CN106633943B - A kind of Warm-mix hard asphalt and preparation method thereof - Google Patents
A kind of Warm-mix hard asphalt and preparation method thereof Download PDFInfo
- Publication number
- CN106633943B CN106633943B CN201510730958.0A CN201510730958A CN106633943B CN 106633943 B CN106633943 B CN 106633943B CN 201510730958 A CN201510730958 A CN 201510730958A CN 106633943 B CN106633943 B CN 106633943B
- Authority
- CN
- China
- Prior art keywords
- warm
- pitch
- temperature
- mixing agent
- mix
- 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
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
Abstract
The present invention provides a kind of Warm-mix hard asphalt and preparation method thereof, the component including following mass fraction: 0.5 ~ 7 part of warm-mixing agent, 93 ~ 99.5 parts of matrix pitch.The warm-mixing agent is prepared using following methods: under the action of catalyst, macromolecule alkane first reacts to obtain intermediate under certain temperature and pressure with halogen simple substance；Aromatic naphtha is uniformly mixed to obtain aromatic hydrocarbons complexing components with complex compound；Then aromatic hydrocarbons complexing components are reacted at a certain temperature to obtain warm-mixing agent used in the present invention with intermediate.Warm-mixing agent used in Warm-mix hard asphalt of the invention can not only play warm mix effect to pitch, take into account the high temperature performance of pitch, and the thermal stability of pitch can be improved, and improve anti-aging property；The use temperature of pitch is reduced, pernicious gas occurrence quantity is reduced, improves the caking property of pitch.
Description
Technical field
The present invention relates to a kind of warm-mixed asphalts, and specifically a kind of Warm-mix hard asphalt and preparation method thereof, belongs to petroleum
Industry and basic material chemical field.
Background technique
Asphalt used in previous road engineering is generally divided into two types according to mix construction temperature: cold mixing drip
Green mixture CMA (Cold Mix Asphalt) and hot-mix asphalt mixture HMA (Hot Mix Asphalt).Cold-mix asphalt is mixed
Material is closed generally using emulsified asphalt or liquid asphalt and gather materials mix, making under normal temperature state, without to gathering materials and combine
Material is heated, and can save mass energy in this way.But cold-mix asphalt mixture early strength is lower, it is difficult to it is public to meet high speed
The requirement of the important engineerings such as road, Heavy Traffic road.Hot-mix asphalt mixture be widely used, the good mixing of pavement performance
Material.But in hot-mix asphalt mixture production process, pitch and building stones need the mix under 150 ~ 180 DEG C of hot conditions.No
Only consume a large amount of energy, and can generate in hot-mix asphalt mixture production process a large amount of flue dust and CO2, CO, SO2,
The pernicious gases such as NOx, flammable organic gas, not only pollute environment, but also influence the health of staff, meanwhile,
Mix under hot conditions also easily causes pitch and heat ageing occurs, and reduces active time of the pitch on road surface, shortens pitch
The service life on road surface.
It is energy saving to protect environment, extend the bituminous pavement service life, the developed countries such as later period the 1990s America and Europe open
The research of Warm-Mix Bitumen Mixture WMA (Warm Mix Asphalt) is opened up.The purpose is to by reducing mixing for asphalt
Temperature is closed, the energy consumption reduced in Process of Pitch Mixture Production is reached, reduces dust and harmful gas emission, while guaranteeing temperature
Mix workability of the asphalt with the pavement performance essentially identical with hot-mix asphalt mixture and construction.
There are mainly three types of modes for warm-mixed asphalt technology: first is that using the higher emulsified asphalt of evaporated residue content, 80
DEG C ~ 120 DEG C at a temperature of with building stones mix, which is about 30 DEG C ~ 50 DEG C low compared with the temperature of hot asphalt；Second is that in mixing mixture
When water (or aqueous solution of surfactant) and pitch are added simultaneously in mix tank, due to the presence of water, make asphalt foaming, reach
To viscosity reducing effect.But above two method can generate a large amount of vapor, easily cause equipment corrosion, mountain flour also frequently occurs
Conglomeration even causes mixing equipment blockage problem, makes troubles to production.Further, since remaining non-volatile moisture be retained in it is mixed
It closes in material, will affect mixture initial performance.The third method is that warm-mixing agent is added in pitch in advance, then takes and leads to
The same production method of normal hot-mix asphalt mixture is easy to be received by production unit convenient for operation.This kind of method passes through pre-
Warm-mixing agent is first added in pitch, is reduced the high temperature viscosity of pitch, is changed the viscosity-temperature curve of pitch, to reduce pitch
With the mix temperature of building stones, reach warm mix effect.But presently used warm-mixing agent is while reducing asphalt high-temperature viscosity, usually
Also the reduction that can cause 60 DEG C of viscosity of pitch, makes the high-temperature stability of asphalt incur loss；Or on the contrary, not reducing
When 60 DEG C of viscosity, the loss of pitch ductility can be caused, to reduce the cryogenic property of pitch.In short, presently used temperature
It mixes agent and is while making pitch reach warm mix effect, be high-temperature behavior to lose pitch or cryogenic property as cost.
