CN111575034B - Formed coke and preparation method and application thereof - Google Patents
Formed coke and preparation method and application thereof Download PDFInfo
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- CN111575034B CN111575034B CN202010394649.1A CN202010394649A CN111575034B CN 111575034 B CN111575034 B CN 111575034B CN 202010394649 A CN202010394649 A CN 202010394649A CN 111575034 B CN111575034 B CN 111575034B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/08—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form in the form of briquettes, lumps and the like
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Abstract
The invention relates to the field of coal chemical industry, in particular to formed coke and a preparation method and application thereof. The preparation method of the formed coke comprises the following steps: (1) pressing blended coal obtained by mixing raw materials to obtain molded coal; based on the total weight of the raw materials, the raw materials comprise: 15-25wt% of coke powder, 60-70wt% of fat coal and 5-15wt% of anthracite; (2) and (3) putting the molded coal into a coke oven at room temperature, heating the coke oven from room temperature to 1200 ℃ at the speed of 6-10 ℃/h, and performing dry distillation at the temperature of 1000 ℃ to 1200 ℃ for 380-480h to obtain the formed coke. The formed coke obtained by the method has the advantages of few internal cracks, large blocking degree, high heat strength and low ash content, so that the formed coke has wide application prospect.
Description
Technical Field
The invention relates to the field of coal chemical industry, in particular to formed coke and a preparation method and application thereof.
Background
The formed coke is coke with uniform shape produced by a pressure forming method, the formed coal coking is to mix and knead part of raw material coal and press the mixture into formed blocks with certain shape and size, and then the formed blocks are matched with the raw material coal according to a certain proportion and are loaded into a coke oven for coking. The briquette coking is beneficial to improving the bulk density of the coal as fired and improving the coke quality, and can increase the dosage of weakly caking coking coal and reduce the coal blending cost of enterprises on the basis of stabilizing the coke quality. Compared with the conventional coke, the formed coke has the advantages that the size and the shape can be prepared according to the needs of users, the formed coke is compact in coke body, small in air holes and uniform in distribution, and is more suitable for being applied to the fields of metallurgy, chemical industry, automobiles and the like.
The existing coke preparation method adopts the raw materials of main coke coal, a thinning agent, a binder and the like to prepare coal, and the coal is dried and distilled for 15 to 24 hours at the temperature of 800-: 1. a binder must be used; 2. the produced formed coke has poor heat strength, low crushing strength and low yield, and is difficult to produce in large scale and high efficiency, thereby limiting the large-scale application of the formed coke.
Disclosure of Invention
The invention aims to overcome the problems of poor heat strength, low crushing strength and low yield of formed coke in the prior art, provides the formed coke, a preparation method and application thereof, and realizes the preparation of the formed coke with high heat strength and large granularity under the condition of no binder.
In order to achieve the above object, a first aspect of the present invention provides a process for producing formed coke, comprising:
(1) pressing blended coal obtained by mixing raw materials to obtain molded coal; based on the total weight of the raw materials, the raw materials comprise: 15-25wt% of coke powder, 60-70wt% of fat coal and 5-15wt% of anthracite;
(2) and (3) putting the molded coal into a coke oven at room temperature, heating the coke oven from room temperature to 1200 ℃ at the speed of 6-10 ℃/h, and performing dry distillation at the temperature of 1000 ℃ to 1200 ℃ for 380-480h to obtain the formed coke.
In a second aspect, the present invention provides a formed coke produced by the process according to the invention.
The third aspect of the invention provides the use of the formed coke of the invention in foundry coke and extended length coke.
The invention heats the molded coal in the coking furnace at a lower heating rate and cokes for a long time, so that colloid in the fat coal is completely melted to generate enough colloid, the fat coal can be fully bonded with coke powder with strong anti-shrinkage capability and coal particles of anthracite with good grindability, the stress difference caused by shrinkage in the coking process is also reduced, the formed coke is ensured to have larger lumpiness, the heat intensity of the formed coke is improved, and the limitation that the large-block formed coke can be generated only by using a binder is broken; the formed coke obtained by the method has few internal cracks, large blocking degree (more than 70wt% of the formed coke has the blocking degree larger than or equal to 90mm), high thermal strength (larger than or equal to 60 wt%), and low ash content (less than 10 wt%), so that the formed coke has wide application prospect.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of formed coke, which comprises the following steps:
(1) pressing blended coal obtained by mixing raw materials to obtain molded coal; based on the total weight of the raw materials, the raw materials comprise: 15-25wt% of coke powder, 60-70wt% of fat coal and 5-15wt% of anthracite;
(2) and (3) putting the molded coal into a coke oven at room temperature, heating the coke oven from room temperature to 1200 ℃ at the speed of 6-10 ℃/h, and performing dry distillation at the temperature of 1000 ℃ to 1200 ℃ for 380-480h to obtain the formed coke.
