CN107541248A - A kind of environmentally-frierubber rubber filling oil and preparation method thereof - Google Patents
A kind of environmentally-frierubber rubber filling oil and preparation method thereof Download PDFInfo
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- CN107541248A CN107541248A CN201710762711.6A CN201710762711A CN107541248A CN 107541248 A CN107541248 A CN 107541248A CN 201710762711 A CN201710762711 A CN 201710762711A CN 107541248 A CN107541248 A CN 107541248A
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Abstract
The present invention discloses a kind of environmentally-frierubber rubber filling oil and preparation method thereof, the rubber filling oil is to be mixed to carry out catalytic desulfurhydrogenation reaction and catalyzed alkene saturated reaction with hydrogen by furfural extract oil, desulfurization process oil is obtained, desulfurization process oil is separated off H through hydrogen air lift2S, then mixed with hydrogen and carry out catalytic hydrogenation reaction, gas-liquid separation is carried out after the completion of reaction and is obtained.Arene content in environmentally-frierubber rubber filling oil prepared by the present invention is less than 2%, it is environmentally friendly, nontoxic to have the characteristics that, and using furfural extract oil as raw material in preparation method, realize the high value added utilization to byproduct in production of lube base oils, and preparation method is simple and easy, there is good application prospect.
Description
Technical field
The invention belongs to oil and petroleum distillate manufacture field, it is related to rubber filling oil, more particularly to a kind of environment-friendly type rubber
Glue filling oil and preparation method thereof.
Technical background
Rubber filling oil is a kind of auxiliary agent during rubber production, is in rubber industry as the Plasticising system of rubber
The third-largest material of rubber and carbon black is only second to, the characteristics such as the elasticity of rubber, pliability, workability, easily mixing property can be improved.
Rubber filling oil can be divided into aromatic naphtha, naphthenic oil, paraffine base crude oil according to its hydro carbons composition, and aromatic naphtha contains higher polarity
Compound, it has excellent blending with rubber, has good processability, tensile strength with the rubber size of its filling, pulls apart
Elongation and lancinating, but product has contaminative, elastic relatively low, poor performance at low temperatures；The saturated hydrocarbon content of paraffin oil is high, with fourth
Benzene, butyronitrile, the blending of butadiene rubber are poor, and emulsibility, cryogenic property are poor；Naphthene base crude oil has preferably blending property with rubber,
Emulsibility and compatibility are preferable, with the colour stable of the oil-extended rubber of its preparation, excellent spring, are widely used in light-colour rubber system
In product.
Generally production domestic at present and rubber oil used are in the majority with aromatic hydrocarbon rubber filling oil, but its contain it is higher thick
PAH, easily cause environmental pollution.Early in 2005, European Union existed《On limiting the instruction of polycyclic aromatic hydrocarbon》(2005/69/EC
Instruction) clear stipulaties just are made to condensed-nuclei aromatics content in rubber filling oil：Benzene content and 8 kinds of condensed-nuclei aromatics contents do not meet mark
Accurate rubber filling oil can not launch EU market, it is impossible to be used in European Union's tire and associated components production.The country meets Europe at present
Rubber filling oil as defined in alliance 2005/69/EC is completely dependent on import, expensive.Therefore, environmentally-frierubber rubber filling oil is China
The Development Trend of rubber oil and requirement at this stage.