CN201010233760.9 use alkylamine, amide, quaternary cationic surfactant and calcium chloride, water for
Warm-mixing agent is made in raw material.It is called " asphalt warm-mix agent " with it, is in fact exactly a kind of aqueous solution of surfactant.Preparing pitch
It is added in pitch when mixture, then adds building stones again.When being stirred together with pitch, this aqueous surfactant solution
It can foam after heated, drive pitch also to foam, play warm mix effect.But due to foaming effect, bumping is easily caused, operation is not
Just, vapor is also easy to cause equipment corrosion and mountain flour conglomeration occluding device, not susceptible to user acceptance.
CN200910069522.6 discloses a kind of warm-mixed asphalt additive and preparation method thereof, the additive be pass through by
Deionized water is added in the polyvinyl alcohol water solution being made into advance, then sequentially adds rosin quaternary ammonium salt, aromatic hydrocarbon quaternary ammonium salt
Emulsifier, aliphatic hydrocarbon quaternary ammonium salt emulsifier, nonionic surface active agent, stirring and dissolving, then the polyacrylamide that will be made into advance
Amine aqueous solution and triethanolamine are added, and mixing to is finished product after being uniformly dissolved.The additive can be substantially reduced pitch
Mix temperature, asphalt items pavement performance index also comply with requirement, but the additive not only complicated component, increase
The difficulty and cost of preparation, are unfavorable for practical application.Although and be added to the high temperature viscosity that can reduce pitch in pitch,
Simultaneously also bring along negative effect reduce pitch softening point and 60 DEG C of viscosity can make to have lost high-temperature stability
Road surface is easy to happen track or gathers around packet.
CN201110158370.4 discloses a kind of warm-mixed asphalt additive and preparation method thereof, is adopted in dicyandiamide solution
The additive formed with a kind of organic silicon modified by polyether polymer.40 DEG C of asphalt mixing temperature or so, and temperature can be effectively reduced
Pitch performance indexes is mixed not less than hot asphalt, but lacks relevant test method and instance data support.
CN200880116767.7 is prepared for asphalt warm-mix agent using surface active agent composition, wax component, resin Composition.Its
In surface active agent composition be amine, including diamines, polyamines, amide etc., using its lubricating action, play warm mix effect；Wax
Component includes vegetable wax, animal wax, mineral wax, amide waxe, oxidized wax etc., resin Composition include propolis and Petropols such as
Tall oil pitch, pine tar pitch, rosin, phenolic resin etc..Wax component and resin Composition play Efficient Adhesive Promotion, with make up due to
The loss of asphalt viscosity caused by above-mentioned surface active agent composition.Component used in the patent is excessive, although can use wherein
Surface active agent composition lubricating action, play warm mix effect, but be easily reduced 60 DEG C of viscosity of pitch, influence pitch
High-temperature stability can also reduce the caking property of pitch and building stones.Although the resin Composition such as rosin, phenolic resin etc. of addition can be more
The loss of the asphalt viscosity due to caused by above-mentioned surface active agent composition is mended, but the compatibility of resin Composition and pitch is bad, it is long
Time easily causes pitch layering when storing, simultaneously because its hardness is higher, can only improve the high-temperature behavior of pitch, and cannot change
The cryogenic property of kind pitch, easily causes pitch cold cracking, also will affect the caking property of pitch.
CN201310174417.5 is prepared for asphalt warm-mix agent using amides, aromatic naphtha, binder component.Acyl therein
Amine is ethylene double one or both of oleamides and erucyl amide, and the mix temperature of pitch is reduced using its lubricity；
Binder is dimethylamino propylamine, N- aminoethylpiperazine, diethylenetriamines, trien, tetren
One or more of.Method is will to be first uniformly mixed after amides and aromatic naphtha heating and melting, then adds binder, then stir
It mixes uniformly mixed.It is cooled to later thick, is granulated, dried, crushed, be sieved, obtain graininess of the partial size less than 20 mesh
Substance, as asphalt warm-mix agent.Amides are while reducing asphalt mixing temperature in the patent, it is easy to reduce the 60 of pitch
DEG C viscosity, influences the high-temperature stability of asphalt, can also reduce the caking property of pitch.Although taking doing for addition binder
Method, " promote the caking property of pitch and building stones or eliminate amide substance for the adverse effect of pitch and building stones caking property ",
But heating temperature is higher when in use for these binders, can generate a large amount of noxious vapors, and the smell is awful, influences environment, damage
The health of operator.
CN201010511415 describes a kind of oil-resistant road asphalt modifier and preparation method thereof.The oil resistivity road
Asphalt modifier includes 20 ~ 50 parts of styrene-ethylene/butylene-styrene block copolymer (SEBS), polyolefin in mass
10 ~ 30 parts of resin, 15 ~ 45 parts of macromolecule wax, rich in aromatic hydrocarbons extraction oil 10 ~ 30.Wherein macromolecule wax is Fischer-Tropsch wax, is rich in aromatic hydrocarbons
Extraction oil is furfural extract oil or phenol treating extraction oil.Preparation method is: material is launched in proportion to twin-screw extrusion
120 DEG C ~ 200 DEG C of extrusion temperature, oil-resistant road asphalt modifier is made in stretching and granulation in machine.The oil resistivity of the patent introduction
Asphalt modifier is to be directed to for pitch used in the places such as parking lot, airplane parking area, one developed to improve its oil resistivity
Kind of modifying agent, for the warm mix effect of pitch, there is no enough attention, in the process of development, only with twin-screw extrusion
Machine has carried out simple extrusion mixing, due to unsaturated bond limited amount on polymer molecule used, in Screw Extrusion
In only a small amount of graft reaction, enough chemical reactions do not occur, substantially a kind of simple physical mixed, for drip
Green warm mix effect is very limited.
