阅读说明：本技术 一种利用焦化洗油合成水煤浆分散剂的方法 (Method for synthesizing coal water slurry dispersant by using coking wash oil ) 是由 董翠平 马丽涛 彭城 尤健健 杨道顺 于 2019-11-19 设计创作，主要内容包括：本发明提供一种利用焦化洗油合成水煤浆分散剂的方法,涉及水煤浆分散剂技术领域,包括以下步骤：1)将焦化洗油进行磺化处理；2)步骤1)保温结束后降温至120℃,向其中缓慢滴加甲醛,滴毕后继续保温,得A料；3)配制B液：将吊白块加入去离子水中,然后依次加入苯乙烯磺酸钠、3-巯基丙酸、丙烯酸混合均匀,得B液；4)向四口烧瓶中加入PEG200、去离子水,搅拌混合均匀后加入过硫酸铵,搅拌均匀,10min后向四口烧瓶内滴入B液；5)B液滴加完毕后,向其中加入A料,继续反应1-4h；6)步骤5)结束后向其中加入32％液体氢氧化钠继续搅拌反应0.5-1.5h,即得分散剂MO。本避免了焦化洗油直接处理时的资源浪费,实现了焦化洗油在新领域的应用。(The invention provides a method for synthesizing a coal water slurry dispersant by utilizing coking wash oil, which relates to the technical field of the coal water slurry dispersant and comprises the following steps: 1) carrying out sulfonation treatment on the coking wash oil; 2) step 1), cooling to 120 ℃ after heat preservation, slowly dripping formaldehyde into the mixture, and continuing heat preservation after dripping to obtain a material A; 3) preparing a solution B: adding the sodium formaldehyde sulfoxylate into deionized water, and then sequentially adding sodium styrene sulfonate, 3-mercaptopropionic acid and acrylic acid, and uniformly mixing to obtain solution B; 4) adding PEG200 and deionized water into a four-neck flask, stirring and mixing uniformly, adding ammonium persulfate, stirring uniformly, and dripping the solution B into the four-neck flask after 10 min; 5) after the dropwise addition of the solution B is finished, adding the material A into the solution B, and continuously reacting for 1-4 h; 6) and 5) after the step 5) is finished, adding 32% liquid sodium hydroxide into the mixture, and continuously stirring and reacting for 0.5-1.5h to obtain the dispersant MO. The method avoids resource waste when the coking wash oil is directly treated, and realizes the application of the coking wash oil in the new field.)

1. A method for synthesizing a coal water slurry dispersing agent by using coking wash oil is characterized by comprising the following steps:

1) weighing the raw materials in proportion, and sulfonating the weighed coking wash oil, wherein the method comprises the following specific steps: heating the coking wash oil to 150 ℃, dropwise adding 98% concentrated sulfuric acid into the coking wash oil, and preserving heat for 2-4h at 160 ℃ after dropwise adding;

2) step 1), cooling to 120 ℃ after heat preservation, slowly dripping formaldehyde into the mixture for 1-3h, and continuing heat preservation for 2-4h after dripping is finished, wherein the obtained material is marked as material A for later use;

3) preparing a solution B: adding the sodium formaldehyde sulfoxylate into deionized water, and then sequentially adding sodium styrene sulfonate, 3-mercaptopropionic acid and acrylic acid, and uniformly mixing to obtain solution B for later use;

4) adding PEG200 and deionized water into a four-neck flask, stirring and uniformly mixing, adding ammonium persulfate, continuously stirring until the mixture is uniformly mixed, and dripping the solution B into the four-neck flask after 10min, wherein the dripping time of the solution B is 1.5-3.5 h;

5) step 4), after the dropwise addition of the solution B is finished, adding the material A into the solution B, and continuously reacting for 1-4 hours;

6) and 5) after the step 5) is finished, adding 32% liquid sodium hydroxide into the mixture, continuously stirring and reacting for 0.5 to 1.5 hours to obtain the dispersant MO.

