CN113801674A - No. 90A-grade road petroleum asphalt and preparation method thereof - Google Patents
No. 90A-grade road petroleum asphalt and preparation method thereof Download PDFInfo
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- CN113801674A CN113801674A CN202010552133.5A CN202010552133A CN113801674A CN 113801674 A CN113801674 A CN 113801674A CN 202010552133 A CN202010552133 A CN 202010552133A CN 113801674 A CN113801674 A CN 113801674A
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- polyphosphoric acid
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- acid
- shearing
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- 239000010426 asphalt Substances 0.000 title claims abstract description 75
- 239000003208 petroleum Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 74
- 239000002893 slag Substances 0.000 claims abstract description 42
- 239000003623 enhancer Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 238000010008 shearing Methods 0.000 claims description 70
- 239000003921 oil Substances 0.000 claims description 64
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 42
- 238000011161 development Methods 0.000 claims description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 30
- 238000004821 distillation Methods 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 26
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 claims description 2
- -1 maleoyl chloride Chemical compound 0.000 claims description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010724 circulating oil Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 15
- 230000018109 developmental process Effects 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The invention discloses No. 90A-grade road petroleum asphalt and a preparation method thereof. The refractory inferior slag is used as a raw material to be cooperated with polyphosphoric acid, an initiator, a component regulator and a low-temperature ductility enhancer to prepare the No. 90A-grade road asphalt meeting the standard requirement. The asphalt has excellent low-temperature performance, particularly ageing resistance, so that the 90A asphalt still has good low-temperature extensibility after ageing.
Description
Technical Field
The invention relates to road asphalt and a preparation method thereof, in particular to 90A road petroleum asphalt and a preparation method thereof.
Background
Along with the increasing heaviness of crude oil, the yield of the vacuum residue oil is gradually improved, the heavy metal content, the sulfur content and the like in the residue oil are increased, the processing difficulty of the residue oil for lightening is increased, and the production of asphalt by using inferior residue oil is a simpler processing scheme and has higher economic benefit. The production of Chinese asphalt mainly adopts a distillation blending process, but with the deterioration of residual oil and the injection of light oil in the mining process, the relative content of saturated components and asphaltenes in the residual oil is increased, the relative content of aromatic components and colloids is reduced, the association degree of the asphaltenes is increased, and the existing form is more complicated. At the moment, qualified road asphalt is difficult to produce by adopting a simple distillation blending process, and the production of No. 90A road asphalt with higher requirements on crude oil properties is more difficult.
For example, the thick oil of the tower river is an important petroleum resource, but the structural composition and the physical and chemical properties of the thick oil of the tower river are greatly different from those of other oil sources, and the yield of the vacuum residue of the tower river exceeds 70 percent, and the thick oil of the tower river belongs to residue with high sulfur, high carbon residue, high asphaltene and high heavy metal content. The Tahe refining Limited liability company produces Tahe No. 90 grade A asphalt in 2005, and when the asphalt is in the process, the vacuum residue oil penetration is 60-70 ℃, and the flash point is 260-270 ℃. Along with the development time, the tower and river crude oil gradually becomes heavier, the slag-reducing asphaltene content reaches 15% and 23% in 2007 and 2009 respectively, and the asphaltene content exceeds 40% in 2019. Therefore, only the residue from the Tahe refinery can be coked or No. 60 bitumen can be produced, but this greatly reduces the industrial economic benefit. Therefore, it is important to develop a production scheme for acceptable 90A bitumen for the currently increasingly inferior crude oils.
CN109593541A discloses No. 90A-grade road petroleum asphalt and a preparation method thereof. The No. 90A-grade road asphalt is prepared from No. 70A-grade road petroleum asphalt, catalytic cracking slurry oil fraction and polyphosphoric acid, the penetration degree of the asphalt is improved through the catalytic cracking slurry oil fraction, and indexes such as viscosity, softening point and the like are improved through the polyphosphoric acid. The method only simply blends a plurality of materials, although the No. 70A road petroleum asphalt can be finally blended to be 90A, the ageing resistance and the low-temperature elongation performance of the asphalt are correspondingly reduced due to the addition of the catalytic cracking slurry oil, the flash point of the asphalt is also reduced due to the addition of the light components, and the 90A asphalt cannot be produced by the method for poor oil sources.
CN110484009A discloses No. 110 road petroleum asphalt and a preparation method thereof. The method blends and stirs the No. 70 road petroleum asphalt, the three-line wax oil and the polyphosphoric acid to obtain a product which accords with the No. 110A-grade road petroleum asphalt standard, and the preparation process is simple and convenient. But the direct addition of the three-line wax reducing oil reduces the flash point of the asphalt, the direct doping of the polyphosphoric acid does not play the real role, and the delay increasing effect of the three-line wax reducing oil is also inhibited to a certain extent.
CN103102498A discloses a production method of styrene butadiene rubber modified asphalt. The method greatly increases the low-temperature extensibility of the asphalt and solves the problem that the asphalt with high asphaltene and low aromatic substance is difficult to modify. However, the method only increases the low-temperature ductility of the asphalt and does not substantially contribute to the flash point, the ageing resistance and the like of the asphalt. And the added styrene butadiene rubber has poor ageing resistance and is easy to decompose under the heating condition, so that the elongation of the prepared asphalt is quickly reduced after ageing.
In conclusion, the above methods are not suitable for producing high-grade road asphalt from degraded raw materials, and the traditional blending method can not enable the obtained product to simultaneously meet the requirements of low-temperature performance and flash point. Therefore, for the raw materials with high asphaltene and low aromatic component, a new asphalt production process needs to be developed in a targeted manner to improve the added value of low-quality resources.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide No. 90A-grade road petroleum asphalt and a preparation method thereof. The invention takes the difficult-to-process inferior normal slag as the raw material to prepare the No. 90A-grade road asphalt which can meet the standard requirement. The asphalt has excellent low-temperature performance, particularly ageing resistance, so that the 90A asphalt still has good low-temperature extensibility after ageing.
