阅读说明：本技术 一种2-萘酚蒸馏残渣改性水煤浆分散剂及其制备方法 (2-naphthol distillation residue modified coal water slurry dispersing agent and preparation method thereof ) 是由 董翠平 马丽涛 王超 尤健健 崔岩 杨道顺 欧大康 于 2020-06-15 设计创作，主要内容包括：本发明涉及水煤浆分散剂,具体涉及一种2-萘酚蒸馏残渣改性水煤浆分散剂及其制备方法。所述的2-萘酚蒸馏残渣改性水煤浆分散剂,按重量份计,由以下组分配制而成：蒸馏-精馏残渣5-150份、萘油/蒽油/洗油80-200份、浓硫酸160-300份、甲醛60-120份、液体氢氧化钠130-315份、水解水0-40份、补水200-350份。本发明中采用二萘酚蒸馏、精馏废渣用于改性水煤浆分散剂,经接枝引入酚羟基、高沸点有机物等活性基团作用于煤颗粒,起到了分散效果,同时增强了水煤浆的稳定性,为水煤浆分散剂的研究开辟了新的方向。同时本发明是利用二萘酚蒸馏、精馏残渣改性水煤浆分散剂,避免了残渣直接处理时的资源浪费,避免废物排放对环境的污染,并实现了二萘酚蒸馏、精馏残渣在新领域的应用。(The invention relates to a coal water slurry dispersing agent, in particular to a 2-naphthol distillation residue modified coal water slurry dispersing agent and a preparation method thereof. The 2-naphthol distillation residue modified coal water slurry dispersing agent is prepared from the following components in parts by weight: 5-150 parts of distillation-rectification residues, 80-200 parts of naphthalene oil/anthracene oil/wash oil, 300 parts of concentrated sulfuric acid, 60-120 parts of formaldehyde, 315 parts of liquid sodium hydroxide, 0-40 parts of hydrolysis water and 350 parts of water supplement. In the invention, the dinaphthol distillation and the rectification waste residues are used for modifying the coal water slurry dispersing agent, and active groups such as phenolic hydroxyl groups, high-boiling-point organic matters and the like are introduced to act on coal particles through grafting, so that the dispersing effect is achieved, the stability of the coal water slurry is enhanced, and a new direction is opened up for the research of the coal water slurry dispersing agent. Meanwhile, the invention utilizes the dinaphthol distillation and rectification residues to modify the coal water slurry dispersing agent, avoids resource waste when the residues are directly treated, avoids environmental pollution caused by waste discharge, and realizes the application of the dinaphthol distillation and rectification residues in new fields.)

1. The 2-naphthol distillation residue modified coal water slurry dispersant is characterized by being prepared from the following components in parts by weight: 5-150 parts of distillation and rectification residues, 80-200 parts of naphthalene oil/anthracene oil/wash oil, 300 parts of concentrated sulfuric acid, 60-120 parts of formaldehyde, 315 parts of liquid sodium hydroxide, 0-40 parts of hydrolysis water and 350 parts of water supplement.

2. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to claim 1, which is prepared from the following components in parts by weight: 70 parts of distillation and rectification residues, 180 parts of naphthalene oil, 200 parts of concentrated sulfuric acid, 80 parts of formaldehyde, 212 parts of liquid sodium hydroxide, 15 parts of hydrolysis water and 260 parts of water supplement.

3. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to claim 1, which is prepared from the following components in parts by weight: 120 parts of distillation-rectification residues, 150 parts of anthracene oil, 235 parts of concentrated sulfuric acid, 95 parts of formaldehyde, 228 parts of liquid sodium hydroxide, 30 parts of hydrolysis water and 300 parts of water supplement.

4. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to any one of claims 1 to 3, wherein the concentration of the concentrated sulfuric acid is 98 to 113 wt%.

5. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to any one of claims 1 to 3, wherein the concentration of the naphthalene oil is 45 to 85 wt%.

6. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to any one of claims 1 to 3, wherein the concentration of the anthracene oil is 55 to 82 wt%.

7. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to any one of claims 1 to 3, wherein the naphthalene content in the wash oil is 40 to 47 wt%.

8. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to any one of claims 1 to 3, wherein the distillation-rectification residue comprises 1-naphthol, 2-naphthol, 1-naphthol-2-naphthol condensate, benzanthracene-7, 12-dione, 1' -binaphthyl, naphthalene sulfonate and an auxiliary agent.

9. The 2-naphthol distillation residue modified water-coal-slurry dispersant according to claim 8, wherein the content of the naphthalene sulfonate is 25 to 30 wt%.

10. The preparation method of the 2-naphthol distillation residue modified coal-water slurry dispersing agent according to any one of claims 1 to 9, which is characterized by comprising the following steps:

1) sulfonation: adding naphthalene oil/anthracene oil/wash oil and distillation-rectification residues into a four-neck flask with a stirrer according to parts by weight, heating to 150 ℃ for melting, dropwise adding concentrated sulfuric acid, controlling the temperature to be between 150 and 160 ℃, and preserving heat for 2-5 hours at the temperature of 155 and 160 ℃ after dropwise adding;

2) hydrolysis: after the sulfonation heat preservation is finished, sampling, detecting acidity, cooling, adding hydrolysis water, and then performing hydrolysis heat preservation for 20-40 min;

3) condensation: after hydrolysis, beginning to drip formaldehyde at the temperature of 100-;

4) neutralizing: and after condensation and heat preservation are finished, adding the rest of water supplement, cooling to 60-70 ℃, then adding liquid sodium hydroxide under stirring, and adjusting the pH value to 7-9 to obtain the product.

Technical Field

The invention relates to a coal water slurry dispersing agent, and particularly relates to a 2-naphthol distillation residue modified coal water slurry dispersing agent and a preparation method thereof.

Background

Since the explosion of oil crisis, coal water slurry is highly regarded as a new oil-substituting fuel in many countries. The coal water slurry is prepared by physically mixing 55-70% of coal powder, 30-45% of water and a small amount of additive, and has good economic, environmental-friendly and energy-saving benefits. The coal water slurry is a solid-liquid two-phase coarse dispersion system, has lower viscosity and better fluidity in normal use, has higher viscosity when in rest, is not easy to form precipitates, and is necessary to add a small amount of chemical additives in the process of preparing the coal water slurry. The additives for pulping mainly comprise a dispersant, a stabilizer and other auxiliary medicaments, wherein the dispersant plays a key role. Since 1982, under the continuous efforts of scientific research personnel, the coal water slurry technology and the application scale of China reach the advanced level in the world. The coal water slurry is used except coal with the highest consumption and cost in the production and application process of the coal water slurry, so that the research on the novel coal water slurry with good dispersity, low cost and good adaptability has a very good prospect and also becomes a necessary research and development direction. At present, the application of the naphthalenesulfonate formaldehyde condensate in the China coal water slurry dispersant market is wider, the research of the naphthalenesulfonate formaldehyde condensate reaches a higher level, the cost is lower than that of similar products abroad, but the problems of narrow range of adapting to coal types and high cost still exist.

2-naphthol, also known as ethyl naphthol, 2-hydroxynaphthalene, beta-hydroxynaphthalene, white glossy flakes or white powder, is an important organic raw material and dye intermediate, is used for producing tobias acid, butyric acid, 2-naphthol-3-formic acid, and is used for producing antioxidant D, antioxidant DNP, other antioxidants, organic pigments, bactericides and the like. The product has low toxicity, can be used as feed preservative, and can be used for fresh-keeping of citrus. The 2-naphthol is mainly prepared by sulfonating, alkali melting to obtain crude phenol and then distilling and refining. The existing sulfonation alkali fusion method is a widely adopted production method at home and abroad.

The residue left after the distillation and rectification of the 2-naphthol mainly comprises high-boiling-point organic matters, a small amount of residual 1-naphthol, 2-naphthol and inorganic salt. The current treatment method is to discharge the high-temperature residue into the stirring cold water under a certain pressure, the residue is solidified into particles after being cooled, then the water is removed, and a part of the waste is sent to relevant units for treatment. At present, the related patents of preparing fuel oil by using distillation residues are also provided, the problem of environmental protection is solved, but the working procedures are complex and the investment required is large when the distillation residue is used. In general, current treatment methods are not economically valuable and may pollute the environment.

