CN102191082A - Distillate Aromatic Extract and preparation method thereof - Google Patents
Distillate Aromatic Extract and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing a Distillate Aromatic Extract (DAE), comprising the following steps: raw oil is contacted with a primary extraction solvent in a first extraction tower, lube base oil extract oil or secondary extracting oil from a second extraction tower and an anti-solvent are added to primary extracting oil from the first extraction tower, then the mixture is sent to the second extraction tower as raw material of the secondary extraction and contacted with a secondary extraction solvent in the second extraction tower, secondary refined oil is separated from second raffinate from the second extraction tower. The primary extraction solvent comprises a main solvent, the secondary extraction solvent comprises a main solvent and the anti-solvent, wherein, the arene dissolvability of the main solvent is higher than the alkane dissolvability of that. The DAE prepared by the method disclosed in the invention has a low level of benzo [a] pyrene, and a low level of PAHs total content of benz [a] anthracene, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [j] fluoranthene, benzo [a] pyrene, benzo [e] pyrene and dibenz [a, h] anthracene, meeting the requirement of the European Union directive 2005/69/EC that the polycyclicaromatics content is less than 3wt%.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic rubber oil.
Background technology
Characteristics such as elasticity, snappiness, workability and easy mixing property for improving rubber need add rubber oil usually in rubber.Rubber oil is pressed the different of mineral oil molecular structure and composition, is divided into paraffinic hydrocarbons type, naphthenic type and aromatic hydrocarbon type rubber wet goods; Can be divided into rubber filling oil, rubber processing oil, Rubber Softener etc. by the difference of using object.Aromatic hydrocarbon rubber oil (Distillate Aromatic Extract, be abbreviated as DAE) have aromatic carbon content height, density is big, viscosity is high, with characteristics such as the good and processing characteristics of polar rubber affinity is superior, be the good tenderizer of tire and the used rubber of footwear product.In the production process of styrene-butadiene rubber(SBR), aromatic hydrocarbon rubber oil generally accounts for about 30% of total rubber quality.
Aromatic hydrocarbon rubber oil generally is to be formed through processing and blending by solvent-refined extraction oil or oil slurry from catalytically cracked heavy oil in the lubricant base production technique.Aromatic hydrocarbon rubber oil (DAE) is one of main raw material of producing rubber and tire process, contains the polycyclic aromatic hydrocarbons (polycyclicaromatics is abbreviated as PCA, adopts the method IP346 of Institute of Petroleum(IP) to measure) of 10%-30% usually.Wherein, polycyclic aromatic hydrocarbons (PCA) is meant three rings and the above polycyclic aromatic hydrocarbons of three rings.At present, along with the increasingly stringent of environmental regulation, PCA has become universally acknowledged organic pollutant.As far back as 1994, the classification of European Union chemical with indicate mechanism the PCA mass content be classified as toxic substance greater than 3% DAE.The signature instruction 2005/69/EC of European Union in 2005, this instruction has clearly limited the content of eight kinds of carcinogenic condensed-nuclei aromaticss in the tyre rubber oil: wherein benzo (a) pyrene content is not more than 1mg/kg, benzo (a) anthracene,
, (a, h) eight kinds of special condensed-nuclei aromaticss of anthracene (PAHs) total content is not more than 10mg/kg for benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (j) fluoranthene, benzo (a) pyrene, benzo (e) pyrene and dibenzo.This instruction regulation was from January 1st, 2010, the rubber oil that does not meet european union directive 2005/69/EC requirement can not be thrown in European Union market, can not be used to produce tire and parts thereof, the tire that enters the European Union zone must use the rubber oil that meets above-mentioned specification of quality to produce.Therefore, need the new production technique of exploitation, with production satisfy European Union to benzo (a) pyrene content and benzo (a) anthracene,
, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (j) fluoranthene, benzo (a) pyrene, benzo (e) pyrene and dibenzo (a, h) the rubber oil that requires of the total content of eight kinds of condensed-nuclei aromaticss of anthracene (PAHs).