The invention provides 90A road petroleum asphalt which comprises the following raw material components in parts by weight:
slag-smelting: 100 parts of (A);
polyphosphoric acid: 0.1-2.5 parts, preferably 0.2-2.0 parts;
initiator: 0.02-0.15 part, preferably 0.04-0.1 part;
component regulator: 5-35 parts, preferably 10-30 parts;
low-temperature ductility enhancer: 2-20 parts, preferably 3-10 parts;
the properties of the normal slag comprise: the flash point is 246-258 ℃, the sulfur content is 2.77-3.63 wt%, the saturated component accounts for 26.1-37.7 wt%, the aromatic component accounts for 20.2-34.5 wt%, the colloid accounts for 18.3-24.8 wt%, the asphaltene accounts for 21.3-30.1 wt%, and the asphaltene is preferably 21.3-25.0 wt%.
The normal slag also has the following basic properties: the carbon residue value is 19-28 wt%, the total content of nickel and vanadium is 310-365 mug/g, and the condensation index CI is 0.22-0.30.
The normal slag can be tower and river normal slag or other normal slag meeting the properties. The normal slag is a fraction with an initial boiling point of more than 350 ℃.
The polyphosphoric acid comprises a first polyphosphoric acid and a second polyphosphoric acid, the first polyphosphoric acid is polyphosphoric acid with high phosphoric acid content, the second polyphosphoric acid is polyphosphoric acid with low phosphoric acid content, the polyphosphoric acid with high phosphoric acid content accounts for 50% -80% of the total mass of the polyphosphoric acid, and the polyphosphoric acid with low phosphoric acid content accounts for 20% -50% of the total mass of the polyphosphoric acid.
The low-phosphoric-acid-content polyphosphoric acid refers to phosphoric acid (as H) contained in polyphosphoric acid3PO4Calculated) is 105-125 percent, preferably 110-120 percent.
The high-phosphoric-acid-content polyphosphoric acid refers to phosphoric acid (as H) contained in polyphosphoric acid3PO4Measured), the mass content is 130-145%, preferably 130-140%.
The initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium metabisulfite, azobisisobutyronitrile, azobisisoheptonitrile and cumene hydroperoxide.
The component regulator is one or more of coker gas oil, extract oil, catalytic slurry oil and coking cycle oil. The component regulator comprises, by mass, 25-50% of a saturated component, 30-60% of an aromatic component, 10-30% of a colloid, and 0-3% of an asphaltene, wherein the boiling range of the component regulator is from 295-310 ℃ at an initial boiling point and from 430-455 ℃ at a final boiling point.
The low-temperature ductility agent comprises the following components in parts by weight:
aromatic-rich distillate oil: 100 parts of (A);
styrene-butadiene rubber: 5-30 parts, preferably 10-20 parts;
modifying agent: 2-8 parts, preferably 3-6 parts;
auxiliary agent: 0.5-3 parts, preferably 0.5-2 parts;
catalyst: 0.01 to 0.5, preferably 0.01 to 0.2 parts.
The mass content of aromatic hydrocarbon of the aromatic hydrocarbon-rich distillate oil is 30-90%, the initial boiling point of the boiling range of the aromatic hydrocarbon-rich distillate oil is 300-315 ℃, the final boiling point of the aromatic hydrocarbon-rich distillate oil is 440-478 ℃, and the aromatic hydrocarbon-rich distillate oil can be one or a mixture of a first-line-reduced extract oil, a second-line-reduced extract oil, a third-line-reduced extract oil and a fourth-line-reduced extract oil, and is preferably one or a mixture of the third-line-reduced extract oil and the fourth-line-reduced extract oil.
The styrene butadiene rubber is one or the mixture of low-temperature poly-Emulsion Styrene Butadiene Rubber (ESBR) and solution polymerized styrene butadiene rubber (SSBR).
The modifier is one or a mixture of acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate, ethyl methacrylate, maleimide, fumaric acid, itaconic acid, citraconic acid, monomethyl maleate, dimethyl maleate, maleoyl chloride and alpha-ethacrylic acid.
The auxiliary agent is one or a mixture of more of diethylene glycol, 1, 4-butanediol, triethylene glycol, dipropylene glycol, polyethylene glycol 400, polyethylene glycol 2000, pentaerythritol, sorbitol and tetraethylene glycol.
The catalyst is one or a mixture of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptonitrile.
The invention also provides a preparation method of the 90A road petroleum asphalt, which comprises the following steps:
(1) preparing a low-temperature ductility enhancer;
(2) adding the normal slag and the first polyphosphoric acid which are heated to flow states into a reaction kettle, continuously stirring and heating to a reaction temperature, reacting under a protective gas, and carrying out heat preservation treatment after the reaction is finished;
(3) adding a second polyphosphoric acid, an initiator and a component regulator into the material obtained in the step (2), uniformly stirring, and then shearing;
(4) carrying out reduced pressure distillation on the material sheared in the step (3) to obtain slag reduction;
(5) and (3) adding the low-temperature ductility agent prepared in the step (1) into the slag reduction obtained in the step (4), shearing again, then developing under stirring, and obtaining the 90A road petroleum asphalt after the development is finished.
Wherein, the low-temperature ductility agent in the step (1) adopts the following preparation method:
after being crushed, styrene butadiene rubber is added into preheated aromatic hydrocarbon-rich distillate oil and is sheared under the heating condition to obtain a pre-modifier; and reacting the obtained pre-modifier with a modifier and a catalyst in an inert atmosphere, adding an auxiliary agent after the reaction is finished, stirring for development, preserving heat after the development is finished, and preserving heat to obtain the low-temperature ductility enhancer.
