阅读说明：本技术 一种含酚废水合成分散剂的方法 (Method for synthesizing dispersing agent from phenol-containing wastewater ) 是由 董翠平 马丽涛 尤健健 杨道顺 邢凯 刘子恒 于 2020-11-03 设计创作，主要内容包括：本发明提供了一种含酚废水合成分散剂的方法,包括以下步骤：(1)称取以下质量份的原料：含酚废水50-400份、磺化剂18-100份、对氨基苯磺酸钠50-180份、苯酚30-105份、液体氢氧化钠溶液20-80份、水150-400份、甲醛溶液160-280份、丙酮10-100份；(2)将含酚废水、磺化剂、对氨基苯磺酸钠、液体氢氧化钠溶液以及部分水搅拌混合均匀；(3)然后开始缓慢滴加丙酮,滴加完毕后继续磺化；结束后,加热至55-60℃开始加入苯酚,搅拌混合均匀后开始缓慢滴加甲醛溶液；(4)滴加完毕后继续升温至90-95℃,保温2-4h,保温结束后降温至70℃,加入剩余量水。本发明减轻了生产苯酚、丙酮过程中精制过程废水处理的难题,降低了分散剂的成本,分散剂适应性广、分散性好。(The invention provides a method for synthesizing a dispersing agent from phenol-containing wastewater, which comprises the following steps: (1) weighing the following raw materials in parts by mass: 50-400 parts of phenol-containing wastewater, 18-100 parts of sulfonating agent, 50-180 parts of sodium sulfanilate, 30-105 parts of phenol, 20-80 parts of liquid sodium hydroxide solution, 400 parts of water, 160 parts of formaldehyde solution and 280 parts of acetone; (2) stirring and mixing the phenol-containing wastewater, a sulfonating agent, sodium sulfanilate, a liquid sodium hydroxide solution and part of water uniformly; (3) then slowly dripping acetone, and continuing sulfonation after dripping is finished; after the reaction is finished, heating to 55-60 ℃, adding phenol, stirring and mixing uniformly, and then slowly dropwise adding a formaldehyde solution; (4) after the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2-4h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest water is added. The invention reduces the problem of wastewater treatment in the refining process in the process of producing phenol and acetone, reduces the cost of the dispersant, and has wide adaptability and good dispersibility.)

1. A method for synthesizing a dispersing agent from phenol-containing wastewater is characterized by comprising the following steps:

(1) weighing the following raw materials in parts by mass: 50-400 parts of phenol-containing wastewater, 18-100 parts of sulfonating agent, 50-180 parts of sodium sulfanilate, 30-105 parts of phenol, 20-80 parts of liquid sodium hydroxide, 400 parts of water, 160 parts of formaldehyde solution and 280 parts of acetone;

(2) stirring and uniformly mixing the phenol-containing wastewater, the sulfonating agent, the sodium sulfanilate, the liquid sodium hydroxide and part of water in parts by mass;

(3) then slowly dripping acetone for 15-30min, and continuing sulfonating for 30-35min after dripping; after the sulfonation is finished, heating to 55-60 ℃, adding phenol in parts by mass, stirring uniformly, and then slowly dropwise adding a formaldehyde solution for 2-5h, wherein the temperature is controlled at 60-85 ℃ in the dropwise adding process;

(4) after the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2-4h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest water is added.

2. The method for synthesizing the dispersing agent from the phenolic wastewater as claimed in claim 1, wherein in the step (1), the following raw materials are weighed according to parts by weight: 300 parts of phenol-containing wastewater, 40 parts of sulfonating agent, 105 parts of sodium sulfanilate, 80 parts of phenol, 25 parts of liquid sodium hydroxide, 200 parts of water, 192 parts of formaldehyde solution and 30 parts of acetone.

3. The method for synthesizing the dispersing agent from the phenolic wastewater as claimed in claim 1, wherein in the step (1), the following raw materials are weighed according to parts by weight: 200 parts of phenol-containing wastewater, 30 parts of sulfonating agent, 120 parts of sodium sulfanilate, 85 parts of phenol, 25 parts of liquid sodium hydroxide, 250 parts of water, 180 parts of formaldehyde solution and 28 parts of acetone.