The invention heats the molded coal in the coking furnace at a lower heating rate and cokes the molded coal for a long time, so that the colloid in the fat coal is completely melted to generate enough colloid, and the molded coal is matched with the coke powder with strong anti-shrinkage capability and the anthracite with good grindability, thereby not only fully bonding the coal particles of the blended coal, but also reducing the stress difference generated by shrinkage in the coking process, ensuring that the formed coke has larger lumpiness, improving the thermal strength of the formed coke and breaking the limitation that the large-sized formed coke can be generated only by using the binder.
In order to further improve the heat strength and the caking property of the formed coke and reduce cracks in the formed coke, the raw material preferably comprises the following components in percentage by weight based on the total weight of the raw material: 18-22wt% of coke powder, 65-70wt% of fat coal and 9-13wt% of anthracite.
In the present invention, in order to improve the caking index G of the fat coal under preferable conditions in the lump degree and the heat strength of the formed cokeFertilizer≧ 90, such as 90, 91, 92, 95 or any value therebetween; the grindability index HGI of the anthracite coalIs free ofNot less than 70wt%, for example, 70, 73, 75, 80 or any value between the above values; in a preferred embodiment of the present invention, the caking index of fat coal, which is preferably the caking index of the fat coal, and the grindability index of anthracite coal, are simultaneously adjusted to further improve the lumpiness and the cold-hot strength of the formed cokeThe number satisfies 90 ≤ GFertilizerNot more than 95 percent, and the grindability index of the anthracite meets the HGI of not more than 70 percent by weightIs free of75 wt% or less, more preferably, the caking index of the fat coal is 91.5 and the grindability index of the anthracite coal is 73.
In the invention, under the preferable conditions, the coke powder is petroleum coke and/or asphalt coke, the ash content in the petroleum coke and the asphalt coke is low, the anti-shrinkage capability is strong, on one hand, the ash content of the formed coke can be reduced, and on the other hand, the generation of internal cracks of the formed coke can be reduced.
In the invention, the caking index of the raw material affects the caking index and the ash content, the volatile matter, the sulfur content and the grindability index of the raw material, and in order to further improve the caking index and the cold and hot strength of the formed coke, the fat coal simultaneously meets the following performance indexes under the preferable conditions: a. theFertilizer D≤13wt％，25wt％≤Vdaf, fertilizer≤29wt％，St, d, fertilizerLess than or equal to 3wt percent; the anthracite coal simultaneously meets the following performance indexes: a. thed is absent≤9wt％，10wt％≤Vdaf, do≤16wt％，St, d, noneLess than or equal to 3wt percent; the coke powder simultaneously meets the following performance indexes: a. thed powder≤0.5wt％，13wt％≤Vdaf, powder≤17wt％，St, d, powderLess than or equal to 3 weight percent. Further preferably, the fat coal simultaneously meets the following performance indexes: a. theFertilizer D≤12wt％，26wt％≤Vdaf, fertilizer≤28wt％，St, d, fertilizerLess than or equal to 0.5 wt%; the anthracite coal simultaneously meets the following performance indexes: a. thed is absent≤8wt％，12wt％≤Vdaf, do≤15wt％，St, d, noneLess than or equal to 0.5 wt%; the coke powder simultaneously meets the following performance indexes: a. thed powder≤0.45wt％，14wt％≤Vdaf, powder≤16wt％，St, d, powder≤0.5wt％。
In the present invention, in order to mix the raw materials sufficiently, improve the synergistic effect between the raw materials, and further improve the heat strength of the formed coke, the coke powder is pre-crushed under a preferable condition, and the average particle size of 95wt% or more of the coke powder is less than 3mm based on the total weight of the coke powder.
In the present invention, in order to mix the raw materials uniformly, it is preferable that 97wt% or more of the blended coal have an average particle size of less than 3mm, and more preferably 97wt% to 99 wt% of the blended coal have an average particle size of less than 3mm, based on the total weight of the blended coal.
