CN103554926B - A kind of low grade asphalt for high grade road and preparation method thereof - Google Patents
A kind of low grade asphalt for high grade road and preparation method thereof Download PDFInfo
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- CN103554926B CN103554926B CN201310484652.2A CN201310484652A CN103554926B CN 103554926 B CN103554926 B CN 103554926B CN 201310484652 A CN201310484652 A CN 201310484652A CN 103554926 B CN103554926 B CN 103554926B
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Abstract
The invention discloses a kind of low grade asphalt for high grade road, component containing following weight part: vacuum residuum 25 ~ 75 de-oiled asphalt, solvent treatment extract out in the hard vacuum residuum of oil and unmodified one or more 25 ~ 75, described vacuum residuum is catalytic slurry is introduced the vacuum residuum entering vacuum still at the bottom of atmospheric distillation tower and obtained by underpressure distillation improveing together with long residuum.Also disclose the preparation method of above-mentioned low grade asphalt for high grade road, this low grade asphalt for high grade road can solve the Dependence Problem to crude oil kind, catalytic slurry in prior art can also be solved and produce the problem of asphalt for high grade road ageing resistance difference, the low grade asphalt for high grade road of low value-added catalytic slurry production high added value can be utilized; In addition, this preparation method's technique is simple, and cost is low.
Description
Technical field
The invention belongs to road bitumen technical field, be specifically related to a kind of low grade asphalt for high grade road and preparation method thereof.
Background technology
In recent years along with highway in China transport and communications amount sharply increases, seriously, the damaged condition of pavement structure is increasingly sharpened for overload, heavily loaded phenomenon.Bituminous concrete high-temperature stability deficiency forms rut, is one of Major Diseases form of China Higher level asphalt highway.For addressing this problem, highway division trends towards using high-quality low grade pitch, and this comprises No. 50 bi tumenf orr oads formulated in the Ministry of Communications standard specification for construction and acceptance of highway asphalt pavement JTGF40-2004.
No. 50 hard petroleum asphalt that Chinese invention patent application prospectus CN201010511480.X relates to crude oil obtains through Atmospheric vacuum technique are heated to certain temperature, add some amount styrene-butadiene block copolymer, by colloidal mill, they are dispersed, then obtain No. 50 A level road bitumens through the stirring of certain hour at a certain temperature by processing the pitch obtained.The main weak point of this method is that manufacturer must have equipment of producing modified asphalt, and adds polymer substance and need long-time stirring just can mix." refining of petroleum and chemical industry " (the 8th phase in 2009,63 ~ 67 pages) report Kelamayi petrochemical industry branch office with Kelamayi cycloalkyl viscous crude for raw material adopts propane deasphalting explained hereafter to go out No. 50 A level road bitumens." petroleum pitch " (the 4th phase in 2005,33 ~ 37 pages) report middle extra large pitch Taizhou limited liability company and adopt atmospheric and vacuum distillation to produce No. 50 A level road bitumens with Shuizhong 36-1 petroleum." petroleum pitch " (the 1st phase in 2011,9 ~ 12 pages) report Zhenghai branch office of China Petrochemical Industry with Kuwait Crude Oil or mix refining Basra crude oil and produce No. 50 A level road bitumens by atmospheric and vacuum distillation." petroleum pitch " (the 3rd phase in 2011,57 ~ 60 pages) report CNPC Fuel Oil Co., Ltd. subordinate pitch station-service auspicious oil of South America horse and bank oil in Persian adopts distil process to produce No. 50 A level road bitumens.The weak point of solvent deasphalting process or atmospheric vacuum distillation method is adopted to be the dependency of crude oil kind larger.Minority oil is only had to plant and directly can produce No. 50 A level road bitumens by these methods.