4. The method for synthesizing the dispersant from the phenol-containing wastewater according to claim 1, wherein the sulfonating agent is at least one of sodium sulfite, sodium metabisulfite and sodium bisulfite.

5. The method for synthesizing the dispersing agent for the phenolic wastewater as claimed in claim 1, wherein the mass fraction of the liquid sodium hydroxide is 32%.

6. The method for synthesizing the dispersing agent by using the phenolic wastewater as claimed in claim 1, wherein the mass fraction of the formaldehyde solution is 35-37%.

7. The method for synthesizing a dispersant according to the phenolic wastewater of claim 1, wherein in the step (3), the phenol is previously melted in a water bath at 80 to 90 ℃.

Technical Field

The invention relates to the technical field of dispersing agents, and particularly relates to a method for synthesizing a dispersing agent from phenol-containing wastewater.

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.

The water reducing agent is used as the most one of concrete admixtures and is also one of dispersing agents, so that the water consumption in concrete admixtures can be reduced, and the water reducing agent has a good effect on improving the concrete performance. At present, the three-generation water reducing agent is researched and produced at home and abroad, the first generation is a common water reducing agent, the aliphatic water reducing agent (sulfonated acetone-formaldehyde condensate), the sulfamic acid high-efficiency water reducing agent (sulfamic acid-formaldehyde condensate) and the naphthalene water reducing agent (naphthalene sulfonate-formaldehyde condensate) are used as the second generation high-efficiency water reducing agent, and compared with the third generation which is a polycarboxylic acid high-performance water reducing agent, the water reducing and collapse keeping performances of the second generation high-efficiency water reducing agent are much poorer due to the defects of the structure of the second generation high-efficiency water reducing agent, but the naphthalene water reducing agent, the aliphatic water reducing agent and the sulfamic acid high-efficiency water reducing agent have wide raw material sources.

Phenol and acetone are important basic organic synthesis raw materials in the chemical industry, and downstream products of phenol relate to a plurality of fields and have wide industrial application. The production of phenol has originated from the extraction of natural phenol from coal tar, and since the use of phenol-formaldehyde resins has been increasingly developed, the demand for phenol has increased, thus leading to a process for synthesizing phenol by the sulfonation alkali fusion process. However, the method has complex reaction and backward process, and needs to consume a large amount of sodium hydroxide and sulfuric acid, so that the production cost of phenol is high; meanwhile, a large amount of sulfur dioxide and sodium sulfite are produced as byproducts, which cause serious corrosion and pollution and are basically eliminated. Subsequently, chlorination process, Raschig process, cyclohexane process, toluene oxidation process, and cumene process, etc. have appeared in succession. Among the above methods, the cumene method is most competitive, and the process steps are as follows: benzene and propylene are decomposed into phenol and acetone by cumene hydroperoxide under the action of a catalyst. The cumene method is characterized in that the phenol is produced and the acetone is simultaneously produced. The cumene process is also currently the primary process for the production of acetone.

The isopropyl benzene method has the outstanding advantages of low product cost, strong market competitiveness and the like because two products are produced by the same device. But later development of the process may be affected by-products. The disadvantages of this method are: firstly, the equipment is more, the flow is long, and the corrosivity is large. Because the raw materials and the products are subjected to three chemical reaction procedures, each reaction product is subjected to a separation and refining process. Secondly, the number of byproducts is extremely large, and in the production process, the byproducts exist in all three reactions, and about 100kg of tar is discharged every 1t of phenol produced. Thirdly, the device discharges large amounts of waste water, waste gas and waste residues, and has high treatment requirements and great difficulty.

In the process of refining phenol and acetone, a large amount of wastewater is generated, and the wastewater mainly contains organic substances such as acetone, acetophenone, cumene, alpha-methyl styrene (AMS), cumylphenol, phenol, 2-methylbenzofuran (2-MBF), alpha-methyl styrene dimer and the like, and the composition of the components is complex and the processing is difficult.

