CN103709415A - Preparation method of composite slow-breaking slow-curing asphalt emulsifier - Google Patents
Preparation method of composite slow-breaking slow-curing asphalt emulsifier Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite slow-breaking slow-curing asphalt emulsifier, which comprises the following steps: adding vegetable oil and concentrated sulfuric acid into a reaction vessel, stirring to react, adding water, and stirring to react to obtain hydroxylated vegetable oil; and stirring the hydroxylated vegetable oil and glycerol to react, adding water, uniformly mixing, cooling, adding sodium hydroxide, stirring to react, and adding phosphate to obtain the composite slow-breaking slow-curing asphalt emulsifier. The vegetable oil used as the raw material belongs to renewable resources, and therefore, the method has the advantages of wide sources, low price, simple synthesis technique, feasible technological conditions and zero discharge of three wastes in the preparation process, and thus, conforms to the trend of national environmental protection policy and industry. The composite emulsifier has the advantages of a nonionic surfactant and an anionic surfactant, has a synergistic action, and has the characteristics of high emulsifying capacity and low consumption; and the prepared asphalt emulsion is uniform and fine, and has high storage stability.
Description
Technical field
The present invention relates to a kind of compound preparation method of splitting slowly slow-curing asphalt emulsifying agent, belong to organic fine field of chemicals.
Background technology
Petroleum pitch is important starting material in the fields such as road traffic, buildings waterproof and industrial antisepsis.Emulsified bitumen is easy to use because of it, saves the energy, reduces and pollutes, and extends the plurality of advantages such as engineering time, range of application expanding day.The crucial starting material of preparing bitumen emulsion are asphalt emulsifiers, and conventional asphalt emulsifier has negatively charged ion, positively charged ion, zwitter-ion and nonionic surface active agent at present.The asphalt emulsifier of single variety is difficult to meet the petroleum pitch of different sources, the needs of different types of building stones and different road construction use properties, by different types of asphalt emulsifier compound use, not only can overcome shortcoming separately, and there is synergism, improve the use properties of emulsified bitumen, broadened application scope.In recent years, the compound asphalt emulsifier of reported in literature mainly concentrates on the composite of different sorts tensio-active agent: patent CN1060661A and discloses that a kind of to take wooden amine tensio-active agent be main body, other cats product of admixture and suitable auxiliary agent; Patent CN101745340A discloses a kind ofly take amides cats product as host, and admixture fatty alcohol-polyoxyethylene ether nonionogenic tenside and suitable auxiliary agent improve the stability in storage of bitumen emulsion, have improved the use properties of bitumen emulsion.The gorgeous China of Lu. composite asphalt emulsifying agent development [J]. northern traffic, 2007, (4), report employing anion surfactant and nonionogenic tenside Compositional type emulsifying agent is prepared bitumen emulsion, solved preferably the poor problem of strong basicity building stones and cationic emulsified bitumen compatibleness.
Vegetables oil is the grease extracting from the fruits and seeds of natural phant, and wide material sources are the important renewable resourcess of a class.Natural phant main body of oil is fatty acid triglyceride, contains much and can, for functional group's (as two keys, hydroxyl, carbonyl etc.) of modification, the functional group modification of vegetables oil can be prepared to various plants oil derivative.In recent years, relevant plant oil modified reported in literature mainly concentrates on the fields such as macromolecular material auxiliary agent, biofuel, ink addition agent, vegetable oil polyol, synthetic resins and resin curing agent, lubricant, catalyzer and tensio-active agent.Abide by etc. synthetic [J] of sulforicinoleic acid. application chemical industry, 2007,36 (2): reported with concentrated acid sulfonation Viscotrol C and prepared sulforicinoleic acid anion surfactant.Zeng little Jun etc. the preparation and property of Novel Nonionic Waterborne Polyurethane Surfactants [J]. polymer material science and engineering, 2008,24 (3): reported and take Viscotrol C, tolylene diisocyanate, polyoxyethylene glycol and prepare nonionogenic tenside as raw material.Patent CN102726384A discloses a kind of new vegetable oil farm chemical emulgent, by triglycerin fat acid esters, propandiol butyl ether, glycerine and long-chain fat amine composite forming by a certain percentage.Adopt the method for present patent application to prepare compound asphalt emulsifier, there is not yet reported in literature.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of nonionic/anion surfactant the compound preparation method of splitting slowly slow-curing asphalt emulsifying agent for above-mentioned prior art, with the bitumen emulsion that this product makes, have and split slowly slow hardening performance, while being applicable to use alkaline building stones in road traffic construction, the priming oil of bituminous pavement, basic unit's sealing, and high-speed railway negatively charged ion CA mortar.
