阅读说明：本技术 一种中间相沥青及其制备方法 (Mesophase pitch and preparation method thereof ) 是由 何旺 翟拥军 邓文广 徐立 于 2021-08-31 设计创作，主要内容包括：本发明公开了一种中间相沥青及其制备方法,所述中间相沥青原料为环烷基减压渣油,制备方法包括如下步骤：S1：采用丁烷脱沥青装置进行处理,获得胶质油：S2：采用高压反应釜进行三段液相碳化工艺处理,对胶质油进行热处理,浓缩生成中间相沥青；所述环烷基减压渣油采用环烷基原油经过常、减压蒸馏装置蒸馏后,初馏点大于420℃的减压塔底渣油；所述丁烷脱沥青装置采用的溶剂为异丁烷；所述丁烷脱沥青装置操作参数如下：抽提器进料温度为95-125℃；胶质沉降温度为110-145℃；溶剂与渣油质量比为2.5-3.7：1沉降器压力控制为4.00-4.40MPa。本发明采用的原料易得,价格低廉,能确保生产出来的高品质中间相沥青的产品成本低,实现高品质中间相沥青规模化生产和可持续发展。(The invention discloses mesophase pitch and a preparation method thereof, wherein the mesophase pitch raw material is naphthenic base vacuum residue oil, and the preparation method comprises the following steps: s1: treating by adopting a butane deasphalting device to obtain the colloid oil: s2: performing three-stage liquid phase carbonization process treatment by using a high-pressure reaction kettle, performing heat treatment on the colloid oil, and concentrating to generate mesophase pitch; the naphthenic vacuum residue adopts naphthenic base crude oil, and is distilled by a normal and vacuum distillation device, and vacuum tower bottom residue with an initial boiling point of more than 420 ℃; the butane deasphalting device adopts isobutane as a solvent; the butane deasphalting unit operating parameters were as follows: the feeding temperature of the extractor is 95-125 ℃; the colloid settling temperature is 110-145 ℃; the mass ratio of the solvent to the residual oil is 2.5-3.7: 1 the pressure of the settler is controlled to be 4.00-4.40 MPa. The raw materials adopted by the invention are easy to obtain and low in price, the low cost of the produced high-quality mesophase pitch can be ensured, and the large-scale production and sustainable development of the high-quality mesophase pitch are realized.)

1. A mesophase pitch and a preparation method thereof are characterized in that: the intermediate phase asphalt raw material is naphthenic base vacuum residue, and the preparation method comprises the following steps:

s1: treating by adopting a butane deasphalting device to obtain the colloid oil:

s2: and (3) carrying out three-stage liquid phase carbonization process treatment by using a high-pressure reaction kettle, carrying out heat treatment on the colloid oil, and concentrating to generate the mesophase pitch.

2. The mesophase pitch and the method of producing the same according to claim 1, wherein: the naphthenic vacuum residue adopts naphthenic base crude oil, and vacuum tower bottom residue with initial boiling point higher than 420 ℃ is obtained after distillation in a normal and vacuum distillation device.

3. The mesophase pitch and the method of producing the same according to claim 1, wherein: the butane deasphalting device adopts isobutane as a solvent.

4. The mesophase pitch and the method of producing the same according to claim 1, wherein: the butane deasphalting unit operating parameters were as follows:

the feeding temperature of the extractor is 95-125 ℃; the colloid settling temperature is 110-145 ℃;

the mass ratio of the solvent to the residual oil is 2.5-3.7: 1 the pressure of the settler is controlled to be 4.00-4.40 MPa.

5. The mesophase pitch and the method of producing the same according to claim 1, wherein: the conditions of the three-stage liquid phase carbonization reaction are as follows:

under the protection of nitrogen or superheated steam, the rotating speed of the stirrer is 100-;

a first-stage reaction: the temperature is 450-470 ℃; absolute pressure is 3.5MPa-5.5 MPa; the time is 1-5 hours;

and (3) secondary reaction: the temperature is 420-450 ℃; absolute pressure is 1.5MPa-3.5 MPa; the time is 2 to 6 hours;

three-stage reaction: the temperature is 400-410 ℃; reacting at normal pressure; the time is 1-3 hours.

Technical Field

The invention relates to the technical field of petrochemical processing, in particular to mesophase pitch and a preparation method thereof.