Further, in the preparation method of the low-temperature ductility improver, the particle size of the pulverized styrene-butadiene rubber is 0.1-3.0 cm, preferably 0.1-1 cm. Preheating the aromatic hydrocarbon-rich distillate oil at 100-110 ℃, heating at 120-140 ℃ during shearing, shearing at a speed of 2000-5000 r/min, preferably 3000-4500 r/min, and shearing for 40-120 min, preferably 40-80 min. The weight ratio of the styrene butadiene rubber to the aromatic-rich oil is (5-30): 100, preferably (10-20): 100. Before the reaction, the reaction kettle is purged by inert gas, and the inert gas and/or N are/is used as the inert atmosphere in the reaction process2The reaction maintaining pressure is 0.5-1.0 MPa, the reaction time is 3-5 h, the reaction temperature is 120-150 ℃, and the stirring speed in the reaction process is 600-1000 r/min. The development stage is still carried out under the protection of inert gas, and the stirring speed is high200-500 r/min, the development temperature is 110-120 ℃, and the development time is 120-180 min; the temperature for heat preservation is 80-100 ℃, and the heat preservation time is 3-6 h.
In the step (2), the reaction kettle is a high-pressure reaction kettle, and the initial temperature of the reaction kettle is adjusted to be 100-120 ℃.
In the step (2), the first polyphosphoric acid added is a polyphosphoric acid having a high phosphoric acid content (referred to as phosphoric acid (in terms of H) contained in the polyphosphoric acid)3PO4Calculated) is 130-145 percent, preferably 130-140 percent), and the adding amount of the first polyphosphoric acid is 50-80 percent of the total mass of the polyphosphoric acid.
In the step (2), the stirring speed is 600-900 r/min. The heating to the reaction temperature is realized by adopting temperature programming heating to the reaction temperature, the heating rate is 1-3 ℃/min, the heating temperature is 130-150 ℃, and the preferable temperature is 135-150 ℃.
In the step (2), the protective gas is inert gas and/or N2The amount of the shielding gas is such that the pressure in the reaction kettle is maintained at 0.2-0.9 MPa, preferably 0.3-0.8 MPa. The reaction time is 3-6 h. The heat preservation treatment condition is that the heat preservation is carried out for 8-12 hours at the temperature of 80-110 ℃.
In the step (3), the second polyphosphoric acid added is polyphosphoric acid having a low phosphoric acid content (which means phosphoric acid contained in polyphosphoric acid as H3PO4Calculated) is 105-125 percent, preferably 110-120 percent, and the adding amount of the second polyphosphoric acid is 20-50 percent of the total mass of the polyphosphoric acid.
In the step (3), the shearing speed is 2000-4000 r/min, the shearing time is 40-100 min, and the temperature required by shearing is 130-150 ℃.
In the step (4), the reduced pressure distillation is carried out in a reduced pressure distillation kettle. The reduced pressure distillation conditions are as follows: the temperature of the bottom of the reduced pressure distillation tower is controlled to be above 400 ℃ (converted atmospheric temperature), the final temperature of reduced pressure distillation is 425-440 ℃, and the rotation speed of the rotor in the reduced pressure distillation kettle is 100-300 r/min in the process of reduced pressure distillation.
In the step (5), the shearing rate is 2000-4500 r/min, preferably 3000-4000 r/min, the shearing time is 40-80 min, and the required temperature during shearing is 120-160 ℃, preferably 120-140 ℃. The stirring speed is 300-600 r/min, preferably 400-600 r/min, and the stirring time is 2-4 h. The temperature for development is 130-160 ℃, and preferably 140-160 ℃.
Compared with the prior art, the 90A road petroleum asphalt and the preparation method thereof have the following advantages:
(1) the invention adopts the normal slag with special properties as the raw material, which can influence the normal production of asphalt, for example, the qualified No. 90A grade road asphalt can not be obtained by adopting the existing mode for the tower and river normal slag with high asphaltene content, very special existing form and extremely poor comprehensive performance as the raw material. However, the invention adopts the specific cooperation of the normal slag, the polyphosphoric acid, the initiator, the component regulator and the low-temperature ductility enhancer, and the obtained No. 90A-grade road asphalt has excellent low-temperature performance, and the flash point and other indexes can also meet the standard requirements of No. 90A-grade road asphalt.
(2) The polyphosphoric acid is added twice, and the types and reaction conditions of the polyphosphoric acid are different in different adding periods, so that the asphaltene cluster and the chain-shaped light component in the residual oil are subjected to targeted adjustment, the process of replacing the light component by middle fraction is more thorough, the distillation effect is better, and the flash point is improved more obviously.
(3) In the invention, other suitable component regulators are introduced besides polyphosphoric acid added in a specific mode, and all components have synergistic effect, so that light components in the residual oil are distilled out and middle fractions are supplemented in an enhanced mixed distillation mode, and the composition structure of the residual oil is regulated in a micro-scale.
(4) In the preparation process of the low-temperature ductility improver, the preferable aromatic-rich distillate oil and the butadiene styrene rubber can be stably compatible, so that the low-temperature ductility of the asphalt is greatly improved; the reversible covalent bond is introduced in the modification process of the styrene butadiene rubber, the self-repairing capability of the polymer is improved, the elongation is prevented from being greatly reduced due to the thermo-oxidative aging decomposition of the polymer, and the early aging of the polymer is avoided under the protection of inert gas in the whole process of preparing the low-temperature ductility enhancer, so that the low-temperature ductility enhancer has better performance and stronger subsequent aging resistance; the introduction of the functional auxiliary agent in the preparation process of the low-temperature ductility enhancer further improves the stability of the styrene butadiene rubber, so that the low-temperature ductility enhancer and the asphalt have better compatibility.
(5) According to the invention, the composition structure is adjusted by only introducing a small amount of additives, rather than introducing a large amount of other oil source asphalt for traditional blending, so that the process is simpler, the production cost is lower, and the used additives have high boiling points and no volatilization and are harmless to human bodies and the environment.
