CN112028528A

CN112028528A - Resource utilization method of 1-aminoanthraquinone production wastewater

Info

Publication number: CN112028528A
Application number: CN202010541427.8A
Authority: CN
Inventors: 马丽涛; 董翠平; 尤健健; 杨道顺; 李曼; 乔琼琼
Original assignee: Anhui Xin Solid Environmental Co ltd
Current assignee: Anhui Xin Solid Environmental Co ltd
Priority date: 2020-06-15
Filing date: 2020-06-15
Publication date: 2020-12-04

Abstract

The invention discloses a resource utilization method of 1-aminoanthraquinone 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 rest after the reaction with acetone and the molecules which participate in the primary polymerization with formaldehyde are grafted and copolymerized with the sodium lignosulphonate together to obtain a mixture containing more active groups; hydrophilic groups such as sulfonic groups, hydroxyl groups and phenolic hydroxyl groups, hydrophobic groups such as anthraquinone, benzene rings and methyl groups, and active groups in the sodium lignosulphonate act simultaneously, so that the water reducing effect and the dispersing effect are enhanced, and the production cost of the water reducing agent or the dispersing agent is reduced.

Description

Resource utilization method of 1-aminoanthraquinone production wastewater

Technical Field

The invention relates to 1-aminoanthraquinone, in particular to a resource utilization method of 1-aminoanthraquinone 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.

The sodium lignosulfonate is a natural high molecular polymer, has certain dispersibility, has different degrees of dispersibility due to different molecular weights and functional groups, is a surface active substance, and can be adsorbed on the surfaces of various solid substances. At present, a great deal of research and application are carried out at home and abroad on the application of the sodium lignosulphonate in the industries of building admixtures, chemical engineering, pesticides, coal water slurry dispersing agents, dyes and the like. In the synthesis and performance research of the sodium lignosulfonate grafted aliphatic superplasticizer published by Marigo, Paohai, Liuxing, Wanghao rain, Liuji and Dongliping, the proposal is that sodium lignosulfonate (sodium lignosulfonate) is introduced into the traditional aliphatic superplasticizer for graft copolymerization to synthesize the aliphatic superplasticizer containing a sodium lignosulfonate structure, and the aliphatic superplasticizer has obvious advantages in both cost and performance. The applicant finds that the 1-aminoanthraquinone or DSD acid production wastewater is used for modifying an aminosulfonic acid formaldehyde condensate or a sulfonated acetone formaldehyde condensate, so that the water reducing rate of a water reducing agent of the amino sulfonic acid formaldehyde condensate or the sulfonated acetone formaldehyde condensate can be increased, and the water reducing agent can be used as a dispersing agent of the coal water slurry. However, the applicant finds that when the product is applied to a concrete water reducing agent, the gas content is low and the freezing resistance is poor; when the coal water slurry is used in the field of coal water slurry, the adaptability of the coal water slurry to coal is not ideal.

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 third purpose of the invention is to utilize 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 and sulfonating agents to carry out graft copolymerization on the residual part after the reaction with acetone and molecules participating in preliminary polymerization with formaldehyde and the sodium lignosulphonate, so as to obtain a new product containing more active groups. Hydrophilic groups such as sulfonic acid group, hydroxyl group and phenolic hydroxyl group, hydrophobic groups such as anthraquinone, benzene ring and methyl group and active groups in the sodium lignosulphonate act simultaneously, a stable bridge is formed between cement particles and water or between coal and water, and 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; the fifth purpose of the invention is to graft and modify the product by adding the sodium lignosulphonate, so that the air entraining effect of the product is improved, and when the modified lignosulphonate is applied to the coal water slurry dispersant, more active groups are introduced, so that the modified lignosulphonate can be better matched with coal according to the similarity and intermiscibility principle, and the adaptability and stability of the modified lignosulphonate to the coal are better improved.

In order to realize the aim, the invention provides a resource utilization method of 1-aminoanthraquinone 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 for a period of time after the dropwise adding is finished, adding the wood sodium, continuing preserving heat, 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 and sulfonating agents are subjected to graft copolymerization with residual parts after reaction with acetone and molecules which participate in preliminary polymerization with formaldehyde and sodium lignosulfonate to obtain a new product containing more active groups. Hydrophilic groups such as sulfonic acid group, hydroxyl group and phenolic hydroxyl group, hydrophobic groups such as anthraquinone, benzene ring and methyl group and active groups in the sodium lignosulphonate act simultaneously, a stable bridge is formed between cement particles and water or between coal and water, and the water reducing effect and the dispersing effect are enhanced.

