阅读说明：本技术 一种复合型水煤浆添加剂的制备方法 (Preparation method of composite coal water slurry additive ) 是由 黎茜茜 于 2020-04-27 设计创作，主要内容包括：本发明涉及水煤浆助剂技术领域,尤其涉及一种复合型水煤浆添加剂的制备方法。本发明以溴代十六烷基吡啶、乙二胺作为模板剂,以正硅酸乙酯作为原料,利用硅烷偶联剂作为辅助剂,制备得到树枝状多孔颗粒,随后再与丙烯酰胺单体进行混合,在引发剂的作用下,进行聚合,对多孔颗粒进行包裹,再将其与造纸黑液进行混合,通过对造纸黑液进行絮凝,得到里面丰富的木质素物质,在将其在碱性条件下,通过环氧氯丙烷的作用下进行交联,形成微型球状结构,并吸附在多孔颗粒表面,通过载体的负载以及颗粒的球状结构,提高了添加剂的稳定性能,而且在一定程度降低了粘度。(The invention relates to the technical field of coal water slurry additives, in particular to a preparation method of a composite coal water slurry additive. The preparation method comprises the steps of taking bromohexadecylpyridine and ethylenediamine as template agents, taking ethyl orthosilicate as raw materials, taking silane coupling agent as an auxiliary agent, preparing dendritic porous particles, mixing the dendritic porous particles with acrylamide monomers, polymerizing the mixture under the action of an initiator, wrapping the porous particles, mixing the porous particles with papermaking black liquor, flocculating the papermaking black liquor to obtain abundant lignin substances in the porous particles, crosslinking the lignin substances under the action of epoxy chloropropane under an alkaline condition to form a micro spherical structure, adsorbing the micro spherical structure on the surface of the porous particles, improving the stability of an additive through the load of a carrier and the spherical structure of the particles, and reducing the viscosity to a certain extent.)

1. The preparation method of the compound coal water slurry additive is characterized by comprising the following steps:

(1) adjusting the pH value of a template agent and a composite solvent by using ammonia water according to the mass ratio of 1: 4-6, adding tetraethoxysilane which is 3-5 times of the mass of the template agent and a silane coupling agent which is 10-30% of the mass of the template agent, ultrasonically oscillating, adjusting the pH value, and heating;

(2) after heating, standing, centrifuging, washing, drying, collecting a dried substance, ball-milling the dried substance, an additive and water according to a mass ratio of 8:3: 12-15, collecting a ball-milled mixture, and taking 120-130 parts of water, 40-50 parts of the ball-milled mixture, 20-25 parts of a monomer and 3-5 parts of an initiator according to parts by weight;

(3) putting water, the ball-milled mixture and the monomer into a reaction kettle, stirring and mixing under the protection of nitrogen, preheating, adding an initiator, heating, stirring for reaction, cooling to room temperature, discharging, spray-drying, washing with ethanol, and collecting washings;

(4) stirring and mixing the washing matter and the papermaking black liquor according to the mass ratio of 4: 12-14, standing, filtering, collecting filter residues, mixing the filter residues, a sodium hydroxide solution and a dispersing agent according to the mass ratio of 4-8: 13:1, adding an auxiliary agent accounting for 10-13% of the mass of the filter residues, heating, stirring and mixing, freeze-drying, and collecting freeze-dried matters;

(5) mixing the freeze-dried substance and water according to the mass ratio of 6: 12-14, adding sodium thiosulfate accounting for 20% of the mass of the freeze-dried substance, heating, cooling, adding formaldehyde, stirring, adjusting the pH value, standing, performing spray drying, and collecting the spray-dried substance to obtain the composite coal water slurry additive.

2. The preparation method of the composite coal water slurry additive according to claim 1, wherein the template agent in the step (1) is formed by mixing bromohexadecylpyridine and ethylenediamine according to a mass ratio of 7: 3-5.