The naphthalene oil is coal tar distillate with the distillation range of 210-230 ℃ in the process of preparing industrial naphthalene or refined naphthalene, the wash oil is used for washing out absorption oil of benzene or naphthalene compounds from coal gas and is 230-300 ℃ distillate in coal tar or petroleum, the distillate with the temperature of 280-360 ℃ in coal tar fractionation is called anthracene oil, wherein the naphthalene content is 40-95%, and a small amount of compounds with complex components such as phenols, indole and the like are contained. Because the boiling points are close, the components are complex and difficult to separate and purify, and secondary pollution is caused to the environment.

Disclosure of Invention

The invention aims to recycle 2-naphthol distillation and rectification residues and naphthalene oil/wash oil/anthracene oil, prevent the residues from polluting and damaging the environment and human body, simultaneously carry out any treatment such as other physical and chemical treatments on distillation and rectification, can be directly recycled, and save energy consumption.

The invention also aims to modify the naphthalenesulfonate formaldehyde condensate by utilizing high-boiling-point organic matters, 2-naphthol and other substances in rectification and distillation residues in the 2-naphthol process, and provides a method for synthesizing the coal water slurry dispersant which is environment-friendly, low in cost, large in steric hindrance and good in stability.

The invention particularly provides a 2-naphthol distillation residue modified coal water slurry dispersant which is prepared from the following components in parts by weight: 5-150 parts of distillation-rectification residues, 80-200 parts of naphthalene oil/anthracene oil/wash oil, 300 parts of concentrated sulfuric acid, 60-120 parts of formaldehyde, 315 parts of liquid sodium hydroxide, 0-40 parts of hydrolysis water and 350 parts of water supplement.

As a preferable technical scheme of the invention, the 2-naphthol distillation residue modified coal water slurry dispersing agent is prepared from the following components in parts by weight: 70 parts of distillation-rectification residues, 180 parts of naphthalene oil, 200 parts of concentrated sulfuric acid, 80 parts of formaldehyde, 212 parts of liquid sodium hydroxide, 15 parts of hydrolysis water and 260 parts of water supplement.

As a preferable technical scheme of the invention, the 2-naphthol distillation residue modified coal water slurry dispersing agent is prepared from the following components in parts by weight: 120 parts of distillation-rectification residues, 150 parts of anthracene oil, 235 parts of concentrated sulfuric acid, 95 parts of formaldehyde, 228 parts of liquid sodium hydroxide, 30 parts of hydrolysis water and 300 parts of water supplement.

As a preferable technical scheme of the invention, the concentration of the concentrated sulfuric acid is 98-113 wt%.

As a preferable technical scheme of the invention, the concentration of the naphthalene oil is 45-85 wt%.

According to a preferable technical scheme of the invention, the concentration of the anthracene oil is 55-82 wt%.

As a preferable technical scheme of the invention, the naphthalene content in the wash oil is 40-47 wt%.

As a preferable technical scheme of the invention, the distillation-rectification residue comprises 1-naphthol, 2-naphthol, 1-naphthol-2-naphthol condensate, benzanthracene-7, 12-diketone, 1' -binaphthyl, naphthalene sulfonate and an auxiliary agent.

As a preferable technical scheme of the invention, the content of the naphthalene sulfonate is 25-30 wt%.

The second aspect of the invention provides a preparation method of the 2-naphthol distillation residue modified coal-water slurry dispersing agent, which comprises the following steps:

1) sulfonation: adding naphthalene oil/anthracene oil/wash oil and distillation-rectification residues into a four-neck flask with a stirrer according to parts by weight, heating to 150 ℃ for melting, dropwise adding concentrated sulfuric acid, controlling the dropwise adding temperature to be between 150 and 160 ℃, and preserving heat for 2-5 hours at 155 and 160 ℃ after dropwise adding is finished;

2) hydrolysis: after the sulfonation heat preservation is finished, sampling, detecting acidity, cooling, adding hydrolysis water, and then performing hydrolysis heat preservation for 20-40 min;

3) condensation: after hydrolysis, beginning to drip formaldehyde at the temperature of 100-;

4) neutralizing: and after condensation and heat preservation are finished, adding the rest of water supplement, cooling to 60-70 ℃, then adding liquid sodium hydroxide under stirring, and adjusting the pH value to 7-9 to obtain the product.

