Powder-form environment-friendly multifunctional coal water slurry additive with sulfomethylated phenolic resin as main component and application of powder-form environment-friendly multifunctional coal water slurry additive

Abstract

The invention relates to a powder-form environment-friendly multifunctional coal water slurry additive taking sulfomethylated phenolic resin as a main component and application. The coal water slurry additive comprises the following components in percentage by mass: 50%-100% of powder-form sulfomethylated phenolic resin and 0%-50% of several of powder-form sodium lignin sulfonate, sodium naphthalene sulfonate-formaldehyde condensate and sulfonated acetone-formaldehyde condensation polymer, wherein the sulfomethylated phenolic resin is uniformly mixed with other components. The dry-powder coal water slurry additive is prepared by taking the sulfomethylated phenolic resin as a main component and adopting an environment-friendly and non-toxic powdery material, is convenient to store and transport, is simple and convenient to use, can reduce the viscosity of the prepared coal water slurry, obviously improves the fluidity, the concentration and the stability, and greatly improves the performance of the coal water slurry.

Description

Technical Field

[0001] The invention relates to the field of coal chemical additives, and in particular to an environmentally friendly multifunctional water-coal slurry additive in powder form suitable for a coal chemical coal slurry preparation process, with sulfomethylphenolic resin as a main component, and its application. Background Art

[0002] Coal-water slurry is a slurry obtained by fully mixing coal powder of a certain graded fineness, water and coal-water slurry additives. It is a slurry-like coal product with certain stability and fluidity, and is widely used in coal chemical fields such as synthetic methanol, ammonia, olefins, fuel oil, and natural gas. Since coal-water slurry has significant technical and economic advantages such as high energy efficiency, low pollution, and low cost, it has become one of the key technologies for my country to implement the clean coal strategy.

[0003] Coal is mainly a hydrophobic non-polar hydrocarbon. In the process of forming a slurry with water, the role of coal water slurry additives is to disperse coal powder in water to form a fluid, uniform, and stable slurry. Its dispersion mechanism is mainly to effectively adsorb on the surface of coal particles, improve the hydrophilicity of coal particles, and form a double electric layer and steric hindrance on the surface of coal particles. Coal water slurry additives are generally divided into two categories: anionic and non-ionic surfactants. In view of the use effect, cost, and availability of raw materials, anionic coal water slurry additives are more common. The coal water slurry additives widely used in the market currently mainly include lignin series, such as alkali lignin, lignin sulfonate; naphthalene series, such as naphthalene sulfonate formaldehyde condensate; aliphatic additives, such as sulfonated acetone-formaldehyde condensate, etc.; or a combination of two or more of the above products.

[0004] The disadvantage of current coal-water slurry additive products is that most coal-water slurry additives on the market are aqueous solutions of a certain concentration, and powdered coal-water slurry additives are relatively rare, which is not conducive to transportation and storage. Current coal-water slurry additives are all surfactants, and their working principle is to use the hydrophilic and hydrophobic groups in the molecules to align in an aqueous solution, change the interface state of the solution system, thereby significantly reducing the surface tension of the solution system and mixing the repelling coal particles with water. Although these additives can effectively adjust the stability of the water-coal system and prepare coal-water slurries with better performance, the coal-water slurry formed by the dispersion effect of the surfactant alone is prone to water-coal stratification after a period of standing, and the stability is poor. Moreover, most of the surfactant components in the existing additives have certain toxicity, which can cause greater pollution during use.

[0005] As national and local environmental protection laws and regulations become increasingly stringent, it is necessary to develop new and efficient water-coal slurry additive products that are more environmentally friendly, safe, easy to use, and more efficient.

[0006] Sulfomethylphenol-formaldehyde resin is a colloid produced by using phenol, formaldehyde, sodium pyrosulfite and anhydrous sodium sulfite as raw materials, and undergoing multiple condensation reactions and sulfonation reactions simultaneously under alkaline catalysis conditions. The final powder product can be obtained after spray drying. At present, sulfomethylphenol-formaldehyde resin is usually used in the field of oil drilling as a fluid loss reducer in drilling fluid additives or as a viscosity reducer. At present, in the field of water-coal slurry additives, there is no public scheme using sulfomethylphenol-formaldehyde resin as the main component. Summary of the invention

[0007] The first invention purpose of the present invention is to provide an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethyl phenolic resin as the main component, in order to solve the problems that the existing water-coal slurry additives described in the background technology usually use surfactants, which are toxic and easily cause environmental pollution, and the water-coal slurry formed by relying solely on the dispersing effect of the surfactant is prone to water-coal stratification after a period of standing, and has poor stability. At the same time, the existing water-coal slurry additives are usually liquid additives, which are not convenient for transportation and storage.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0009] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and their mass percentages are as follows: 50% to 100% of the sulfomethylphenolic resin in powder form, 0% to 50% of several kinds of sodium lignin sulfonate, sodium naphthalenesulfonate formaldehyde condensate and sulfonated acetone-formaldehyde polycondensate in powder form, and the sulfomethylphenolic resin is uniformly mixed with the other components.