3. The preparation method of the compound coal water slurry additive according to claim 1, wherein the compound solvent in the step (1) is obtained by mixing an ethanol solution and n-amyl alcohol according to a volume ratio of 5: 3-7.

4. The preparation method of the compound coal water slurry additive according to claim 1, wherein the silane coupling agent in the step (1) is formed by mixing aminopropyltriethoxysilane and vinyltriethoxysilane according to a mass ratio of 6: 2-4.

5. The preparation method of the compound coal water slurry additive according to claim 1, wherein the additive in the step (2) is prepared by mixing chitosan and maleic anhydride according to a mass ratio of 10: 1-3.

6. The preparation method of the composite coal water slurry additive according to claim 1, wherein the monomer is acrylamide.

7. The preparation method of the composite coal water slurry additive according to claim 1, wherein the initiator is any one of potassium persulfate and ammonium persulfate.

8. The preparation method of the compound coal water slurry additive according to claim 1, wherein the dispersant in the step (4) is any one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.

9. The preparation method of the composite coal water slurry additive according to claim 1, wherein the adjuvant in the step (4) is epichlorohydrin.

Technical Field

The invention relates to the technical field of coal water slurry additives, in particular to a preparation method of a composite coal water slurry additive.

Background

The coal water slurry is a coal-based fluid oil-substituted fuel prepared from 60-70% of coal, 30-40% of water and a small amount of additives through a certain processing technology, not only maintains the original characteristics of the coal, but also has the same fluidity and stability as those of petroleum, can be stored, pumped, atomized and stably combusted, has the advantages of energy conservation, environmental protection and the like, and is widely applied to the fields of oil-substituted combustion power generation, heat supply, chemical industry and the like. Since the research and development of the early 80 th of the 20 th century, the gasification of coal water slurry, one of clean coal technologies, has been generally applied after many years of continuous scientific and technological attack and production practice, and the scale of production and application is the first in the world. The high-concentration coal water slurry not only keeps the original physical and chemical characteristics of coal, but also has good fluidity and stability like petroleum, and simultaneously has better safety than petroleum. Coal water slurry is used as an ideal oil-saving fuel instead of oil, and is generally concerned all over the world once appearing. With the rapid expansion of the coal chemical industry which gasifies water coal slurry into taps, the application scale of gasified water coal slurry keeps a strong growth momentum. However, the low concentration and poor stability of the coal water slurry are always the problems which plague various large coal chemical industry production enterprises.

The preparation process of the coal water slurry needs to add a small amount of additives, and the additives are low in dosage and are key for preparing the high-concentration coal water slurry. It is a chemical agent capable of promoting dispersed phase (coal particles in water coal slurry) to be uniformly dispersed in dispersion medium (water in water coal slurry), and is a chemical auxiliary agent which is largely used in the processes of combustion, gasification and transportation of water coal slurry. The coal water slurry additive with good performance can enable the coal water slurry to have higher slurry concentration, rheological property of shear thinning, good stability and excellent atomization combustion performance. Generally, the quality requirements for coal water slurries are low viscosity, high concentration, and good flow and stability. The coal water slurry additive is one of the keys influencing the quality of the coal water slurry and also influencing the production cost of the coal water slurry. The coal water slurry additive can be divided into three categories of dispersant, stabilizer and auxiliary agent, wherein the dispersant is the most important. The coal water slurry additives developed and screened at present mainly comprise anionic, nonionic and organic high molecular polymers and other compound additives, wherein the additives mainly comprise naphthalene, humic acid, lignin, polyolefin, acrylic acid and the like.

