阅读说明：本技术 一种复合粘结剂、煤焦油渣-腐殖酸盐复合气化型煤成型原料及生产方法 (Composite binder, coal tar residue-humate composite gasified molded coal forming raw material and production method ) 是由 杨国祥 姜喜义 傅敏燕 于 2021-07-29 设计创作，主要内容包括：本发明涉及危废焦油渣资源化利用技术领域,具体来说涉及一种复合粘结剂、一种煤焦油渣-腐殖酸盐复合气化型煤成型原料及其生产方法,所述复合粘结剂煤焦油渣和腐殖酸盐,所述腐殖酸盐为腐殖酸的可溶盐。本发明所提供的一种复合粘结剂、一种煤焦油渣-腐殖酸盐复合气化型煤成型原料及其生产方法,通过煤焦油渣提高型煤防水性；结合腐殖酸盐显著提高煤气化原料的机械强度和热稳定性,还可均化气化炉内成型颗粒破裂程度,稳定蒸汽和氧气利用率；同时通过本发明原料生产的气化型煤热稳定性好,机械强度高,生产成本低,气化时不易发生热爆粉化,可满足煤气化对颗粒原料的要求。(The invention relates to the technical field of resource utilization of hazardous waste tar residues, in particular to a composite binder, a coal tar residue-humate composite gasified molded coal forming raw material and a production method thereof. According to the composite binder, the coal tar residue-humate composite gasified molded coal forming raw material and the production method thereof, the water resistance of the molded coal is improved through the coal tar residue; the mechanical strength and the thermal stability of the coal gasification raw material are obviously improved by combining humate, the cracking degree of formed particles in the gasification furnace can be homogenized, and the utilization rate of steam and oxygen is stabilized; meanwhile, the gasified molded coal produced by the raw material of the invention has good thermal stability, high mechanical strength and low production cost, is not easy to generate thermal explosion and pulverization during gasification, and can meet the requirement of coal gasification on particle raw materials.)

1. The composite binder is used for producing molded coal and is characterized by comprising coal tar residue and humate, wherein the humate is soluble salt of humic acid.

2. The composite binder of claim 1 wherein the humic acid salt is prepared from humic acid, a base and water.

3. The composite binder of claim 2, wherein the humate is prepared from the following raw materials in weight percent: 100 parts by mass of humic acid; ammonia water with NH₃0-35 parts by mass; 5-25 parts by mass of sodium hydroxide; the dosage of the raw materials is the dosage with water being deducted, and the mass percentage of the humate solution is more than or equal to 12%, the pH range is 11-13.5, the mass fraction of the sodium hydroxide solution is 25-45%, and the mass fraction of the ammonia water is 10-25%.

4. The composite binder according to claim 3, wherein the humic acid salt, represented by R-COOH, is reacted during the preparation process,

upon addition of sodium hydroxide, the following reaction occurs:

COOH + NaOH = R-COONa + H₂O ；

upon addition of ammonia, the following reaction occurs:

COOH + NH₃.H₂O = R-COONH₄ + H₂O。

5. the coal tar residue-humate composite gasified molded coal forming raw material is characterized by comprising 100 parts by mass of raw material coal powder; 1-10 parts by mass, preferably 3-5 parts by mass of hydrated lime calculated by calcium oxide and the composite binder as claimed in any one of claims 1-4, wherein 1-15 parts by mass, preferably 8-10 parts by mass of coal tar residue; 1 to 10 parts by mass of humate, preferably 4 to 6 parts by mass; the above raw materials are all the amount with water removed.

6. A production method of a coal tar residue-humate composite gasified molded coal forming raw material is characterized by comprising the following steps: s1, fully mixing and reacting the raw material coal dust, the coal tar residue raw material, hydrated lime and humate to obtain a mixture to be pressed, and retting the mixture for 24 hours; s2, carrying out extrusion forming on the retted materials to obtain a forming mixture; s3, mixing the molding compound with CO₂Carbonizing the mixture through reaction to obtain a coal tar residue-humate composite gasified molded coal forming raw material product; the molding mixture is mixed with CO₂The reaction proceeds to carbonization, and the following reaction occurs: CO 2₂ + Ca(OH)₂ = CaCO₃ + H₂O； RCOOH + NaOH = RCOONa + H₂O。

7. The method for producing the coal tar residue-humate composite gasified molded coal forming raw material as claimed in claim 6, wherein the production method further comprises the steps of: s0.1, pretreating the raw material coal powder, namely crushing and screening the raw material coal powder to ensure that the particle size of the raw material coal powder is less than or equal to 2 mm.

