CN113881450A

CN113881450A - Coking additive solution and application thereof

Info

Publication number: CN113881450A
Application number: CN202111193996.9A
Authority: CN
Inventors: 刘其鹏; 杨桂芝; 卢伟
Original assignee: Shandong Polytechnic College
Current assignee: Shandong Polytechnic College
Priority date: 2021-10-13
Filing date: 2021-10-13
Publication date: 2022-01-04

Abstract

The invention relates to the technical field of coking, in particular to a coking additive solution and application thereof. A coking additive solution comprises the following components in percentage by mass: 0-40% of ammonium borate, 3-80% of silica sol, 0-30% of titanium sol, 0-3% of water glass, 0-0.5% of pH regulator, 0-2% of water reducing agent and the balance of water. The coking additive solution can be diluted and used for soaking coke; or mixing with coke quenching water; or mixing with coal and then carrying out coal blending and coking operation. The coking additive solution can reduce the coal blending cost and improve the coke quality, and has the advantages of small addition proportion, simple process, good fluidity and more uniformity during coal blending and coking.

Description

Coking additive solution and application thereof

Technical Field

The invention relates to the technical field of coking, in particular to a coking additive solution and application thereof.

Background

With the development of blast furnace technology, the requirement on coke quality is gradually increased, and the coking coal resources have less and less strong caking coal, which is particularly prominent in China. The increasing scarcity of high quality coking coal resources has become an important factor affecting coke production, quality and cost. In consideration of economic benefits and practical situations, various coking plants at home and abroad are dedicated to the research of coal blending schemes. In recent years, in order to expand coking coal resources, reduce coking cost and improve coke quality, a plurality of new coking technologies such as coal preheating, tamping, formed coke, briquette coal preparation, additive addition and the like are developed. The additive can improve the coking performance of raw coal, improve the coke quality, enlarge the coking coal types and reduce the coking cost, and is an effective means for solving the problem of insufficient resources of high-quality coking coal in China. The additive is widely applied because the process change is small, the operation is simple and flexible, the cost is low, and the coke quality is improved and stable.

Additives for coking can be divided into active additives and inert additives. From the viewpoint of coal petrology, coal can be divided into two parts of active components and inert components, and coke strength is best when the content of the active components and the inert components in the coal reaches the optimal ratio. The additives commonly used in the coal blending coking process mainly comprise a binder, a thinning agent and a passivating agent, the binder belongs to an active additive, and the commonly used binder is mainly divided into a petroleum binder and a coal binder. The petroleum binder includes petroleum asphalt, residue after crude oil distillation, vacuum residue oil, etc. The coal-based binder includes coal pitch, coal tar, tar residue, and the like (2011, 6,100 to 101). The thinning and passivating agents are inert additives. The commonly used thinning agents include anthracite powder, semi-coke powder, petroleum delayed coke, petroleum coke and the like. The petroleum series DK type additive is widely applied to coal blending coking production in Russian (fuel and chemical industry, 2018,47(1), 27-29). SiO for Zhanglin₂The 5 per mill aqueous solution of the mass passivating agent is directly sprayed to quench the coke, so that the CSR (strength after reaction) is better improved (fuel and chemical industry, 2010,41(4), 15-17). Passivating agent mainly containing boric acid is used in Kunzi steel, Ji steel and other units, and patent CN109022098A discloses a coke passivating agent and a preparation method thereof. The coke passivator comprises the following components in parts by weight: 30-40 parts of a boron-containing compound, 10-15 parts of silicon dioxide, 5-10 parts of titanium dioxide, 3-5 parts of barium carbonate, 1-3 parts of aluminum fluoride and 0.5-1 part of yttrium chloride, wherein the boron-containing compound comprises boric acid, borax and boron oxide, and the boric acid comprises the following components in parts by weight: borax: the boron oxide is 1: 1-3, and the technical effects are as follows: the coke passivator can obviously reduce the reactivity of the coke and improve the strength after reaction. Patent CN102703100B discloses a coal blending additive for improving the thermal property of coke and an application method thereof, wherein the coal blending additive is TiB₂And (3) micro powder. The binder and the thinning agent have the problems of large addition amount and high price in the coking process. The inert additive becomes a new development direction, but the inert additive exists in a solid state and is preparedThe fluidity is poor during coal coking, and the distribution is not uniform during coal blending and coking.