It is solvent that US6802960 discloses with furfural, phenol or N-Methyl pyrrolidone, adopt two sections extractings, first section extractive raffinate carries out the extracting second time with solvent again, and second section extractive Extract reclaims the extraction oil that obtains behind the solvent as aromatic rubber oil.The aromatic rubber oil PCA mass content that this method is produced is less than 3%, but the total content of its eight kinds of condensed-nuclei aromaticss (PAHs) does not still reach the requirement of 2005/69/EC.Chinese patent 200810224694.1 discloses a kind of aromatic rubber oil and production method thereof, and this method is a raw material to subtract three-way distillate, carries out extracting with furfural and obtain raffinate and Extract in extraction tower, and Extract reclaims solvent and obtains extracting out oil.Extract oil out and carry out the secondary extracting with furfural again, obtain secondary raffinate and Extract, the secondary raffinate reclaims solvent and obtains secondary refining oil, after the clay treatment as rubber oil.This method needs the quadruplet solvent recovering system, and reclaims twice Extract and need big energy, the treated oil that obtains also need to carry out clay-filtered could be as aromatic rubber oil.Chinese patent 200910088932.5 discloses a kind of environment-friendly rubber oil and preparation method thereof, and this method is a raw material to subtract three-way distillate, carries out extracting with furfural and obtain raffinate and Extract in extraction tower, and raffinate reclaims solvent and obtains treated oil.Treated oil carries out the secondary extracting with furfural again, obtains secondary raffinate and Extract, and the secondary Extract reclaims solvent and obtains secondary extraction oil, as rubber oil.This method also needs to reclaim the secondary Extract, and recovery system needs quadruplet, is equivalent to two cover solvent extraction devices.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of aromatic rubber oil, and this method adopts the double tower extracting to combine with anti-solvent extraction technology, and the aromatic rubber oil that European Union environmental protection requires is satisfied in preparation in a cover solvent extraction device.
A kind of preparation method of aromatic rubber oil, comprise, stock oil is contacted in first extraction tower with first extraction solvent, in the Extract of first extraction tower, after adding lubricant base extraction oil and/or second extraction tower extraction oil and injecting anti-solvent, deliver to second extraction tower as the second extraction tower raw material, in second extraction tower, contact, from the raffinate of second extraction tower, isolate the second extraction tower treated oil with second extraction solvent; Described first extraction solvent contains main solvent, and described second extraction solvent contains main solvent and anti-solvent, described main solvent to the solvability of aromatic hydrocarbons greater than solvability to alkane.
In the method for the present invention, obtain the first extraction tower raffinate, the second extraction tower raffinate and the second extraction tower Extract respectively after the extracting of stock oil process double tower, can obtain the first extraction tower treated oil, the second extraction tower treated oil and second extraction tower and extract three products of oil out after solvent recuperation, wherein the second extraction tower treated oil is as aromatic rubber oil.Adopt the prepared aromatic rubber oil of method of the present invention, benzo (a) pyrene content is low, benzo (a) anthracene,
, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (j) fluoranthene, benzo (a) pyrene, benzo (e) pyrene and dibenzo (a, h) total content of eight kinds of special condensed-nuclei aromaticss of anthracene (PAHs) is low, satisfy the 2005/69/EC command request, polycyclic aromatic hydrocarbon content is less than 3wt%.
Description of drawings
Fig. 1 is the schematic flow sheet of the inventive method.
Embodiment
A kind of preparation method of aromatic rubber oil, comprise, stock oil is contacted in first extraction tower with first extraction solvent, in the Extract of first extraction tower, after adding lubricant base extraction oil and/or second extraction tower extraction oil and injecting anti-solvent, deliver to second extraction tower as the second extraction tower raw material, in second extraction tower, contact, from the second extraction tower raffinate, isolate the second extraction tower treated oil with second extraction solvent; Described first extraction solvent contains main solvent, and described second extraction solvent contains main solvent and anti-solvent, described main solvent to the solvability of aromatic hydrocarbons greater than solvability to alkane.
Described main solvent is meant greater than the solvability to alkane that to the solvability of aromatic hydrocarbons the solubleness of the aromatic hydrocarbons in the stock oil in main solvent is greater than the solubleness of the alkane in the stock oil in main solvent.
In the Extract of first extraction tower, when adding lubricant base extraction oil or adding lubricant base extraction oil and second extraction tower extraction oil, total mass with the first extraction tower raw material is a benchmark, the add-on that lubricant base is extracted oil out is preferably more than 0 to 100%, and more preferably 20% to 50%.
In the Extract of first extraction tower, adding second extraction tower extracts oil out or adds second extraction tower and extract oil and lubricant base out and extract out when oily, total mass with the first extraction tower raw material is a benchmark, the add-on that second extraction tower is extracted oil out is preferably more than 0 to 100%, and more preferably 20% to 50%.
Described lubricant base is extracted oil out and is meant the extraction oil that lubricating oil solvent technology obtains, and is preferably first solvent dewaxing, and oil is extracted in the solvent treatment of back solvent treatment flow process out.
Described main solvent can be the solvent of this area routine, for example, can be selected from furfural, phenol, dimethyl sulfoxide (DMSO), tetramethylene sulfone and the N-Methyl pyrrolidone one or more.
Described anti-solvent is meant stock oil insoluble, or to alkane in the stock oil and the little solvent of the three following aromatic hydrocarbons solubleness of ring.