Background

The mesophase pitch is usually used as a precursor of an excellent carbon material due to excellent performance, namely, the mesophase pitch is used for preparing various high-performance carbon materials, such as mesophase pitch-based carbon fibers, foam carbon, mesophase carbon microspheres and other products, and plays a great role in numerous fields of aerospace, national defense, medical treatment, construction, sports equipment and the like.

Through massive search, the publication numbers of the prior art are found to be: CN110437862B discloses a preparation method of mesophase pitch coke, which comprises the following steps: adding an alcohol substance and an aromatic hydrocarbon solvent into coal tar pitch for pretreatment, and removing quinoline insoluble substances to obtain refined pitch; step (2), adding a viscosity regulator into the refined asphalt obtained in the step (1) to adjust the viscosity, so as to obtain a prepared asphalt; step (3), heating the prepared asphalt obtained in the step (2) for thermal polymerization reaction to obtain mesophase asphalt; and (4) carbonizing the intermediate phase asphalt obtained in the step (3) to obtain intermediate phase asphalt coke. The ash content of the mesophase pitch coke obtained by the preparation method is less than or equal to 0.1 percent, the true density is greater than or equal to 1.9, the anisotropy is greater than or equal to 95 percent, and the graphitization degree after graphitization can be more than 98 percent.

In summary, the availability of raw materials is becoming more and more difficult, making the source of anisotropic high softening point asphalts a bottleneck problem. Therefore, it is highly desirable to develop a method for large-scale production of high-quality mesophase pitch

Disclosure of Invention

The invention aims to provide mesophase pitch and a preparation method thereof, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the mesophase pitch material is naphthenic base vacuum residue oil, and the preparation method comprises the following steps:

s1: treating by adopting a butane deasphalting device to obtain the colloid oil:

s2: and (3) carrying out three-stage liquid phase carbonization process treatment by using a high-pressure reaction kettle, carrying out heat treatment on the colloid oil, and concentrating to generate the mesophase pitch.

Preferably, the naphthenic vacuum residue is vacuum tower bottom residue with initial boiling point more than 420 ℃ after naphthenic crude oil is distilled by an atmospheric distillation unit and a vacuum distillation unit.

Preferably, the solvent used in the butane deasphalting device is isobutane.

Preferably, the operating parameters of the butane deasphalting unit are as follows:

the feeding temperature of the extractor is 95-125 ℃; the colloid settling temperature is 110-145 ℃;

the mass ratio of the solvent to the residual oil is 2.5-3.7: 1 the pressure of the settler is controlled to be 4.00-4.40 MPa.

Preferably, the conditions of the three-stage liquid phase carbonization reaction are as follows:

under the protection of nitrogen or superheated steam, the rotating speed of the stirrer is 100-;

a first-stage reaction: the temperature is 450-470 ℃; absolute pressure is 3.5MPa-5.5 MPa; the time is 1-5 hours;

and (3) secondary reaction: the temperature is 420-450 ℃; absolute pressure is 1.5MPa-3.5 MPa; the time is 2 to 6 hours;

three-stage reaction: the temperature is 400-410 ℃; reacting at normal pressure; the time is 1-3 hours.

Compared with the prior art, the invention has the beneficial effects that: the mesophase pitch prepared by the method has a softening point of 290 +/-10 ℃; the content of the intermediate phase is more than 98 percent; the ash content is less than 0.01 percent, the carbon residue value is more than 80 percent, and the method adopts easily available raw materials and low price, can ensure that the product cost of the produced high-quality mesophase pitch is low, and realizes the large-scale production and sustainable development of the high-quality mesophase pitch.

Drawings

FIG. 1 is a graph showing the results of an example test according to the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "rear", "both ends", "one end", "the other end", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "connected," and the like are to be construed broadly, such as "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.

Referring to fig. 1, ten embodiments of the present invention are shown:

the first embodiment is as follows:

a mesophase pitch and a preparation method thereof, wherein the mesophase pitch raw material is naphthenic base vacuum residue, and the preparation method comprises the following steps:

s1: treating by adopting a butane deasphalting device to obtain the colloid oil:

s2: and (3) carrying out three-stage liquid phase carbonization process treatment by using a high-pressure reaction kettle, carrying out heat treatment on the colloid oil, and concentrating to generate the mesophase pitch.