Catalytic slurry is the byproduct of catalytic cracking unit production process.Refinery is generally taked to reduce the measure of getting rid of part slurry oil outside slurry oil recycle ratio.Externally extracting oil as cheap low-volatility fuel oil treatment, causes the great wasting of resources mostly.Therefore, rational and efficient use catalytic slurry, produces high value added product and has good application prospect.Chinese invention patent application prospectus CN201110237462.1 proposes catalytic slurry to be heated to 350 ~ 380 DEG C and enters to vacuumize and remain in the vacuum still of 40mmHg, obtains oil fuel, aromatic hydrocarbon oil and pitch in turn by continuous underpressure distillation.Do not mention the performance index after the Thin Film Oven Test TFOT of gained pitch in this specification sheets, its ageing resistance whether can touch the mark require unknown.Chinese invention patent CN1102847A proposition Fecl
3, P
2o
5pitch is produced for catalytic slurry oxidation modification is concocted with vacuum residuum or de-oiled asphalt by catalyzer again.This patent slurry oil is oxidized improving SNR be used for producing pitch again but only fundamentally can not solve the existence of light constituent in catalytic slurry and cause by being oxidized the drawback that pitch flash points is defective, wax content is high.Propose to carry out vacuum fractionation process to catalytic slurry in Chinese invention patent CN101045872A to obtain plug heavy oil slurry and concoct with de-oiled asphalt again and obtain asphalt for high grade road.Close with it Chinese invention patent CN1861759A, CN1302841A and Chinese invention patent application prospectus CN2010166362.X in addition.These are all carry out plug to catalytic slurry to remove light constituent in slurry oil, then by plug heavy oil slurry for the production of pitch.But gained pitch is easily by the impact of slurry oil character, and its ageing resistance is also poor.Chinese invention patent application prospectus CN201010139912.9 proposes one and deasphalted oil extraction process, solvent de-asphalting process, catalytic cracking process, catalytic slurry plug technique and mixing asphalt five kinds of techniques is combined, and produces asphalt for high grade road with plug catalytic slurry and de-oiled asphalt.Close with it have Chinese invention patent CN101050383A.The complete processing that these combination procesies relate to is too much, and asphalt production process is complicated.Oil is extracted in Chinese invention patent CN1493653A proposition solvent treatment out and catalytic slurry composition is active additive, produces asphalt for high grade road together with one or more the composition in crude oil, long residuum, vacuum residuum by underpressure distillation.The intensifying distillation agent of this patent is that oil and catalytic slurry composition are extracted in solvent treatment out, and the raw material that it enters vacuum distillation tower is one or more composition in crude oil, long residuum and vacuum residuum and intensifying distillation agent.The proportion of composing of the active additive that this method is used and consumption larger with the natural fluctuations being reinforced distillating material.And crude oil kind used only concentrates on Tahe Crude Oil, do not mention production No. 50 A level road bitumens yet.
Summary of the invention
The object of the present invention is to provide a kind of low grade asphalt for high grade road, this low grade asphalt for high grade road can solve the Dependence Problem to crude oil kind, catalytic slurry in prior art can also be solved and produce the problem of asphalt for high grade road ageing resistance difference, the low grade asphalt for high grade road of low value-added catalytic slurry production high added value can be utilized.
The present invention also aims to the preparation method providing above-mentioned low grade asphalt for high grade road, this preparation method's technique is simple, and cost is low.
First object of the present invention is achieved by the following technical solution: a kind of low grade asphalt for high grade road, the component containing following weight part:
Vacuum residuum 25 ~ 75
De-oiled asphalt, solvent treatment extract out oil and unmodified hard vacuum residuum in one or more 25 ~ 75
Described vacuum residuum is introduced by catalytic slurry at the bottom of atmospheric distillation tower to enter vacuum still obtains improvement vacuum residuum by underpressure distillation together with long residuum.
In catalytic slurry of the present invention, aromaticity content is greater than 50%, and wherein catalytic slurry accounts for 1 ~ 7% of long residuum gross weight, and such catalytic slurry is high due to aromaticity content, contributes to the ductility improving vacuum residuum.
One or both products through air distillation gained in long residuum of the present invention to be crude oil attribute be intermediate base and cycloalkyl.As a rule, crude oil is divided into paraffinic base, intermediate base and cycloalkyl three kinds, and the residual oil penetration degree of paraffinic crude is bigger than normal, and wax content is high, is not suitable for for producing pitch, and what produce that pitch selects is all the residual oil of the crude oil of intermediate base and cycloalkyl.
The inlet temperature of stabilizer of catalytic slurry of the present invention is preferably 330 ~ 350 DEG C, and the working pressure of vacuum still is preferably 95 ~ 100kpa, and column bottom temperature is preferably 360 ~ 380 DEG C.
The technique of underpressure distillation of the present invention adopts reduced pressure distillation process known by the engineering technical personnel of this area and equipment.
It is the PDA asphalt of solvent through propane deasphalting technique gained that de-oiled asphalt of the present invention is preferably with propane, and its penetration number is 70 ~ 13010
-1mm.Such de-oiled asphalt, penetration degree is not very large, ductility better performances.Be used for blend asphalt, both can improve the ductility performance of blend asphalt product, penetration degree can not be caused again obviously to become large, exceed the indication range of No. 50 pitches.
It is that in solvent refining processes, gained extracts one or more the composition in oil out with furfural that the oily frivolous oil preferably subtracting four lines and solvent deasphalting is extracted in solvent treatment of the present invention out.The aromaticity content that oil is extracted in these solvent treatments out is high, obviously can improve the stretch indexe of blend asphalt.The main index restricting No. 50 A level asphalt productions is exactly stretch indexe.
The hard vacuum residuum of unmodified of the present invention be preferably oil attribute be one or more composition in intermediate base and cycloalkyl through atmospheric and vacuum distillation gained, its penetration number is 30 ~ 6010
-1between mm.Because the softening temperature of the vacuum residuum after part improvement is on the low side, wax content is higher.And the softening temperature of the vacuum residuum that these are not improved is high, wax content is on the low side, the softening temperature of product can be improved by blending, reduce wax content.
Second object of the present invention is achieved by the following technical solution: the preparation method of above-mentioned low grade asphalt for high grade road, containing following steps: catalytic slurry to be introduced the vacuum residuum entering vacuum distillation tower at the bottom of atmospheric tower and obtained by underpressure distillation improveing together with long residuum, one or more described vacuum residuum and de-oiled asphalt, solvent treatment being extracted out in the hard vacuum residuum of oily, unmodified prepare low grade asphalt for high grade road by blending method.
Blending method of the present invention is adopt conventional mixing asphalt means, and blending temperature is preferably 120 ~ 150 DEG C, and mixing time is preferably 4 ~ 16 hours.
Low grade asphalt for high grade road of the present invention is preferably No. 50 A level road bitumens.
Tool of the present invention has the following advantages: the present invention carries out underpressure distillation by adding catalytic slurry to long residuum, improve the performance of gained vacuum residuum, the vacuum residuum after improvement is by concocting with other component No. 50 A level bi tumenf orr oads can produced and meet " the Ministry of Communications's standard specification for construction and acceptance of highway asphalt pavement " (JTGF40-2004) index.Present invention improves prior art and produce No. 50 A level road bitumens to the dependency of crude oil kind, improve the shortcoming of the road bitumen ageing resistance difference that prior art catalytic slurry is produced, improve the utility value of catalytic slurry.
Embodiment
The reagent adopted in following embodiment, if no special instructions, is commercially available.
Embodiment 1
3.84%(is referred to catalytic slurry accounts for the mass ratio of long residuum, lower with) catalytic slurry join and carried in the long residuum adding crude oil (3:2) mixing gained by Indonesia Europe crude oil-Libya Xi Er, enter vacuum still together and obtain vacuum residuum.
Wherein in catalytic slurry, aromaticity content is greater than 50%, and the aromaticity content of every batch of catalytic slurry has fluctuation, can select the catalytic slurry of Maoming branch office, and its aromaticity content is general all more than 50%, lower same.
The inlet temperature of stabilizer of catalytic slurry is 330 ~ 350 DEG C, and the working pressure of vacuum still is 95 ~ 100kpa, and column bottom temperature is 360 ~ 380 DEG C.Vacuum residuum needed for every tank blend asphalt generally wants that Continuous maching 24 hours ability meets supply and in the so long course of processing, these indexs can fluctuate within the scope of this.Preferably inlet temperature of stabilizer is about 340 DEG C, and working pressure is about 98kpa, and column bottom temperature is about 370 DEG C, lower same.
This vacuum residuum and the vacuum residuum by Iranian heavy crude-mixing gained of Iranian Suo Lushi crude oil (1:1), the vacuum residuum by Sandi Light Crude through the de-oiled asphalt of propane deasphalting technique gained by 49.4:30.2:20.4(mass ratio) concoct and produce road bitumen, the results are shown in Table 1.This pitch meets the standard of No. 50 A level road bitumens.
Wherein de-oiled asphalt take propane as the PDA asphalt of solvent through propane deasphalting technique gained, and its penetration number is 70 ~ 13010
-1mm, preferably 8010
-1about mm.
Be wherein the hard vacuum residuum of unmodified by the vacuum residuum of Iranian heavy crude-mixing gained of Iranian Suo Lushi crude oil (1:1), its penetration number is 30 ~ 6010
-1between mm, preferably 4010
-1about mm.
Adopt conventional mixing asphalt means when blending is produced, blending temperature is 120 ~ 150 DEG C, and 140 DEG C of mixing times are 4 ~ 16 hours, general 4 hours, within 4 hours, analyzes, just stops blending if qualified, if defective, continues blending.
