CN106633941B - A kind of warm mix Sulphur asphalt and preparation method thereof - Google Patents
A kind of warm mix Sulphur asphalt and preparation method thereof Download PDFInfo
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- CN106633941B CN106633941B CN201510730841.2A CN201510730841A CN106633941B CN 106633941 B CN106633941 B CN 106633941B CN 201510730841 A CN201510730841 A CN 201510730841A CN 106633941 B CN106633941 B CN 106633941B
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Abstract
The present invention provides a kind of warm mix Sulphur asphalt, the component including following mass fraction: 0.5 ~ 7 part of warm-mixing agent, 33 ~ 79.5 parts of matrix pitch, 20 ~ 60 parts of sulphur.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 Sulphur 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.It is prepared into warm-mixed asphalt with warm-mixing agent and pitch, the melting temperature and viscosity at this temperature for reducing pitch can reduce the preparation temperature of Sulphur asphalt especially when preparing Sulphur asphalt, reduce the occurrence quantity of pernicious gas.
Description
Technical field
The present invention relates to a kind of warm-mixed asphalts, and specifically a kind of warm mix Sulphur 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 adhesiveness 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 adhesiveness of pitch and building stones.
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 adhesiveness of pitch and building stones.Although addition is taken to bond
The method of agent, " to promote the adhesiveness of pitch and building stones or eliminate amide substance for the unfavorable of pitch and building stones adhesiveness
Influence ", but added binder can only improve the caking property of asphalt, can not improve the adherency of pitch and building stones
Property, make conceptual mistake.And heating temperature is higher when in use for these binders, can generate a large amount of noxious vapors, gas
It smells foul, 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 10 ~ 30 parts of oil of aromatic hydrocarbons extraction.Wherein macromolecule wax is Fischer-Tropsch wax, rich in virtue
Hydrocarbon extraction oil is furfural extract oil or phenol treating extraction oil.Preparation method is: material being launched to twin-screw in proportion and is squeezed
120 DEG C ~ 200 DEG C of extrusion temperature, oil-resistant road asphalt modifier is made in stretching and granulation in machine out.The oil resistant of the patent introduction
Property asphalt modifier be to be developed for for pitch used in the places such as parking lot, airplane parking area in order to improve its oil resistivity
A kind of modifying agent, for the warm mix effect of pitch, there is no enough attention, in the process of development, squeeze only with twin-screw
Machine has carried out simple extrusion mixing out, due to unsaturated bond limited amount on polymer molecule used, in Screw Extrusion mistake
Only have a small amount of graft reaction in journey, enough chemical reactions do not occur, substantially a kind of simple physical mixed, for
The warm mix effect of pitch 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 91wt% ~ 94wt%, 3wt% ~
5wt% thermoplastic elastomer (TPE), 2wt% ~ 4wt% grafting rate be 4wt% ~ 10wt% maleic anhydride grafted polyethylene wax (MA-g-
PE), the operation oil of 0.1wt% ~ 1wt%, viscosity of the composition at 135 DEG C are no more than 700cp, and the composition meets height simultaneously
The requirement of warm plasticity_resistant deformation and anti-low-temperature cracking.But the 135 of the bituminous composition DEG C of viscosity are still very big, 135 in embodiment
DEG C viscosity is 675 cp and 690 cp, and do not provide matrix pitch 135 DEG C of viscosity and as compare not plus MA-g-
Asphalt viscosity when PE, can not know mix temperature reduces how many actually, only from the point of view of the 135 DEG C of viscosity numbers provided, not
Reach warm mix effect.
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.
In natural gas processing and petroleum refining process, in order to produce clean fuel, sulphur therein need to be removed, to generate
A large amount of sulphur byproduct, makes sulphur market show easy situation.How to effectively utilize sulphur, solve sulphur
Market, become natural gas processing and oil refining enterprise's urgent problem to be solved.In addition, due to the increasing of China's vehicle and
The reasons such as the heavy loading of transport, track, which occurs, for bituminous pavement, gathers around phenomena such as packet is on the rise, and hot area is especially in south China
It is prominent.The phenomenon has become one of main failure mode of the current bituminous highway in China, has seriously affected bituminous pavement driving peace
Complete and service life.Studies have shown that sulphur is added to the making for being used for road in pitch, the application of sulphur can not only be expanded
Field, the market for expanding sulphur, but also can be improved the anti-rut behavior of bituminous pavement.