In the invention, the sodium lignosulphonate can be one or two of solid or liquid, and the pure sodium lignosulphonate accounts for 1-30% of the total mass of the material.

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: 1-3:1.

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 1.5-5h 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 2-sulfonic acid anthraquinone, 2, 6-disulfonic acid anthraquinone, 2-methyl, 5-nitrobenzenesulfonic acid, 4-dinitrostilbene-2, 2-disulfonic acid and other organic sulfonic hydrophilic groups, anthraquinone hydrophobic groups and active groups in sodium lignosulphonate in 1-aminoanthraquinone production wastewater and DSD acid production wastewater to form a stable bridge between cement particles and water or between coal and water in a grafting modification mode, thereby enhancing the water reducing effect and the dispersing effect. 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. 5. When the product is used as a concrete water reducing agent, the gas content of the product can be increased, and the frost resistance of the product can be enhanced; the dispersant can be used for the coal water slurry, and the adaptability and the stability of the dispersant can be improved.

Drawings

FIG. 1 is a graph showing the particle size distribution of the Shenmu coal in example 6 of the present invention.

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 instrument and the detection method for the characteristics of concrete paste and slump 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. Concrete net slurry and slump detection method and steps are detected according to GB/T80077-2012 and GB/T50080-2002

3. The concrete gas content detection instrument is a concrete gas content determinator, and the detection method comprises the following steps:

step 1) firstly measuring the air content Ag of the aggregate (sand and stone materials are weighed according to the proportion of sand and stone in the mixture ratio and the proportion of the volume of an air content barrel to 1 cubic meter); step 2) measuring the gas content of the concrete: (1) filling concrete into the barrel in three layers, inserting the right edge of each layer towards the center for 25 times, and knocking the outer wall of the barrel by a rubber hammer for 10-15 times; (2) leveling by a scraper; (3) installing the instrument, opening the water discharging and feeding valve, injecting water (until no bubbles exist in the water discharged from the water discharging port), closing the water discharging valve, and then closing the water feeding valve; (4) inflating, responding to pressure, and pressing an operation valve to obtain data A0; and 3) gas content A = A0-Ag in the concrete.

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 steps are as follows: firstly, a power supply of the experimental instrument is connected, and 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 procedure is that 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 the 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)/H × 100%, and hard precipitation rate = (H-H2)/H × 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 environmental temperature of the laboratory is low, the preheating time needs to be prolonged properly. (if repeat test, this step can be skipped)

② opening the test software of LS100Q

a, controlling a tab-selecting automatic cleaning (the step can be manually operated on a water bath box); 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; c, turning on a pump (which can also be carried out on a water bath tank) in software, measuring an option card, manually setting, and measuring a display window; d, option bar: selecting test contents in a measurement option window; column for substance e: setting optical characteristics, selecting correct sample substance names and dispersing agent names, and inputting test sample numbers or names; f, calculating the result: selecting model tab-general-determine; g, measurement 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%).

Example 1

A method for recycling 1-aminoanthraquinone production wastewater comprises the following steps of:

step (1), weighing 200 parts of 1-aminoanthraquinone wastewater in a four-neck flask, 200 parts of clear water and 140 parts of sodium sulfite (90%), and stirring and mixing uniformly.

And (2) weighing 100 percent of acetone (99.9 percent) in a constant-pressure funnel, starting to slowly dropwise add, controlling the dropwise adding time to be about 30min, and continuing to sulfonate and preserving heat for 30min after dropwise adding.

And (3) weighing 280 parts of formaldehyde into a constant-pressure funnel after heat preservation is finished, starting slow dripping, controlling the dripping time for 2 hours, and controlling the temperature to be 90-95 ℃ after the dripping is finished.

And (4) after the formaldehyde is dripped, preserving heat for 0.5h at the temperature of 90-95 ℃, adding 10 parts of sodium lignosulphonate powder, stirring and mixing uniformly, preserving heat for 2h, cooling to 70 ℃, and adding 50 parts of clear water.

Example 2

step (1), weighing 200 parts of solvent of 1-aminoanthraquinone wastewater into a four-neck flask, adding 200 parts of clear water and 130 parts of sodium sulfite (90%), and stirring and mixing uniformly.

And (2) weighing 100 parts of acetone (99.9%) in a constant-pressure funnel, slowly dripping for about 30min, and continuing sulfonation and heat preservation for 30min after dripping is finished.

And (3) weighing 260 parts of formaldehyde into a constant-pressure funnel after heat preservation is finished, starting slow dropwise adding, controlling the dropwise adding time for 2 hours, and controlling the temperature to be 90-95 ℃ after dropwise adding is finished.

