CN104388109A - Preparation method of soluble intermediate phase asphalt - Google Patents

Preparation method of soluble intermediate phase asphalt Download PDF

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Publication number
CN104388109A
CN104388109A CN201410761063.9A CN201410761063A CN104388109A CN 104388109 A CN104388109 A CN 104388109A CN 201410761063 A CN201410761063 A CN 201410761063A CN 104388109 A CN104388109 A CN 104388109A
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Prior art keywords
mesophase pitch
solvable
preparation
intermediate phase
phase asphalt
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CN201410761063.9A
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CN104388109B (en
Inventor
刘安华
姚艳波
刘玲
丁绍楠
李风萍
刘星煜
胡志明
何国梅
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Xiamen University
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Xiamen University
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    • 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
    • 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

Abstract

The invention discloses a preparation method of soluble intermediate phase asphalt and relates to intermediate phase asphalt. The method comprises the steps of: 1) oxidizing the intermediate phase asphalt with potassium permanganate by taking deionized water as a solvent in a hot bath, and 2) allowing the oxidized intermediate phase asphalt obtained in Step 1) and a alkyl compound or a polymer with amino or hydroxyl functional groups to carry out condensation reaction to form the soluble intermediate phase asphalt. A chemical method is used for the first time to introduce the carboxyl group capable of being functionalized into the intermediate phase asphalt. The use of a hydrogenation agent for reducing a softening point and improving solubility is avoided in a process of synthesizing the intermediate phase asphalt traditionally, a new chemical reaction method is opened up, and the multiple groups can be introduced into the intermediate phase asphalt via ingenious design, so that a multiscale carbon material can be prepared by methods of self-assembly, phase separation, spincoating, adhesion coating and the like. A large condensed ring structure of the intermediate phase asphalt is not damaged by controlling the quantity of potassium permanganate, and the inherent outstanding performance of the intermediate phase asphalt is kept.