CN102585901A discloses a kind of preparation method of low arene content environmental-friendly rubber filling oil, and this method is included such as
Lower step：(1) cycloalkyl distillate is subjected to solvent refining, obtains refined liquid, refined oil is obtained after recycling design；(2) by essence
Liquefaction hydrogenated processing, hydro dewaxing and hydrofining, obtain being hydrogenated with full distillate oil；Hydrogenation full distillate oil is distilled, obtained
To rubber oil with low aromatic hydrocarbon content, this method is and tight to process engineering requirements using the distillate of high-quality naphthene base crude as raw material
It is severe.CN102604674A discloses a kind of environmentally-frierubber rubber filling oil and preparation method thereof：(1) to subtracting three, line distillate hydrogenation is handled
Obtain desulfurization process oil；(2) desulfurization process oil is once extracted, raffinate is obtained extracting column overhead, after recycling design
Obtain primary purification oil；(3) primary purification oil is subjected to secondary extracting, obtains extract solution in bottom of towe, two are obtained after recycling design
Secondary tapped oil is the environmental-friendly rubber filling oil.CN201310543756.6 discloses a kind of utilize and refines oil plant by-products preparation
The method of rubber oil, the invention is using the accessory substance decompression residuum of oil plant, catalytic cracked oil pulp as raw material, through deasphalted oil, extraction
Take, adsorb, eluting four sections of processes, output high-quality aromatic hydrocarbon rubber filling oil and environment-friendly rubber oil, while obtaining pitch original
Material and catalytically cracked material, realize oil plant decompression residuum and the outer processing and comprehensive utilization for getting rid of catalytic cracked oil pulp.But subtract
Pressure residual oil is the caused byproduct in oil plant production process, if be simply just used, not only added value is low, and
And cause petroleum resources waste.It is increasingly in short supply with petroleum resources, integrated treatment to residual oil and it is badly in need of solution using turning into
Key issue certainly.
The content of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides a kind of environmentally-frierubber rubber filling oil and preparation method thereof, this
Environmental-friendly rubber filling oil is prepared by raw material of furfural extract oil in invention, and its arene content is less than 2%, and acid number content is low, right
Metal erosion is small, and has the characteristics that environmentally friendly, nontoxic.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of environmentally-frierubber rubber filling oil, it is to mix progress catalytic hydrogenation with hydrogen by furfural extract oil to take off
Reaction of Salmon-Saxl and the reaction of catalytic hydrogenation Porous deproteinized bone, obtain desulfurization process oil, desulfurization process oil are separated off into H through hydrogen air lift2S,
Mixed again with hydrogen and carry out catalytic hydrogenation reaction, carried out gas-liquid separation after the completion of reaction, obtain environmentally-frierubber rubber filling oil.
The furfural extract oil is the byproduct in production of lube base oils, belongs to typical high aromatic oil, tool
There is the features such as range of viscosities is big, arene content is high.As one embodiment of the present of invention, described furfural extract oil is to prepare profit
Byproduct during lubricating oil after solvent refining, boiling range are 260~550 DEG C, and 20 DEG C of density is 0.950~0.995kg/m3,
40 DEG C of kinematic viscosity are 4000mm~6000mm2/s。
The CA values of heretofore described furfural extract oil are 40%~55%, CN values 10~20%, CP values are 35~
45%.CA values refer to that the aromatic ring structure carbon content in the various molecular structure of compounds that oil product contains accounts for the matter of total carbon content
Percentage is measured, CN values refer to that the saturated rings structure carbon content in the various molecular structure of compounds that oil product contains accounts for total carbon content
Mass percent, CP values refer to that the straight-chain hydrocarbons structure carbon content in the various molecular structure of compounds that oil product contains accounts for total carbon
The mass percent of content.The measure of the CA values, CN values and CP values is with reference to ASTM D2140.
As one embodiment of the present of invention, in the preparation method, catalytic desulfurhydrogenation reaction is anti-in the first fixed bed
Answer in device and carry out.While catalytic desulfurhydrogenation reacts progress, the part unsaturated olefin in tapped oil can be also hydrogenated with
Reaction.
The condition of catalytic desulfurhydrogenation reaction is 350~410 DEG C, 8~14Mpa of hydrogen dividing potential drop of reaction temperature, hydrogen and furfural
The volume ratio of tapped oil is 400~800, and the liquid hourly space velocity (LHSV) of the fixed bed reactors is 0.8~3.0h-1。
The catalyst of catalytic desulfurhydrogenation reaction loads NiO, MoO using aluminum oxide as carrier3And alkali metal oxide,
The alkali metal is sodium or potassium.In the catalyst reacted as one embodiment of the present of invention, catalytic desulfurhydrogenation, NiO matter
Measure percentage composition 5%~20%, MoO3Weight/mass percentage composition 5%~15%, the weight/mass percentage composition of alkali metal oxide
0.25%~2%, surplus is aluminum oxide.
