CN102766478B - Method for producing low-Na+ high-QI (quinoline insoluble) mid-temperature pitch - Google Patents
Method for producing low-Na+ high-QI (quinoline insoluble) mid-temperature pitch Download PDFInfo
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- CN102766478B CN102766478B CN201210258296.8A CN201210258296A CN102766478B CN 102766478 B CN102766478 B CN 102766478B CN 201210258296 A CN201210258296 A CN 201210258296A CN 102766478 B CN102766478 B CN 102766478B
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Abstract
The invention discloses a method for producing low-Na+ high-QI (quinoline insoluble) mid-temperature pitch. Increase of QI and reduction of Na+ are achieved simultaneously. The method includes the steps of subjecting soft pitch made from mid-temperature pitch to centrifugal separation, static settling and flash separation to obtain sediment which is 20-45% in QI mass percentage and 7-30% in yield; adding common coal tar 1.5-3 times of the sediment into the sediment to obtain adjustable high-QI coal tar; subjecting the adjustable high-QI coal tar to tar distillation to obtain high-QI and high Na+ mid-temperature pitch; and adding tail pitch into the high-QI and high Na+ mid-temperature pitch to obtain low-Na+ and high-QI mid-temperature pitch. The method is simple in process, and mixing technique has no high requirement on equipment. The produced low-Na+ high-QI mid-temperature pitch meets the requirement for producing different carbon products.
Description
Technical field
The present invention relates to coal tar deep processing technical field, particularly the low Na of a kind of production
+method with high quinoline insolubles mid-temperature pitch.
Background technology
In coal tar distillation processing technology, need to add Na
2cO
3prevent equipment corrosion, so just have Na
+enter into Process of Tar Processing, wherein most Na
+enter into pitch at the bottom of the tower of coal tar distillation.Na in coal tar
+at 100ppm left and right, the Na in coal-tar pitch
+in 300ppm left and right.
Mid-temperature pitch is tar distillation raffinate part, and productive rate accounts for 54～56% of tar, and it forms by aromatics more than three rings with containing oxygen, nitrogenous, sulfur heterocyclic compound and a small amount of polymer carbon element material.The molecular weight of asphalt component, between 200～2000, reaches as high as 3000.Mid-temperature pitch is according to softening temperature different demarcation, and it is mid-temperature pitch that softening temperature is 65～90 ℃.Wang Xiudan is published in the article " thermosol filtration method remove the research of in coal-tar pitch quinoline insolubles " of < < charcoal element technology > > on the 1st phase in 2007, and by Japanese's stone well one by being published in < < fuel and " production technology of low quinoline insolubles tar-bitumen " of chemical industry > > in March, 2004 shows, in coal tar quinoline insolubles (hereinafter to be referred as QI) generally 1～2%, the QI of the mid-temperature pitch generating by coal tar distillation is between 3～4%.The mid-temperature pitch that distillation generates can be used as manufacturing carbon black oil, the dipping agent bitumen of carbon material, and modified pitch and pitch coke, high true density pitch coke and carbonaceous mesophase spherules.Carbon black oil, dipping agent bitumen and modified pitch require the Na in raw material mid-temperature pitch
+in certain limit.The data that provide according to Nanjing Mei Shan Bao Ning company, produce dipping agent bitumen and modified pitch and require Na in mid-temperature pitch
+concentration is below 150ppm, and Suzhou treasuredization carbon plant requires Na in mid-temperature pitch
+concentration is below 300ppm.Modified pitch, high true density pitch coke and carbonaceous mesophase spherules (MCMB) need the mid-temperature pitch of high QI, and for example modified pitch need of production QI content is more than 5%; Manufacture power-type lithium ion battery negative material carbonaceous mesophase spherules, need mid-temperature pitch QI in 8% left and right.Therefore, prepare low Na
+with high quinoline insolubles medium temperature coal pitch, the development of carbon material is had great importance.
