CN102911689A - Impregnated pitch with low quinoline insoluble content, low softening point and high residual carbon and preparation process and application of impregnated pitch - Google Patents
Impregnated pitch with low quinoline insoluble content, low softening point and high residual carbon and preparation process and application of impregnated pitch Download PDFInfo
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- CN102911689A CN102911689A CN201110221468XA CN201110221468A CN102911689A CN 102911689 A CN102911689 A CN 102911689A CN 201110221468X A CN201110221468X A CN 201110221468XA CN 201110221468 A CN201110221468 A CN 201110221468A CN 102911689 A CN102911689 A CN 102911689A
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Abstract
The invention relates to the field of chemical engineering and discloses a preparation process of impregnated pitch. The preparation process includes the steps: (1) adding purified earth pitch serving as raw materials into a reactor, heating the raw materials to the temperature of 375-410 DEG C with the heating rate of 6-8 DEG C/min under the condition of stirring, and carrying out constant pressure pyrocondensation polymerization reaction for 30-75min at the temperature of 375-410 DEG C; and (2) stirring and decreasing the temperature in the reactor to be lower than 300 DEG C with the cooling speed of 8-10 DEG C/min. A softening point of the prepared impregnated pitch with the low quinoline insoluble content, the low softening point and the high residual carbon ranges from 84 DEG C to 91 DEG C, the quinoline insoluble content is less than 0.3%, the coking value ranges from 46% to 49.5%, the toluene insoluble content ranges from 15% to 22%, and the impregnated pitch can be used for impregnation and densification of carbon products such as graphite electrodes.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of impregnating pitch, especially a kind of low quinoline insolubles content, low softening point, high carbon residue impregnating pitch and preparation technology and application.
Background technology
Owing to reasons such as technique, equipment, the carbon products such as Graphite Electrodes all exist hole to some extent in batching extrusion molding process, and hole accounts for about 25% of carbon product volume.The existence of hole reduces the volume density of carbon product, and physical strength descends, and thermal conduction, electroconductibility are also all poor.With the carbon product behind the dipping agent bitumen dipping not only volume density increased, and its physical strength, electroconductibility and thermal conductivity all improve, therefore, dipping is the important means that improves the carbon product performance.
The domestic standard that there is no of impregnating pitch quality index only has by it dipping ability and the dipping effect of electrode is estimated.The factor that affects dipping ability and dipping effect is a lot, mainly contains from impregnating pitch itself: quinoline insolubles (QI) content, coking value (CV), softening temperature (SP) etc.Contaminant particles take quinoline insolubles (QI) as representative in the dipping agent bitumen is easily stopped up pore in steeping process, make dipping be difficult to carry out, therefore the lower then bituminizing of QI content effect is better, and especially when electrode contact repeatedly flooded, the impact of QI content was more and more obvious; The softening temperature of dipping agent bitumen is another important factor of dipping effect, the dipping agent bitumen of high softening-point mobile relatively poor, thereby the dip operation of carbon product is difficult to carry out; The accessible residual quantity of soaker of carbon product in the follow-up calcining process of coking value (CV) index expression carbon product, if this index is excessively low, then the density effect of carbon product is difficult to reach requirement.
The external Carbon Materials productions such as ultra-high power graphite electrode generally adopt special low QI content pitch as dipping agent bitumen.Its quality index scope is: softening temperature (SP): 80-100 ℃; Quinoline insolubles (QI) content: less than 0.5%; Coking value (CV): 46-52%.Because China there is no special low QI content dipping agent bitumen Industrial products at present, the soaker of domestic Carbon Materials production usefulness generally adopts mid-temperature pitch, its QI value is generally at 6-8%, be higher than external dipping agent bitumen corresponding index far away, dipping effect is subject to larger impact, thus the quality of carbon product and same kind of products at abroad to compare gap larger.
In recent years, domestic special-purpose dipping agent bitumen has been done a large amount of research work, main technology of preparing such as the table 1 of present domestic dipping agent bitumen are listed:
The major technique of the domestic dipping agent bitumen preparation of table 1
The common issue with that above technology exists is that quality product fails to satisfy high-quality dipping agent bitumen to the composite request of the key technical index such as quinoline insolubles (QI) content, coking value (CV), softening temperature (SP).
