CN110437632B - Modifier mother liquor and road asphalt and preparation method thereof - Google Patents

Modifier mother liquor and road asphalt and preparation method thereof Download PDF

Info

Publication number
CN110437632B
CN110437632B CN201810420564.9A CN201810420564A CN110437632B CN 110437632 B CN110437632 B CN 110437632B CN 201810420564 A CN201810420564 A CN 201810420564A CN 110437632 B CN110437632 B CN 110437632B
Authority
CN
China
Prior art keywords
parts
mother liquor
modifier
stirring
anthracene oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810420564.9A
Other languages
Chinese (zh)
Other versions
CN110437632A (en
Inventor
徐青柏
陈杰
宣根海
宁爱民
李志军
程国香
申峻
侯荣国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201810420564.9A priority Critical patent/CN110437632B/en
Publication of CN110437632A publication Critical patent/CN110437632A/en
Application granted granted Critical
Publication of CN110437632B publication Critical patent/CN110437632B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/329Phosphorus containing acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Working-Up Tar And Pitch (AREA)

Abstract

The invention discloses a modifier mother liquor, road asphalt and a preparation method thereof. The modifier mother liquor comprises the following raw materials in parts by weight: 78-94 parts of modified anthracene oil, 0.4-3.5 parts of polyphosphoric acid and 4-20 parts of SBS. The modified anthracene oil in the modifier mother liquor is obtained by modifying anthracene oil by adopting long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid, so that the flexibility of the modified anthracene oil is improved. And secondly, performing condensation modification on the modified anthracene oil by using polyphosphoric acid, particularly modifying the anthracene oil by using a two-step method so as to enable the anthracene oil to reach a proper condensation degree. The mother liquid of the modifier is matched with petroleum asphalt and coal asphalt to prepare road asphalt, so that the colloid structure of a road asphalt product is more reasonable, the high and low temperature performances of the asphalt are enhanced, and the toxicity of the asphalt is reduced.