Among the present invention, described anti-solvent is preferably one or more in the Fatty Alcohol(C12-C14 and C12-C18) that water and carbon number are 1-8; One or more in water, methyl alcohol, ethanol, Virahol, propyl carbinol, n-hexyl alcohol, isooctyl alcohol and the ethylene glycol more preferably.
Under the preferred situation, the main solvent in first extraction solvent is identical with main solvent in second extraction solvent, and the anti-solvent phase that injects in the anti-solvent in second extraction solvent and the first extraction tower Extract is same.
First extraction solvent among the present invention also can contain anti-solvent.Under the preferred situation, the main solvent in second extraction solvent is identical with main solvent in first extraction solvent, and the anti-solvent phase that injects in anti-solvent in second extraction solvent and the anti-solvent in first extraction solvent and the first extraction tower Extract is same.In described first extraction solvent, be benchmark with the total mass of first extraction solvent, the content of anti-solvent is greater than 0 to 5.0%, is preferably greater than 0 to 3.5%; The content of main solvent is 95.0% to less than 100%, and preferred 96.5% to less than 100%.
Among the present invention, preferably in the first extraction tower Extract outlet line, add lubricant base and extract oil and/or second extraction tower extraction oil out and inject anti-solvent, after mixing tank mixes, deliver to second extraction tower again as the second extraction tower raw material.The effect of mixing tank is the mixed effect that strengthens Extract and anti-solvent, and it belongs to prior art, can adopt the liquid mixer of this area routine.
Among the present invention, preferably in the first extraction tower Extract outlet line, add lubricant base and extract oil and/or second extraction tower extraction oil out and inject anti-solvent, to the second extraction tower feeding temperature, deliver to second extraction tower then as the second extraction tower raw material through the interchanger heat exchange.
Under the further preferred situation, in the first extraction tower Extract outlet line, adding lubricant base extracts oil and/or second extraction tower extraction oil out and injects anti-solvent, after mixing tank mixes, again through the interchanger heat exchange to the second extraction tower feeding temperature, deliver to second extraction tower then as the second extraction tower raw material.
In second extraction solvent of the present invention, be benchmark with the total mass of second extraction solvent, the content of anti-solvent is 0.5%-12.0%, is preferably 1.5%-8.0%, and the content of main solvent is 88.0%-99.5%, is preferably 92.0-98.5%.
Among the present invention, the mass ratio of described first extraction solvent and stock oil can be 0.5-5.0: 1, be preferably 1-4.0: and 1,1-3.0 more preferably: 1; The mass ratio of described second extraction solvent and stock oil can be 0.1-4.0: 1, be preferably 0.2-3.0: and 1,0.3-2.0 more preferably: 1.Wherein, the quality of described stock oil is meant the quality of the stock oil that enters first extraction tower.
Among the present invention, the quality of the anti-solvent that injects in the first extraction tower Extract accounts for the 0.5%-15.0% of the first extraction solvent total mass, is preferably 2.0-12.0%.
Among the present invention, under the preferred situation, the density of main solvent is greater than the density of stock oil, the described first extraction tower raffinate is the top effluent of first extraction tower, the described first extraction tower Extract is the bottom effluent of first extraction tower, the described second extraction tower raffinate is the top effluent of second extraction tower, and the described second extraction tower Extract is the bottom effluent of second extraction tower.
Among the present invention, described stock oil be crude oil the second line of distillation distillate, subtract three-way distillate, subtract four line distillates, decompression wide fraction oil, solvent-deasphalted oils, or the pressed oil of above-mentioned raw materials.Described crude oil can be paraffinic base, intermediate base or cycloalkyl, preferred intermediate base and naphthenic base crude.Described solvent-deasphalted oils is that the vacuum residuum with crude oil is raw material, is that solvent produces with propane.Described pressed oil is that to adopt the mixture of methylethylketone and toluene be solvent, adopts filter at low temperature to remove the second line of distillation distillate of crude oil, subtracts three-way distillate, subtracts four line distillates, the method preparation of the high melting point component in the decompression wide fraction oil, solvent-deasphalted oils.
Among the present invention, the described first extraction tower column bottom temperature can be 50-115 ℃, is preferably 55-105 ℃, more preferably 60-100 ℃; The described first extraction tower tower top temperature can be 65-140 ℃, is preferably 70-135 ℃, more preferably 75-130 ℃.
Among the present invention, the described second extraction tower column bottom temperature can be 40-95 ℃, is preferably 45-90 ℃, more preferably 50-85 ℃; The described second extraction tower tower top temperature can be 50-110 ℃, is preferably 55-105 ℃, more preferably 60-100 ℃.
Preferably, described method also comprises, isolates treated oil from the raffinate of described first extraction tower, and this treated oil can be used as lubricant base raw materials for production or other device raw material of downstream.