Embodiment 2
The catalytic slurry of 4.15% joins to be carried in the long residuum adding crude oil (2:3) mixing gained by Indonesia Europe crude oil-Libya Xi Er, enters vacuum still together and obtains vacuum residuum.
Wherein in catalytic slurry, aromaticity content is greater than 50%.
The inlet temperature of stabilizer of catalytic slurry is 330 ~ 350 DEG C, and the working pressure of vacuum still is 95 ~ 100kpa, and column bottom temperature is 360 ~ 380 DEG C.
This vacuum residuum and the vacuum residuum by Iranian heavy crude-mixing gained of Iranian Suo Lushi crude oil (1:1), the vacuum residuum by Sandi Light Crude to be concocted in the ratio of 40:38:22 through the de-oiled asphalt of propane deasphalting technique gained and are produced road bitumen, the results are shown in Table 1.This pitch meets the standard of No. 50 A level road bitumens.
Be wherein the hard vacuum residuum of unmodified by the vacuum residuum of Iranian heavy crude-mixing gained of Iranian Suo Lushi crude oil (1:1), its penetration number is 30 ~ 6010
-1between mm.
Adopt conventional mixing asphalt means when blending is produced, blending temperature is 120 ~ 150 DEG C, and mixing time is 4 ~ 16 hours.
Embodiment 3
The catalytic slurry of 1.0% joins by the long residuum of Canadian AWB crude oil-mixing gained of Iranian Bai Ruogen crude oil (1:1), enters vacuum still together and obtains vacuum residuum.
Wherein in catalytic slurry, aromaticity content is greater than 50%.
The inlet temperature of stabilizer of catalytic slurry is 330 ~ 350 DEG C, and the working pressure of vacuum still is 95 ~ 100kpa, and column bottom temperature is 360 ~ 380 DEG C.
This vacuum residuum and the vacuum residuum by matter crude oil gained in Saudi Arabia, the vacuum residuum by Oman's crude oil to be concocted in the ratio of 74.6:12.8:12.6 through the de-oiled asphalt of propane deasphalting technique gained and are produced road bitumen, the results are shown in Table 1.This pitch meets the standard of No. 50 A level road bitumens.
Be wherein the hard vacuum residuum of unmodified by the vacuum residuum of matter crude oil gained in Saudi Arabia, its penetration number is 30 ~ 6010
-1between mm.
Adopt conventional mixing asphalt means when blending is produced, blending temperature is 120 ~ 150 DEG C, and mixing time is 4 ~ 16 hours.
Embodiment 4
The catalytic slurry of 1.9% joins by the long residuum of Brazilian Alba carat crude oil-mixing gained of Canadian AWB crude oil (5:1), enters vacuum still together and obtains vacuum residuum.
Wherein in catalytic slurry, aromaticity content is greater than 50%.
The inlet temperature of stabilizer of catalytic slurry is 330 ~ 350 DEG C, and the working pressure of vacuum still is 95 ~ 100kpa, and column bottom temperature is 360 ~ 380 DEG C.
This vacuum residuum and the vacuum residuum by Iranian heavy crude-mixing gained of Iranian Suo Lushi crude oil (1:1), the vacuum residuum by Sandi Light Crude to be concocted in the ratio of 55:33.5:11.5 through the de-oiled asphalt of propane deasphalting technique gained and are produced road bitumen, the results are shown in Table 2.This pitch meets the standard of No. 50 A level road bitumens.
Be wherein the hard vacuum residuum of unmodified by the vacuum residuum of Iranian heavy crude-mixing gained of Iranian Suo Lushi crude oil (1:1), its penetration number is 30 ~ 6010
-1between mm.
Adopt conventional mixing asphalt means when blending is produced, blending temperature is 120 ~ 150 DEG C, and mixing time is 4 ~ 16 hours.
Embodiment 5
The catalytic slurry of 6.5% joins to be carried in the long residuum adding crude oil (3:1) mixing gained by Canadian cold air lake crude oil-Libya Xi Er, enters vacuum still together and obtains vacuum residuum.
Wherein in catalytic slurry, aromaticity content is greater than 50%.
The inlet temperature of stabilizer of catalytic slurry is 330 ~ 350 DEG C, and the working pressure of vacuum still is 95 ~ 100kpa, and column bottom temperature is 360 ~ 380 DEG C.