Disclosure of Invention

Aiming at the problems of poor fluidity, uneven distribution during coal blending and coking and the like of a coke additive in the prior art, the invention provides a coking additive solution and application thereof to solve the problems. The invention provides a coking additive solution with water solubility as the main characteristic, which can reduce the coal blending cost and improve the quality of coke in use, and has the advantages of small addition proportion, simple process and more uniformity.

The technical scheme of the invention is as follows:

a coking additive solution comprises the following components in percentage by mass: 0-40% of ammonium borate, 3-80% of silica sol, 0-30% of titanium sol, 0-3% of water glass, 0-0.5% of pH regulator, 0-2% of water reducing agent and the balance of water. The silica sol and the titanium sol used in the invention are counter-gasification agents which play two roles in the coking process. First, secondary catalysis (reverse gasification); secondly, the part is bonded at high temperature in the heating process, the colloidal particles are firmly attached to the surface of an object, and the particles are mutually combined, so that the adhesive is a good adhesive, and can improve the performances of the coke, such as granularity, cohesiveness and mechanical strength, reduce reactivity, improve strength after reaction and the like.

Preferably, the coking additive solution consists of the following components in percentage by mass: 5% of ammonium borate, 50% of silica sol, 5% of titanium sol, 0% of water glass, 0.5% of pH regulator, 0.5% of water reducing agent and 34% of water.

Preferably, the silica sol further comprises boron-modified silica sol and aluminum-modified silica sol.

Preferably, the silica sol is one or more of acidic silica sol, neutral silica sol and alkaline silica sol.

Preferably, the ammonium borate is ammonium borate trihydrate or ammonium pentaborate tetrahydrate.

Preferably, the water glass is sodium metasilicate with a modulus of greater than 2.5.

Preferably, the pH regulator is one or more of sodium hydroxide solution, potassium hydroxide or ammonia water solution, dilute hydrochloric acid and dilute sulfuric acid. The pH regulator regulates the pH of the coking additive solution to 7-8.5.

Preferably, the water reducing agent is selected from one or two of aliphatic hydroxyl sulfonate polymer, methylene dimethyl dinaphthyl sodium sulfonate or polycarboxylic acid high-performance water reducing agent. The water reducing agent can improve the fluidity of the coking additive solution and reduce the viscosity of the coking additive solution.

Preferably, the titanium sol has a solid content of more than 10 wt%.

Preferably, the solid content of the silica sol is 15-40 wt%.

According to the preparation method of the coking additive solution, the components are mixed and stirred uniformly to obtain the coking additive solution.

The additive solution prepared by the invention can be applied in the following way:

(1) soaking the coke obtained by coking in diluted coking additive solution;

(2) mixing the coke with coke quenching water for coke quenching;

(3) mixing the coking additive solution with coal, and then coking;

the effective solid content in the coking additive solution accounts for 0.5-15 per mill of the coke consumption; the effective solid content in the coking additive solution accounts for 0.5-15 per mill of the coal consumption.

The invention has the beneficial effects that:

the invention provides a coking additive solution with water solubility as the main characteristic, which can reduce the coal blending cost and improve the coke quality, and has the advantages of small addition proportion, simple process, good fluidity and more uniformity during coal blending and coking.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.

Example 1

A coking additive solution comprises the following components in percentage by mass: 5kg of ammonium borate, 50kg of silica sol (with the solid content of 30%), 5kg of titanium sol (with the solid content of 10%), 0kg of water glass, 0.01kg of pH regulator (dilute hydrochloric acid with the concentration of 1%), 0.5kg of water reducing agent (sodium methylene dimethyl dinaphthalene sulfonate) and 34kg of water.

And mixing the components and uniformly stirring to obtain the coking additive solution.

Example 2

A coking additive solution comprises the following components in percentage by mass: 1kg of ammonium borate, 60kg of silica sol (solid content: 40%), 10kg of titanium sol (solid content: 10%), 1kg of water glass, 0kg of pH regulator (dilute hydrochloric acid with concentration: 1%), 1kg of water reducing agent (aliphatic hydroxy sulfonate ASH) and 23kg of water.

Example 3

A coking additive solution comprises the following components in percentage by mass: 4kg of ammonium borate, 40kg of silica sol (with the solid content of 30%), 10kg of titanium sol, 1kg of water glass, 0.01kg of pH regulator (diluted hydrochloric acid with the concentration of 1%), 1kg of water reducing agent (aliphatic hydroxy sulfonate ASH) and 45kg of water.