8. The method for producing the coal tar residue-humate composite gasified briquette molding raw material according to claim 6, characterized in that the production method further comprises S0.2, and the hydrated lime preparation step: crushing and sieving quicklime (80-100 meshes), adding water or dilute ammonia water, mixing and slaking to obtain slaked lime, wherein the slaked lime reacts as follows in the preparation process: CaO + H₂O = Ca(OH)₂ ； CaO + CO₂ = CaCO₃ 。

9. The method for producing the coal tar residue-humate composite gasified briquette molding raw material according to claim 6, characterized by further comprising: s0.3, preparing humate: mixing humic acid and alkali to react to obtain humate, wherein the alkali comprises one or two of sodium hydroxide and ammonia water.

10. The method for producing the coal tar residue-humate composite gasified molded coal forming raw material according to any one of claims 6 to 9, characterized by comprising the following steps: in the step S3, the formed mixture is dried after being carbonized, so that the moisture content of the product meets the requirement of gasification of the coal tar residue.

Technical Field

The invention relates to the technical field of resource utilization of hazardous waste coal tar residues, in particular to a composite binder, a coal tar residue-humate composite gasification type coal forming raw material and a production method thereof.

Background

The coal tar slag is a black or black brown viscous paste solid which is formed by cooling solid components such as coal dust, coke powder, graphite and the like carried by coal gas in the process of coal gasification or coking and organic tar gas through a gas collecting pipe and a primary cooler, and has high viscosity and difficult oil-water separation. The components of the coal tar residue are extremely complex, mainly contain various pollutants such as benzene series, polycyclic aromatic hydrocarbon, nitrogen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds, heavy metals and the like, are often stacked in factories as wastes, and become a type of industrial waste residue which is difficult to treat. Therefore, resource utilization of the coal tar residue becomes one of the problems to be solved urgently by enterprises, and is also a hot spot concerned by researchers in China at present.

Chinese patent CN91106220.3 discloses a briquette using coal tar residue as binder; chinese patent CN200510027429.0 discloses a briquette composite binder; chinese patent CN202010021944.2 discloses a briquette based on coal tar residue and a coking and coal blending method thereof; chinese patent CN201811188959.7 discloses a method for preparing a briquette binder by using coking wastes, wherein the briquette composite binder is prepared by using coal tar residues and additives or other industrial wastes.

Humic acid is a macromolecular organic substance widely existing in nature, and is widely applied to various fields of agriculture, forestry, pasture, petroleum, chemical industry, building materials, medicine, health, environmental protection and the like. In the prior art, a precedent that humic acid and coal tar residue are combined to prepare a composite binder is not seen.

Disclosure of Invention

The invention aims to provide a novel composite binder, which further improves the performance of the composite binder and the performance of a briquette raw material doped with the composite binder.

In view of the above objects, a first aspect of the present invention provides a composite binder made by co-processing coal tar residue and humate, comprising coal tar residue and humate, the humate being a soluble salt of humic acid. Further, the humate is prepared from humic acid, alkali and water. Further, the humate is prepared from the following raw materials in percentage by weight: rotten food100 parts by mass of reproductive acid; ammonia water with NH₃0-35 parts by mass; 5-25 parts by mass of sodium hydroxide;

the dosage of the raw materials is the dosage with water being deducted, and the mass percentage of the humate solution is more than or equal to 12 percent, the pH range is 11-13.5, the mass fraction of the sodium hydroxide solution is 25-45 percent, and the mass fraction of the ammonia water is 10-25 percent.