CN201010558295 describes a kind of asphalt mixture warm-mixing modifier and preparation method thereof.It is by following quality
The composition of part is made, fischer-tropsch wax: 50 ~ 85 parts, plasticizer: 15 ~ 50 parts, polyacid: 0 ~ 10 part, synthetic resin: 0 ~ 20 part, gathering
Ester compounds: 0 ~ 5 part.Wherein, synthetic resin is polyisobutene of the molecular weight between 400 ~ 5000.Preparation method: (1) matter is pressed
Amount ratio weighs each component；(2) each component is melted and is stirred at 120 DEG C~130 DEG C, be allowed to be sufficiently mixed uniformly to get institute
The asphalt mixture warm-mixing modifier stated.In the warm-mixing agent development process, there is no changing to react between each component, only simply
Physical mixed.Although the mix temperature of pitch can be reduced, the ductility of pitch will receive loss i.e. asphalt
It is easy to happen cold cracking.
CN201110443825.7 discloses a kind of composition for warm-mix asphalt pavements, by the pitch of 91 ~ 94 mass %, 3 ~ 5 mass %
Thermoplastic elastomer (TPE), 2 ~ 4 mass % grafting rate be 4 ~ 10 mass % maleic anhydride grafted polyethylene wax (MA-g-PE), 0.1 ~ 1
The operation oil of quality %, viscosity of the composition at 135 DEG C are no more than 700cp, and the composition meets the anti-plasticity of high temperature simultaneously and becomes
The requirement of shape and anti-low-temperature cracking.But the 135 of the bituminous composition DEG C of viscosity are still very big, 135 DEG C of viscosity in embodiment are 675
Cp and 690 cp, and do not provide 135 DEG C of viscosity of matrix pitch and do not add pitch when MA-g-PE viscous as what is compared
Degree, can not know mix temperature reduces how many actually, only from the point of view of the 135 DEG C of viscosity numbers provided, and not up to warm mix effect.
CN201110169620.4 discloses a kind of Warm-mix hard asphalt and preparation method thereof, by the matrix of 91 ~ 94 mass %
The polyethylene wax grafting horse of pitch, the cracking polyethylene wax of 5 ~ 15 mass %, the Petropols of 5 ~ 10 mass %, 0.1 ~ 0.3 mass %
Carry out the silane coupling agent of acid anhydrides, 0.2 ~ 1.0 mass %.The needle penetration of the matrix pitch is 60 ~ 90(0.1mm), specific method is
Matrix pitch is melted, cracking polyethylene wax, Petropols, polyethylene wax grafted maleic anhydride, silane coupling agent is then added,
It stirs evenly, needle penetration is made as the Warm-mix hard asphalt of 20 ~ 35(0.1mm).
In existing warm-mixed asphalt preparation process, while reducing asphalt mixture mixing temperature, it will usually reduce pitch
60 DEG C of viscosity or ductility, to affect the high-temperature stability or low temperature anti-cracking performance of asphalt.How to use
A kind of special warm-mixing agent becomes without influencing its high and low temperature service performance while reducing asphalt mixing and forming temperature
A hot issue of warm-mixed asphalt is developed at present.
CN201510022090.9 discloses a kind of Warm-Mix Bitumen Mixture and preparation method thereof, used in warm mix
Agent is and to add halogen and catalyst preparation obtains using macromolecule alkane and aromatic naphtha as raw material.Although the patent is at certain
It solves the above problem in degree, but during preparing warm-mixing agent, since the reaction temperature of intermediate is low, and lacks catalysis
Agent, reaction speed is slower, and intermediate activity is lower, affects the extent of reaction of intermediate and aromatic naphtha, and reaction depth is not allowed yet
Easy to control, obtained warm-mixing agent property is unstable, affects the application effect in pitch.In addition, the warm-mixing agent is used to drip
In blueness, the poor problem of anti-aging property is had also appeared.
With Petroleum Processing Technology continuously improve and seeking results maximize, in petroleum refining process, often take
The techniques such as decompression residuum deep drawing and solvent deasphalting, keep the light component yield of decompression residuum higher and higher, can generate so a large amount of
25 DEG C of needle penetrations be 1 ~ 50(0.1mm) hard grades of bitumen, wherein needle penetration is 1 ~ 30(0.1mm) to can be used as building anti-for hard grades of bitumen
Water material, heating temperature when use are generally 175 DEG C ~ 185 DEG C；Needle penetration can be used as and build for 30 ~ 50(0.1mm) hard grades of bitumen
Pipeline material is used for hot area, and heating temperature when use is generally 160 DEG C ~ 170 DEG C.Due to using temperature higher, heating
Not only waste of energy when melting, but also a large amount of bitumen flue gas is generated, cause environmental pollution.With constantly mentioning for environmental requirement
Height is restricted the use of these hards grades of bitumen.It how to be reduced using temperature, the generation of bitumen flue gas is reduced, has become
For urgent problem to be solved.Further, since heating temperature is excessively high when using, make pitch that heat ageing sharply occur in a short time,
Cause hard grades of bitumen caking property poor, this problem is never well solved for many years.