And (4) after the formaldehyde is dripped, preserving heat for 0.5h at the temperature of 90-95 ℃, adding 20 parts of sodium lignosulphonate powder, stirring and mixing uniformly, continuing preserving heat for 2h, cooling to 70 ℃ after heat preservation is finished, and adding 50 parts of clear water.

Example 3

step (1), weighing 300 parts of 1-aminoanthraquinone wastewater in a four-neck flask, adding 90 parts of clear water, 40 parts of sodium sulfite (90%), 30 parts of sodium metabisulfite, 40 parts of sodium sulfanilate and 39 parts of liquid sodium hydroxide (32%), and stirring and mixing uniformly.

And (2) weighing 100 parts of acetone (99.9%) in a constant-pressure funnel, and slowly dropwise adding for about 30 min.

And (3) after the acetone is dropwise added, weighing 265 parts of formaldehyde into a constant-pressure funnel, slowly dropwise adding, controlling the dropwise adding time to be 2 hours, and controlling the temperature to be 90-95 ℃ after the dropwise adding is finished.

And (4) after the formaldehyde is dripped, keeping the temperature of 90-95 ℃ for 1h, then adding 50 parts of the sodium lignosulphonate (45%) solution, stirring and mixing uniformly, keeping the temperature of 90-95 ℃ for 1.5h, cooling to 70 ℃ after the temperature is kept, and adding 50 parts of clear water.

Example 4

step (1), weighing 400 parts of 1-aminoanthraquinone wastewater in a four-neck flask, 85 parts of sodium sulfite (90%), 30 parts of sodium metabisulfite and 39 parts of liquid sodium hydroxide (32%), and stirring and mixing uniformly.

And (3) weighing 270 parts of formaldehyde in a constant-pressure funnel after heat preservation is finished, starting slow dripping, controlling the dripping time for 2 hours, and controlling the temperature to be 90-95 ℃ after the dripping is finished.

Step (4), after the formaldehyde is dripped, keeping the temperature of 90-95 ℃ for 0.5h, adding 50 parts of sodium lignosulphonate solution (45%), stirring and mixing uniformly, keeping the temperature of 86-95 ℃ for 2h, cooling to 70 ℃ after the temperature is over,

example 5

step (1), weighing 400 parts of 1-aminoanthraquinone wastewater in a four-neck flask, 110 parts of sodium sulfite (90%), 20 parts of sodium metabisulfite and 39 parts of liquid sodium hydroxide (32%), and stirring and mixing uniformly.

And (4) after the formaldehyde is dripped, keeping the temperature of 90-95 ℃ for 0.5h, adding 50 parts of the sodium lignosulphonate powder, stirring and mixing uniformly, and keeping the temperature of 90-95 ℃ for 2.5 h.

And (5) cooling to 70 ℃ after the heat preservation is finished.

Example 6

And (4) after the formaldehyde is dripped, preserving heat for 0.5h at the temperature of 90-95 ℃, adding 50 parts of sodium lignosulphonate powder, stirring and mixing uniformly, and then continuously preserving heat for 1.5h at the temperature of 90-95 ℃.

And (5) cooling to 70 ℃ after the heat preservation is finished.

Example 7

step (1), weighing 400 parts of 1-aminoanthraquinone wastewater in a four-neck flask, 80 parts of sodium sulfite (90%), 45 parts of sodium metabisulfite, 30 parts of sodium sulfanilate and 55 parts of liquid sodium hydroxide (32%), and stirring and mixing uniformly.

And (4) after the formaldehyde is dripped, keeping the temperature at 90-95 ℃ for 0.5h, adding 50 parts of the sodium lignosulphonate powder, stirring and mixing uniformly, and keeping the temperature at 90-95 ℃ for 2 h.

And (5) cooling to 70 ℃ after the heat preservation is finished.

Example 8

step (1), weighing 400 parts of 1-aminoanthraquinone wastewater in a four-neck flask, and uniformly stirring and mixing 80 parts of sodium sulfite (90%), 45 parts of sodium metabisulfite, 30 parts of sodium sulfanilate, 55 parts of liquid sodium hydroxide (32%) and 30 parts of sodium lignosulphonate powder.

And (3) weighing 270 parts of formaldehyde in a constant-pressure funnel after heat preservation is finished, starting slow dripping, controlling the dripping time for 1.5h, and controlling the temperature to be 90-95 ℃ after the dripping is finished.

And (4) after the formaldehyde is dripped, keeping the temperature at 90-95 ℃ for 2 h.

And (5) cooling to 70 ℃ after the heat preservation is finished.

