CN1339557A - Process for preparing modified asphalt with improved storage stability - Google Patents
Process for preparing modified asphalt with improved storage stability Download PDFInfo
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- CN1339557A CN1339557A CN 00123513 CN00123513A CN1339557A CN 1339557 A CN1339557 A CN 1339557A CN 00123513 CN00123513 CN 00123513 CN 00123513 A CN00123513 A CN 00123513A CN 1339557 A CN1339557 A CN 1339557A
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Abstract
The preparation process of modified asphalt with improved stroage stability includes the contact of polymer 2.0-20.0 wt% and compatilizer 0.1-20.0 wt% at 10-250 deg.c for 0.1-72 hr, mixing of the treated polymer and heated asphalt in 50-97.7 wt% material for 0.1-6 hr to obtain asphalt mother liquor, adding coupling agent 0.1-10.0 wt% and polar compound 0.1-10.0 wt% to the asphalt mother liquor at 100-250 deg.c and reaction for 5-300 min. The modified asphalt produced through the method of the present invention has excellent stability and may be used in spreading high grade road and air port runway.
Description
The invention belongs to a kind of bituminous material preparation of compositions method, more particularly, is to belong to a kind of preparation method who improves the polymer modified asphalt of stability in storage.
Bituminous material is very fast as the pavement material development of road and building trade, but the performance of road bitumen and compound thereof is subjected to the influence of many factors, limits best performance of its performance such as visco-elasticity, plasticity-, adhesivity etc.In numerous influence factors, the influence factor maximum of climate.On motorway, the rut that summer high temperature season, driving caused is the principal element that causes the road surface infringement.Simultaneously, the winter temperature rapid drawdown and the bituminous pavement temperature draw seam that causes that heats up repeatedly are the horizontal rimose major causes in road surface.In the rainy season in south, the infringement of rainwater also will make the interface of pitch and compound have an effect, and the bituminous adhesion property is reduced, and pitch and building stones are peeled off easily.Therefore, be necessary the bituminous rheological property is improved.Adding polymkeric substance in pitch is the effective ways that improve asphalt performance.Polymkeric substance added bituminous viscosity is increased, improve bituminous high temperature resistance characteristic, reduce the bituminous temperature sensitivity, low-temperature performance also can improve simultaneously.
The Asphaltenes and Asphalts that writes at T.F.Yen etc., among the I Developments inPetroleum Science olefin polymer modifying asphalt is commented, the addition of polymkeric substance is 6 heavy %, various polymer modified asphalts stable as shown in table 1.
Table 1
Polymer type | Do not have | ??APP | ???LDPE | ???EPDM | ???SBS | |
Penetration degree (25 ℃, 100g, 5s), dmm | ??133 | ???145 | ????41 | ????50 | ????72 | |
Softening temperature (ring and ball method), ℃ | ??44 | ????47 | ????98 | ????66 | ????98 | |
Segregation experiment (163 ℃, 48 hours) | The upper strata softening temperature, ℃ | ??- | ????55 | ????>100 | ????87 | ?>100 |
Lower floor's softening temperature, ℃ | ??- | ????45 | ????52 | ????52 | ????61 | |
Softening temperature is poor, ℃ | ??- | ????10 | ????>50 | ????35 | ??>40 |
As can be seen from Table 1, join polymer AP P (Atactic Polypropelene), LDPE (new LDPE (film grade)), EPDM (ethene-propene-diene terpolymer thing), SBS (styrene-butadiene-styrene triblock copolymer) in the pitch respectively, most polymers all is separated with pitch, will directly influence the use properties of bitumen/polymer composition like this.
EP639630A1 discloses a kind of method for preparing stable asphalt-polymer composition, this method filters out the asphalt stock that the meets definite composition raw material as modifying asphalt earlier, next uses triblock polymer SBS as polymer modifiers, in inert environments, use vinyl aromatic (co) hydrocarbon compound (as vinylbenzene) to add in the asphalt-polymer composition and react, prepare the good sample of stability as auxiliary agent.This method has certain restriction to the raw material sources of modifying asphalt, and styrene compound can not help the dispersion of SBS in pitch as reaction promoter.Owing to need nitrogen as reaction environment, also will increase reaction cost.