Preferably, in the catalyst of catalytic desulfurhydrogenation reaction, NiO weight/mass percentage composition 8%~15%, MoO3Matter
Percentage composition 8%~12% is measured, the weight/mass percentage composition 0.4%~1% of alkali metal oxide, surplus is aluminum oxide.
The hydrogen air lift is carried out in stripper, and operating condition is 80~150 DEG C of temperature, 0.6~1.2MPa of pressure.
Desulfurization process oil sulfur content after hydrogen stripping process is 0~50ppm.The sulfur content is with reference to GB/
T11060.8-2012 is tested.
As one embodiment of the present of invention, the catalytic hydrogenation Porous deproteinized bone reaction is entered in the second fixed bed reactors
OK.The condition of catalytic hydrogenation Porous deproteinized bone reaction is 260~320 DEG C, 14~18Mpa of hydrogen dividing potential drop of reaction temperature, hydrogen oil volume
Than 600~1000,0.5~2.0h of liquid hourly space velocity (LHSV)-1。
For the catalyst of the catalytic hydrogenation Porous deproteinized bone reaction using aluminum oxide as carrier, the active component of load is NiO and Pt.
As one embodiment of the present of invention, in the catalyst of catalytic hydrogenation Porous deproteinized bone reaction, Pt weight/mass percentage composition 0.1%~
1%, NiO weight/mass percentage composition 4%~15%, surplus are aluminum oxide.
Preferably, in the catalyst of catalytic hydrogenation Porous deproteinized bone reaction, Pt weight/mass percentage composition 0.3%~0.8%, NiO
Weight/mass percentage composition 6%~12%, surplus is aluminum oxide.
A kind of environmentally-frierubber rubber filling oil, is prepared by the above method.The environmentally-frierubber rubber filling oil of the present invention is 40
Kinematic viscosity at DEG C is 50~100mm2/ s, 20 DEG C of density is 0.89~0.91g/cm3, 20 DEG C of index of refraction for 1.48~
1.50.The acid number of the environmentally-frierubber rubber filling oil is 0.001-0.02mgKOH/g, and method of testing is with reference to GB/T264-1983.
Further, the CA values of the environmentally-frierubber rubber filling oil are that 0.1~2%, CN values are that 45~60%, CP values are
45-55%.The measure of the CA values, CN values and CP values is with reference to ASTM D2140.
The present invention further provides a kind of rubber composition, including the environmentally-frierubber rubber filling oil.
The invention has the advantages that：
For the environmentally-frierubber rubber filling oil of the present invention using the furfural extract oil rich in aromatic hydrocarbons as raw material, product appearance is transparent clear
Bright, colorless and odorless, cryogenic property are excellent, can be filled with a large proportion in rubber, and the preparation flow of rubber filling oil is simple, cost
It is cheap.
Embodiment
The present invention can be by examples below further instruction, but embodiment is not the limit to the scope of the present invention
System.Subtract four line furfural extract oil of the raw material furfural extract oil used in following examples from sinopec Maoming branch company, its
Nature parameters and method of testing are shown in Table 1.
Table 1
Embodiment 1
The preparation method of environmentally-frierubber rubber filling oil is as follows：
Raw material furfural extract oil and hydrogen are mixed into the first fixed bed reactors, carry out catalytic desulfurhydrogenation reaction,
Used catalyst is γ-Al2O3The 0.4%K of load2O-8%NiO-8%MoO3, hydrodesulfurization reaction condition is reaction temperature
350 DEG C, hydrogen dividing potential drop 8Mpa, H2It is 400 with furfural extract oil volume ratio, liquid hourly space velocity (LHSV) 2.5h-1；The desulfurization of first reactor outflow
Processing oil is under conditions of 80 DEG C of temperature, pressure 0.6MPa, in the H of hydrogen stripped tower elimination reaction generation2S, make desulfurization process
Sulfur content in oil reaches 29ppm, then is mixed into the second fixed bed reactors with hydrogen, in the presence of hydrogenation dearomatization catalyst
Hydrogenation dearomatization hydrocarbon reaction is carried out, the second fixed bed reactors used catalyst is γ-Al2O3The 0.4%Pt-10%NiO of load,
Reaction condition is 260 DEG C of reaction temperature, hydrogen dividing potential drop 16Mpa, H2It is 600 with desulfurization process oil volume ratio, liquid hourly space velocity (LHSV) 2.0h-1,
Reaction product enters gas-liquid separator, isolated environmentally-frierubber rubber filling oil.