In the invention, under the preferable conditions, in the step (1), the density of the briquette is 1200-1300kg/m3For example, 1200kg/m may be set3、1250kg/m3、1300kg/m3Or any value therebetween, most preferably 1270kg/m3。
In the invention, the molded coal is added into a coke oven at room temperature, and the coke oven is heated at a lower heating rate for coking for a long time, so that the colloid in the blended coal can be completely melted to generate a sufficient amount of colloidal substances, the stress difference in the coking process can be reduced, the generation of cracks is reduced, and the obtained formed coke has larger lumpiness and higher heat strength, wherein the heating rate is 6-10 ℃/h, for example, 6 ℃/h, 7 ℃/h, 8 ℃/h, 9 ℃/h, 10 ℃/h or any value or combination of the values, preferably 7-9 ℃/h, and most preferably 8 ℃/h under the optimal condition. Under the preferable conditions, the coking time is 380-. Preferably, the coking temperature is 1100 ℃ to 1200 ℃, for example 1100 ℃, 1150 ℃, 1200 ℃ or any value between the above values, more preferably 1150 ℃.
In the invention, after the dry distillation is finished, the formed coke is quenched in a coke oven, the quenching in the coke oven can reduce the temperature difference of cold and hot in the quenching process, reduce the generation of formed coke cracks and improve the lumpiness of the formed coke, the quenching mode can be dry quenching or wet quenching, preferably wet quenching, and more preferably, the specific process of the wet quenching is as follows: and (3) introducing water into the coke oven to flush the formed coke until the formed coke is cooled to room temperature.
The invention also provides formed coke prepared by the preparation method. Under the preferable conditions, the performance indexes of the formed coke are as follows: a. thed, type＜10wt％；1wt％≤Vdaf％＜1.5wt％；St, d, C＜0.8wt％；M40, carbon≥90wt％；CRICarbon (C)≤25wt％；CSRModel (III)More than or equal to 60 wt%; the block degree of the formed coke with more than 70wt% is more than or equal to 90 mm.
The formed coke prepared by the method has low ash content, large bulk and high thermal strength, and can be used as casting coke and cotton extending coke.
The present invention will be described in detail below by way of examples. In the following examples, the ash content (A) of the formed cokedWt.%), volatile components (V)dafThe/wt%) index was measured according to GB/T2001-1991 method for analyzing and determining coke industry; the particle size index of the formed coke is obtained by testing according to GB/T2005-1994 method for measuring the content of coke powder and the screening composition of metallurgical coke; mechanical Strength (M) of formed Coke40The% by weight is determined according to GB/T1996-2003 Metallurgical Coke; sulfur content (S) of formed coket,dThe content of the sulfur-containing compound is measured according to GB/T2286-1991 method for measuring the total sulfur content of the coke; the thermal properties (CRI/wt%, CSR/wt%) of the formed coke were determined according to GB/T4000-1996 method for determining reactivity and strength of coke after reaction.
Example 1
The properties of the raw materials for producing formed coke in this example are shown in table 1, and the compositions of the raw materials are shown in table 2; the preparation method of the formed coke comprises the following steps:
(1) pre-crushing petroleum coke to obtain petroleum coke powder, wherein the average particle size of 95wt% of the petroleum coke powder is less than 3mm based on the total weight of the petroleum coke powder; pressing blended coal obtained by mixing petroleum coke powder, fat coal and anthracite into briquettes with the specification of 500 multiplied by 450 multiplied by 420cm, and stacking the briquettes into briquette stacks with the specification of 2 multiplied by 2; wherein, based on the total weight of the blended coal, 98 wt% of the blended coal has an average particle size of less than 3mm, and the density of the molded coal is 1270kg/m3，
(2) And (3) putting the briquette stack into a coke oven at room temperature, heating the coke oven from room temperature to 1100 ℃ at the speed of 8 ℃/h, performing dry distillation at the temperature of 1100 ℃ for 400h, after the dry distillation is finished, introducing water into the coke oven to flush the formed coke, and cooling the formed coke to the room temperature to obtain formed coke A1.
The properties of the formed coke a1 obtained in this example are shown in table 6.
Examples 2 to 5
The properties of the raw materials for producing formed coke in examples 2 to 5 are shown in Table 1, and the compositions of the raw materials are shown in Table 2.
The formed coke was prepared in the same manner as in example 1 to obtain formed coke A2-A5.
The properties of the formed coke A2-A5 obtained in examples 2-5 are shown in Table 6.
Table 1: property parameters of the starting materials in examples 1 to 5
Table 2: compositions of the raw materials in examples 1 to 5
Example 6
The properties of the raw materials for producing formed coke in this example are shown in Table 3, and the compositions of the raw materials are the same as those in example 1.
The process for producing formed coke was the same as in example 1 to obtain formed coke a 6.
The properties of the formed coke a6 obtained in this example are shown in table 6.
Table 3: property parameters of the starting Material in example 6
Example 7
The properties of the raw materials for producing formed coke in this example are shown in Table 4, and the compositions of the raw materials are the same as those in example 1.