USP5,336,705, USP5,627,225 and USP5,348,994 use oleums or other sulphonating agents with asphalt stock and polymer modifiers sulfonation earlier, make the both introduce acidic-group, neutralize with alkali again, and neutralizing agent mainly uses CaO, ZnO etc.This method will prolong technical process, increase production cost, use sulphonating agent also will cause the corrosion of equipment.
USP5,306,750 disclose a kind of method for preparing stable modifying asphalt, and this method is that 0.05~2 heavy % contains the polymkeric substance of epoxy group(ing) and pitch in covalent reaction under the temperature more than 100 ℃ more than 1 hour.In 163 ℃~177 ℃ baking oven, store 4 days by the prepared modifying asphalt of this method, phenomenon of phase separation do not occur.
USP5,331,028 disclose a kind of preparation method of polymer modified asphalt, and this method is reacted the ethylene copolymer that contains glycidyl of 90~99.5 heavy % pitches and 0.5~10 heavy % 6~36 hours down at 170 ℃~220 ℃ earlier, obtains reaction product; Getting the reaction product of 100 parts by weight and the vinylbenzene of 0.3~25 parts by weight/conjugated diene block copolymer then mixes.
Though USP5,331,028 and USP5,306,750 polymkeric substance and the bituminous compatiblenesies of using are better, the preparation cost of polymkeric substance and to react difficulty be its main controlling factor.
The purpose of this invention is to provide a kind of process for preparing modified asphalt that improves stability in storage.
Method provided by the invention comprises the following steps:
(1), 2.0~20.0 heavy % polymkeric substance contacted 0.1~72 hour best 0.5~48 hour, the polymkeric substance after obtaining handling with 0.1~20.0 heavy % compatilizer under 10 ℃~250 ℃ best 20 ℃~200 ℃;
(2), 50~97.7 heavy % asphalt stocks are heated to 100 ℃~250 ℃;
(3), the asphalt stock after the polymkeric substance after will handling and the heating mixed 0.1~6 hour, obtained asphalt mother liquid, and with the temperature maintenance of asphalt mother liquid at 100 ℃~250 ℃;
(4), in asphalt mother liquid, add crosslinked body of 0.1~10.0 heavy % and 0.1~10.0 heavy % polar compound, reacted 5~300 minutes, obtain modifying asphalt.
The weight percentage of above-mentioned each component is respectively the weight percent of each component and modified asphalt composite.
In the step (1) polymkeric substance can be static mixing with the way of contact of compatilizer, dynamically mix, grind, the brute force stirring.
Described asphalt stock is one or more the mixture that is selected from petroleum pitch, coal-tar pitch, oil sands bitumen and the rock asphalt, and wherein petroleum pitch is one or more the mixture that is selected from straight-run pitch, solvent deoiling pitch, oxidized bitumen and the mediation pitch.Straight-run pitch long residuum or vacuum residuum that to be crude oil obtain through normal pressure distillation or underpressure distillation, its 25 ℃ of penetration degrees are 20~300dmm (being 1/10mm); Solvent deoiling pitch is meant uses C
3~C
5The de-oiled asphalt that a kind of solvent among the hydro carbons or more than one mixed-solvent extraction residual oil obtain, its 25 ℃ of penetration degrees are 5~200dmm.
Described polymkeric substance is styrene butadiene 20~45: 80~55 polymeric triblock polymers in molar ratio, mainly refers to the SBS base polymer.The structure of SBS is star-like or line style, and molecular weight is 100,000~350, between 000.Triblock polymer can be dried glue, also can be the polymkeric substance that charges into 2~60 heavy % extending oils.
Described compatilizer be selected from styrene tar, Yatall MA, contain sour Yatall MA, catalytically cracked oil, heavy deasphalted oil, solvent treatment extract one or more the mixture in oil, desulfurization naphthenic acid, naphthenic oil, white oil and the coal tar fraction out.
Described crosslinked body is to be selected from crystallization sulphur, active sulphur, sulfur donor and " symbol " to give one or more mixture in the sulfur-crosslinked body.Wherein active sulphur is SULPHUR POWDER, colloid sulphur or its mixture, and colloid sulphur is SULPHUR POWDER or precipitation sulphur and dispersant, and the median size that makes through grinding is the colloid of 1~5 μ m.Sulfur donor is one or more the mixture in morpholine kind compound, thiuram compound and the poly sulfide that is selected from sulfur-bearing.
X=1~4, R
1, R
2, R
3, R
4: C
1~C
4Alkyl.
Poly sulfide: R
1-(S)
n-R
2, R
1, R
2Be aliphatics, aromatic heterocyclic group, as cycloheptasulfur for imines alkylphenol sulfo-thing, alkylphenol monosulphide.
" symbol " mainly refers to the metal oxide cross-linked agent for sulfur-crosslinked body, and master metal wherein will refer to divalent metal such as Ca, Mg, Zn, Pb etc." symbol " gives sulfur-crosslinked body is one or more the mixture that is selected among CaO, MgO, ZnO and the PbO.
Described polar compound mainly is meant the compound that has polar group, is one or more the mixture that is selected from amine, acids, epoxy resin and the aldehyde compound.
Wherein said aminated compounds mainly refers to fatty amine, aromatic amine compounds.
Described acid compounds is one or more the mixture that is selected from carboxylic-acid, anhydrides, sulfonic acid class, boric acid class and the phosphate compound.
Described carboxylic acid compound is one or more the mixture that is selected from lipid acid and the aromatic acid.
Described anhydrides compound is Tetra hydro Phthalic anhydride and derivative or maleic anhydride and derivative thereof.
R
1, R
2, R
3=H or C
1~C
5Alkyl
Described phosphate compound is one or more the mixture that is selected from polyphosphoric acid, phosphorous acid, modification Tripyrophosphoric acid and the phosphate compounds.
Described aldehyde compound is one or more the mixture that is selected from glycidaldehyde, formaldehyde, dialdehyde and the furfural, and wherein dialdehyde is terephthalaldehyde and derivative or m-terephthal aldehyde and derivative thereof.
Modifying asphalt by method preparation provided by the invention has good preservation stability, and the difference of the softening temperature of isolation test is lower than 2.5 ℃.Because its viscosity and adhesivity are big, and be strong with the attached ability of wrapping up in of building stones,, and needn't use the antistripping agent that is used to increase building stones and asphalt adhesion so this modifying asphalt can directly use in rainy humid area.The basic material that also be can be used as emulsified bitumen by the modifying asphalt of method provided by the invention preparation uses, and can realize by adding a certain proportion of water and emulsifying agent.
Below in conjunction with embodiment method provided by the invention is further specified, but not thereby limiting the invention.
Used asphalt stock A, the B of the present invention is respectively straight-run pitch, propane solvent de-oiled asphalt, and its character is as shown in table 2, and polymkeric substance SBS model is 1403, produced by chemical plant, the Yanshan Mountain, Beijing.The shredder model is FD3/60-20, is produced by Shanghai Fu Luke Mechanical and Electrical Equipment Company.Isolation test is to test according to the method that ASTM D 5892-96a provides, and the testing method of softening temperature is measured according to the GB/T4507 method.
Embodiment 1
35 gram SBS contact 2 hours with 75 grammes per square metre deasphalted oils under 180 ℃, add 385 gram asphalt stock A, 1.5 gram colloid sulphur (producing) and 3.5 gram maleic anhydrides (producing) then among the SBS after handling by Lanzhou chemical industrial company by Maoming petro-chemical corporation, reacted 2 hours down at 180 ℃, obtain modifying asphalt, its character sees Table 3, can find out that from table 3 difference of the softening temperature of isolation test only is 2.5 ℃.
Embodiment 2
15 gram SBS contact 48 hours with 2.5 gram naphthenic oils under 25 ℃, add 479 gram asphalt stock A, 1 gram alkyl phenol monosulfide (producing) and 2.5 gram polyphosphoric acid (producing) then among the SBS after handling by the Beijing Chemical Plant by the Beijing Chemical Plant, reacted 3 hours down at 150 ℃, obtain modifying asphalt, its character sees Table 3, can find out that from table 3 difference of the softening temperature of isolation test only is 2 ℃.
Embodiment 3
15 gram SBS contact 7 hours with 30 gram catalytically cracked oils under 100 ℃, add 450 gram asphalt stock B, 2.5 gram zinc oxide (producing) and 2.5 gram phenyl aldehydes (producing) then among the SBS after handling by Yanshan Petrochemical factory by the Beijing Chemical Plant, reacted 1 hour down at 200 ℃, obtain modifying asphalt, its character sees Table 3, can find out that from table 3 difference of the softening temperature of isolation test only is 1 ℃.
Embodiment 4
75 gram SBS contact 5 hours with 100 gram styrene tars under 150 ℃, add 275 gram asphalt stock B, 25 gram crystallization sulphur (producing) and 25 gram Tetra hydro Phthalic anhydrides (producing) then among the SBS after handling by the chemical plant, Qingdao by the Beijing Chemical Plant, reacted 2.5 hours down at 170 ℃, obtain modifying asphalt, its character sees Table 3, can find out that from table 3 difference of the softening temperature of isolation test only is 1 ℃.
Table 2
Asphalt stock | ????A | ????B |
Penetration degree (25 ℃, 100g, 5s), dmm softening temperature (ring and ball method), ℃ extensibility (15 ℃, 5cm/min), cm | ????69 ????48 ????>150 | ????90 ????47.5 ????>150 |
Viscosity (135 ℃), centistoke | ????732 | ????455 |
Sticking toughness (25 ℃), Newton meter | ????4.3 | ????3.2 |
Stable hydrocarbon, heavy % aromatic hydrocarbon, heavy % colloid, heavy % bituminous matter, heavy % | ????18.5 ????31.3 ????35.3 ????14.9 | ????7.4 ????51.5 ????31.8 ????9.3 |
Table 3
Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
Asphalt stock, heavy % SBS, heavy % compatilizer, the crosslinked body of heavy %, heavy % polar compound, heavy % product property penetration degree (25 ℃), dmm softening temperature (ring and ball method), (5 ℃ of ℃ ductilities, 5cm/min), centimetre isolation test, ℃ viscosity (135 ℃), centistoke glues toughness (25 ℃), (163 ℃ of Newton meter thin film ovens, 5h) penetration ratio, % ductility (5 ℃), centimetre | ???A/77 ????7 ????15 ????0.3 ????0.7 ? ????45 ????92 ????65 ????2.5 ????1895 ????31.2 ? ????95.3 ????46 | ???A/95.8 ????3 ????0.5 ????0.2 ????0.5 ? ????60 ????58.5 ????42 ????2.0 ????975 ????16.8 ? ????76.5 ????31 | ???B/90 ????3 ????6 ????0.5 ????0.5 ? ????85 ????56 ????53 ????1.0 ????876 ????14.2 ? ????68.5 ????36 | ???B/55 ????15 ????20 ????5 ????5 ? ????75 ????74.3 ????54 ????1.0 ????2658 ????33.5 ? ????86.8 ????35 |
Claims (15)
1, a kind of process for preparing modified asphalt that improves stability in storage comprises the following steps:
(1), 2.0~20.0 heavy % polymkeric substance contact 0.1~72 hour, the polymkeric substance after obtaining handling with 0.1~20.0 heavy % compatilizer under 20 ℃~250 ℃;
(2), 50~97.7 heavy % asphalt stocks are heated to 100 ℃~250 ℃;
(3), the asphalt stock after the polymkeric substance after will handling and the heating mixed 0.1~6.0 hour, obtained asphalt mother liquid, and with the temperature maintenance of asphalt mother liquid at 100 ℃~250 ℃;
(4), in asphalt mother liquid, add crosslinked body of 0.1~10.0 heavy % and 0.1~10.0 heavy % polar compound, reacted 5~300 minutes, obtain modifying asphalt.
2, according to the method for claim 1, the contact temperature that it is characterized in that step (1) is 20 ℃~200 ℃, and be 0.5~48 hour duration of contact.
3, according to the method for claim 1, it is characterized in that described asphalt stock is one or more the mixture that is selected from petroleum pitch, coal-tar pitch, oil sands bitumen and the rock asphalt, wherein petroleum pitch is one or more the mixture that is selected from straight-run pitch, solvent deoiling pitch, oxidized bitumen and the mediation pitch.
4,, it is characterized in that described polymkeric substance is styrene butadiene 20~45: 80~55 polymeric triblock polymers in molar ratio according to the method for claim 1.
5, according to the method for claim 1, it is characterized in that described compatilizer be selected from styrene tar, Yatall MA, contain sour Yatall MA, catalytically cracked oil, heavy deasphalted oil, solvent treatment extract one or more the mixture in oil, desulfurization naphthenic acid, naphthenic oil, white oil and the coal tar fraction out.
6,, it is characterized in that described crosslinked body is to be selected from crystallization sulphur, active sulphur, sulfur donor and " symbol " to give one or more mixture in the sulfur-crosslinked body according to the method for claim 1.
7, according to the method for claim 6, it is characterized in that described active sulphur is SULPHUR POWDER, colloid sulphur or its mixture, colloid sulphur is SULPHUR POWDER or precipitation sulphur and dispersant, the median size that makes through grinding is the colloid of 1~5 μ m.
8,, it is characterized in that described sulfur donor is one or more the mixture in morpholine kind compound, thiuram compound and the poly sulfide that is selected from sulfur-bearing according to the method for claim 6.
9,, it is characterized in that described " symbol " gives sulfur-crosslinked body is the oxide compound linking agent of divalent metal according to the method for claim 6.
10,, it is characterized in that described polar compound is one or more the mixture that is selected from amine, acids, epoxy resin and the aldehyde compound according to the method for claim 1.
11,, it is characterized in that described aminated compounds is one or more the mixture that is selected from fatty amine and the aromatic amine according to the method for claim 10.
12,, it is characterized in that described acid compounds is one or more the mixture that is selected from carboxylic-acid, anhydrides, sulfonic acid class, boric acid class and the phosphate compound according to the method for claim 10.
13,, it is characterized in that described carboxylic acid compound is one or more the mixture that is selected from lipid acid and the aromatic acid according to the method for claim 12.
14,, it is characterized in that described phosphate compound is one or more the mixture that is selected from polyphosphoric acid, phosphorous acid, modification Tripyrophosphoric acid and the phosphate compounds according to the method for claim 12.
15, according to the method for claim 10, it is characterized in that described aldehyde compound is one or more the mixture that is selected from glycidaldehyde, formaldehyde, dialdehyde and the furfural, wherein dialdehyde is terephthalaldehyde and derivative or m-terephthal aldehyde and derivative thereof.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CN 00123513 CN1111195C (en) | 2000-08-18 | 2000-08-18 | Process for preparing modified asphalt with improved storage stability |
CA002355408A CA2355408C (en) | 2000-08-18 | 2001-08-16 | A storage-stable modified asphalt composition and its preparation process |
US09/931,846 US6713539B2 (en) | 2000-08-18 | 2001-08-17 | Storage-stable modified asphalt composition and its preparation process |
JP2001249485A JP4171194B2 (en) | 2000-08-18 | 2001-08-20 | Storage stability modified asphalt composition and method for producing the same |
SA01220584A SA01220584B1 (en) | 2000-08-18 | 2001-12-23 | A modified asphalt composition that is stable in storage and a process for its preparation |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100340609C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Polymer modified asphalt with storage stability and its preparation method |
CN100363462C (en) * | 2005-12-16 | 2008-01-23 | 中国石油天然气股份有限公司 | Preparation process of SBS modified asphalt |