Detailed Description
The technical solution of the present invention is further described by the following examples, but these examples do not limit the scope of the present invention, and the wt% referred to is mass fraction.
Example 1
(1) Firstly, crushing 15 parts of solution polymerized styrene butadiene rubber (SSBR) to the particle size of 0.5cm, then adding the crushed SSBR into 100 parts of aromatic-rich distillate oil (the aromatic content is 45wt%, the boiling range is 310-450 ℃) preheated to 110 ℃, and shearing at 130 ℃ for 60min at the shearing speed of 4000 r/min; after shearing, pouring the mixture into a reaction kettle, and enabling the reaction kettle to pass through N in advance2Purging for 20min, adding 2 parts of methacrylic acid, 2 parts of maleimide and 0.05 part of sodium persulfate into the reaction kettle, and adding the mixture into the reaction kettle in the presence of N2Stirring and reacting for 4 hours at 135 ℃ in the atmosphere, wherein the reaction pressure is maintained at 0.8MPa, and the stirring speed is 800 r/min; after the reaction is finished, 0.8 part of sorbitol is added into the reaction kettle to be stirred and developed, and N is still used in the development stage2Maintaining the pressure of 0.8MPa, stirring at 400r/min, development temperature of 115 deg.C, and development time of 120 min; after the development is finished, the mixture is placed in an oven with the temperature of 100 ℃ for heat preservation for 4 hours to obtain the low-temperature ductility agent for later use.
(2) Adding 100 parts of tower river slag (properties shown in Table 1) heated to flow state into a high-pressure reaction kettle at 110 deg.C, stirring, and adding 0.2 part of phosphoric acid (as H)3PO4Calculated) 135 percent of polyphosphoric acid is slowly added into the reaction kettle (after the polyphosphoric acid is added within 3 min), the temperature is programmed to be 140 ℃ according to the speed of 2 ℃/min under the stirring speed of 600r/min, and N is added after the temperature is increased2The reaction is carried out in the atmosphere, the pressure in the reaction kettle is maintained at 0.5 MPa, and the reaction time is prolongedIs 4 h; after the reaction is finished, the mixture is placed in an oven for heat preservation, the heat preservation temperature is 100 ℃, and the heat preservation time is 8 hours.
(3) 0.1 part of phosphoric acid (in terms of H)3PO4Calculated) 110% of polyphosphoric acid is added into the tower river normal slag reacted in the step (2), after uniform stirring, 0.05 part of dicumyl peroxide and 0.01 part of azobisisobutyronitrile are added, after uniform mixing, 15 parts of component regulator (calculated by mass, the saturated component accounts for 25%, the aromatic component accounts for 50%, the colloid accounts for 24%, and the asphaltene accounts for 1%) are added, and the mixed system is subjected to high-speed shearing, wherein the shearing speed is 4000r/min, the shearing time is 50min, and the heating temperature during shearing is 140 ℃.
(4) And (4) putting the mixture obtained in the step (3) into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of the rotor in the kettle to be 300 r/min, and ending the reduced pressure distillation until the temperature reaches 430 ℃ (the normal pressure temperature after conversion) to obtain reduced residue A1.
(5) Adding 5 parts of low-temperature ductility agent into the slag-reduced A1 obtained in the step (4), and shearing at 130 ℃ for 50min at the shearing rate of 4000 r/min; after shearing, stirring and developing at 140 ℃, wherein the stirring speed is 400r/min, the stirring time is 3h, and 90A asphalt A11 is obtained after the development is finished, and the specific properties are shown in Table 2.
Example 2
(1) Firstly, crushing 15 parts of solution polymerized styrene butadiene rubber (SSBR) to the particle size of 0.5cm, then adding the crushed SSBR into 100 parts of aromatic-rich distillate oil (the aromatic content is 45wt%, the boiling range is 310-450 ℃) preheated to 110 ℃, and shearing at 120 ℃ for 80min at the shearing speed of 4000 r/min; after shearing, pouring the mixture into a reaction kettle, and enabling the reaction kettle to pass through N in advance2Purging for 20min, adding 2 parts of methacrylic acid, 2 parts of fumaric acid and 0.05 part of potassium persulfate into the reaction kettle, and adding the mixture into the reaction kettle under the condition of N2Stirring and reacting for 3h at 140 ℃ in the atmosphere, maintaining the reaction pressure at 1MPa and the stirring speed at 800 r/min; after the reaction is finished, 0.8 part of pentaerythritol is added into the reaction kettle to be stirred and developed, and N is used in the development stage2Maintaining the pressure of 0.8MPa, stirring at 500 r/min, development temperature of 115 deg.C, and development time of 120 min; after the development is finished, the mixture is placed in an oven with the temperature of 100 ℃ for heat preservation for 4 hours to obtain the low-temperature ductility agent for later use.
(2) The subsequent preparation procedure was the same as in example 1, yielding slag-reduced A2, having the same properties as A1, yielding 90A pitch A22.
Example 3
(1) The conditions for preparing the low temperature ductility agent were the same as in example 1.
(2) Adding 100 parts of the tower river slag (properties shown in Table 1) into a high-pressure reaction kettle at the temperature of 110 ℃, stirring, and adding 0.2 part of phosphoric acid (expressed as H)3PO4Calculated) 135 percent of polyphosphoric acid is slowly added into the reaction kettle (after the polyphosphoric acid is added within 3 min), the temperature is programmed to be 140 ℃ according to the speed of 2 ℃/min under the stirring speed of 600r/min, and N is added after the temperature is increased2Carrying out reaction in the atmosphere, wherein the pressure in the reaction kettle is maintained at 0.5 MPa, and the reaction time is 4 h; after the reaction is finished, the mixture is placed in an oven for heat preservation, the heat preservation temperature is 100 ℃, and the heat preservation time is 8 hours.
