Non-tar active coke and method for preparing the same

Abstract

The present application belongs to the technical field of flue gas treatment, and specifically provides a preparation method of non-tar active coke, comprising the following steps: (1) adding phenolic resin powder, carboxymethyl cellulose powder and short glass fiber into pitch in a stirring state to obtain a mixture; (2) mixing bituminous coal and active coke grinding waste coke powder to obtain coal powder; (3) putting the coal powder into a kneader and starting stirring, adding the mixture into the kneader, then adding a Tween aqueous solution, and performing kneading to obtain a kneaded material; (4) granulating and drying the kneaded material, and then performing carbonization and activation to obtain the non-tar active coke. The preparation method uses waste coke under the vibrating screen of the regeneration tower of a desulfurization and denitrification system as the main raw material, and replaces part of the coal to reduce the preparation cost of the active coke. And a step-by-step mixing method is adopted, and a series of high molecular organic materials with different functions are matched to replace tar and improve the environmental friendliness of the preparation process.

Description

Technical Field

[0001] This invention belongs to the field of flue gas treatment technology, specifically relating to a non-tar activated coke and its preparation method. Background Technology

[0002] Activated coke is a type of carbon particle with a porous structure, abundant surface functional groups, and a certain strength. The porous structure and abundant surface functional groups enable activated coke to adsorb sulfur dioxide and catalyze nitrogen oxides, while its strength ensures its suitability for moving beds. Activated coke desulfurization and denitrification methods, characterized by adsorption / desorption cycles, are widely used in the treatment of flue gas from steel sintering. The performance of activated coke materials determines the flue gas purification capacity of the desulfurization and denitrification system.

[0003] Activated coke is typically produced from various types of caking coal, combined with binders such as tar and pitch, through granulation and carbonization activation. Because it requires large quantities of coal and uses tar, which has a certain degree of toxicity and environmental pollution, activated coke production still faces challenges such as high cost and environmental unfriendliness. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of high cost and environmental pollution in the preparation of activated coke in the prior art.

[0005] Therefore, the present invention provides a method for preparing non-tar activated coke, comprising the following steps:

[0006] (1) Phenolic resin powder, carboxymethyl cellulose powder and short glass fiber are added to asphalt under stirring to obtain a mixture;

[0007] (2) Grind bituminous coal and activated coke abrasion waste coke into powder and mix them into coal powder;

[0008] (3) Put coal powder into the kneader and start stirring. Add the mixture into the kneader, then add Tween water solution and knead to obtain kneaded material.

[0009] (4) After granulation and drying, the kneaded material is carbonized and activated, and then cooled to obtain non-tar activated coke.

[0010] Specifically, in step (1) above, the time interval between adding phenolic resin powder, carboxymethyl cellulose powder, and short glass fiber is 1 minute.

[0011] Specifically, in the mixture of step (1) above, the mass ratio of asphalt is 60-70%; the mass ratio of phenolic resin powder, carboxymethyl cellulose powder and short glass fiber is (3-4):2:2.

[0012] Specifically, in step (2) above, the mass percentage of activated coke abrasion waste coke in the pulverized coal is 40-60%; the bituminous coal includes coking coal, and the mass percentage of coking coal in the bituminous coal is 1:4-2:3.

[0013] Specifically, the bituminous coal in step (2) above also includes one or more of the following: coking coal, 1 / 3 coking coal, and lean coal.

[0014] Specifically, in step (3) above, the mass ratio of the mixture to the pulverized coal is 1:15-1:25.

[0015] Specifically, in the Tween aqueous solution of step (3) above, Tween accounts for 1-5% of the water mass; the mass ratio of Tween aqueous solution to coal powder is 1:10-1:20.

[0016] Specifically, in step (4) above, the carbonization temperature is 500-600℃ and the carbonization time is 1-2h; the activation temperature is 700-900℃ and the activation time is 0.3-0.45h.

[0017] Specifically, in step (4) above, the carbonization process is protected by inert gas, and the activation process is protected by water vapor / inert gas.

[0018] In addition, the present invention also provides a non-tar activated coke product prepared by the above method.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0020] The method for preparing non-tar activated coke provided by this invention uses the waste coke undersize from the vibrating screen after the regeneration tower of the desulfurization and denitrification system as the main raw material to replace part of the coal, thereby reducing the cost of activated coke preparation. Furthermore, by combining a series of high-molecular organic compounds with different functional focuses and employing a stepwise mixing method, the combination of high-molecular organic compounds replaces tar, improving the environmental friendliness of the preparation process. Specifically, polycarboxymethyl cellulose powder provides cold strength to the raw material and strengthens the interlocking force between particles during the kneading and granulation process; phenolic resin decomposes during carbonization to provide sufficient molten colloid, promoting the production of the carbon skeleton; and short glass fibers not only provide cold strength to the raw material during kneading and granulation but also play a certain binding role through melting during carbonization. Detailed Implementation

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Although representative embodiments of the present invention have been described in detail, those skilled in the art will understand that various modifications and changes can be made to the present invention without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limited to the embodiments, but should be defined by the appended claims and their equivalents.

[0022] This invention provides a method for preparing non-tar activated coke, comprising the following steps:

[0023] (1) Add sieved (200 mesh or higher) asphalt powder to the mixing tank and start stirring. While stirring, add phenolic resin powder, carboxymethyl cellulose powder and short glass fiber to the asphalt in sequence, with a 1-minute interval between additions, to obtain a mixture. After all raw materials are added, stir for 10 minutes, take out the mixture and sieve it, and use the portion with a mesh size of 200 or higher. The mass ratio of asphalt in the mixture is 60-70%; the mass ratio of phenolic resin powder, carboxymethyl cellulose powder and short glass fiber is (3-4):2:2.

[0024] (2) Bituminous coal and activated coke abrasion waste coke are ground into powder by a coal mill, and the portion with a mesh size of 200 or larger is screened and mixed into coal powder; the mass ratio of activated coke abrasion waste coke in the coal powder is 40-60%; the bituminous coal includes coking coal, and the mass ratio of coking coal in bituminous coal is 1:4-2:3; bituminous coal also includes one or more of fat coal, 1 / 3 coking coal, and lean coal.

[0025] (3) Add the pulverized coal into the kneader and start the mixer. Add the mixture into the kneader. The mass ratio of the mixture to the pulverized coal is 1:15-1:25. Immediately after adding the mixture, add the Tween aqueous solution and knead for at least 5 minutes to obtain the kneaded material. The Tween 80 aqueous solution contains 1-5% Tween by mass of water. The mass ratio of the Tween aqueous solution to the pulverized coal is 1:10-1:20.

[0026] (4) The kneaded material is granulated and added to a granulator for granulation, preferably cylindrical particles with a length of 8-12 mm. The particles are naturally air-dried in a dry and cool environment until the moisture content is below 15%, and then sent to an integrated carbonization and activation device for carbonization and activation. After cooling, non-tar-type activated coke is obtained.

[0027] The carbonization activation device has programmed temperature control. The carbonization program temperature is 500-600℃, and the carbonization time is 1-2 hours. The carbonization process is protected by an inert gas, preferably nitrogen, with a flow rate of 1.0 L / min. The activation program temperature is 700-900℃, and the activation time is 0.3-0.45 hours. The activation process is protected by steam / inert gas, preferably steam / nitrogen. The steam flow rate is 1.0-5.0 ml / min / 100g carbonized material, and the nitrogen flow rate is 0.5 L / min.

[0028] The effects of the preparation method of the non-tar activated coke of the present invention will be studied through specific embodiments below.

[0029] Example 1:

[0030] This embodiment provides a method for preparing non-tar activated coke, including the following steps:

[0031] (1) Add 400g of sieved (200 mesh or higher) asphalt powder to the mixing tank and start stirring. While stirring, add 75g of phenolic resin powder, 50g of carboxymethyl cellulose powder and 50g of short glass fiber to the asphalt in sequence at 1min intervals. After all raw materials are added, stir for 10min. Take out the mixture and sieve it through a screen to screen out the part with a mesh size of 200 or higher for later use.

[0032] (2) Coking coal, lean coal and activated coke abrasion waste coke are ground into powder by a coal mill and the portion with a mesh size of 200 or larger is screened.

[0033] (3) Take 600g of ground coking coal, 1400g of bituminous coal, and 2400g of activated coke abrasion waste coke, and pour them into a kneader and stir for 1 minute. Add the mixture to the kneader. After the mixture is added, while the kneader is continuously stirring, immediately add an aqueous solution containing 5 wt.% Tween 80 into the kneader and knead for 10 minutes to obtain the kneaded material; the amount of Tween 80 aqueous solution is 440g.

[0034] (4) The kneaded material is added to the granulator for granulation to obtain cylindrical particles with a length of 8-12 mm. The particles are naturally air-dried in a dry and cool environment until the moisture content is below 15%, and then sent to the integrated carbonization and activation device for carbonization and activation. After cooling, non-tar-type activated coke is obtained.

[0035] The carbonization temperature was 560℃, the carbonization time was 1 hour, and nitrogen protection was used during the carbonization process at a flow rate of 1.0 L / min. The activation temperature was 760℃, the activation time was 30 minutes, and steam / nitrogen protection was used during the activation process at a steam flow rate of 3.0 ml / min / 100g carbonized material and a nitrogen flow rate of 0.5 L / min.

[0036] The performance of the non-tar activated coke prepared in this embodiment was tested using the method in GB / T30202.3-2013, and the results are shown in Table 1.

[0037] Example 2:

[0038] This embodiment provides a method for preparing non-tar activated coke, including the following steps:

[0039] (1) Add 420g of sieved (200 mesh or higher) asphalt powder to the mixing tank and start stirring. While stirring, add 140g of phenolic resin powder, 70g of carboxymethyl cellulose powder and 70g of short glass fiber to the asphalt in sequence at 1min intervals. After all raw materials are added, stir for 10min. Take out the mixture and sieve it through a screen to screen out the part with a mesh size of 200 or higher for later use.

[0040] (2) Coking coal, lean coal and activated coke abrasion waste coke are ground into powder by a coal mill and the portion with a mesh size of 200 or larger is screened.

[0041] (3) Take 1680g of ground coking coal, 2520g of lean coal, and 6300g of activated coke abrasion waste coke, and pour them into a kneader and stir for 2 minutes. Add the mixture to the kneader. After the mixture is added, while the kneader is continuously stirring, immediately add an aqueous solution containing 5wt.% Tween 80 into the kneader and knead for 10 minutes to obtain the kneaded material. The mass ratio of Tween 80 aqueous solution to coal powder is 1:20.

[0042] (4) The kneaded material is added to the granulator for granulation to obtain cylindrical particles with a length of 8-12 mm. The particles are naturally air-dried in a dry and cool environment until the moisture content is below 15%, and then sent to the integrated carbonization and activation device for carbonization and activation. After cooling, non-tar-type activated coke is obtained.

[0043] The carbonization temperature was 560℃, the carbonization time was 1 hour, and nitrogen protection was used during the carbonization process at a flow rate of 1.0 L / min. The activation temperature was 760℃, the activation time was 30 minutes, and steam / nitrogen protection was used during the activation process at a steam flow rate of 3.0 ml / min / 100g carbonized material and a nitrogen flow rate of 0.5 L / min.

[0044] The performance of the non-tar activated coke prepared in this embodiment was tested using the method in GB / T30202.3-2013, and the results are shown in Table 1.

[0045] Comparative Example 1:

[0046] This comparative example provides an activated carbon prepared using the following steps:

[0047] (1) Weigh out 400g of asphalt powder, 75g of phenolic resin powder, 50g of carboxymethyl cellulose powder, 50g of short glass fiber, 600g of coking coal, 1400g of bituminous coal, and 2400g of activated coke abrasion waste coke, pass them through a 200-mesh sieve, and stir for 1 minute.

[0048] (2) Add 440g of an aqueous solution containing 5wt.% Tween 80 to a kneader and knead for 25min to obtain kneaded material.

[0049] (3) The kneaded material is added to the granulator for granulation to obtain cylindrical particles with a length of 8-12 mm. The particles are naturally air-dried in a dry and cool environment until the moisture content is below 15%, and then sent to the integrated carbonization and activation device for carbonization and activation. After cooling, non-tar-type activated coke is obtained.

[0050] The carbonization temperature was 560℃, the carbonization time was 1 hour, and nitrogen protection was used during the carbonization process at a flow rate of 1.0 L / min. The activation temperature was 760℃, the activation time was 30 minutes, and steam / nitrogen protection was used during the activation process at a steam flow rate of 3.0 ml / min / 100g carbonized material and a nitrogen flow rate of 0.5 L / min.

[0051] The performance of the activated carbon prepared in this comparative example was tested using the method in GB / T30202.3-2013, and the results are shown in Table 1.

[0052] Comparative Example 2:

[0053] This comparative example provides an activated coke, the preparation method of which differs from that of Example 1 in that step (1) is as follows: weigh 400g of asphalt powder, 75g of phenolic resin powder, 50g of carboxymethyl cellulose powder and 50g of short glass fiber respectively, pass them through a 200-mesh sieve, and add them to a mixing tank and stir for 13min.

[0054] The performance of the test gel prepared in this comparative example was tested using the method in GB / T30202.3-2013, and the results are shown in Table 1.

[0055] Comparative Example 3:

[0056] This comparative example provides an activated coke, the preparation method of which differs from that of Example 1 in that step (1) involves adding 87g of carboxymethyl cellulose powder and 87g of short glass fiber to asphalt in sequence.

[0057] The performance of the test gel prepared in this comparative example was tested using the method in GB / T30202.3-2013, and the results are shown in Table 1.

[0058] Table 1. Test results of activated carbon performance

[0059] abrasion resistance Compressive strength First-class product ≥97％ ≥40Kgf qualified products ≥94％ ≥30Kgf Example 1 96.1％ 44Kgf Example 2 97.8％ 48Kgf Comparative Example 1 95.7％ 44Kgf Comparative Example 2 95.1％ 43Kgf Comparative Example 3 94.4％ 42Kgf

[0060] The above examples are merely illustrative of the present invention and do not constitute a limitation on the scope of protection of the present invention. All designs that are the same as or similar to the present invention are within the scope of protection of the present invention.

Claims

1. A method for preparing non-tar-type activated coke, characterized in that, Includes the following steps: (1) Phenolic resin powder, carboxymethyl cellulose powder and short glass fiber are added to asphalt in sequence under stirring to obtain a mixture; the time interval between adding phenolic resin powder, carboxymethyl cellulose powder and short glass fiber is 1 min; the mass ratio of asphalt in the mixture is 60-70%; the mass ratio of phenolic resin powder, carboxymethyl cellulose powder and short glass fiber is (3-4):2:2; (2) Grind bituminous coal and activated coke abrasion waste coke into powder and mix them into coal powder; (3) Put coal powder into the kneader and start stirring. Add the mixture into the kneader, then add Tween water solution and knead to obtain kneaded material; the mass ratio of the mixture to coal powder is 1:15-1:

25. (4) After granulation and drying, the kneaded material is carbonized and activated, and then cooled to obtain non-tar activated coke.

2. The method for preparing non-tar activated coke as described in claim 1, characterized in that: The mass percentage of activated coke abrasion waste coke in the pulverized coal in step (2) is 40-60%; the bituminous coal includes coking coal, and the mass percentage of coking coal in the bituminous coal is 1:4-2:

3.

3. The method for preparing non-tar activated coke as described in claim 2, characterized in that: The bituminous coal in step (2) also includes one or more of the following: coking coal, 1 / 3 coking coal, and lean coal.

4. The method for preparing non-tar activated coke as described in claim 1, characterized in that: In step (3), Tween accounts for 1-5% of the water mass in the Tween aqueous solution; the mass ratio of Tween aqueous solution to coal powder is 1:10-1:

20.

5. The method for preparing non-tar activated coke as described in claim 1, characterized in that: In step (4), the carbonization temperature is 500-600℃ and the carbonization time is 1-2h; the activation temperature is 700-900℃ and the activation time is 0.3-0.45h.

6. The method for preparing non-tar activated coke as described in claim 1, characterized in that: In step (4), the carbonization process is protected by inert gas, and the activation process is protected by water vapor / inert gas.

7. A non-tar activated coke product prepared by the method according to any one of claims 1-6.