At present, a lot of enterprises carry out technological transformation in tar processing technology, to reducing Na
+concentration is explored.For example Shanxi Province, China Coking Company 300,000 t/a coal tar processings adopt French IRH advanced person after add alkali technology, show by analysis, the sodium ion in Shanxi Coking Plant coal-tar pitch is about 3 * 10～10 * 10ppm.This method is a kind of new tar complete processing, applies this technique and can effectively reduce Na
+concentration, but to effectively reduce Na for other some tar complete processings
+concentration will be made technique, the change of equipment Shangdi.At present also do not find that there is new technology and reduce Na in mid-temperature pitch
+concentration.The Li Yongjun of Coking Plant, Shijiazhuang is published in the method that has proposed QI content in some raising coal tar in < < Hebei chemical industry > > the 3rd phase in 2000 " quinoline insolubles content in a raising modified pitch " literary composition, it is low containing quinoline insolubles in tar that its method is thought, relevant with furnace roof room temps, therefore contact with coking subsidiary factory, suitably adjust throat temperature.It is very little containing quantity space that this method improves in coal tar QI, and there is to certain influence in the life-span of stove.Along with special carbon industry is being brought into play more and more important effect in military field, as the carbonaceous mesophase spherules (MCMB) of special carbon material and the development of high true density pitch coke quality ground, will be the important factor of the special carbon material development of restriction high quality, low Na
+modified pitch and dipping agent bitumen will be the important factor of the large specification ultra-high power graphite electrode development of restriction exploitation.Also do not have at present good technology improve the QI of coal tar and reduce Na
+concentration.
Summary of the invention
The invention provides the low Na of a kind of production
+with the method for high quinoline insolubles mid-temperature pitch, can improve QI simultaneously and reduce Na
+.
The low Na of a kind of production provided by the invention
+comprise the following steps with the method for high quinoline insolubles mid-temperature pitch:
A. the viscid bitumen that mid-temperature pitch is mixed with is by centrifugation, quiescent settling, flash separation, obtain quinoline non-soluble amount percentage composition 20～45%, yield is at 7～30% slag, the temperature of centrifugation is at 70～120 ℃, the temperature of quiescent settling is at 70～250 ℃, the temperature of vacuum flashing separation is at 250～380 ℃, and absolute pressure is at-60～-90Kpa;
B. in the slag that is 20～45% at quinoline non-soluble amount percentage composition, allocate 1.5-3 common coal tar doubly into, obtain having the high quinoline insolubles coal tar of mobility, mixing temperature is controlled at 70～100 ℃, then by allocating again 0.5-2 common coal tar doubly into, obtain adjustable high quinoline insolubles coal tar, mixing temperature is controlled at 70～100 ℃;
C. obtain adjustable high quinoline insolubles coal tar and pass through again tar distillation, obtain high quinoline insolubles, high Na
+mid-temperature pitch;
D. high quinoline insolubles, high Na
+mid-temperature pitch in allocate 0.5 times into and prepare the tail pitch that carbonaceous mesophase spherules obtains, the quinoline insolubles that this tail pitch is 2～4% containing mass percent, the Na of 10～30ppm
+, at 130～180 ℃, mix, make low Na
+with high quinoline insolubles mid-temperature pitch.
Compared with prior art, its significant beneficial effect is embodied in the present invention:
Prior art can improve the quinoline insolubles in coal tar by improving oven top of coke oven room temps, but increase rate is limited, and raising oven top of coke oven room temps has impact definitely to the life-span of stove.Technique of the present invention is simple, and mixed technology does not propose higher requirement to equipment; The low Na producing
+meet with high quinoline insolubles mid-temperature pitch the needs of making different carbon products.
Accompanying drawing explanation
Fig. 1 is the low Na of a kind of production
+production technological process with high quinoline insolubles mid-temperature pitch.
Embodiment
Below in conjunction with accompanying drawing, with embodiment, the present invention is described in more detail.
Embodiment 1
As shown in Figure 1, the viscid bitumen that mid-temperature pitch is mixed with is by centrifugation, quiescent settling, flash separation, obtain high quinoline insolubles (hereinafter to be referred as QI) content at 20～45% slag, with common coal tar, be respectively that 1:1.5,1:2,1:2.5,1:3 mix in mass ratio, in 82 ± 2 ℃ of stirrings of constant temperature, bits are dissolved, and mixed oil viscosity reduce successively.Through 20h, almost without bits, separate out.Viscosity test adopts HO: residue=1:1 contrasts, and viscosimetric analysis adopts NDJ-31 type rotational viscosimeter, and rotor adopts No. 1 rotor, rotating speed 60, and 80 ℃ of design temperatures, test-results is as table 1:
Table 1 viscosimetric analysis result
| Common coal tar (ratio) | Residue (ratio) | Viscosity number (mpa.s) |
| 1.5 | 1 | 90 |
| 2 | 1 | 70 |
| 2.5 | 1 | 80 |
| 3 | 1 | 60 |
The high QI coal tar being made into has good mobility, can carry or shipping, shipping are prepared adjustable high QI coal tar by industrial pipeline.
