CN106633943A - Warm mix hard asphalt, and preparation method thereof - Google Patents
Warm mix hard asphalt, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a warm mix hard asphalt, and a preparation method thereof. The warm mix hard asphalt comprises, by mass, 0.5 to 7 parts of a warm mixing agent, and 93 to 99.5 parts of matrix asphalt. The preparation method comprises following steps: under the action of a catalyst, a high-molecular alkane is reacted with a halogen elementary substance at a certain temperature under a certain pressure so as to obtain an intermediate; an aromatic hydrocarbon oil and a complex are uniformly mixed so as to obtain an aromatic hydrocarbon complex compound; the aromatic hydrocarbon complex compound and the intermediate are reacted at a certain temperature so as to obtain the warm mixing agent. The warm mixing agent added in the warm mix hard asphalt is capable of realizing warm mixing of asphalt, giving consideration to the high and low temperature performance of asphalt, increasing thermal stability of asphalt, improving aging resistance, reducing application temperature of asphalt, reducing generation amount of harmful gas, and improving the cohesiveness of asphalt.
Description
Technical field
The present invention relates to a kind of warm-mixed asphalt, specifically a kind of Warm-mix hard asphalt and preparation method thereof, belongs to petroleum industry and basic material chemical field.
Background technology
In the past the asphalt used in road engineering was generally divided into two types according to mix construction temperature：Cold-mix asphalt compound CMA (Cold
Mix Asphalt) and hot-mix asphalt mixture HMA (Hot Mix Asphalt).Cold-mix asphalt compound typically using emulsified asphalt or liquid asphalt and mix, the making under normal temperature state of gathering materials, without the need for gathering materials and binder is heated, can so save mass energy.But cold-mix asphalt compound early strength is relatively low, it is difficult to meet the requirement of the important engineerings such as highway, Heavy Traffic road.Hot-mix asphalt mixture be widely used, the compound that pavement performance is good.But in hot-mix asphalt mixture production process, pitch needs the mix under 150 ~ 180 DEG C of hot conditions with building stones.Not only consume the substantial amounts of energy, and can produce the pernicious gases such as substantial amounts of flue dust and CO2, CO, SO2, NOx, flammable organic gas in hot-mix asphalt mixture production process, not only pollute environment, and impact staff's is healthy, simultaneously, mix under hot conditions also easily causes pitch that heat ageing occurs, and reduces active time of the pitch on road surface, shortens the service life of bituminous paving.
For environmental protection, energy saving, extend the bituminous paving life-span, the developed country such as the later stage nineties 20th century America and Europe has carried out Warm-Mix Bitumen Mixture WMA (Warm
Mix Asphalt) research.Its objective is the mix temperature by reducing asphalt, reduce the energy consumption in Process of Pitch Mixture Production, dust and harmful gas emission are reduced, while ensureing that Warm-Mix Bitumen Mixture has the workability of the pavement performance essentially identical with hot-mix asphalt mixture and construction.
Warm-mixed asphalt technology mainly has three kinds of modes：One is that, with building stones mix at a temperature of 80 DEG C ~ 120 DEG C, which is low compared with the temperature of hot asphalt about 30 DEG C ~ 50 DEG C using the higher emulsified asphalt of evaporated residue content；Two is water in mixing compound（Or the aqueous solution of surfactant）Add in mix tank simultaneously with pitch, due to the presence of water, make asphalt foaming, reach viscosity reducing effect.But above two method can produce substantial amounts of vapor, easily cause equipment corrosion, stone flour conglomeration also frequently occurs and even causes mixing equipment blockage problem, make troubles to production.Further, since remaining non-volatile moisture is retained in compound, compound initial performance can be affected.The third method is that warm-mixing agent is added in pitch in advance, then takes the mode of production same with common hot-mix asphalt mixture, is easy to operation, is easily received by production unit.This kind of method reduces the high temperature viscosity of pitch by adding warm-mixing agent in pitch in advance, changes the viscosity-temperature curve of pitch, so as to reduce the mix temperature of pitch and building stones, reaches warm mix effect.But presently used warm-mixing agent can generally also cause the reduction of 60 DEG C of viscosity of pitch while asphalt high-temperature viscosity is reduced, and the high-temperature stability for making asphalt incurs loss；Or conversely, when 60 DEG C of viscosity is not reduced, the loss of pitch ductility can be caused, so as to reduce the cryogenic property of pitch.In a word, it is to lose the high-temperature behavior or cryogenic property of pitch as cost while making pitch reach warm mix effect that presently used warm-mixing agent is.
