阅读说明：本技术 1-氨基蒽醌和dsd酸生产废水的资源化利用方法 (Resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater ) 是由 董翠平 马丽涛 尤健健 杨道顺 李曼 于 2020-06-15 设计创作，主要内容包括：本发明公开了一种1-氨基蒽醌和DSD酸生产废水的资源化利用方法,所述方法包括如下步骤：步骤一,向反应釜中加入所述生产废水、磺化剂、苯酚、水、氢氧化钠,溶解搅拌混合均匀；步骤二,滴加丙酮,进行磺化反应,磺化反应结束后开始滴加甲醛溶液；步骤三,滴加完毕后进行保温；步骤四,保温结束即得混凝土减水剂或者水煤浆分散剂；所述步骤一中废水为1-氨基蒽醌生产废水和DSD酸生产废水中的一种或者两种；对磺化丙酮甲醛缩合物或者氨基磺酸系甲醛缩合物进行接枝改性,增强了减水效果和分散效果；防止其对环境、对人体造成污染与损害,同时可直接循环利用,节省能耗,不会造成二次污染和资源的浪费；降低了减水剂或者分散剂的生产成本。(The invention discloses a resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater, which comprises the following steps: step one, adding the production wastewater, a sulfonating agent, phenol, water and sodium hydroxide into a reaction kettle, and dissolving, stirring and mixing uniformly; step two, dropwise adding acetone to carry out sulfonation reaction, and dropwise adding a formaldehyde solution after the sulfonation reaction is finished; step three, preserving heat after finishing the dropwise adding; step four, obtaining a concrete water reducing agent or a coal water slurry dispersing agent after heat preservation is finished; the wastewater in the first step is one or two of 1-aminoanthraquinone production wastewater and DSD acid production wastewater; the sulfonated acetone-formaldehyde condensate or the sulfamic acid formaldehyde condensate is subjected to graft modification, so that the water reducing effect and the dispersing effect are enhanced; the pollution and damage to the environment and the human body are prevented, and meanwhile, the waste can be directly recycled, so that the energy consumption is saved, and the secondary pollution and the waste of resources are avoided; the production cost of the water reducing agent or the dispersing agent is reduced.)

1. A resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater is characterized by comprising the following steps:

step one, adding the production wastewater, a sulfonating agent, phenol, water and sodium hydroxide into a reaction kettle, and dissolving, stirring and mixing uniformly;

step two, dropwise adding acetone to carry out sulfonation reaction, and dropwise adding a formaldehyde solution after the sulfonation reaction is finished;

step three, preserving heat after finishing the dropwise adding;

step four, obtaining a concrete water reducing agent or a coal water slurry dispersing agent after heat preservation is finished;

and the wastewater in the first step is one or two of 1-aminoanthraquinone production wastewater and DSD acid production wastewater.

2. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that sulfonated acetone formaldehyde condensate or aminosulfonic acid formaldehyde condensate is subjected to graft modification.

3. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that said sulfonating agent is one or more of sodium sulfite, sodium pyrosulfite, sodium bisulfite, sodium sulfanilate, sulfanilic acid, SO 3.

4. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that one or more of sodium hydroxide liquid sodium hydroxide and solid sodium hydroxide are added to make the pH value of the material be 7-10.

5. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that the phenol accounts for 0-10.5% of the total mass of the materials; the acetone accounts for 0-12% of the total mass of the material.

6. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that the ratio of the mass of the formaldehyde solution to the total amount of phenol acetone is 1.4: 1-2.8:1.

7. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that the sulfonation heat preservation time is 0-1.5h, and the temperature is 20-60 ℃.

8. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that the acetone dropping time is 20-50min, and the dropping temperature is 20-56 ℃.

9. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that the formaldehyde dropping time is 1.5-5h, and the temperature after dropping is not more than 96 ℃.

10. The resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater according to claim 1, characterized in that the heat preservation time of the formaldehyde after dripping is 1.5-3h, and the heat preservation temperature is 90-96 ℃.

Technical Field

The invention relates to 1-aminoanthraquinone and DSD acid production wastewater, and particularly relates to a resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater.

Background

The water reducing agent is used as the most used additive of concrete additives, and has a good effect of improving the specific performance of concrete. At present, the naphthalene water reducer is used in China with the largest amount, but compared with a third-generation polycarboxylate water reducer, the naphthalene water reducer, the aliphatic water reducer, the sulfamic acid high-efficiency water reducer and the naphthalene water reducer are used as a second-generation water reducer, and have the defects of poor water reducing and collapse keeping performances due to structural defects of the naphthalene water reducer, but the naphthalene water reducer has the characteristics of high water reducing rate, basically no air entraining, no retardation, relatively low cost, variable polymerization degree, adjustable molecular weight and the like, and is widely applied.

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.

1-aminoanthraquinones are important intermediates in the production of vat, disperse, reactive dyes and anthraquinone-based acid dyes. The 1-aminoanthraquinone is prepared by taking anthraquinone as a raw material and carrying out chemical processes such as nitration, neutralization, refining, reduction and the like. DSD acid, known as 4, 4' -diaminostilbene-disulfonic acid, is also an important dye intermediate, which is used primarily for the manufacture of optical brighteners, direct yellows, and the like. The DSD acid is prepared by using p-nitrotoluene as a raw material through chemical processes of sulfonation, oxidation, condensation, reduction and the like. At present, the raw material utilization rate of the production process of 1-aminoanthraquinone and DSD acid is low, and the wastewater discharged in the production process often contains a large amount of anthraquinone and benzene derivatives, and is dark in color and strong in acid-base property. Most of organic matters in the wastewater have amino, sulfonic acid and other substituent groups, so that the organic matters have strong toxicity to microorganisms. The global demand of 1-aminoanthraquinone and DSD acid is very large, the discharged wastewater is very much, and the wastewater treatment efficiency is low, so that the treatment difficulty is high and the wastewater is difficult to reach the standard.

The main components of the 1-aminoanthraquinone production wastewater are sodium sulfite, 2-sulfonic acid anthraquinone, 2, 6-disulfonic acid anthraquinone and the like, as long as the wastewater is discharged in the process of refining sodium sulfite. The waste water discharged in the production process of DSD acid is mainly filtered liquor after oxidation and condensation, and its main components are sodium sulfite, 2-methyl, 5-nitrobenzenesulfonic acid, 4-dinitrostilbene-2, 2-disulfonic acid. The waste water contains more intermediate byproducts and inorganic salts, mainly polycyclic aromatic compounds and sodium sulfite, is not easy to oxidize and has poor biodegradability, which brings certain difficulty to the waste water treatment. The traditional method for treating the 1-aminoanthraquinone dye wastewater and the DSD acid production wastewater is more. The physical and chemical methods comprise neutralization, coagulating sedimentation, air floatation, sand filtration and the like; chemical precipitation, ozone oxidation, hydrogen peroxide and peroxide oxidation, electrolytic oxidation; biodegradation, and the like.

Disclosure of Invention

The invention aims to recycle the 1-aminoanthraquinone production wastewater and the DSD production wastewater, prevent the wastewater from causing pollution and damage to the environment and human bodies, and simultaneously, the wastewater can be directly recycled without any treatment such as other physical treatment, chemical treatment and the like, thereby saving energy consumption and avoiding secondary pollution and resource waste; the invention aims to utilize sodium sulfite and acetone in the 1-aminoanthraquinone production wastewater and the DSD acid production wastewater to carry out sulfonation reaction, and then obtain aliphatic water reducing agents or water-coal-slurry dispersing agents with different polymerization degrees through formaldehyde condensation, and simultaneously reduce the production cost of the water reducing agents or the dispersing agents; the invention aims to solve the problems that the organic matters such as 2-sulfonic anthraquinone, 2, 6-disulfonic anthraquinone, 2-methyl, 5-nitrobenzenesulfonic acid, 4-dinitrostilbene-2, 2-disulfonic acid and the like in the 1-aminoanthraquinone production wastewater and the DSD acid production wastewater are used as sulfonating agents, acetone and formaldehyde are polymerized, then a sulfonated acetone formaldehyde condensate or an aminosulfonic acid formaldehyde condensate is subjected to graft modification, and new groups are introduced, wherein the hydrophilicity of sulfonic groups and the hydrophobicity of anthraquinone and benzene rings form a stable bridge between cement particles and water or between coal and water, so that the water reducing effect and the dispersing effect are enhanced; the invention aims to utilize organic matters in the 1-aminoanthraquinone production wastewater and the DSD acid production wastewater to generate more heat and gas in the process of burning or gasifying the coal water slurry.

In order to achieve the aim, the invention provides a resource utilization method of the 1-aminoanthraquinone and DSD acid production wastewater, which comprises the following steps: and adding the production wastewater, a sulfonating agent, phenol, water and sodium hydroxide into a reaction kettle, and dissolving, stirring and mixing uniformly. And (3) dropwise adding acetone to carry out sulfonation reaction, beginning dropwise adding a formaldehyde solution after the sulfonation reaction is finished, preserving heat after the dropwise adding is finished, and obtaining the concrete water reducing agent or the water-coal-slurry dispersing agent after the heat preservation is finished.

The wastewater in the invention is one or two of 1-aminoanthraquinone production wastewater and DSD acid production wastewater.

In the invention, organic matters such as 2-sulfonic anthraquinone, 2, 6-disulfonic anthraquinone, 2-methyl, 5-nitrobenzenesulfonic acid, 4-dinitrostilbene-2, 2-disulfonic acid and the like in the 1-aminoanthraquinone production wastewater and the DSD acid production wastewater are used as sulfonating agents to graft and modify a sulfonated acetone formaldehyde condensate or an aminosulfonic acid formaldehyde condensate after acetone and formaldehyde polymerization, wherein the hydrophilicity of sulfonic acid groups and the hydrophobicity of anthraquinone and benzene rings form a stable bridge between cement particles and water or between coal and water, so that the water reducing effect and the dispersing effect are enhanced.

The sulfonating agent in the invention is one or more of sodium sulfite, sodium metabisulfite, sodium bisulfite, sulfanilic acid and SO 3.

The sodium hydroxide in the invention is: one or more of liquid sodium hydroxide and solid sodium hydroxide is added to ensure that the pH value of the material is 7-10.

In the invention, phenol accounts for 0-10.5% of the total mass of the material.

In the invention, the acetone accounts for 0-12% of the total mass of the material.

The ratio of the mass of the formaldehyde solution to the total amount of phenol and acetone in the invention is 1.4: 1-2.8:1.

The sulfonation heat preservation time is 0-1.5h, and the temperature is 20-60 ℃.

The dropping time of the acetone is 20-50min, and the dropping temperature is 20-56 ℃.

The formaldehyde dripping time is 1.5-5h, and the temperature is not more than 96 ℃ after dripping.

The invention has the advantages that the heat preservation time is 1.5-3h after the formaldehyde is dripped, and the heat preservation temperature is 90-96 ℃.

Compared with the prior art, the invention has the beneficial effects that: 1. the invention realizes the reutilization of the 1-aminoanthraquinone and DSD acid production wastewater, prevents the wastewater from causing pollution and damage to the environment and human bodies, does not need to carry out other physical, chemical and other treatments, can be directly recycled, saves energy consumption, has simple production reaction conditions, is easy to control and does not discharge three wastes.

2. According to the invention, the sulfonation reaction is carried out on sodium sulfite and acetone in the 1-aminoanthraquinone production wastewater and the DSD acid production wastewater, and then the water reducing agent or the water-coal-slurry dispersing agent with different polymerization degrees is obtained by controlling the reaction conditions, so that the production cost of the water reducing agent or the dispersing agent is reduced.

3. The invention utilizes the hydrophilicity of sulfonic acid groups of organic matters such as 1-aminoanthraquinone production wastewater and DSD acid production wastewater, such as 2-sulfonic anthraquinone, 2, 6-disulfonic anthraquinone, 2-methyl, 5-nitrobenzenesulfonic acid, 4-dinitrostilbene-2, 2-disulfonic acid and the like, and the hydrophobicity of anthraquinone to form a stable bridge between cement particles and water or between coal and water, thereby enhancing the water reducing effect and the dispersing effect, and being particularly suitable for coal types with high volatile contents when used as a dispersing agent.

4. The invention utilizes organic matters in the 1-aminoanthraquinone production wastewater and the DSD acid production wastewater to generate more heat and gas in the process of burning or gasifying the coal water slurry.

Drawings

FIG. 1 is a graph of the particle size distribution of the present invention for the Hibiscus sabdariffa coal.

FIG. 2 is a truncated cone and circular model of the invention.

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.

In the following examples, aliphatic water reducing agents (hereinafter referred to as "conventional ZFA") and sulfamic acid-based formaldehyde condensates (hereinafter referred to as "conventional AJ") manufactured by Anhuxin environmental protection technologies, Inc. were used for comparative tests.

The concrete paste and slump characteristic detection instrument and the detection method comprise the following steps:

1. the experimental apparatus comprises an NJ-160A cement paste mixer, a glass plate (400 x 400mm, thickness 5mm), a steel ruler (300mm), a scraper, a 50ml beaker and a standard slump bucket. 2. The experimental methods and procedures were as described in GB/T80077-2012 and GB/T50080-2002.

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. experimental apparatus a. truncated cone circular mold: 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, as shown in figure 2. 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: the stability is detected by adopting a rod dropping method, and the required experimental instrument and the detection method are as follows:

an experimental instrument, 150ml beaker, electronic balance, preservative film, 300mm ruler and 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)/hx 100%, hard precipitation rate = (H-H2)/hx 100%.

The method for detecting the granularity of the coal water slurry comprises the following steps:

1. the experimental instrument was an LS100Q laser particle size analyzer.

2. The working principle is as follows: scattering theory of light by particles it is well known that light is a cell wave that interacts with particles as they encounter them during propagation, some of which will deviate from the original direction of travel, called scattering. The working principle of the instrument, namely the laser particle analyzer, comprises a measuring unit, a sample cell, a computer and a printer. The measuring unit is the core of the instrument and is responsible for emission of laser, photoelectric conversion of scattered signals, preprocessing of photoelectric signals and A/D conversion. The circulating sample cell is used for conveying a sample to be measured to a measuring area of the measuring unit. The computer is used for processing the photoelectric signals, converting the energy distribution of scattered light into the particle size distribution of the sample and forming a test report, and the printer is used for outputting a hard copy of the test report, namely printing the test report.

3. Operating procedures

Test unit preheating

The main switch of the instrument power supply is turned on, and the laser power can be stabilized after at least half an hour. If the ambient temperature of the laboratory is low, the preheating time needs to be prolonged appropriately (if the test is repeated, this step can be skipped).

② opening the test software of LS100Q

Step a, controlling a tab-selecting automatic cleaning (the step can be manually operated on a water bath box);

step b, setting the rotating speed of the pump: setting the intensity and time of ultrasound if necessary, adding a proper amount of dispersion medium (usually distilled water) into a 20ml beaker;

step c, turning on a pump (which can also be carried out on a water bath box) in software, measuring an option card, manually setting, and measuring a display window;

step d, selecting a column: selecting test contents in a measurement option window;

step e, materials column: setting optical characteristics, selecting correct sample substance names and dispersing agent names, and inputting test sample numbers or names;

step f, calculating a result: selecting model tab-general-determine;

step g, measuring column: setting pump speed, ultrasonic time and intensity and test content in a measurement tab, and testing a background value before first measurement;

and h, clicking the start of the measurement display window, slowly adding the sample by using a disposable dropper, and starting to measure the sample when the laser shading degree is within a set range (8% -12%).