Disclosure of Invention

The invention provides a method for synthesizing a dispersing agent from phenol-containing wastewater, which reduces the problem of wastewater treatment in the refining process in the process of producing phenol and acetone, reduces the cost of the dispersing agent, and has wide adaptability and good dispersibility.

In order to achieve the purpose, the invention is realized by the following technical scheme:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by mass: 50-400 parts of phenol-containing wastewater, 18-100 parts of sulfonating agent, 50-180 parts of sodium sulfanilate, 30-105 parts of phenol, 20-80 parts of liquid sodium hydroxide, 400 parts of water, 160 parts of formaldehyde solution and 280 parts of acetone;

(2) stirring and uniformly mixing the phenol-containing wastewater, the sulfonating agent, the sodium sulfanilate, the liquid sodium hydroxide and part of water in parts by mass;

(3) then slowly dripping acetone for 15-30min, and continuing sulfonating for 30-35min after dripping; after the sulfonation is finished, heating to 55-60 ℃, adding phenol in parts by mass, stirring uniformly, and then slowly dropwise adding a formaldehyde solution for 2-5h, wherein the temperature is controlled at 60-85 ℃ in the dropwise adding process;

(4) after the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2-4h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest water is added.

Preferably, in the step (1), the following raw materials are weighed in parts by weight: 300 parts of phenol-containing wastewater, 40 parts of sulfonating agent, 105 parts of sodium sulfanilate, 80 parts of phenol, 25 parts of liquid sodium hydroxide, 200 parts of water, 192 parts of formaldehyde solution and 30 parts of acetone.

Preferably, in the step (1), the following raw materials are weighed in parts by weight: 200 parts of phenol-containing wastewater, 30 parts of sulfonating agent, 120 parts of sodium sulfanilate, 85 parts of phenol, 25 parts of liquid sodium hydroxide, 250 parts of water, 180 parts of formaldehyde solution and 28 parts of acetone.

Preferably, the sulfonating agent is at least one of sodium sulfite, sodium metabisulfite and sodium bisulfite.

Preferably, the mass fraction of the liquid sodium hydroxide is 32%.

Preferably, the mass fraction of the formaldehyde solution is 35-37%.

Preferably, in step (3), the phenol is melted in advance in a water bath at 80 to 90 ℃.

The invention has the beneficial effects that:

1. the invention realizes the reutilization of the wastewater in the refining process of preparing phenol and acetone by the isopropyl benzene method, prevents the wastewater from polluting and damaging the environment and human body, does not need to carry out other physical, chemical and other treatments, can be directly recycled, saves energy consumption and reduces the problem of wastewater treatment in the refining process in the process of producing phenol and acetone.

2. The invention utilizes phenol and acetone in the wastewater as raw materials for synthesizing the coal water slurry dispersing agent, thereby reducing the cost of the dispersing agent.

3. According to the invention, AMS, 2-MBF, cumylphenol, cumene and acetophenone in the wastewater are firstly sulfonated and condensed, then the coal water slurry dispersing agent is modified, and a benzene ring, isopropyl, methyl and 2-methyl styrene polymeric structure, more sulfonic groups and other active groups are introduced to the molecular chain of the coal water slurry dispersing agent, so that the coal water slurry dispersing agent can be compatible with naphthalene, benzene, hydrocarbon and various derivatives thereof in coal similarly, the oleophylic capability and the hydrophilic effect are increased, and the dispersing agent with wide adaptability and better dispersibility is provided.

4. The invention utilizes the fact that heavy components such as dimer and the like in the wastewater are dissolved in the dispersant, increases heat energy in the gasification and combustion processes of the coal water slurry, and does not introduce other impurities to cause pollution.

5. The invention carries out graft modification on the sulfamic acid formaldehyde condensate and the sulfonated acetone formaldehyde condensate to synthesize the dispersant containing more active groups such as phenolic hydroxyl, benzene ring, carbonyl, amino, alkyl, sulfonic group and the like, and the dispersibility, the stability and the adaptability of the dispersant are improved.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all 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.