The present invention solves the problems of the technologies described above adopted technical scheme: the compound preparation method of splitting slowly slow-curing asphalt emulsifying agent, comprises following concrete steps:
1) vegetables oil and the vitriol oil 1.0: 2.0 in molar ratio～4.0 are joined in reaction vessel, stirring reaction 1.0～3.0h under normal temperature, then adding with vegetables oil mol ratio is 3.0～6.0: 1 water, at 40～60 ℃ of stirring reaction 0.5～1.5h, obtains hydroxylation vegetables oil;
2) by hydroxylation vegetables oil and glycerol with mol ratio 1.0: 3.0～5.0 after 70～95 ℃ of stirring reaction 3～8h, add the water that accounts for vegetables oil quality 50～100%, after mixing, be cooled to below 50 ℃, adding with vegetables oil mol ratio is 5.0～10.0: 1.0 sodium hydroxide, at 40～60 ℃ of stirring reaction 1.0～3.0h, add the phosphoric acid salt that accounts for vegetables oil quality 5～20%, obtain the compound slow-curing asphalt emulsifying agent that splits slowly.
Press such scheme, described vegetables oil is Viscotrol C, soya-bean oil, rapeseed oil, tung oil, Oleum Gossypii semen or Semen Maydis oil.
Press such scheme, described phosphoric acid salt is sodium phosphate, tertiary sodium phosphate or phosphoric acid five sodium.
The present invention be take vegetables oil as raw material, after hydroxylating, carry out transesterification reaction with glycerine and prepare monoglyceride nonionogenic tenside, then add alkali by partial glycerol ester saponification, prepare anion surfactant, obtain the compound slow-curing asphalt emulsifying agent that splits slowly of nonionic/anion surfactant.Take Semen Maydis oil as example, and reaction equation involved in the present invention is as follows:
The invention has the advantages that: take vegetables oil as raw material, belong to renewable resources, wide material sources, low price, synthesis technique is simple, and processing condition easily realize, and in preparation process, " three wastes " zero release, meets national environmental protection policy and industrial development direction.Monoglyceride is conventional nonionic surface active agent, and hard soap is conventional anion surfactant, and long aliphatic chain polyhydroxylated makes two class tensio-active agents have stronger emulsifying capacity and to the better adaptability of petroleum pitch.Nonionogenic tenside and anion surfactant compound use, not only have advantages of nonionogenic tenside and anion surfactant, and have synergism, and the emulsifying capacity of mixed emulsifier is strong, consumption is few; The bitumen emulsion uniform and smooth of preparation, stability in storage is good.Poly-hydroxy on long aliphatic chain in mixed emulsifier and glycerine provide slow fragility energy for bitumen emulsion, phosphatic add and reaction process in the sodium sulfate that generates as the stablizer of bitumen emulsion, for bitumen emulsion provides better stability.
Embodiment
Embodiment described below is that range of application of the present invention is not subject to the impact of specific embodiment in order to further illustrate particular content of the present invention, concrete embodiment can according to technical scheme of the present invention and with time particular case determine.
Embodiment 1
By the about 0.1mol of 93.2g() Viscotrol C and 40.0g(0.4mol) vitriol oil adds in reaction vessel, after stirring at normal temperature reaction 1.5h, adds 7.2g(0.4mol) water, at 50 ℃ of stirring reaction 1.0h, obtain hydroxyl Viscotrol C (about 0.1mol).Then add 35.0g(0.38mol) glycerine, after 80 ℃ of stirring reaction 6h, add 80.0g water, after being uniformly mixed, be cooled to below 50 ℃, add 95.0g(0.95mol) 40% sodium hydroxide solution, at 50～55 ℃ of stirring reaction 1.5h, be cooled to 30 ℃, add 10.0g tertiary sodium phosphate, after stirring and dissolving, obtain compound asphalt emulsifier.
Emulsifier aqueous solution preparation
5.0g emulsifying agent is joined in the 100.0g hot water of 60～70 ℃, after stirring and dissolving, obtain emulsifier aqueous solution, heat preservation for standby use.
The preparation of bitumen emulsion
Open colloidal mill, first the emulsifier aqueous solution of 60～70 ℃ is joined in the colloidal mill after preheating, then by the 150.0g PetroChina Company Limited. 70 that is heated to 125～135 ℃
#petroleum pitch adds in colloidal mill with thread shape, and circular grinding 1 minute, obtains even, fine and smooth bitumen emulsion.
Bitumen emulsion performance test
Embodiment 2
By the about 0.1mol of 88.0g() soya-bean oil and 40.0g(0.4mol) vitriol oil adds in reaction vessel, after stirring at normal temperature reaction 1.5h, adds 9.0g(0.5mol) water, at 50 ℃ of stirring reaction 1.0h, obtain hydroxyl soya-bean oil (about 0.1mol).Then add 35.0g(0.38mol) glycerine, after 80 ℃ of stirring reaction 5h, add 70.0g water, after being uniformly mixed, be cooled to 50 ℃, add 95.0g(0.95mol) 40% sodium hydroxide solution, at 50～55 ℃ of stirring reaction 1.5h, be cooled to 30 ℃, add 10.0g sodium phosphate, after stirring and dissolving, obtain compound asphalt emulsifier.