CN102464989A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
CN102464988A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high-softening-point asphalt particles for drilling fluid |
CN102585525A (en) * | 2012-01-12 | 2012-07-18 | 山东华瑞道路材料技术有限公司 | SBS (styrene-butadiene-styrene) modified asphalt with stable thermal storage and preparation process thereof |
CN102924935A (en) * | 2012-11-07 | 2013-02-13 | 中交第一公路勘察设计研究院有限公司 | Method used for modifying low-temperature coal tar asphalt into paving asphalt |
CN103305014A (en) * | 2013-05-06 | 2013-09-18 | 中海油(青岛)重质油加工工程技术研究中心有限公司 | SBS (stimulated brillouin scattering) modified asphalt and preparation method thereof |
CN103819912A (en) * | 2014-02-21 | 2014-05-28 | 武汉理工大学 | Catalytic reaction type SBS modified asphalt regenerant and preparation method thereof |
CN105102544A (en) * | 2013-02-22 | 2015-11-25 | 拉斐尔·莱奥纳尔多·巴雷特·瓦莱罗 | Catalyst for asphalt mix |
CN105542823A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Oil slurry blended asphalt preparation method |
CN106221108A (en) * | 2016-07-25 | 2016-12-14 | 北京中路铺面技术有限公司 | A kind of asphalt mixed material modifier granule and preparation method thereof |
CN110922769A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Direct-vat-set high-viscosity asphalt modifier and preparation method thereof |
CN111393862A (en) * | 2020-03-20 | 2020-07-10 | 中国海洋石油集团有限公司 | High-modulus modified asphalt and preparation method thereof |
-
2000
- 2000-08-18 CN CN 00123513 patent/CN1111195C/en not_active Expired - Lifetime
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CN100340609C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Polymer modified asphalt with storage stability and its preparation method |
CN100363462C (en) * | 2005-12-16 | 2008-01-23 | 中国石油天然气股份有限公司 | Preparation process of SBS modified asphalt |
CN102464988B (en) * | 2010-11-04 | 2014-03-05 | 中国石油化工股份有限公司 | Preparation method of high-softening-point asphalt particles for drilling fluid |
CN102464989A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
CN102464988A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of high-softening-point asphalt particles for drilling fluid |
CN102464989B (en) * | 2010-11-04 | 2014-04-02 | 中国石油化工股份有限公司 | Preparation method of high softening point asphalt |
CN102585525A (en) * | 2012-01-12 | 2012-07-18 | 山东华瑞道路材料技术有限公司 | SBS (styrene-butadiene-styrene) modified asphalt with stable thermal storage and preparation process thereof |
CN102924935A (en) * | 2012-11-07 | 2013-02-13 | 中交第一公路勘察设计研究院有限公司 | Method used for modifying low-temperature coal tar asphalt into paving asphalt |
CN102924935B (en) * | 2012-11-07 | 2015-07-08 | 中交第一公路勘察设计研究院有限公司 | Method used for modifying low-temperature coal tar asphalt into paving asphalt |
CN105102544A (en) * | 2013-02-22 | 2015-11-25 | 拉斐尔·莱奥纳尔多·巴雷特·瓦莱罗 | Catalyst for asphalt mix |
CN103305014A (en) * | 2013-05-06 | 2013-09-18 | 中海油(青岛)重质油加工工程技术研究中心有限公司 | SBS (stimulated brillouin scattering) modified asphalt and preparation method thereof |
CN103305014B (en) * | 2013-05-06 | 2015-08-26 | 中国海洋石油总公司 | A kind of SBS modifying asphalt and preparation method thereof |
CN103819912A (en) * | 2014-02-21 | 2014-05-28 | 武汉理工大学 | Catalytic reaction type SBS modified asphalt regenerant and preparation method thereof |
CN105542823A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Oil slurry blended asphalt preparation method |
CN105542823B (en) * | 2014-11-03 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of preparation method of slurry oil reconciliation pitch |
CN106221108A (en) * | 2016-07-25 | 2016-12-14 | 北京中路铺面技术有限公司 | A kind of asphalt mixed material modifier granule and preparation method thereof |
CN106221108B (en) * | 2016-07-25 | 2018-10-19 | 国路高科(北京)工程技术研究院有限公司 | A kind of asphalt mixed material modifier particle and preparation method thereof |
CN110922769A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Direct-vat-set high-viscosity asphalt modifier and preparation method thereof |
CN111393862A (en) * | 2020-03-20 | 2020-07-10 | 中国海洋石油集团有限公司 | High-modulus modified asphalt and preparation method thereof |
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