(3) 0.2 part of phosphoric acid (in terms of H)3PO4Calculated) 110% of polyphosphoric acid is added into the tower river normal slag reacted in the step (2), 0.1 part of dicumyl peroxide is added after uniform stirring, 18 parts of component regulators (the saturated component accounts for 20%, the aromatic component accounts for 55%, the colloid accounts for 24.5%, and the asphaltene accounts for 0.5%) are added after uniform mixing, the mixed system is subjected to high-speed shearing, the shearing speed is 4000r/min, the shearing time is 50min, and the heating temperature during shearing is 140 ℃.
(4) And (4) putting the mixture obtained in the step (3) into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of the rotor in the kettle to be 300 r/min, and ending the reduced pressure distillation until the temperature reaches 430 ℃ (the normal pressure temperature after conversion) to obtain reduced residue A3.
(5) Adding 10 parts of low-temperature ductility agent into the slag reducing A3 in the step (4), and shearing at 130 ℃ for 50min at the shearing rate of 4000 r/min; and after shearing, stirring and developing at 140 ℃, wherein the stirring speed is 400r/min, the stirring time is 3h, and 90A asphalt A33 is obtained after the development is finished.
Example 4
(1) Firstly, 15 parts of low-temperature poly-latex butadiene rubber (ESBR) is crushed to the particle size of 1cm, and then the crushed ESBR is added into 100 parts of aromatic-rich distillate oil preheated to 110 ℃ (the aromatic content is 45wt percent)At 305-450 deg.c), shearing at 130 deg.c for 60min at 4000 r/min; after shearing, pouring the mixture into a reaction kettle, and enabling the reaction kettle to pass through N in advance2Purging for 20min, adding 2 parts of methacrylic acid, 2 parts of methyl methacrylate and 0.02 part of sodium persulfate into the reaction kettle, and adding the mixture into the reaction kettle in the presence of N2Stirring and reacting for 4 hours at 135 ℃ in the atmosphere, wherein the reaction pressure is maintained at 0.8MPa, and the stirring speed is 800 r/min; after the reaction is finished, 1 part of 1, 4-butanediol is added into the reaction kettle to be stirred and developed, and N is still used in the development stage2Maintaining the pressure of 0.8MPa, stirring at 500 r/min, development temperature of 110 deg.C, and development time of 150 min; after the development is finished, the mixture is placed in a 100 ℃ oven for heat preservation for 5 hours to obtain the low-temperature ductility enhancer for later use.
(2) 100 parts of the tower-river slag (properties shown in Table 1) are added into a high-pressure reaction kettle at the temperature of 110 ℃ and stirred, and 1.2 parts of phosphoric acid (as H) is added3PO4Calculated) 135 percent of polyphosphoric acid is slowly added into the reaction kettle (after the polyphosphoric acid is added within 3 min), the temperature is increased to 135 ℃ according to the speed program of 1.5 ℃/min under the stirring speed of 600r/min, and N is added after the temperature increase is finished2Carrying out reaction in the atmosphere, wherein the pressure in the reaction kettle is maintained at 0.4 MPa, and the reaction time is 4 h; after the reaction is finished, the mixture is placed in an oven for heat preservation, the heat preservation temperature is 100 ℃, and the heat preservation time is 8 hours.
(3) 0.4 part of phosphoric acid (in terms of H)3PO4Calculated) 115% of polyphosphoric acid is added into the tower river normal slag reacted in the step (2), 0.05 part of benzoyl peroxide and 0.01 part of azodiisobutyronitrile are added after uniform stirring, 30 parts of component regulators (30% of saturated component, 56% of aromatic component, 14% of colloid and 0% of asphaltene) are added after uniform mixing, the mixed system is subjected to high-speed shearing, the shearing speed is 4000r/min, the shearing time is 50min, and the heating temperature during shearing is 140 ℃.
(4) And (4) putting the mixture obtained in the step (3) into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of the rotor in the kettle to be 200 r/min, and ending the reduced pressure distillation to 425 ℃ (the normal pressure temperature after conversion) to obtain the reduced residue A4.
(5) Adding 8 parts of low-temperature ductility agent into the slag reducing A4 in the step (4), and shearing at 135 ℃ for 45min at the shearing rate of 4500 r/min; and after shearing, stirring and developing at 140 ℃, wherein the stirring speed is 400r/min, the stirring time is 3h, and 90A asphalt A44 is obtained after the development is finished.
Comparative example 1
(1) Firstly, crushing 15 parts of solution polymerized styrene butadiene rubber (SSBR) to the particle size of 0.5cm, then adding the crushed SSBR into 100 parts of aromatic-rich distillate oil (the aromatic content is 45wt%, the boiling range is 310-450 ℃) preheated to 110 ℃, and shearing at 130 ℃ for 60min at the shearing speed of 4000 r/min; after shearing, pouring the mixture into a reaction kettle, and stirring and developing the mixture for 120min under the nitrogen atmosphere, wherein the stirring speed is 400r/min, and the development temperature is 115 ℃; after the development is finished, the mixture is placed in a 100 ℃ oven for heat preservation for 5 hours to obtain the low-temperature ductility enhancer for later use.
(2) Directly putting the tower and river normal slag into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of an inner rotor in the kettle to be 300 r/min, and ending the reduced pressure distillation to 430 ℃ (the normal pressure temperature after conversion) to obtain reduced slag B1.
(3) Adding 5 parts of the low-temperature ductility agent obtained in the step (1) into the slag reduction B1 obtained in the step (2), and shearing at 130 ℃ for 50min at the shearing rate of 4000 r/min; and (3) after shearing, stirring and developing at 140 ℃, wherein the stirring speed is 400r/min, the stirring time is 3h, and 90A asphalt B11 is obtained after the development is finished.