2. The method for synthesizing the coal-water slurry dispersant by using the coking wash oil according to claim 1, wherein in the step 1), the raw material components and the use amounts are as follows according to parts by weight: 40-120 parts of coking wash oil, 40-150 parts of 98% concentrated sulfuric acid, 5-30 parts of 32% liquid sodium hydroxide, 10-30 parts of formaldehyde, 1-3 parts of ammonium persulfate, 240 parts of deionized water and 530 parts of sodium hydrosulfite, 0.5-1.5 parts of 3-mercaptopropionic acid, 200200-320 parts of PEG, 1-3 parts of sodium formaldehyde sulfoxylate, 20-40 parts of acrylic acid and 5-10 parts of sodium styrene sulfonate.

3. The method for synthesizing the coal-water slurry dispersant by using the coking wash oil according to claim 2, wherein in the step 1), the raw material components and the use amounts are as follows according to parts by weight: 50 parts of coking wash oil, 60 parts of 98% concentrated sulfuric acid, 10 parts of 32% liquid sodium hydroxide, 15 parts of formaldehyde, 1.8 parts of ammonium persulfate, 450 parts of deionized water, 1.3 parts of 3-mercaptopropionic acid, 200300 parts of PEG, 1.6 parts of sodium formaldehyde sulfoxylate, 35 parts of acrylic acid and 8 parts of sodium styrene sulfonate.

4. The method for synthesizing the coal-water slurry dispersant by using the coking wash oil according to claim 2, wherein in the step 1), the raw material components and the use amounts are as follows according to parts by weight: 100 parts of coking wash oil, 115 parts of 98% concentrated sulfuric acid, 8 parts of 32% liquid sodium hydroxide, 30 parts of formaldehyde, 2 parts of ammonium persulfate, 400 parts of deionized water, 1.5 parts of 3-mercaptopropionic acid, 200280 parts of PEG, 1.8 parts of sodium formaldehyde sulfoxylate, 30 parts of acrylic acid and 7.8 parts of sodium styrene sulfonate.

5. The method for synthesizing the water-coal-slurry dispersant by using the coking wash oil according to claim 1, wherein the amount of the deionized water in the step 3) is 80 to 160 parts.

6. The method for synthesizing the coal-water slurry dispersant by using the coking wash oil as claimed in claim 1, wherein the amount of the deionized water in the step 4) is 160-370 parts.

7. The use of the dispersant prepared by the method for synthesizing the dispersant for coal water slurry by using the coking wash oil according to any one of claims 1 to 6 for dispersing the coal water slurry.

Technical Field

The invention relates to the technical field of coal water slurry dispersants, and particularly relates to a method for synthesizing a coal water slurry dispersant by using coking wash oil.

Background

The coking wash oil is a byproduct of the coking process-a distillate mixture obtained during the processing of coal tar. The washing oil has more complex components and extremely wide application of single component, so that the deep processing of the washing oil to extract precious compounds in the washing oil becomes a development trend of future washing oil utilization, but the depth of domestic washing oil research and utilization is not enough. The deep processing and utilization of the coking washing oil can bring the economic and social benefits into play in the national economic development.

The coal water slurry is produced in the international oil crisis period at the end of the 70 s in the 21 st century, is a high and new technology product for planning to replace petroleum and utilizing coal, and mainly comprises about 60-70% of coal, about 30-40% of water and a small amount of water coal slurry additive, has good fluidity and stability, and has an appearance similar to that of heavy oil. The coal water slurry technology is characterized in that solid coal is converted into liquid coal-based fuel through a physical process, and the liquid coal-based fuel has good combustion characteristics and partial advantages of heavy oil, so that the solid coal-based fuel can be applied to industries such as power generation and the like instead of the heavy oil, and the coal water slurry is a novel clean fuel for replacing oil, which is simple in preparation process, easy to transport and store, safe and reliable in general. Since the advent, coal water slurries have found widespread use in western developed countries. China is a country rich in coal and lean in oil, and along with the acceleration of the industrialization pace of China, the rapid development of the coal water slurry technology, popularization and application, become important means for guaranteeing the energy safety of China and promoting sustainable development. The research of the coal water slurry additive as one of the important raw materials of the coal water slurry technology is bound to become the direction of the research and development of China.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a method for synthesizing a coal water slurry dispersing agent by using coking wash oil, which carries out deep processing on the coking wash oil to synthesize the coal water slurry dispersing agent, avoids resource waste when the coking wash oil is directly treated, and realizes the application of the coking wash oil in the new field.