Description

Modifier mother liquor and road asphalt and preparation method thereof
Technical Field
The invention belongs to the technical field of chemical industry, mainly relates to a modifier mother liquor and road asphalt and a preparation method thereof, and particularly relates to a preparation method of road asphalt produced by taking coal asphalt and petroleum asphalt as raw materials.
Background
With the continuous expansion of highway construction scale, the demand of road asphalt market is also increased at a high speed. Currently, petroleum resources are increasingly deficient, while coal tar pitch (coal pitch) has a low added value in processing and a market price of about half of that of petroleum pitch, and therefore researchers are constantly researching whether coal pitch can be used as a raw material for producing road pitch. The coal tar pitch produced by the traditional method has the defects of poor heat sensitivity, easy aging, poor ductility and the like, and can not meet the requirements of road engineering construction. Aiming at the defects of the coal tar pitch in the service performance, the coal tar pitch and the petroleum pitch are mixed, so that the performance of the road asphalt material can be improved, and the method is one of feasible practical technologies.
The modified petroleum asphalt prepared by taking SBS as a polymer modifier improves the high-low temperature performance and the temperature sensitivity of the petroleum road asphalt due to the modification effect of SBS, so that the bearing capacity and the fatigue resistance of the modified asphalt pavement are improved.
CN101985526A discloses a composite modified asphalt for high-grade roads and a preparation method thereof, which is a method for preparing the composite modified asphalt by adopting 69-90% of petroleum asphalt, 5-30% of coal asphalt, 1-10% of styrene-butadiene-styrene block copolymer and the like, and the preparation process comprises the steps of heating the petroleum asphalt, the coal asphalt, the styrene-butadiene-styrene block copolymer and the like together, grinding by a colloid mill, stirring and developing to prepare a target product. The conventional production process of the modified asphalt is adopted to grind and shear all materials, the grinding time is long, the power consumption is high, and the asphalt flexibility is poor, the elasticity and the low-temperature performance are poor and the thermal storage stability is poor due to the fact that the asphalt content of the coal asphalt is too high, the number of rubber cores in an asphalt colloid structure is too much, and the colloid structure composition of the asphalt is influenced.
CN103694716A discloses a modified coal pitch and a preparation method thereof, which is a method for preparing modified pitch by adopting 10-20 parts of petroleum pitch, 50-30 parts of coal pitch, 1-4 parts of SBS, 5-35 parts of waste rubber powder, 0.5-1 part of flame retardant and the like. In the method, the coal tar pitch accounts for a relatively high proportion (50-30 parts of coal tar pitch), the petroleum pitch accounts for a relatively small proportion (10-20 parts of petroleum pitch), and meanwhile, due to the fact that the asphaltene content of the coal tar pitch is too high (generally more than 20%), the asphaltene content in an asphalt colloid structure is too high, the asphalt colloid composition is unreasonably matched, the asphalt flexibility is poor, and the low-temperature performance and the heat storage stability are poor. In addition, the addition of 5 to 35 parts of waste rubber powder to asphalt results in excessively high blending temperature and poor thermal storage stability of asphalt. The preparation process comprises the steps of premixing the petroleum asphalt, the coal asphalt and the cosolvent with SBS, grinding by a colloid mill, and grinding the components with larger proportion such as the petroleum asphalt, the coal asphalt, the cosolvent and SBS by the colloid mill in the grinding process, wherein the grinding amount is large and the power consumption is large.
Neither of the above techniques addresses the detoxification properties of bitumen.
CN102585527A discloses a modified coal pitch and a preparation method thereof, wherein 70-80% of petroleum pitch, 10-20% of coal pitch and 10-20% of diatomite are subjected to hot-melt mixing, the prepared mixed pitch has good adhesiveness, the dynamic stability of the prepared asphalt mixture is improved by 3-4 times, and the anti-rutting capability is improved. Meanwhile, the diatomite is adopted to adsorb unsaturated aromatic hydrocarbons such as naphthalene and phenol contained in the coal tar pitch, so that the toxicity of the coal tar pitch is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modifier mother liquor, road asphalt and a preparation method thereof, in particular to road asphalt produced by coal asphalt and petroleum asphalt raw materials and a preparation method thereof. The mother liquid of the modifier is matched with petroleum asphalt and coal asphalt to prepare road asphalt, so that the colloid structure of a road asphalt product is more reasonable, the high and low temperature performances of the asphalt are enhanced, and the toxicity of the asphalt can be reduced.
