阅读说明：本技术 一种吸附于焦炭表面的钾钠钙镁在高炉炼铁过程加速焦炭溶损反应的验证方法及其应用 (Verification method for accelerating coke dissolution loss reaction in blast furnace ironmaking process by using potassium, sodium, calcium and magnesium adsorbed on coke surface and application of me) 是由 樊尧桂 程祥 刘林刚 郑呈祥 刘涛 于 2019-11-05 设计创作，主要内容包括：本发明公开了一种吸附于焦炭表面的钾、钠、钙、镁在高炉炼铁过程加速焦炭溶损反应的验证方法,包括试样制备、焦炭原始球样反应性及反应后强度检测、检测焦炭的钾、钠、钙、镁含量及检测获取吸附有碱金属的焦炭球样的反应性及反应后强度等。本发明通过将传统的浸碱操作替换为喷洒有机金属粉末,精准控制焦炭的余温,利用余温充分熔融金属粉末,使其充分分散地附着于焦炭表面,避免了传统浸碱工艺中浸碱后水分难以彻底烘干等缺点,本发明检测数据精密度高、准确度好、操作简便、劳动强度低、可操作性强。(The invention discloses a method for verifying that potassium, sodium, calcium and magnesium adsorbed on the surface of coke accelerate coke dissolution loss reaction in a blast furnace ironmaking process, which comprises the steps of sample preparation, coke original ball sample reactivity and post-reaction strength detection, coke potassium, sodium, calcium and magnesium content detection, alkali metal adsorbed coke ball sample reactivity and post-reaction strength detection and the like. According to the invention, the traditional alkali leaching operation is replaced by spraying organic metal powder, the residual temperature of the coke is accurately controlled, the metal powder is fully melted by the residual temperature, and is fully and dispersedly attached to the surface of the coke, so that the defects that the moisture is difficult to completely dry after the alkali leaching in the traditional alkali leaching process and the like are avoided, and the method has the advantages of high precision of detection data, good accuracy, simplicity and convenience in operation, low labor intensity and strong operability.)

1. A method for verifying that potassium, sodium, calcium and magnesium adsorbed on the surface of coke accelerate the coke dissolution loss reaction in a blast furnace ironmaking process comprises the following steps:

(1) sample preparation: taking a coke sample, wherein one part of the coke sample is not treated, and the other part of the coke sample is used for uniformly adhering target metal elements of potassium, sodium, calcium and magnesium to the coke sample; the granularity of the two parts of samples is 40mm-60mm, the coke foam and the coke on the furnace head are abandoned, the coke is made into approximate spherical particles of 23mm-25mm, a plurality of ball samples are taken, one part is used as the original sample ball of the coke, and the other part is used as the coke ball sample absorbed with alkali metal;

(2) detecting the reactivity and the strength after reaction of the coke original ball sample: the coke original ball-like reactivity was recorded as CRI% ₁The strength after the coke original ball sample reaction is CSR% ₁；

(3) Taking out the coke ball sample adsorbed with the alkali metal, dividing the coke ball sample into two parts according to a certain proportion, wherein one part adopts an inductively coupled plasma atomic emission spectrometer to detect the potassium, sodium, calcium and magnesium contents of the coke, and the other part is used for obtaining the reactivity and the post-reaction strength of the coke ball sample adsorbed with the alkali metal through detection to obtain a detection result: coke ball-like reactivity CRI% with adsorbed alkali metal% ₂The post-reaction strength CSR% of the coke ball sample having the alkali metal adsorbed thereon ₂；

(4) Calculating the coke dissolution loss reaction degree by different potassium, sodium, calcium and magnesium ion contents:

after the reaction, the rate of change in thermal reactivity K1 was ((CRI% ₂-CRI％ ₁)÷CRI％ ₁)×100％

After the reaction, the change in strength K2 was ((CSR% ₂-CSR％ ₁)÷CSR％ ₁)×100％

Wherein: CRI% ₁Thermal reactivity of raw coke

CRI％ ₂Thermal reactivity of coke balls with adsorbed alkali metal

CSR％ ₁Strength of coke as received after thermal reaction

CSR％ ₂-the thermal post-reaction strength of the coke balls with adsorbed alkali metal.