CN201010233760.9 adopts alkylamine, acid amides, quaternary cationic surfactant and calcium chloride, water to make warm-mixing agent for raw material.It is called " asphalt warm-mix agent " with it, is exactly in fact a kind of aqueous solution of surfactant.It is added to when asphalt is prepared in pitch, building stones is then added again.When stirring together with pitch, this aqueous surfactant solution can foam after being heated, and drive pitch also to foam, and play warm mix effect.But due to foaming effect, easily cause bumping, operation is inconvenient, and vapor is also easy to cause equipment corrosion and stone 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 by the way that deionized water to be added to the polyvinyl alcohol water solution being made into advance in, then rosin quaternary ammonium salt, aromatic hydrocarbon quaternary ammonium salt emulsifier, aliphatic hydrocarbon quaternary ammonium salt emulsifier, nonionic surface active agent are sequentially added, stirring and dissolving, the polyacrylamide solution being made into advance and triethanolamine are added again, is mixed to and be after being uniformly dissolved finished product.The additive can substantially reduce asphalt mixing temperature, and asphalt items pavement performance index also complies with requirement, but the additive not only complicated component, the difficulty and cost of preparation is increased, it is unfavorable for practical application.Although and be added in pitch and can reduce the high temperature viscosity of pitch, while also bringing along softening point and 60 DEG C of viscosity that negative effect reduces pitch, so as to have lost high-temperature stability, road surface can be made to be susceptible to rut or gather around bag.
CN201110158370.4 discloses a kind of warm-mixed asphalt additive and preparation method thereof, is using a kind of additive of organic silicon modified by polyether polymer composition in dicyandiamide solution.40 DEG C or so of asphalt mixing temperature can be effectively reduced, and warm-mixed asphalt property indices are not less than hot asphalt, but lack the method for testing and instance data support of correlation.
CN200880116767.7 is prepared for asphalt warm-mix agent using surface active agent composition, wax component, resin Composition.Surface active agent composition therein is amine, including diamines, polyamines, acid amides etc., using its lubrication, plays warm mix effect；Wax component includes vegetable wax, animal wax, mineral wax, amide waxe, oxidized petroleum waves etc., and resin Composition includes propolis and Petropols such as tall oil pitch, pine tar pitch, rosin, phenolic resin etc..Wax component and resin Composition play Efficient Adhesive Promotion, to make up the loss of the asphalt viscosity caused due to above-mentioned surface active agent composition.Component used by the patent is excessive, although can utilize the lubrication of surface active agent composition therein, play warm mix effect, but is easily reduced 60 DEG C of viscosity of pitch, affects the high-temperature stability of pitch, can also reduce the caking property of pitch and building stones.Although resin Composition such as rosin, phenolic resin etc. of addition can make up the loss of the asphalt viscosity caused due to above-mentioned surface active agent composition, but resin Composition is bad with the compatibility of pitch, pitch is easily caused to be layered during long-time storage, simultaneously because its hardness is higher, the high-temperature behavior of pitch can only be improved, and the cryogenic property of pitch can not be improved, and easily cause pitch cold cracking, can also affect the caking property of pitch.
CN201310174417.5 is prepared for asphalt warm-mix agent using amide-type, aromatic naphtha, binder component.Amide-type therein is one or two in ethylene double oleamides and erucyl amide, and using its lubricity the mix temperature of pitch is reduced；Binding agent is one or more in dimethylamino propylamine, N- aminoethylpiperazines, diethylenetriamines, trien, tetren.Method is first will to be well mixed after amide-type and aromatic naphtha heating and melting, then adds binding agent, is stirred for being well mixed.It is cooled to afterwards thick, is granulated, dries, is crushed, sieved, obtains particulate material of the particle diameter less than 20 mesh, as asphalt warm-mix agent.Amide-type is while asphalt mixing temperature is reduced in the patent, it is easy to reduce by 60 DEG C of viscosity of pitch, affects the high-temperature stability of asphalt, can also reduce the caking property of pitch.Although taking the method for addition binding agent, " to lift the caking property of pitch and building stones or eliminate amide substance for pitch and the adverse effect of building stones caking property ", but when in use heating-up temperature is higher for these binding agents, substantial amounts of noxious vapors can be produced, the smell is awful, environment is affected, the healthy of operating personnel is damaged.