The invention provides a modifier mother solution, which comprises the following raw materials in parts by weight:
78 to 94 parts of modified anthracene oil, preferably 80 to 92 parts,
0.4 to 3.5 parts of polyphosphoric acid, preferably 0.8 to 3.2 parts,
4 to 20 parts of SBS, preferably 6 to 18 parts,
wherein the modified anthracene oil is obtained by modifying anthracene oil with long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid.
The modified anthracene oil comprises the following raw materials in parts by weight:
75-98 parts of anthracene oil, preferably 85-95 parts,
2-25 parts of long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid, preferably 5-15 parts,
0.5-6 parts of catalyst, preferably 1-5 parts.
The distillation range of the anthracene oil is 300-385 ℃, and the preferred distillation range is 320-360 ℃.
The carbon number of the long-chain fatty olefine aldehyde is 10-20, and the long-chain fatty olefine aldehyde is preferably one or a mixture of undecene aldehyde, dodecenal, tridecene aldehyde, tetradecene aldehyde, hexadecene aldehyde and octadecene aldehyde.
The carbon number of the long-chain fatty olefine acid is 10-20, and the long-chain fatty olefine acid is preferably one or a mixture of more of undecylenic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, hexadecenoic acid and octadecenoic acid.
The catalyst is one or a mixture of more of sodium bisulfate, potassium bisulfate and phosphotungstic acid.
The method for preparing the modified anthracene oil comprises the following steps: adding anthracene oil into a reaction kettle, adding long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid and a catalyst, heating and raising the temperature, controlling the reaction temperature to be 150-270 ℃, preferably 160-260 ℃, stirring for 0.5-5.0 hours at the stirring speed of 200-1000 rpm, and obtaining the modified anthracene oil.
The molecular weight of SBS is 10-20 ten thousand, and it is linear structure or star structure.
The polyphosphoric acid concentration of the polyphosphoric acid is 105-116 wt%.
In a second aspect, the present invention provides a process for preparing a modifier mother liquor, comprising:
(1) adding the modified anthracene oil into a reaction kettle, adding part of polyphosphoric acid, heating to raise the temperature, controlling the reaction temperature to be 80-140 ℃, preferably 90-130 ℃, and stirring;
(2) heating continuously, adding the rest polyphosphoric acid, controlling the reaction temperature to be 120-220 ℃, preferably 140-180 ℃, and stirring to obtain a modified mother liquor intermediate;
(3) and adding SBS into the reaction kettle, controlling the temperature of the reaction kettle to be 120-180 ℃, preferably 140-160 ℃, and stirring to obtain the modifier mother liquor.
In the method for preparing the modifier mother liquor, part of polyphosphoric acid is added in the step (1), and the rest polyphosphoric acid is added in the step (2), wherein the mass ratio of the polyphosphoric acid added in the step (1) to the polyphosphoric acid added in the step (2) is 1: 3-2: 3.
in the method for preparing the modifier mother liquor, the stirring time in the step (1) is 0.5-5.0 hours, and the stirring speed is 200-1000 rpm.
In the method for preparing the modifier mother liquor, the stirring time in the step (2) is 0.5-5.0 hours, and the stirring speed is 200-2000 rpm.
In the method for preparing the modifier mother liquor, the stirring time in the step (3) is 1-10 hours, and the stirring speed is 2000-6000 rpm.
The third aspect of the invention provides road asphalt, which comprises the following raw materials in parts by weight:
5-40 parts of coal tar pitch,
50-70 parts of petroleum asphalt,
8-20 parts of modifier mother liquor.
The coal pitch is medium-temperature coal pitch with the asphaltene content of less than 30wt%, and the softening point is 72-95 ℃.
The petroleum asphalt has an asphaltene content of less than 10wt% and a softening point of 40-50 ℃.
The fourth aspect of the invention also provides a preparation method of the road asphalt, which comprises the following steps:
adding coal pitch, petroleum pitch and the modifier mother liquor into a reaction kettle, and stirring for 1-10 hours at the temperature of 100-180 ℃ and preferably at the temperature of 120-160 ℃ at the stirring speed of 500-4000 revolutions per minute to obtain a road pitch product.
The modifier mother liquor prepared by the method can be used for modifying finished road asphalt, building asphalt and petroleum fraction heavy distillate oil.