Description

A kind of preparation method of solvable mesophase pitch
Technical field
The present invention relates to mesophase pitch, especially relate to a kind of preparation method of solvable mesophase pitch.
Background technology
Mesophase pitch is before the organism such as pitch are solid-state charcoal by isotropic transition in liquid phase carbonation process, there is the intermediate product of anisotropic optical characteristic, it has easy greying and the high advantage of carbonization productive rate, is to produce the outstanding precursor of high performance carbon material.Mesophase pitch be the earliest the sixties in last century by the coking of Brooks and Taylor at Study on Coal in [the Brooks J.D. that finds, Taylor G.H., Chemistry and physics of Carbon [M] .New York:Marcel Dekker, 1968:243-244; Brooks J.D., Taylor G.H.Carbon, 1965,3 (2): 185-186], the preparation of mesophase pitch has been reacted mainly through thermal polycondensation, after raw material is carried out pre-treatment, 350 ~ 500 DEG C of insulation for some time, product carries out being isolated mesophase spherule [Moriyama R., Hayashi J., et al.Carbon, 2002,40 (1): 53-64].Experienced by semicentennial development, form the ambits such as chemistry, hydro carbons carbonization chemistry, mesophase spherule optical texture, mesophase spherule formation chemical kinetics at mesophase spherule and achieve significant progress.And achieve in high-performance asphalt base carbon fiber, needle coke, secondary lithium battery negative material, high-specific surface area activated carbon, high heat conduction Mesophase Pitch-Derived Carbon Foam etc. and use widely.
But the molecular bulk structure of mesophase pitch is condensed-nuclei aromatics, strong π-π Intermolecular Forces, cause its softening temperature higher, poorly soluble, though in strong solubility solvent is as N-Methyl pyrrolidone also major part can not dissolve, as the naphthalene mesophase pitch that softening temperature is 270 DEG C, in its N-Methyl pyrrolidone, insoluble point reaches 62.1% [Yao Y, Chen J, Liu L, DongY, Liu A J Mater Sci, 2012,47:5509].Because the softening temperature of mesophase pitch is high, poorly soluble, limit and prepare application in multiple dimensioned carbon material in the method for " from bottom to top " of use.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of solvable mesophase pitch.
The preparation method of described a kind of solvable mesophase pitch, comprises the following steps:
1) under hot water bath, deionized water makees solvent, uses potassium permanganate oxidation mesophase pitch;
2) by step 1) alkylate of gained oxidation mesophase pitch or hydroxy functional group amino with band or polymkeric substance carry out condensation reaction, obtains solvable mesophase pitch;
In step 1) in, the temperature of described hot water bath can be 40 ~ 100 DEG C; Described mesophase pitch comprises coal measures, petroleum and naphthalene system mesophase pitch; The mass ratio of mesophase pitch and potassium permanganate can be 1: (0.5 ~ 10).
In step 2) in, described alkylate can comprise C nh 2n+1nH 2or C nh 2n+1oH, wherein n=6 ~ 20; Described polymkeric substance can comprise the one in the polyethylene oxide, polystyrene, polymethylmethacrylate, poly(lactic acid) etc. of being with single-ended base; Described single-ended base can be amino or hydroxyl etc.; Described condensation reaction can be selected to be acyl chlorides and alkylate or polymer reaction by the converting carboxylate groups of oxidized bitumen; Or use dewatering agent directly oxidized bitumen and alkylate or polymer reaction to be prepared solvable mesophase pitch; Described dewatering agent can be selected from the one in Carbodiimides, carbonyl dimidazoles, the vitriol oil, anhydrous sodium sulphate, anhydrous magnesium sulfate, trichlorine phosphine oxide etc., and described Carbodiimides can be selected from the one in dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride etc.
The present invention adopts neutral potassium permanganate as oxygenant, is obtained by reacting the oxidized bitumen of band function base carboxyl, then oxidized bitumen and alkylate is reacted, prepare solvable mesophase pitch with coal measures, petroleum and naphthalene system mesophase pitch.In obtained solvable mesophase pitch, because the oxidizing condition selected is gentleer, therefore the large condensed cyclic structure of mesophase pitch can more completely keep.The condensed cyclic structure of mesophase pitch is that it has high carbonization productive rate and easy graphited key structure factor, and therefore, selection gentleness again effective oxidizing condition is key of the present invention.The invention solves existing mesophase pitch softening temperature high, the problem such as poorly soluble, and can autotelic introducing polymer chain etc., self-assembly can be utilized, be separated, spin coating, be stained with the methods such as painting and prepare the carbon material multiple dimensioned, there is Graphitic carbon structure.
The present invention first can functionalization group introduce mesophase pitch, select suitable oxidizing condition, the functional groups such as carboxyl are introduced mesophase pitch, subsequently, the polymkeric substance of long alkyl chain, different polymerization degree etc. is reacted with the mesophase pitch after oxidation, prepares solvable mesophase pitch.Polymkeric substance containing alkyl chain is the excellent raw material preparing various material surface carbon coating; Solvable mesophase pitch containing polymer segment, method prepares multiple dimensioned, to have Graphitic carbon structure carbon material can to utilize self-assembly, be separated etc.
Compared with prior art, advantage of the present invention is as follows:
1) first with chemical method can functionalization carboxyl introduce mesophase pitch.
2) tradition is avoided in the process of synthetic mesophase asphalt phase, hydrogenant agent is used to reduce softening temperature and improve solvability, open new chemical reaction method, multiple group can be introduced mesophase pitch by design cleverly, thus self-assembly can be utilized, be separated, spin coating, be stained with the methods such as painting and prepare multiple dimensioned carbon material.
3) by controlling the amount of potassium permanganate, thus the large condensed cyclic structure realizing mesophase pitch is not destroyed, and keeps mesophase pitch excellent properties inherently.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of MP-COOH pyrolysis carbonization at different temperatures.In FIG, (a) 900 DEG C; (b) 1200 DEG C; X-coordinate is 2 times of diffraction angle (°), and ordinate zou is relative diffracted intensity.
Fig. 2 is the solvable mesophase pitch tetrahydrofuran solution of different concns.In fig. 2, (a) 3mg/mL; (b) 2mg/mL; (c) 1mg/mL.