CN201010511415 describes a kind of oil-resistant road asphalt modifier and preparation method thereof.The oil-resistant road asphalt modifier, in mass comprising 20 ~ 50 parts of styrene-ethylene/butylene-styrene block copolymer (SEBS), 10 ~ 30 parts of vistanex, 15 ~ 45 parts of macromolecule wax, rich in aromatic hydrocarbons tapped oil 10 ~ 30.Wherein macromolecule wax is Fischer-Tropsch wax, is furfural extract oil or phenol treating tapped oil rich in aromatic hydrocarbons tapped oil.Preparation method is：Material is rendered in proportion stretching and granulation in double screw extruder, 120 DEG C ~ 200 DEG C of extrusion temperature is obtained oil-resistant road asphalt modifier.The oil resistivity asphalt modifier of the patent introduction is for for parking lot, pitch used by the places such as airplane parking area, a kind of modifying agent developed to improve its oil resistivity, for the warm mix effect of pitch does not have enough attention, on stream, simple extrusion mixing has been carried out only with double screw extruder, due to unsaturated bond limited amount on polymer molecule used, only has a small amount of graft reaction in Screw Extrusion, there is no enough chemical reactions, substantially a kind of simple physical mixed, it is very limited for the warm mix effect of pitch.
CN201010558295 describes a kind of asphalt mixture warm-mixing modifier and preparation method thereof.It is made up of constituting for following masses part, fischer-tropsch wax：50 ~ 85 parts, plasticizer：15 ~ 50 parts, polyacid：0 ~ 10 part, synthetic resin：0 ~ 20 part, petchem：0 ~ 5 part.Wherein, synthetic resin is polyisobutene of the molecular weight between 400 ~ 5000.Preparation method：(1) each component is weighed in mass ratio；(2) each component is melted and is stirred at 120 DEG C～130 DEG C, be allowed to be sufficiently mixed uniformly, obtain final product described asphalt mixture warm-mixing modifier.In the warm-mixing agent development process, biochemical reaction is not sent out between each component, only simple physical mixed.Although the mix temperature of pitch can be reduced, the ductility of the pitch i.e. asphalt that can incur loss is susceptible to cold cracking.
CN201110443825.7 discloses a kind of composition for warm-mix asphalt pavements, by the maleic anhydride grafted polyethylene wax that the percent grafting of the pitch of 91 ~ 94 mass %, 3 ~ 5 mass % thermoplastic elastomer (TPE)s, 2 ~ 4 mass % is 4 ~ 10 mass %（MA-g-PE）, 0.1 ~ 1 mass % operation oil, viscosity of the said composition at 135 DEG C is less than 700cp, and said composition meets the requirement of high temperature plasticity_resistant deformation and anti-low-temperature cracking simultaneously.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 as the asphalt viscosity not plus during MA-g-PE for comparing, cannot know mix temperature reduces how many actually, only from the point of view of the 135 DEG C of viscosity numbers for being given, and not up to warm mix effect.
CN201110169620.4 discloses a kind of Warm-mix hard asphalt and preparation method thereof, by the matrix pitch of 91 ~ 94 mass %, the cracking Tissuemat E of 5 ~ 15 mass %, the Petropols of 5 ~ 10 mass %, the Tissuemat E grafted maleic anhydride of 0.1 ~ 0.3 mass %, 0.2 ~ 1.0 mass % silane coupler.The needle penetration of the matrix pitch is 60 ~ 90（0.1mm）, concrete grammar is that matrix pitch is melted, and is subsequently adding cracking Tissuemat E, Petropols, Tissuemat E grafted maleic anhydride, silane coupler, is stirred, and it is 20 ~ 35 that needle penetration is obtained（0.1mm）Warm-mix hard asphalt.
In existing warm-mixed asphalt preparation process, while asphalt mixture mixing temperature is reduced, it will usually 60 DEG C of viscosity or ductility of pitch are reduced, so as to have impact on the high-temperature stability or low temperature anti-cracking performance of asphalt.How a kind of special warm-mixing agent is adopted, while asphalt mixing and forming temperature is reduced its high and low temperature performance is not affected, become a hot issue for developing warm-mixed asphalt at present.
CN201510022090.9 discloses a kind of Warm-Mix Bitumen Mixture and preparation method thereof, wherein warm-mixing agent used is with macromolecule alkane and aromatic naphtha as raw material, and adds halogen and catalyst preparation obtains.Although the patent solves to a certain extent the problems referred to above, but during warm-mixing agent is prepared, due to the reaction temperature of intermediate it is low, and lacking catalyst, reaction speed is slower, and intermediate activity is relatively low, have impact on the extent of reaction of intermediate and aromatic naphtha, reaction depth is also not easily controlled, and the warm-mixing agent property for obtaining is unstable, have impact on the application effect in pitch.Additionally, the warm-mixing agent is used in pitch, the poor problem of ageing resistace is have also appeared.
With updating and seeking results maximization for Petroleum Processing Technology, in petroleum refining process, the techniques such as decompression residuum deep drawing and solvent deasphalting are often taken, the light component yield more and more higher of decompression residuum is made, substantial amounts of 25 DEG C of needle penetration can be so produced for 1 ~ 50（0.1mm）Hard grades of bitumen, wherein needle penetration are 1 ~ 30（0.1mm）Hard grades of bitumen can be used as architectural waterproof material, and heating-up temperature when using is generally 175 DEG C ~ 185 DEG C；Needle penetration is 30 ~ 50（0.1mm）Hard grades of bitumen can be used as road-making material, and for hot area, heating-up temperature when using is generally 160 DEG C ~ 170 DEG C.Due to higher using temperature, the energy is not only wasted when heat fusing is added, but also produce substantial amounts of bitumen flue gas, cause environmental pollution.With the continuous improvement of environmental requirement, the use for making these hards grades of bitumen is restricted.How to reduce it and use temperature, reduce the generation of bitumen flue gas, it has also become problem demanding prompt solution.Further, since heating-up temperature is too high when using, make pitch that heat ageing drastically to occur at short notice, cause hard grades of bitumen caking property poor, this problem is never solved well for many years.
The content of the invention
Hard grades of bitumen uses temperature drift in solve prior art, though easily cause reduce using temperature after environmental pollution or addition warm-mixing agent, but the not good problem of the heat endurance and ageing resistace of pitch, the present invention provides a kind of Warm-mix hard asphalt and preparation method thereof, add a kind of self-control warm-mixing agent, the use temperature of hard grades of bitumen can substantially be reduced, save energy, reduce pollution of the bitumen flue gas to environment, simultaneously heat ageing can also be mitigated, improve the caking property of pitch, it is possible to increase the heat endurance of pitch, improve ageing resistace.
The technical purpose of the present invention is achieved through the following technical solutions：
A kind of Warm-mix hard asphalt, 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. macromolecule alkane is added and add after heat fusing halogen simple substance and catalyst, be passed through shielding gas, reaction obtains intermediate；
B. add complex compound in aromatic naphtha, be uniformly mixing to obtain aromatic hydrocarbons complexing components；
C. shielding gas in the intermediate in the steps for importing a of aromatic hydrocarbons complexing components described in step b, will be passed through, reaction obtains the warm-mixing agent；
The macromolecule alkane is mixing macromolecule alkane of the alkane molar content of C30 ~ C130 more than 90%；
The catalyst is selected from anhydrous CuCl2, anhydrous MnCl2, anhydrous CrCl3With anhydrous NiCl2In at least one；
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)6] at least one.
Further, in the Warm-mix hard asphalt of above mass fraction composition, the addition of the warm-mixing agent is preferably 1 ~ 7 part.
Further, the macromolecule alkane is mixing macromolecule alkane of the alkane molar content of C60 ~ C130 more than 90%, and the macromolecule alkane is linear paraffin, branched paraffin or its mixture.
Further, the macromolecule alkane is preferably using metals such as Fe, Co, Ni as catalyst, the CO that will be obtained after coal gasification, with H2Synthetic reaction is carried out, mixing macromolecule alkane of the alkane molar content more than 90% that carbon number is 30 ~ 130 is obtained.Wherein H2Mol ratio when synthetic reaction is carried out with CO is 2 ~ 2.5,320 DEG C ~ 340 DEG C of reaction temperature, 2.0 ~ 2.2MPa of pressure.