The modifier mother liquor is characterized in that the long-chain fatty olefine aldehyde or/and the long-chain fatty olefine acid contains independent carbonyl, has high relative activity, can mainly perform complex chemical reactions such as nucleophilic addition reaction of the carbonyl with anthracene oil, and improves the flexibility of the modified anthracene oil. And secondly, performing condensation modification on the modified anthracene oil by using polyphosphoric acid, particularly modifying the anthracene oil by using a two-step method so as to enable the anthracene oil to reach a proper condensation degree. The mother liquid of the modifier is matched with petroleum asphalt and coal asphalt to prepare road asphalt, so that the colloid structure of a road asphalt product is more reasonable, the high and low temperature performances of the asphalt are enhanced, and the toxicity of the asphalt is reduced.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to examples, which are only used for illustrating the present invention and should not be construed as limiting the scope of the present invention. In the invention, the parts are parts by weight, and the wt% is mass fraction.
Example 1
Adding 90 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 10 parts of undecylenic aldehyde and 4 parts of potassium bisulfate, heating, controlling the reaction temperature at 210 ℃, stirring for 3 hours at the stirring speed of 500 rpm, and obtaining the modified anthracene oil A1.
84 parts of modified anthracene oil is added into a reaction kettle, 0.9 part of polyphosphoric acid (the concentration of polyphosphoric acid is 110wt percent, the same is applied below) is added, the temperature is heated to 110 ℃, and the mixture is stirred for 2 hours. And continuously heating to about 160 ℃, adding 1.8 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.
12 parts of SBS (star structure, molecular weight of 15 ten thousand, the same below) is added into the modified anthracene oil A1, and the mixture is heated to 150 ℃ and stirred for 5 hours to obtain the modifier mother liquor A2.
Example 2
Adding 94 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 13 parts of undecylenic aldehyde and 3 parts of sodium bisulfate, heating, controlling the reaction temperature to be 250 ℃, stirring for 3 hours at the stirring speed of 500 revolutions per minute, and obtaining the modified anthracene oil A3.
Adding 81 parts of modified anthracene oil into a reaction kettle, adding 0.4 part of polyphosphoric acid, heating to 100 ℃, and stirring for 2 hours. And continuously heating to about 150 ℃, adding 1.1 part of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.
Adding 14 parts of SBS into the modified anthracene oil A3, heating to 155 ℃, and stirring for 6 hours to obtain the modifier mother liquor A4.
Example 3
Adding 86 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 7 parts of undecylenic aldehyde and 4 parts of potassium bisulfate, heating, controlling the reaction temperature at 180 ℃, stirring for 3 hours at the stirring speed of 500 rpm, and obtaining the modified anthracene oil A5.
Adding 84 parts of modified anthracene oil into a reaction kettle, adding 0.9 part of polyphosphoric acid, heating to 110 ℃, and stirring for 2 hours. And continuously heating to 160 ℃, adding 2.1 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.
Adding 10 parts of SBS into the modified anthracene oil A5, heating to 150 ℃, and stirring for 6 hours to obtain the modifier mother liquor A6.
Example 4
Adding 90 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 10 parts of undecylenic acid and 4 parts of phosphotungstic acid, heating, raising the temperature, controlling the reaction temperature to be 180 ℃, stirring for 3 hours at the stirring speed of 500 rpm, and obtaining the modified anthracene oil A7.
Adding 84 parts of modified anthracene oil into a reaction kettle, adding 0.9 part of polyphosphoric acid, heating to 110 ℃, and stirring for 2 hours. And continuously heating to 160 ℃, adding 1.8 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.
Adding 12 parts of SBS into the modified anthracene oil A1, heating to 150 ℃, and stirring for 5 hours to obtain the modifier mother liquor A8.
Example 5
60 parts of petroleum asphalt M1 (the content of asphaltene is 8 wt%) with the softening point of 45 ℃ and 20 parts of coal asphalt N1 (the content of asphaltene is 24 wt%) with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor A2 are added, the rotating speed of a stirrer is 2500 revolutions per minute, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Example 6
68 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 36 parts of coal asphalt N2 (the content of asphaltene is 20 wt%) with the softening point of 78 ℃ are heated to 120 ℃, 18 parts of modifier mother liquor A2 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Example 7
