CN102766478A

CN102766478A - Method for producing low-Na+ high-QI (quinoline insoluble) mid-temperature pitch

Info

Publication number: CN102766478A
Application number: CN2012102582968A
Authority: CN
Inventors: 徐桂英; 白金锋; 高占先; 吴鲲魁
Original assignee: University of Science and Technology Liaoning USTL
Current assignee: University of Science and Technology Liaoning USTL
Priority date: 2012-07-23
Filing date: 2012-07-23
Publication date: 2012-11-07
Anticipated expiration: 2032-07-23
Also published as: CN102766478B

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

Na is hanged down in a kind of production +Method with high quinoline insolubles mid-temperature pitch

Technical field

The present invention relates to the coal tar deep processing technical field, Na is hanged down in particularly a kind of production ⁺Method with high quinoline insolubles mid-temperature pitch.

Background technology

Need to add Na in the coal tar distillation processing technology ₂CO ₃Prevent equipment corrosion, so just have Na ⁺Enter into the tar course of processing, wherein most Na ⁺Enter into pitch at the bottom of the tower of coal tar distillation.Na in the coal tar ⁺About 100ppm, the Na in the coal-tar pitch ⁺About 300ppm.

Mid-temperature pitch is a tar distillation raffinate part, and productive rate accounts for 54～56% of tar, it by the above aromatics of three rings with contain oxygen, nitrogenous, sulfur heterocyclic compound and a small amount of polymer carbon element material and form.The molecular weight of asphalt component reaches as high as 3000 between 200～2000.Mid-temperature pitch is divided according to softening temperature is different, and softening temperature is 65～90 ℃ and is mid-temperature pitch.Wang Xiudan is published in the article " the thermosol filtration method removes the research of quinoline insolubles in the coal-tar pitch " on " charcoal plain technology " the 1st phase in 2007 and is shown by " production technology of low quinoline insolubles tar-bitumen " that be published on " fuel and chemical industry " in March, 2004 by Japanese's stone well one; In the coal tar quinoline insolubles (hereinafter to be referred as QI) generally 1～2%, the QI of the mid-temperature pitch that generates through coal tar distillation is between 3～4%.The mid-temperature pitch that distillation generates can be used as carbon black oil, the dipping agent bitumen of making 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 the raw material mid-temperature pitch ⁺In certain limit.According to the data that Nanjing Mei Shan Bao Ning company provides, produce dipping agent bitumen and modified pitch and require Na in the mid-temperature pitch ⁺Concentration is below 150ppm, and Suzhou treasuredization carbon plant requires Na in the 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 production needs QI content more than 5%; Make power-type lithium ion battery negative material carbonaceous mesophase spherules, need mid-temperature pitch QI about 8%.Therefore, the low Na of preparation ⁺Development to carbon material has great importance with high quinoline insolubles medium temperature coal pitch.

At present, a lot of enterprises carry out technological transformation on the tar processing technology, to reducing Na ⁺Concentration is explored.Add the alkali technology behind the French IRH advanced person of for example Chinese Shanxi Coking Plant company's 300,000 t/a coal tar processing employing, through analysis revealed, the sodium ion in the Shanxi Coking Plant coal-tar pitch is about 3 * 10～10 * 10ppm.This method is a kind of new tar complete processing, uses this technology and can reduce Na effectively ⁺Concentration, but to effectively reduce Na for other some tar complete processings ⁺Concentration will be made ground change on technology, the equipment.Also do not have at present to find have new technology to reduce Na in the 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 the raising modified pitch " literary composition; Its method thinks that to contain quinoline insolubles in the tar low; Relevant with the furnace roof room temps; Therefore get in touch with coking subsidiary factory, suitably adjust throat temperature.This method improves in the coal tar QI, and to contain quantity space very little, and there is 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, will be the important factor of the special carbon material development of restriction high quality as the carbonaceous mesophase spherules (MCMB) of special carbon material and the development of high true density pitch coke quality ground, low Na ⁺Modified pitch and dipping agent bitumen will be the important factor of the big specification ultra-high power graphite electrode development of restriction exploitation.Also there is not at present good technology to improve the QI and minimizing Na of coal tar ⁺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 ⁺

Na is hanged down in a kind of production provided by the invention ⁺May further comprise the steps with the method for high quinoline insolubles mid-temperature pitch:

A. the viscid bitumen that is mixed with of mid-temperature pitch is through spinning, quiescent settling, flash separation; Obtain quinoline non-soluble amount percentage composition 20～45%; Yield is at 7～30% slag, and the temperature of spinning is at 70～120 ℃, and the temperature of quiescent settling is at 70～250 ℃; The isolating temperature of vacuum flashing is at 250～380 ℃, absolute pressure-60～-90Kpa;

B., quinoline non-soluble amount percentage composition allocates 1.5-3 common coal tar doubly in being 20～45% slag into; Obtain having mobile high quinoline insolubles coal tar; Mixing temperature is controlled at 70～100 ℃; By allocating 0.5-2 common coal tar doubly again into, obtain adjustable high quinoline insolubles coal tar then, mixing temperature is controlled at 70～100 ℃;

C. obtain adjustable high quinoline insolubles coal tar and pass through tar distillation again, obtain high quinoline insolubles, high Na ⁺Mid-temperature pitch;

D. high quinoline insolubles, high Na ⁺Mid-temperature pitch in allocate 0.5 times of tail pitch of obtaining of preparation carbonaceous mesophase spherules into, it is 2～4% quinoline insolubles that this tail pitch contains mass percent, the Na of 10～30ppm ⁺, mix at 130～180 ℃, make low Na ⁺With high quinoline insolubles mid-temperature pitch.