2. The method for verifying the acceleration of coke dissolution loss reaction of potassium, sodium, calcium and magnesium adsorbed on the coke surface in the blast furnace ironmaking process according to claim 1, wherein the method comprises the following steps: the preparation method of the spherical particles comprises the following steps: 1) cutting a coke sample into cubes with the diameter of 23-25mm, and grinding the coke sample into spheroids with the diameter of 23-25mm by a grinding wheel tool; 2) soaking the sample in a volatile solution for 1h, and drying at 115 ℃; 3) the intact seamless samples were selected as test samples.

3. The method for verifying the acceleration of coke dissolution loss reaction of potassium, sodium, calcium and magnesium adsorbed on the coke surface in the blast furnace ironmaking process according to claim 1, wherein the method comprises the following steps: the method for uniformly adhering target metal elements such as potassium, sodium, calcium, magnesium and the like to a sample comprises: the coke output by the coke oven is conveyed to the blast furnace through the automatic conveying system, the coke is cooled through the temperature cooling device in the conveying process, when the temperature of the coke reaches the melting point of the target metal organic powder, a powder spraying system with a mesh screen structure is adopted to uniformly spray a certain amount of powdery organic compound containing the target metal to the coke, and the organic powder is melted and dispersed by utilizing the heat of the coke, so that the organic powder is fully attached to the surface of the coke.

4. The method for verifying the acceleration of coke dissolution loss reaction of potassium, sodium, calcium and magnesium adsorbed on the coke surface in the blast furnace ironmaking process according to claim 1, wherein the method comprises the following steps: the organic powder can be potassium citrate, sodium citrate, calcium citrate, and magnesium citrate.

5. The method for verifying the acceleration of coke dissolution loss reaction of potassium, sodium, calcium and magnesium adsorbed on the coke surface in the blast furnace ironmaking process according to claim 3, wherein the method comprises the following steps: the coke reactivity and strength after reaction were determined as follows:

A. drying the dried sample at the temperature of 180 ℃ for 2h, placing the dried sample into a dryer to cool to room temperature, and then screening the dried sample by using a sieve with phi 23mm and phi 23mm to remove coke powder adhered to a coke block;

B. weighing 200g +/-2 g, recording as m, and putting a sample into a reactor to be paved;

C. heating the electric furnace at a heating speed of 8-16 ℃/min; when the temperature of the material layer reaches 400 ℃, nitrogen is introduced at the flow rate of 0.8L/min; preheating the outlet of a carbon dioxide gas cylinder when the temperature of a material layer reaches 1050 ℃, stabilizing for 10 minutes when the temperature of the material layer reaches 1100 ℃, cutting off nitrogen, changing into carbon dioxide with the flow of 5L/min, returning the temperature of the material layer to 1100 +/-3 ℃ within 5-10 min after the material layer is changed into carbon dioxide, reacting for 2 hours, stopping heating, cutting off the carbon dioxide, and changing the flow of the nitrogen into 2L/min;

D. discharging the reactor, reducing the temperature to be below 100 ℃ under the protection of nitrogen, and stopping introducing the nitrogen;

E. the reactor was opened, the coke poured out, weighed and recorded as m 1;

F. all the reacted coke is loaded into an I-shaped rotary drum, co-rotating for 30min at the rotating speed of 20r/min, then taking out and sieving by using a phi 10mm circular hole sieve, and weighing the mass on the sieve, wherein the mass is recorded as m 2; G. and (3) calculating the result: reactivity is CRI ₂The strength after reaction is CSR% ₂。

6. An intelligent device for improving the reactivity of a coke blast furnace by controlling the addition of target alkaline earth metal of the coke comprises the coke furnace, the blast furnace, a transmission system, a powder spraying system, a spraying rate control system, a cooling system, a temperature control system, a weighing sensor and a computer system; wherein link coke oven export and blast furnace entry through transmission system, powder spraying system and cooling system have on transmission system, powder spraying system is connected with spraying rate control system, powder spraying system is used for spraying target organic metal powder to the coke on the transmission system, spraying rate control system control organic metal powder speed and the volume of spraying that sprays, cooling system is used for carrying out accurate cooling to the coke, weighing sensor links to each other with powder spraying system, temperature control system and weighing sensor all link to each other with the computer system, the computer is used for controlling the procedure of spraying according to the melting point of target organic powder, and the volume of spraying, the rate of spraying of automatic control powder based on this procedure.