Preferably, described method also comprises, isolates from the Extract of described second extraction tower and extracts oil out, and this extraction oil can be used as common aromatic rubber oil or mixing asphalt agent.
According to the general understanding of this area, during by solvent extraction separating liquid mixture, liquid mixture to be separated the solvent-rich phase of a small amount of material to be separated occurred containing with after solvent fully contacts, and is called Extract, removes to obtain extracting out oil after desolvating; And the separating mixture phase that a small amount of solvent occurred containing, be called raffinate, raffinated oil except that after desolvating, claim raffinate oil or treated oil again.
The method of solvent is well known in the art in described separation Extract and the raffinate, for example respectively logistics is sent into solvent recovery tower except that desolvating.Being set at of the tower top temperature of solvent recovery tower and column bottom temperature is conventionally known to one of skill in the art, does not repeat them here.Among the present invention, the solvent after the recovery can contain a spot of stock oil component.
Among the present invention, after both main solvent and anti-solvent can being pre-mixed, mixture is imported in the extraction tower; Also can be before the colvent inlet of extraction tower, on-line mixing main solvent and anti-solvent are imported in the extraction tower then, for example from the main solvent of pipeline 10 and anti-solvent from pipeline 11, after mixing before the extraction tower colvent inlet, enter in the extraction tower.
According to the present invention, the extraction tower that uses can be packed extraction column, rotating disc contactor or rotating disk-filler combination tower, the theory of extraction tower extraction hop count is preferably three sections or greater than three sections, the flow velocity of each logistics is not particularly limited, according to the first extraction tower combined feed total feed flow and solvent and stock oil ratio, those skilled in the art can determine the solvent feed flow of solvent, stock oil and second extraction tower of first extraction tower according to prior art.
Below in conjunction with description of drawings a kind of preferred implementation of the present invention.
Stock oil enters first extraction tower, 1 bottom through pipeline 3, first extraction solvent enters first extraction tower, 1 top through pipeline 4, the stock oil and first extraction solvent be counter current contact in first extraction tower 1, cat head flows out the first extraction tower raffinate through pipeline 5, obtain first extraction tower raffinate oil (not marking solvent recuperation among the figure) through solvent recuperation, raw material as lubricant base raw materials for production or other downstream processing unit (plant), the first extraction tower Extract is flowed out through pipeline 6 in the bottom of first extraction tower 1, in pipeline 6, inject anti-solvent by pipeline 7, part is extracted oil out through second extraction tower of solvent recuperation and is recycled in the first extraction tower Extract pipeline 6 through pipeline 16 and pipeline 17, also can in the first extraction tower Extract, sneak into the extraction oil that the lubricant base production equipment is produced simultaneously through pipeline 15, above logistics is after mixing tank 8 mixes, again through the interchanger heat exchange to the second extraction tower feeding temperature, enter second extraction tower, 2 bottoms through pipeline 9, as second extraction tower, 2 raw materials; Second extraction solvent enters second extraction tower, 2 tops by pipeline 10, with second extraction tower, 2 raw materials counter current contact in second extraction tower 2, cat head flows out the second extraction tower raffinate through pipeline 12, obtain second extraction tower raffinate oil (not marking solvent recuperation among the figure) through solvent recuperation, as aromatic rubber oil, the second extraction tower Extract is flowed out through pipeline 13 in second extraction tower, 2 bottoms, obtain extracting out oil through solvent recuperation 14, part is extracted oil out and is recycled in the first extraction tower Extract pipeline 6 through pipeline 17, part is extracted oil out through pipeline 18 carrying devices, as common aromatic rubber oil or mixing asphalt agent etc.
Below in conjunction with embodiment the present invention is described further.
With the second line of distillation distillate is raw material, and its character sees Table 1, is extracting aromatic hydrocarbons in three sections the packed extraction column (Sopwith staff cun Φ 25 * 2500 * 2.5) at theoretical extraction section number, and the combined feed total feed flow of the solvent of first extraction tower and stock oil is 1200 Grams Per Hours.
The extracting condition is: first extraction tower, 1 tower top temperature is 100 ℃, first extraction tower, 1 column bottom temperature is 75 ℃, first extraction solvent that uses in first extraction tower is furfural, the mass ratio of first extraction solvent and stock oil is 2.5: 1, inject the water that accounts for the first extraction solvent total mass 6% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 80 ℃, second extraction tower, 2 column bottom temperatures are 60 ℃, and second extraction solvent is the mixture of furfural and water, wherein, moisture quality percentage is that 4.0%, the second extraction solvent and stock oil mass ratio are 1.4: 1 in second extraction solvent.The second extraction tower Extract obtains extracting oil out after solvent recuperation 14 reclaims, and the extraction that will be equivalent to extraction tower 1 raw materials quality 50% is oil circulation in the first extraction tower Extract.