[0010] In the above scheme, the components and mass percentages included are: 75% to 90% of sulfomethylphenolic resin in powder form and 10% to 25% of several kinds of sodium lignin sulfonate, sodium naphthalenesulfonate formaldehyde condensate and sulfonated acetone-formaldehyde polycondensate in powder form.

[0011] Another object of the present invention is to provide an application method of an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component does not need to be pre-configured into an aqueous solution, but only needs to be directly put into the coal slurry and mixed evenly with the water-coal slurry by high-speed stirring to obtain a stable water-coal slurry.

[0012] In the above scheme, the method for preparing water-coal slurry is to crush the coal sample in advance to obtain coal particles with a particle size of less than 1 cm, and according to the set coal slurry concentration, add the coal particles, coal grinding water, and water-coal slurry additives in powder form into the rod mill at the same time according to the ratio. The coal particles are converted into coal powder with a predetermined particle size distribution by the force of the steel rod, and the various components are evenly mixed by the high-speed stirring of the rod mill to obtain water-coal slurry with low viscosity, high concentration, fluidity and stability.

[0013] The present invention utilizes the three-dimensional network structure formed by sulfomethylphenolic resin after dissolving in water and its strong stability, rheological properties, lubricity and other characteristics, to provide a new type of high-efficiency and environmentally friendly powder water-coal slurry additive, and has the advantages of environmental protection, easy transportation and storage, convenient use and good slurry performance. The specific description is as follows:

[0014] Ordinary water-coal slurry additives can only disperse the water-coal system through their own hydrophilic and hydrophobic groups, so uneven dispersion is prone to occur, affecting the stability of the system. At the same time, most of the surfactant components in the additives are toxic, which will cause great pollution during use, and most additives are in liquid form, which is not conducive to transportation and storage. Even additives in powder form must be dissolved into solutions in advance before use.

[0015] The mechanism of action of sulfomethyl phenolic resin is different from that of surfactants. In addition to relying on its own hydrophilic and hydrophobic groups, sulfomethyl phenolic resin can also form a network structure to disperse the suspension system after dissolving in water, preventing coal particles or water from aggregating. The slurry formed by the combination of the two is more stable. At the same time, the network structure has viscoelasticity, which can block pores and reduce the movement of free water molecules, thereby reducing the occurrence of water-coal stratification after standing. The more mature application of sulfomethyl phenolic resin is as a fluid loss reducer in the drilling industry, which prevents the aggregation and loss of water through its unique network structure.

[0016] Sulfomethylphenolic resin also has the characteristics of high temperature resistance, salt resistance, and strong alkali resistance. With the increase of temperature, salt content, and pH, the dispersion effect is gradually improved. During the use of sulfomethylphenolic resin, a cross-linking reaction will occur. The hydroxymethyl on the phenol ring undergoes a dehydration condensation reaction with active hydrogen to generate a stable phenol ring connected by a methylene bridge, the molecular weight increases, and the network structure is strengthened, thereby improving the dispersion effect and stability of the system. The increase in temperature is conducive to the sulfonated group of sulfomethylphenolic resin adsorbing coal particles in the system, and is also conducive to high-temperature cross-linking reaction. With the increase in salt content, the number of anions and cations increases, the salting-out effect is enhanced, the resin molecules aggregate with each other, and the probability of cross-linking reaction increases. With the increase in pH value, the phenol in the sulfomethylphenolic resin is gradually converted into the form of phenol oxide anions, that is, phenol generates sodium phenol. Since the positioning effect of phenol oxide anions is stronger than that of phenol hydroxyl groups, the addition of alkali is conducive to the electrophilic reaction, making the electrophilic reaction on the benzene ring easy to proceed, that is, promoting the cross-linking reaction. Therefore, the high temperature of the coal pulverizing system, the anions and cations in the coal pulverizing water, and other compounded alkaline additive components can all enhance the dispersing and stabilizing effects of the sulfomethylphenol-formaldehyde resin.