Further, in the preparation process of the humate, R-COOH represents humic acid, the following reaction occurs:

upon addition of sodium hydroxide, the following reaction occurs:

R-COOH + NaOH = R-COONa + H₂O ；

upon addition of ammonia, the following reaction occurs:

R-COOH + NH₃.H₂O = R-COONH₄ + H₂O。

in another aspect of the invention, a coal tar residue-humate composite gasified molded coal forming raw material is provided, which comprises:

100 parts of raw material coal powder;

1 to 10 parts by mass, preferably 3 to 5 parts by mass of hydrated lime based on calcium oxide,

and the composite binder according to any one of claims 1 to 4, wherein,

1-15 parts by mass of coal tar residue, preferably 8-10 parts by mass;

1 to 10 parts by mass of humate, preferably 4 to 6 parts by mass;

the above raw materials are all the amount with water removed.

In another aspect of the invention, a method for producing a coal tar residue-humate composite gasified molded coal forming raw material is provided, which comprises the following steps:

s1, fully mixing and reacting the raw material coal dust, the coal tar residue raw material, hydrated lime and humate to obtain a mixture to be pressed, and retting the mixture for 24 hours;

s2, carrying out extrusion forming on the retted materials to obtain a forming mixture;

s3, mixing the molding compound with CO₂Carbonizing the mixture through reaction to obtain the coal cokeOil residue-humate composite gasified molded coal forming raw material products.

The molding mixture is mixed with CO₂The reaction proceeds to carbonization, and the following reaction occurs:

CO₂ + Ca(OH)₂ = CaCO₃ + H₂O；

RCOOH + NaOH = RCOONa + H₂O。

further, the production method further comprises the following steps:

s0.1, pretreating the raw material coal powder, namely crushing and screening the raw material coal powder to ensure that the particle size of the raw material coal powder is less than or equal to 2 mm.

Further, the production method further comprises:

s0.2, preparing hydrated lime: and (3) crushing and sieving quicklime (80-100 meshes), adding water or dilute ammonia water, mixing and curing to obtain the slaked lime.

During the preparation process of the hydrated lime, the following reaction occurs:

CaO + H₂O = Ca(OH)₂ ；

CaO + CO₂ = CaCO₃ 。

further, the production method further comprises:

s0.3, preparing humate: mixing humic acid and alkali to react to obtain humate, wherein the alkali comprises one or two of sodium hydroxide and ammonia water.

Based on the above method, in step S3, after the molding mixture is carbonized, the molding mixture is dried to make the moisture content of the product meet the requirement of gasification of the coal tar residue.

Advantageous effects of the invention

Compared with the prior art, the advantages of the composite binder, the coal tar residue-humate composite gasified molded coal forming raw material and the production method provided by the invention comprise the following aspects:

1) the coal tar residue can improve the water resistance of the molded coal and the mechanical strength of the molded coal at normal temperature; meanwhile, a large amount of solid carbon and organic components in the coal tar residue are utilized to realize resource utilization and reduce the usage amount of raw coal.

2) The hydrated lime can form a calcium carbonate skeleton of a formed particle, adjust coal gasification reaction, stabilize a gasification bed layer and have a sulfur fixation effect; the silicon-calcium ratio of the gasified slag can be adjusted, and the reasonable acidity and alkalinity of the slag can be ensured when the slag is gasified.

3) The humate can be prepared by reacting humic acid with alkali, has strong cohesiveness and thermal stability, can remarkably improve the mechanical strength and thermal stability of the coal gasification raw material, can also homogenize the breakage degree of formed particles in the gasification furnace, and stabilizes the utilization rate of steam and oxygen.

4) Humic acid is a group of organic substances which are produced and accumulated by animal and plant remains, mainly plant remains, through decomposition and transformation by microorganisms and a series of processes of geochemistry. The humic acid mainly comprises C, H, O elements, is similar to the coal and coal tar residue elements, has no pollution to raw materials, and does not cause adverse effect on a coal gasification process; humic acid is widely existed in nature, has abundant reserves and is suitable for large-scale use.

5) The raw material ammonia water can be from the byproduct ammonia water of a gasification plant, so that the ammonia water is recycled in an environment-friendly way; CO for carbonization and drying production process₂Can be from boiler flue gas or low-pressure vent gas to realize CO₂Can realize the cyclic utilization of CO₂And the ammonia water is recycled in an environment-friendly way, so that the energy is saved and the emission is reduced.