Emulsifier aqueous solution preparation (with embodiment 1)
Bitumen emulsion preparation (with embodiment 1)
Bitumen emulsion performance test
Embodiment 3
By the about 0.1mol of 100.0g() rapeseed oil and 35.0g(0.35mol) vitriol oil adds in reaction vessel, after stirring at normal temperature reaction 1.5h, adds 7.2g(0.4mol) water, at 50 ℃ of stirring reaction 1.0h, obtain hydroxylation rapeseed oil (about 0.1mol).Then add 35.0g(0.38mol) glycerine, after 75～80 ℃ of stirring reaction 6h, add 85.0g water, after being uniformly mixed, be cooled to 50 ℃, add 85.0g(0.85mol) 40% sodium hydroxide solution, at 50～55 ℃ of stirring reaction 1.5h, be cooled to 30 ℃, add 10.0g phosphoric acid five sodium, after stirring and dissolving, obtain compound asphalt emulsifier.
Emulsifier aqueous solution preparation (with embodiment 1)
Bitumen emulsion preparation (with embodiment 1)
Bitumen emulsion performance test
Embodiment 4
Emulsifying agent preparation
By the about 0.1mol of 87.0g() tung oil and 40.0g(0.4mol) vitriol oil adds in reaction vessel, after stirring at normal temperature reaction 2.0h, adds 10.0g(0.56mol) water, at 55 ℃ of stirring reaction 1.5h, obtain hydroxylated tung oil (about 0.1mol).Then add 35.0g(0.38mol) glycerine, after 80～85 ℃ of stirring reaction 5h, add 70.0g water, after being uniformly mixed, be cooled to 50 ℃, add 95.0g(0.95mol) 40% sodium hydroxide solution, at 50～55 ℃ of stirring reaction 2.0h, be cooled to 30 ℃, add 10.0g tertiary sodium phosphate, after stirring and dissolving, obtain compound asphalt emulsifier.
Emulsifier aqueous solution preparation (with embodiment 1)
Bitumen emulsion preparation (with embodiment 1)
Bitumen emulsion performance test
Embodiment 5
Emulsifying agent preparation
By the about 0.1mol of 88.0g() Oleum Gossypii semen and 25.0g(0.25mol) vitriol oil adds in reaction vessel, after stirring at normal temperature reaction 1.5h, adds 7.2g(0.4mol) water, at 50 ℃ of stirring reaction 1.0h, obtain hydroxylation Oleum Gossypii semen (about 0.1mol).Then add 35.0g(0.38mol) glycerine, after 80～85 ℃ of stirring reaction 5h, add 70.0g water, after being uniformly mixed, be cooled to 50 ℃, add 65.0g(0.65mol) 40% sodium hydroxide solution, at 45～50 ℃ of stirring reaction 1.5h, be cooled to 30 ℃, add 10.0g phosphoric acid five sodium, after stirring and dissolving, obtain compound asphalt emulsifier.
Emulsifier aqueous solution preparation (with embodiment 1)
Bitumen emulsion preparation (with embodiment 1)
Bitumen emulsion performance test
Embodiment 6
Emulsifying agent preparation
By the about 0.1mol of 88.0g() Semen Maydis oil and 30.0g(0.3mol) vitriol oil adds in reaction vessel, after stirring at normal temperature reaction 1.5h, adds 8.1g(0.45mol) water, at 50 ℃ of stirring reaction 1.0h, obtain hydroxylation Semen Maydis oil (about 0.1mol).Then add 35.0g(0.38mol) glycerine, after 80～85 ℃ of stirring reaction 5h, add 70.0g water, after being uniformly mixed, be cooled to 50 ℃, add 75.0g(0.75mol) 40% sodium hydroxide solution, at 45～50 ℃ of stirring reaction 1.5h, be cooled to 30 ℃, add 10.0g tertiary sodium phosphate, after stirring and dissolving, obtain compound asphalt emulsifier.