Fig. 3 is the solvable mesophase pitch solution of different concns, uses the SEM figure being stained with the carbon coating being coated with the standby ceramic fiber surface of legal system.In figure 3, (a, d and g) surface, (b, e and h) cross section and (c, f and i) mass of fibers, solvents tetrahydrofurane, strength of solution 3mg/mL (a, b and c), 2mg/mL (d, e and f) and 1mg/mL (g, h and i).
Embodiment
Embodiment 1
1) naphthalene system mesophase pitch and potassium permanganate are closed stirring very much in water, the mass ratio of mesophase pitch and potassium permanganate and water is 1: 8: 40;
2) by step 1) mixture of gained is at 50 DEG C, Keep agitation reaction 24h, question response terminates, be cooled to room temperature, add hcl acidifying, under maintenance acidic conditions, drip hydrogen peroxide, until bubble-free produces, with the by product Manganse Dioxide generated except deoxidation, then filter, wash and obtain for three times being oxidized mesophase pitch.Oxidation mesophase pitch is 900 DEG C of pyrolysis, its carbonization productive rate 75%, XRD figure spectrum (Fig. 1) after carbonization illustrates that oxidized bitumen can crystallization, retains easy the to be graphited essence of mesophase pitch, illustrate in oxidising process, the large condensed cyclic structure of mesophase pitch is not destroyed;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 6.0g carbonyl dimidazoles anhydrous tetrahydro furan (100ml) is middle and mixes, under room temperature after ultrasonic activation 12h, room temperature drips tetrahydrofuran (THF) (40ml) solution of 6.0g amino dodecane, is added dropwise to complete rear continuation room temperature ultrasonic vibration 12h.Be spin-dried for solvent after reaction terminates, add deionized water, filter, after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely (Fig. 2) in THF;
4) step 3) the solvable mesophase pitch of gained adds the THF solution that tetrahydrofuran (THF) is made into 3mg/mL 2mg/mL, 1mg/mL.Silicon carbide fiber bundle (about 500) is immersed in MP-CONH (C 12h 25)/THF solution, ultrasonic, slowly take out.Hang stretching under dry room temperature environment, after solvent evaporates, by pre-soaking fiber bundle at 210 DEG C of baking oven internal oxidition 1min, steeping process repeats 1 ~ 10 time, can realize the continuous covering of fiber surface, and coat-thickness on demand controls impregnating speed and number of times simultaneously.Finally, pyrolysis under high temperature (700 ~ 1100 DEG C) under an inert atmosphere, precursor generation removing impurities matter, dehydrogenation and carbonization, be converted into the carbon coating being attached to fiber surface.By scanning electronic microscope, fiber and coating are characterized, between fibrous bundle after this art breading without bonding phenomenon (Fig. 3), fiber surface coating dense uniform (Fig. 3), top coat can controlled in tens nanometer range (Fig. 3).
Embodiment 2
1) naphthalene system mesophase pitch and potassium permanganate are closed stirring very much in water, the mass ratio of mesophase pitch and potassium permanganate and water is 1: 3: 40;
2) by step 1) mixture of gained is at 70 DEG C, Keep agitation reaction 24h, question response terminates, and is cooled to room temperature, add hcl acidifying, hydrogen peroxide is dripped, until bubble-free produces, with the by product Manganse Dioxide generated except deoxidation under maintenance acidic conditions, then filter, wash and obtain for three times being oxidized mesophase pitch, the 900 DEG C of pyrolysis of oxidation mesophase pitch, its carbonization productive rate 76%;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 4.0g dicyclohexylcarbodiimide anhydrous tetrahydro furan (100ml) is middle and mixes, under ultrasonic disperse, room temperature drips tetrahydrofuran (THF) (40ml) solution of 4.0g amino dodecane, is added dropwise to complete rear continuation room temperature ultrasonic vibration 12h.Be spin-dried for solvent after reaction terminates, add deionized water, filter, after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, and then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely in THF.
Embodiment 3
1) coal measures mesophase pitch and potassium permanganate are closed stirring very much in water, the mass ratio of mesophase pitch and potassium permanganate and water is 1: 1: 40;
2) by step 1) mixture of gained is at 90 DEG C, Keep agitation reaction 24h, question response terminates, and is cooled to room temperature, add hcl acidifying, hydrogen peroxide is dripped, until bubble-free produces, with the by product Manganse Dioxide generated except deoxidation under maintenance acidic conditions, then filter, wash and obtain for three times being oxidized mesophase pitch, the 900 DEG C of pyrolysis of oxidation mesophase pitch, its carbonization productive rate 78%;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 10.0g anhydrous sodium sulphate anhydrous tetrahydro furan (100ml) is middle and mixes, under ultrasonic disperse, room temperature drips tetrahydrofuran (THF) (40ml) solution of the monohydroxy oxyethane of 10.0g molecular weight 550, is added dropwise to complete rear continuation room temperature ultrasonic vibration 12h.Be spin-dried for solvent after reaction terminates, add deionized water, filter, after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, and then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely in THF.
Embodiment 4
1) petroleum mesophase pitch and potassium permanganate are closed stirring very much in water, the mass ratio of mesophase pitch and potassium permanganate and water is 1: 6: 40;
2) by step 1) mixture of gained is at 80 DEG C, Keep agitation reaction 24h, question response terminates, and is cooled to room temperature, add hcl acidifying, hydrogen peroxide is dripped, until bubble-free produces, with the by product Manganse Dioxide generated except deoxidation under maintenance acidic conditions, then filter, wash and obtain for three times being oxidized mesophase pitch, the 900 DEG C of pyrolysis of oxidation mesophase pitch, its carbonization productive rate 77%;
3) by step 2) 5.0g of gained is oxidized mesophase pitch and 12.0g trichlorine phosphine oxide anhydrous tetrahydro furan (100ml) is middle and mixes, ultrasonic disperse under room temperature, drip tetrahydrofuran (THF) (40ml) solution that 8.0g molecular weight is the monohydroxy oxyethane of 550, be added dropwise to complete rear continuation room temperature ultrasonic vibration 12h.Be spin-dried for solvent after reaction terminates, add deionized water, filter, after washing three times, gained solid is at use dissolve with ethanol, filters, washing with alcohol three times, and then namely 50 DEG C of dry 24h of vacuum drying oven obtain solvable mesophase pitch, can dissolve completely in THF.