The invention has the beneficial effects that: 1. the dinaphthol distillation and rectification waste residues are used for modifying the coal water slurry dispersing agent, active groups such as phenolic hydroxyl groups, high-boiling-point organic matters and the like are introduced to act on coal particles through grafting, the dispersing effect is achieved, meanwhile, the stability of the coal water slurry is enhanced, and a new direction is opened for the research of the coal water slurry dispersing agent.

2. Meanwhile, the invention utilizes the dinaphthol distillation and rectification residues to modify the coal water slurry dispersing agent, avoids resource waste when the residues are directly treated, avoids environmental pollution caused by waste discharge in physical and chemical treatment, and realizes the application of the dinaphthol distillation and rectification residues in the new field.

3. The invention utilizes high boiling point organic matter in the residue to replace partial naphthalene oil/anthracene oil/wash oil/naphthalene, the prepared water-coal-slurry dispersing agent greatly reduces the cost of the dispersing agent, and can act on water-coal-slurry alone to play a good dispersing role under the synergistic effect of lignin, and the dispersing effect, the adaptability and the stability of the product can be greatly improved when the dispersing agent is compounded with other dispersing agents (such as naphthalene sulfonate formaldehyde condensate, sulfamic acid formaldehyde condensate, polycarboxylic acid dispersing agent and the like) according to a certain proportion.

Drawings

FIG. 1 is a FTIR test chart of distillation-rectification residue in this application.

FIG. 2 is a GC-MS test chart of the distillation-rectification residue in the present application.

FIG. 3 is an NMR test chart of a distillation-rectification residue in the present application.

FIG. 4 is an XRD test pattern of distillation-rectification residue ash in the present application.

FIG. 5 is a TGA test plot of distillation-rectification residues herein.

FIG. 6 is a graph showing the results of particle size analysis of the coal-water slurry in example 1.

FIG. 7 is a diagram of a metal product experimental apparatus used in a fluidity experiment.

Detailed Description

The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

The term "prepared from" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The invention provides a 2-naphthol distillation residue modified coal water slurry dispersant which is prepared from the following components in parts by weight: 5-150 parts of distillation-rectification residues, 80-200 parts of naphthalene oil/anthracene oil/wash oil, 300 parts of concentrated sulfuric acid, 60-120 parts of formaldehyde, 315 parts of liquid sodium hydroxide, 0-40 parts of hydrolysis water and 350 parts of water supplement.

In some embodiments, the 2-naphthol distillation residue modified coal water slurry dispersant is prepared from the following components in parts by weight: 70 parts of distillation-rectification residues, 180 parts of naphthalene oil, 200 parts of concentrated sulfuric acid, 80 parts of formaldehyde, 212 parts of liquid sodium hydroxide, 15 parts of hydrolysis water and 260 parts of water supplement.

In some embodiments, the 2-naphthol distillation residue modified coal water slurry dispersant is prepared from the following components in parts by weight: 120 parts of distillation-rectification residues, 150 parts of anthracene oil, 235 parts of concentrated sulfuric acid, 95 parts of formaldehyde, 228 parts of liquid sodium hydroxide, 30 parts of hydrolysis water and 300 parts of water supplement. The hydrolysis water is water used for hydrolyzing the sample and is conventional water.

The concentration of the concentrated sulfuric acid is 98-113 wt%; preferably, the concentration is 103 wt%.

The concentration of the naphthalene oil is 45-85 wt%; preferably, the concentration is 82 wt%. The naphthalene oil used in the comparative test of the examples in the application is a fraction at 230 ℃ of 210 ℃ and 230 ℃ obtained by distilling coal tar, the yield is about 10-13% of the coal tar, and the naphthalene content in the naphthalene oil used in the examples is 40-55%.