Further, reaction temperature when intermediate is prepared in step a is 400 DEG C ~ 480 DEG C, and reaction pressure is 3 ~ 5MPa, and the reaction time is 30～60min.
Further, the consumption of halogen simple substance described in step a is 0.25 ~ 0.75 times of the molal quantity of macromolecule alkane, and the consumption of the catalyst is the 0.3%～0.9% of macromolecule alkane in mass.
Further, the one kind of the halogen simple substance in fluorine, chlorine and bromine, preferably chlorine or bromine.
Further, stir 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, wherein arene content is more than in parts by weight 57%, and preferably arene content is more than 70%, can be the mixture of one or more in subtract four line tapped oil, furfural extract oil, phenol treating tapped oil or catalytic cracked oil pulp.The consumption of the complex compound is 3%～9% of arene content in aromatic naphtha in mass.
Further, by the intermediate in aromatic hydrocarbons complexing components steps for importing a in step c, its mixed proportion is 1 ~ 7 in terms of the quality of raw material macromolecule alkane and aromatic naphtha:7~1.Reaction temperature is 350 DEG C ~ 400 DEG C, and reaction pressure is 2 ~ 4MPa, 60 ~ 120min of reaction time.
Further, shielding gas described in step a and c is nitrogen.
Further, the matrix pitch can select the asphalt that various crude oil and different process are produced, such as one or more in straight asphalt, oxidized asphalt, solvent deoiling pitch.It is 1 ~ 50 that the matrix pitch is 25 DEG C of needle penetrations（0.1mm）Matrix pitch.
Present invention also offers the preparation method of Warm-mix hard asphalt, comprises the following steps：First matrix pitch is heated into 160 DEG C ~ 185 DEG C, stirs and add warm-mixing agent, then while stirring temperature is reduced into 140 DEG C ~ 155 DEG C, continue constant temperature stirring, obtain the Warm-mix hard asphalt.
Further, add to be stirred after warm-mixing agent and lower the temperature again after 10 ~ 30min, after cooling the temperature to 140 DEG C ~ 155 DEG C, the time for continuing constant temperature stirring is 10 ~ 30min.
Warm-mix hard asphalt of the present invention compared with prior art, has the advantage that：
1st, the warm-mixing agent used by the present invention is homemade warm-mixing agent, intermediate is prepared under higher temperature, pressure and increases catalyst, not only shorten the reaction time, and can steadily control reaction process, easily hold the performance of intermediate, so as to get warm-mixing agent stable performance.
2nd, during warm-mixing agent is prepared, add complex compound in aromatic naphtha to stir, then reacted with intermediate again, the warm-mixing agent for obtaining not only has warm mix effect to pitch, taken into account the high temperature performance of pitch, and the heat endurance of pitch is also improved, improve ageing resistace.
3rd, Warm-mix hard asphalt of the present invention is low using temperature, save energy, while also reducing the generating capacity of pernicious gas, is conducive to the health of environmental protection and operating personnel.
4th, Warm-mix hard asphalt of the present invention, as a result of homemade warm-mixing agent, hence it is evident that reduce and use temperature, 20 DEG C ~ 30 DEG C is reduced than matrix pitch using temperature；Heat ageing is alleviated, and is improved the caking property and ductility of hard grades of bitumen.
Specific embodiment
Technical scheme is described in detail with reference to following embodiments, but the invention is not restricted to following examples.
Embodiment 1
（1）Prepare warm-mixing agent
Using Ni metals as catalyst, the CO that will be obtained after coal gasification, with H2Synthetic reaction is carried out, the mixed alkanes that the alkane that carbon number is 30 ~ 60 accounts for 90% are obtained.
1. above-mentioned mixed alkanes 1000g, about 1.2mol are weighed, is placed in closed container, be heated to 480 DEG C, the anhydrous CuCl of addition 3g catalyst2, keep introducing the chlorine of 0.89 mol at a temperature of this, and being passed through nitrogen makes the pressure of reaction vessel be maintained at 3MPa, reaction 30min obtains intermediate；
2. line tapped oil 7000g that subtracts four that arene content is 70% is weighed, the complex compound (Cu of 441g is added to（NH3）4〕SO4, it is mounted in another container and is heated to 350 DEG C, at this temperature constant temperature stirring 180min, obtains aromatic hydrocarbons complexing components；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, keeping temperature is 400 DEG C, makes pressure be maintained at 2MPa full of nitrogen, and isothermal reaction 60min obtains the warm-mixing agent used by the present invention.Each group distribution ratio is shown in Table 1.
（2）Prepare Warm-mix hard asphalt
Above-mentioned warm-mixing agent 7kg is weighed, it is 50 to be added to the husky Crude Oil needle penetration that quality is 93 kg, temperature is 160 DEG C（0.1mm）Straight asphalt in, stir 10min, warm-mixing agent is fully merged with pitch, then while stirring temperature is gradually lowered into 140 DEG C, stirring 10min obtains Warm-mix hard asphalt（Numbering WBA-1）.It is shown in Table 2 using temperature, and pernicious gas generating capacity is shown in Table 3.
Embodiment 2
（1）Prepare warm-mixing agent
Using Co metals as catalyst, the CO that will be obtained after coal gasification, with H2Synthetic reaction is carried out, the mixed alkanes that the alkane that carbon number is 30 ~ 130 accounts for 90% are obtained.
1. above-mentioned mixed alkanes 3500g, about 4.5mol are weighed, is placed in closed container, be heated to 400 DEG C, the anhydrous MnCl of addition 31.5g catalyst2, keep introducing the chlorine of 1.16mol at a temperature of this, and being passed through nitrogen makes the pressure of reaction vessel be maintained at 5MPa, reaction 60min obtains intermediate；
2. the catalytic cracked oil pulp 1000g that arene content is 63% is weighed, the complex compound K of 19g is added to4〔Fe（CN）6), it is mounted in another container and is heated to 270 DEG C, at this temperature constant temperature stirring 120min, obtains aromatic hydrocarbons complexing components；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, keeping temperature is 350 DEG C, makes pressure be maintained at 4MPa full of nitrogen, and isothermal reaction 120min obtains the warm-mixing agent used by the present invention.Each group distribution ratio is shown in Table 1.
（2）Prepare Warm-mix hard asphalt
Above-mentioned warm-mixing agent 0.5kg is weighed, it is 25 to be added to the LIAOHE CRUDE needle penetration that quality is 99.5 kg, temperature is 165 DEG C（0.1mm）Oxidized asphalt in, stir 20min, warm-mixing agent is fully merged with pitch, then while stirring temperature is gradually lowered into 145 DEG C, 20 min of stirring obtain Warm-mix hard asphalt（Numbering WBA-2）.It is shown in Table 2 using temperature, and pernicious gas generating capacity is shown in Table 3.
Embodiment 3
（1）Prepare warm-mixing agent
Using Fe metals as catalyst, the CO that will be obtained after coal gasification, with H2Synthetic reaction is carried out, the mixed alkanes that the alkane that carbon number is 70 ~ 90 accounts for 90% are obtained.
1. above-mentioned mixed alkanes 1000g, about 0.8mol are weighed, is placed in closed container, be heated to 440 DEG C, the anhydrous NiCl of addition 6g catalyst2, keep introducing the fluorine of 0.31mol at a temperature of this, and being passed through nitrogen makes the pressure of reaction vessel be maintained at 4MPa, reaction 45min obtains intermediate；
2. phenol treating tapped oil 3500g that arene content is 78% is weighed, the complex compound (Ni (CO) of 164g is added to4), it is mounted in another container and is heated to 310 DEG C, at this temperature constant temperature stirring 160min, obtains aromatic hydrocarbons complexing components；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, keeping temperature is 375 DEG C, makes pressure be maintained at 3MPa full of nitrogen, and isothermal reaction 90min obtains the warm-mixing agent used by the present invention.Each group distribution ratio is shown in Table 1.
（2）Prepare Warm-mix hard asphalt
Above-mentioned warm-mixing agent 4kg is weighed, it is 1 to be added to the Shengli crude needle penetration that quality is 96 kg, temperature is 180 DEG C（0.1mm）Solvent deoiling pitch in, stir 30min, warm-mixing agent is fully merged with pitch, then while stirring temperature is gradually lowered into 150 DEG C, 30 min of stirring obtain Warm-mix hard asphalt（Numbering WBA-3）.It is shown in Table 2 using temperature, and pernicious gas generating capacity is shown in Table 3.
Embodiment 4
（1）Prepare warm-mixing agent
Using Fe metals as catalyst, the CO that will be obtained after coal gasification, with H2Synthetic reaction is carried out, the mixed alkanes that the alkane that carbon number is 110 ~ 130 accounts for 90% are obtained.
