阅读说明：本技术 一种煤基活性炭专用的粘结剂及其制备方法 (Binder special for coal-based activated carbon and preparation method thereof ) 是由 杨光明 李学振 李静伟 于 2021-09-30 设计创作，主要内容包括：本发明公开了一种煤基活性炭专用的粘结剂及其制备方法,所述粘结剂包括高温沥青45-65重量份；蒽油15-45重量份；酚油8-15重量份；和洗油2-5重量份,并且通过本发明研发的制备工艺制备得到。本发明的粘结剂制备工艺简单,生产的活性炭产品强度好、表明光滑浮灰少,适合规模化生产。(The invention discloses a binder special for coal-based activated carbon and a preparation method thereof, wherein the binder comprises 45-65 parts by weight of high-temperature asphalt; 15-45 parts of anthracene oil; 8-15 parts of phenol oil; and 2-5 parts by weight of washing oil, and is prepared by the preparation process developed by the invention. The preparation process of the binder is simple, and the produced activated carbon product has good strength and less surface smooth floating ash, and is suitable for large-scale production.)

1. The special binder for the coal-based activated carbon comprises the following components in parts by weight:

2. the binder of claim 1 wherein the pitch content of the binder is between 50% and 65%.

3. The binder as claimed in claim 1 or 2, wherein the high temperature pitch is a residue of coal tar after distillation to remove liquid fraction, and has a softening point of 95-100 ℃.

4. Method for preparing a binder according to any one of claims 1 to 3, characterized in that it comprises the following steps:

(1) conveying anthracene oil into a reaction kettle, and controlling the temperature of the reaction kettle to be 160 +/-5 ℃;

(2) adding a first part of high-temperature asphalt into the reaction kettle and uniformly stirring;

(3) adding wash oil into the product obtained in the step (2), stirring, adding a second part of high-temperature asphalt, and then uniformly stirring;

(4) adding the phenol oil into the product obtained in the step (3), and uniformly stirring and mixing to obtain a binder;

wherein the dosage of the first part of high-temperature asphalt and the second part of high-temperature asphalt is 1:1-5:3, and the temperature is 200 +/-10 ℃.

5. The preparation method according to claim 4, wherein in steps (2) and (3), the high-temperature asphalt raw material is kept still in a storage tank for at least 48 hours to remove impurities before adding the high-temperature asphalt, and the temperature of the storage tank is controlled to be 200 +/-10 ℃.

6. The method according to claim 5, wherein in the step (2), the first portion of the high temperature asphalt is divided into 4 to 6 times of addition in total.

7. The method according to claim 5, wherein in the step (3), the second portion of the high temperature asphalt is divided into 2 to 4 times of addition in total.

8. The method according to claim 6 or 7, wherein in the steps (2) and (3), the stirring time is 15-20min after each addition of the high-temperature asphalt, and the stirring speed is controlled to be 5-10 r/min.

9. The method for preparing the adhesive according to claim 8, wherein the adhesive obtained in the step (4) is delivered to a product tank for standby, and the temperature of the product tank is 100 +/-10 ℃.

10. The preparation method according to any one of claims 4 to 9, characterized in that 20 to 40 percent of anthracene oil, 8 to 15 percent of wash oil, 2 to 5 percent of phenol oil and 50 to 60 percent of high-temperature asphalt are added in the binder by weight of the binder.

Technical Field

The invention relates to the technical field of coal-based activated carbon, in particular to a binder special for coal-based activated carbon and a preparation method thereof.

Background

In the process of preparing the coal granular activated carbon, the kneading molding working section has great influence on the strength, the appearance and the yield of the final product of the granular activated carbon, the process is that the coal powder, a certain proportion of the adhesive and water are fully mixed at a set temperature, so that the added adhesive, water and the coal powder are fully infiltrated, permeated and uniformly dispersed, the coal powder generates interface chemical agglomeration to form loose bulk materials in the presence of the adhesive and the water, and the coal granular activated carbon has plasticity of extrusion deformation and is easy to mold and improve the strength of the product.

The function of adding the binder in the kneading molding section is to bind the coal dust, so that the coal dust and the binder are uniformly mixed and then are easy to mold under the action of pressure; secondly, the prepared carbon strip is easy to form the strength required by the use of the active carbon in the carbonization process. The binder can be coal tar, starch, sodium hydroxymethylbenzene sulfonate, lignin, etc. At present, the binder adopted in the industrial production of coal granular activated carbon is still coal tar, but the adopted coal tar is a product obtained by deep processing of the coal tar, so that the index change of the product is large, and the quality is good and uneven. The main reasons are that firstly, the pitch content in the coal tar which is the coking byproduct of a coking enterprise is about 40 percent, the index requirement of 50-65 percent of the pitch content of the coal tar required by the active carbon can not be met, and other products are blended to meet the requirement of 50-65 percent of the pitch content. And secondly, large-scale coking enterprises implement industrial and technical transformation, light oil, wash oil, anthracene oil, naphthalene, phenol and the like in the primary coal tar are rectified to separate high value-added components, and the rest components are taken as secondary tar and supplied to downstream users. A downstream user is doped with substances such as benzene residue or oil residue, although the pitch content of the coal tar can meet the technical requirement of purchasing, the content of main products in the coal tar is greatly changed, and no effective means is available for detection and analysis. The fluidity of the product is extremely poor in the using process, the molding strip is fragile in the production process, and the produced active carbon has large floating ash on the appearance and poor surface smoothness.