The concentration of the anthracene oil is 55-82 wt%; preferably, the concentration is 78 wt%. The anthracene oil used in the comparative tests of the examples of the present application has a naphthalene content of 42-60%.

The naphthalene content in the washing oil is 40-47 wt%.

The liquid sodium hydroxide in the present invention is an aqueous solution of sodium hydroxide. In some embodiments, the liquid sodium hydroxide has a concentration of 30 to 35 wt%; preferably, the concentration is 32 wt%.

The formaldehyde in the invention is an aqueous solution of formaldehyde. In some embodiments, the formaldehyde is at a concentration of 30 to 37 wt%; preferably, the concentration is 35-37 wt%.

The distillation-rectification residue is obtained by distillation and rectification of 2-naphthol produced by Xiao county Wooder chemical technology Co., Ltd, and the distillation-rectification residue is obtained by analysis and comprises the following components: the examined main components of the residue from the distillation of dinaphthol used in the examples include: 4.0 to 5.0 wt% of 1-naphthol (CAS number: 90-15-3), 6.0 to 7.0 wt% of 2-naphthol (CAS number: 135-19-3), 10.0 to 11.0 wt% of 1-naphthol-2-naphthol condensate (CAS number: 611-49-4), 6.0 to 7.0 wt% of N-methylsaccharide (CAS number: 602-09-5), 6 to 7.0 wt% of benzanthracene-7, 12-dione (CAS number: 2498-66-0), 5.0 to 6.0 wt% of naphthalene (CAS number: 91-20-3), 9.0 to 10.0 wt% of 1,1 ' -binaphthyl (CAS number: 604-53-5), 8.0 to 9.0 wt% of 1,1 ' -bi-2-naphthol (CAS number: 602-09-5), 27.0 to 28.0 wt% of naphthalene sulfonate, 1, 2-phtho (CAS number: 1,1 ', 2' -d) furan (CAS number: 207-93-2), 6.0-7.0 wt% and other additives 6.0-10.0 wt%, wherein the additives comprise 8-isoproyl-1, 3-dimethyl-phenanthrene (CAS number: 135886-06-5), 5,6,6 ', 11,12, 12' -Hexahydro-6 ', 12' -methyl-chrysene-5, 11-dione (CAS No.: 111977-22-1), 4H-1-Benzopyran-4-one,2- (3,4-dimethoxyphenyl) -3, 7-dimethoxyxy (CAS number: 17093-86-6), 6-hydroxyanthraon (CAS No.: 37515-51-8).

The distillation-rectification residues used in the examples were sampled and analyzed, and the results of the conventional analysis are shown in FIGS. 1 to 5.

The second aspect of the invention provides a preparation method of the 2-naphthol distillation residue modified coal-water slurry dispersing agent, which comprises the following steps:

1) sulfonation: adding naphthalene oil/anthracene oil/wash oil and distillation-rectification residues into a four-neck flask with a stirrer according to parts by weight, heating to 150 ℃ for melting, dropwise adding concentrated sulfuric acid, controlling the dropwise adding temperature to be between 150 and 160 ℃, and preserving heat for 2-5 hours at 155 and 160 ℃ after dropwise adding is finished;

2) hydrolysis: after the sulfonation heat preservation is finished, sampling, detecting acidity, cooling, adding hydrolysis water, and then performing hydrolysis heat preservation for 20-40 min;

3) condensation: after hydrolysis, beginning to drip formaldehyde at the temperature of 100-;

4) neutralizing: and after condensation and heat preservation are finished, adding the rest of water supplement, cooling to 60-70 ℃, then adding liquid sodium hydroxide under stirring, and adjusting the pH value to 7-9 to obtain the product.

The present invention is further described below by way of examples, but the scope of the present invention is not limited by these examples. Comparative experiments in the following examples naphthalene sulphonate formaldehyde condensates from showa waddy chemical technology ltd are replaced by NX and sodium lignosulphonate on the market, respectively.