The mass ratio that adopts common coal tar and bits is that the QI content of the high QI coal tar made of 2:1 is 12%, then allocate into 1-2 doubly common coal tar the results are shown in Table 2:
The table 2 centrifuging tar measurement result that is mixed
| QI content is 12% coal tar | Common coal tar | Coal tar QI content after mixed, % |
| 1 | 0.5 | 6.2 |
| 1 | 1 | 6.5 |
| 1 | 2 | 4.8 |
The high QI coal tar obtaining and the adjustable static stability of high QI coal tar are very good, and long-term placement separated out without bits.
Get adjustable QI and be 4.8% coal tar and distill that to obtain QI be 9.1% mid-temperature pitch, and containing low Na
+prepare the tail pitch that carbonaceous mesophase spherules (hereinafter to be referred as MCMB) obtains and mix by 1:0.5, at 150 ℃, obtain low Na
+with high QI mid-temperature pitch, measuring its QI content is 7.3%, Na
+content is 201ppm, and softening temperature is 79 ℃.Be made into low Na
+observe by mirror lens with high QI mid-temperature pitch, the QI of the inside is evenly distributed, and agglomeration is few, tests (24hr) do not find that QI distributes, content by static stability, is applicable to the raw material as carbon material.
Embodiment 2
As shown in Figure 1, derive from common coal tar that flash separation obtains by centrifugation, quiescent settling, flash separation, obtain high QI content at 20～45% slag, in mass ratio for 1:2 mixes, under about 100 ℃ of constant temperature stir, bits are dissolved with common coal tar.Through about 18h, almost without bits, separate out.The QI content of the high QI coal tar of making is 10.5%, then allocates doubly common coal tar of 1-2 into, obtains adjustable high QI coal tar and the results are shown in Table 3:
The table 3 flash separation method tar measurement result that is mixed
| QI content is 10.5% coal tar | Common coal tar | Coal tar QI content after mixed, % |
?
| 1 | 1 | 5.8 |
| 1 | 2 | 4.9 |
The high QI coal tar obtaining and the adjustable static stability of high QI coal tar are very good, and long-term placement separated out without bits.
Get adjustable QI and be 4.9% coal tar and distill that to obtain QI be 8.8% mid-temperature pitch.Mid-temperature pitch and containing low Na
+the tail pitch that preparation MCMB obtains is mixed to get low Na by 1:0.4 at 150 ℃
+with high quinoline insolubles mid-temperature pitch, measuring QI content is 6.5%, Na
+content is 214ppm, and softening temperature is 83 ℃, is applicable to for producing modified pitch.Be made into low Na
+observe by mirror lens with high quinoline insolubles mid-temperature pitch, the QI of the inside is evenly distributed, and agglomeration is few, tests (24hr) do not find that QI distributes, content by static stability, is applicable to the raw material as carbon material.
Embodiment 3
Derive from the common coal tar of quiescent settling method and the mass ratio of bits is 1:1, under about 95 ℃ of constant temperature stir, bits are dissolved.Through 18h, almost without bits, separate out.The QI content of the high QI coal tar of making is 19%, then allocates in proportion 2-3 common coal tar doubly into, and its data 0 are in Table 4:
The table 4 quiescent settling method tar measurement result that is mixed
| QI content is 19% coal tar | Common coal tar | Coal tar QI content after mixed, % |
| 1 | 2 | 6.9 |
| 1 | 3 | 5.5 |
The high QI coal tar obtaining and the adjustable static stability of high QI coal tar are very good, and long-term placement separated out without bits.
Get adjustable QI and be 5.5% coal tar and distill that to obtain QI be 10.1% mid-temperature pitch.Mid-temperature pitch and containing low Na
+the tail pitch that preparation MCMB obtains is mixed to get low Na by 1:1 at 150 ℃
+with high quinoline insolubles mid-temperature pitch, measuring its QI content is 7.1%, Na
+content is 96ppm, and softening temperature is 87 ℃, is applicable to for producing modified pitch.Be made into low Na
+observe by mirror lens with high quinoline insolubles mid-temperature pitch, the QI of the inside is evenly distributed, and agglomeration is few, tests (24hr) do not find that QI distributes, content by static stability, is applicable to the raw material as carbon material.