Early in 1900, people just started with sulphur come modified pitch, but since sulphur price is surging at that time and sulphur changes drip
Green mixture discharges H in process of production2The problem of sulfurous gas such as S, constrains the development of sulphur modified asphalt technology.Later, with
The exploitation of polymer modified asphalt, sulphur are also applied in pitch, primarily as the stabilization of polymer modified asphalt
Agent, to improve product storage stability.But dosage of the sulphur in polymer modified asphalt is seldom, only 0.01wt% ~
0.1wt%, the extensive application for being not enough to promote sulphur in pitch.Therefore, how a large amount of sulphur to be used in pitch, and not
Cause air pollution, this is the contradictory problems for needing to solve.
CN1690126 describes a kind of by a certain proportion of sulphur, carbon, smog inhibitor and plasticizer addition matrix pitch
The middle method for preparing modified asphalt mixture by SEAM.
CN103030984A, which is described, a kind of to be added to sulphur and crystal whisker of gypsum, smog inhibitor in matrix pitch and prepares
The method of sulfur modified pitch.
CN102321373A describes a kind of preparation method of warm mix Sulphur asphalt, and sulphur, plasticizer are specifically mixed 1
~ 24 hours formation linear polymeric substances, then by above-mentioned linear polymeric substance and eliminating smell agent, fumet be added 130 DEG C ~
It is mixed in 160 DEG C of matrix pitches at least 30 minutes and obtains warm-mixed asphalt.
It first is prepared into polymer modified asphalt with matrix pitch and SBS etc. in CN101443558B, then in modified pitch
Middle addition sulphur, diatomite etc. are prepared into warm-mixed asphalt, there is addition fiber etc. in mixture mix, be prepared into warm mix antiskid,
Noise-reduction asphalt road surface material.
CN201510022090.9 discloses a kind of Warm-Mix Bitumen Mixture and preparation method thereof, used in warm-mixing agent
It is and to add halogen and catalyst preparation obtains using macromolecule alkane and aromatic naphtha as raw material.Although the patent is in certain journey
It solves the above problem on 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 problem of anti-aging property is deteriorated is had also appeared.
Above-mentioned patent is not effectively reduced using temperature, the preparation of sulfur modified pitch during preparing Sulphur asphalt
With use temperature higher, the toxic gases such as hydrogen sulfide, sulfur dioxide can be released, to the health hazard of environment and construction personnel compared with
Greatly, although be added that smog inhibitor, fumet, eliminating smell agent etc. can partially inhibit these toxic gases distributes or cover its thorn
Swash property smell, but cannot all to solve Sulphur asphalt smell during making and using from the root larger and toxic for these methods
The problem of.
Summary of the invention
Temperature drift is used to solve Sulphur asphalt 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 sulphur drip
Blueness joined a kind of self-control warm-mixing agent, can be substantially reduced the production of Sulphur asphalt and using temperature, mitigate Sulphur asphalt in life
Caused air pollution in production and use, while the thermal stability of pitch can also be improved, improve anti-aging property.It can add
More sulphur promotes application of the sulphur in pitch, expands the application of sulphur.
Technical purpose of the invention is achieved through the following technical solutions:
A kind of warm mix Sulphur asphalt, the pitch include the component of following mass fraction:
0.5 ~ 7 part of warm-mixing agent
33 ~ 79.5 parts of matrix pitch
20 ~ 60 parts of sulphur
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 Sulphur 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 being 270 DEG C ~ 350 DEG C in 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 or blend asphalt.
Further, the sulphur is sulphur caused by petroleum or natural gas processing process, can be technical grade, can also
To be food-grade；It can be rhombic sulfur or monoclinic sulphur；It can be sheet, powdered or graininess in form.