At present, a plurality of resin binders are researched in laboratories, and are mostly in the research stage of the laboratories and are not applied industrially. For example, patent CN111849100 provides an activated carbon binder and a preparation method thereof, wherein polyvinyl alcohol, water and emulsified silicone oil are mixed according to the mass percentage of 10-40%, 40-60% and 5-15%, and then heated to 60-100 ℃ under stirring, and after all are dissolved, stirred for 5-15min under heat preservation for standby; slowly adding potassium hydroxide into the prepared water, stirring and cooling continuously, mixing according to the mass percentage of 40-60% of water and 10-30% of potassium hydroxide, and completely dissolving; slowly adding the prepared potassium hydroxide solution into the polyvinyl alcohol solution to form a uniform solution, adding the modifier, the flexibilizer and the cross-linking agent at one time, and cooling to room temperature to obtain the finished product binder. However, the raw materials are required to be more in variety, the preparation is complex, and the large-scale application is difficult.

CN108298537 provides an environment-friendly active carbon binder and a preparation method thereof, and raw material asphalt is prepared: mixing 10-15% of intermediate phase oil, 35-50% of asphalt and 0.1-0.2% of emulsifier I in proportion, heating to 80-100 ℃ under stirring, and stirring for 5-10min under heat preservation after all the intermediate phase oil is dissolved; preparing a soap solution: mixing water, emulsifier II 0.2-0.5% and sodium hydroxide 0.1-0.5% in the above ratio, and stirring to dissolve completely. Slowly adding the prepared raw material asphalt into the soap solution to form a uniform black solution, and cooling to room temperature to obtain the finished product. However, the asphalt emulsion is prepared by blending and stirring raw materials such as asphalt, emulsified oil, an emulsifier and the like, and the product after application has low strength, a complex preparation process and uncontrollable large-scale application.

CN102533375A discloses a method for preparing activated carbon binder from coal tar processed products. The binder is prepared by adding thinner such as washing oil and anthracene oil into coal tar without industrial naphthalene, and adjusting indexes such as viscosity of the tar and asphalt content to meet the use requirement of the binder raw material for the activated carbon. However, the coal tar without naphthalene material is used as the base material, and washing oil and anthracene oil naphthalene components are added, so that the quality of the coal tar as the base material is changed greatly, and the quality fluctuation of the prepared product binder is large.

Disclosure of Invention

In view of the above, the invention aims to provide a binder special for coal-based activated carbon and a preparation method thereof, and the binder is simple in process, good and stable in product quality, and suitable for large-scale production.

In order to achieve one aspect of the above object of the invention, the binder for coal-based activated carbon of the present invention adopts the following technical scheme:

the special binder for the coal-based activated carbon comprises the following components in parts by weight:

the binder according to the invention preferably has a pitch content of 50% to 65%, such as 51%, 57% or 62%.

According to the binder of the invention, preferably, the high-temperature pitch is residue of coal tar after liquid fraction is removed through distillation, and the softening point is 95-100 ℃.

In order to achieve the above object, in another aspect, the present invention further provides a method for preparing the above binder, the method comprising the steps of:

(1) the anthracene oil is conveyed into a reaction kettle, and the temperature of the reaction kettle is controlled to be 160 +/-5 ℃ (namely 155 ℃ -165 ℃);

(2) adding a first part of high-temperature asphalt into the reaction kettle and uniformly stirring;

(3) adding wash oil into the product obtained in the step (2), stirring, adding a second part of high-temperature asphalt, and then uniformly stirring;

(4) adding the phenol oil into the product obtained in the step (3), and uniformly stirring and mixing to obtain a binder;

wherein the dosage of the first part of high-temperature asphalt and the second part of high-temperature asphalt is 1:1-5:3, and the temperature is 200 +/-10 ℃.

According to the preparation method of the invention, preferably, in the steps (2) and (3), before adding the high-temperature asphalt, the high-temperature asphalt raw material is kept still in a storage tank for at least 48 hours to remove impurities, so that the impurities are settled and are convenient to remove, and the temperature of the storage tank is controlled to be 200 +/-10 ℃.

According to the preparation method of the present invention, preferably, in the step (2), the first portion of the high temperature asphalt is added equally divided into 4 to 6 times, for example, 5 times in total.

According to the preparation method of the present invention, preferably, in the step (3), the second portion of the high temperature asphalt is added in 2 to 4 times, for example, 3 times, in total.

According to the preparation method of the invention, preferably, in the steps (2) and (3), the stirring time is 15-20min after each addition of the high-temperature asphalt, and the stirring speed is controlled at 5-10 r/min.

According to the preparation method of the invention, the adhesive obtained in the step (4) is preferably conveyed to a product tank for standby, and the temperature of the product tank is 100 +/-10 ℃.

According to the preparation method of the invention, preferably, the binder is added with 20-40% of anthracene oil, such as 30%, 8-15% of washing oil, such as 12%, 2-5% of phenolic oil, such as 3%, and 50-60% of high-temperature asphalt, such as 55% by weight of the binder.

The invention takes high-temperature asphalt as a base material, develops a binder formula added with anthracene oil, washing oil and phenol oil in a proper proportion, and further realizes the preparation of the high-efficiency binder special for the coal-based activated carbon by controlling the processing technological parameters of the binder special for the activated carbon.

Detailed Description

The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples listed, and it should include equivalent modifications and variations to the technical solutions defined in the appended claims. In the present invention, the percentages are all by mass unless otherwise specified.

Example 1

Adding 20% anthracene oil by mass (the mass ratio of the anthracene oil to the total raw material amount, the same below) into a reaction kettle at 160 ℃, starting a stirring paddle, controlling the rotating speed at 10r/min, adding 7.5% high-temperature asphalt by mass into the reaction kettle, stirring for 15min, sequentially adding 4 times of equal high-temperature asphalt, and repeating the steps;

then adding 15% of washing oil by mass ratio, continuously stirring at the rotating speed of 5r/min, stirring for 10min, adding 7.5% of high-temperature asphalt by mass ratio (the softening point is 95-100 ℃, the same is applied below) into the reaction kettle at the rotating speed of 10r/min, stirring for 15min, sequentially adding 2 times of equal high-temperature asphalt, and repeating the steps;

then adding 5% phenol oil by mass ratio, controlling the rotating speed at 5r/min, continuously stirring for 2h, and conveying the homogenized special binder for the activated carbon to a storage tank. The asphalt content of Binder No. 1 was tested to be 62 wt%.

Example 2

Adding 30% anthracene oil by mass into a reaction kettle at 160 ℃, starting a stirring paddle, controlling the rotating speed at 8r/min, adding 6.88% high-temperature asphalt by mass into the reaction kettle, stirring for 15min, sequentially adding 4 times of equal high-temperature asphalt, and repeating the steps;

then adding 12% of washing oil by mass ratio, continuously stirring at the rotating speed of 4r/min for 10min, adding 6.88% of high-temperature asphalt by mass ratio into the reaction kettle at the rotating speed of 8r/min, stirring for 15min, sequentially adding 2 times of equal amount of high-temperature asphalt, and repeating the steps;

then adding 3% phenol oil by mass ratio, controlling the rotating speed at 5r/min, continuously stirring for 2h, and conveying the homogenized special binder for the activated carbon to a storage tank. The asphalt content of Binder No. 2 was tested to be 57 wt%.

Example 3

Adding 40% anthracene oil by mass into a reaction kettle at 160 ℃, starting a stirring paddle, controlling the rotating speed at 8r/min, adding 6.25% high-temperature asphalt by mass into the reaction kettle, stirring for 15min, sequentially adding 4 times of equal high-temperature asphalt, and repeating the steps;

then adding washing oil with the mass ratio of 8% and continuing stirring, controlling the rotating speed at 4r/min, stirring for 10min, then adding high-temperature asphalt with the mass ratio of 6.25% into the reaction kettle, controlling the rotating speed at 10r/min, stirring for 15min, then sequentially adding 2 times of high-temperature asphalt with the same amount, and repeating the steps;

then adding phenol oil with the mass ratio of 2%, controlling the rotating speed at 5r/min, continuously stirring for 2h, and conveying the homogenized special binder for the activated carbon to a storage tank. The asphalt content of Binder No. 3 was tested to be 51 wt%.

Example 4

The three prepared binders 1# -3# and the binder (high-temperature coal tar purchased from western Lai-Feng coking plant) with the asphalt content of 56% purchased in the market and the coal dust (ash content of 2.5-2.8% from Taixi coal washery of Shenhua Ningxia coal industry group, which is crushed to 200-mesh and 330-mesh Taylor standard sieve) are added into a kneader according to the proportion of the coal dust, the binder and the water being 100:35:10, stirred for 15 minutes and then put into a hydraulic press for 63T test to prepare the carbon strip with the thickness of 4.8 mm. Drying in the shade for 48h, and carrying out carbonization and activation tests. The carbonization temperature is 650 ℃ and the time is 20 min. The activation temperature is 900 ℃, and the activation time is 120 min. The sample indexes are analyzed and detected, and the results are shown in table 1.

TABLE 1

As can be seen from Table 1, the activated carbon prepared by using the binder of the present invention has better strength and less surface ash, and the adsorption performance indexes such as carbon tetrachloride and iodine adsorption values are basically equivalent to those of the activated carbon using the commercially available binder. Meanwhile, in the forming process, the forming strip prepared by the binder has a smooth surface.