Claims (1)
1. produce low Na for one kind
+with the method for high quinoline insolubles mid-temperature pitch, it is characterized in that the method comprises the following steps:
A. the viscid bitumen that mid-temperature pitch is mixed with is by centrifugation, quiescent settling, flash separation, obtain quinoline non-soluble amount percentage composition 20～45%, yield is at 7～30% slag, the temperature of centrifugation is at 70～120 ℃, the temperature of quiescent settling is at 70～250 ℃, the temperature of vacuum flashing separation is at 250～380 ℃, and gauge pressure scope is at-60～-90kPa;
B. in the slag that is 20～45% at quinoline non-soluble amount percentage composition, allocate the common coal tar of 1.5-3 times of quality into, obtain having the high QI coal tar of mobility, mixing temperature is controlled at 70～100 ℃, and then allocate 0.5-2 common coal tar doubly into, obtain adjustable high QI coal tar, mixing temperature is controlled at 70～100 ℃;
C. obtain adjustable high quinoline insolubles coal tar and pass through again tar distillation, obtain high quinoline insolubles, high Na
+mid-temperature pitch;
D. high quinoline insolubles, high Na
+mid-temperature pitch in allocate 0.5 times into and prepare the tail pitch that carbonaceous mesophase spherules obtains, the quinoline insolubles that this tail pitch is 2～4% containing mass percent, the Na of 10～30ppm
+, at 130～180 ℃, mix, make low Na
+with high quinoline insolubles mid-temperature pitch.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210258296.8A CN102766478B (en) | 2012-07-23 | 2012-07-23 | Method for producing low-Na+ high-QI (quinoline insoluble) mid-temperature pitch |
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|---|---|---|---|
| CN201210258296.8A CN102766478B (en) | 2012-07-23 | 2012-07-23 | Method for producing low-Na+ high-QI (quinoline insoluble) mid-temperature pitch |
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|---|---|
| CN102766478A CN102766478A (en) | 2012-11-07 |
| CN102766478B true CN102766478B (en) | 2014-01-29 |
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| CN106520165B (en) * | 2015-09-10 | 2019-05-03 | 宝武炭材料科技有限公司 | High-softening-point asphalt and preparation method of foam carbon based on asphalt |
| CN110317623B (en) * | 2019-08-08 | 2021-06-25 | 山西永鑫煤焦化有限责任公司 | Preparation method for extracting superfine carbon material from asphalt |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4019303A1 (en) * | 1989-12-11 | 1991-06-13 | Ruetgerswerke Ag | Carbon intermediate recovery from prepn. of bituminous coal tar - by sepg. tars contg. quinoline insolubles, and distilling |
| 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 |
| CN101824329A (en) * | 2010-05-17 | 2010-09-08 | 朱兴建 | Novel process for eliminating quinoline insoluble substances in coal tar medium temperature pitch |
| CN101928583A (en) * | 2009-06-23 | 2010-12-29 | 上海宝钢化工有限公司 | Method for purifying soft asphalt |
| CN102432306A (en) * | 2011-08-29 | 2012-05-02 | 云南昆钢煤焦化有限公司 | Method for intensively producing refractory material binder by coal tar pitch needle coke |
-
2012
- 2012-07-23 CN CN201210258296.8A patent/CN102766478B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4019303A1 (en) * | 1989-12-11 | 1991-06-13 | Ruetgerswerke Ag | Carbon intermediate recovery from prepn. of bituminous coal tar - by sepg. tars contg. quinoline insolubles, and distilling |
| 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 |
| CN101928583A (en) * | 2009-06-23 | 2010-12-29 | 上海宝钢化工有限公司 | Method for purifying soft asphalt |
| CN101824329A (en) * | 2010-05-17 | 2010-09-08 | 朱兴建 | Novel process for eliminating quinoline insoluble substances in coal tar medium temperature pitch |
| CN102432306A (en) * | 2011-08-29 | 2012-05-02 | 云南昆钢煤焦化有限公司 | Method for intensively producing refractory material binder by coal tar pitch needle coke |
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