Embodiment 2
The preparation method of environmentally-frierubber rubber filling oil is as follows：
Raw material furfural extract oil and hydrogen are mixed into the first fixed bed reactors, carry out catalytic desulfurhydrogenation reaction,
Used catalyst is γ-Al2O3The 0.75%K of load2O-12%NiO-12%MoO3, hydrodesulfurization condition is reaction temperature
380 DEG C of degree, hydrogen dividing potential drop 11Mpa, H2It is 800 with furfural extract oil volume ratio, liquid hourly space velocity (LHSV) 1.5h-1；First reactor outflow
Desulfurization process oil is under conditions of 120 DEG C of temperature, pressure 0.9MPa, in the H of hydrogen stripped tower elimination reaction generation2S, make desulfurization
Sulfur content in processing oil reaches 13ppm, then is mixed into the second fixed bed reactors with hydrogen, is deposited in hydrogenation dearomatization catalyst
In lower progress hydrogenation dearomatization hydrocarbon reaction, the second fixed bed reactors used catalyst is γ-Al2O3The 0.6%Pt-6% of load
NiO, reaction condition are 280 DEG C of reaction temperature, hydrogen dividing potential drop 14Mpa, H2It is 800 with desulfurization process oil volume ratio, liquid hourly space velocity (LHSV)
1.2h-1, reaction product enters gas-liquid separator, isolated environmentally-frierubber rubber filling oil.
Embodiment 3
The preparation method of environmentally-frierubber rubber filling oil is as follows：
Raw material furfural extract oil and hydrogen are mixed into the first fixed bed reactors, carry out catalytic desulfurhydrogenation reaction,
Used catalyst is γ-Al2O3The 1%K of load2O-15%NiO-10%MoO3, hydrodesulfurization condition is reaction temperature
410 DEG C, hydrogen dividing potential drop 13Mpa, H2It is 600 with furfural extract oil volume ratio, liquid hourly space velocity (LHSV) 1.0h-1；First reactor outflow takes off
Sulphuring treatment oil is under conditions of 150 DEG C of temperature, pressure 1.2MPa, in the H of hydrogen stripped tower elimination reaction generation2S, make at desulfurization
Sulfur content in reason oil reaches 8ppm, then is mixed into the second fixed bed reactors with hydrogen, exists in hydrogenation dearomatization catalyst
Lower progress hydrogenation dearomatization hydrocarbon reaction, the second fixed bed reactors used catalyst is γ-Al2O3The 0.8%Pt-12% of load
NiO, reaction condition are 320 DEG C of reaction temperature, hydrogen dividing potential drop 18Mpa, H2It is 1000 with desulfurization process oil volume ratio, liquid hourly space velocity (LHSV)
0.5h-1, reaction product enters gas-liquid separator, isolated environmentally-frierubber rubber filling oil.
Testing example
The embodiment 1-3 environmentally-frierubber rubber filling oils prepared are detected, method of testing and data are shown in Table 2.
Table 2
Contain from the data in table 2, it can be seen that the arene content in environmentally-frierubber rubber filling oil prepared by the present invention is less than 2%, acid number
Measure it is low, it is small to metal erosion, have the characteristics that environmentally friendly, nontoxic, and using furfural extract oil as raw material in preparation method, realize to profit
The high value added utilization of byproduct in lubricant base oil production process, and preparation method is simple and easy, before there is application well
Scape.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope.It will be understood by those of skill in the art that some deductions can be carried out to technical scheme or are waited
With replacing, without departing from the spirit and scope of technical solution of the present invention.