Claims (10)

1. a preparation method for solvable mesophase pitch, is characterized in that comprising the following steps:
1) under hot water bath, deionized water makees solvent, uses potassium permanganate oxidation mesophase pitch;
2) by step 1) alkylate of gained oxidation mesophase pitch or hydroxy functional group amino with band or polymkeric substance carry out condensation reaction, obtains solvable mesophase pitch.
2. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, is characterized in that in step 1) in, the temperature of described hot water bath is 40 ~ 100 DEG C.
3. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, is characterized in that in step 1) in, described mesophase pitch comprises coal measures, petroleum and naphthalene system mesophase pitch.
4. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, is characterized in that in step 1) in, the mass ratio of described mesophase pitch and potassium permanganate is 1: (0.5 ~ 10).
5. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, is characterized in that in step 2) in, described alkylate comprises C nh 2n+1nH 2or C nh 2n+1oH, wherein n=6 ~ 20.
6. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, is characterized in that in step 2) in, described polymkeric substance comprises polyethylene oxide, polystyrene, polymethylmethacrylate, the one in poly(lactic acid) of being with single-ended base.
7. the preparation method of a kind of solvable mesophase pitch as claimed in claim 6, is characterized in that described single-ended base is for amino or hydroxyl.
8. the preparation method of a kind of solvable mesophase pitch as claimed in claim 1, is characterized in that in step 2) in, described condensation reaction selects the converting carboxylate groups of oxidized bitumen to be acyl chlorides and alkylate or polymer reaction; Or use dewatering agent directly oxidized bitumen and alkylate or polymer reaction to be prepared solvable mesophase pitch.
9. the preparation method of a kind of solvable mesophase pitch as claimed in claim 8, is characterized in that described dewatering agent is selected from the one in Carbodiimides, carbonyl dimidazoles, the vitriol oil, anhydrous sodium sulphate, anhydrous magnesium sulfate, trichlorine phosphine oxide.
10. the preparation method of a kind of solvable mesophase pitch as claimed in claim 9, is characterized in that described Carbodiimides is selected from the one in dicyclohexylcarbodiimide, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
CN201410761063.9A 2014-12-11 2014-12-11 The preparation method of a kind of solvable mesophase pitch Expired - Fee Related CN104388109B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108219814A (en) * 2018-01-16 2018-06-29 中钢集团鞍山热能研究院有限公司 A kind of carboxyl pitch and its preparation process and purposes
CN110540853A (en) * 2019-08-12 2019-12-06 中国科学院山西煤炭化学研究所 Method for preparing spinnable asphalt from pyromellitic dianhydride and polystyrene modified coal pitch
CN114437398A (en) * 2020-11-02 2022-05-06 中国石油化工股份有限公司 Amino-enriched asphalt hollow pellet and preparation method and application thereof
CN114437749A (en) * 2020-11-02 2022-05-06 中国石油化工股份有限公司 Preparation method of amino-enriched asphalt and microspheres thereof
CN114959949A (en) * 2022-04-27 2022-08-30 北京化工大学 Fused ring aromatic carbon fiber and preparation method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108219814A (en) * 2018-01-16 2018-06-29 中钢集团鞍山热能研究院有限公司 A kind of carboxyl pitch and its preparation process and purposes
CN108219814B (en) * 2018-01-16 2020-08-04 中钢集团鞍山热能研究院有限公司 Carboxyl asphalt and preparation process and application thereof
CN110540853A (en) * 2019-08-12 2019-12-06 中国科学院山西煤炭化学研究所 Method for preparing spinnable asphalt from pyromellitic dianhydride and polystyrene modified coal pitch
CN110540853B (en) * 2019-08-12 2021-03-26 中国科学院山西煤炭化学研究所 Method for preparing spinnable asphalt from pyromellitic dianhydride and polystyrene modified coal pitch
CN114437398A (en) * 2020-11-02 2022-05-06 中国石油化工股份有限公司 Amino-enriched asphalt hollow pellet and preparation method and application thereof
CN114437749A (en) * 2020-11-02 2022-05-06 中国石油化工股份有限公司 Preparation method of amino-enriched asphalt and microspheres thereof
CN114437398B (en) * 2020-11-02 2023-04-11 中国石油化工股份有限公司 Amino-enriched asphalt hollow pellet and preparation method and application thereof
CN114959949A (en) * 2022-04-27 2022-08-30 北京化工大学 Fused ring aromatic carbon fiber and preparation method thereof

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