The naphthenic vacuum residue adopts naphthenic base crude oil, and vacuum tower bottom residue with initial boiling point more than 420 ℃ is distilled by a normal and vacuum distillation device, and has the following characteristics: the density at 20 ℃ was 1.013g/cm 3.

The solvent used by the butane deasphalting unit is isobutane.

The butane deasphalting unit operating parameters were as follows:

the feeding temperature of the extractor is 95-125 ℃; the colloid settling temperature is 110-145 ℃;

the mass ratio of the solvent to the residual oil is 2.5-3.7: 1 the pressure of the settler is controlled to be 4.00-4.40 MPa.

Example two:

the conditions of the three-stage liquid phase carbonization reaction are as follows:

under the protection of nitrogen or superheated steam, the rotating speed of the stirrer is 100-;

a first-stage reaction: the temperature is 450-470 ℃; absolute pressure is 3.5MPa-5.5 MPa; the time is 1-5 hours;

and (3) secondary reaction: the temperature is 420-450 ℃; absolute pressure is 1.5MPa-3.5 MPa; the time is 2 to 6 hours;

three-stage reaction: the temperature is 400-410 ℃; reacting at normal pressure; the time is 1-3 hours.

Example three:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, raising the temperature to 450 ℃, controlling the pressure to be 4.8MPa, and reacting for 3 hours at the stirring speed of 150 r/min; then slowly releasing to 3.2MPa, cooling to 427 ℃, and reacting for 4.5 hours; then slowly releasing to normal pressure, cooling to 402 ℃, and reacting for 3 hours to obtain the target product mesophase pitch.

Example four:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, raising the temperature to 455 ℃, controlling the pressure to be 5.0MPa, and reacting for 3 hours at the stirring speed of 150 r/min; then slowly releasing to 3.0MPa, cooling to 425 ℃, and reacting for 5 hours; then slowly releasing to normal pressure, cooling to 400 ℃, and reacting for 3 hours to obtain the target product mesophase pitch.

Example five:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, heating to 457 ℃, controlling the pressure to be 5.0MPa, and reacting for 3 hours at the stirring speed of 150 r/min; then slowly releasing to 2.0MPa, cooling to 430 ℃, and reacting for 4 hours; then slowly releasing to normal pressure, cooling to 400 ℃, and reacting for 2 hours to obtain the target product mesophase pitch.

Example six:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, raising the temperature to 460 ℃, controlling the pressure to be 5.2MPa, and reacting for 4 hours at the stirring speed of 150 r/min; then slowly releasing to 3.0MPa, cooling to 420 ℃, and reacting for 2.5 hours; then slowly releasing to normal pressure, cooling to 400 ℃, and reacting for 2 hours to obtain the target product mesophase pitch.

Example seven:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, raising the temperature to 465 ℃, controlling the pressure to be 5.5MPa, and reacting for 2 hours at the stirring speed of 150 r/min; then slowly releasing to 3.5MPa, cooling to 425 ℃, and reacting for 5 hours; then slowly releasing to normal pressure, cooling to 406 ℃, and reacting for 2.5 hours to obtain the target product mesophase pitch.

Example eight:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, raising the temperature to 468 ℃, controlling the pressure to 5.5MPa, and reacting for 1 hour, wherein the stirring speed is 150 r/min; then slowly releasing to 3.0MPa, cooling to 420 ℃, and reacting for 6 hours; then slowly releasing to normal pressure, cooling to 410 ℃, and reacting for 1 hour to obtain the target product mesophase pitch.

Example nine:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, raising the temperature to 460 ℃, controlling the pressure to be 4.0MPa, and reacting for 3 hours at the stirring speed of 150 r/min; then slowly releasing to 2.6MPa, cooling to 428 ℃, and reacting for 4 hours; then slowly releasing to normal pressure, cooling to 400 ℃, and reacting for 1.5 hours to obtain the target product mesophase pitch.

Example ten:

adding 50KG of colloid oil into a high-pressure reaction kettle, introducing nitrogen, raising the temperature to 453 ℃, controlling the pressure to be 5.0MPa, and reacting for 2 hours at the stirring speed of 150 r/min; then slowly releasing to 3.0MPa, cooling to 445 ℃, and reacting for 3 hours; then slowly releasing to normal pressure, cooling to 402 ℃, and reacting for 2 hours to obtain the target product mesophase pitch.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.