WO2014026492A1 - 生物沥青、生物沥青组合物及其制备方法 - Google Patents

生物沥青、生物沥青组合物及其制备方法 Download PDF

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Publication number
WO2014026492A1
WO2014026492A1 PCT/CN2013/075536 CN2013075536W WO2014026492A1 WO 2014026492 A1 WO2014026492 A1 WO 2014026492A1 CN 2013075536 W CN2013075536 W CN 2013075536W WO 2014026492 A1 WO2014026492 A1 WO 2014026492A1
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Prior art keywords
bio
asphalt
oil
component
mass
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PCT/CN2013/075536
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English (en)
French (fr)
Inventor
曹东伟
何敏
张海燕
吴小维
唐国奇
钟科
范勇军
Original Assignee
交通运输部公路科学研究所
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Priority claimed from CN201210287249.6A external-priority patent/CN102796547B/zh
Priority claimed from CN2012102874025A external-priority patent/CN102766340A/zh
Application filed by 交通运输部公路科学研究所 filed Critical 交通运输部公路科学研究所
Priority to US14/234,598 priority Critical patent/US9752098B2/en
Priority to EP13829699.1A priority patent/EP2883914B1/en
Publication of WO2014026492A1 publication Critical patent/WO2014026492A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/18—Working-up tar by extraction with selective solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/19—Working-up tar by thermal treatment not involving distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/30—Coherent pavings made in situ made of road-metal and binders of road-metal and other binders, e.g. synthetic material, i.e. resin
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/35—Toppings or surface dressings; Methods of mixing, impregnating, or spreading them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/50—Inorganic non-macromolecular ingredients
    • C08L2555/52—Aggregate, e.g. crushed stone, sand, gravel or cement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/60—Organic non-macromolecular ingredients, e.g. oil, fat, wax or natural dye
    • C08L2555/62—Organic non-macromolecular ingredients, e.g. oil, fat, wax or natural dye from natural renewable resources
    • C08L2555/64—Oils, fats or waxes based upon fatty acid esters, e.g. fish oil, olive oil, lard, cocoa butter, bees wax or carnauba wax

Definitions

  • Bio-asphalt bio-asphalt composition and preparation method thereof
  • the invention relates to the technical field of road asphalt materials, in particular to a bio-leachable, bio-asphalt composition prepared by using bio-oil and a preparation method thereof. Background technique
  • Petroleum asphalt is derived from crude oil processing and refining, and its resources are declining, which inevitably makes petroleum asphalt increasingly tight. Due to the current over-exploitation and use, oil resources are about to face the danger of depletion. scientistss predict that by the middle of this century, around 2050, oil resources will be exhausted.
  • Biomass resources are huge. In China, for example, about 700 million tons of agricultural and sideline products can be used as energy. Among them, the annual output of crop straw is about 600 million tons; other agricultural waste is about 130 million tons; forestry biomass resources can be used for energy use about 300 million tons per year; the annual production of municipal solid waste is about 250 million tons. . Compared with petrochemical energy, biomass energy has two outstanding advantages: environmental friendliness and renewable.
  • Biomass pyrolysis also known as thermal cracking or cracking, usually means that in the absence of oxygen or anoxic environment, biomass is heated and heated to cause molecular decomposition to produce coke.
  • the process of condensable volatiles and gaseous products, the condensable volatiles are rapidly cooled into a flowable liquid to become bio-oil or tar, and the yield is about 40% - 60%.
  • the bio-oil crude oil produced by pyrolysis is subjected to further processing such as grading, refining and separation to obtain gasoline, diesel, methanol, ethanol fuel oil and chemical products.
  • bio-oil Currently produced bio-oils are usually burned directly as low-grade fuels.
  • bio-oil The nature of the heavy components is very close to that of road asphalt, which can be modified into road construction asphalt - bio-asphalt, which can realize the relative "waste" reuse in the energy and chemical industry, turning waste into treasure, and forming a circular economy. Complementary production system.
  • the bio-asphalt obtained by the extraction process and the oxidation process of the bio-oil has excellent adhesion and can be used for road paving.
  • a method of modifying it to improve the performance of the asphalt is generally used.
  • the fatigue resistance of the bio-asphalt is remarkably improved, and the temperature sensitivity is remarkably lowered, exhibiting excellent low-temperature crack resistance.
  • bio-asphalt preparation process is simple, easy to handle, and easy to implement.
  • the raw material bio-oil used in the preparation of bio-asphalt is not limited to lignin-rich bio-oil, which makes the raw material prepared by bio-asphalt more adaptable. Summary of the invention
  • the object of the present invention is to provide a method for preparing bio-asphalt using bio-oil and a bio-asphalt and bio-asphalt composition prepared to solve the problem of increasingly reduced resources, continuous price increase, unsustainable development and performance of petroleum asphalt currently in widespread use. Excellent question.
  • the present invention provides a method for preparing bio-asphalt, characterized in that the bio-oil is obtained by an extraction process and an oxidation process, wherein the bio-oil is an oily liquid product obtained by pyrolysis of biomass,
  • the biomass is preferably lignin-rich biomass such as corn stover, oak, switch grass, rice husk, and the like.
  • the method for preparing a bio-asphalt according to the present invention wherein the extraction process is a process of extracting bio-oil by water and centrifuging to obtain a water-insoluble bio-oil component.
  • the oxidation process of 0. 5-2h is carried out by contacting the water-insoluble bio-oil component obtained by the extraction process with air at 90-12 CTC and stirring.
  • the method for preparing a bio-asphalt according to the present invention wherein the oxidation process is that the water-insoluble bio-oil component obtained by the extraction process is contacted with air at 90-12 CTC, and mixed with an alcohol substance and stirred. 5-2h oxidation process.
  • the method for preparing a bio-asphalt according to the present invention wherein the alcohol substance is ethylene glycol, 1, 2-propanediol, glycerin, benzyl alcohol or polyethylene glycol, and is insoluble based on the extraction process.
  • the total mass of the bio-oil component in water is from 5 to 30% by mass based on the content of the alcohol.
  • the present invention also provides a bio-asphalt, characterized in that the bio-asphalt is obtained by the bio-asphalt preparation method of the present invention, and the bio-asphalt has a penetration degree of 25-150 d ⁇ at 25 ° C, and the softening point is 40-80 ° C, 25 ° C ductility of 10 50 cm or 15 ° C ductility of 0-40 cm, adhesion to stone is 4-5.
  • the present invention also provides a bio-asphalt composition, characterized in that the bio-asphalt composition comprises: component (A) a bio-oil component or a solution in which the bio-oil of the present invention is insoluble in water after an extraction process Bio-asphalt, component (B) petroleum pitch or aromatic oil or combination thereof, and component (C) polymer material, based on the total mass of the bio-asphalt composition, the content of the component (A) is 30-60% by mass, preferably 35-55 mass%, the content of the component (B) is 40-70% by mass, preferably 50-60% by mass, and the content of the component (C) is 0- 10% by mass, preferably 5 to 10% by mass.
  • component (A) a bio-oil component or a solution in which the bio-oil of the present invention is insoluble in water after an extraction process Bio-asphalt
  • component (B) petroleum pitch or aromatic oil or combination thereof component (C) polymer material, based on the total mass of the bio-
  • bio-asphalt composition according to the present invention, wherein the bio-asphalt composition has a penetration of 40-150 dmm at 25 ° C, a softening point of 45-90 ° C, a 10 ° C ductility of 10 _ 80 cm, and adhesion to stone. Sex is level 5.
  • bio-asphalt composition wherein the polymer material is rubber, a resin, a thermoplastic elastomer or a combination thereof.
  • bio-asphalt uses sawdust and straw, rice husk and other agricultural and forestry by-products or waste as raw materials. , determines its renewability and environmental protection.
  • the method suitable for processing asphalt in bio-oil can be separated and oxidized and modified to obtain bio-asphalt, which can be used in whole or in part to replace (30-70%) petroleum asphalt for construction and maintenance. Highways can reduce asphalt production costs by about 15%.
  • the light component content in the bio-asphalt intermediate product can be controlled to ensure the thermochemical properties of the bio-asphalt intermediate product in the production process, and inhibit the bio-asphalt production process.
  • the volatilization of the light and light components improves the performance stability and eco-friendlyness of the asphalt material.
  • bio-oil is mainly used as a fuel, and this usage not only reduces the added value of its products, but also causes environmental pollution.
  • the invention uses bio-oil to prepare bio-asphalt, which greatly saves the cost of raw materials.
  • the raw materials of the invention are derived from low-cost biomass resources, and the raw materials are abundant; the bio-asphalt prepared therefrom can replace petroleum resources and reduce dependence on petroleum resources.
  • bio-asphalt By preparing bio-asphalt, biomass resources such as agricultural and forestry by-products are efficiently recycled.
  • the invention has the characteristics of simple preparation, low cost and excellent performance. detailed description
  • the present invention provides bio-asphalt and bio-asphalt compositions and methods for their preparation.
  • the bio-asphalt preparation method described in the present invention is that the bio-oil is prepared by an extraction process and an oxidation process.
  • the bio-oil is an oily liquid product obtained by pyrolysis using biomass as a raw material.
  • the biomass preferably used includes corn straw, oak, and agro-forestry by-products. Switchgrass, rice husks and municipal solid waste.
  • the extracting process and the oxidizing process according to the present invention are: the water-insoluble bio-oil component obtained by centrifuging the bio-oil is directly contacted with air at a temperature of from 90 ° C to 120 ° C and continuously stirred. 2h steps. 5-1. 5h, More preferably 0. 5-lh.
  • the temperature is preferably from 95 ° C to 1 10 ° C, more preferably from 100 ° C to 105 ° C
  • the stirring time is preferably 0. 5-1. 5h, more preferably 0. 5-lh.
  • the mixture of the water-insoluble organic oil component is 0. 5-2h step. 5-1. 5h, More preferably 0. 5-lh.
  • the temperature is preferably from 95 ° C to 105 ° C, more preferably 95 ° 0100 ° 0, the stirring time is preferably 0. 5-1. 5h, more preferably 0. 5-lh.
  • the alcohol substance is ethylene glycol, 1, 2-propanediol, glycerol, benzyl alcohol or polyethylene glycol, and based on the total mass of the bio-oil component which is insoluble in water after the extraction process, the alcohol substance The content is 5 to 30% by mass.
  • the mixing and agitating can be carried out before, after or simultaneously with the contact with air, preferably simultaneously.
  • the bio-asphalt of the invention has a penetration degree of 25-150 d ⁇ at 25° C, a softening point of 40-80° C., a ductility of 10° 50° at 25° C. or a ductility of 0 ⁇ 40 cm at 15° C., and adhesion to stone materials.
  • the degree of penetration is 4_5; the test methods for penetration, softening point, ductility and adhesion are respectively referred to the industrial standard of the People's Republic of China JTG E20-2011, according to the experiments T0604-2011, T0606-201 K ⁇ 0605-2011, T0616- In 1993.
  • the bio-asphalt composition of the present invention combines the bio-oil component which is insoluble in water after the bio-oil extraction process or the bio-asphalt, petroleum asphalt and/or aromatic oil and polymer material are combined according to a certain ratio .
  • the bio-oil component or the bio-asphalt content of the bio-oil after the extraction process is 30-60% by mass, preferably 35-55 mass, based on the total mass of the bio-asphalt composition.
  • the content of the petroleum pitch or aromatic oil or a combination thereof is 40 to 70% by mass, preferably 50 to 60% by mass
  • the content of the polymer material is 0 to 10% by mass, preferably 5 to 10% by mass.
  • the petroleum pitch is preferably petroleum pitches Nos.
  • the polymer material is rubber, resin, thermoplastic elastomer or a combination thereof.
  • the rubber is selected from one or more of natural rubber, neoprene, styrene butadiene rubber, ethylene propylene diene rubber, nitrile rubber, and butadiene rubber.
  • the resin is selected from one or more of polyethylene, polystyrene, polypropylene, and ethylene-vinyl acetate copolymer.
  • the thermoplastic elastomer is a styrene-butadiene-styrene copolymer
  • the polymer material may be a waste polymer material, and the waste polymer material is recycled plastic or waste rubber powder, and the waste rubber powder has a particle diameter of 30-80 mesh.
  • the bio-asphalt composition of the present invention has a penetration of 40-150 dmm at 25 ° C, a softening point of 45-90 ° C, a 10 ° C ductility of 10-80 cm, and an adhesion to stone of 5 grades;
  • the test methods for penetration, softening point, ductility and adhesion were respectively carried out according to the industrial standard JTG E20-2011 of the People's Republic of China, according to the experiments T0604-201 1, ⁇ 0606-201 1, T0605-201 K T0616-1993.
  • the bio-asphalt composition of the present invention may be a bio-oil component which is insoluble in water after the bio-oil of the present invention is subjected to an extraction process or the bio-asphalt, petroleum pitch or aromatic oil or a combination thereof, a polymer material It is prepared by mixing, shearing or a combination thereof.
  • bio-asphalt and bio-asphalt compositions of the present invention can be used in paving roads.
  • Bio-oil China Anhui Yi Neng Biomass Energy Co., Ltd.; China Shandong Yoneng Bioenergy has Limited company, model specification YNP2009/3D/rice.
  • Petroleum asphalt China Zhonghai No. 70 petroleum asphalt; China Zhonghai 110 petroleum asphalt.
  • Aromatic oil Shandong Furunda Chemical Co., Ltd., saturated components, aromatic components, colloids, asphaltene percentages are: 25. 77%, 65.8%, 8. 2%, 0. 23% .
  • SBS China Yueyang Petrochemical, grade YH-791H, S/B ratio 30/70, density 0. 94g/cm 3 , melt index (190 ° C, 2. 16Kg) 0. 5 g/10min.
  • Glycerol Xiqiao Chemical Co., Ltd., analytical grade.
  • Ethylene glycol Beijing Chemical Plant, analytical grade.
  • 1,2-propanediol Xiqiao Chemical Co., Ltd., analytical grade.
  • bio-oil Under high-speed agitation, 500 g of bio-oil was dripped into a beaker containing 2000 mL of distilled water immersed in an ice water bath (5 ° C). After all the bio-oil was dripped, it was stirred for another half an hour, and the water was removed by a centrifugal dehydrator. The obtained water-insoluble bio-oil component was directly contacted with air at 90 ° C and continuously stirred for 1 h to obtain bio-asphalt 1 .
  • Example 1 The water-insoluble bio-oil component of Example 1 was directly contacted with air at 90 ° C and continuously stirred for 90 minutes to obtain bio-asphalt 2 .
  • the bio-asphalt 3 was obtained by directly contacting the water-insoluble bio-oil component of Example 1 with air at 90 ° C and stirring for 45 min.
  • Example 4 Extraction Oxidation 4
  • Example 1 The water-insoluble bio-oil component of Example 1 was directly contacted with air at 100 ° C and continuously stirred for 1 h to obtain bio-asphalt 4 .
  • Example 1 The water-insoluble bio-oil component of Example 1 was directly contacted with air at 100 ° C and continuously stirred for 90 minutes to obtain bio-asphalt 5 .
  • Example 1 The water-insoluble bio-oil component of Example 1 was directly contacted with air at 100 ° C and continuously stirred for 45 minutes to obtain bio-asphalt 6 .
  • Example 1 The water-insoluble bio-oil component of Example 1 was directly contacted with air at 110 ° C and continuously stirred for 45 minutes to obtain bio-asphalt 7 .
  • Example 1 The water-insoluble bio-oil component of Example 1 was directly contacted with air at 110 ° C and continuously stirred for 30 minutes to obtain bio-asphalt 8 .
  • Example 12 extraction oxidation 12
  • bio-asphalt 2 300 g of bio-asphalt 2 and 700 g of No. 70 petroleum pitch were stirred at 130 ° C for 10 min, and the obtained product was a bio-asphalt composition 1.
  • bio-asphalt composition 2 600 g of bio-asphalt 3 and 400 g of No. 70 petroleum pitch were stirred at 130 ° C for 10 min, and the obtained product was a bio-asphalt composition 2 .
  • Example 16 water-insoluble bio-oil component + SBS + aromatic oil
  • Example 17 water-insoluble bio-oil component + SBS + aromatic oil
  • Example 18 water-insoluble bio-oil component + SBR + petroleum pitch
  • Example 19 water-insoluble bio-oil component + SBR + petroleum pitch
  • 300g of No. 110 petroleum pitch was heated to 130 ° C, added with 30g of SBR, stirred at 140 ° C for 30min, then moved to high speed shear for shearing, shear temperature of 180 ° C, shear rate of 5000r / min, shearing After 30 minutes, 300 g of the water-insoluble bio-oil component obtained in Example 1 was added, and the mixture was stirred at 120 ° C for 80 minutes, and the obtained product was a bio-asphalt composition 6.
  • Example 20 water-insoluble bio-oil component + SBR + petroleum pitch
  • 300g of No. 110 petroleum pitch was heated to 130 ° C, added with 30g of SBR, stirred at 140 ° C for 30min, then moved to high speed shear for shearing, shear temperature of 180 ° C, shear rate of 5000r / min, shearing After 30 minutes, 300 g of the water-insoluble bio-oil component obtained in Example 1 was added, and HOrnin was stirred at 120 ° C to obtain a bio-asphalt composition 7. Performance Testing
  • bio-asphalt and bio-asphalt composition of the present invention can be used for construction of heavy traffic roads.

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  • General Chemical & Material Sciences (AREA)
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  • Physics & Mathematics (AREA)
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Abstract

本发明提供一种生物沥青和生物沥青组合物及其制备方法，属于沥青材料技术领域。本发明方法以生物油为原料，采用萃取工艺和氧化工艺的组合制备得到生物沥青，并利用普通石油沥青和/或芳烃油与高分子材料对生物油萃取工艺后的产物或生物沥青进行改性得到生物沥青组合物。本发明的制备方法简单易行，生产过程污染小，原料简单易得。所得到的生物沥青或生物沥青组合物可以直接用于生产道路沥青混合料铺装道路。

Description

生物沥青、 生物沥青组合物及其制备方法 技术领域
本发明涉及道路沥青材料技术领域， 特别涉及用生物油制备的生物沥 青、 生物沥青组合物及其制备方法。 背景技术
石油沥青来源于原油加工炼制， 其资源的日益减少， 必然使得石油沥青 日趋紧俏。 由于目前的过度开采和使用， 石油资源即将面临枯竭的危险， 科 学家预计到本世纪中叶， 即 2050年左右， 石油资源将会开采殆尽。
石油资源现状和环境发展的问题迫使我们不断寻找和应用新的、可再生 的替代材料。 目前， 全世界全力研发的生物质能源就是一种取之不尽、 用之 不竭的可再生能源。这种材料由于具有原料广泛、可再生和生物降解的特性， 因此已经进入工业化的步伐。
生物质资源量巨大， 以中国为例， 约有 7亿吨农副产品可作为能源利用。 其中， 农作物秸杆年产量约 6亿吨； 其他农业废弃物约 1. 3亿吨； 林业生物质 资源每年可用于能源用途约 3亿吨； 城市固体废弃物年产生量约 2. 5亿吨。 与 石化能源相比， 生物质能源具有环境友好和可再生两大突出优点。
热解制油是目前生物能源生产利用的最主要技术途径， 生物质热解又称 热裂解或裂解， 通常是指在无氧或缺氧的环境下， 生物质被加热升温引起分 子分解产生焦炭、 可凝性挥发分和气体产物的过程， 可凝性挥发分被快速冷 却成可流动的液体， 成为生物油或焦油， 其产率约为 40 % -60 %。 经过热解 生成的生物油原油要经过进一步的处理， 例如分级、 精炼以及分离， 才能得 到汽油、 柴油、 甲醇、 乙醇燃料油和化工产品。
当前生产的生物油通常都直接作为低级燃料直接燃烧掉。但是， 生物油 的重组分的性质与道路用沥青很接近，可以改性为道路建设沥青——生物沥 青， 这样既可以实现能源化工领域的相对 "废料"的再利用， 变废为宝， 又 可以形成循环经济的互补生产系统。
生物油经过萃取工艺和氧化工艺得到的生物沥青具有优良的粘接性， 可 以用于道路铺装。 为了进一步提高低温抗裂性能， 通常使用对其进行改性以 提高沥青性能的方法。 通过向生物沥青中添加石油沥青和高分子材料， 生物 沥青的耐疲劳性明显提高， 并且温度敏感性明显降低， 表现出优良的低温抗 裂性能。
该生物沥青制备工艺简单， 易于操控， 便于实施。 而且生物沥青制备所 用原料生物油， 不仅局限于富含木质素生物油， 使得生物沥青制备的原料适 应性更强。 发明内容
发明要解决的问题
本发明的目的是提供用生物油制备生物沥青的方法和制备的生物沥青 以及生物沥青组合物，用以解决目前正在广泛使用的石油沥青的资源日益减 少、 价格持续攀升、 不能持续发展以及性能不优良的问题。
用于解决问题的方案
本发明提供一种生物沥青的制备方法， 其特征在于， 将生物油经萃取工 艺和氧化工艺得到所述生物沥青， 其中所述生物油是生物质经过热解制得的 油状液体产物， 所述生物质优选为富含木质素生物质， 如玉米秸杆、 橡木、 柳枝稷、 稻壳等。
根据本发明所述的生物沥青的制备方法，其中所述萃取工艺为将生物油 经水萃取， 离心分离得到不溶于水的生物油组分的工艺。 根据本发明所述的生物沥青的制备方法，其中所述氧化工艺为将经萃取 工艺所得不溶于水的生物油组分在 90-12CTC下与空气接触并搅拌 0. 5-2h的 氧化工艺。
根据本发明所述的生物沥青的制备方法，其中所述氧化工艺为将经萃取 工艺所得不溶于水的生物油组分在 90-12CTC下与空气接触， 并且与醇类物质 混合并搅拌 0. 5-2h的氧化工艺。
根据本发明所述的生物沥青的制备方法， 其中所述醇类物质为乙二醇， 1， 2-丙二醇， 丙三醇， 苯甲醇或聚乙二醇， 且基于所述经萃取工艺后不溶于 水的生物油组分总质量， 醇类物质的含量为 5-30质量％。
本发明还提供一种生物沥青， 其特征在于， 所述生物沥青通过本发明的 所述生物沥青制备方法得到， 并且所述生物沥青的 25°C针入度为 30-150d匪， 软化点为 40-80°C， 25°C延度为 10_50cm或 15°C延度为 0-40cm， 与石料的粘附 性为 4-5级。
本发明还提供一种生物沥青组合物， 其特征在于， 所述的生物沥青组合 物包含： 组分 （A) 本发明所述的生物油经萃取工艺后不溶于水的生物油组 分或所述的生物沥青， 组分 （B ) 石油沥青或芳烃油或其组合， 和组分 （C ) 高分子材料， 基于所述生物沥青组合物的总质量， 所述组分 （A ) 的含量为 30-60质量％， 优选为 35-55质量％， 所述组分 （B ) 的含量为 40-70质量％， 优 选为 50-60质量％， 所述组分 （C ) 的含量为 0-10质量％， 优选为 5-10质量％。
根据本发明所述的生物沥青组合物， 其中所述生物沥青组合物的 25°C针 入度为 40-150dmm， 软化点为 45_90 °C， 10 °C延度为 10_80cm， 与石料的粘附 性为 5级。
根据本发明所述的生物沥青组合物， 其中所述的高分子材料为橡胶、 树 脂、 热塑性弹性体或其组合。 发明的效果
首先， 用生物沥青替代石油沥青可降低沥青生产成本， 从长远看， 对比 石油沥青的资源枯竭和不可再生等问题， 生物沥青采用锯末和秸杆、 稻壳等 农林业副产物或废弃物为原材料， 决定了其可再生性和绿色环保性。
其次， 用本发明的方法可将生物油中适合于加工沥青的组分分离、 经过 氧化改性制得生物沥青， 可以用其全部或者部分替代 （30-70%)石油沥青用 于建设和养护公路， 可以降低沥青生产成本约 15%。
再次， 通过控制萃取氧化过程中的氧化温度、 氧化时间等参数， 可以控 制生物沥青中间产物中的轻组分含量，保证生物沥青中间产物在生产过程中 热化学性质稳定， 抑制在生物沥青生产过程中轻组分的挥发， 从而提高沥青 材料的性能稳定性和生态环保性。
当前生物油主要被用作燃料， 这种用法不仅降低了其产品附加值， 而且 容易造成环境污染。 本发明将生物油用于制备生物沥青， 大大节省了原材料 成本。
此外， 本发明原材料来源于价格低廉的生物质资源， 原材料来源丰富； 由其制备得到的生物沥青可以代替石油资源， 降低对石油资源的依赖性。
通过制备生物沥青， 使农林副产物等生物质资源得到高效循环利用。 本发明具有制备简单、 成本低、 性能优异的特点。 具体实施方式
本发明提供生物沥青和生物沥青组合物以及它们的制备方法。
本发明中所述的生物沥青制备方法是将生物油经萃取工艺和氧化工艺 制备得到所述生物沥青。所述的生物油是利用生物质为原料， 经过热解制得 的油状液体产物。优选使用的生物质包括农林业副产物中的玉米秸杆、橡木、 柳枝稷、 稻壳以及城市生活垃圾等。
本发明所述的萃取工艺和氧化工艺为将生物油经水洗， 离心分离所得的 不溶于水的生物油组分在 90 °C -120 °C条件下与空气直接接触并不断搅拌 0. 5-2h的步骤。 所述温度条件优选为 95 °C -1 10°C， 更优选 100 °C _105 °C， 所 述搅拌时间优选为 0. 5-1. 5h， 更优选 0. 5-lh。
本发明所述的氧化工艺进一步为将经萃取工艺所得的不溶于水的生物 油组分在 90°C -120°C条件下与空气接触， 并且与醇类物质混合搅拌 0. 5-2h的 步骤。 所述温度条件优选为 95°C-105°C， 更优选95°0100°0， 所述搅拌时间 优选为 0. 5-1. 5h， 更优选 0. 5-lh。 所述醇类物质为乙二醇， 1， 2-丙二醇， 丙 三醇， 苯甲醇或聚乙二醇， 且基于所述经萃取工艺后不溶于水的生物油组分 总质量， 醇类物质的含量为 5-30质量％。 所述混合搅拌可以在与空气接触之 前、 之后或同时进行， 优选同时进行。
本发明所述的生物沥青的 25°C针入度为 30-150d匪， 软化点为 40-80 °C ， 25°C延度为 10_50cm或 15°C延度为 0_40cm， 与石料的粘附性为 4_5级； 所述针 入度、软化点、延度及粘附性测试方法分别参照中华人民共和国行业标准 JTG E20-2011 , 根据实验 T0604-2011、 T0606-201 K Τ0605- 2011、 T0616-1993进 行。
本发明所述的生物沥青组合物由所述的生物油经萃取工艺后不溶于水 的生物油组分或所述的生物沥青、 石油沥青和 /或芳烃油与高分子材料按照 一定的比例组合。 其中基于所述生物沥青组合物的总质量， 所述的生物油经 萃取工艺后不溶于水的生物油组分或所述的生物沥青的含量为 30-60质量％， 优选为 35-55质量％， 所述石油沥青或芳烃油或其组合的含量为 40-70质量％， 优选为 50-60质量％，所述高分子材料的含量为 0-10质量％，优选为 5-10质量％。 所述的石油沥青优选为 70号、 90号和 110号石油沥青。 所述的高分子材料为橡胶、 树脂、 热塑性弹性体或其组合。 所述的橡胶 选自天然橡胶、 氯丁橡胶、 丁苯橡胶、 三元乙丙橡胶、 丁腈橡胶、 顺丁橡胶 的一种或多种。
所述的树脂选自聚乙烯、 聚苯乙烯、 聚丙烯、 乙烯 -醋酸乙烯酯共聚物 的一种或者多种。 所述的热塑性弹性体为苯乙烯-丁二烯-苯乙烯共聚物
( SBS ) o
所述的高分子材料可以为废旧高分子材料，所述废旧高分子材料为回收 塑料或废胶粉， 所述废胶粉的粒径为 30-80目。
所述的回收塑料的密度在 0. 89g/cm3-0. 96g/cm3， 熔点在 110 °C _135 °C， 在 190 °C、 2. 16Kg下的熔融指数在 0. 5g/min-10g/min范围内。
本发明所述的生物沥青组合物的 25 °C针入度为 40-150dmm， 软化点为 45-90 °C , 10 °C延度为 10_80cm， 与石料的粘附性为 5级； 所述针入度、 软化 点、延度及粘附性测试方法分别参照中华人民共和国行业标准 JTG E20-2011 , 根据实验 T0604-201 1、 Τ0606- 201 1、 T0605-201 K T0616-1993进行。
本发明所述的生物沥青组合物可以通过将本发明所述的生物油经萃取 工艺后不溶于水的生物油组分或所述的生物沥青， 石油沥青或芳烃油或其组 合， 高分子材料经过混合、 剪切或其组合工艺制备得到。
本发明所述的生物沥青和生物沥青组合物均可用于铺装道路。
以下将通过实施例来说明本发明的实施方案，但是本发明并不限于这些 特定的实施例。 实施例
各实施例中所使用的原材料：
生物油： 中国安徽易能生物质能源有限公司； 中国山东易能生物能源有 限公司， 型号规格 YNP2009/3D/稻。
石油沥青： 中国中海 70号石油沥青； 中国中海 110号石油沥青。
芳烃油： 山东孚润达化工有限公司， 饱和组分， 芳香组分， 胶质， 沥青 质的百分含量分别为： 25. 77%, 65. 8%, 8. 2%, 0. 23%。
SBS: 中国岳阳石化， 牌号 YH-791H, S/B比为 30/70， 密度 0. 94g/cm3， 熔 融指数 （190°C， 2. 16Kg) 0. 5 g/10min。
SBR: 山东高氏科工贸有限公司， 牌号： 1502。
丙三醇： 西陇化工股份有限公司， 分析纯。
乙二醇： 北京化工厂， 分析纯。
1，2-丙二醇： 西陇化工股份有限公司， 分析纯。
沥青材料的性能测试按照中国交通运输部行业标准《公路工程沥青及沥 青混合料试验规程 (JTG E20-2011) ))进行。
〈生物沥青实施例〉
实施例 1 (萃取氧化 1 )
在高速搅拌的条件下， 将 500g生物油逐滴滴入浸没在冰水浴 （5°C ) 中 的盛有 2000mL蒸馏水的烧杯中。 待生物油全部滴入后， 再搅拌半小时， 利用 离心脱水机将水脱除。所得不溶于水的生物油组分在 90°C条件下与空气直接 接触并不断搅拌 lh后得生物沥青 1。
实施例 2 (萃取氧化 2 )
将实施例 1中的不溶于水的生物油组分在 90°C条件下与空气直接接触并 不断搅拌 90min后得生物沥青 2。
实施例 3 (萃取氧化 3 )
将实施例 1中的不溶于水的生物油组分在 90°C条件下与空气直接接触并 不断搅拌 45min后得生物沥青 3。 实施例 4 (萃取氧化 4)
将实施例 1中的不溶于水的生物油组分在 100 °C条件下与空气直接接触 并不断搅拌 lh后得生物沥青 4。
实施例 5 (萃取氧化 5 )
将实施例 1中的不溶于水的生物油组分在 100 °C条件下与空气直接接触 并不断搅拌 90min后得生物沥青 5。
实施例 6 (萃取氧化 6 )
将实施例 1中的不溶于水的生物油组分在 100 °C条件下与空气直接接触 并不断搅拌 45min后得生物沥青 6。
实施例 7 (萃取氧化 7 )
将实施例 1中的不溶于水的生物油组分在 110 °C条件下与空气直接接触 并不断搅拌 45min后得生物沥青 7。
实施例 8 (萃取氧化 8 )
将实施例 1中的不溶于水的生物油组分在 110 °C条件下与空气直接接触 并不断搅拌 30min后得生物沥青 8。
实施例 9 (萃取氧化 9 )
将 300g实施例 1中的不溶于水的生物油组分在 95°C条件下与空气接触， 并且与 30g丙三醇不断搅拌 35min后得生物沥青 9。
实施例 10 (萃取氧化 10 )
将 300g实施例 1中的不溶于水的生物油组分在 95°C条件下与空气接触， 并且与 60g丙三醇不断搅拌 65min后得生物沥青 10。
实施例 11 (萃取氧化 11 )
将 300g实施例 1中的不溶于水的生物油组分在 95°C条件下与空气接触， 并且与 90g丙三醇不断搅拌 70min后得生物沥青 11。 实施例 12 (萃取氧化 12 )
将 300g实施例 1中的不溶于水的生物油组分在 95°C条件下与空气接触， 并且与 30g乙二醇不断搅拌 80min后得生物沥青 12。
实施例 13 (萃取氧化 13 )
将 300g实施例 1中的不溶于水的生物油组分在 95°C条件下与空气接触， 并且与 60g 1， 2-丙二醇不断搅拌 60min后得生物沥青 13。
〈生物沥青组合物实施例〉
实施例 14 (3生物沥青 +7石油沥青）
将 300g生物沥青 2与 700g 70号石油沥青在 130°C加热条件下搅拌 lOmin, 所得产品为生物沥青组合物 1。
实施例 15 (6生物沥青 +4石油沥青）
将 600g生物沥青 3与 400g 70号石油沥青在 130°C加热条件下搅拌 lOmin, 所得产品为生物沥青组合物 2。
实施例 16 (不溶于水的生物油组分 +SBS+芳烃油）
将 30g SBS加入至 300g芳烃油中， 130°C下搅拌 lh后加入 200g实施例 1所 得的不溶于水的生物油组分， 120°C条件下搅拌 45min， 所得产品为生物沥青 组合物 3。
实施例 17 (不溶于水的生物油组分 +SBS+芳烃油）
将 30g SBS加入至 300g芳烃油中， 130°C下搅拌 lh后加入 200g实施例 1所 得的不溶于水的生物油组分， 120°C条件下搅拌 90min， 所得产品为生物沥青 组合物 4。
实施例 18 (不溶于水的生物油组分 +SBR+石油沥青）
将 300g 110号石油沥青加热至 130°C， 加入 30g SBR， 140°C下搅拌 30min， 然后移至高速剪切机中剪切， 剪切温度 180°C， 剪切速率 5000r/min， 剪切 30min后加入 300g实施例 1所得的不溶于水的生物油组分， 120 °C下搅拌 50min, 所得产品为生物沥青组合物 5。
实施例 19 (不溶于水的生物油组分 +SBR+石油沥青）
将 300g 110号石油沥青加热至 130°C， 加入 30g SBR， 140°C下搅拌 30min， 然后移至高速剪切机中剪切， 剪切温度 180°C， 剪切速率 5000r/min， 剪切 30min后加入 300g实施例 1所得的不溶于水的生物油组分， 120 °C下搅拌 80min， 所得产品为生物沥青组合物 6。
实施例 20 (不溶于水的生物油组分 +SBR+石油沥青）
将 300g 110号石油沥青加热至 130°C， 加入 30g SBR， 140°C下搅拌 30min， 然后移至高速剪切机中剪切， 剪切温度 180°C， 剪切速率 5000r/min， 剪切 30min后加入 300g实施例 1所得的不溶于水的生物油组分， 120 °C下搅拌 HOrnin, 所得产品为生物沥青组合物 7。 性能测试
分别对上述实施例的生物沥青 1-13 (实施例 1-13 )， 生物沥青组合物 1-7 (实施例 14-20)， 进行软化点、 25°C针入度、 延度 （25°C/15°C/10°C ) 的测 试， 并对沥青与石料的粘附性进行了测试， 测试结果见表 1。
以上试验方法按照中国交通运输部行业标准《公路工程沥青及沥青混合 料试验规程 (JTG E20-2011)》 进行。
通过表 1的测试结果可以看出， 本发明的生物沥青及生物沥青组合物可 以用于重交通道路建设使用。
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Claims

权 利 要 求 书
1. 一种生物沥青的制备方法， 其特征在于， 将生物油经萃取工艺和氧 化工艺得到所述生物沥青， 其中所述生物油是富含木质素生物质经过热解制 得的油状液体产物。
2. 根据权利要求 1所述的生物沥青的制备方法，其中所述富含木质素生 物质包括玉米秸杆、 橡木、 柳枝稷、 稻壳。
3. 根据权利要求 1或 2所述的生物沥青的制备方法， 其中所述萃取工艺 为将生物油经水萃取， 离心分离得到不溶于水的生物油组分的工艺。
4. 根据权利要求 1所述的生物沥青的制备方法， 其中所述氧化工艺为将 经萃取工艺所得不溶于水的生物油组分在 90-12CTC下与空气接触并搅拌 0. 5-2h的氧化工艺。
5. 根据权利要求 1所述的生物沥青的制备方法， 其中所述氧化工艺为将 经萃取工艺所得不溶于水的生物油组分在 90-12CTC下与空气接触， 并且与醇 类物质混合并搅拌 0. 5-2h的氧化工艺。
6. 根据权利要求 5所述的生物沥青的制备方法， 其中所述醇类物质为乙 二醇， 1，2-丙二醇， 丙三醇， 苯甲醇或聚乙二醇， 且基于所述经萃取工艺后 不溶于水的生物油组分总质量， 醇类物质的含量为 5-30质量％。
7. 一种生物沥青， 其特征在于， 所述生物沥青通过权利要求 1-6任一项 的方法得到， 并且所述生物沥青的 25 °C针入度为 30-150dmm， 软化点为 40-80 °C , 25 °C延度为 10_50cm或 15 °C延度为 0-40cm， 与石料的粘附性为 4_5 级。
8. 一种生物沥青组合物， 其特征在于， 所述的生物沥青组合物包含： 组分（A)权利要求 3所述的生物油经萃取工艺后不溶于水的生物油组分或权 利要求 7所述的生物沥青，组分（B )石油沥青或芳烃油或其组合，和组分（C ) 高分子材料， 基于所述生物沥青组合物的总质量， 所述组分 （A ) 的含量为 30-60质量％， 优选为 35-55质量％， 所述组分 （B ) 的含量为 40-70质量％， 优 选为 50-60质量％， 所述组分 （C ) 的含量为 0-10质量％， 优选为 5-10质量％。
9. 根据权利要求 8所述的生物沥青组合物， 其中所述生物沥青组合物的 25 °C针入度为 40-150dmm， 软化点为 45_90 °C， 10 °C延度为 10_80cm， 与石料 的粘附性为 5级。
10. 根据权利要求 8或 9所述的生物沥青组合物，其中所述的高分子材料 为橡胶、 树脂、 热塑性弹性体或其组合。
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