Example 9

step (1), weighing 400 parts of 1-aminoanthraquinone wastewater in a four-neck flask, 87 parts of sodium sulfite (90%), 45 parts of sodium metabisulfite, 30 parts of sodium sulfanilate, 55 parts of liquid sodium hydroxide (32%), and 50 parts of sodium lignosulphonate powder, and uniformly stirring and mixing.

And (4) after the formaldehyde is dripped, keeping the temperature at 90-95 ℃ for 2 h. And after the heat preservation is finished, cooling to 70 ℃.

Example 10

step (1), weighing 400 parts of 1-aminoanthraquinone wastewater in a four-neck flask, and uniformly stirring and mixing 87 parts of sodium sulfite (90%), 45 parts of sodium metabisulfite, 55 parts of liquid sodium hydroxide (32%) and 50 parts of sodium lignosulfonate.

And (4) after the formaldehyde is dripped, keeping the temperature of 90-95 ℃ for 1h, beginning to generate a gel phenomenon, and forcibly stopping the experiment.

Example 11

step (1), weighing 200 parts of 1-aminoanthraquinone wastewater, 60 parts of DSD acid production wastewater, 80 parts of sodium sulfite (90%), 55 parts of liquid sodium hydroxide (32%) and 400 parts of liquid sodium lignosulphonate (45%) in a four-neck flask, and uniformly stirring and mixing.

And (2) weighing 50 parts of acetone (99.9%) in a constant-pressure funnel, slowly dripping for about 30min, and continuing sulfonation and heat preservation for 30min after dripping is finished.

And (3) weighing 140 parts of formaldehyde (36-37%) in a constant-pressure funnel after heat preservation is finished, starting slow dripping, controlling the dripping time for 1.5h, and controlling the temperature to be 90-95 ℃ after finishing dripping.

And (4) after the formaldehyde is dripped, preserving the heat at 90-95 ℃ for 2h, and cooling to 70 ℃ after the heat preservation is finished.

When the mixing amount of the water reducing agent is 1.0%, the experimental results of each group are analyzed by detecting the slump of the neat paste and the concrete, and are shown in the following table 1:

TABLE 1

We selected three coal samples, Shenmu coal, Wuqi Turkey coal, Samonte coal, Xinjiang coal and inner Mongolia coal, for blending coal to analyze the results of each group of experiments. The coal quality characteristics and the results are shown in the following table.

TABLE 2

TABLE 3

TABLE 4

Fig. 1 and table 5 are particle size distribution curves and corresponding data tables for the shenmuke coal of example 6. The obtained graphs are more than one, and the rest are not identical to one in the attached graph.

TABLE 5 particle size-volume fraction of example 6 in Hibiscus sabdariffa

As shown in Table 1, the water reducing agent has low cost, good water reducing and collapse keeping effects, high gas content and good freezing resistance compared with conventional ZFA and conventional AJ. As shown in tables 2-5, compared with the conventional ZFA, the dispersant disclosed by the invention is low in cost, better in dispersibility, improved in adaptability, stability and dispersibility, free from hard settling phenomenon within 72 hours, wide in adaptability, higher in cost performance and worthy of popularization.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

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.

Claims

1. A resource utilization method of 1-aminoanthraquinone 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, after the dropwise adding is finished, keeping the temperature for a period of time, adding the sodium lignosulphonate, and keeping the temperature;

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 production wastewater according to claim 1, characterized in that the residual portion after the reaction with acetone and the molecules which participate in the preliminary polymerization with formaldehyde are graft-copolymerized with sodium lignosulphonate to obtain a product containing a larger number of and a larger variety of active groups.

3. The resource utilization method of 1-aminoanthraquinone production wastewater according to claim 1, characterized in that in the invention, the sodium lignosulphonate can be one or two of solid or liquid, and pure sodium lignosulphonate accounts for 1% -30% of the total mass of the materials.

4. The method for recycling 1-aminoanthraquinone production wastewater according to claim 1, wherein the sulfonating agent is one or more of sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium sulfanilate, sulfanilic acid and SO 3; the sodium hydroxide is one or more of liquid sodium hydroxide and solid sodium hydroxide, and the pH value of the material is 7-10 after the sodium hydroxide is added.

5. The resource utilization method of 1-aminoanthraquinone 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 production wastewater according to claim 1, characterized in that the ratio of the mass of the formaldehyde solution to the total amount of phenol and acetone is 1.4: 1-3:1.

7. The resource utilization method of 1-aminoanthraquinone 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 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 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 production wastewater according to claim 1, characterized in that the heat preservation time of the formaldehyde after dripping is 1.5-5h, and the heat preservation temperature is 90-96 ℃.