The present invention also provides the preparation methods of warm mix Sulphur asphalt, comprising the following steps: is first heated to matrix pitch
130 DEG C ~ 160 DEG C, warm-mixing agent is stirred and added, sulphur, stirring is added.
Further, being added after warm-mixing agent and being stirred to react the time is 30 ~ 60min, is added after sulphur and is stirred to react the time and is
40~120min。
Further, in the preparation method of the warm mix Sulphur asphalt, production process is carried out and is installed additional in closed container
There is pumped vacuum systems, the pernicious gas generated in production process is collected, is absorbed by aqueous slkali, such as sodium hydroxide.
Warm mix Sulphur 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 Sulphur asphalt of the present invention is first prepared into warm-mixed asphalt with warm-mixing agent and pitch before adding sulphur, drops
The low melting temperature of pitch, then adds sulphur again, can reduce the preparation temperature of Sulphur asphalt, reduce pernicious gas
Occurrence quantity.
4, warm mix Sulphur asphalt production process of the present invention is carried out in closed container, is added to vacuumize on reactor and is
System, can be the pernicious gas generated in production process such as H2After S etc. is collected, row environmental protection is absorbed by sodium hydroxide aqueous slkali
Processing reduces air pollution when Sulphur asphalt production.
5, more sulphur can be added in warm mix Sulphur asphalt of the present invention, promoted application of the sulphur in pitch, expanded
The market of sulphur, reduces cost of building the road, saves a large amount of pitch resource.
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 Sulphur asphalt is prepared
It is de- to be added to No. 50 solvents of husky Crude Oil that quality is 33kg, temperature is 160 DEG C for the above-mentioned warm-mixing agent for weighing 7kg
In oil asphalt, 60min is stirred, warm-mixed asphalt is obtained；Then the sulphur of 60kg is added in above-mentioned warm-mixed asphalt, stirring 120
Min obtains warm mix Sulphur asphalt (number A-1) of the present invention.
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 Sulphur asphalt is prepared
The above-mentioned warm-mixing agent for weighing 0.5kg is added to No. 90 oxygen of LIAOHE CRUDE that quality is 79.5kg, temperature is 140 DEG C
Change in pitch, stirs 30min, obtain warm-mixed asphalt；Then the sulphur of 20kg is added in above-mentioned warm-mixed asphalt, is stirred
40min obtains warm mix Sulphur asphalt (number A-2) of the present invention.
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 Sulphur asphalt is prepared
The above-mentioned warm-mixing agent of 4kg is weighed, No. 70 blend asphalts of Tahe Crude Oil that quality is 56kg, temperature is 150 DEG C are added to
In, 45min is stirred, warm-mixed asphalt is obtained；Then the sulphur of 40kg is added in above-mentioned warm-mixed asphalt, stirs 80min, obtains
Warm mix Sulphur asphalt (number A-3) of the present invention.
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 Sulphur asphalt is prepared
The above-mentioned warm-mixing agent of 1kg is weighed, No. 110 straight asphaltes of Oman's crude oil that quality is 49kg, temperature is 130 DEG C are added to
In, 40min is stirred, warm-mixed asphalt is obtained；Then the sulphur of 50kg is added in above-mentioned warm-mixed asphalt, stirs 100min, obtains
To warm mix Sulphur asphalt (number A-4) of the present invention.
According to matrix pitches various in above-described embodiment and the high temperature viscosity of warm-mixed asphalt, viscosity-temperature curve is drawn, by viscous temperature
Curve obtains the mix of every kind of pitch and forming temperature is listed in table 2.
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 Sulphur asphalt is prepared
Warm mix Sulphur 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, Oman's crude oil that quality is 49kg, temperature is 130 DEG C is added to
In No. 110 straight asphaltes, 30min is stirred；Then the sulphur for adding 50kg, stirs 100min, obtains a kind of Sulphur asphalt.Mix
And forming temperature is shown in Table 2.
Comparative example 3
The furfural extract oil 1kg for being 57% by arene content, is added to Oman that quality is 49kg, temperature is 130 DEG C
In No. 110 straight asphaltes of crude oil, 30min is stirred；Then the sulphur for adding 50kg, stirs 100 min, obtains a kind of sulphur drip
It is green.Mix and forming temperature are shown in Table 2.