Comparative example 2
(1) Firstly, crushing 15 parts of solution polymerized styrene butadiene rubber (SSBR) to the particle size of 0.5cm, then adding the crushed SSBR into 100 parts of aromatic-rich distillate oil (the aromatic content is 45wt%, the boiling range is 310-450 ℃) preheated to 110 ℃, and shearing at 130 ℃ for 60min at the shearing speed of 4000 r/min; after shearing, pouring the mixture into a reaction kettle, and stirring and developing the mixture for 120min under the nitrogen atmosphere, wherein the stirring speed is 400r/min, and the development temperature is 115 ℃; after the development is finished, the mixture is placed in a 100 ℃ oven for heat preservation for 5 hours to obtain the low-temperature ductility enhancer for later use.
(2) The same procedure as in example 1 was used to prepare the slag reduction: adding 100 parts of tower river slag (properties shown in Table 1) heated to flow state into a high-pressure reaction kettle at 110 deg.C, stirring, and adding 0.2 part of phosphoric acid (as H)3PO4Calculated) 135% of polyphosphoric acidSlowly adding into a reaction kettle (adding is completed within 3 min), heating to 140 ℃ at a stirring speed of 600r/min according to a speed program of 2 ℃/min, and heating to N2Carrying out reaction in the atmosphere, wherein the pressure in the reaction kettle is maintained at 0.5 MPa, and the reaction time is 4 h; after the reaction is finished, the mixture is placed in an oven for heat preservation, the heat preservation temperature is 100 ℃, and the heat preservation time is 8 hours.
(3) 0.1 part of phosphoric acid (in terms of H)3PO4Calculated) 110% of polyphosphoric acid is added into the tower river normal slag reacted in the step (2), after uniform stirring, 0.05 part of dicumyl peroxide and 0.01 part of azobisisobutyronitrile are added, after uniform mixing, 15 parts of component regulator (calculated by mass, the saturated component accounts for 25%, the aromatic component accounts for 50%, the colloid accounts for 24%, and the asphaltene accounts for 1%) are added, and the mixed system is subjected to high-speed shearing, wherein the shearing speed is 4000r/min, the shearing time is 50min, and the heating temperature during shearing is 140 ℃.
(4) And (3) putting the mixture in the step (3) into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of an inner rotor in the kettle to be 300 r/min, and ending the reduced pressure distillation to 430 ℃ (the normal pressure temperature after conversion) to obtain residue-reduced B2 with the property of A1.
(5) Adding 5 parts of low-temperature ductility agent into the slag-reduced A1 obtained in the step (4), and shearing at 130 ℃ for 50min at the shearing rate of 4000 r/min; and (3) after shearing, stirring and developing at 140 ℃, wherein the stirring speed is 400r/min, the stirring time is 3h, and 90A asphalt B22 is obtained after the development is finished.
Comparative example 3
(1) Firstly, crushing 15 parts of solution polymerized styrene butadiene rubber (SSBR) to the particle size of 0.5cm, then adding the crushed SSBR into 100 parts of aromatic-rich distillate oil (the aromatic content is 45wt%, the boiling range is 310-450 ℃) preheated to 110 ℃, and shearing at 130 ℃ for 60min at the shearing speed of 4000 r/min; after shearing, pouring the mixture into a reaction kettle, and enabling the reaction kettle to pass through N in advance2Purging for 20min, adding 2 parts of methacrylic acid, 2 parts of maleimide and 0.05 part of sodium persulfate into the reaction kettle, and adding the mixture into the reaction kettle in the presence of N2Stirring and reacting for 4h at 130 ℃ in the atmosphere, maintaining the reaction pressure at 0.8MPa and stirring at the speed of 800 r/min; after the reaction is finished, 0.8 part of sorbitol is added into the reaction kettle and stirredN is still used in the stage of development and development2Maintaining the pressure of 0.8MPa, stirring at 500 r/min, development temperature of 115 deg.C, and development time of 120 min; after the development is finished, the mixture is placed in an oven with the temperature of 100 ℃ for heat preservation for 4 hours to obtain the low-temperature ductility agent for later use.
(2) Directly putting the tower and river normal slag into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of an inner rotor in the kettle to be 300 r/min, and ending the reduced pressure distillation to 430 ℃ (the normal pressure temperature after conversion) to obtain reduced slag B3.
(3) Adding 5 parts of low-temperature ductility agent into the slag reduction B1 in the step (2), and shearing at 130 ℃ for 50min at the shearing rate of 4000 r/min; and (3) after shearing, stirring and developing at 140 ℃, wherein the stirring speed is 400r/min, the stirring time is 3h, and 90A asphalt B33 is obtained after the development is finished.
Comparative example 4
The same as example 1, except that the content of 0.1 part of phosphoric acid (in terms of H) is not added in the preparation process of the modified slag-reducing agent3PO4Calculated) 110% polyphosphoric acid, 0.05 parts dicumyl peroxide, and 0.01 parts azobisisobutyronitrile. This comparative example yielded a vacuum residue of B4 and a 90A pitch of B44.
Comparative example 5
The same as example 1, except that the content of 0.2 part of phosphoric acid (in terms of H) is not added in the preparation process of the modified slag-reducing agent3PO4Calculated) 135% of the polyphosphoric acid was reacted. This comparative example yielded a vacuum residue of B5 and a 90A pitch of B55.
Test example
Performing a key index test (according to road engineering asphalt and asphalt mixture test regulation JTG E20-2011) on the Tahe slag reduction and 90A asphalt obtained in the embodiment and the comparative example, wherein each index of a qualified 90A asphalt product needs to meet the related requirements of road petroleum asphalt technical requirement JTG F40-2004; the examples and the comparative examples were subjected to aging resistance tests at different aging temperatures, and the change of 15 ℃ ductility before and after aging of 90A asphalt prepared by different preparation methods was examined.