Patent CN1262304A adopts (SP:68 ℃ of centering temperature coal-tar pitch; CV:43.01%) the heat treated mode of pressurization prepares dipping agent bitumen, and the reaction conditionss such as naturally cooling that the method finishes by control reaction times, temperature, temperature rise rate and stress reaction are controlled the quality of dipping agent bitumen.The main control parameters of the method: temperature of reaction: 380-450 ℃; Reaction pressure: 0.8-2.0MPa; Temperature rise rate: 3-5 ℃/min; Reaction times: 6-15h.The product quality indicator of its acquisition is: coking value (CV): 50.83-71.93%; Softening temperature: 85-146 ℃; Product yield: 55-80%, quinoline insolubles (QI) be not control then.
This technology Main Problems is:
1. quality key index quinoline insolubles (QI) content is not done any control, in general, the quinoline insolubles of coal-tar middle oil pitch (QI) content is greater than 3%, and the pitch heat treatment process will inevitably produce the secondary quinoline insolubles, so inevitable this index considerably beyond external product of the quinoline insolubles of this patent products obtained therefrom (QI) content's index.
2. impregnation technology requires dipping agent bitumen to have higher coking value (CV) and lower softening temperature, but from the embodiment of this patent, this technology fails to solve preferably this technical problem.
3. the operational condition of High Temperature High Pressure is higher to equipment requirements, and especially for industrialization, high-tension apparatus brings higher investment.
In heat treatment process, can make the asphalt component polymerization under the high temperature, some high molecular product just becomes secondary quinoline insolubles, even original QI value is not high in the purification of raw materials viscid bitumen, QI also can increase much after thermal treatment.Therefore, finding to make pitch polymerization upgrading, improve CV, is very important and do not make the too high condition of QI.Need to be improved prior art, be overcome the shortcoming of product in the above-mentioned technique.
Summary of the invention
The present invention aims to provide the preparation technology of a kind of low quinoline insolubles content, low softening point, high carbon residue impregnating pitch.
Dipping agent bitumen is that the technical characteristics of the purification viscid bitumen modification of target is to solve two problems, the one, and the inhibition secondary QI generation that method for modifying produces and the contradiction between the raising coking value; The 2nd, the contradiction between the high coking value in the pitch self property and the high workability (characterizing with softening temperature).
The preparation technology of a kind of low quinoline insolubles content, low softening point, high carbon residue impregnating pitch, step comprises:
(1) purification of raw materials viscid bitumen (QI＜0.1%) is added reactor, with 6-8 ℃/min temperature rise rate heating raw materials is arrived 375-410 ℃ under the agitation condition, and the normal pressure thermal polycondensation reacts 30-75min under this temperature; The index parameter of raw material: QI (quinoline insolubles) content＜0.1%, TI (toluene insolubles) content 3%-8%, 22-30 ℃ of SP (softening point temperature), CV (coking value): 23-30%
(2) stir and with the rate of temperature fall of 8-10 ℃/min reactor temperature is down to below 300 ℃.
Stirring velocity is 500-800rpm in step (1) and (2).
Low QI content, low softening point, high carbon residue impregnating pitch that above-mentioned technique is prepared, softening temperature is 84～91 ℃, quinoline insolubles (QI) content＜0.3%; Preferred, CV (coking value) 46%～49.5%, TI (toluene insolubles) content 15%～22%.This impregnating pitch have quinoline insolubles (QI) content low, than the characteristics of low softening point and high coking value, overcome the shortcoming of product in the existing technique.
This impregnating pitch can be used for Graphite Electrodes, especially the dipping density of superpower, ultra-high power graphite electrode and other high-end carbon product.
The invention has the advantages that:
1. this technical process is reacted under normal pressure, and similar technique such as CN1262304A, CN1270981A under high pressure carry out.Can reduce industrialized investment, reduce energy consumption, improve security.