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 added in No. 110 straight asphaltes of Oman's crude oil that quality is 49kg, temperature is 130 DEG C, 30min is stirred,
Then the sulphur for adding 50kg, stirs 100min, obtains a kind of Sulphur asphalt.Mix and forming temperature are shown in Table 2.
Comparative example 5
The sulphur for weighing 50kg is added in No. 110 straight asphaltes of Oman's crude oil that quality is 50kg, temperature is 130 DEG C,
100 min are stirred, a kind of Sulphur asphalt is obtained.Mix and forming temperature are shown in Table 2.
Table 1. prepares warm-mixing agent each group distribution ratio
The comparison of the warm mix Sulphur asphalt of the present invention of table 2. and matrix pitch and comparative example
3. film experimental result of table
As can be seen from Table 2, the high temperature viscosity of warm mix Sulphur asphalt of the present invention is all significantly lower than corresponding matrix pitch and general
Logical Sulphur asphalt, so that mix and forming temperature be made to reduce by 20 DEG C ~ 25 DEG C.Warm mix Sulphur asphalt of the present invention and corresponding matrix
Pitch and Sulphur asphalt compare, and when needle penetration is essentially identical, softening point and 60 DEG C of viscosity are improved significantly, and 10 DEG C of ductilities are bright
It is aobvious to increase, illustrate that warm mix Sulphur asphalt of the present invention not only can reach warm mix effect, but also in high-temperature stability and low temperature ductility
Aspect is better than corresponding matrix pitch and common Sulphur asphalt.
By comparing example as it can be seen that mixing macromolecule alkane and/or extraction oil or sulphur are simply directly added to pitch
In, the improvement to pitch warm mix effect is good not as good as warm mix effect of the present invention, but also can cause the loss or 60 DEG C of viscosity of ductility
Decline, the technology of " standard specification for construction and acceptance of highway asphalt pavement " JTG F40-2004 cannot be reached by resulting even in asphaltic nature
It is required that.Warm mix Sulphur asphalt of the present invention significantly reduces mix and forming temperature, can reduce pernicious gas occurrence quantity.
Anti-aging property is characterized by film experimental result, and as shown in table 3, comparison is as it can be seen that using temperature used in the present invention
The pitch that the warm mix Sulphur asphalt anti-aging property that agent obtains is significantly better than any comparative example is mixed, i.e., warm-mixing agent of the present invention is being realized
While warm mix effect, the thermal stability of pitch is improved, anti-aging property is improved, and warm mix used in comparative example 1
Agent has negative effect to the anti-aging property of pitch.
Claims (6)
1. a kind of warm mix Sulphur asphalt, it is characterised in that: the pitch includes the component of following mass fraction:
0.5 ~ 7 part of warm-mixing agent
33 ~ 79.5 parts of matrix pitch
20 ~ 60 parts of sulphur
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 Sulphur 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 Sulphur asphalt according to claim 1, it is characterised in that: when preparing warm-mixing agent, be in temperature in step b
It is stirred at 270 DEG C ~ 350 DEG C, mixing time is 120 ~ 180min.
4. warm mix Sulphur 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. the preparation method of warm mix Sulphur asphalt described in claim 1 ~ 4 any one, comprising the following steps: first drip matrix
Blueness is heated to 110 DEG C ~ 140 DEG C, stirs and add warm-mixing agent, and sulphur, stirring is added.
6. the preparation method of warm mix Sulphur asphalt according to claim 5, it is characterised in that: production process is in closed container
Middle progress simultaneously adds pumped vacuum systems, and the pernicious gas generated in production process is collected, is absorbed by aqueous slkali.
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| CN102321373B (en) * | 2011-08-17 | 2013-03-20 | 爱思开(北京)公路科技有限公司 | Warm mixed asphalt 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 |
| CN104591605B (en) * | 2015-01-16 | 2016-05-18 | 辽宁兆利高新路面材料有限公司 | A kind of Warm-Mix Bitumen 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 |
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