52 parts of petroleum asphalt M2 (the content of asphaltene is 9 wt%) with the softening point of 47 ℃ and 10 parts of coal asphalt N3 (the content of asphaltene is 22 wt%) with the softening point of 82 ℃ are heated to 160 ℃, 10 parts of modifier mother liquor A4 are added, the rotating speed of a stirrer is 2500 revolutions per minute, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Example 8
68 parts of petroleum asphalt M3 (the content of asphaltene is 6 wt%) with the softening point of 43 ℃ and 20 parts of coal asphalt N2 with the softening point of 78 ℃ are heated to 120 ℃, 10 parts of modifier mother liquor A6 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Example 9
60 parts of petroleum asphalt M1 (the content of asphaltene is 8 wt%) with the softening point of 45 ℃ and 20 parts of coal asphalt N1 (the content of asphaltene is 24 wt%) with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor A8 are added, the rotating speed of a stirrer is 2500 revolutions per minute, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Comparative example 1
Adding 84 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 0.9 part of polyphosphoric acid, heating to 110 ℃, and stirring for 2 hours. And continuously heating to 160 ℃, adding 1.8 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.
And adding 12 parts of SBS into the modified mother liquor intermediate, heating to 150 ℃, and stirring for 5 hours to obtain the modifier mother liquor DA 1.
60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal asphalt N1 with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor DA1 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Comparative example 2
84 parts of modified anthracene oil A1 obtained in example 1 is added into a reaction kettle, 12 parts of SBS is added, the temperature is heated to about 150 ℃, and the mixture is stirred for 5 hours to obtain modifier mother liquor DA 2.
60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal asphalt N1 with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor DA2 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Comparative example 3
84 parts of modified anthracene oil A1 obtained in example 1 was charged in a reaction vessel, 2.7 parts of polyphosphoric acid and 12 parts of SBS were added, the mixture was heated to about 160 ℃ and stirred for 2 hours to obtain modifier mother liquor DA 3.
60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal asphalt N1 with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor DA3 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Comparative example 4
Adding 81 parts of furfural aromatic hydrocarbon extract oil into a reaction kettle, adding 0.4 part of polyphosphoric acid, heating to about 100 ℃, and stirring for 2 hours. And continuously heating to 150 ℃, adding 1.1 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.
And adding 14 parts of SBS into the modified mother liquor intermediate, heating to 155 ℃, and stirring for 6 hours to obtain the modifier mother liquor DA 4.
52 parts of petroleum asphalt M2 with the softening point of 47 ℃ and 10 parts of coal pitch N3 with the softening point of 82 ℃ are heated to 160 ℃, 10 parts of modifier mother liquor DA4 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.
Comparative example 5
60 parts of petroleum asphalt M1 with a softening point of 45 ℃ and 20 parts of coal asphalt N1 with a softening point of 86 ℃ are heated to 140 ℃, 10.3 parts of anthracene oil, 1.1 parts of undecylenic aldehyde, 0.5 part of potassium hydrogen sulfate, 0.4 part of polyphosphoric acid and 1.7 parts of SBS are added, and stirring is carried out at a stirrer rotating speed of 2500 revolutions per minute for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product. The starting materials were the same as in examples 1 and 5.
Comparative example 6
60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal pitch N1 with the softening point of 86 ℃ are heated to 140 ℃, 10.3 parts of anthracene oil, 1.1 parts of undecylenic acid, 0.5 part of phosphotungstic acid, 0.4 part of PPA and 1.7 parts of SBS are added, and the mixture is stirred at the rotating speed of 2500 revolutions per minute for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product. The starting materials were the same as in examples 4 and 9.
TABLE 1 Properties of road asphalt products obtained in examples and comparative examples
Numbering Example 5 Example 6 Example 7 Example 8 Example 9
Penetration at 25 ℃ of 1/10mm 60 59 64 61 63
Softening point, DEG C 51.9 52.5 51.1 51.6 51.4
Ductility, cm at 10 ℃ 112 102 126 106 112
Fluoranthene removal rate% 69 65 72 61 66
TABLE 2 Properties of the road asphalt product obtained in the comparative example
Numbering Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
Penetration at 25 ℃ of 1/10mm 73 77 65 72 65 67
Softening point, DEG C 48.0 46.3 50.5 47.0 49.1 48.8
Ductility, cm at 10 ℃ 70 94 67 50 78 78
Fluoranthene removal rate% 9 39 41 3 36 34