[0017] Among the components of the present invention, the sulfomethylphenolic resin, sodium lignin sulfonate, sodium naphthalenesulfonate formaldehyde condensate and sulfonated acetone-formaldehyde polycondensate are all environmentally friendly and non-toxic substances, and are all in powder form, which are easy to transport and store after being evenly mixed.

[0018] Among the components of the present invention, there is also a composite synergistic effect between sulfomethylphenolic resin and sodium lignin sulfonate, sodium naphthalenesulfonate formaldehyde condensation product and sulfonated acetone-formaldehyde polycondensation product. Because the mechanism of action of sulfomethylphenolic resin is completely different from that of surfactant, when it presents a leading role in the additive as a whole, it can take the lead in forming a network structure in an aqueous medium, and this structure is very stable, and other components compounded therein such as sodium lignin sulfonate, naphthalenesulfonate formaldehyde condensation product, sulfonated acetone-formaldehyde polycondensation product etc. are interspersed and entangled in the coal particles through their own hydrophilic and hydrophobic groups to form a spatial network structure, and are embedded in the network structure of sulfomethylphenolic resin, greatly enhancing the spatial steric effect, thereby enhancing the suspension of the system. Most of the water-coal slurry additive components all present stronger alkalinity, and can also enhance the dispersing and stabilizing effects of sulfomethylphenolic resin.

[0019] The environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component is easy to use and does not need to be prepared into an aqueous solution when used. It can be directly put into the coal slurry and only needs to be uniformly mixed at a high speed to obtain a stable water-coal slurry. DETAILED DESCRIPTION

[0020] The technical scheme of the present invention is clearly and completely described below through embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Example 1

[0022] The invention discloses an environment-friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components thereof are: 100% of sulfomethylphenolic resin in powder form.

[0023] Example 2

[0024] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component, comprising the following components and mass percentages: 75% of sulfomethylphenolic resin in powder form and 25% of sodium lignin sulfonate in powder form, wherein the sulfomethylphenolic resin and the sodium lignin sulfonate are uniformly mixed.

[0025] Example 3

[0026] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and mass percentages thereof are: 75% of sulfomethylphenolic resin in powder form and 25% of sodium naphthalenesulfonate formaldehyde condensate in powder form. The sulfomethylphenolic resin and the sodium naphthalenesulfonate formaldehyde condensate are uniformly mixed.

[0027] Example 4

[0028] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and mass percentages thereof are: 75% of sulfomethylphenolic resin in powder form and 25% of sulfonated acetone-formaldehyde polycondensate in powder form. The sulfomethylphenolic resin and the sulfonated acetone-formaldehyde polycondensate are uniformly mixed.

[0029] Example 5

[0030] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component, comprising the following components and mass percentages: 90% sulfomethylphenolic resin in powder form and 10% sodium lignin sulfonate in powder form, wherein the sulfomethylphenolic resin and the sodium lignin sulfonate are uniformly mixed.

[0031] Example 6

[0032] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and mass percentages thereof are: 90% of sulfomethylphenolic resin in powder form and 10% of sodium naphthalenesulfonate formaldehyde condensate in powder form. The sulfomethylphenolic resin and the sodium naphthalenesulfonate formaldehyde condensate are uniformly mixed.

[0033] Example 7

[0034] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and mass percentages thereof are: 90% of sulfomethylphenolic resin in powder form and 10% of sulfonated acetone-formaldehyde polycondensate in powder form. The sulfomethylphenolic resin and the sulfonated acetone-formaldehyde polycondensate are uniformly mixed.

[0035] Example 8

[0036] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and mass percentages thereof are: 50% of sulfomethylphenolic resin in powder form, 25% of sodium lignin sulfonate in powder form, and 25% of sodium naphthalenesulfonate formaldehyde condensate. The sulfomethylphenolic resin, sodium lignin sulfonate and sodium naphthalenesulfonate formaldehyde condensate are uniformly mixed.

[0037] Example 9

[0038] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and mass percentages thereof are: 50% of sulfomethylphenolic resin in powder form, 25% of sodium lignin sulfonate in powder form, and 25% of sulfonated acetone-formaldehyde polycondensate. The sulfomethylphenolic resin, sodium lignin sulfonate and sulfonated acetone-formaldehyde polycondensate are uniformly mixed.