6) The gasified molded coal produced by the raw materials of the invention has good thermal stability, high mechanical strength and low production cost, is not easy to generate thermal explosion and pulverization during gasification, and can meet the requirements of coal gasification on particle raw materials.

Drawings

FIG. 1 is a schematic diagram illustrating a process flow of the production of a coal tar residue-humate composite gasified molded coal forming raw material provided by the invention.

Detailed Description

The technical solutions adopted by the present invention are further described below by the accompanying drawings and examples to help those skilled in the art to better understand the present invention.

As shown in figure 1, in each embodiment of the invention, the coal tar residue-humate composite gasified briquette forming raw material is produced according to the following steps:

1) preparing hydrated lime: adding water or dilute ammonia water into a lime bin in a metering manner, and stirring and curing to obtain hydrated lime with the water content of 15-17%;

2) preparing humate: adding quantitative water into a reaction kettle, adding sodium hydroxide and ammonia water (optional), heating to a specified temperature through steam, adding humic acid to prepare a sodium humate or ammonium humate solution, and producing humate which mainly comprises sodium humate and ammonium humate (when ammonia water is added) and has strong bonding property;

3) crushing: screening raw coal, mixing with coal tar residues and slaked lime, crushing by a crusher, adding a prepared sodium humate or ammonium humate solution, fully stirring and mixing by a double-shaft stirrer, conveying to a retting bin for retting for 24 hours, and preparing a mixture to be pressed;

4) molding: conveying the mixture to be pressed to a forming machine for extrusion forming to obtain a formed mixture;

5) carbonizing and drying: feeding the formed mixture into a carbonization tank and CO₂The circulating gas is carbonized and dried simultaneously, and CO is added₂The coal tar residue-humate composite gasified molded coal forming particle raw material can be obtained from boiler flue gas or low-pressure vent gas.

The composite adhesive is prepared from humate and coal tar residues, wherein the humate and the coal tar residues jointly form the composite adhesive, and the humate is prepared from the following raw materials in percentage by weight: 100 parts by mass of humic acid; ammonia water with NH₃0-35 parts by mass; 5-25 parts by mass of sodium hydroxide; the dosage of the raw materials is the dosage with water being deducted, and the mass percentage of the humate solution is more than or equal to 12 percent, the pH range is 11-13.5, the mass fraction of the sodium hydroxide solution is 25-45 percent, and the mass fraction of the ammonia water is 10-25 percent.

The humate is soluble salt of humic acid, such as ammonium humate, sodium humate, potassium humate, etc.

R-COOH represents humic acid, and the following reaction occurs when preparing the humic acid: upon addition of sodium hydroxide, the following reaction occurs: R-COOH + NaOH = R-COONa + H₂When ammonia water is added to O, the following reaction occurs： R-COOH + NH₃.H₂O = R-COONH₄ + H₂O。

Examples 1 to 3

The raw materials and the proportions used in the above production methods and examples are detailed in Table 1.

Note: the dry weight is the mass after drying or after deducting the moisture; humic acid salts comprise incompletely reacted humic acid which may be present during their preparation (all as explained herein); NaOH and humic acid are the weight of which water is subtracted.

The physical and chemical properties of the coal tar residue-humate composite gasified molded coal molding raw materials prepared in the examples are detected, and the detection results are shown in table 2. Because the tests of the thermal stability, the drop strength and the cold compressive strength of the formed particles of the coal tar slag have no national and industrial standards, the tests are respectively carried out by referring to an industrial coal thermal stability test method MT/T924-2004, an industrial coal drop strength test method MT/T925-2004 and an industrial coal cold pressure strength determination method MT/T748-2007, the analysis test conditions are kept consistent with the relevant standards, but when the thermal stability test data are processed, the diameter of the formed particles of the coal tar slag is less than 13mm, the proportion of the formed particles of the coal tar slag with the measured particle diameter of more than 6mm is recorded as BTS +6, and the processing methods of other analysis test data are the same as the standards.

As can be seen from Table 2, the thermal stability, drop strength and cold compressive strength of the coal tar residue molding raw material are greatly improved in the present invention as compared with the comparative examples.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be within the technical scope of the present invention, and the technical solutions and novel concepts according to the present invention should be covered by the scope of the present invention.