Example 1:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by mass: 300 parts of phenol-containing wastewater, 40 parts of sodium sulfite (with the purity of 90%), 105 parts of sodium sulfanilate, 80 parts of phenol, 25 parts of liquid sodium hydroxide (with the mass fraction of 32%), 200 parts of water, 192 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 30 parts of acetone.

(2) And stirring and mixing the phenol-containing wastewater, the sodium sulfite, the sodium sulfanilate, the liquid sodium hydroxide and 100 parts of water uniformly.

(3) Then slowly dripping acetone for 30min, and continuing to sulfonate for 30min after dripping; after the sulfonation is finished, heating to 60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding a formaldehyde solution for 2.5h, wherein the temperature is controlled to be 80-85 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously raised to 90-95 ℃, the temperature is kept for 2.5h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest 100 parts of water are added.

Example 2:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by mass: 200 parts of phenol-containing wastewater, 30 parts of sodium sulfite (with the purity of 90%), 120 parts of sodium sulfanilate, 85 parts of phenol, 25 parts of liquid sodium hydroxide (with the mass fraction of 32%), 250 parts of water, 180 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 28 parts of acetone.

(2) And stirring and mixing the phenol-containing wastewater, sodium sulfite, sodium sulfanilate, liquid sodium hydroxide and 150 parts of water uniformly.

(3) Then slowly dripping acetone for 0min, and continuing to sulfonate for 30min after dripping; after the sulfonation is finished, heating to 60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding a formaldehyde solution, wherein the dropwise adding time is about 2 hours, and the temperature is controlled to be 80-85 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 3h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest 100 parts of water are added.

Example 3:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by weight: 100 parts of phenol-containing wastewater, 20 parts of sodium sulfite (with the purity of 90%), 132 parts of sodium sulfanilate, 90 parts of phenol, 30 parts of liquid sodium hydroxide (with the mass fraction of 32%), 350 parts of water, 180 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 18 parts of acetone.

(2) And stirring and mixing the phenol-containing wastewater, sodium sulfite, sodium sulfanilate, liquid sodium hydroxide and 250 parts of water uniformly.

(3) Then slowly dripping acetone for 30min, and continuing to sulfonate for 30min after dripping; after the sulfonation is finished, heating to 60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding a formaldehyde solution, wherein the dropwise adding time is about 3 hours, and the temperature is controlled to be 60-65 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest 100 parts of water are added.

Example 4:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by weight: 60 parts of phenol-containing wastewater, 18 parts of sodium sulfite (with the purity of 90%), 136 parts of sodium sulfanilate, 92 parts of phenol, 32 parts of liquid sodium hydroxide (with the mass fraction of 32%), 400 parts of water, 180 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 16 parts of acetone.

(2) And stirring and mixing the phenol-containing wastewater, sodium sulfite, sodium sulfanilate, liquid sodium hydroxide and 300 parts of water uniformly.

(3) Then slowly dripping acetone for 20min, and continuing to sulfonate for 30min after dripping is finished; after the sulfonation is finished, heating to 55 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding a formaldehyde solution, wherein the dropwise adding time is about 3 hours, and the temperature is controlled to be 65-70 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 4h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest 100 parts of water are added.

Example 5:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by weight: 100 parts of phenol-containing wastewater, 50 parts of sodium sulfite (with the purity of 90%), 82 parts of sodium sulfanilate, 86 parts of phenol, 26 parts of liquid sodium hydroxide (with the mass fraction of 32%), 350 parts of water, 210 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 30 parts of acetone.

(2) And stirring and mixing the phenol-containing wastewater, sodium sulfite, sodium sulfanilate, liquid sodium hydroxide and 250 parts of water uniformly.

(3) Then slowly dripping acetone for 15-30min, and continuing sulfonation for 30min after dripping; after the sulfonation is finished, heating to 55-60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding a formaldehyde solution for about 2-5h, wherein the temperature is controlled to be 80-85 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2-4h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest 100 parts of water are added.

Example 6:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by weight: 400 parts of phenol-containing wastewater, 100 parts of sodium sulfite (with the purity of 90%), 50 parts of sodium sulfanilate, 30 parts of phenol, 30 parts of liquid sodium hydroxide (with the mass fraction of 32%), 260 parts of water, 230 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 72 parts of acetone.

(2) And stirring and mixing the phenol-containing wastewater, sodium sulfite, sodium sulfanilate, liquid sodium hydroxide and 160 parts of water uniformly.

(3) Then slowly dripping acetone for 30min, and continuing to sulfonate for 30min after dripping; after the sulfonation is finished, heating to 60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding the formaldehyde solution, wherein the dropwise adding time is about 2.5h, and the temperature is controlled at 75-80 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest 100 parts of water are added.

Example 7:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by weight: 200 parts of phenol-containing wastewater, 30 parts of sodium metabisulfite (with the purity of 98%), 102 parts of sodium sulfanilate, 80 parts of phenol, 62 parts of liquid sodium hydroxide (with the mass fraction of 32%), 200 parts of water, 190 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 28.6 parts of acetone.

(2) And uniformly stirring and mixing the phenol-containing wastewater, sodium metabisulfite, sodium sulfanilate, liquid sodium hydroxide and 100 parts of water in parts by mass.

(3) Then slowly dripping acetone for 30min, and continuing to sulfonate for 30min after dripping; after the sulfonation is finished, heating to 60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding a formaldehyde solution, wherein the dropwise adding time is about 3 hours, and the temperature is controlled at 75-80 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2h, the temperature is reduced to 70 ℃ after the temperature is kept, and the rest 100 parts of water are added.

Comparative example 1:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by weight: 200 parts of phenol-containing wastewater, 10 parts of sodium sulfite (with the purity of 90%), 112 parts of sodium sulfanilate, 90 parts of phenol, 30 parts of liquid sodium hydroxide (with the mass fraction of 32%), 220 parts of water, 250 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 25 parts of acetone.

(2) And uniformly stirring and mixing the phenol-containing wastewater, the sulfonating agent, the sodium sulfanilate, the liquid sodium hydroxide and 120 parts of water in parts by mass.

(3) Then slowly dripping acetone for 30min, and continuing to sulfonate for 30min after dripping; after the sulfonation is finished, heating to 60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding the formaldehyde solution, wherein the dropwise adding time is about 2 hours, and the temperature is controlled at 75-80 ℃ in the dropwise adding process.

(4) After the dropwise addition, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 2h, and the materials begin to gel after the temperature is kept for 1 h.

Comparative example 2:

a method for synthesizing a dispersing agent from phenol-containing wastewater comprises the following steps:

(1) weighing the following raw materials in parts by weight: 300 parts of phenol-containing wastewater, 10 parts of sodium sulfite (with the purity of 90%), 132 parts of sodium sulfanilate, 90 parts of phenol, 40 parts of liquid sodium hydroxide (with the mass fraction of 32%), 200 parts of water, 230 parts of formaldehyde solution (with the mass fraction of 35% -37%) and 15 parts of acetone.

(2) And stirring and mixing the phenol-containing wastewater, the sodium sulfite, the sodium sulfanilate, the liquid sodium hydroxide and 100 parts of water uniformly.

(3) Then slowly dripping acetone for 30min, and continuing to sulfonate for 30min after dripping; after the sulfonation is finished, heating to 60 ℃, adding phenol in parts by mass (the phenol is melted in a water bath at 80-90 ℃ in advance), stirring and mixing uniformly, and then slowly dropwise adding the formaldehyde solution, wherein the dropwise adding time is about 2 hours, and the temperature is controlled at 75-80 ℃ in the dropwise adding process.

(4) After the dripping is finished, the temperature is continuously increased to 90-95 ℃, the temperature is kept for 3h, the temperature is reduced to 70 ℃ after the temperature is kept for 30min, and the gel begins to appear.

In comparative examples 1 and 2, the reason for gelation was that the sulfonating agent sodium sulfite was small, but the amount of formaldehyde was large, so that gelation occurred easily

In the examples of the present invention, a formaldehyde condensate of sulfamic acid (hereinafter, referred to as "AJ") produced by Anhuxin environmental protection science and technology Co., Ltd., a formaldehyde condensate of naphthalene sulfonic acid (hereinafter, referred to as "NX") and a dispersant of lignin sulfonate (hereinafter, referred to as "MA") and a formaldehyde condensate of sulfonated acetone (hereinafter, referred to as "fas-1") were used for comparison.

The instrument and the detection method for detecting the characteristics of the coal water slurry are as follows:

1. the experimental apparatus is a Brookield Bohler fly DV1 viscometer, a 150ml beaker, and a halogen moisture meter, USA.

2. The experimental procedure is that the power supply of the experimental instrument is switched on, the level is adjusted and the zero is automatically adjusted. And secondly, putting the same amount of sample in a 150ml beaker to ensure the temperature and the quality of the measured sample. The beaker is placed under the instrument, the rotor is brought into the sample until the scale mark on the rotor, and the start key is pressed to start the test. Measuring the viscosity of the sample by using a 62# rotor at the speed of 20 parts of the shearing speed. The viscosity comparison must be carried out under the same instrument, rotor, speed, vessel, temperature and test time.

The experimental instrument and the detection method used for the fluidity experiment are as follows:

1. an experimental instrument:

a. truncated cone circular die: the diameter of the upper opening is 36mm, the diameter of the lower opening is 60mm, the height is 60mm, and the inner wall is smooth and seamless.

b. Glass plates (400X 400mm, thickness 5 mm); c. straight steel rule, (300mm) d.

2. The experimental steps are as follows: firstly, the glass plate is placed in a horizontal position, and the surface of the glass plate, the truncated cone round die, the stirrer and the stirring pot are wetted by wet cloth without water stain. And secondly, placing the truncated cone round die in the center of the glass plate and covering the truncated cone round die with wet cloth for later use. Thirdly, the coal water slurry is quickly injected into the truncated cone circular mold, the truncated cone circular mold is scraped by a scraper, the coal water slurry is lifted vertically to flow on the glass plate until the coal water slurry does not flow, the maximum diameters of two mutually vertical directions of the flowing part are measured by a ruler, and the average value is taken as the fluidity of the coal water slurry.

3. And (3) stability testing, namely testing the stability by adopting a rod dropping method, wherein the required experimental apparatus and the detection method are as follows:

experimental apparatus, 150ml beaker, electronic balance, preservative film, 300mm ruler, timer.

Experimental procedure 150g of coal water slurry was weighed into a 150ml beaker, completely sealed with a sealing film, left at room temperature, and the depth (H1 and H2) of a 10 × 200mm glass rod was measured at 10s for 5 minutes and the actual depth (H) was measured simultaneously over 24 hours to calculate the soft precipitation rate and the hard precipitation rate according to the following equation. Soft precipitation rate (H-H1)/Hx100%, and hard precipitation rate (H-H2)/Hx100%

According to the relevant regulations of the water reducing agent in GB 8076-2008 concrete admixture, the slump of the concrete mixed with the water reducing agent prepared in the embodiment of the invention and AJ and fas-1 during the machine-out process, as well as the slump of the concrete after 10min (T10), 20min (T20), 30min (T30), 40min (T40), 50min (T50) and 60min (T60) are measured. The experiment adopts honest cement, and the mixing amount of the water reducing agent is 0.85 percent (folded and fixed) of the weight of the cement. Specific detection results are shown in table 1.

Table 1:

as can be seen from Table 1, the dispersant obtained by the invention can be used in concrete as a water reducing agent, and has good water reducing and collapse keeping effects.

The results of each group of experiments were analyzed by selecting three coal samples as coal blends of shenmug coal, wuqi tukeke coal, sammonte coal, xinjiang coal and naughty coal. The coal quality characteristics and the results are shown in tables 2-4.

Table 2:

table 3:

table 4:

as shown in tables 2-4, the dispersants with various ratios obtained in the examples have better dispersibility, improved adaptability, stability and dispersibility compared with the conventional NX and MA, consume a large amount of phenol-containing wastewater in the process, and are worthy of popularization.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.