7. The intelligent device for improving the reactivity of the coke blast furnace according to claim 6, wherein the spraying amount and the spraying rate are target alkaline earth metal addition amounts which are beneficial to improving the reactivity of the coke and are obtained by the verification method of the claims 1 to 5.

8. A control method of the intelligent device for improving the reactivity of the coke blast furnace as claimed in claim 6, wherein the coke output from the coke oven is transferred to the blast furnace through an automatic transfer system, the coke is cooled by a temperature cooling device during the transfer, when the temperature of the coke is slightly higher than the melting point of the target metal organic powder, a powder spraying system with a mesh screen structure is adopted to uniformly spray a certain amount of powdery organic compound containing the target metal to the coke, and the organic powder is melted and dispersed by using the heat of the coke, so that the organic powder is fully attached to the surface of the coke.

9. A control method of the intelligent device for improving reactivity of the coke blast furnace according to claim 8, wherein: the amount of the target metal-containing powdery organic compound is a target alkaline earth metal addition amount advantageous for improving coke reactivity obtained by the verification method described in claims 1 to 5 above. Various data acquired by the computer device can be transmitted to a mobile phone and an ipad mobile terminal through a wireless network, and the computer can be controlled through the mobile terminal.

10. A method for controlling an apparatus for improving reactivity of a coke blast furnace according to claim 8, wherein: the target alkaline earth metal can be potassium citrate, sodium citrate, calcium citrate and magnesium citrate powder.

Technical Field

The invention relates to the technical field of blast furnace ironmaking and smelting, and particularly relates to a method for verifying that potassium, sodium, calcium and magnesium adsorbed on the surface of coke accelerate coke dissolution loss reaction in a blast furnace ironmaking process.

Background

Most of domestic long-flow steel and iron combination enterprises are provided with coking plants, and in the coking plants, because desulfurization waste liquid, residual ammonia water in the coking process, denitration waste liquid, power generation boiler scaling washing water, biochemical dephenolization water and the like directly enter a coke quenching tank to participate in water coke quenching operation, k +, Na + and Ca in coke quenching water ²⁺、Mg ²⁺S, N, etc. are adsorbed on the surface of the coke.

The coke is used as a smelting fuel in a great amount in metallurgical enterprises, potassium, sodium, calcium and magnesium ions are adsorbed on the surface of the coke, and the potassium, sodium, calcium and magnesium ions adsorbed on the surface of the coke are vaporized after the upper part of the blast furnace is heated, so that the coke making process is changed under the catalytic action of carbon dissolution loss reaction of the coke, and the structure of the coke is changed to a certain extent. In the prior art, the research on the alkaline earth metal in the coke is usually to add a target metal element by using an alkali immersion test, and the method is easy to cause moisture residue in the coke, so that a test result has larger error.

Therefore, the evaluation of the coke performance through an accurate laboratory analysis method becomes more and more important, how to scientifically and effectively evaluate the influence of the contents of potassium, sodium, calcium and magnesium adsorbed on the coke surface on the production of the blast furnace and how to effectively improve the CO in the blast furnace ₂And coke reactivity, and the accurate and objective evaluation of coke quality becomes a new problem in the industry based on the technology.

Disclosure of Invention

The invention firstly provides a verification method for accelerating coke dissolution loss reaction of potassium, sodium, calcium and magnesium adsorbed on the surface of coke in a blast furnace ironmaking process, and by adopting the method, the catalytic action and the capability of the potassium, sodium, calcium and magnesium content adsorbed on the surface of the coke on the coke dissolution loss reaction in the blast furnace ironmaking process can be scientifically evaluated, so that necessary technical support is provided for blast furnace condition trend judgment and blast furnace stable and high yield. The invention also provides an intelligent device and a control method thereof for improving the reactivity of the coke blast furnace by controlling the addition of alkaline earth metal of the coke, and the intelligent control device and the intelligent control method can better control the reactivity and the post-reaction strength of the coke based on the effective data and conclusion obtained by the verification method.