Currently, the coal water slurry additives in use are classified into the following categories according to their chemical compositions: first, a naphthalene sulfonate condensate. The additive has the advantages of good wetting and dispersing performance, good slurry flow pattern and wide application range; however, the slurry has poor stability, is prone to water precipitation and irreversible hard precipitation, and is expensive. Second, lignosulfonates. The additive has the advantages of wide raw material source, low price and good slurry stability; however, the raw materials are complex in components and unstable in performance, and the requirements of industrial application are difficult to meet when the raw materials are used alone. Third, humate. The additive has the advantages of good dispersion performance, but is sensitive to metal ions in water, easy to form precipitate and poor in slurry stability. Fourth, polycarboxylic acid series. The additive has the advantages of good slurry fluidity and stability, but higher price and narrower application range. Fifth, the polyolefin series. The additive has the advantages of dispersion stabilizing effect on the low-ash coal water slurry, but has higher price.

The most widely used products in the market are naphthalene sulfonate condensates with various substituents, and the naphthalene sulfonate condensates have the characteristics of good dispersibility, strong viscosity reducing effect, good slurry fluidity and wide application range, can be used in combination with various dispersants, but have poor slurry stability and are easy to generate hard precipitates. The coal water slurry additive sold in the market at present is mainly prepared by mixing a naphthalene sulfonate condensate with sodium lignosulfonate in proportion, and a large amount of sulfuric acid is added in the preparation processes of the lignosulfonate and the naphthalene sulfonate condensate, so that the concentration of sulfate in the additive is higher, and the problems of the coal water slurry such as the increase of the concentration, the reduction of the stability and the like are caused.

Generally speaking, because most of coal water slurry additives have the problems of poor stability and high viscosity, the development of additives with high efficiency, low price and wide adaptability is a research direction in the future.

Disclosure of Invention

The technical problems to be solved by the invention are as follows: aiming at the problems of poor stability and high viscosity of the existing coal water slurry additive, the invention provides a preparation method of a composite coal water slurry additive.

In order to solve the technical problems, the invention adopts the following technical scheme:

a preparation method of a compound coal water slurry additive comprises the following steps:

(1) adjusting the pH value of a template agent and a composite solvent by using ammonia water according to the mass ratio of 1: 4-6, adding tetraethoxysilane which is 3-5 times of the mass of the template agent and a silane coupling agent which is 10-30% of the mass of the template agent, ultrasonically oscillating, adjusting the pH value, and heating;

(2) after heating, standing, centrifuging, washing, drying, collecting a dried substance, ball-milling the dried substance, an additive and water according to a mass ratio of 8:3: 12-15, collecting a ball-milled mixture, and taking 120-130 parts of water, 40-50 parts of the ball-milled mixture, 20-25 parts of a monomer and 3-5 parts of an initiator according to parts by weight;

(3) putting water, the ball-milled mixture and the monomer into a reaction kettle, stirring and mixing under the protection of nitrogen, preheating, adding an initiator, heating, stirring for reaction, cooling to room temperature, discharging, spray-drying, washing with ethanol, and collecting washings;

(4) stirring and mixing the washing matter and the papermaking black liquor according to the mass ratio of 4: 12-14, standing, filtering, collecting filter residues, mixing the filter residues, a sodium hydroxide solution and a dispersing agent according to the mass ratio of 4-8: 13:1, adding an auxiliary agent accounting for 10-13% of the mass of the filter residues, heating, stirring and mixing, freeze-drying, and collecting freeze-dried matters;

(5) mixing the freeze-dried substance and water according to the mass ratio of 6: 12-14, adding sodium thiosulfate accounting for 20% of the mass of the freeze-dried substance, heating, cooling, adding formaldehyde, stirring, adjusting the pH value, standing, performing spray drying, and collecting the spray-dried substance to obtain the composite coal water slurry additive.

The template agent in the step (1) is formed by mixing bromohexadecylpyridine and ethylenediamine according to the mass ratio of 7: 3-5.

The composite solvent in the step (1) is obtained by mixing an ethanol solution and n-amyl alcohol according to a volume ratio of 5: 3-7.

The silane coupling agent in the step (1) is formed by mixing aminopropyltriethoxysilane and vinyl triethoxysilane according to the mass ratio of 6: 2-4.