Test example 1

Mixing the fertilizer gas coal: coal fertilizing: one third coking coal: coking coal: the lean coal is as follows: 3: 3: 3: 4, mixing, pre-crushing, blending coal and tamping to obtain blended coal, then loading the blended coal into a carbonization chamber, coking the blended coal for 24 hours at 1250 ℃, and detecting the performance indexes of the blended coal as follows:

TABLE 1 test results 1

Ash content	Volatile component	Sulfur content	Reactivity	Strength after reaction
					12.08％	1.25％	0.74％	26.8％	61.3％

Test example 2

4 parts of the coking additive solution prepared in example 1 was mixed with 96 parts of water to prepare a coking additive solution I. The coke prepared in test example 1 was then soaked in coking additive liquor i for 12 hours and 24 hours. The coke was then tested for performance criteria as in table 2 below:

TABLE 2 test results 2

	Ash content	Volatile component	Sulfur content	Reactivity	Strength after reaction
						Soaking for 12h	12.29％	1.13％	0.72％	26.7％	63.3％
Soaking for 24h	12.22％	1.20％	0.72％	26.4％	64.8％

As can be seen from the comparison of the results in Table 2 with those in Table 1, the strength after the reaction is significantly increased and the other properties are not greatly changed after the coking coal is soaked in the coking additive solution.

Test example 3

The coking additive solution I prepared in test example 2 was added to quenching water in a mass ratio of 1:50, and then the coke in test example 1 was subjected to wet quenching. The coke was then tested for performance criteria as in table 3 below:

TABLE 3 test results 3

Ash content	Volatile component	Sulfur content	Reactivity	Strength after reaction
					12.20％	1.22％	0.72％	26.4％	65.2％

As can be seen from the comparison of the results in Table 3 with those in Table 1, when the additive liquid for coking was used as the quenching water, the strength of the resultant coke after the reaction was remarkably increased and the other properties were not largely changed.

Test example 4

The coking additive solution I prepared in the test example 2 is mixed with the blended coal of the test example 1 according to the mass ratio of 2:100, and the mixture is subjected to coking treatment. The coke was then tested for performance criteria as follows in table 4:

TABLE 4 test results 4

Ash content	Volatile component	Sulfur content	Reactivity	Strength after reaction
					12.32％	1.15％	0.72％	25.8％	65.2％

As can be seen from the comparison of the results in Table 4 with Table 1, when the coal as the coking additive solution is mixed first and then subjected to the coking treatment, the strength of the resultant coke after the reaction is remarkably increased and other properties are not largely changed.

In conclusion, after the coking additive solution prepared by the invention is mixed and treated with coal or coking coal in various forms, the strength of the obtained coke is obviously improved after reaction on the premise of not influencing the overall performance of the coke.

Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. The coking additive solution is characterized by comprising the following components in percentage by mass: 0-40% of ammonium borate, 3-80% of silica sol, 0-30% of titanium sol, 0-3% of water glass, 0-0.5% of pH regulator, 0-2% of water reducing agent and the balance of water.

2. The coking additive solution according to claim 1, wherein the silica sol is one or more of acidic silica sol, neutral silica sol and alkaline silica sol, and the solid content of the silica sol is 15-40 wt%.

3. The coking additive solution according to claim 1, wherein the silica sol is a boron-modified silica sol or an aluminum-modified silica sol, and the boron-modified silica sol or the aluminum-modified silica sol has a solid content of more than 15 wt%.

4. The coking additive solution according to claim 1 wherein the ammonium borate is ammonium borate trihydrate or ammonium pentaborate tetrahydrate.

5. The coking additive solution of claim 1 wherein the titanium sol has a solids content of greater than 10 wt%.

6. The coking additive solution according to claim 1 wherein the water glass is sodium metasilicate having a modulus greater than 2.5.

7. The coking additive solution according to claim 1, wherein the pH of the coking additive solution is 7 to 8.5.

8. The coking additive solution according to claim 1, wherein the water reducing agent is one or two selected from the group consisting of an aliphatic hydroxysulfonate polymer, sodium methylenedimethyldinaphthalene sulfonate, and a polycarboxylic acid-based high performance water reducing agent.

9. Use of the additive coking solution of claim 1 diluted for soaking coke; or mixing with coke quenching water; or mixing with coal and then carrying out coal blending and coking operation.

10. The use of claim 9, wherein the effective solid content of the coking additive solution is 0.5-15% of the coke dosage.