Comparative Examples 1
With embodiment 1 identical second line of distillation distillate is raw material, and its character sees Table 1, prepares aromatic rubber oil on identical device.
The extracting condition is: first extraction tower, 1 tower top temperature is 100 ℃, first extraction tower, 1 column bottom temperature is 75 ℃, first extraction solvent that uses in first extraction tower is furfural, the mass ratio of first extraction solvent and stock oil is 2.5: 1, inject the water that accounts for the first extraction solvent total mass 6% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 80 ℃, second extraction tower, 2 column bottom temperatures are 60 ℃, and second extraction solvent is the mixture of furfural and water, wherein, moisture quality percentage is that 4.0%, the second extraction solvent and stock oil mass ratio are 1.0: 1 in second extraction solvent.
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is, is raw material to subtract three-way distillate, and its character sees Table 1, the first extraction solvent and uses phenol and water, and moisture quality percentage is 3.5% in first extraction solvent.The extracting condition is: first extraction tower, 1 tower top temperature is 90 ℃, first extraction tower, 1 column bottom temperature is 60 ℃, the mass ratio of first extraction solvent and stock oil is 1.6: 1, the Extract pipeline injects the water that accounts for the first extraction solvent total mass 3.0% to first extraction tower bottom, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 70 ℃, second extraction tower, 2 column bottom temperatures are 55 ℃, and second extraction solvent is the mixture of phenol and water, wherein, moisture quality percentage is that 5.5%, the second extraction solvent and stock oil mass ratio are 1.8: 1 in second extraction solvent.In the first extraction tower Extract, add density (15 ℃) 998.1kg/m
3, viscosity (100 ℃) 27.62mm
2/ s, 3 ℃ of pour points subtract three-way lubex, adding solvent treatment, to extract oil mass out be 100% of extraction tower 1 raw materials quality.
Comparative Examples 2
Preparing aromatic rubber oil according to the method identical with embodiment 2, is raw material to subtract three-way distillate, and its character sees Table 1, the first extraction solvent and uses phenol and water, and moisture quality percentage is 3.5% in first extraction solvent.The extracting condition is: first extraction tower, 1 tower top temperature is 90 ℃, first extraction tower, 1 column bottom temperature is 60 ℃, the mass ratio of first extraction solvent and stock oil is 1.6: 1, the Extract pipeline injects the water that accounts for the first extraction solvent total mass 3.0% to first extraction tower bottom, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 70 ℃, second extraction tower, 2 column bottom temperatures are 55 ℃, and second extraction solvent is the mixture of phenol and water, wherein, moisture quality percentage is that 5.5%, the second extraction solvent and stock oil mass ratio are 0.5: 1 in second extraction solvent.Difference is, does not add in the first extraction tower Extract and extracts oil out.
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is, is raw material to subtract four line distillates, and its character sees Table the mixture that 1, the first extraction solvent uses furfural and dimethyl sulfoxide (DMSO), and wherein furfural accounts for 50% of mixed solvent total mass.The extracting condition is: the mass ratio of first extraction solvent and stock oil is 4.0: 1, first extraction tower, 1 tower top temperature is 135 ℃, first extraction tower, 1 column bottom temperature is 105 ℃, inject the water that accounts for the first extraction solvent total mass 2.0% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 100 ℃, second extraction tower, 2 column bottom temperatures are 85 ℃, second extraction solvent and stock oil mass ratio are 2.5: 1, second extraction solvent uses the mixture of furfural, dimethyl sulfoxide (DMSO) and water, wherein furfural accounts for 20% of mixed solvent total mass, and water accounts for 1% of mixed solvent total mass.The second extraction tower Extract obtains extracting oil out after solvent recuperation 14 reclaims, and the extraction oil 16 that will be equivalent to extraction tower 1 raw materials quality 40% is recycled in the first extraction tower Extract.
Comparative Examples 3
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is, is raw material to subtract four line distillates, and its character sees Table the mixture that 1, the first extraction solvent uses furfural and dimethyl sulfoxide (DMSO), and wherein furfural accounts for 50% of mixed solvent total mass.The extracting condition is: the mass ratio of first extraction solvent and stock oil is 4.0: 1, first extraction tower, 1 tower top temperature is 135 ℃, first extraction tower, 1 column bottom temperature is 105 ℃, inject the water that accounts for the first extraction solvent total mass 2.0% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 100 ℃, second extraction tower, 2 column bottom temperatures are 85 ℃, second extraction solvent and stock oil mass ratio are 2.0: 1, second extraction solvent uses the mixture of furfural, dimethyl sulfoxide (DMSO) and water, wherein furfural accounts for 20% of mixed solvent total mass, and water accounts for 1% of mixed solvent total mass.