The present invention compared with prior art, its significant beneficial effect is embodied in:

Temperature can improve the quinoline insolubles in the coal tar to prior art between the Coke Oven head space through improving, but increase rate is limited, and improves temperature between the Coke Oven head space there is influence definitely in life-span of stove.Technology of the present invention is simple, and mixed technology does not propose higher requirement to equipment; The low Na that produces ⁺Satisfy the needs of making different carbon products with high quinoline insolubles mid-temperature pitch.

Description of drawings

Fig. 1 is the low Na of a kind of production ⁺Technological process of production figure with high quinoline insolubles mid-temperature pitch.

Embodiment

Below in conjunction with accompanying drawing with embodiment to further explain of the present invention.

Embodiment 1

As shown in Figure 1; The viscid bitumen that mid-temperature pitch is mixed with is through spinning, quiescent settling, flash separation, obtains high quinoline insolubles (hereinafter to be referred as QI) content at 20～45% slag, with common coal tar; Be 1:1.5,1:2,1:2.5,1:3 mixing by mass ratio respectively; In 82 ± 2 ℃ of stirrings of constant temperature, make the bits dissolving, and the viscosity of contaminated product reduces successively.Through 20h, almost do not have bits and separate out.Viscosity test adopts HO: residue=1:1 compares, and NDJ-31 type rotational viscosimeter is adopted in viscosimetric analysis, and rotor adopts No. 1 rotor, rotating speed 60, and 80 ℃ of design temperatures, test-results such 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 that is made into has good flowability, can be through industrial pipeline conveying or shipping, high QI coal tar that the shipping preparation is adjustable.

The mass ratio that adopts common coal tar and bits is that the QI content of the high QI coal tar processed of 2:1 is 12%, allocate into then 1-2 doubly the result of common coal tar see table 2:

The table 2 centrifuging tar that is mixed is measured the result

QI content is 12% coal tar	Common coal tar	Mix back coal tar QI content, %
			1	0.5	6.2
1	1	6.5
			1	2	4.8

High QI coal tar that obtains and the adjustable static stability of high QI coal tar are very good, place no bits and separate out for a long time.

Get adjustable QI and be 4.8% coal tar and distill that to obtain QI be 9.1% mid-temperature pitch, and contain low Na ⁺The tail pitch that preparation carbonaceous mesophase spherules (hereinafter to be referred as MCMB) obtains mixes by 1:0.5, obtains low Na at 150 ℃ ⁺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 through mirror lens with high QI mid-temperature pitch, the QI of the inside is evenly distributed, and agglomeration is few, does not find that through static stability test (24hr) QI distributes, content, is fit to the raw material as carbon material.

Embodiment 2

As shown in Figure 1; Derive from common coal tar that flash separation obtains through spinning, quiescent settling, flash separation; Obtaining high QI content at 20～45% slag, is that 1:2 mixes with common coal tar by mass ratio, stirs about 100 ℃ of constant temperature bits are dissolved.Through about 18h, almost do not have bits and separate out.The QI content of the high QI coal tar of processing is 10.5%, allocates the doubly common coal tar of 1-2 then into, obtains adjustable high QI coal tar result and sees table 3:

The table 3 flash separation method tar that is mixed is measured the result

QI content is 10.5% coal tar

Common coal tar

Mix back coal tar QI content, %

1	1	5.8
			1	2	4.9

Get adjustable QI and be 4.9% coal tar and distill that to obtain QI be 8.8% mid-temperature pitch.Mid-temperature pitch hangs down Na with containing ⁺The tail pitch that preparation MCMB obtains obtains low Na by 1:0.4 150 ℃ of mixing ⁺With high quinoline insolubles mid-temperature pitch, measuring QI content is 6.5%, Na ⁺Content is 214ppm, and softening temperature is 83 ℃, is fit to be used for producing modified pitch.Be made into low Na ⁺Observe through mirror lens with high quinoline insolubles mid-temperature pitch, the QI of the inside is evenly distributed, and agglomeration is few, does not find that through static stability test (24hr) QI distributes, content, is fit to the raw material as carbon material.

Embodiment 3

Deriving 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, makes the bits dissolving.Through 18h, almost do not have bits and separate out.The QI content of the high QI coal tar of processing is 19%, allocates 2-3 common coal tar doubly then in proportion into, and its data 0 are seen table 4:

The table 4 quiescent settling method tar that is mixed is measured the result

QI content is 19% coal tar	Common coal tar	Mix back coal tar QI content, %
			1	2	6.9
1	3	5.5

Get adjustable QI and be 5.5% coal tar and distill that to obtain QI be 10.1% mid-temperature pitch.Mid-temperature pitch hangs down Na with containing ⁺The tail pitch that preparation MCMB obtains obtains low Na by 1:1 150 ℃ of mixing ⁺With high quinoline insolubles mid-temperature pitch, measuring its QI content is 7.1%, Na ⁺Content is 96ppm, and softening temperature is 87 ℃, is fit to be used for producing modified pitch.Be made into low Na ⁺Observe through mirror lens with high quinoline insolubles mid-temperature pitch, the QI of the inside is evenly distributed, and agglomeration is few, does not find that through static stability test (24hr) QI distributes, content, is fit to the raw material as carbon material.

Claims

1. produce low Na for one kind ⁺With the method for high quinoline insolubles mid-temperature pitch, it is characterized in that this method may further comprise the steps:

B., quinoline non-soluble amount percentage composition allocates 1.5-3 common coal tar doubly in being 20～45% slag into; Obtain having mobile high QI coal tar; Mixing temperature is controlled at 70～100 ℃; By allocating 0.5-2 common coal tar doubly again into, obtain adjustable high QI coal tar then, mixing temperature is controlled at 70～100 ℃;