2. this technological reaction time shortens greatly, and 30-75min can finish reaction.General pitch thermal polycondensation then needs can greatly enhance productivity more than the 5h.
3. this technique does not produce secondary QI in the thermal polycondensation process, and product QI content is low, TI content is high, coking value is high, softening temperature is lower, can satisfy high-end carbon element industry to the requirement of dipping agent bitumen, and domestic other impregnating pitches not yet solves QI, the contradiction of softening temperature and coking value can not satisfy high-end carbon element industry to the requirement of dipping agent bitumen.
Embodiment
Embodiment 1
With purification of raw materials viscid bitumen 800g (QI:＜0.1%) add in the there-necked flask, under the speed of 541rpm stirs, with the temperature rise rate of 7.5 ℃/min with heating raw materials to 395 ℃, behind the normal pressure thermal polycondensation 45min, with the rate of temperature fall of 8 ℃/min product is dropped to below 300 ℃, obtain impregnating pitch 576g, QI content: 0.10%, TI content 20.4%, coking value: 47.3%, softening temperature: 84.8 ℃.
Embodiment 2
With purification of raw materials viscid bitumen 800g (QI:＜0.1%) add in the there-necked flask, under the speed of 622rpm stirs, with the temperature rise rate of 7.5 ℃/min with heating raw materials to 375 ℃, behind the normal pressure thermal polycondensation 75min, with the rate of temperature fall of 8 ℃/min product is dropped to below 300 ℃, obtain impregnating pitch 680g, QI content: 0.30%, TI content 17.4%, coking value: 46.6%, softening temperature: 88.6 ℃.
Embodiment 3
With purification of raw materials viscid bitumen 800g (QI:＜0.1%) add in the there-necked flask, under the speed of 786rpm stirs, with the temperature rise rate of 8 ℃/min with heating raw materials to 410 ℃, behind the normal pressure thermal polycondensation 30min, with the rate of temperature fall of 10 ℃/min product is dropped to below 300 ℃, obtain impregnating pitch 584g, QI content: 0.14%, TI content 19.4%, coking value: 48.76%, softening temperature: 91 ℃.
Embodiment 4
With purification of raw materials viscid bitumen 800g (QI:＜0.1%) add in the there-necked flask, under certain speed stirs, 721R/min with the temperature rise rate of 7 ℃/min with heating raw materials to 395 ℃, behind the normal pressure thermal polycondensation 60min, with the rate of temperature fall of 8 ℃/min product is dropped to below 300 ℃, obtain impregnating pitch 580g, QI content: 0.28%, TI content 22.04%, coking value: 49.48%, softening temperature: 89.6 ℃.
Quality index and the yield of embodiment 1～4 product are as shown in table 2.
Quality index and the product yield of table 2 dipping agent bitumen product
Claims (6)
1. the preparation technology of one kind low quinoline insolubles content, low softening point, high carbon residue impregnating pitch is characterized in that, comprises the steps:
(1) the purification of raw materials viscid bitumen is added reactor, with 6-8 ℃/min temperature rise rate heating raw materials is arrived 375-410 ℃ under the agitation condition, and the normal pressure thermal polycondensation reacts 30-75min under this temperature;
(2) stir and with the rate of temperature fall of 8-10 ℃/min reactor temperature is down to below 300 ℃.
2. the preparation technology of the described low quinoline insolubles content of claim 1, low softening point, high carbon residue impregnating pitch is characterized in that, the speed of step (1) and (2) described stirring is 500-800rpm.
3. the preparation technology of the described low quinoline insolubles content of claim 1, low softening point, high carbon residue impregnating pitch is characterized in that, in the described purification of raw materials viscid bitumen, quinoline insolubles content I＜0.1%, toluene insolubles content 3%-8%, softening temperature 22-30 ℃, coking value 23%-30%.
4. one kind low quinoline insolubles content, low softening point, high carbon residue impregnating pitch, it is characterized in that, by each described technique preparation of claim 1～3, softening temperature is 84～91 ℃, quinoline insolubles content＜0.3%, coking value 46%～49.5%, toluene insolubles content 15%～22%.