This vacuum residuum and the vacuum residuum by Kuwait Crude Oil gained, the vacuum residuum by Sandi Light Crude to be concocted in the ratio of 31:44.5:24.5 through the de-oiled asphalt of propane deasphalting technique gained and are produced road bitumen, the results are shown in Table 2.This pitch meets the standard of No. 50 A level road bitumens.
Be wherein the hard vacuum residuum of unmodified by the vacuum residuum of Kuwait Crude Oil gained, its penetration number is 30 ~ 6010
-1between mm.
Adopt conventional mixing asphalt means when blending is produced, blending temperature is 120 ~ 150 DEG C, and mixing time is 4 ~ 16 hours.
Embodiment 6
The catalytic slurry of 2.5% joins by the long residuum of matter crude oil in Saudi Arabia-Colombia's Castilla crude oil (7:3) mixing gained, enters vacuum still together and obtains vacuum residuum.
Wherein in catalytic slurry, aromaticity content is greater than 50%.
The inlet temperature of stabilizer of catalytic slurry is 330 ~ 350 DEG C, and the working pressure of vacuum still is 95 ~ 100kpa, and column bottom temperature is 360 ~ 380 DEG C.
This vacuum residuum and the vacuum residuum by Iranian heavy crude-Colombia's Castilla crude oil (7:3) mixing gained, the vacuum residuum by Oman's crude oil to be concocted in the ratio of 25.2:65.9:7.5:1.4 through the de-oiled asphalt of propane deasphalting technique gained, furfural extract oil and are produced road bitumen, the results are shown in Table 2.This pitch meets the standard of No. 50 A level road bitumens.
Be wherein the hard vacuum residuum of unmodified by the vacuum residuum of Iranian heavy crude-Colombia's Castilla crude oil (7:3) mixing gained, its penetration number is 30 ~ 6010
-1between mm.
Adopt conventional mixing asphalt means when blending is produced, blending temperature is 120 ~ 150 DEG C, and mixing time is 4 ~ 16 hours.
The character-1 of table 1 embodiment 1-3 blend asphalt
The character-2 of table 2 embodiment 4-6 blend asphalt
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (7)
1. a low grade asphalt for high grade road, is characterized in that the component containing following weight part:
Vacuum residuum 25 ~ 75
De-oiled asphalt, solvent treatment extract out oil and unmodified hard vacuum residuum in one or more 25 ~ 75
Described vacuum residuum is introduced by catalytic slurry at the bottom of atmospheric distillation tower to enter vacuum still obtains improvement vacuum residuum by underpressure distillation together with long residuum;
The inlet temperature of stabilizer of described catalytic slurry is 330 ~ 350 DEG C, and the working pressure of vacuum still is 95 ~ 100kpa, and column bottom temperature is 360 ~ 380 DEG C;
Described de-oiled asphalt take propane as the PDA asphalt of solvent through propane deasphalting technique gained, and its penetration number is 70 ~ 13010
-1mm;
Described low grade asphalt for high grade road is No. 50 A level road bitumens.
2. low grade asphalt for high grade road according to claim 1, it is characterized in that: in described catalytic slurry, aromaticity content is greater than 50%, catalytic slurry accounts for 1 ~ 7% of long residuum gross weight.
3. low grade asphalt for high grade road according to claim 1, is characterized in that: one or both products through air distillation gained in described long residuum to be crude oil attribute be intermediate base and cycloalkyl.
4. low grade asphalt for high grade road according to claim 1, is characterized in that: it is that in solvent refining processes, gained extracts one or more the composition in oil out with furfural that the oily frivolous oil for subtracting four lines and solvent deasphalting is extracted in described solvent treatment out.
5. low grade asphalt for high grade road according to claim 1, it is characterized in that: one or more the composition in the hard vacuum residuum of described unmodified to be oil attribute be intermediate base and cycloalkyl is through atmospheric and vacuum distillation gained, and its penetration number is 30 ~ 6010
-1between mm.
6. the preparation method of the low grade asphalt for high grade road described in any one of claim 1-5, it is characterized in that containing following steps: catalytic slurry is introduced the vacuum residuum entering vacuum distillation tower at the bottom of atmospheric tower and obtained by underpressure distillation improveing together with long residuum, one or more described vacuum residuum and de-oiled asphalt, solvent treatment being extracted out in the hard vacuum residuum of oily, unmodified prepare low grade asphalt for high grade road by blending method.
7. the preparation method of low grade asphalt for high grade road according to claim 6, is characterized in that: described blending method is adopt conventional mixing asphalt means, and blending temperature is 120 ~ 150 DEG C, and mixing time is 4 ~ 16 hours.
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