(II) technical scheme

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

a method for synthesizing a coal water slurry dispersing agent by using coking wash oil comprises the following steps:

1) weighing the raw materials in proportion, and sulfonating the weighed coking wash oil, wherein the method comprises the following specific steps: heating the coking wash oil to 150 ℃, dropwise adding 98% concentrated sulfuric acid into the coking wash oil, and preserving heat for 2-4h at 160 ℃ after dropwise adding;

2) step 1), cooling to 120 ℃ after heat preservation, slowly dripping formaldehyde into the mixture for 1-3h, and continuing heat preservation for 2-4h after dripping is finished, wherein the obtained material is marked as material A for later use;

3) preparing a solution B: adding the sodium formaldehyde sulfoxylate into deionized water, and then sequentially adding sodium styrene sulfonate, 3-mercaptopropionic acid and acrylic acid, and uniformly mixing to obtain solution B for later use;

4) adding PEG200 and deionized water into a four-neck flask, stirring and uniformly mixing, adding ammonium persulfate, continuously stirring until the mixture is uniformly mixed, and dripping the solution B into the four-neck flask after 10min, wherein the dripping time of the solution B is 1.5-3.5 h;

5) step 4), after the dropwise addition of the solution B is finished, adding the material A into the solution B, and continuously reacting for 1-4 hours;

6) and 5) after the step 5) is finished, adding 32% liquid sodium hydroxide into the mixture, continuously stirring and reacting for 0.5 to 1.5 hours to obtain the dispersant MO.

Further, in the step 1), the raw material components and the use amount are as follows according to parts by weight: 40-120 parts of coking wash oil, 40-150 parts of 98% concentrated sulfuric acid, 5-30 parts of 32% liquid sodium hydroxide, 10-30 parts of formaldehyde, 1-3 parts of ammonium persulfate, 240 parts of deionized water and 530 parts of sodium hydrosulfite, 0.5-1.5 parts of 3-mercaptopropionic acid, 200200-320 parts of PEG, 1-3 parts of sodium formaldehyde sulfoxylate, 20-40 parts of acrylic acid and 5-10 parts of sodium styrene sulfonate.

Further, in the step 1), the raw material components and the use amount are as follows according to parts by weight: 50 parts of coking wash oil, 60 parts of 98% concentrated sulfuric acid, 10 parts of 32% liquid sodium hydroxide, 15 parts of formaldehyde, 1.8 parts of ammonium persulfate, 450 parts of deionized water, 1.3 parts of 3-mercaptopropionic acid, 200300 parts of PEG, 1.6 parts of sodium formaldehyde sulfoxylate, 35 parts of acrylic acid and 8 parts of sodium styrene sulfonate.

Further, in the step 1), the raw material components and the use amount are as follows according to parts by weight: 100 parts of coking wash oil, 115 parts of 98% concentrated sulfuric acid, 8 parts of 32% liquid sodium hydroxide, 30 parts of formaldehyde, 2 parts of ammonium persulfate, 400 parts of deionized water, 1.5 parts of 3-mercaptopropionic acid, 200280 parts of PEG, 1.8 parts of sodium formaldehyde sulfoxylate, 30 parts of acrylic acid and 7.8 parts of sodium styrene sulfonate.

Further, in the step 3), the using amount of the deionized water is 80-160 parts.

Further, in the step 4), the amount of the deionized water is 160-370 parts.

The dispersant prepared by the method for synthesizing the coal water slurry dispersant by using the coking wash oil is applied to the field of coal water slurry dispersion.

(III) advantageous effects

The invention provides a method for synthesizing a coal water slurry dispersing agent by using coking wash oil, which has the following beneficial effects:

1. according to the invention, the coking wash oil is subjected to sulfonation treatment and condensation with part of formaldehyde, and then is continuously modified and polymerized with the polycarboxylic acid intermediate product to synthesize the coal water slurry dispersing agent, and the product contains more active groups such as hydroxyl, carboxyl, carbonyl, ester group and the like to act on coal water slurry particles, so that the dispersing effect of the coal water slurry is enhanced, and a new direction is developed for the research of the coal water slurry dispersing agent.

2. Compared with the conventional comb-type coal water slurry dispersing agent, the comb-type coal water slurry dispersing agent has the advantages that the sulfonic group, the naphthylmethyl group and other groups are added, the action mechanism of the comb-type coal water slurry dispersing agent is different from that of the conventional coal water slurry dispersing agent, and the dispersing effect of the dispersing agent is improved.

3. The invention utilizes the coking wash oil to synthesize the coal water slurry dispersant, belongs to the deep processing treatment technology of the coking wash oil, avoids resource waste when the coking wash oil is directly treated, and realizes the application of the coking wash oil in the new field.

4. The invention utilizes the coking wash oil sulfonated condensation product and a carboxylic acid system to modify, and obtains a novel coal water slurry dispersant.

5. The coal water slurry dispersing agent prepared by the invention has low production cost, can act on coal water slurry alone to play a good dispersing role, and if the coal water slurry dispersing agent is compounded with other dispersing agents (such as naphthalene sulfonic acid formaldehyde condensate, aliphatic dispersing agents, sodium lignosulfonate and the like) and soda ash according to a certain proportion for use, the dispersing effect, the adaptability and the stability of the product can be greatly improved compared with the single use.

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.

The coker wash oil used in the present invention is a by-product of a coking plant and has the main components shown in table 1.

Table 1:

composition (I)	Naphthalene	Methylnaphthalene	Dimethylnaphthalenes	Acenaphthene	Naphthalene derivatives
						Content (wt.)	10-15％	20-25％	12-27％	10-20％	5-10％

In the following examples, a naphthalene sulfonate formaldehyde condensate produced by Anhuxin environmental protection technology, Inc. was used for comparison, and NX was used in place of the condensate.

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 ① was conducted by turning on the power supply of the experimental instrument, adjusting the level and auto-zero-ing ② the same amount of sample was placed in a 150ml beaker to ensure the temperature and quality of the sample measured, the beaker was placed under the instrument with the rotor in the sample until the graduation mark on the rotor, the start key was pressed to start the test ③ the viscosity of the sample was measured with the 62# rotor at a speed of 20 shear rate.

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 of the metal product is smooth and has no seam; b. glass plates (400X 400mm, thickness 5 mm); c. straight steel rule, (300mm) d.

2. The experimental steps include ① placing the glass plate in a horizontal position, wetting the surface of the glass plate, the truncated cone round mold, the stirrer and the stirring pot with wet cloth without water stain, ② placing the truncated cone round mold in the center of the glass plate and covering with wet cloth for standby, ③ quickly injecting the coal water slurry into the truncated cone round mold, scraping with a scraper, vertically lifting the truncated cone round mold until the coal water slurry flows on the glass plate until the coal water slurry does not flow, measuring the maximum diameter of the flowing part in two mutually perpendicular directions with a ruler, and taking the average value 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:

an experimental instrument: 150ml beaker, electronic balance, preservative film, 300mm ruler and timer.

The experimental steps are as follows: 150g of the coal water slurry was weighed into a 150ml beaker, completely sealed with a sealing film, left to stand at room temperature, and the depths (H1 and H2) of 10X 200mm glass rods at 10s for 5 minutes were measured within 24 hours while the actual depths (H) were measured to calculate the soft precipitation rate and the hard precipitation rate in accordance with the following equation. Soft precipitation rate (H-H1)/hx 100%, and hard precipitation rate (H-H2)/hx 100%.