Summary of the invention
Temperature drift is used to solve hard grades of bitumen in the prior art, though easily cause energy after environmental pollution or addition warm-mixing agent
It reduces and uses temperature, but the thermal stability of pitch and the bad problem of anti-aging property, the present invention provides a kind of warm mix hard drip
Blueness and preparation method thereof joined a kind of self-control warm-mixing agent, can be substantially reduced the use temperature of hard grades of bitumen, save the energy,
Pollution of the bitumen flue gas to environment is reduced, while heat ageing can also be mitigated, improves the caking property of pitch, can be improved the heat of pitch
Stability improves anti-aging property.
Technical purpose of the invention is achieved through the following technical solutions:
A kind of Warm-mix hard asphalt, the pitch include the component of following mass fraction:
0.5 ~ 7 part of warm-mixing agent
93 ~ 99.5 parts of matrix pitch
The warm-mixing agent is prepared using following methods:
A. halogen simple substance and catalyst will be added after macromolecule alkane heating melting, is passed through protection gas, reaction obtains centre
Body；
B. complex compound is added into aromatic naphtha, is uniformly mixing to obtain aromatic hydrocarbons complexing components；
C. by the intermediate in aromatic hydrocarbons complexing components steps for importing a described in step b, it is passed through protection gas, reaction obtains
The warm-mixing agent；
The macromolecule alkane is mixing macromolecule alkane of the alkane molar content of C30 ~ C130 90% or more；
The catalyst is selected from anhydrous CuCl2, anhydrous MnCl2, anhydrous CrCl3With anhydrous NiCl2At least one of；
The complex compound is selected from [Cu (NH3)4]SO4、[Pt(NH3)2]Cl2、K[Pt(C2H4)Cl3]、K4[Fe(CN)6]、K3
[Fe(CN)6]、Fe4[Fe(CN)6]3、Ni(CO)4、[Co(NH3)5Cl]SO4、(NH4)3[Cr(NCS)6At least one of].
Further, in the Warm-mix hard asphalt of above mass fraction composition, the additive amount of the warm-mixing agent is preferably 1
~ 7 parts.
Further, the macromolecule alkane is mixing macromolecule of the alkane molar content of C60 ~ C130 90% or more
Alkane, the macromolecule alkane are or mixtures thereof linear paraffin, branched paraffin.
Further, the macromolecule alkane will obtain preferably using metals such as Fe, Co, Ni as catalyst after coal gasification
The CO arrived, with H2Synthetic reaction is carried out, mixing macromolecule alkane of the alkane molar content that carbon number is 30 ~ 130 90% or more is obtained
Hydrocarbon.Wherein H2With CO carry out synthetic reaction when molar ratio be 2 ~ 2.5,320 DEG C ~ 340 DEG C of reaction temperature, pressure 2.0 ~
2.2MPa。
Further, reaction temperature when preparing intermediate in step a is 400 DEG C ~ 480 DEG C, and reaction pressure is 3 ~ 5MPa,
Reaction time is 30~60min.
Further, the dosage of halogen simple substance described in step a is 0.25 ~ 0.75 times of the molal quantity of macromolecule alkane,
The dosage of the catalyst is the 0.3%~0.9% of macromolecule alkane in mass.
Further, the halogen simple substance is selected from one of fluorine, chlorine and bromine, preferably chlorine or bromine.
Further, it is stirred at 270 DEG C ~ 350 DEG C of temperature in step b, mixing time is 120 ~ 180min.
Further, the aromatic naphtha is a kind of component rich in aromatic hydrocarbons, and wherein arene content is greater than as mass fraction
57%, preferably arene content is greater than 70%, can be that the line that subtracts four extraction oil, furfural extract oil, phenol treating extraction is oily or urges
Change the mixture of one or more of cracking slurry oil.The dosage of the complex compound is arene content in aromatic naphtha in mass
3%~9%.
Further, by the intermediate in aromatic hydrocarbons complexing components steps for importing a in step c, mixed proportion is with raw material
The quality meter of macromolecule alkane and aromatic naphtha is 1 ~ 7:7 ~ 1.Reaction temperature is 350 DEG C ~ 400 DEG C, and reaction pressure is 2 ~ 4MPa,
60 ~ 120min of reaction time.
Further, protection gas described in step a and c is nitrogen.
Further, the asphalt that the matrix pitch can select various crude oil and different process to produce, such as straight run
One or more of pitch, oxidized asphalt, solvent deoiling pitch.The matrix pitch is that 25 DEG C of needle penetrations are 1 ~ 50
The matrix pitch of (0.1mm).
The present invention also provides the preparation methods of Warm-mix hard asphalt, comprising the following steps: is first heated to matrix pitch
160 DEG C ~ 185 DEG C, warm-mixing agent is stirred and added, temperature is then reduced to 140 DEG C ~ 155 DEG C while stirring, continues constant temperature and stirs
It mixes, obtains the Warm-mix hard asphalt.
Further, cool down again after stirring 10 ~ 30min after addition warm-mixing agent, after cooling the temperature to 140 DEG C ~ 155 DEG C, after
The time of continuous constant temperature stirring is 10 ~ 30min.
Warm-mix hard asphalt of the present invention compared with prior art, has the advantages that
1, the warm-mixing agent used in the present invention is homemade warm-mixing agent, and intermediate is prepared under higher temperature, pressure and is increased
Add catalyst, not only shorten the reaction time, but also can steadily control reaction process, is easy to hold the performance of intermediate, make
Obtained warm-mixing agent performance is stablized.
2, during preparing warm-mixing agent, complex compound is added in aromatic naphtha and is stirred evenly, is then carried out again with intermediate
Reaction, obtained warm-mixing agent not only has warm mix effect to pitch, has taken into account the high temperature performance of pitch, but also also improves drip
Green thermal stability, improves anti-aging property.
3, Warm-mix hard asphalt of the present invention is low using temperature, saves the energy, while also reducing the occurrence quantity of pernicious gas,
It is good for the environment the health with operator.
4, Warm-mix hard asphalt of the present invention, due to using homemade warm-mixing agent, hence it is evident that reduce using temperature, than base
Matter pitch reduces by 20 DEG C ~ 30 DEG C using temperature；Heat ageing is alleviated, and improves the caking property of hard grades of bitumen and ductility.
Specific embodiment
In conjunction with following embodiments technical solution that the present invention will be described in detail, but the present invention is not limited to following embodiments.
Embodiment 1
(1) warm-mixing agent is prepared
Using Ni metal as catalyst, the CO that will be obtained after coal gasification, with H2Carry out synthetic reaction, obtain carbon number be 30 ~
60 alkane accounts for 90% mixed alkanes.
1. weighing above-mentioned mixed alkanes 1000g, about 1.2mol is placed in closed container, is heated to 480 DEG C, addition 3g is urged
The anhydrous CuCl of agent2, keep introducing the chlorine of 0.89 mol at a temperature of this, and being passed through nitrogen is maintained at the pressure of reaction vessel
3MPa, reaction 30min obtain intermediate；
2. weighing the line that subtracts four that arene content is 70% extracts oil 7000g out, thereto complex compound (the Cu of addition 441g
(NH3)4〕SO4, in another container and 350 DEG C are heated to, constant temperature stirs 180min at this temperature, obtains aromatic hydrocarbons complexing group
Point；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, keeping temperature is 400 DEG C, is maintained at pressure full of nitrogen
2MPa, isothermal reaction 60min obtain warm-mixing agent used in the present invention.Each group distribution ratio is shown in Table 1.
(2) Warm-mix hard asphalt is prepared
Above-mentioned warm-mixing agent 7kg is weighed, being added to the husky Crude Oil needle penetration that quality is 93 kg, temperature is 160 DEG C is 50
In the straight asphalt of (0.1mm), 10min is stirred, warm-mixing agent is merged sufficiently with pitch, then while stirring gradually drops temperature
As low as 140 DEG C, 10min is stirred, Warm-mix hard asphalt (number WBA-1) is obtained.It is shown in Table 2 using temperature, and pernicious gas occurs
Amount is shown in Table 3.
Embodiment 2
(1) warm-mixing agent is prepared
Using Co metal as catalyst, the CO that will be obtained after coal gasification, with H2Carry out synthetic reaction, obtain carbon number be 30 ~
130 alkane accounts for 90% mixed alkanes.
1. weighing above-mentioned mixed alkanes 3500g, about 4.5mol is placed in closed container, is heated to 400 DEG C, adds 31.5g
The anhydrous MnCl of catalyst2, the chlorine of introducing 1.16mol at a temperature of this is kept, and being passed through nitrogen is maintained at the pressure of reaction vessel
5MPa, reaction 60min obtain intermediate；
2. weighing the catalytic cracked oil pulp 1000g that arene content is 63%, the complex compound K of 19g is added thereto4〔Fe
(CN)6), in another container and 270 DEG C are heated to, constant temperature stirs 120min at this temperature, obtains aromatic hydrocarbons complexing components；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, keeping temperature is 350 DEG C, is maintained at pressure full of nitrogen
4MPa, isothermal reaction 120min obtain warm-mixing agent used in the present invention.Each group distribution ratio is shown in Table 1.
(2) Warm-mix hard asphalt is prepared
Above-mentioned warm-mixing agent 0.5kg is weighed, being added to the LIAOHE CRUDE needle penetration that quality is 99.5 kg, temperature is 165 DEG C is
In oxidized asphalt 25(0.1mm), stir 20min, merge warm-mixing agent sufficiently with pitch, then while stirring by temperature gradually
145 DEG C are reduced to, 20 min is stirred, obtains Warm-mix hard asphalt (number WBA-2).It is shown in Table 2 using temperature, pernicious gas hair
Raw amount is shown in Table 3.
Embodiment 3
(1) warm-mixing agent is prepared
Using Fe metal as catalyst, the CO that will be obtained after coal gasification, with H2Carry out synthetic reaction, obtain carbon number be 70 ~
90 alkane accounts for 90% mixed alkanes.
1. weighing above-mentioned mixed alkanes 1000g, about 0.8mol is placed in closed container, is heated to 440 DEG C, addition 6g is urged
The anhydrous NiCl of agent2, the fluorine of introducing 0.31mol at a temperature of this is kept, and being passed through nitrogen is maintained at the pressure of reaction vessel
4MPa, reaction 45min obtain intermediate；
2. weighing the phenol treating that arene content is 78% extracts oil 3500g out, the complex compound (Ni of 164g is added thereto
(CO)4), in another container and 310 DEG C are heated to, constant temperature stirs 160min at this temperature, obtains aromatic hydrocarbons complexing components；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, keeping temperature is 375 DEG C, is maintained at pressure full of nitrogen
3MPa, isothermal reaction 90min obtain warm-mixing agent used in the present invention.Each group distribution ratio is shown in Table 1.
(2) Warm-mix hard asphalt is prepared
Above-mentioned warm-mixing agent 4kg is weighed, being added to the Shengli crude needle penetration that quality is 96 kg, temperature is 180 DEG C is 1
In the solvent deoiling pitch of (0.1mm), stir 30min, merge warm-mixing agent sufficiently with pitch, then while stirring by temperature by
150 DEG C are gradually reduced to, 30 min is stirred, obtains Warm-mix hard asphalt (number WBA-3).It is shown in Table 2 using temperature, pernicious gas
Occurrence quantity is shown in Table 3.
Embodiment 4
(1) warm-mixing agent is prepared
Using Fe metal as catalyst, the CO that will be obtained after coal gasification, with H2Carry out synthetic reaction, obtain carbon number be 110 ~
130 alkane accounts for 90% mixed alkanes.
1. weighing above-mentioned mixed alkanes 7000g, about 4.2mol is placed in closed container, is heated to 400 DEG C, addition 21g is urged
The anhydrous CrCl of agent3, the bromine of introducing 1.15mol at a temperature of this is kept, and being passed through nitrogen is maintained at the pressure of reaction vessel
4MPa, reaction 45min obtain intermediate；
2. weighing the furfural extract oil 1000g that arene content is 57%, the complex compound (NH of 17g is added thereto4)3
〔Cr(NCS)6), in another container and 310 DEG C are heated to, constant temperature stirs 160min at this temperature, obtains aromatic hydrocarbons complexing
Component；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, makes 375 DEG C of temperature, be maintained at pressure full of nitrogen
3MPa, isothermal reaction 90min obtain warm-mixing agent used in the present invention.Each group distribution ratio is shown in Table 1.
(2) Warm-mix hard asphalt is prepared
Above-mentioned warm-mixing agent 1kg is weighed, being added to the Shengli crude needle penetration that quality is 99 kg, temperature is 185 DEG C is 3
In the solvent deoiling pitch of (0.1mm), stir 30min, merge warm-mixing agent sufficiently with pitch, then while stirring by temperature by
155 DEG C are gradually reduced to, 30 min is stirred, obtains Warm-mix hard asphalt (number WBA-4).It is shown in Table 2 using temperature, pernicious gas
Occurrence quantity is shown in Table 3.
Comparative example 1
(1) prepare warm-mixing agent (according to the method in CN201510022090.9)
To be carried out by raw material of natural gas the obtained carbon number of synthetic reaction be 130, molecular weight 1822, weight 700kg
Macromolecule alkane heating melting be placed in closed container, be heated to 400 DEG C, keep introducing at a temperature of this 115 moles of bromine,
180min is stirred, intermediate is obtained；The furfural extract oil 100kg that arene content is 57% is weighed, another closed container is mounted in
150 DEG C are inside heated to, adds the anhydrous FeCl of 0.17kg thereto3, stir 30min.It then will among the above under stirring
Mesosome is injected in furfural extract oil with mist, after all spraying into, 150 DEG C of constant temperature, is stirred to react 180min, is obtained pair
Compare warm-mixing agent.Each group distribution ratio is shown in Table 1.
(2) Warm-mix hard asphalt is prepared
Warm-mix hard asphalt is prepared according to method identical with the embodiment of the present invention 4.
Comparative example 2
Mixed alkanes 1kg same as Example 4 is weighed, the triumph that quality is 99kg, temperature is 185 DEG C is directly appended to
In solvent deoiling pitch of the crude oil needle penetration for 3(0.1mm), 30 min are stirred, a kind of hard grades of bitumen is obtained.It is seen using temperature
Table 2, pernicious gas occurrence quantity are shown in Table 3.
Comparative example 3
The furfural extract oil 1kg for being 57% by arene content, is directly appended to that quality is 99 kg, temperature is 185 DEG C
Shengli crude needle penetration be 3(0.1mm) solvent deoiling pitch in, stir 30 min, obtain a kind of hard grades of bitumen.It is used
Temperature is shown in Table 2, and pernicious gas occurrence quantity is shown in Table 3.
Comparative example 4
Weigh the furfural extract oil that mixed alkanes 0.875kg and arene content same as Example 4 are 57%
0.125kg, while being directly appended to the Shengli crude needle penetration that quality is 99kg, temperature is 185 DEG C is 3(0.1mm) solvent
In de-oiled asphalt, 30 min are stirred, a kind of hard grades of bitumen is obtained.It is shown in Table 2 using temperature, and pernicious gas occurrence quantity is shown in Table 3.