Emulsifier aqueous solution preparation (with embodiment 1)
Bitumen emulsion preparation (with embodiment 1)
Bitumen emulsion performance test
Claims (3)
1. the compound preparation method of splitting slowly slow-curing asphalt emulsifying agent, comprises following concrete steps:
1) vegetables oil and the vitriol oil 1.0: 2.0 in molar ratio～4.0 are joined in reaction vessel, stirring reaction 1.0～3.0h under normal temperature, then adding with vegetables oil mol ratio is 3.0～6.0: 1 water, at 40～60 ℃ of stirring reaction 0.5～1.5h, obtains hydroxylation vegetables oil;
2) by hydroxylation vegetables oil and glycerol with mol ratio 1.0: 3.0～5.0 after 70～95 ℃ of stirring reaction 3～8h, add the water that accounts for vegetables oil quality 50～100%, after mixing, be cooled to below 50 ℃, adding with vegetables oil mol ratio is 5.0～10.0: 1.0 sodium hydroxide, at 40～60 ℃ of stirring reaction 1.0～3.0h, add the phosphoric acid salt that accounts for vegetables oil quality 5～20%, obtain the compound slow-curing asphalt emulsifying agent that splits slowly.
2. by the compound preparation method of splitting slowly slow-curing asphalt emulsifying agent claimed in claim 1, it is characterized in that described vegetables oil is Viscotrol C, soya-bean oil, rapeseed oil, tung oil, Oleum Gossypii semen or Semen Maydis oil.
3. by the compound preparation method of splitting slowly slow-curing asphalt emulsifying agent described in claim 1 or 2, it is characterized in that described phosphoric acid salt is sodium phosphate, tertiary sodium phosphate or phosphoric acid five sodium.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754358A (en) * | 2016-03-14 | 2016-07-13 | 同济大学 | Plant oil-based asphalt regenerating agent and preparation method thereof |
| CN105778525A (en) * | 2016-03-14 | 2016-07-20 | 同济大学 | Vegetable oil regenerated asphalt and preparation method thereof |
| CN107118136A (en) * | 2017-05-26 | 2017-09-01 | 山西省交通科学研究院 | A kind of both sexes asphalt emulsifier and preparation method thereof |
| US10570286B2 (en) | 2016-08-30 | 2020-02-25 | Iowa State University Research Foundation, Inc. | Asphalt products and methods of producing them for rejuvenation and softening of asphalt |
| US10604655B2 (en) | 2014-08-29 | 2020-03-31 | Iowa State University Research Foundation, Inc. | Asphalt products and materials and methods of producing them |
| US10961395B2 (en) | 2016-02-29 | 2021-03-30 | Iowa State University Research Foundation, Inc. | Rejuvenation of vacuum tower bottoms through bio-derived materials |
| US11773265B2 (en) | 2019-09-18 | 2023-10-03 | Iowa State University Research Foundation, Inc. | Biosolvents useful for improved asphalt products utilizing recycled asphalt pavement or other brittle asphalt binders such as vacuum tower bottom |
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| CN101085943A (en) * | 2006-06-07 | 2007-12-12 | 上海桑迪精细化工研究所有限公司 | Method for preparing vegetable oil based polyatomic alcohol for hard bubble polyurethane |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10604655B2 (en) | 2014-08-29 | 2020-03-31 | Iowa State University Research Foundation, Inc. | Asphalt products and materials and methods of producing them |
| US10961395B2 (en) | 2016-02-29 | 2021-03-30 | Iowa State University Research Foundation, Inc. | Rejuvenation of vacuum tower bottoms through bio-derived materials |
| US11958974B2 (en) | 2016-02-29 | 2024-04-16 | Iowa State University Research Foundation, Inc. | Rejuvenation of vacuum tower bottoms through bio-derived materials |
| CN105754358A (en) * | 2016-03-14 | 2016-07-13 | 同济大学 | Plant oil-based asphalt regenerating agent and preparation method thereof |
| CN105778525A (en) * | 2016-03-14 | 2016-07-20 | 同济大学 | Vegetable oil regenerated asphalt and preparation method thereof |
| CN105754358B (en) * | 2016-03-14 | 2018-08-28 | 同济大学 | One vegetable oil base bitumen regenerant and preparation method thereof |
| CN105778525B (en) * | 2016-03-14 | 2018-10-26 | 同济大学 | One vegetable oil regeneration asphalt and preparation method thereof |
| US10570286B2 (en) | 2016-08-30 | 2020-02-25 | Iowa State University Research Foundation, Inc. | Asphalt products and methods of producing them for rejuvenation and softening of asphalt |
| US11370918B2 (en) | 2016-08-30 | 2022-06-28 | Iowa State University Research Foundation, Inc. | Asphalt products and methods of producing them for rejuvenation and softening of asphalt |
| CN107118136A (en) * | 2017-05-26 | 2017-09-01 | 山西省交通科学研究院 | A kind of both sexes asphalt emulsifier and preparation method thereof |
| US11773265B2 (en) | 2019-09-18 | 2023-10-03 | Iowa State University Research Foundation, Inc. | Biosolvents useful for improved asphalt products utilizing recycled asphalt pavement or other brittle asphalt binders such as vacuum tower bottom |
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