A method for verifying that potassium, sodium, calcium and magnesium adsorbed on the surface of coke accelerate the coke dissolution loss reaction in a blast furnace ironmaking process comprises the following steps:

(1) sample preparation: taking a coke sample, wherein one part of the coke sample is not treated, and the other part of the coke sample is uniformly adhered with target metal elements such as potassium, sodium, calcium, magnesium and the like; the granularity of the two parts of samples is 40mm-60mm, the coke foam and the coke on the furnace head are abandoned, the coke is made into approximate spherical particles of 23mm-25mm, a plurality of ball samples are taken, one part is used as the original sample ball of the coke, and the other part is used as the coke ball sample absorbed with alkali metal;

(2) detecting the reactivity and the strength after reaction of the coke original ball sample: the coke original ball-like reactivity was recorded as CRI% ₁The strength after the coke original ball sample reaction is CSR% ₁；

(3) Taking out the coke ball sample adsorbed with the alkali metal, dividing the coke ball sample into two parts according to a certain proportion, wherein one part adopts an inductively coupled plasma atomic emission spectrometer to detect the potassium, sodium, calcium and magnesium contents of the coke, and the other part is used for obtaining the reactivity and the post-reaction strength of the coke ball sample adsorbed with the alkali metal through detection to obtain a detection result: coke ball-like reactivity CRI% with adsorbed alkali metal% ₂The post-reaction strength CSR% of the coke ball sample having the alkali metal adsorbed thereon ₂；

(4) Calculating the coke dissolution loss reaction degree by different potassium, sodium, calcium, magnesium and other ion contents:

after the reaction, the rate of change in thermal reactivity K1 was ((CRI% ₂-CRI％ ₁)÷CRI％ ₁)×100％

After the reaction, the change in strength K2 was ((CSR% ₂-CSR％ ₁)÷CSR％ ₁)×100％

Wherein: CRI% ₁Thermal reactivity of raw coke

CRI％ ₂Thermal reactivity of coke balls with adsorbed alkali metal

CSR％ ₁- - -atomSample coke strength after thermal reaction

CSR％ ₂-the thermal post-reaction strength of the coke balls with adsorbed alkali metal.

Preferably, the preparation method of the spherical particles comprises the following steps: 1) cutting a coke sample into cubes with the diameter of 23-25mm, and grinding the coke sample into spheroids with the diameter of 23-25mm by a grinding wheel tool; 2) soaking the sample in a volatile solution for 1h, and drying at 115 ℃; 3) the intact seamless samples were selected as test samples.

Preferably, the method of uniformly adhering the target metal elements such as potassium, sodium, calcium, and magnesium to the sample is: the coke output by the coke oven is conveyed to the blast furnace through the automatic conveying system, the coke is cooled through the temperature cooling device in the conveying process, when the temperature of the coke reaches the melting point of the target metal organic powder, a powder spraying system with a mesh screen structure is adopted to uniformly spray a certain amount of powdery organic compound containing the target metal to the coke, and the organic powder is melted and dispersed by utilizing the heat of the coke, so that the organic powder is fully attached to the surface of the coke.

Preferably, the organic powder may be potassium citrate, sodium citrate, calcium citrate and magnesium citrate.

Preferably, the coke reactivity and post-reaction strength are determined as follows:

A. drying the dried sample at the temperature of 180 ℃ for 2h, placing the dried sample into a dryer to cool to room temperature, and then screening the dried sample by using a sieve with phi 23mm and phi 23mm to remove coke powder adhered to a coke block;

B. weighing 200g +/-2 g, recording as m, and putting a sample into a reactor to be paved;

C. heating the electric furnace at a heating speed of 8-16 ℃/min; when the temperature of the material layer reaches 400 ℃, nitrogen is introduced at the flow rate of 0.8L/min; preheating the outlet of a carbon dioxide gas cylinder when the temperature of a material layer reaches 1050 ℃, stabilizing for 10 minutes when the temperature of the material layer reaches 1100 ℃, cutting off nitrogen, changing into carbon dioxide with the flow of 5L/min, returning the temperature of the material layer to 1100 +/-3 ℃ within 5-10 min after the material layer is changed into carbon dioxide, reacting for 2 hours, stopping heating, cutting off the carbon dioxide, and changing the flow of the nitrogen into 2L/min;

D. discharging the reactor, reducing the temperature to be below 100 ℃ under the protection of nitrogen, and stopping introducing the nitrogen;

