CN106147251B - A kind of warm-mixed asphalt additive and preparation method thereof - Google Patents

A kind of warm-mixed asphalt additive and preparation method thereof Download PDF

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CN106147251B
CN106147251B CN201510172010.8A CN201510172010A CN106147251B CN 106147251 B CN106147251 B CN 106147251B CN 201510172010 A CN201510172010 A CN 201510172010A CN 106147251 B CN106147251 B CN 106147251B
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warm
mixed asphalt
asphalt additive
mixed
powdery solid
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CN106147251A (en
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杨飞飞
回军
陈保莲
宁爱民
李宝忠
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a kind of warm-mixed asphalt additives and preparation method thereof.Warm-mixed asphalt additive of the present invention, formula include: powdery solid object, fischer-tropsch wax, branching type high molecular polymer and N, N '-ethylenebisstearamide;Wherein, the powdery solid object is the solid product isolated after the processing of greasy filth extraction heat dewatering process by oily sludge.In warm-mixed asphalt additive of the present invention, each component synergistic effect, it can play the role of summing it up synergy, the Warm-Mix Bitumen Mixture prepared using this warm-mixing additive, it mixes and stirs and forming temperature is below 135 DEG C, have the advantages that be substantially reduced mix temperature and forming temperature, and its mixture properties is suitable with hot asphalt.

Description

A kind of warm-mixed asphalt additive and preparation method thereof
Technical field
The present invention relates to a kind of asphalt mixture warm-mixing additives and preparation method thereof, belong to bitumen for road use technical field.
Background technique
Asphalt used in road engineering is generally divided into two types according to construction temperature is mixed and stirred at present: cold mixing drip Green mixture CMA (Cold Mix Asphalt) and hot-mix asphalt mixture HMA (Hot Mix Asphalt).Cold-mix asphalt is mixed Close material generally mixed and stirred under normal temperature state using emulsified asphalt or liquid asphalt and gathering materials, making, without to gathering materials and combine Material is heated, and can save mass energy in this way.But cold-mix asphalt mixture initial stage pavement performance is poor, 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 most widely used, a kind of pavement performance mixture the most good.But it is mixed in heat In Process of Pitch Mixture Production, pitch needs to mix and stir under 150 ~ 180 DEG C of hot conditions with building stones.Building stones, pitch are heated To so high temperature, mass energy is consumed.In addition a large amount of CO is produced in hot-mix asphalt mixture production process2、 Flue dust and pernicious gas (CO, SO2、NOxDeng), it not only polluted environment, have an effect on the health of staff.Meanwhile high temperature Under the conditions of mix and stir the aging for also resulting in pitch, reduce the pavement performance of asphalt.
For protection environment, energy saving, the middle and later periods the 1990s Europe and the countries such as U.S. carried out warm mix drip The research of green mixture WMA (Warm Mix Asphalt), the purpose is to the temperature of mixing and stirring and pave by reducing asphalt Degree reaches the energy consumption reduced in Process of Pitch Mixture Production, reduces CO2Equal gases and dust discharge amount, while guaranteeing warm mix Asphalt has the pavement performance and construction workability essentially identical with hot-mix asphalt mixture.
As the warm-mixed asphalt additive of one of warm mix technology, because of the advantages that preparation process is simple, invalid special installation And by the concern of people.Existing warm-mixed asphalt additive mainly has zeolite, organic additive, surfactant three types Product.Such as, Chinese patent literature CN103242666A discloses a kind of warm-mixed asphalt additive, by the original of following parts by weight Material is made: 15 ~ 20 parts of polyethylene wax, 15 ~ 20 parts of chlorinated paraffin -70,30 ~ 50 parts of diatomite, 1 ~ 3 part of stearmide, solid-state is anti- 1 ~ 4 part of exfoliant.The warm-mixed asphalt additive can be widely used for the different types of asphalt such as AC, SMA.