[0039] Example 10

[0040] The invention discloses an environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component. The components and mass percentages thereof are: 70% of sulfomethylphenolic resin in powder form, 10% of sodium lignin sulfonate in powder form, 10% of sodium naphthalenesulfonate formaldehyde condensate, and 10% of sulfonated acetone-formaldehyde polycondensate. The sulfomethylphenolic resin is uniformly mixed with the sodium lignin sulfonate, the sodium naphthalenesulfonate formaldehyde condensate, and the sulfonated acetone-formaldehyde polycondensate.

[0041] When the environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component of the above-mentioned embodiments 1-10 of the present invention is used to prepare water-coal slurry, the environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component does not need to be pre-configured into an aqueous solution, but only needs to be directly put into the coal slurry and mixed evenly with the water-coal slurry by high-speed stirring to obtain a stable water-coal slurry.

[0042] The method for preparing water-coal slurry is to crush the coal sample in advance to obtain coal particles with a particle size of less than 1 cm, and add the coal particles, coal grinding water, and water-coal slurry additives in powder form to the rod mill according to the set coal slurry concentration. The coal particles are converted into coal powder with a predetermined particle size distribution by the force of the steel rod, and the components are uniformly mixed by the high-speed stirring of the rod mill to obtain a water-coal slurry with low viscosity, high concentration, fluidity and stability. The coal slurry concentration can be set as needed, for example, it can be set to 56%-66%.

[0043] Comparative Example 1

[0044] Coal water slurry was prepared by using existing coal water slurry additives with surfactant as main component and coal water slurry additives of Examples 1-10 of the present invention respectively. The preparation method is: crushing, drying and grinding the coal sample, and then screening with a stainless steel standard analysis sieve to obtain coal powder with a certain particle size distribution, and mixing coal powder with a certain grade, coal grinding water and additives at a high speed according to the set coal slurry concentration, and testing the quality technical indicators such as the concentration, viscosity, fluidity, and 48-hour stability of the coal water slurry.

[0045] Comparative Example 2

[0046] 25% of sulfomethylphenolic resin was added to the existing surfactant, and water-coal slurry was prepared by the method of Comparative Example 1. The quality technical indicators of the water-coal slurry, such as concentration, viscosity, fluidity, and 48-hour stability, were tested.

[0047] The test results are shown in the following table:

[0048]

[0049]

[0050] It can be seen from the test results in the above table that the coal-water slurry additives of Examples 1-10 of the present invention can significantly reduce the viscosity of the coal-water slurry produced, significantly improve the fluidity, and have higher stability, and there is no hard precipitation after standing for 48 hours, compared with the existing coal-water slurry additives in Comparative Example 1. The coal-water slurry additives with sulfomethylphenol-formaldehyde resin as the main component in Examples 1-10 of the present invention can significantly reduce the viscosity of the coal-water slurry produced, and significantly improve the fluidity and stability, compared with the coal-water slurry additives with surfactant as the main component and only a small amount of sulfomethylphenol-formaldehyde resin added in Comparative Example 2.

[0051] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component, characterized in that: The components and mass percentages thereof are: 50% to 100% of powdered sulfomethylphenolic resin, 0% to 50% of several kinds of powdered sodium lignin sulfonate, sodium naphthalene sulfonate formaldehyde condensate and sulfonated acetone-formaldehyde polycondensate, and the sulfomethylphenolic resin and other components are uniformly mixed.

2. The environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component according to claim 1, characterized in that , the components and mass percentages included are: 75% to 90% of sulfomethylphenol-formaldehyde resin in powder form and 10% to 25% of several kinds of sodium lignin sulfonate, sodium naphthalene sulfonate formaldehyde condensate and sulfonated acetone-formaldehyde condensate in powder form.

3. A method for applying the environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component according to any one of claims 1 to 2, characterized in that: The environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component does not need to be pre-configured into an aqueous solution, but only needs to be directly added to the coal slurry and mixed evenly with the water-coal slurry by high-speed stirring to obtain a stable water-coal slurry.

4. The method for applying the environmentally friendly multifunctional water-coal slurry additive in powder form with sulfomethylphenolic resin as the main component according to claim 3, characterized in that: The method for preparing water-coal slurry is to crush the coal sample in advance to obtain coal particles with a particle size of less than 1 cm, and according to the set coal slurry concentration, add the coal particles, coal grinding water, and water-coal slurry additives in powder form into the rod mill at the same time according to the ratio. The coal particles are converted into coal powder with a predetermined particle size distribution through the force of the steel rod, and the various components are evenly mixed through the high-speed stirring of the rod mill to obtain water-coal slurry with low viscosity, high concentration, fluidity and stability.

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