Claims (25)

1. The modifier mother liquor comprises the following raw materials in parts by weight:
78-94 parts of modified anthracene oil,
0.4 to 3.5 parts of polyphosphoric acid,
4 to 20 parts of SBS (styrene butadiene styrene),
the modified anthracene oil is obtained by modifying anthracene oil with long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid;
the preparation method of the modifier mother liquor comprises the following steps:
(1) adding the modified anthracene oil into a reaction kettle, adding part of polyphosphoric acid, heating, raising the temperature, controlling the reaction temperature to be 80-140 ℃, and stirring;
(2) heating continuously, adding the rest polyphosphoric acid, controlling the reaction temperature to be 120-220 ℃, and stirring to obtain a modified mother liquor intermediate;
(3) and adding SBS into the reaction kettle, controlling the temperature of the reaction kettle to be 120-180 ℃, and stirring to obtain the modifier mother liquor.
2. The modifier mother liquor as set forth in claim 1, wherein: the using amount of the modified anthracene oil is 80-92 parts; the dosage of the polyphosphoric acid is 0.8-3.2 parts; the amount of SBS is 6-18 parts.
3. The modifier mother liquor as set forth in claim 1, wherein: the modified anthracene oil comprises the following raw materials in parts by weight:
75-98 parts of anthracene oil;
2-25 parts of long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid;
0.5-6 parts of a catalyst.
4. The modifier mother liquor as set forth in claim 3, wherein: the using amount of the anthracene oil is 85-95 parts; 5-15 parts of long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid; the amount of the catalyst is 1-5 parts.
5. Modifier liquor as claimed in claim 1 or 3, wherein: the distillation range of the anthracene oil is 300-385 ℃.
6. Modifier liquor as claimed in claim 1 or 3, wherein: the distillation range of the anthracene oil is 320-360 ℃.
7. Modifier liquor as claimed in claim 1 or 3, wherein: the carbon number of the long-chain aliphatic olefine aldehyde is 10-20.
8. The modifier mother liquor as set forth in claim 7, wherein: the carbon number of the long-chain fatty olefine aldehyde is one or a mixture of more of undecene aldehyde, dodecenal, tridecene aldehyde, tetradecene aldehyde, hexadecene aldehyde and octadecene aldehyde.
9. Modifier liquor as claimed in claim 1 or 3, wherein: the carbon number of the long-chain fatty olefine acid is 10-20.
10. The modifier mother liquor as set forth in claim 9, wherein: the carbon number of the long-chain fatty olefine acid is one or a mixture of more of undecylenic acid, dodecenoic acid, tridecenoic acid, arachidonic acid, hexadecenoic acid and octadecenoic acid.
11. The modifier mother liquor as set forth in claim 3, wherein: the catalyst is one or a mixture of more of sodium bisulfate, potassium bisulfate and phosphotungstic acid.
12. The modifier mother liquor as set forth in claim 1 or 3, wherein the modified anthracene oil is prepared by a process comprising: adding anthracene oil into a reaction kettle, adding long-chain fatty olefine aldehyde or/and long-chain fatty olefine acid and a catalyst, heating, raising the temperature, controlling the reaction temperature to be 150-270 ℃, stirring for 0.5-5.0 hours, and stirring at the speed of 200-1000 rpm to obtain the modified anthracene oil.
13. The modifier mother liquor as set forth in claim 12, wherein: the reaction temperature is controlled to be 160-260 ℃.
14. The modifier mother liquor as set forth in claim 1, wherein: the molecular weight of SBS is 10-20 ten thousand, and it is linear structure or star structure.
15. The modifier mother liquor as set forth in claim 1, wherein: the polyphosphoric acid concentration of the polyphosphoric acid is 105-116 wt%.
16. The method for preparing the modifier mother liquor as claimed in any one of claims 1 to 15, comprising:
(1) adding the modified anthracene oil into a reaction kettle, adding part of polyphosphoric acid, heating, raising the temperature, controlling the reaction temperature to be 80-140 ℃, and stirring;
(2) heating continuously, adding the rest polyphosphoric acid, controlling the reaction temperature to be 120-220 ℃, and stirring to obtain a modified mother liquor intermediate;
(3) and adding SBS into the reaction kettle, controlling the temperature of the reaction kettle to be 120-180 ℃, and stirring to obtain the modifier mother liquor.
17. The method of claim 10, wherein: adding polyphosphoric acid in the steps (1) and (2) according to the mass ratio of 1: 3-2: 3.
18. the method of claim 16, wherein: in the step (1), the reaction temperature is controlled to be 90-130 ℃.
19. The method of claim 16, wherein: and (2) controlling the reaction temperature to be 140-180 ℃.
20. The method of claim 16, wherein: and (3) controlling the temperature of the reaction kettle to be 140-160 ℃.
21. A method according to any of claims 16 to 20, wherein: stirring for 0.5-5.0 hours in the step (1), and stirring at a speed of 200-1000 rpm; stirring for 0.5-5.0 hours in the step (2), and stirring at a speed of 200-2000 rpm; and (4) stirring for 1-10 hours at a stirring speed of 2000-6000 rpm.
22. The road asphalt comprises the following raw materials in parts by weight:
5-40 parts of coal tar pitch,
50-70 parts of petroleum asphalt,
8-20 parts of modifier mother liquor as claimed in any one of claims 1-15.
23. The road asphalt of claim 22, wherein: the coal pitch is medium-temperature coal pitch with the asphaltene content of less than 30wt%, and the softening point is 72-95 ℃; the content of asphaltene in the petroleum asphalt is less than 10wt%, and the softening point is 40-50 ℃.
24. A process for producing the road asphalt of any one of claims 22 to 23, comprising:
adding coal pitch, petroleum pitch and the modifier mother liquor of any one of claims 1 to 15 into a reaction kettle, and stirring for 1 to 10 hours at the temperature of 100 to 180 ℃ in the reactor at the stirring speed of 500 to 4000 revolutions per minute to obtain a road pitch product.
25. The method of claim 24, wherein: the temperature of the reactor is 120-160 ℃.
CN201810420564.9A 2018-05-04 2018-05-04 Modifier mother liquor and road asphalt and preparation method thereof Active CN110437632B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810420564.9A CN110437632B (en) 2018-05-04 2018-05-04 Modifier mother liquor and road asphalt and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810420564.9A CN110437632B (en) 2018-05-04 2018-05-04 Modifier mother liquor and road asphalt and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110437632A CN110437632A (en) 2019-11-12
CN110437632B true CN110437632B (en) 2021-05-04

