises: pressure 12-18MPa, temperature 180-300 DEG C, and volume space velocity is 0.5-1.5h
-1, hydrogen to oil volume ratio is 200-1000: 1.
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