TABLE 1 Properties of Tahe Normal slag used in examples and comparative examples
| Density (20 ℃ C.)/(g/cm)3） | 1.0211 |
| Carbon residue value/wt% | 24.1 |
| Flash point (open)/°c | 248 |
| Carbon content/wt% | 87.02 |
| Hydrogen content/wt% | 8.67 |
| Sulfur content/wt.% | 2.86 |
| Fraction of saturation/%) | 29.8 |
| Fraction of aroma/%) | 28.7 |
| Percent of pectin | 19.4 |
| Asphaltene/% | 22.1 |
| Nickel content/(μ g/g) | 43.8 |
| Vanadium content/(μ g/g) | 271.1 |
| Kinematic viscosity (80 ℃ C.)/(mm)2/s） | ＞20000 |
| Kinematic viscosity (100 ℃ C.)/(mm)2/s） | 6596 |
| Condensation index CI | 0.23 |
TABLE 2 Properties of the reduced slag and 90A asphalts obtained in the examples and comparative examples
| Penetration/0.1 mm at 25 ℃ | Softening point/. degree.C | Ductility/cm at 15 DEG C | Flash point/. degree.C | PI value | Viscosity at 60 ℃ in Pa.s | |
| Standard requirements | 80～100 | ≥45 | ≥100 | ≥245 | -1.5～+1.0 | ≥160 |
| A1 | 62 | 53 | 21 | 267 | 0.826 | 1473 |
| A11 | 92 | 49 | 112 | 254 | 0.592 | 422 |
| A22 | 90 | 48 | 124 | 251 | 0.644 | 420 |
| A3 | 58 | 59 | 30 | 267 | 0.916 | 1534 |
| A33 | 90 | 52 | 128 | 249 | 0.501 | 374 |
| A4 | 60 | 54 | 23 | 260 | 1.025 | 1497 |
| A44 | 93 | 45 | 134 | 247 | 0.764 | 399 |
| B1 | 34 | 73 | 0 | 267 | 2.865 | 2861 |
| B11 | 70 | 63 | 30 | 260 | 1.323 | 870 |
| B2 | 61 | 53 | 20 | 266 | 0.837 | 1477 |
| B22 | 91 | 48 | 107 | 255 | 0.571 | 401 |
| B3 | 33 | 74 | 0 | 268 | 2.774 | 2799 |
| B33 | 69 | 63 | 31 | 261 | 1.004 | 866 |
| B4 | 50 | 54 | 17 | 264 | 0.871 | 1514 |
| B44 | 83 | 45 | 98 | 251 | 0.734 | 592 |
| B5 | 47 | 60 | 13 | 261 | 1.012 | 1526 |
| B55 | 81 | 52 | 84 | 241 | 0.873 | 643 |
TABLE 3 comparison of the ageing resistance of the bitumens of examples and of comparative example 90A
| Original shape 15 ℃ ductility/cm | 15 ℃ ductility/cm after TFOT at 123 ℃ | Elongation/cm at 15 ℃ after TFOT at 143 ℃ | 15 ℃ ductility/cm after 163 ℃ TFOT | 15 ℃ ductility/cm after 183 ℃ TFOT | |
| A11 | 112 | 110 | 109 | 104 | 18 |
| A22 | 124 | 121 | 118 | 112 | 29 |
| A33 | 128 | 122 | 121 | 115 | 27 |
| A44 | 134 | 130 | 126 | 119 | 31 |
| B11 | 30 | 25 | 19 | 0 | 0 |
| B22 | 110 | 102 | 100 | 95 | 9 |
| B33 | 31 | 25 | 21 | 11 | 0 |
| B44 | 98 | 93 | 89 | 69 | 0 |
| B55 | 84 | 80 | 76 | 63 | 0 |
Claims (18)
1. A90A road petroleum asphalt is characterized in that: the material comprises the following raw materials in parts by weight:
slag-smelting: 100 parts of (A);
polyphosphoric acid: 0.1-2.5 parts, preferably 0.2-2.0 parts;
initiator: 0.02-0.15 part, preferably 0.04-0.1 part;
component regulator: 5-35 parts, preferably 10-30 parts;
low-temperature ductility enhancer: 2 to 20 parts, preferably 3 to 10 parts.
2. The 90A road petroleum asphalt of claim 1, characterized in that: the low-temperature ductility agent comprises the following components in parts by weight:
aromatic-rich distillate oil: 100 parts of (A);
styrene-butadiene rubber: 5-30 parts, preferably 10-20 parts;
modifying agent: 2-8 parts, preferably 3-6 parts;
auxiliary agent: 0.5-3 parts, preferably 0.5-2 parts;
catalyst: 0.01 to 0.5, preferably 0.01 to 0.2 parts.
3. The 90A road petroleum asphalt of claim 2, characterized in that: the mass content of aromatic hydrocarbon of the aromatic hydrocarbon-rich distillate oil is 30-90%, the initial boiling point of the boiling range of the aromatic hydrocarbon-rich distillate oil is 300-315 ℃, the final boiling point of the aromatic hydrocarbon-rich distillate oil is 440-478 ℃, one or more of first-line-reduced extract oil, second-line-reduced extract oil, third-line-reduced extract oil and fourth-line-reduced extract oil are preferably selected and mixed, and one or more of third-line-reduced extract oil and fourth-line-reduced extract oil are further preferably selected and mixed.
4. The 90A road petroleum asphalt of claim 2, characterized in that:
the styrene butadiene rubber is one or the mixture of low-temperature poly-emulsion butadiene styrene rubber and solution-polymerized styrene butadiene rubber;
the modifier is one or a mixture of acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate, ethyl methacrylate, maleimide, fumaric acid, itaconic acid, citraconic acid, monomethyl maleate, dimethyl maleate, maleoyl chloride and alpha-ethacrylic acid;
the auxiliary agent is one or a mixture of more of diethylene glycol, 1, 4-butanediol, triethylene glycol, dipropylene glycol, polyethylene glycol 400, polyethylene glycol 2000, pentaerythritol, sorbitol and tetraethylene glycol;
the catalyst is one or a mixture of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptonitrile.
5. The 90A road petroleum asphalt of claim 1, characterized in that: the properties of the normal slag comprise: the flash point is 246-258 ℃, the sulfur content is 2.77-3.63 wt%, the saturated component accounts for 26.1-37.7 wt%, the aromatic component accounts for 20.2-34.5 wt%, the colloid accounts for 18.3-24.8 wt%, the asphaltene accounts for 21.3-30.1 wt%, and the asphaltene is preferably 21.3-25.0 wt%.
6. The 90A road petroleum asphalt of claim 1, characterized in that: the normal slag has the following properties: the carbon residue value is 19-28 wt%, the total content of nickel and vanadium is 310-365 mug/g, and the condensation index CI is 0.22-0.30.
7. The 90A road petroleum asphalt of claim 1, characterized in that: the polyphosphoric acid comprises a first polyphosphoric acid and a second polyphosphoric acid, the first polyphosphoric acid is polyphosphoric acid with high phosphoric acid content, the second polyphosphoric acid is polyphosphoric acid with low phosphoric acid content, the polyphosphoric acid with high phosphoric acid content accounts for 50% -80% of the total mass of the polyphosphoric acid, and the polyphosphoric acid with low phosphoric acid content accounts for 20% -50% of the total mass of the polyphosphoric acid.
8. The 90A road petroleum asphalt of claim 7, characterized in that: the polyphosphoric acid with low phosphoric acid content refers to phosphoric acid contained in polyphosphoric acid, and H is used as H3PO4The mass content is 105-125%, preferably 110-120%; the high-phosphoric-acid-content polyphosphoric acid refers to polyphosphoric acidPhosphoric acid contained, as H3PO4The mass content is 130-145%, preferably 130-140%.
9. The 90A road petroleum asphalt of claim 1, characterized in that: the initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium metabisulfite, azobisisobutyronitrile, azobisisoheptonitrile and cumene hydroperoxide.
10. The 90A road petroleum asphalt of claim 1, characterized in that: the component regulator is one or more of coker gas oil, extract oil, catalytic slurry oil and coker circulating oil; the component regulator comprises, by mass, 25-50% of a saturated component, 30-60% of an aromatic component, 10-30% of a colloid, and 0-3% of an asphaltene, wherein the boiling range of the component regulator is from 295-310 ℃ at an initial boiling point and from 430-455 ℃ at a final boiling point.
11. A method for producing 90A road petroleum asphalt according to any one of claims 1 to 10, characterized by comprising the steps of:
(1) preparing a low-temperature ductility enhancer;
(2) adding the normal slag and the first polyphosphoric acid which are heated to flow states into a reaction kettle, continuously stirring and heating to a reaction temperature, reacting under a protective gas, and carrying out heat preservation treatment after the reaction is finished;
(3) adding a second polyphosphoric acid, an initiator and a component regulator into the material obtained in the step (2), uniformly stirring, and then shearing;
(4) carrying out reduced pressure distillation on the material sheared in the step (3) to obtain slag reduction;
(5) and (3) adding the low-temperature ductility agent prepared in the step (1) into the slag reduction obtained in the step (4), shearing again, then developing under stirring, and obtaining the 90A road petroleum asphalt after the development is finished.
12. The method of claim 11, wherein: the low-temperature ductility agent in the step (1) is prepared by adopting the following method:
after being crushed, styrene butadiene rubber is added into preheated aromatic hydrocarbon-rich distillate oil and is sheared under the heating condition to obtain a pre-modifier; and reacting the obtained pre-modifier with a modifier and a catalyst in an inert atmosphere, adding an auxiliary agent after the reaction is finished, stirring for development, preserving heat after the development is finished, and preserving heat to obtain the low-temperature ductility enhancer.
13. The method of manufacturing according to claim 12, wherein: the particle size of the pulverized styrene butadiene rubber is 0.1-3.0 cm, preferably 0.1-1 cm; preheating aromatic hydrocarbon-rich distillate oil at the temperature of 100-110 ℃, shearing at the temperature of 120-140 ℃, shearing at the speed of 2000-5000 r/min, preferably 3000-4500 r/min, and shearing for 40-120 min, preferably 40-80 min; the weight ratio of the styrene butadiene rubber to the aromatic-rich oil is (5-30): 100, preferably (10-20): 100; the reaction maintaining pressure is 0.5-1.0 MPa, the reaction time is 3-5 h, the reaction temperature is 120-150 ℃, and the stirring speed in the reaction process is 600-1000 r/min.
14. The method of claim 11, wherein: in the step (2), the first polyphosphoric acid added is polyphosphoric acid with a high phosphoric acid content, which means phosphoric acid contained in polyphosphoric acid, and H is used as H3PO4The mass content is 130-145%, preferably 130-140%, and the adding amount of the first polyphosphoric acid is 50-80% of the total mass of the polyphosphoric acid.
15. The method of claim 11, wherein: in the step (2), the heating to the reaction temperature is realized by adopting temperature programming heating to the reaction temperature, the heating rate is 1-3 ℃/min, and the heating is carried out to 130-150 ℃, preferably 135-150 ℃.
16. The method of claim 11, wherein: in the step (2), the protective gas is inert gas and/or N2The amount of the protective gas is used for maintaining the pressure in the reaction kettle to be 0.20.9MPa, preferably 0.3-0.8 MPa; the reaction time is 3-6 h; the heat preservation treatment condition is that the heat preservation is carried out for 8-12 hours at the temperature of 80-110 ℃.
17. The method of claim 11, wherein: in the step (3), the second polyphosphoric acid added is polyphosphoric acid with a low phosphoric acid content, which means phosphoric acid contained in polyphosphoric acid, and H is used as H3PO4The mass content is 105-125%, preferably 110-120%, and the adding amount of the second polyphosphoric acid is 20-50% of the total mass of the polyphosphoric acid.
18. The method of claim 11, wherein: in the step (3), the shearing speed is 2000-4000 r/min, the shearing time is 40-100 min, and the temperature required by shearing is 130-150 ℃.
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Effective date of registration: 20231120 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |