CN111994975A - Recycling method of cyclohexanone wastewater - Google Patents
Recycling method of cyclohexanone wastewater Download PDFInfo
- Publication number
- CN111994975A CN111994975A CN202010871585.XA CN202010871585A CN111994975A CN 111994975 A CN111994975 A CN 111994975A CN 202010871585 A CN202010871585 A CN 202010871585A CN 111994975 A CN111994975 A CN 111994975A
- Authority
- CN
- China
- Prior art keywords
- formaldehyde condensate
- cyclohexanone
- formaldehyde
- acetone
- wastewater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for recycling cyclohexanone wastewater, which utilizes sodium hydroxide in the cyclohexanone wastewater as a raw material of a sulfonated acetone-formaldehyde condensate and an aminosulfonic acid-series formaldehyde condensate to provide an alkaline reaction condition in a sulfonation process; modifying by sulfonating and condensing cyclohexanone in the cyclohexanone wastewater and then carrying out block polymerization on a sulfonated acetone-formaldehyde condensate; carboxyl, hydroxyl and ester groups with good hydrophilicity are introduced by utilizing carboxylic acid substances, so that the hydrophilicity of the sulfonated acetone-formaldehyde condensate and the sulfamic acid formaldehyde condensate is enhanced, and the dispersibility and the water reducing rate of the sulfonated acetone-formaldehyde condensate and the sulfamic acid formaldehyde condensate are improved; the invention obtains diversified products by controlling and adjusting the molecular structure and molecular weight distribution design through reaction conditions, the products can be applied to different coals as dispersing agents and stabilizing agents or as water reducing agents of concrete, and have the advantages of easily obtained raw materials, environmental protection, low price, good dispersibility and the like, and the cyclohexanone wastewater does not need evaporation, rectification and biochemical treatment, thereby realizing resource recycling.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a cyclohexanone wastewater resource utilization method.
Background
The comprehensive consideration of energy safety and environmental problems, and the clean utilization of coal resources are increasingly paid attention. The clean coal technology has been proposed for 30-40 years, and the following three improvements are mainly provided for further improving the utilization rate of coal, meeting the environmental protection standard and improving the economic utilization value of coal: the discharge amount of greenhouse gas carbon dioxide is reduced by improving the recycling of carbon; combustion technology is improved so as to improve the effective utilization rate of coal; and the emission of environmental pollutants such as sulfur dioxide, nitrogen oxides, solid particles and the like is controlled. In the current world facing the oil crisis, new energy substitutes are researched, and coal water slurry is one of the substitutes.
The coal water slurry is used for replacing coal for combustion, and has the advantages of high combustion benefit, environmental pollution reduction, convenience in load adjustment, coal saving, labor condition improvement and the like. The coal water slurry technology is a clean coal technology which is efficient, safe, economical, clean and simple to operate. Coal water slurry is beginning to be highly valued as a new oil-substituting fuel in many countries. 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 influence factors influencing the high-efficiency utilization of the coal water slurry are quite many, and the development of the dispersing agent has a key effect on the coal water slurry technology.
In recent years, many researches are made on coal water slurry additives at home and abroad, and a series of competitive products are produced. The research and application of the coal water slurry dispersing agent are prominent in foreign Nippon oil ester company, Kao corporation, and the Across corporation. A series of good dispersants such as sodium polystyrene sulfonate (PSS), naphthalene sulfonate polymer (NSF), etc. have been developed by japanese researchers and have been used in industrial production. The national brewing company of America synthesizes a nonionic dispersant as the water-coal-slurry dispersant, which can lead the concentration of the prepared water-coal-slurry to reach 70 percent and has ideal stability and fluidity. The coal water slurry NDF dispersant developed by Nanjing university at home is suitable for wide coal types and has good performance. The water coal slurry additive synthesized by Kunzhan fine chemical company of Kunzhan city, Jiangsu province has certain performance even exceeding that of similar Japanese products. HNF developed by Huainan mining group synthetic material Limited liability company can simultaneously give consideration to the dispersibility and stability of the coal water slurry.
In the existing pulping technology, low-rank coal is difficult to prepare high-concentration coal water slurry. And the dispersants used for the water-coal-slurry mainly include naphthalene series, lignin series, humic acid series, sulfonated acetone-formaldehyde condensate, sulfamic acid-formaldehyde condensate, nonionic dispersants and the like. However, most of these dispersants are produced from petroleum products, which are expensive and easily cause environmental pollution. And the pulp concentration of the coal is not high, and the pulp concentration of the coal is between 59 and 61 by using low-rank coal and immature coal generally.
At present, the research on the domestic water reducing agent mainly focuses on two aspects of physical compound modification and chemical reaction modification. The physical compounding mainly refers to that the performance level of the water reducing agent is improved and improved by selecting proper auxiliary agents such as a retarder, an air entraining agent and the like or different types of water reducing agents are scientifically and reasonably compounded to obtain the compound water reducing agent. The chemical reaction modification mainly refers to improving or fundamentally changing and improving the performance of the water reducing agent by chemical reaction methods such as polymerization, graft copolymerization, sulfonation, oxidation, alkylation and the like.
At present, the production method for manufacturing cyclohexanone in China mainly comprises two processes of a cyclohexane liquid-phase oxidation method and a cyclohexene hydration method, and a large amount of wastewater is generated in the production process. The process for preparing cyclohexanone by cyclohexane liquid-phase oxidation method mainly uses benzene and hydrogen as main raw materials, and comprises the steps of benzene hydrogenation, cyclohexane oxidation, cyclohexanol dehydrogenation and finally distillation refining to obtain the cyclohexanone. In the production process, the organic acid in the oxidizing solution and the organic acid ester in the saponified oxidizing solution are neutralized mainly by using an aqueous solution of sodium hydroxide. However, since sodium hydroxide and organic acid in the wastewater can not completely react, the main components of the wastewater are sodium hydroxide, cyclohexanone, cyclohexanol, carboxylic acids (such as dibasic acid, valeric acid, polyacrylic acid, polybutene acid, polypentenoic acid, etc.) and lipids thereof. For wastewater treatment, most of the cyclohexanone production enterprises in China adopt an incineration process, mainly because COD content in wastewater is relatively high, the effect on microbial activity is large, and biochemical degradation is difficult. The organic chemical wastewater has high concentration and strong toxicity, and the organic carboxylic acids, cyclohexanone, lipids and alcohol substances contained in the cyclohexanone production wastewater have great harm to the environment. If the waste water is directly discharged without being effectively treated, the waste water can cause serious pollution to the surrounding ecological environment. After being discharged into the water body, the organic carboxylic acids can change the pH value of the water body, deteriorate the ecological environment of the water body, interfere the self-purification capability of the water body and are unfavorable for the growth of fishery and aquatic organisms. Cyclohexanone, carboxylic acid and alcohol substances are artificially synthesized organic substances which are generally not easily degraded by microorganisms, are not necessarily easily removed by a biological treatment process, and are not easily degraded by natural biological self-purification when discharged into natural environments such as water bodies. Therefore, they are accumulated and stored in natural environments such as water, soil and the like, enter organisms through the action of food chains, are gradually enriched and finally enter human bodies, and are harmful to human health. The cyclohexanone waste water has complex components and large energy consumption for recycling and distilling. The incineration process solves the problem of treatment of three wastes in the production process of cyclohexanone, but has higher production and operation cost and lower economic benefit. However, with the increasing enhancement of environmental protection consciousness of people, the method for sustainable development, circular economy, resource recovery and environmental protection is the main direction for the utilization of cyclohexanone waste water in the future, and the research of various methods should be continuously enhanced in the future to find a process method suitable for the characteristics of the method and meet the requirement of actual production.
Disclosure of Invention
The invention aims to provide a cyclohexanone waste water resource utilization method, 1) sodium hydroxide in the cyclohexanone waste water is used as a raw material of a sulfonated acetone-formaldehyde condensate and an aminosulfonic acid formaldehyde condensate to provide an alkaline reaction condition in the sulfonation process, so that the cost is reduced; 2) modifying by sulfonating and condensing cyclohexanone in the cyclohexanone wastewater and then carrying out block polymerization on a sulfonated acetone-formaldehyde condensate; 3) carboxyl, hydroxyl of alcohol, partial small amount of ester group and the like in carboxylic acid substances are modified after condensation, and the carboxyl, the hydroxyl and the ester group with better hydrophilicity are introduced to enhance the hydrophilicity of the sulfonated acetone-formaldehyde condensate and the sulfamic acid formaldehyde condensate, so that the dispersibility and the water reducing rate of the sulfonated acetone-formaldehyde condensate and the sulfamic acid formaldehyde condensate are improved; 4) the diversified process product system is obtained by controlling and adjusting the molecular structure and molecular weight distribution design through reaction conditions, so that the diversified process product system can be applied to different coals as a dispersing agent and a stabilizing agent or as a water reducing agent of concrete; 5) the invention has the advantages of easily available raw materials, environmental protection, low price, good dispersibility and the like, and the cyclohexanone wastewater does not need evaporation, rectification and biochemical treatment, thereby realizing resource recycling.
The purpose of the invention can be realized by the following technical scheme:
a method for recycling cyclohexanone wastewater comprises the steps of preparing a sulfonated acetone-formaldehyde condensate and an aminosulfonic acid-formaldehyde condensate by using the cyclohexanone wastewater as a raw material, and specifically comprises the following steps:
preparation of sulfonated acetone-formaldehyde condensate: adding cyclohexanone wastewater and a sulfonating agent into a reaction kettle with a condensing device, stirring and mixing uniformly, adding clear water/liquid sodium hydroxide, and continuously stirring and mixing uniformly to obtain a mixed solution; then slowly dripping acetone into the mixed solution, naturally sulfonating and preserving heat, slowly dripping a formaldehyde solution after heat preservation is finished, and continuously preserving heat for 1.5-3 hours after the dripping of the formaldehyde solution is finished to obtain a sulfonated acetone-formaldehyde condensate;
preparation of aminosulfonic acid Formaldehyde condensate: adding cyclohexanone wastewater into a reaction kettle with a condenser, heating to 40 ℃, adding sodium sulfanilate/sulfanilic acid, stirring and mixing uniformly, then continuing to heat to 60 ℃, adding phenol, detecting the pH value, adding clear water/liquid alkali according to the pH value condition, continuing to stir and mix uniformly, beginning to dropwise add a formaldehyde solution, heating and preserving heat after dropwise adding is finished, finishing the heat preservation, supplementing water and cooling to obtain the aminosulfonic acid formaldehyde condensation compound.
Further, in the preparation process of the sulfonated acetone-formaldehyde condensate, the using amount of the cyclohexanone waste water is not more than 50% of the total amount.
Further, in the preparation process of the sulfonated acetone-formaldehyde condensate, the pH value of the mixed solution before the acetone is dripped is 8-10.
Further, in the preparation process of the sulfonated acetone-formaldehyde condensate, the temperature of dropping acetone and the sulfonation heat preservation temperature are not more than 55 ℃, the time of dropping acetone is 20-40min, and the sulfonation heat preservation time is 20-60 min; the temperature of the formaldehyde is between 30 and 96 ℃, and the dripping time is 1.5 to 6 hours.
Further, in the preparation process of the sulfonated acetone-formaldehyde condensate, the sulfonating agent is one or more of sodium metabisulfite, sodium bisulfite and sulfur trioxide, or is mixed with sodium sulfite for use; the mass ratio of the sulfonating agent to the acetone is 1.2:1-1.49: 1; the mass ratio of the formaldehyde solution to the acetone is 2.4:1-2.9: 1.
Further, the amount of cyclohexanone waste water used in the preparation of the aminosulfonic acid formaldehyde condensate does not exceed 60% of the total amount.
Further, adding phenol in the preparation process of the amino sulfonic formaldehyde condensate, quickly detecting the pH value, and adding clear water if the pH value is more than 8.5; if the pH value is less than 8.5, adding liquid alkali to make the pH value between 8.5 and 10.
Further, the speed of dripping formaldehyde is controlled in the preparation process of the sulfamic acid formaldehyde condensate, the temperature is not more than 80 ℃ in the dripping process, the dripping time is 2-6 hours, the temperature is raised to 90-95 ℃ after dripping, and the temperature is kept for 1.5-3 hours.
Furthermore, the mass ratio of the sodium sulfanilate/the sulfanilic acid to the phenol in the preparation process of the sulfamic acid formaldehyde condensate is 1.55:1-1.85: 1.
Further, the mass fraction of the formaldehyde solution is 35-37%.
The invention has the beneficial effects that:
1. the reaction conditions of the invention are normal temperature and normal pressure, the reaction conditions are easy to control, the production process is simple, and no three wastes are discharged. Compared with the incineration process, the chemical treatment method solves the problem of difficult wastewater treatment in the cyclohexanone production process, realizes the regeneration and cyclic utilization of resources and has better economic benefit.
2. The additive has better dispersibility to coal or cement at lower mixing amount.
3. Can obviously improve the concentration of the water-coal-slurry and increase the water reducing rate.
4. The stability of the slurry is prolonged, and the stability is good.
5. Realizes the resource utilization of the cyclohexanone waste water with different concentrations.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
1. 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 stirrer, a glass plate (400 multiplied by 400mm, the thickness is 5mm), a steel ruler (300mm), a scraper, a 50mL beaker and a standard slump bucket.
2. The experimental method and the steps are detected according to 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, placing the same amount of sample in a 150mL beaker to ensure the temperature and 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:
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.