Table 1. prepares warm-mixing agent each group distribution ratio
The comparison of the Warm-mix hard asphalt of the present invention of table 2. and matrix pitch and comparative example
The comparison of 3. pernicious gas occurrence quantity of table
As can be seen from Table 2, the high temperature viscosity of Warm-mix hard asphalt of the present invention is all significantly lower than corresponding matrix pitch, can incite somebody to action
20 DEG C ~ 30 DEG C are reduced using temperature.Warm-mix hard asphalt of the present invention is compared with corresponding matrix pitch, the basic phase of needle penetration
Meanwhile softening point increases, 10 DEG C of ductilities increase, and illustrate Warm-mix hard asphalt of the present invention not only and can reach warm mix effect, Er Qie
Corresponding matrix pitch is better than in terms of high-temperature stability and low temperature ductility.In addition, caking property also be improved significantly.
By comparing example as it can be seen that directly simply mixing macromolecule alkane and/or extraction oil are added in hard grades of bitumen,
Improvement to pitch warm mix effect, hence it is evident that good not as good as warm mix effect of the present invention.
Seen from table 3, compared with matrix pitch and comparative example, Warm-mix hard asphalt of the present invention can obviously reduce pernicious gas
Occurrence quantity is good for the environment.
It is compared by film experimental result as it can be seen that the Warm-mix hard asphalt for using warm-mixing agent used in the present invention to obtain is anti-ageing
Change the pitch that performance is significantly better than any comparative example, i.e., warm-mixing agent of the present invention improves pitch while realizing warm mix effect
Thermal stability, improve anti-aging property, and warm-mixing agent used in comparative example 1 has negatively the anti-aging property of pitch
It influences.
Claims (7)
1. a kind of Warm-mix hard asphalt, it is characterised in that: the pitch includes the component of following mass fraction:
0.5 ~ 7 part of warm-mixing agent
93 ~ 99.5 parts of matrix pitch
The warm-mixing agent is prepared using following methods:
A. halogen simple substance and catalyst will be added after macromolecule alkane heating melting, is passed through protection gas, reaction obtains intermediate；
B. complex compound is added into aromatic naphtha, is uniformly mixing to obtain aromatic hydrocarbons complexing components；
C. it in the intermediate in aromatic hydrocarbons complexing components steps for importing a described in step b, will be passed through protection gas, reaction obtains described
Warm-mixing agent；
The macromolecule alkane is mixing macromolecule alkane of the alkane molar content of C30 ~ C130 90% or more；
The catalyst is selected from anhydrous CuCl2, anhydrous MnCl2, anhydrous CrCl3With anhydrous NiCl2At least one of；
The complex compound is selected from [Cu (NH3)4]SO4、[Pt(NH3)2]Cl2、K[Pt(C2H4)Cl3]、K4[Fe(CN)6]、K3[Fe
(CN)6]、Fe4[Fe(CN)6]3、Ni(CO)4、[Co(NH3)5Cl]SO4、(NH4)3[Cr(NCS)6At least one of]；
When preparing warm-mixing agent, the dosage of halogen simple substance described in step a is 0.25 ~ 0.75 times of the molal quantity of macromolecule alkane,
The dosage of the catalyst is the 0.3%~0.9% of macromolecule alkane in mass；
Arene content in aromatic naphtha described in step b is greater than 57% as mass fraction, and the dosage of the complex compound is with quality
Meter is 3%~9% of arene content in aromatic naphtha；
By in the intermediate in aromatic hydrocarbons complexing components steps for importing a in step c, mixed proportion is with raw material macromolecule alkane and virtue
The quality meter of hydrocarbon ils is 1 ~ 7:7 ~ 1.
2. Warm-mix hard asphalt according to claim 1, it is characterised in that: prepared when preparing warm-mixing agent, in step a intermediate
The reaction temperature of body is 400 DEG C ~ 480 DEG C, and reaction pressure is 3 ~ 5MPa, and the reaction time is 30~60min.
3. Warm-mix hard asphalt according to claim 1, it is characterised in that: when preparing warm-mixing agent, in temperature in step b
It is stirred at 270 DEG C ~ 350 DEG C, mixing time is 120 ~ 180min.
4. Warm-mix hard asphalt according to claim 1, it is characterised in that: when preparing warm-mixing agent, the reaction temperature of step c
It is 350 DEG C ~ 400 DEG C, reaction pressure is 2 ~ 4MPa, 60 ~ 120min of reaction time.
5. Warm-mix hard asphalt according to claim 1, it is characterised in that: the matrix pitch be 25 DEG C of needle penetrations be 1 ~
50 matrix pitch.
6. the preparation method of Warm-mix hard asphalt described in claim 1 ~ 5 any one, comprising the following steps: first drip matrix
Blueness is heated to 160 DEG C ~ 185 DEG C, stirs and add warm-mixing agent, and temperature is then reduced to 140 DEG C ~ 155 DEG C while stirring, continues
Constant temperature stirring, obtains the Warm-mix hard asphalt.
7. the preparation method of Warm-mix hard asphalt according to claim 6, it is characterised in that: stir 10 after warm-mixing agent is added
Cool down again after ~ 30min, after cooling the temperature to 140 DEG C ~ 155 DEG C, the time for continuing constant temperature stirring is 10 ~ 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510730958.0A CN106633943B (en) | 2015-11-02 | 2015-11-02 | A kind of Warm-mix hard asphalt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510730958.0A CN106633943B (en) | 2015-11-02 | 2015-11-02 | A kind of Warm-mix hard asphalt and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106633943A CN106633943A (en) | 2017-05-10 |
| CN106633943B true CN106633943B (en) | 2019-01-08 |
Family
ID=58810702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510730958.0A Active CN106633943B (en) | 2015-11-02 | 2015-11-02 | A kind of Warm-mix hard asphalt and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106633943B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110631961A (en) * | 2019-09-27 | 2019-12-31 | 深圳市市政工程总公司 | Method for determining optimal mixing amount of warm-mix agent of fiber warm-mix asphalt mixture |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532920A (en) * | 2010-12-17 | 2012-07-04 | 中国石油天然气股份有限公司 | Warm mixed asphalt cement and preparation method thereof |
| KR101178221B1 (en) * | 2012-04-24 | 2012-08-29 | 주식회사 대운 | Modifier for warm asphalt, manufacturing method of this and the asphalt mixture with this, manufacturing method of the same |
| CN102816448A (en) * | 2012-09-17 | 2012-12-12 | 山东建筑大学 | Warm-mixing heavy traffic asphalt and preparation method thereof |
| KR101439294B1 (en) * | 2013-10-22 | 2014-09-12 | 한국석유공업 주식회사 | Warm-mix asphalt additive composition and asphalt for low carbon dioxide green growth using the same |
| CN104591605A (en) * | 2015-01-16 | 2015-05-06 | 辽宁兆利高新路面材料有限公司 | Warm-mix asphalt mixture and preparation method thereof |
| CN104609790A (en) * | 2015-01-16 | 2015-05-13 | 辽宁兆利高新路面材料有限公司 | Warm mixing type anti-rutting asphalt mixture and preparation method thereof |
-
2015
- 2015-11-02 CN CN201510730958.0A patent/CN106633943B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532920A (en) * | 2010-12-17 | 2012-07-04 | 中国石油天然气股份有限公司 | Warm mixed asphalt cement and preparation method thereof |
| KR101178221B1 (en) * | 2012-04-24 | 2012-08-29 | 주식회사 대운 | Modifier for warm asphalt, manufacturing method of this and the asphalt mixture with this, manufacturing method of the same |
| CN102816448A (en) * | 2012-09-17 | 2012-12-12 | 山东建筑大学 | Warm-mixing heavy traffic asphalt and preparation method thereof |
| KR101439294B1 (en) * | 2013-10-22 | 2014-09-12 | 한국석유공업 주식회사 | Warm-mix asphalt additive composition and asphalt for low carbon dioxide green growth using the same |
| CN104591605A (en) * | 2015-01-16 | 2015-05-06 | 辽宁兆利高新路面材料有限公司 | Warm-mix asphalt mixture and preparation method thereof |
| CN104609790A (en) * | 2015-01-16 | 2015-05-13 | 辽宁兆利高新路面材料有限公司 | Warm mixing type anti-rutting asphalt mixture and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 有机降粘温拌沥青的研究进展;尚丽娜 等;《石油沥青》;20091225;第23卷(第6期);全文 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106633943A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104591605B (en) | A kind of Warm-Mix Bitumen Mixture and preparation method thereof | |
| CN106633947B (en) | A kind of warm mix polymer modified asphalt and preparation method thereof | |
| CN104774656B (en) | Method and apparatus for producing hydrocarbon fuel and compositionss | |
| CN106630763B (en) | Warm mix polymer modified asphalt mixture and preparation method thereof | |
| CN103554927A (en) | Compound asphalt warm-mixed viscosity reducer and preparation method thereof | |
| CN105861108A (en) | Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils | |
| CN101945934A (en) | Method for reducing hydrogen sulfide evolution from asphalt | |
| CN106630765B (en) | Warm-mix hard asphalt mixture and preparation method thereof | |
| CN104558732B (en) | A kind of high temperature mix type Crumber rubber modified asphalt enhancer compositions and preparation method thereof | |
| CN110171937A (en) | The modified Warm-Mix Bitumen Mixture of a kind of warm-mixing agent, SBS/SBR and preparation method | |
| CN105585859B (en) | Asphalt warm-mix agent and its preparation method and application | |
| CN106633943B (en) | A kind of Warm-mix hard asphalt and preparation method thereof | |
| CN106630762B (en) | A kind of warm mix polymer modified asphalt mixture and preparation method thereof | |
| CN105585860B (en) | A kind of warm-mixed asphalt and preparation method thereof | |
| CN106630766B (en) | Warm mix Sulphur asphalt mixture and preparation method thereof | |
| CN106633944B (en) | Asphalt warm-mix agent, preparation method and application | |
| CN106633949B (en) | Warm-mix hard asphalt and preparation method thereof | |
| Cui et al. | Chemical modification process of heavy residue from FCC slurry oil for producing high-grade paving asphalt | |
| CN106633935B (en) | Warm mixed epoxy bitumen and preparation method thereof | |
| CN106630759B (en) | Warm mixed epoxy bitumen mixture and preparation method thereof | |
| CN106630764B (en) | A kind of Warm-mix hard asphalt mixture and preparation method thereof | |
| CN106633948B (en) | Warm mix polymer modified asphalt and preparation method thereof | |
| CN106633929B (en) | A kind of asphalt warm-mix agent, preparation method and application | |
| CN106633941B (en) | A kind of warm mix Sulphur asphalt and preparation method thereof | |
| CN105985041B (en) | A kind of asphalt mixture additive 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: 20230828 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. |