When warm-mixed asphalt additive in above-mentioned technology is used for asphalt, SBS modified asphalt mixture can be made Mix and compacting temperature reduce by 20 DEG C or more;And while reducing the mix and compacting temperature of asphalt, Neng Gouyou Effect ensures that the performances such as high-temperature stability, the anti-water damage of made Warm-Mix Bitumen Mixture reach at or above hot asphalt mixing Performance level is widely portable to the pavement of road of different geographical conditions and climatic province.But in above-mentioned technology, due to temperature The polyethylene wax and chlorinated paraffin -70 added in mixed asphalt additive can not only reduce temperature when being used for warm-mixed asphalt mixed material The ductility of pitch is mixed, and then influences the low temperature service performance of bitumen for road use, is easy to cause cold cracking, the warm-mixed asphalt addition Agent is only applied to SBS modified pitch, and mix temperature and compacting temperature are still relatively high, not for non-SBS modified pitch Function well as the effect for reducing mix temperature.In addition, the diatomite contained in additive belongs to inorganic additive, it to be used for temperature There are problems that when mixed asphalt additive with organic filler poor compatibilities other in warm-mixed asphalt additive, cause diatomite easily to be analysed Out;And the warm-mixed asphalt additive is when being used for Warm-Mix Bitumen Mixture, having in the diatomite and Warm-Mix Bitumen Mixture of precipitation Machine substance the problem of there is also poor compatibilities, pitch and building stones binding force is caused to reduce, and then influence Warm-Mix Bitumen Mixture Pavement performance.It the problem of in order to avoid diatomite inorganic filler precipitation, needs to be added antistripping agent in the patented technology, and resists The cost that the addition of exfoliant will lead to warm-mixed asphalt additive increases.
Summary of the invention
The present invention in the prior art due to using polyethylene wax and chlorinated paraffin -70 as warm-mixed asphalt additive, So that Warm-Mix Bitumen Mixture has poor performance at low temperatures, and inorganic additive and other organic additives are collectively as temperature When mixed asphalt additive, the problem of there is also poor compatibilities, and then provide a kind of low temperature performance well, compatibility it is good, it is at low cost, The warm-mixed asphalt additive and preparation method thereof of environmental protection.
In order to solve the above-mentioned technical problems, the present invention provides a kind of warm-mixed asphalt additives, including the following raw material: powdery Solids, fischer-tropsch wax, branching type high molecular polymer and N, N '-ethylenebisstearamide;Wherein, the powdery solid object It is the solid product isolated after the processing of greasy filth extraction heat dewatering process by oily sludge.
The warm-mixed asphalt additive, by percentage to the quality, formula include: powdery solid object: 50wt%~96wt%; Fischer-tropsch wax: 2wt%~20wt%;Branching type high molecular polymer: 1wt%~10wt%;N, N '-ethylenebisstearamide: 1wt% ~20wt%.
The warm-mixed asphalt additive, by percentage to the quality, formula include: powdery solid object: 65wt%~88wt%; Fischer-tropsch wax: 5wt%~15wt%;Branching type high molecular polymer: 3wt%~8wt%;N, N '-ethylenebisstearamide: 4wt% ~12wt%.
The particle size range of the powdery solid object is 0.02~1mm.
The powdery solid object is the solid product isolated after the processing of greasy filth extraction heat dewatering process by oily sludge. Steps are as follows for the greasy filth extraction heat dewatering process: oily sludge being sent into centrifuge, while flocculation being added into centrifuge Agent, the additional amount of flocculant make containing flocculant 0.005wt%~1wt% in final powdery solid object, and oily sludge is by centrifugation Enter extraction process after processing;By the oily sludge and extractant (1:1) in mass ratio~(1:80) after centrifugation, preferably (1:30) ~(1:50), is mixed, and is normal pressure in pressure, heating temperature is extracted under the conditions of being 95 DEG C ~ 120 DEG C, extraction time 8 Hour ~ 12 hours, oil and solids in oily sludge are transferred in extractant, after separation, obtain solid sediment;It is described Solid sediment is again normal pressure in operating pressure, and heating temperature carries out stripping deoiling treatment under the conditions of being 100 DEG C ~ 140 DEG C, handles Time: 0.5 hour ~ 3.0 hours, the powdery solid object is obtained after stripping deoiling treatment.
The flocculant is styrene sulfonate, ligninsulfonate, acrylic acid, methacrylic acid, polyacrylic acid, poly- third Olefin(e) acid sodium, calcium polyacrylate (CPA), polyacrylamide, starch and its derivative, fatty alcohol polyoxyethylene ether ammonium sulfate, coconut oleoyl amine third One or more of base glycine betaine, polyoxyethylene oleic acid ester, alcohol ether phosphate, biological flocculant mixture.In powdery solid In object preparation process, the flocculant being added finally is substantially remained in powdery solid object.
The boiling range of the extractant is that 100 DEG C ~ 600 DEG C wide boiling point is oily, preferably 100 DEG C ~ 250 DEG C;Wherein, the wide boiling point Oil is deploys to obtain using one or more distillates, or using the boiling spread that meets recycled during oily waste water treatment Sump oil.
Oil, solid, water three-phase are typically contained in the oily sludge.By percentage to the quality, oil contains in the oily sludge Amount is 3wt% ~ 95wt%, and solid content is 2wt% ~ 95wt%, water content 2wt% ~ 95wt%.The oily sludge can have following next Source but be not limited to following source: for example, the oily sludge that generates of oil extraction, oil field gathering and transportation process generate oily sludge, The oily sludge etc. that sewage from oil refinery Treatment stations generate.
The powdery solid object is grouped as by following group by percentage to the quality: inorganic matter component 60wt% ~ 80wt% has Machine object component 20wt% ~ 40wt%;Wherein, the inorganic matter component is mostly derived from the solid component in oily sludge, such as SiO2,、 Al2O3Deng;The organic constituents are mostly derived from oil and flocculant in oily sludge, such as asphalitine, colloid, flocculant Component etc..
The branching type high molecular polymer is anti-by polymerization and coupling by butadiene, styrene and isoprene monomer Branching type high molecular polymer of the molecular weight that should be synthesized 1000 ~ 20000.
The branching type high molecular polymer is star-branched high molecular polymer.
Further, the present invention also provides the preparation method of the warm-mixed asphalt additive, include the following steps: powder Shape solids, fischer-tropsch wax, branching type high molecular polymer, N, N '-ethylenebisstearamide put into Screw Extrusion according to the ratio Machine is uniformly mixed under the conditions of temperature is 80 DEG C~110 DEG C and squeezes out finished product to get asphalt mixture warm-mixing additive is arrived.
Warm-mixed asphalt additive of the present invention has the advantages that compared with prior art
(1) warm-mixed asphalt additive of the present invention is isolated after the processing of extraction heat dewatering process with oily sludge Powdery solid object replaces the inorganic fillers such as diatomite in the prior art, as warm-mixed asphalt additive raw material, since the powdery is solid Body object belongs to oily packet soil structure, and the surface of powdery solid object is not needed in addition to add antistripping agent by powder covered with organic Form good mutual tolerance with components other in warm-mixed asphalt additive, especially with branching type high molecular polymer collective effect When, stable there are space networks since branching type high molecular polymer can be formed between the macromolecular in solidification state and pitch The colloidal dispersion of network structure, powdery solid object can be filled in the network structure, be conducive to improve ductility, improved low-temperature resistance and opened Fragility energy is easily precipitated to well solve inorganic filler in the prior art, leads to warm-mixed asphalt mixture pavement performance difference On the other hand problem since the powdery solid object is oily sludge regenerant, has many advantages, such as environmentally friendly, at low cost;In addition, branch Change type high molecular polymer also has the branched structure of suitable length, and in shear at high temperature, curtailment is so that branch itself It tangles, so that intermolecular distance increases, intermolecular interaction weakens, and makes the reduction of system shear viscosity, and with N, N '-is sub- When ethyl bis-stearamides and fischer-tropsch wax collective effect, additionally it is possible to reduce asphalt viscosity, there is outstanding greasy property, simultaneously Increase the ductility and 60 DEG C of viscosity of pitch, therefore can be improved it while improving Warm-Mix Bitumen Mixture construction workability and resist Cold cracking property and Rut resistance deformability;In warm-mixed asphalt additive of the present invention, each component synergistic effect, Ke Yiqi It mixes and stirs using Warm-Mix Bitumen Mixture prepared by this warm-mixing additive to the effect of adduction synergy and forming temperature is below 135 DEG C, have the advantages that be substantially reduced mix temperature and forming temperature, and its mixture properties is suitable with hot asphalt.
(2) warm-mixed asphalt additive of the present invention further limits by percentage to the quality, the warm-mixed asphalt addition Agent prescription includes: powdery solid object: 50wt%~96wt%;Fischer-tropsch wax: 2wt%~20wt%;Branching type high molecular polymer: 1wt%~10wt%;N, N '-ethylenebisstearamide: 1wt%~20wt%, under the conditions of above-mentioned percentage, between each component Synergistic effect can reach excellent warm mix effect.Especially further preferred powdery solid object 65wt%~88wt%, Fischer-Tropsch Wax: 5wt%~15wt%, branching type high molecular polymer: 3wt%~8wt%, N, N '-ethylenebisstearamide: 4wt%~ 12wt% when the warm-mixed asphalt additive being prepared is used to prepare warm-mixed asphalt, can reduce the temperature for paving and rolling, Gas discharge significantly reduces when construction, and environmental benefit is significant, can also while improving Warm-Mix Bitumen Mixture high temperature Rut resistance Anti-water damage ability is improved, the service life on road surface can be effectively extended.
(3) warm-mixed asphalt additive of the present invention further limits powdery solid object by the inorganic matter of 60wt% ~ 80wt% Component, the organic constituents composition of 20wt% ~ 40wt%;Wherein, the inorganic matter component contains SiO2And Al2O3, the organic matter Component contains asphalitine, colloid, flocculant component, due to the flocculant component in organic constituents can be formed with pitch it is cementing Effect can play the power that be combined with each other for reinforcing asphalite arogel ramming material system, and then can change asphalt to temperature The sensibility of variation improves the peeling resistance of pitch and building stones, to extend the service life of road.
Specific embodiment
With reference to embodiments, the present invention is further described in detail, but not limited to this.
Raw materials are for example non-special in embodiment of the present invention, are commercial product.
Embodiment 1
Warm-mixed asphalt additive described in the present embodiment, following mass percent meter are formulated as follows:
Powdery solid object: 96wt%;Wherein, inorganic matter component accounts for 80wt% in powdery solid object, and organic constituents account for 20wt%;
Fischer-tropsch wax: 3wt%;
Branching type high molecular polymer (molecular weight 20000): 1wt%;
N, N '-ethylenebisstearamide: 1wt%;
Powdery solid object is oily sludge (wherein oil content is 90wt%, solid content 5wt%) by oil in the present embodiment Mud extraction heat dewatering process obtains, and process is as follows: oily sludge being sent into centrifuge, while flocculation being added into centrifuge Agent, that is, polyacrylamide, the additional amount of flocculant make containing flocculant 0.03wt% in final powdery solid object, and oily sludge passes through Enter extraction process after centrifugal treating;Oily sludge after centrifugation is mixed with extractant 1:60 in mass ratio, in pressure For normal pressure, heating temperature is extracted under the conditions of being 95 DEG C, and extraction time is 12 hours, and the oil and solids in oily sludge turn It moves on in extractant, after separation, obtains solid sediment;The solid sediment is again normal pressure, heating temperature in operating pressure Degree carries out stripping deoiling treatment under the conditions of being 140 DEG C, handles the time: 0.5 hour, obtaining particle size range after stripping deoiling treatment For the powdery solid object of 0.02 ~ 1mm.In obtained solid material, the content of organic constituents is 20wt%, and inorganic matter component contains Amount is 80wt%.Extractant used in it be aviation kerosine, light diesel fuel and heavy diesel fuel mixing preparation obtain boiling point be 100 DEG C ~ 600 DEG C of wide boiling point oil.
Embodiment 2
Warm-mixed asphalt additive described in the present embodiment, following mass percent meter are formulated as follows:
Powdery solid object: 88wt%, wherein inorganic matter component accounts for 75wt% in powdery solid object, and organic constituents account for 25wt%;
Fischer-tropsch wax: 5wt%;
Branching type high molecular polymer (molecular weight 9000): 3wt%;
N, N '-ethylenebisstearamide: 4wt%;
Powdery solid object described in the present embodiment the preparation method is as follows: by oily sludge (wherein oil content be 69wt%, Solid content is 24wt%) it is sent into centrifuge, while flocculant, that is, polyoxyethylene oleic acid ester being added into centrifuge, flocculant Additional amount makes containing flocculant 0.05wt% in final powdery solid object, and oily sludge enters after centrifugal treating to be extracted Journey;Oily sludge after centrifugation is mixed with extractant 1:50 in mass ratio, is normal pressure, heating temperature 115 in pressure It is extracted under the conditions of DEG C, extraction time is 9 hours, and the oil and solids in oily sludge are transferred in extractant, through separating Afterwards, solid sediment is obtained;The solid sediment is again normal pressure in operating pressure, and heating temperature carries out under the conditions of being 130 DEG C Deoiling treatment is stripped, the time is handled: 1 hour, the powdery solid that particle size range is 0.02 ~ 1mm is obtained after stripping deoiling treatment Object.In obtained solid material, the content of organic constituents is 25wt%, and the content of inorganic matter component is 75wt%.Used in it Extractant is that aviation kerosine, light diesel fuel and heavy diesel fuel mixing preparation obtain the wide boiling point oil that boiling point is 100 DEG C ~ 600 DEG C.
Embodiment 3
Warm-mixed asphalt additive described in the present embodiment, following mass percent meter are formulated as follows:
Powdery solid object: 74.2wt%: where inorganic matter component accounts for 70wt% in powdery solid object, and organic constituents account for 30wt%;
Fischer-tropsch wax: 9.2wt%;
Star-branched type high molecular polymer (molecular weight 6000): 5.8wt%;
N, N '-ethylenebisstearamide: 10.8wt%;
Powdery solid object described in the present embodiment the preparation method is as follows:
Oily sludge (wherein oil content be 43wt%, solid content 48wt%) is sent into centrifuge, while to centrifuge The middle mixture (the two mass ratio is 2:1) that flocculant, that is, Cocoamidopropyl betaine and ligninsulfonate is added, flocculant Additional amount make in final powdery solid object containing flocculant 0.6wt%, oily sludge enters after centrifugal treating to be extracted Journey;Oily sludge after centrifugation is mixed with extractant 1:40 in mass ratio, is normal pressure, heating temperature 110 in pressure It is extracted under the conditions of DEG C, extraction time is 10 hours, and the oil and solids in oily sludge are transferred in extractant, through separating Afterwards, solid sediment is obtained;The solid sediment is again normal pressure in operating pressure, and heating temperature carries out under the conditions of being 120 DEG C Deoiling treatment is stripped, the time is handled: 1.5 hours, it is solid that the powdery that particle size range is 0.02 ~ 1mm is obtained after stripping deoiling treatment Body object.In obtained solid material, the content of organic constituents is 30wt%, and the content of inorganic matter component is 70wt%.It is wherein used Extractant be that aviation kerosine, light diesel fuel and heavy diesel fuel mixing preparation obtain wide boiling point that boiling point is 100 DEG C ~ 600 DEG C oil.
Embodiment 4
Warm-mixed asphalt additive described in the present embodiment, following mass percent meter are formulated as follows:
Powdery solid object: 65wt%;Wherein, inorganic matter component accounts for 72wt% in powdery solid object, and organic constituents account for 28wt%;
Fischer-tropsch wax: 15wt%;
Star-branched type high molecular polymer (molecular weight 18000): 8wt%;
N, N '-ethylenebisstearamide: 12wt%;
Powdery solid object described in the present embodiment the preparation method is as follows:
Oily sludge (wherein oil content be 69wt%, solid content 24wt%) is sent into centrifuge, while to centrifuge Middle addition flocculant, that is, alcohol ether phosphate, the additional amount of flocculant make to contain in final powdery solid object containing flocculant 0.1wt% Greasy dirt enters extraction process after centrifugal treating;Oily sludge after centrifugation is mixed with extractant 1:30 in mass ratio It closes, is normal pressure in pressure, heating temperature is extracted under the conditions of being 100 DEG C, and extraction time is 11 hours, the oil in oily sludge It is transferred in extractant with solids, after separation, obtains solid sediment;The solid sediment is again normal in operating pressure Pressure, heating temperature carry out stripping deoiling treatment under the conditions of being 110 DEG C, handle the time: 2 hours, obtaining after stripping deoiling treatment Particle size range is the powdery solid object of 0.02 ~ 1mm.In obtained solid material, the content of organic constituents is 28wt%, inorganic matter The content of component is 72wt%.Extractant used in it is that aviation kerosine, light diesel fuel and heavy diesel fuel mixing preparation obtain boiling point and be 100 DEG C ~ 600 DEG C of wide boiling point oil.
Embodiment 5
Asphalt mixture warm-mixing additive is formulated as follows by percentage to the quality:
Powdery solid object: 60.2wt%;Wherein, inorganic matter component accounts for 65wt% in powdery solid object, and organic constituents account for 35wt%;
Fischer-tropsch wax: 14.5wt%;
Star-branched type high molecular polymer (molecular weight 15000): 7wt%;
N, N '-ethylenebisstearamide: 18.3wt%;
Powdery solid object described in the present embodiment the preparation method is as follows:
Oily sludge (wherein oil content be 69wt%, solid content 24wt%) is sent into centrifuge, while to centrifuge Middle addition flocculant, that is, fatty alcohol polyoxyethylene ether ammonium sulfate, the additional amount of flocculant make in final powdery solid object containing flocculation Agent 0.2wt%, oily sludge enter extraction process after centrifugal treating;Oily sludge after centrifugation is pressed into quality with extractant It is mixed than 1:20, is normal pressure in pressure, heating temperature is extracted under the conditions of being 120 DEG C, and extraction time is 8 hours, is contained Oil and solids in greasy dirt are transferred in extractant, after separation, obtain solid sediment;The solid sediment exists again Operating pressure is normal pressure, and heating temperature carries out stripping deoiling treatment under the conditions of being 100 DEG C, the processing time: 2.5 hours, through stripping The powdery solid object that particle size range is 0.02 ~ 1mm is obtained after deoiling treatment.In obtained solid material, the content of organic constituents For 35wt%, the content of inorganic matter component is 65wt%.Extractant used in it is aviation kerosine, light diesel fuel and heavy diesel fuel mixing Allotment obtains the wide boiling point oil that boiling point is 100 DEG C ~ 600 DEG C.
Embodiment 6
Asphalt mixture warm-mixing additive is formulated as follows by percentage to the quality:
Powdery solid object: 50wt%;Wherein, inorganic matter component accounts for 60wt% in powdery solid object, and organic constituents account for 40wt%;
Fischer-tropsch wax: 20wt%;
Star-branched type high molecular polymer (molecular weight 12000): 10wt%;
N, N '-ethylenebisstearamide: 20wt%;
Powdery solid object described in the present embodiment the preparation method is as follows:
Oily sludge (wherein oil content be 69wt%, solid content 24wt%) is sent into centrifuge, while to centrifuge The middle mixture (three's mass ratio is 1:1:1) that flocculant, that is, Sodium Polyacrylate, calcium polyacrylate (CPA) and polyacrylamide is added, wadding The additional amount of solidifying agent makes containing flocculant 0.01wt% in final powdery solid object, and oily sludge enters extraction after centrifugal treating Take process;Oily sludge after centrifugation is mixed with extractant 1:20 in mass ratio, is normal pressure in pressure, heating temperature is It is extracted under the conditions of 120 DEG C, extraction time is 8 hours, and the oil and solids in oily sludge are transferred in extractant, through dividing From rear, solid sediment is obtained;The solid sediment again operating pressure be normal pressure, heating temperature be 100 DEG C under the conditions of into Row stripping deoiling treatment handles the time: 3 hours, it is solid that the powdery that particle size range is 0.02 ~ 1mm is obtained after stripping deoiling treatment Body object.In obtained solid material, the content of organic constituents is 40wt%, and the content of inorganic matter component is 60wt%.The extraction Agent is to recycle after wastewater treatment field oily wastewater is overregulated oil separator, pressurized dissolved air flotation, oil water separator processing, and boiling point is 100 DEG C ~ 600 DEG C of sump oil;
In addition, branching type high molecular polymer of the present invention, which can use, meets commercially available star branch as defined in molecular weight Change high molecular polymer.It can certainly be according to document " the more lithiums initiation synthesis radial styrene-isoprene-fourths of nitrogen functionalization The microstructure and sparkling transition temperature of diene copolymers " (Wang Zhengsheng etc., China Synthetic Rubber Industry, on May 15th, 2007,30 (3), page 175 ~ 178) and " nitrogen is functionalized more lithiums and causes butadiene/isoprene/styrene polymerization dynamics " (Wang Zhengsheng etc., China Synthetic Rubber Industry, on November 15th, 2006,29(6), page 419 ~ 423) as defined in preparation method synthesize above-mentioned all embodiments Described in branching type high molecular polymer.Specific preparation method can refer to as follows:
(1) it uses molar ratio to react for the HMI of 1:1 and n-BuLi first, generates LHMI(, that is, hexamethyleneimino Lithium), DVB (i.e. divinylbenzene) is added on this basis, synthesizes initiator Li;
(2) it is polymerize in 5L stainless steel kettle, with butadiene (Bd), isoprene (Ip), styrene (St) for monomer, Mass fraction is 10%, and the initial concentration (in terms of monomer) of initiator is 7.69 × 10-4Mol/L, with purified nitrogen by hexamethylene pressure Enter repeatedly nitrogen charging, emptying polymeric kettle in, according to the primary hexamethylene that purification is added of metering, St, Ip and Bd, polarity is added Regulator N, N, N ', N '-tetramethylethylenediamine (TMEDA), after temperature in the kettle rises to 50 DEG C, broken with n-BuLi it is miscellaneous, then It after the initiator Li reaction 4h of metering is added, is terminated with ethyl alcohol, it is heavy that the antioxidant 264 industrial alcohol that mass fraction is 1% is added After dropping polymer out, rolls and done to constant mass at 100 DEG C, obtain star-branched high molecular polymer.
The present invention still further provides the preparation method of warm-mixed asphalt additive in above-mentioned all embodiments, specific to prepare Steps are as follows: by powdery solid object, fischer-tropsch wax, branching type high molecular polymer, N, N '-ethylenebisstearamide is according to the ratio Screw extruder is put into, is uniformly mixed under the conditions of temperature is 80 DEG C~110 DEG C and squeezes out finished product to get asphalt mixture warm-mixing is arrived Additive.
Comparative example 1
The present invention is still further provided to be added with the warm-mixed asphalt that document CN103242666A described in background technique provides Add the formula of agent as comparative example 1, warm-mixed asphalt additive has been prepared, specific formula is as follows: 15 parts of polyethylene wax, chlorination 15 parts of paraffin -70,50 parts of diatomite, 2 parts of stearmide, 4 parts of solid-state antistripping agent, the fusing point of the polyethylene wax is preferably 110 DEG C, the solid-state antistripping agent is sodium lignin sulfonate.
Warm-mixed asphalt additive described in this comparative example the preparation method is as follows: polyethylene wax and stearmide are ground respectively The micro mist that partial size is not more than 0.075mm is worn into, then by the poly- second after chlorinated paraffin -70, diatomite, antistripping agent and grinding Alkene wax and stearmide are placed in high speed ball mill together, with the ball milling speed ball milling 30min of 500r/min, obtain warm-mixed asphalt Additive.
Experimental example
According to method as defined in " standard specification for construction and acceptance of highway asphalt pavement " (JTG F40-2004), respectively by embodiment 1 ~ 6 and comparative example 1 in the warm-mixed asphalt additive for preparing used according to pitch with the preparation method of asphalt of the invention The 5wt% of amount puts into asphalt, is prepared into bitumen mixture specimen A, B, C, D, E, F, G.This test uses 90#A grades Pitch, bitumen aggregate ratio (percentage of asphalt from asphalt mixture and building stones mass ratio) are 5.1%, and the gradation of building stones is shown in Table 1, performance Evaluation result is shown in Table 2.It is as follows specifically to mix and stir process:
1, it weighs building stones in 170 DEG C of baking oven by set amount to heat 4 hours, it is small that pitch heats 4 in 150 DEG C of baking ovens When, mixer temperature is set as 150 DEG C.
2, rubble material is first added mixer at a set temperature, uniform stirring 1 minute.
3, mixer is added in asphalt mixture additive, mixes and stirs 1 minute, add pitch, continues under set temperature It mixes and stirs 3 minutes.
1 building stones size grading table of table.
Partial size/mm 16~13.2 13.2~9.5 9.5~4.75 4.75~2.36 2.36~1.18 1.18~0.6 0.6~0.3 0.3~0.15 0.15~0.075 Less than 0.075
Embodiment 1 ~ 6 and comparison Example 1, ratio/wt% 4.6 22 24 14.1 14.7 6.3 4.2 4.3 5.8 --
2 performance of asphalt mixture test result of table.
Project Mix and stir temperature/DEG C Forming temperature/DEG C Stability/kN It soaks residual stability ratio (%) Freeze-thaw split retained strength ratio (%) Low temperature damage strains (μ ε) 60 DEG C of dynamic stabilities (secondary/mm)
A 134 122 11.6 86.5 82.6 2358 1332
B 130 120 10.3 84.7 80.9 2206 1307
C 126 113 9.8 85.2 79.3 2240 1261
D 130 118 10.3 85.5 80.0 2219 1356
E 132 120 10.5 86.6 81.0 2324 1327
F 128 114 9.6 85.8 80.5 2225 1285
G 137 126 7.9 76.2 72.4 1628 1211
Heat is mixed 153 137 10.9 87.2 83.9 2205 1372
Technical standard * -- -- ≥8 ≥80 ≥75 ≥2000 ≥1000
Test data shows the asphalt for replacing diatomite to prepare with asphalt mixture warm-mixing additive of the present invention, Mix and stir be substantially reduced 15~30 DEG C relative to hot-mix asphalt mixture with specimen molding temperature in the case where, performance indexes It is all satisfied the requirement of " standard specification for construction and acceptance of highway asphalt pavement " (JTG F40-2004).
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments, and it is extended from this it is obvious variation or It changes among still in the invention scope of protection of the claims.

Claims (11)

1. a kind of warm-mixed asphalt additive, which is characterized in that formula includes: powdery solid object, fischer-tropsch wax, branching type macromolecule Polymer and N, N '-ethylenebisstearamide;Wherein, the powdery solid object is to be dehydrated by oily sludge through greasy filth extraction heat The solid product isolated after process;By percentage to the quality, in formula each component content are as follows: powdery solid object: 50wt%~96wt%;Fischer-tropsch wax: 2wt%~20wt%;Branching type high molecular polymer: 1wt%~10wt%;N, N '-ethylenebis Stearmide: 1wt%~20wt%;By percentage to the quality, the powdery solid object is grouped as by following group: inorganic matter component 60wt% ~ 80wt%, organic constituents 20wt% ~ 40wt%;Wherein, contain SiO in the inorganic matter component2And Al2O3, described to have Contain asphalitine, colloid and flocculant component in machine object component.
2. warm-mixed asphalt additive according to claim 1, which is characterized in that by percentage to the quality, including the following raw material:
Powdery solid object: 65wt%~88wt%;
Fischer-tropsch wax: 5wt%~15wt%;
Branching type high molecular polymer: 3wt%~8wt%;
N, N '-ethylenebisstearamide: 4wt%~12wt%.
3. warm-mixed asphalt additive according to claim 1, which is characterized in that the particle size range of the powdery solid object is 0.02~1mm.
4. any warm-mixed asphalt additive according to claim 1 ~ 3, which is characterized in that the greasy filth extraction heat dewatering process Steps are as follows: oily sludge being sent into centrifuge, while flocculant being added into centrifuge, the additional amount of flocculant makes finally Contain flocculant 0.005wt%~1wt% in powdery solid object, oily sludge enters extraction process after centrifugal treating;It will be from Oily sludge and extractant (1:1) in mass ratio~(1:80) after the heart, are mixed, and are normal pressure in pressure, heating temperature is It is extracted under the conditions of 95 DEG C ~ 120 DEG C, extraction time is 8 hours ~ 12 hours, and the oil and solids in oily sludge are transferred to In extractant, after separation, solid sediment is obtained;The solid sediment is again normal pressure in operating pressure, and heating temperature is Stripping deoiling treatment is carried out under the conditions of 100 DEG C ~ 140 DEG C, is handled the time: 0.5 hour ~ 3.0 hours, being obtained after stripping deoiling treatment To the powdery solid object.
5. warm-mixed asphalt additive according to claim 4, which is characterized in that the greasy filth extraction heat dewatering process step In, the oily sludge and extractant (1:30) in mass ratio~(1:50) after centrifugation are mixed.
6. warm-mixed asphalt additive according to claim 4, which is characterized in that the extractant is that boiling range is 100 DEG C ~ 600 DEG C wide boiling point oil;Wherein, the wide boiling point oil is to deploy to obtain using one or more distillates, or use at oily wastewater The sump oil for meeting boiling spread recycled during reason.
7. warm-mixed asphalt additive according to claim 6, which is characterized in that the extractant is that boiling range is 100 DEG C ~ 250 DEG C wide boiling point oil.
8. warm-mixed asphalt additive according to claim 4, which is characterized in that by percentage to the quality, the oily sludge Middle oil content is 3wt% ~ 95wt%, and solid content is 2wt% ~ 95wt%.
9. any warm-mixed asphalt additive according to claim 1 ~ 2, which is characterized in that the branching type high molecular polymer It is that the molecular weight that is synthesized by butadiene, styrene and isoprene monomer by polymerization reaction is high in 1000 ~ 20000 branching type Molecularly Imprinted Polymer.
10. any warm-mixed asphalt additive according to claim 1 ~ 2, which is characterized in that the branching type high molecular polymerization Object is star-branched high molecular polymer.
11. the preparation method of any warm-mixed asphalt additive of claim 1 ~ 10, includes the following steps: powdery solid Object, fischer-tropsch wax, branching type high molecular polymer, N, N '-ethylenebisstearamide puts into screw extruder according to the ratio, in temperature Degree is uniformly mixed under the conditions of being 80 DEG C~110 DEG C squeezes out finished product to get warm-mixed asphalt additive is arrived.
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EP3249017A1 (en) * 2016-05-27 2017-11-29 Sasol Wax GmbH A bitumen composition comprising a wax mixture consisting of a petroleum slack wax and a fischer-tropsch wax, the use of the wax mixture in bitumen compositions, the use of the bitumen composition in asphalt compositions, asphalt compositions comprising the bitumen composition and the method of producing asphalt pavements thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0300284A1 (en) * 1987-07-08 1989-01-25 Marco Dr. Fachini A composition for giving bituminous conglomerates high mechanical characteristics and resistance to high and low temperatures, also by using sludge obtained from the treatment of waste lubricating oil
CN101041744A (en) * 2007-04-04 2007-09-26 杨军海 Bitumen modifier
CN102180575A (en) * 2011-03-31 2011-09-14 濮阳市天地人环保工程技术有限公司 Processing method for centralized treatment and reclamation of oil-containing sludge
CN103554936A (en) * 2013-11-14 2014-02-05 辽河石油勘探局 Asphalt-mineral composite material prepared by utilizing thickened oil sludge and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0300284A1 (en) * 1987-07-08 1989-01-25 Marco Dr. Fachini A composition for giving bituminous conglomerates high mechanical characteristics and resistance to high and low temperatures, also by using sludge obtained from the treatment of waste lubricating oil
CN101041744A (en) * 2007-04-04 2007-09-26 杨军海 Bitumen modifier
CN102180575A (en) * 2011-03-31 2011-09-14 濮阳市天地人环保工程技术有限公司 Processing method for centralized treatment and reclamation of oil-containing sludge
CN103554936A (en) * 2013-11-14 2014-02-05 辽河石油勘探局 Asphalt-mineral composite material prepared by utilizing thickened oil sludge and preparation method thereof

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