E. the reactor was opened, the coke poured out, weighed and recorded as m 1;

F. all the reacted coke is loaded into an I-shaped rotary drum, co-rotating for 30min at the rotating speed of 20r/min, then taking out and sieving by using a phi 10mm circular hole sieve, and weighing the mass on the sieve, wherein the mass is recorded as m 2; G. and (3) calculating the result: reactivity is CRI ₂The strength after reaction is CSR% ₂。

An intelligent device for improving the reactivity of a coke blast furnace by controlling the addition of target alkaline earth metal of the coke comprises the coke furnace, the blast furnace, a transmission system, a powder spraying system, a spraying rate control system, a cooling system, a temperature control system, a weighing sensor and a computer system; wherein link coke oven export and blast furnace entry through transmission system, powder spraying system and cooling system have on transmission system, powder spraying system is connected with spraying rate control system, powder spraying system is used for spraying target organic metal powder to the coke on the transmission system, spraying rate control system control organic metal powder speed and the volume of spraying that sprays, cooling system is used for carrying out accurate cooling to the coke, weighing sensor links to each other with powder spraying system, temperature control system and weighing sensor all link to each other with the computer system, the computer is used for controlling the procedure of spraying according to the melting point of target organic powder, and the volume of spraying, the rate of spraying of automatic control powder based on this procedure.

Preferably, the spraying amount and the spraying rate are the target alkaline earth metal addition amount which is obtained by the verification method of the above claims 1 to 5 and is beneficial to improve the reactivity of the coke.

The control method of the intelligent device for improving the reactivity of the coke blast furnace comprises the steps of conveying coke output by the coke furnace to the blast furnace through the automatic conveying system, cooling the coke through the temperature cooling device in the conveying process, uniformly spraying a certain amount of powdery organic compound containing target metal to the coke by adopting the powder spraying system with the mesh screen structure when the temperature of the coke is slightly higher than the melting point of the target metal organic powder, and melting and dispersing the organic powder by utilizing the heat of the coke so as to enable the organic powder to be fully attached to the surface of the coke.

Preferably, the amount of the target metal-containing powdery organic compound is the target alkaline earth metal addition amount advantageous for improving the reactivity of coke, which is obtained by the above-described validation method.

Preferably, the target alkaline earth metal may be potassium citrate, sodium citrate, calcium citrate and magnesium citrate powder.

Preferably, various data acquired by the computer device can be transmitted to mobile terminals such as mobile phones and ipads through a wireless network, and the computer can be controlled through the mobile terminals.

Advantageous effects

1. The method simulates the adsorption process of potassium, sodium, calcium and magnesium ions in the quenching water on the surface of coke in the water quenching process flow; 2. according to the invention, the traditional alkali leaching operation is replaced by spraying organic metal powder, the residual temperature of the coke is accurately controlled, and the metal powder is fully melted by the residual temperature to be fully and dispersedly attached to the surface of the coke, so that the defects that the moisture is difficult to completely dry after the alkali leaching in the traditional alkali leaching process and the like are avoided; 3. the invention starts from a blast furnace ironmaking and smelting process, detects the thermal state performance index of the coke by an improved method, and simulates the process that potassium, sodium, calcium and magnesium adsorbed on the surface of the coke accelerate the coke dissolution loss reaction in the blast furnace ironmaking and smelting process; the improved method for measuring the thermal state performance of the coke can better simulate the complex reaction condition in the heating environment of the coke blast furnace; 4. The traditional process in the field is time-consuming and labor-consuming, intelligent control cannot be realized on reactivity and the like, and the intelligent device for improving the reactivity of the coke blast furnace by controlling the addition amount of alkaline earth metal of the coke and the control method thereof are initiated by the applicant, so that the reactivity of the coke is greatly improved; 5. the verification method disclosed by the invention has the advantages of simple steps, short time consumption, conformity of the verification process with the blast furnace ironmaking smelting process principle and the like; 6. the method has the advantages of high precision of detection data, good accuracy, simple and convenient operation, low labor intensity and strong operability; 7. the method also has the characteristics of quick measurement, high efficiency, intelligence, high flux, environmental protection, wide popularization in the industry and the like.

Description of the drawings:

FIG. 1: a schematic diagram of an intelligent device for improving the reactivity of a coke blast furnace by controlling the addition amount of alkaline earth metal of the coke.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION