阅读说明：本技术 一种炼焦配合煤胶质添加剂的合成及使用方法 (Synthesis and use method of coke making blended coal colloid additive ) 是由 曹银平 *** 程乐意 张福行 余国普 姚国友 于 2018-06-26 设计创作，主要内容包括：本发明涉及一种炼焦配合煤胶质添加剂的合成及使用方法。所述炼焦配合煤胶质添加剂的制备方法,其包含分批次加入尿素和甲醛,通过不断调整温度、甲醛/尿素摩尔比、pH值来获得性能优异的炼焦配合煤胶质添加剂,其可以作为炼焦配合煤胶质粘结剂,在炼焦生产过程中配入焦炉装入煤中可以提高炼焦配合煤粘结性,在不改变配合煤结构的情况下可以提高焦炭冷热强度；或保持焦炭冷热强度不变情况下,降低高价优质炼焦煤的使用比例,降低配合煤成本。(The invention relates to a synthesis and use method of a coking blending coal colloid additive. The preparation method of the coking blending coal colloid additive comprises the steps of adding urea and formaldehyde in batches, and obtaining the coking blending coal colloid additive with excellent performance by continuously adjusting the temperature, the formaldehyde/urea molar ratio and the pH value, wherein the coking blending coal colloid additive can be used as a coking blending coal colloid binder, can improve the caking property of the coking blending coal when being blended into a coke oven to be charged in the coking production process, and can improve the cold and hot strength of the coke under the condition of not changing the structure of the blending coal; or the use proportion of high-price high-quality coking coal is reduced and the cost of blending coal is reduced under the condition of keeping the cold and hot strength of the coke unchanged.)

1. A preparation method of a coking blending coal colloid additive is characterized by comprising the following steps: comprises the following steps:

(1) adding 75-95% of the total amount of formaldehyde into a reactor, stirring, adjusting the pH value to 7.5-8.0, heating to 60-65 ℃, adding a first batch of urea, naturally heating, reacting for 30min, heating to 95-98 ℃, preserving heat for 20min, naturally cooling to 90 ℃, adjusting the pH value to 5.0-5.6 by using ammonium chloride or formic acid, and polymerizing at the temperature of 85-90 ℃ until a glue solution is dropped into water at 40 ℃ to form small comet-shaped colloidal particles;

(2) adjusting the pH value to 7.5-7.8, adding a second batch of urea, stirring for 20min at 65-75 ℃, then acidifying to pH 5.5-6.4 by ammonium chloride or formic acid, and stirring for 30min at 65-75 ℃;

(3) adjusting the pH value to 7.5-7.8, adding the remaining 5% -25% of formaldehyde, and stirring at 65-75 ℃ for 30 min;

(4) adding the third batch of urea, stirring for 20min, adjusting the pH value to 6.4-6.6 by using ammonium chloride or formic acid, and stirring for 30 min;

(5) adjusting the pH value to 7.5-7.8, adding the fourth batch of urea, stirring until the urea is dissolved, adjusting the pH value to 8.0-8.5, cooling to room temperature, and discharging.

2. The method of claim 1, wherein the method comprises the steps of: in steps (1), (2), (3) and (5), the reagent used to adjust the pH to the alkaline range is pure ethylenediamine.

3. The method of claim 1, wherein the method comprises the steps of: in the step (1), adding the first batch of urea to enable the molar ratio of formaldehyde to urea to reach 2.5: 1-2: 1; in the step (2), after adding the second batch of urea, enabling the molar ratio of formaldehyde to urea to reach 2: 1-1.5: 1; in the step (4), after the third batch of urea is added, the molar ratio of formaldehyde to urea is 1.8: 1-1.4: 1; in the step (5), after the fourth batch of urea is added, the molar ratio of formaldehyde to urea is 1.5: 1-1: 1.

4. The method of claim 1, wherein the method comprises the steps of: in the step (1), adding the first batch of urea to enable the molar ratio of formaldehyde to urea to reach 2.5: 1-2: 1; in the step (2), after adding the second batch of urea, enabling the molar ratio of formaldehyde to urea to reach 1.95: 1-1.8: 1; in the step (4), after the third batch of urea is added, the molar ratio of formaldehyde to urea is 1.75: 1-1.5: 1; in the step (5), after the fourth batch of urea is added, the molar ratio of formaldehyde to urea is 1.45: 1-1: 1.

5. The coke making blending coal colloid additive is characterized in that: the coking blending coal gum additive of any one of claims 1 to 4.

6. Use of the coking blending coal gum additive of claim 5 as a coking blending coal gum binder.

7. The use of claim 6, wherein the use of the coking blending coal gum additive as a coking blending coal gum binder comprises the steps of: adding water into the coking blending coal colloid additive to prepare a 20-40% aqueous solution, adding a curing agent, mixing, fully stirring, adjusting the pH value to 4.0-5.0 to obtain a coking blending coal colloid binder, and spraying the coking blending coal colloid binder onto a blending coal belt.

8. Use according to claim 7, characterized in that: the curing agent is one or more of ammonium chloride, hydrochloric acid, formic acid, sulfuric acid, nitric acid and the like.

9. The use of claim 6, wherein the use of the coking blending coal gum additive as a coking blending coal gum binder comprises the steps of:

(1) adding water into the coking blending coal colloid additive to prepare a 20-40% aqueous solution;

(2) adding ammonium chloride in 0.4-0.8 wt% of the coking coal colloid additive, mixing and stirring;

(3) adding 5-15% hydrochloric acid water solution, adjusting pH to 4.0-5.0 to obtain coking blending coal colloid binder, and spraying onto blending coal belt.

Technical Field

The invention belongs to the technical field of coking blending coal, and particularly relates to a coking blending coal colloid additive, and a preparation method and application thereof.

Background

Stabilizing and improving coke quality has become one of the major issues facing the metallurgical coking industry. However, the resource amount of high-quality coking coal is seriously short in the world, so that the price of the coal resource is high, the coking cost is increased, and coking enterprises of a plurality of steel companies begin to search for a new coking technology for developing low-price non-coking coal blending coal to improve the performance index of metallurgical coke, wherein the technology for expanding the coking additive of the blending coal under the existing condition of the coke oven is a good method which can save investment, reduce the reactivity of the coke and improve the thermal state performance of the coke.

In the production of coking blended coal, the additive is adopted in a broad sense, and not only is an oily substance added for improving the caking property of the blended coal taken as the additive, but also the long flame coal is added to reduce and control the cost of coke ash sulfur and blended coal, and the lean coal or anthracite is added to improve the coke lumpiness and the cost of the blended coal, and the additive belongs to the category of the additive. In a narrow sense, only an oily substance such as maltene is added to blended coal to improve the caking property of the blended coal, and the blended coal is used as a blended coal additive. From 85 years, the Bao steel adopts a coal forming process, namely, the soft asphalt is mixed into the pulverized coal and the mixture is formed into coal balls, the coal balls are added into a coke oven, a certain effect is achieved on improving the quality of the coke, but the raw material cost and the energy consumption cost are increased, and the mixing amount of the Bao steel is 0.9-1.2%; oil substances are directly sprayed into the blended coal, and research has been conducted at home and abroad, but the coking process of the blended coal blended with oil causes a large amount of carbon black to be accumulated in a coking chamber of a coke oven, so that the environment of the coke oven is deteriorated, and the method is not popularized. The coking industry at home and abroad has no precedent for adding a colloidal organic binder into blended coal for coking production, and the colloidal binder synthesized by the technical method related to the patent of the invention can be used for the production of coking blended coal.

The invention relates to a product, namely a coking blended coal colloid additive, and relates to a synthetic method of the coking blended coal colloid additive, wherein the general method takes formaldehyde and urea as main raw materials, takes sodium hydroxide and ammonium chloride as pH value regulators, and belongs to the public synthetic technology.

In 1987, Ennigma, Lessokula island, Netheria, reported in China patent "preparation of Urea-Formaldehyde resin with very low molar ratio of Formaldehyde to Urea" (CN200410041265.2), in which urea was added in three portions, the initial urea and formaldehyde were mixed in a molar ratio of about 1: 2. the mixing was allowed to take place for 30 minutes at a pH of 7.0 to 7.4 and a temperature between 80 and 85 ℃; continuing the condensation at a pH of 4.8 to 5.8 and at the same temperature until a viscosity of between 15 and 50mpa.s is reached; adding urea to adjust the molar ratio of urea to formaldehyde to 1: 1.80-1: 1.90, and condensing under acidic condition at the same temperature until the viscosity reaches 35-80 mpa.s; the pH of the reaction mixture is adjusted between 1.0:1.0 and 1.0:1.30 by adding urea at pH5.8 to 6.5, the temperature is allowed to drop freely, the pH is adjusted between 7.0 and 8.0 when the temperature has dropped below 50 ℃, the batch to which the urea is added and the molar ratio of formaldehyde after each batch addition are emphasized, and the method of pH adjustment in the reaction conditions is not critical.

In 6 months 2004, Changzhou paint chemical research institute of China general chemical construction, filed patent "preparation method of water-soluble urea-formaldehyde resin" (CN200410041265.2), formaldehyde and urea are used as raw materials for reaction, the molar ratio of formaldehyde to urea is 1.75-1.95: 1 during the reaction, ammonia or amine which accounts for 5-12% of the weight of urea is used for modification, and low-carbon chain alcohol which accounts for 10-50% of the weight of urea and has the carbon content of less than or equal to 3 is used for etherification; in the production process, the pH value of the methylolation of formaldehyde and urea is 9-10, the pH value of etherification and condensation is 4-5, and the pH value is adjusted to 7-8 after the reaction is finished. The urea-formaldehyde resin obtained is intended to improve its water solubility and water dilution stability and has a short gelling time.

The existing urea-formaldehyde resin synthesis method is used as a coking blending coal additive, the key process parameters and the building decoration requirements are concerned to have larger difference, the urea-formaldehyde resin in the traditional synthesis method contains sodium ions, and the sodium ions can deteriorate the thermal state performance of coke and increase the ash content of the coke in the coking blending coal production.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to solve the technical problem of providing a metal compound-free coking blending coal colloid additive which can be used as a coking blending coal colloid binder, can be added into the charging coal of a coke oven in the coking production process to improve the caking property of the coking blending coal, and can improve the cold and hot strength of the coke under the condition of not changing the structure of the blending coal; or the use proportion of high-price high-quality coking coal is reduced and the cost of blending coal is reduced under the condition of keeping the cold and hot strength of the coke unchanged.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a coking blending coal colloid additive comprises the following steps:

(1) adding 75-95% of the total amount of formaldehyde into a reactor, stirring, adjusting the pH value to 7.5-8.0, heating to 60-65 ℃, adding a first batch of urea, naturally heating, reacting for 30min, heating to 95-98 ℃, preserving heat for 20min, naturally cooling to 90 ℃, adjusting the pH value to 5.0-5.6 by using ammonium chloride or formic acid, and polymerizing at the temperature of 85-90 ℃ until a glue solution is dropped into water at 40 ℃ to form small comet-shaped colloidal particles;

(2) adjusting the pH value to 7.5-7.8, adding a second batch of urea, stirring for 20min at 65-75 ℃, then acidifying to pH 5.5-6.4 by ammonium chloride or formic acid, and stirring for 30min at 65-75 ℃;

(3) adjusting the pH value to 7.5-7.8, adding the remaining 5% -25% of formaldehyde, and stirring at 65-75 ℃ for 30 min;

(4) adding the third batch of urea, stirring for 20min, adjusting the pH value to 6.4-6.6 by using ammonium chloride or formic acid, and stirring for 30 min;

(5) adjusting the pH value to 7.5-7.8, adding the fourth batch of urea, stirring until the urea is dissolved, adjusting the pH value to 8.0-8.5, cooling to room temperature, and discharging.

Preferably, the first and second liquid crystal materials are,

in steps (1), (2), (3) and (5), the reagent used to adjust the pH to the alkaline range is pure ethylenediamine.

In the step (1), after the first batch of urea is added, the molar ratio of formaldehyde to urea is 2.5: 1-2: 1.

In the step (2), after the second batch of urea is added, the molar ratio of formaldehyde to urea is 2: 1-1.5: 1.

In the step (4), after the third batch of urea is added, the molar ratio of formaldehyde to urea is 1.8: 1-1.4: 1.

In the step (5), after the fourth batch of urea is added, the molar ratio of formaldehyde to urea is 1.5: 1-1: 1.

The "formaldehyde/urea molar ratio" referred to in the present invention means a ratio of the total molar amount of formaldehyde already added and urea already added.

It is further preferred that the first and second liquid crystal compositions,

in the step (1), after the first batch of urea is added, the molar ratio of formaldehyde to urea is 2.5: 1-2: 1.

In the step (2), after the second batch of urea is added, the molar ratio of formaldehyde to urea is 1.95: 1-1.8: 1.

In the step (4), after the third batch of urea is added, the molar ratio of formaldehyde to urea is 1.75: 1-1.5: 1.

In the step (5), after the fourth batch of urea is added, the molar ratio of formaldehyde to urea is 1.45: 1-1: 1.

The concentration range of formaldehyde in the invention is 30-50%.

The reactor may be a reaction vessel with stirrer function.

The invention also provides a coking blending coal colloid additive which is prepared by the preparation method.

The finished coking blending coal colloid additive is stored in a plastic bottle to avoid contacting with iron and is stored in a shade place.

The invention also provides an application of the coking blending coal colloid additive as a coking blending coal colloid binder, which comprises the following steps: adding water into the coking blending coal colloid additive to prepare a 20-40% aqueous solution, adding a curing agent, mixing, fully stirring, adjusting the pH value to 4.0-5.0 to obtain a coking blending coal colloid binder, and spraying the coking blending coal colloid binder onto a blending coal belt.

The curing agent is preferably one or more of ammonium chloride, hydrochloric acid, formic acid, sulfuric acid, nitric acid, and the like, and is preferably a mixture of ammonium chloride and hydrochloric acid.

Specifically, the application of the coking blending coal colloid additive as a coking blending coal colloid binder can comprise the following steps:

(1) adding water into the coking blending coal colloid additive to prepare a 20-40% aqueous solution;

(2) adding ammonium chloride or formic acid in 0.4-0.8 wt% of the coking coal colloid additive, mixing and stirring;

(3) adding 5-15% strong acid water solution, adjusting pH to 4.0-5.0 to obtain coking blending coal colloid binder, and spraying onto blending coal belt.

The water-soluble coking blending coal colloidal binder is directly added into blending coal, and is easily and uniformly mixed with coal materials, so that the purpose of blending coal for coking is achieved. The pH value of the water-soluble coking coal blending colloid binder required in the actual coal blending operation is about 4.5, and if the pH value is reduced, the curing time and the working life of the binder are obviously shortened, so that the mixing of the blended coal is not facilitated.

It is further preferred that the first and second liquid crystal compositions,

the application of the coking blending coal colloid additive as a coking blending coal colloid binder can comprise the following steps:

(1) adding water into the coking blending coal colloid additive to prepare a 20-40% aqueous solution;

(2) adding ammonium chloride in 0.4-0.8 wt% of the coking coal colloid additive, mixing and stirring;

(3) adding 5-15% hydrochloric acid water solution, adjusting pH to 4.0-5.0 to obtain coking blending coal colloid binder, and spraying onto blending coal belt.

And (3) the coking blending coal colloid binder in the step (3) is water-soluble, the coking blending coal colloid binder generally enters a box-type hopper, a nozzle is arranged below the hopper, the nozzle directly sprays and drips onto a coal bed on a coal blending belt, and the water-soluble resin adhesive dripped on the surface coal dust falls through the overturning of a plurality of belts, so that the water-soluble coking blending coal colloid binder can be uniformly dispersed on the surface and in pores of the blending coal material until reaching a coal charging system.