Claims (9)
1. a kind of preparation method of environmentally-frierubber rubber filling oil, mix with hydrogen that to carry out catalytic desulfurhydrogenation anti-by furfural extract oil
It should be reacted with catalytic hydrogenation Porous deproteinized bone, obtain desulfurization process oil, desulfurization process oil is separated off H through hydrogen air lift2S, then with
Hydrogen mixing carries out catalytic hydrogenation reaction, carries out gas-liquid separation after the completion of reaction, obtains environmentally-frierubber rubber filling oil.
2. preparation method as claimed in claim 1, it is characterised in that the catalytic desulfurhydrogenation reaction is anti-in the first fixed bed
Answer in device and carry out, the condition of catalytic desulfurhydrogenation reaction is 350~410 DEG C, 8~14Mpa of hydrogen dividing potential drop of reaction temperature, hydrogen and chaff
The volume ratio of aldehyde tapped oil is 400~800, and liquid hourly space velocity (LHSV) is 0.8~3.0h-1。
3. preparation method as claimed in claim 2, it is characterised in that catalytic desulfurhydrogenation reaction catalyst be load NiO,
MoO3And the aluminum oxide of alkali metal oxide.
4. the preparation method of environmentally-frierubber rubber filling oil as claimed in claim 1, it is characterised in that the hydrogen air lift is stripping
Carried out in tower, operating condition is 80~150 DEG C of temperature, 0.6~1.2MPa of pressure.
5. the preparation method of environmentally-frierubber rubber filling oil as claimed in claim 1, it is characterised in that the catalytic hydrogenation Porous deproteinized bone
Reaction is carried out in the second fixed bed reactors, and the condition of the catalytic hydrogenation Porous deproteinized bone reaction is reaction temperature 260~320
DEG C, 14~18Mpa of hydrogen dividing potential drop, hydrogen to oil volume ratio 600~1000,0.5~2.0h of liquid hourly space velocity (LHSV)-1。
6. the preparation method of environmentally-frierubber rubber filling oil as claimed in claim 5, it is characterised in that the catalytic hydrogenation Porous deproteinized bone
For the catalyst of reaction using aluminum oxide as carrier, the active component of load is NiO and Pt.
7. a kind of environmentally-frierubber rubber filling oil, it is prepared by any one of claim 1-3 methods described.
8. environmentally-frierubber rubber filling oil as claimed in claim 7, it is characterised in that the CA values of the environmentally-frierubber rubber filling oil
It is that 45~60%, CP values are 45-55% for 0.1~2%, CN values.
9. a kind of rubber composition, including the environmentally-frierubber rubber filling oil described in claim 7 or 8.
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| CN1775919A (en) * | 2005-12-02 | 2006-05-24 | 中国石油化工集团公司 | Method for producing plastic plasticizer |
| CN101475836A (en) * | 2009-01-19 | 2009-07-08 | 中国科学院山西煤炭化学研究所 | Hydrogenation adsorption desulphurization and catalytic hydro-dearomatization cascade reaction process |
| CN102311784A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for producing environment-friendly aromatic oil |
| CN103013558A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Production method of SBS rubber filling oil |
| CN105586082A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Hydro-denitrification method for heavy oil |
-
2017
- 2017-08-30 CN CN201710762711.6A patent/CN107541248A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775919A (en) * | 2005-12-02 | 2006-05-24 | 中国石油化工集团公司 | Method for producing plastic plasticizer |
| CN101475836A (en) * | 2009-01-19 | 2009-07-08 | 中国科学院山西煤炭化学研究所 | Hydrogenation adsorption desulphurization and catalytic hydro-dearomatization cascade reaction process |
| CN102311784A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for producing environment-friendly aromatic oil |
| CN103013558A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Production method of SBS rubber filling oil |
| CN105586082A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Hydro-denitrification method for heavy oil |
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Application publication date: 20180105 |