The additive in the step (2) is formed by mixing chitosan and maleic anhydride according to a mass ratio of 10: 1-3.

The monomer is acrylamide.

The initiator is any one of potassium persulfate and ammonium persulfate.

The dispersing agent in the step (4) is any one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.

And (4) the auxiliary agent in the step (4) is epichlorohydrin.

Compared with other methods, the method has the beneficial technical effects that:

the preparation method comprises the steps of taking bromohexadecylpyridine and ethylenediamine as template agents, taking ethyl orthosilicate as raw materials, taking silane coupling agent as an auxiliary agent, preparing dendritic porous particles, mixing the dendritic porous particles with acrylamide monomers, polymerizing the mixture under the action of an initiator, wrapping the porous particles, mixing the porous particles with papermaking black liquor, flocculating the papermaking black liquor to obtain abundant lignin substances in the porous particles, crosslinking the lignin substances under the action of epoxy chloropropane under an alkaline condition to form a micro spherical structure, adsorbing the micro spherical structure on the surface of the porous particles, improving the stability of an additive through the load of a carrier and the spherical structure of the particles, and reducing the viscosity to a certain extent.

Detailed Description

The template agent is formed by mixing bromohexadecylpyridine and ethylenediamine according to the mass ratio of 7: 3-5.

The composite solvent is obtained by mixing an ethanol solution and n-amyl alcohol according to a volume ratio of 5: 3-7.

The silane coupling agent is formed by mixing aminopropyltriethoxysilane and vinyl triethoxysilane according to the mass ratio of 6: 2-4.

The additive is formed by mixing chitosan and maleic anhydride according to a mass ratio of 10: 1-3.

The monomer is acrylamide.

The initiator is any one of potassium persulfate and ammonium persulfate.

The dispersant is any one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.

The auxiliary agent is epichlorohydrin.

A preparation method of a compound coal water slurry additive comprises the following steps:

(1) adjusting the pH value of a template agent and a composite solvent to 8.0-8.5 by using ammonia water according to the mass ratio of 1: 4-6, adding tetraethoxysilane which is 3-5 times of the mass of the template agent and a silane coupling agent which is 10-30% of the mass of the template agent, performing ultrasonic oscillation for 20min, adjusting the pH value to be neutral, heating to 60 ℃, and heating for 3 h;

(2) standing for 1h after heating is finished, centrifuging, washing solids with water, drying, collecting dried substances, carrying out ball milling on the dried substances, additives and water at a mass ratio of 8:3: 12-15 at a speed of 600r/min for 30min, collecting ball milling mixtures, and taking 120-130 parts of water, 40-50 parts of ball milling mixtures, 20-25 parts of monomers and 3-5 parts of initiators in parts by weight;

(3) putting water, the ball-milled mixture and the monomer into a reaction kettle, stirring and mixing under the protection of nitrogen, preheating for 15min at 45 ℃, adding an initiator, heating to 70 ℃, stirring and reacting for 7h, cooling to room temperature, discharging, spray drying, washing with ethanol, and collecting washings;

(4) stirring and mixing the washing matter and the papermaking black liquor according to the mass ratio of 4: 12-14, standing for 3 hours at 40 ℃, filtering, collecting filter residues, mixing the filter residues, 1.8mol/L sodium hydroxide solution and a dispersing agent according to the mass ratio of 4-8: 13:1, adding an auxiliary agent accounting for 10-13% of the mass of the filter residues, heating to 80 ℃, stirring and mixing for 4 hours, freeze-drying, and collecting freeze-dried matters;

(5) mixing the freeze-dried substance and water according to the mass ratio of 6: 12-14, adding sodium thiosulfate with the mass of 20% of that of the freeze-dried substance, heating to 105 ℃, heating for 3h, cooling to 90 ℃, adding formaldehyde, stirring for 6h, adjusting the pH value to be neutral, standing for 8h, performing spray drying, and collecting spray-dried substances to obtain the composite coal water slurry additive.