The schematic diagram of the system for blending coal and blending coal by coking and blending coal colloid additive as the coking and blending coal colloid binder is shown in fig. 1 and fig. 2.

One specific operation may be: adding materials such as ammonium chloride, hydrochloric acid and 20-40% coking blending coal colloid additive aqueous solution 30-60 minutes before a blending coal belt system starts to convey and operate; an electric valve 5 below an industrial water tank and a coking blending coal colloid additive storage tank is opened through manual operation, the flow is detected through a flow meter 7, the flow is controlled through a flow control valve 6 according to the set flow, the coking blending coal colloid additive and the industrial water are simultaneously added into a mixing device 1, and the flow ratio of the coking blending coal colloid additive to the industrial water is the additive flow: the industrial water flow is 1:0.4-1:1.6, stirring is carried out while adding, and stirring is carried out for about 10 minutes after adding according to the set amount; then, the lower electric valve 5 of the ammonium chloride tank was opened, the flow rate was detected by the flow meter 7, and the flow rate was controlled by the flow rate control valve 6 according to the set flow rate, as shown in fig. 2.

After the ammonium chloride is added into the mixing device 1 and is fully stirred in the tank for 5-10 minutes, an electric valve below the hydrochloric acid tank is opened, the hydrochloric acid solution is added into the stirring glue-adjusting tank according to the set flow to adjust the pH value, and when the pH value of the mixed solution is detected to reach 4.0-5.0 by a pH detector 9, the electric valve 5 below the hydrochloric acid tank is closed to stop adding the hydrochloric acid.

The adding device 2 and the binder spraying device 3 realize the uniform spraying of the binder on the blended coal through compressed air.

A pressure sensor 8 can be arranged under the coal blending conveying belt 10 corresponding to the adding device 2 and the binder spraying device 3 and used for sensing the conveying process of the coal materials on the belt. When pressure sensor 8 senses that there is material on the blending coal conveyer belt, the motorised valve that sets up under binder storage tank 4 is just in the open mode, and the binder in the inslot just flows into and adds device 2, sprays to the coal charge surface through binder sprinkler 3 under the compressed air effect.

If the system is stopped for a long time or the period of no blending coking coal colloid binder is too long, the residual binder in the pipeline for conveying the coking coal colloid binder is solidified, and only a method of alkaline washing by 10-20% NaOH is needed to remove the pipeline scale.

The sodium-free coking blending coal colloid additive can be stored for more than three months without solidification.

The coking blending coal colloid additive is used as a blending coal colloid binder suitable for coking production, and the coking blending coal colloid additive has low residual formaldehyde content and does not contain metal compounds; the obtained process flow, process control and maintenance method can stably use the blended coal binder for the production of coking blended coal. The use of the invention can improve the caking property of the coking blending coal, and under the condition that the blending proportion of the non-coking coal is increased by 3 percent, the blending proportion of the product of the invention is 3 per mill (0.3 percent), which can ensure that the caking property of the blending coal is not reduced; under the same coal blending structure, 3 per mill of the product of the invention is blended, and the cold strength of the coke can be improved by 1 percent.

The synthetic blended coal colloidal binder suitable for the production of the coking blended coal has no precedent for use at home and abroad, and the cross-field use of the blended coal colloidal binder has no related research at home and abroad at present, even no attention is drawn, so the related technology of the patent has a wide use prospect.

Drawings

FIG. 1 is a schematic view of a process flow of adding a coking blending coal gum additive as a coking blending coal gum binder.

FIG. 2 is a schematic diagram of a system for blending coal with coking blending coal colloid additive as a coking blending coal colloid binder.

Description of reference numerals: 1. a mixing device; 2. an adding device; 3. a binder spraying device; 4. a binder storage tank; 5. an electrically operated valve; 6. a flow control valve; 7. a flow meter; 8. a pressure sensor; 9. a pH detector; 10. a coal conveying belt is blended.

Detailed Description

The present invention will be further described with reference to the following examples.