The process for producing formed coke was the same as in example 1 to obtain formed coke a 7.
The properties of the formed coke a7 obtained in this example are shown in table 6.
Table 4: property parameters of the starting Material in example 7
Example 8
The composition and the material property parameters of the raw materials for preparing the formed coke in the example are the same as those of the example 1, except that: the heating rate of the coke oven and the dry distillation time of the formed coal are different, and specifically, the preparation method of the formed coke comprises the following steps:
(1) pre-crushing petroleum coke to obtain petroleum coke powder, wherein the average particle size of 96 wt% of the petroleum coke powder is less than 3mm based on the total weight of the petroleum coke powder; pressing blended coal obtained by mixing petroleum coke powder, fat coal and anthracite into briquettes with the specification of 500 multiplied by 450 multiplied by 420cm, and stacking the briquettes into briquette stacks with the specification of 2 multiplied by 2; wherein, based on the total weight of the blended coal, 97wt% of the blended coal has an average particle size of less than 3mm, and the density of the molded coal is 1270kg/m3，
(2) And (2) putting the briquette stack into a coke oven at room temperature, heating the coke oven from room temperature to 1050 ℃ at the speed of 6 ℃/h, carrying out dry distillation at 1050 ℃ for 450h, after the dry distillation is finished, injecting water into the coke oven to wash the formed coke until the formed coke is cooled to room temperature, and thus obtaining the formed coke A8.
The properties of the formed coke A8 obtained in this example are shown in table 6.
Example 9
The composition and the material property parameters of the raw materials for preparing the formed coke in the example are the same as those of the example 1, except that: the heating rate of the coke oven and the dry distillation time of the formed coal are different, and specifically, the preparation method of the formed coke comprises the following steps:
(1) pre-crushing petroleum coke to obtain petroleum coke powder, wherein the average particle size of 95wt% of the petroleum coke powder is less than 3mm based on the total weight of the petroleum coke powder; pressing blended coal obtained by mixing petroleum coke powder, fat coal and anthracite into briquettes with the specification of 500 multiplied by 450 multiplied by 420cm, and stacking the briquettes into briquette stacks with the specification of 2 multiplied by 2; wherein, the total weight of the blended coal is usedOn the basis, 98 wt% of the blended coal has an average particle size of less than 3mm, and the density of the molded coal is 1250kg/m3，
(2) And (3) putting the briquette stack into a coke oven at room temperature, heating the coke oven from room temperature to 1200 ℃ at the speed of 10 ℃/h, performing dry distillation for 380h at the temperature of 1200 ℃, after the dry distillation is finished, injecting the formed coke into the coke oven by water, and cooling the formed coke to the room temperature to obtain formed coke A9.
The properties of the formed coke a9 obtained in this example are shown in table 6.
Comparative example 1
The composition and properties of the raw materials for forming coke in this example were the same as in example 1, except that: the heating rate of the coke oven and the dry distillation time of the formed coal are different, and specifically, the preparation method of the formed coke comprises the following steps:
(1) pre-crushing petroleum coke to obtain petroleum coke powder, wherein the average particle size of 95wt% of the petroleum coke powder is less than 3mm based on the total weight of the petroleum coke powder; pressing blended coal obtained by mixing petroleum coke powder, fat coal and anthracite into briquettes with the specification of 500 multiplied by 450 multiplied by 420cm, and stacking the briquettes into briquette stacks with the specification of 2 multiplied by 2; wherein, based on the total weight of the blended coal, 98 wt% of the blended coal has an average particle size of less than 3mm, and the density of the molded coal is 1250kg/m3，
(2) And (3) putting the briquette stack into a coke oven at room temperature, heating the coke oven from room temperature to 1150 ℃ at the speed of 3 ℃/min, performing dry distillation at 1150 ℃ for 300h, after the dry distillation is finished, injecting water into the coke oven to wash the formed coke until the formed coke is cooled to room temperature, and thus obtaining the formed coke B1.
The coke form B1 obtained in this comparative example had the performance parameters shown in table 6.
Comparative example 2
The procedure of example 1 was followed, except that the raw materials for the preparation of formed coke had the following composition: 15wt% of coke powder, 77 wt% of fat coal and 8 wt% of anthracite to obtain formed coke B2.
The properties of the formed coke B2 obtained in comparative example 2 are shown in table 6.
Comparative example 3
The procedure of example 1 was followed, except that the composition of the raw materials and the process for producing formed coke were the same as in example 1: the properties of the raw material for forming coke in this comparative example are shown in Table 5, to obtain formed coke B3.
The properties of the formed coke B3 obtained in this example are shown in table 6.