1. above-mentioned mixed alkanes 7000g, about 4.2mol are weighed, is placed in closed container, be heated to 400 DEG C, the anhydrous CrCl of addition 21g catalyst3, keep introducing the bromine of 1.15mol at a temperature of this, and being passed through nitrogen makes the pressure of reaction vessel be maintained at 4MPa, reaction 45min obtains intermediate；
2. the furfural extract oil 1000g that arene content is 57% is weighed, the complex compound (NH of 17g is added to4)3〔Cr(NCS)6), it is mounted in another container and is heated to 310 DEG C, at this temperature constant temperature stirring 160min, obtains aromatic hydrocarbons complexing components；
3. aromatic hydrocarbons complexing components are imported in above-mentioned intermediate, makes temperature for 375 DEG C, make pressure be maintained at 3MPa full of nitrogen, isothermal reaction 90min obtains the warm-mixing agent used by the present invention.Each group distribution ratio is shown in Table 1.
（2）Prepare Warm-mix hard asphalt
Above-mentioned warm-mixing agent 1kg is weighed, it is 3 to be added to the Shengli crude needle penetration that quality is 99 kg, temperature is 185 DEG C（0.1mm）Solvent deoiling pitch in, stir 30min, warm-mixing agent is fully merged with pitch, then while stirring temperature is gradually lowered into 155 DEG C, 30 min of stirring obtain Warm-mix hard asphalt（Numbering WBA-4）.It is shown in Table 2 using temperature, and pernicious gas generating capacity is shown in Table 3.
Comparative example 1
（1）Prepare warm-mixing agent（According to the method in CN201510022090.9）
By with natural gas as raw material carry out the carbon number that synthetic reaction obtains be 130, molecular weight be to be placed in closed container after macromolecule alkane plus heat fusing of the 1822, weight as 700kg, it is heated to 400 DEG C, keep introducing 115 moles of bromine at a temperature of this, stir 180min, obtain intermediate；The furfural extract oil 100kg that arene content is 57% is weighed, is mounted in another closed container and is heated to 150 DEG C, be added to the anhydrous FeCl of 0.17kg3, stir 30min.Then above-mentioned intermediate is injected in furfural extract oil with vaporific under stirring, after all spraying into, 150 DEG C of constant temperature, stirring reaction 180min obtains contrasting warm-mixing agent.Each group distribution ratio is shown in Table 1.
（2）Prepare Warm-mix hard asphalt
Warm-mix hard asphalt is prepared according to the identical method of the embodiment of the present invention 4.
Comparative example 2
Mixed alkanes 1kg same as Example 4 is weighed, it is 3 to be directly appended to quality for 99kg, the Shengli crude needle penetration that temperature is 185 DEG C（0.1mm）Solvent deoiling pitch in, stir 30 min, obtain a kind of hard grades of bitumen.It is shown in Table 2 using temperature, and pernicious gas generating capacity is shown in Table 3.
Comparative example 3
By the furfural extract oil 1kg that arene content is 57%, it is 3 to be directly appended to the Shengli crude needle penetration that quality is 99 kg, temperature is 185 DEG C（0.1mm）Solvent deoiling pitch in, stirring 30
Min, obtains a kind of hard grades of bitumen.It is shown in Table 2 using temperature, and pernicious gas generating capacity is shown in Table 3.
Comparative example 4
Mixed alkanes 0.875kg same as Example 4 is weighed and furfural extract oil 0.125kg that arene content is 57%, while it is 3 to be directly appended to quality for 99kg, the Shengli crude needle penetration that temperature is 185 DEG C（0.1mm）Solvent deoiling pitch in, stir 30 min, obtain a kind of hard grades of bitumen.It is shown in Table 2 using temperature, and pernicious gas generating capacity is shown in Table 3.
Table 1. prepares warm-mixing agent each group distribution ratio
The contrast of the Warm-mix hard asphalt of the present invention of table 2. and matrix pitch and comparative example
The pernicious gas generating capacity of table 3. is contrasted
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 will reduce by 20 DEG C ~ 30 DEG C using temperature.Warm-mix hard asphalt of the present invention is compared with corresponding matrix pitch, when needle penetration is essentially identical, softening point is raised, 10 DEG C of ductility increases, illustrate that Warm-mix hard asphalt of the present invention not only can reach warm mix effect, and corresponding matrix pitch is better than in terms of high-temperature stability and low temperature ductility.Additionally, caking property also be improved significantly.