5. the described low quinoline insolubles content of claim 4, low softening point, high carbon residue impregnating pitch are used for the dipping density of carbon product.
6. the described low quinoline insolubles content of claim 4, low softening point, high carbon residue impregnating pitch are used for the dipping density of Graphite Electrodes.
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| CN201110221468.XA CN102911689B (en) | 2011-08-03 | 2011-08-03 | Impregnated pitch with low quinoline insoluble content, low softening point and high residual carbon and preparation process and application of impregnated pitch |
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| CN201110221468.XA CN102911689B (en) | 2011-08-03 | 2011-08-03 | Impregnated pitch with low quinoline insoluble content, low softening point and high residual carbon and preparation process and application of impregnated pitch |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031669A (en) * | 2013-03-07 | 2014-09-10 | 神华集团有限责任公司 | Electrode pitch and preparation method thereof |
| CN107032792A (en) * | 2017-05-16 | 2017-08-11 | 江西宁新新材料股份有限公司 | A kind of high-strength high-density graphite material and preparation method thereof |
| CN113088313A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Preparation method of mesophase pitch |
| CN115124852A (en) * | 2022-06-24 | 2022-09-30 | 武汉科技大学 | Impregnated asphalt for carbon-carbon composite material and preparation method thereof |
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| JP2004285130A (en) * | 2003-03-20 | 2004-10-14 | Jfe Chemical Corp | Method for manufacturing impregnating pitch |
| JP2007002124A (en) * | 2005-06-24 | 2007-01-11 | Jfe Chemical Corp | Pitch for impregnation and its manufacturing method |
| CN101289625A (en) * | 2008-06-03 | 2008-10-22 | 山西宏特煤化工有限公司 | Production process of dipping agent bitumen |
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- 2011-08-03 CN CN201110221468.XA patent/CN102911689B/en active Active
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| JP2004285130A (en) * | 2003-03-20 | 2004-10-14 | Jfe Chemical Corp | Method for manufacturing impregnating pitch |
| JP2007002124A (en) * | 2005-06-24 | 2007-01-11 | Jfe Chemical Corp | Pitch for impregnation and its manufacturing method |
| CN101289625A (en) * | 2008-06-03 | 2008-10-22 | 山西宏特煤化工有限公司 | Production process of dipping agent bitumen |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031669A (en) * | 2013-03-07 | 2014-09-10 | 神华集团有限责任公司 | Electrode pitch and preparation method thereof |
| CN107032792A (en) * | 2017-05-16 | 2017-08-11 | 江西宁新新材料股份有限公司 | A kind of high-strength high-density graphite material and preparation method thereof |
| CN107032792B (en) * | 2017-05-16 | 2020-12-11 | 江西宁新新材料股份有限公司 | High-strength high-density graphite material and preparation method thereof |
| CN113088313A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Preparation method of mesophase pitch |
| CN115124852A (en) * | 2022-06-24 | 2022-09-30 | 武汉科技大学 | Impregnated asphalt for carbon-carbon composite material and preparation method thereof |
| CN115124852B (en) * | 2022-06-24 | 2023-12-15 | 武汉科技大学 | Impregnating asphalt for carbon-carbon composite material and preparation method thereof |
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Address after: Weisan Road Chemical Office Building, Baoshan District, Shanghai, 2004 Patentee after: Baowu Carbon Material Technology Co., Ltd. Address before: No. 3501 Tongji Road, Baoshan District, Shanghai 201900 Patentee before: Chemical Co., Ltd. of Baoshan Iron and Steel Group, Shanghai |
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Effective date of registration: 20190211 Address after: 524000 Zhanjiang office building in Zhanjiang Iron and Steel Works, Donghai Island, Zhanjiang City, Guangdong Province Patentee after: Baosteel chemical Zhanjiang Co., Ltd. Address before: Weisan Road Chemical Office Building, Baoshan District, Shanghai, 2004 Patentee before: Baowu Carbon Material Technology Co., Ltd. |