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is, to subtract four line cut pressed oils is raw material, its character sees Table 1, the main solvent of first extraction solvent and second extraction solvent is N-Methyl pyrrolidone, first extraction solvent that uses in first extraction tower is moisture 2.5% N-Methyl pyrrolidone, and second extraction solvent that uses in second extraction tower is moisture 4.0% N-Methyl pyrrolidone.The extracting condition is: first extraction tower, 1 tower top temperature is 70 ℃, first extraction tower, 1 column bottom temperature is 55 ℃, the mass ratio of first extraction solvent and stock oil is 1.0: 1, inject the water that accounts for the first extraction solvent total mass 3.0% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 58 ℃, and second extraction tower, 2 column bottom temperatures are 45 ℃, and second extraction solvent and stock oil mass ratio are 0.3: 1.The second extraction tower Extract obtains extracting oil out after solvent recuperation 14 reclaims, and the extraction that will be equivalent to extraction tower 1 raw materials quality 20% is oil circulation in the first extraction tower Extract.
Comparative Examples 4
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is, to subtract four line cut pressed oils is raw material, its character sees Table 1, the main solvent of first extraction solvent and second extraction solvent is N-Methyl pyrrolidone, first extraction solvent that uses in first extraction tower is moisture 2.5% N-Methyl pyrrolidone, and second extraction solvent that uses in second extraction tower is moisture 4.0% N-Methyl pyrrolidone.The extracting condition is: first extraction tower, 1 tower top temperature is 70 ℃, first extraction tower, 1 column bottom temperature is 55 ℃, the mass ratio of first extraction solvent and stock oil is 1.0: 1, inject the water that accounts for the first extraction solvent total mass 3.0% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 58 ℃, and second extraction tower, 2 column bottom temperatures are 45 ℃, and second extraction solvent and stock oil mass ratio are 0.3: 1.
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is, is raw material with 400 ℃ of-540 ℃ of vacuum distillate pressed oils, and it is furfural that its character sees Table 1, the first extraction solvent, and second extraction solvent is for containing 8.0% alcoholic acid furfural.The extracting condition is: first extraction tower, 1 tower top temperature is 120 ℃, first extraction tower, 1 column bottom temperature is 90 ℃, the mass ratio of first extraction solvent and stock oil is 2.1: 1, inject the ethanol that accounts for the first extraction solvent total mass 10% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 90 ℃, and second extraction tower, 2 column bottom temperatures are 60 ℃, and second extraction solvent and stock oil mass ratio are 1.7: 1.The second extraction tower Extract obtains extracting oil out after solvent recuperation 14 reclaims, and the extraction that will be equivalent to extraction tower 1 raw materials quality 20% is oil circulation in the first extraction tower Extract.In the first extraction tower Extract, add density (15 ℃) 999.0kg/m
3, viscosity (100 ℃) 39.87mm
2/ s, 9 ℃ of pour points subtract four line lubexs, adding solvent treatment, to extract oil mass out be 20% of extraction tower 1 raw materials quality.
Comparative Examples 5
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is, is raw material with 400 ℃ of-540 ℃ of vacuum distillate pressed oils, and it is furfural that its character sees Table 1, the first extraction solvent, and second extraction solvent is for containing 8.0% alcoholic acid furfural.The extracting condition is: first extraction tower, 1 tower top temperature is 120 ℃, first extraction tower, 1 column bottom temperature is 90 ℃, the mass ratio of first extraction solvent and stock oil is 2.1: 1, inject the ethanol that accounts for the first extraction solvent total mass 10% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 90 ℃, and second extraction tower, 2 column bottom temperatures are 60 ℃, and second extraction solvent and stock oil mass ratio are 1.1: 1.
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is that with frivolous asphalt oil is raw material, its character sees Table 1, first extraction solvent uses tetramethylene sulfone, and second extraction solvent is the mixture of tetramethylene sulfone and ethylene glycol, and wherein ethylene glycol accounts for 6% of solvent total mass.The extracting condition is: first extraction tower, 1 tower top temperature is 130 ℃, first extraction tower, 1 column bottom temperature is 90 ℃, the mass ratio of first extraction solvent and stock oil is 2.5: 1, inject the ethylene glycol that accounts for the first extraction solvent total mass 12% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 90 ℃, and second extraction tower, 2 column bottom temperatures are 65 ℃, and second extraction solvent and stock oil mass ratio are 1.7: 1.The second extraction tower Extract obtains extracting oil out after solvent recuperation 14 reclaims, and the extraction that will be equivalent to extraction tower 1 raw materials quality 30% is oil circulation in the first extraction tower Extract.
Comparative Examples 6
Prepare aromatic rubber oil according to the method identical with embodiment 1, difference is that with frivolous asphalt oil is raw material, its character sees Table 1, first extraction solvent uses tetramethylene sulfone, and second extraction solvent is the mixture of tetramethylene sulfone and ethylene glycol, and wherein ethylene glycol accounts for 6% of solvent total mass.The extracting condition is: first extraction tower, 1 tower top temperature is 130 ℃, first extraction tower, 1 column bottom temperature is 90 ℃, the mass ratio of first extraction solvent and stock oil is 2.5: 1, inject the ethylene glycol that accounts for the first extraction solvent total mass 12% to the first extraction tower bottom line, after mixing tank 8 mixes, enter the second extraction tower bottom and second extraction solvent counter current contact in second extraction tower; Second extraction tower, 2 tower top temperatures are 90 ℃, and second extraction tower, 2 column bottom temperatures are 65 ℃, and second extraction solvent and stock oil mass ratio are 1.5: 1.
Table 1
Measured the aromatic rubber oil properties of embodiment 1-6 and Comparative Examples 1-6 according to correlation analysis method, analytical procedure and the results are shown in Table 2.
Table 2
Table 2 (continuing)
Aromatic rubber oil nature by embodiment 1,2,3,4,5 and 6 is found out, its aromatic carbon C
AThe quality percentage composition is all greater than 20%, and PCA quality percentage composition is all less than 3%, benzo (a) pyrene mass content all less than 1,000,000/, special eight kinds of PAHs mass content are all less than 10/1000000ths.The above results shows, the aromatic rubber oil aromatic carbon content height that embodiment 1,2,3,4,5 and 6 is prepared, polycyclic aromatic hydrocarbons (PCA) content is low, and benzo (a) pyrene content and eight kinds of condensed-nuclei aromatics PAHs content all meet the requirement of european union directive 2005/69/EC to environment-friendly aromatic rubber oil.
Adopt the oil circulation embodiment of self-produced extraction 1,3,4 and 6, its aromatic rubber oil yield is all than extracting not round-robin height of oil out, and the aromaticity content of aromatic rubber oil also is higher than and extracts not round-robin of oil out.Employing adds the embodiment 2 that extracts oil out, and its aromatic rubber oil yield is not extracted 40.2 percentage points of innages out than not adding.Employing adds extracts oil and the oil circulation embodiment 5 of self-produced extraction out, and its aromatic rubber oil yield is not extracted 10.3 percentage points of innages out than not adding, and the aromatic carbon of aromatic rubber oil is high 0.8 percentage point.
Claims (29)
1. the preparation method of an aromatic rubber oil, comprise, stock oil is contacted in first extraction tower with first extraction solvent, in the Extract of first extraction tower, after adding lubricant base extraction oil and/or second extraction tower extraction oil and injecting anti-solvent, deliver to second extraction tower as the second extraction tower raw material, in second extraction tower, contact, from the raffinate of second extraction tower, isolate the second extraction tower treated oil with second extraction solvent; Described first extraction solvent contains main solvent, and described second extraction solvent contains main solvent and anti-solvent, described main solvent to the solvability of aromatic hydrocarbons greater than solvability to alkane.
2. method according to claim 1, it is characterized in that, in the Extract of first extraction tower, when adding lubricant base extraction oil or adding lubricant base extraction oil and second extraction tower extraction oil, total mass with the first extraction tower raw material is a benchmark, and the add-on that lubricant base is extracted oil out is greater than 0 to 100%.
3. method according to claim 2, it is characterized in that, in the Extract of first extraction tower, when adding lubricant base extraction oil or adding lubricant base extraction oil and second extraction tower extraction oil, total mass with the first extraction tower raw material is a benchmark, and the add-on that lubricant base is extracted oil out is 20% to 50%.
4. method according to claim 1, it is characterized in that, in the Extract of first extraction tower, adding second extraction tower extracts oil out or adds second extraction tower and extract oil and lubricant base out and extract out when oily, total mass with the first extraction tower raw material is a benchmark, and the add-on that second extraction tower is extracted oil out is greater than 0 to 100%.
5. method according to claim 4, it is characterized in that, in the Extract of first extraction tower, adding second extraction tower extracts oil out or adds second extraction tower and extract oil and lubricant base out and extract out when oily, total mass with the first extraction tower raw material is a benchmark, and the add-on that second extraction tower is extracted oil out is 20% to 50%.
6. method according to claim 1 is characterized in that, the main solvent in first extraction solvent is identical with main solvent in second extraction solvent, the anti-solvent phase that injects in the anti-solvent in second extraction solvent and the first extraction tower Extract with.
7. method according to claim 1 is characterized in that, first extraction solvent contains main solvent and anti-solvent, is benchmark with the total mass of first extraction solvent, and the content of anti-solvent is greater than 0 to 5.0%, and the content of main solvent is 95.0% to less than 100%.
8. method according to claim 7 is characterized in that, is benchmark with the total mass of first extraction solvent, and the content of anti-solvent is greater than 0 to 3.5%, and the content of main solvent is 96.5% to less than 100%.
9. method according to claim 7, it is characterized in that, main solvent in second extraction solvent is identical with main solvent in first extraction solvent, the anti-solvent phase that injects in anti-solvent in second extraction solvent and the anti-solvent in first extraction solvent and the first extraction tower Extract with.
10. according to arbitrary described method in the claim 1,6,7,8,9, it is characterized in that, in the first extraction tower Extract outlet line, adding lubricant base extracts oil and/or second extraction tower extraction oil out and injects anti-solvent, to the second extraction tower feeding temperature, deliver to second extraction tower then through the interchanger heat exchange as the second extraction tower raw material.
11. method according to claim 10, it is characterized in that, in the first extraction tower Extract outlet line, adding lubricant base extracts oil and/or second extraction tower extraction oil out and injects anti-solvent, after mixing tank mixes, again through the interchanger heat exchange to the second extraction tower feeding temperature, deliver to second extraction tower then as the second extraction tower raw material.
12., it is characterized in that described main solvent is selected from one or more in furfural, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), phenol, the tetramethylene sulfone according to arbitrary described method among the claim 1-9.
13., it is characterized in that described anti-solvent is selected from one or more in the Fatty Alcohol(C12-C14 and C12-C18) that water and carbon number are 1-8 according to arbitrary described method among the claim 1-9.
14. method according to claim 13 is characterized in that, described anti-solvent is selected from one or more in water, methyl alcohol, ethanol, Virahol, propyl carbinol, n-hexyl alcohol, isooctyl alcohol and the ethylene glycol.
15. method according to claim 1 is characterized in that, is benchmark with the total mass of first extraction solvent, the quality of the anti-solvent that injects in the first extraction tower Extract is 0.5%-15.0%.
16. method according to claim 15 is characterized in that, the quality of the anti-solvent that injects in the first extraction tower Extract is 2.0%-12.0%.
17. method according to claim 1 is characterized in that, is benchmark with the total mass of second extraction solvent, the content of anti-solvent is 0.5%-12.0%, and the content of main solvent is 88.0%-99.5%.
18. method according to claim 17 is characterized in that, is benchmark with the total mass of second extraction solvent, the content of anti-solvent is 1.5%-8.0%, and the content of main solvent is 92.0%-98.5%.
19., it is characterized in that the density of main solvent is greater than the density of stock oil according to arbitrary described method among the claim 1-9, the first extraction tower Extract is the bottom effluent of first extraction tower, the second extraction tower raffinate is the top effluent of second extraction tower.
20. method according to claim 1 is characterized in that, the mass ratio of first extraction solvent and stock oil is 0.5-5.0: the mass ratio of 1, the second extraction solvent and stock oil is 0.1-4.0: 1; Wherein, the quality of stock oil is the quality that enters the stock oil of first extraction tower.
21. method according to claim 20 is characterized in that, the mass ratio of first extraction solvent and stock oil is 1.0-4.0: the mass ratio of 1, the second extraction solvent and stock oil is 0.2-3.0: 1.
22. method according to claim 1 is characterized in that, at the bottom of the tower of first extraction tower and tower top temperature be respectively 50-115 ℃ and 65-140 ℃.
23. method according to claim 22 is characterized in that, at the bottom of the tower of first extraction tower and tower top temperature be respectively 55-105 ℃ and 70-135 ℃.
24. method according to claim 1 is characterized in that, at the bottom of the tower of second extraction tower and tower top temperature be respectively 40-95 ℃ and 50-110 ℃.
25. method according to claim 24 is characterized in that, at the bottom of the tower of second extraction tower and tower top temperature be respectively 45-90 ℃ and 55-105 ℃.
26. method according to claim 1 is characterized in that, isolates treated oil from the raffinate of first extraction tower.
27. method according to claim 1 is characterized in that, isolates from the Extract of second extraction tower and extracts oil out.
28. method according to claim 1 is characterized in that, described stock oil be crude oil the second line of distillation distillate, subtract three-way distillate, subtract four line distillates, in decompression wide fraction oil, solvent-deasphalted oils and their pressed oil one or more.
29. method according to claim 1 is characterized in that, it is first solvent dewaxing that described lubricant base is extracted oil out, and oil is extracted in the solvent treatment of back solvent treatment flow process out.
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| CN103589453A (en) * | 2012-08-14 | 2014-02-19 | 中国石油化工股份有限公司 | Preparation method of aromatic rubber oil |
| CN104513672A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气集团公司 | Solvent refining equipment |
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| CN103382399A (en) * | 2012-05-04 | 2013-11-06 | 中国石油天然气股份有限公司 | Production method of high-performance environment-friendly rubber oil |
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