Table 5: property parameters of the feedstock in comparative example 3
Comparative example 4
The formed coke is prepared by the method disclosed in the publication number CN 109097084A, and the method comprises the following steps:
a coal blending raw material composition for producing formed coke comprises 3% of binder, 3% of thinning agent, 35% of anthracite and 59% of coking coal; the binder is coal liquefaction residue purified asphalt with a softening point of 130-150 ℃, the granularity is less than 0.5mm, and the ash content is less than 0.2%; the thinning agent is metallurgical coke powder with volatile component less than 1.8%, granularity less than 0.5mm, anthracite granularity less than 1mm, and coking coal granularity less than 1 mm.
And (3) preparing the coal blending raw material composition into molded coal by using a molded coal hydraulic device, conveying the molded coal to a heat recovery coke oven for high-temperature dry distillation at the dry distillation temperature of 900 ℃ to prepare formed coke B4.
The coke form B2 obtained in this comparative example had the performance parameters shown in table 6.
TABLE 6 Performance parameters for formed cokes A1-A9 and B1-B4
As can be seen from the results of the above examples, comparative examples and tables 1 to 6, the coal blending using low ash coke breeze, high ash fat coal having high caking property and high abrasion resistance and lean coal having high abrasion resistance index was carried out in a specific ratio, particularly when the caking index of the fat coal was 90. ltoreq. GFertilizerNot more than 95 percent and the grindability index of the anthracite coal is not less than 70 percent by weight HGIIs free ofAnd when the temperature is less than or equal to 75 wt%, coking is carried out for a long time at a slow temperature rise rate, the lumpiness of the formed coke (more than 70wt% of the lumpiness of the formed coke is more than or equal to 90mm) and the heat strength is high (more than or equal to 60 wt%), and the ash content of the obtained formed coke is low (less than 10 wt%).
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (8)
1. A method for preparing formed coke, which is characterized by comprising the following steps:
(1) pressing blended coal obtained by mixing raw materials to obtain molded coal; based on the total weight of the raw materials, the raw materials consist of the following substances: 15-25wt% of coke powder, 60-70wt% of fat coal and 5-15wt% of anthracite;
(2) putting the molded coal into a coke oven at room temperature, heating the coke oven from room temperature to 1000-1200 ℃ at the speed of 6-10 ℃/h, and performing dry distillation at the temperature of 1000-1200 ℃ for 380-480h to obtain formed coke;
caking index G of the fat coalFertilizerNot less than 90; the grindability index HGI of the anthracite coalIs free of≥70wt%；
The coke powder is petroleum coke and/or asphalt coke.
2. The method of claim 1, wherein the feedstock comprises, based on the total weight of the feedstock: 18-22wt% of coke powder, 65-70wt% of fat coal and 9-13wt% of anthracite.
3. The production method according to claim 1, wherein the caking index of the fat coal satisfies 90 ≦ GFertilizerNot more than 95 percent, and the grindability index of the anthracite meets the HGI of not more than 70 percent by weightIs free of≤75wt%。
4. The preparation method of claim 1, wherein the fat coal simultaneously satisfies the following performance indexes: a. theFertilizer D≤13wt%，25 wt%≤Vdaf, fertilizer≤29 wt%，St, d, fertilizerLess than or equal to 3wt percent; and/or
The anthracite coal simultaneously meets the following performance indexes: a. thed is absent≤9wt%，10wt%≤Vdaf, do≤16wt%，St, d, noneLess than or equal to 3wt percent; and/or
The coke powder simultaneously meets the following performance indexes: a. thed powder≤0.5wt%，13wt%≤Vdaf, powder≤17 wt%，St, d, powder≤3 wt%。
5. The production method according to claims 1 to 4, wherein 95wt% or more of the coke powder has an average particle size of < 3mm, based on the total weight of the coke powder; and/or
Based on the total weight of the blended coal, more than 97wt% of the blended coal has an average particle size of less than 3 mm; and/or
The density of the briquette is 1200-1300kg/m3。
6. The method of claim 1, further comprising: and after the dry distillation is finished, introducing water into the coke oven to flush the formed coke until the formed coke is cooled to room temperature.
7. A formed coke produced by the production method according to any one of claims 1 to 6; the performance indexes of the formed coke are as follows: a. thed, type＜10wt%；1wt%≤Vdaf%＜1.5wt%；St, d, C＜0.8wt%；M40, carbon≥90wt%；CRICarbon (C)≤25 wt%；CSRModel (III)More than or equal to 60 wt%; the block degree of the formed coke with more than 70wt% is more than or equal to 90 mm.
8. Use of the formed coke of claim 7 in foundry coke and extended length coke.
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