It is visible by comparative example, directly simply will mixing macromolecule alkane and/or tapped oil be added in hard grades of bitumen, the improvement to pitch warm mix effect, hence it is evident that not as warm mix effect of the present invention it is good.
From table 3, compared with matrix pitch and comparative example, Warm-mix hard asphalt of the present invention can obviously reduce pernicious gas generating capacity, be conducive to environmental protection.
Contrast visible by film experimental result, the Warm-mix hard asphalt ageing resistace obtained using the warm-mixing agent used by the present invention is significantly better than the pitch of arbitrary comparative example, warm-mixing agent i.e. of the present invention is while warm mix effect is realized, improve the heat endurance of pitch, improved ageing resistace, and the warm-mixing agent used by comparative example 1 has negative effect to the ageing resistace of pitch.
Claims (10)
1. a kind of Warm-mix hard asphalt, it is characterised in that：The pitch includes the component of following mass fraction：
Warm-mixing agent
0.5 ~ 7 part
Matrix pitch
93 ~ 99.5 parts
The warm-mixing agent is prepared using following methods：
A. macromolecule alkane is added and add after heat fusing halogen simple substance and catalyst, be passed through shielding gas, reaction obtains intermediate；
B. add complex compound in aromatic naphtha, be uniformly mixing to obtain aromatic hydrocarbons complexing components；
C. shielding gas in the intermediate in the steps for importing a of aromatic hydrocarbons complexing components described in step b, will be passed through, reaction obtains the warm-mixing agent；
The macromolecule alkane is mixing macromolecule alkane of the alkane molar content of C30 ~ C130 more than 90%；
The catalyst is selected from anhydrous CuCl2, anhydrous MnCl2, anhydrous CrCl3With anhydrous NiCl2In at least one；
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)6] at least one.
2. Warm-mix hard asphalt according to claim 1, it is characterised in that：When preparing warm-mixing agent, the reaction temperature that intermediate is prepared in step a 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, the consumption of halogen simple substance described in step a is 0.25 ~ 0.75 times of the molal quantity of macromolecule alkane, and the consumption of the catalyst is the 0.3%～0.9% of macromolecule alkane in mass.
4. Warm-mix hard asphalt according to claim 1, it is characterised in that：When preparing warm-mixing agent, stir at 270 DEG C ~ 350 DEG C of temperature in step b, mixing time is 120 ~ 180min.
5. Warm-mix hard asphalt according to claim 1, it is characterised in that：When preparing warm-mixing agent, the arene content described in step b in aromatic naphtha is more than in parts by weight 57%, and the consumption of the complex compound is 3%～9% of arene content in aromatic naphtha in mass.
6. Warm-mix hard asphalt according to claim 1, it is characterised in that：When preparing warm-mixing agent, by the intermediate in aromatic hydrocarbons complexing components steps for importing a in step c, its mixed proportion is 1 ~ 7 in terms of the quality of raw material macromolecule alkane and aromatic naphtha:7~1.
7. Warm-mix hard asphalt according to claim 1, it is characterised in that：When preparing warm-mixing agent, the reaction temperature of step c is 350 DEG C ~ 400 DEG C, and reaction pressure is 2 ~ 4MPa, 60 ~ 120min of reaction time.
8. Warm-mix hard asphalt according to claim 1, it is characterised in that：The matrix pitch is the matrix pitch that 25 DEG C of needle penetrations are 1 ~ 50.
9. the preparation method of the Warm-mix hard asphalt described in claim 1 ~ 8 any one, comprises the following steps：First matrix pitch is heated into 160 DEG C ~ 185 DEG C, stirs and add warm-mixing agent, then while stirring temperature is reduced into 140 DEG C ~ 155 DEG C, continue constant temperature stirring, obtain the Warm-mix hard asphalt.
10. the preparation method of Warm-mix hard asphalt according to claim 9, it is characterised in that：Add to be stirred after warm-mixing agent and lower the temperature again after 10 ~ 30min, after cooling the temperature to 140 DEG C ~ 155 DEG C, the time for continuing constant temperature stirring is 10 ~ 30min.
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| 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 |
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