Family

ID=68428031

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810420564.9A Active CN110437632B (en) 2018-05-04 2018-05-04 Modifier mother liquor and road asphalt and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110437632B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101418130A (en) * 2008-12-08 2009-04-29 桂希衡 Weathering resistant asphalt modifier and application technology thereof
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
CN104559232A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Chemically-modified hard asphalt and preparation method thereof
CN104593032A (en) * 2015-01-12 2015-05-06 中钢集团鞍山热能研究院有限公司 Environment-friendly asphalt and preparation method thereof
CN105018048A (en) * 2015-08-08 2015-11-04 天津市大港渤中石油助剂有限公司 Polymer modified asphalt of anti-collapse agent for drilling fluid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101418130A (en) * 2008-12-08 2009-04-29 桂希衡 Weathering resistant asphalt modifier and application technology thereof
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
CN104559232A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Chemically-modified hard asphalt and preparation method thereof
CN104593032A (en) * 2015-01-12 2015-05-06 中钢集团鞍山热能研究院有限公司 Environment-friendly asphalt and preparation method thereof
CN105018048A (en) * 2015-08-08 2015-11-04 天津市大港渤中石油助剂有限公司 Polymer modified asphalt of anti-collapse agent for drilling fluid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"用中温沥青调配燃料油的实践";李强 等;《山东化工》;20160430;第45卷(第7期);第25-30页 *

Also Published As

Publication number Publication date
CN110437632A (en) 2019-11-12

Similar Documents

Publication Publication Date Title
Ding et al. Development of bio oil and bio asphalt by hydrothermal liquefaction using lignocellulose
CN107778887B (en) Modified asphalt and preparation method thereof
CN110437632B (en) Modifier mother liquor and road asphalt and preparation method thereof
CN102690678B (en) Processing method of inferior heavy crude oil
CN104559245B (en) Warm mix asphalt and preparation method thereof
CN104559241B (en) Method for preparing road asphalt through catalytic slurry oil
CN101700990A (en) Method for preparing C9 petroleum resin with light color and high softening-point
CN105017782A (en) High-grade road asphalt and preparation method thereof
CN1995146A (en) Composite modified asphalt material for improving low-temperature ductility
CN103805221B (en) A kind of production method of high softening point bitumen
CN110437628B (en) Modifier mother liquor, road asphalt and synthesis method thereof
Cui et al. Chemical modification process of heavy residue from FCC slurry oil for producing high-grade paving asphalt
WO2015139017A2 (en) Use of an ester additive and paving grade asphalt in built up roofing asphalt composition manufacture
CN110437627B (en) Modifier mother liquor, road asphalt and preparation method thereof
CN108822885A (en) A kind of composite extractant and preparation method thereof for Fischer-Tropsch oil oxide removal
CN105985041A (en) Asphalt mixture additive and preparation method thereof
CN108059970B (en) Method for utilizing catalytic slurry oil
CN106590729B (en) A kind for the treatment of process of softening oil
CN101735847B (en) Method for producing rosin fuel oil
CN108384253B (en) Building asphalt prepared by hard deoiled asphalt
CN115197741A (en) Oil slurry modifier, application of oil slurry modifier in catalytic oil slurry, method for modifying catalytic oil slurry and prepared modified oil slurry
CN106221668A (en) A kind of process preparing high-quality electrode pitch binding agent
CN110437631A (en) A kind of modifying agent mother liquor, road asphalt and its preparation method
CN108070266A (en) A kind of Modified catalytic slurry oil and its method for preparing road asphalt
CN108059837A (en) A kind of modifying agent mother liquor and road asphalt and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230927

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.