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:
laboratory instruments, 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%
The method for detecting the granularity of the coal water slurry comprises the following steps: 1. the experimental instrument is an LS100Q laser particle size analyzer
2. Theory of scattering 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, known as 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
According to one embodiment of the preparation method for synthesizing the sulfonated acetone-formaldehyde condensate from cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 100 parts of cyclohexanone waste water and 155 parts of sodium sulfite (85%) into a reaction kettle with a condensing device, stirring and mixing uniformly, adding 275 parts of clear water, and continuing stirring and mixing uniformly. Then, 98 parts of acetone is slowly dripped, natural sulfonation and heat preservation are carried out, 275 parts of formaldehyde is slowly dripped after heat preservation is finished, the dripping time is about 2 hours, the dripping speed is controlled through reflux conditions, heat preservation at 95 ℃ is continuously carried out for 2 hours after the dripping of the formaldehyde is finished, and 50 parts of clear water is added.
Example 2
According to one embodiment of the preparation method for synthesizing the sulfonated acetone-formaldehyde condensate from cyclohexanone wastewater, the preparation method comprises the following steps of:
200 parts of cyclohexanone waste water, 140 parts of sodium sulfite (85%) and 10 parts of sodium metabisulfite are added into a reaction kettle with a condensing device, and after uniform stirring and mixing, 230 parts of clear water is added, and the mixture is continuously stirred and uniformly mixed. Then, 98 parts of acetone is slowly dripped, natural sulfonation and heat preservation are carried out, 275 parts of formaldehyde is slowly dripped after heat preservation is finished, the dripping time is about 2 hours, the dripping speed is controlled through reflux conditions, and heat preservation at 95 ℃ is continuously carried out for 2 hours after the dripping of the formaldehyde is finished.
Example 3
According to one embodiment of the preparation method for synthesizing the sulfonated acetone-formaldehyde condensate from cyclohexanone wastewater, the preparation method comprises the following steps of:
200 parts of cyclohexanone waste water, 100 parts of sodium sulfite (85%) and 30 parts of sodium metabisulfite are added into a reaction kettle with a condensing device, and after uniform stirring and mixing, 230 parts of clear water is added, and the mixture is continuously stirred and mixed uniformly. Then, 100 parts of acetone is slowly dripped, natural sulfonation and heat preservation are carried out, 275 parts of formaldehyde is slowly dripped after heat preservation is finished, the dripping time is about 2 hours, the dripping speed is controlled through reflux conditions, heat preservation at 95 ℃ is carried out for 2 hours after the dripping of the formaldehyde is finished, and the viscosity of the product is slightly high.
Example 4
According to one embodiment of the preparation method for synthesizing the sulfonated acetone-formaldehyde condensate from cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 300 parts of cyclohexanone waste water, 120 parts of sodium sulfite (85%) and 23 parts of sodium metabisulfite into a reaction kettle with a condensing device, stirring and mixing uniformly, adding 130 parts of clear water, and continuing stirring and mixing uniformly. And then slowly dripping 96 parts of acetone, naturally sulfonating and preserving heat, slowly dripping 270 parts of formaldehyde after heat preservation is finished, wherein the dripping time is about 1.5h, controlling the dripping speed through the reflux condition, and continuously preserving heat for 2.5h at 95 ℃ after the dripping of the formaldehyde is finished.
Example 5
According to one embodiment of the preparation method for synthesizing the sulfonated acetone-formaldehyde condensate from cyclohexanone wastewater, the preparation method comprises the following steps of:
430 parts of cyclohexanone waste water, 100 parts of sodium sulfite (85%) and 47 parts of sodium metabisulfite are added into a reaction kettle with a condensing device, and the mixture is continuously stirred and uniformly mixed. Then slowly dropping 95 parts of acetone, naturally sulfonating and preserving heat, slowly dropping 260 parts of formaldehyde after heat preservation is finished, wherein the dropping time is about 1.5h, the dropping speed is controlled by reflux conditions, and heat preservation is continuously carried out for 2.5h at 95 ℃ after the formaldehyde is dropped.
Example 6
According to one embodiment of the preparation method for synthesizing the sulfonated acetone-formaldehyde condensate from cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 400 parts of cyclohexanone waste water, 80 parts of sodium sulfite (85%), 60 parts of sodium metabisulfite and 18 parts of liquid sodium hydroxide (32%) into a reaction kettle with a condensing device, and continuously stirring and uniformly mixing. Then slowly dripping 93 parts of acetone, naturally sulfonating and preserving heat, slowly dripping 255 parts of formaldehyde after heat preservation is finished, wherein the dripping time is about 2.5 hours, controlling the dripping speed through the reflux condition, and continuously preserving heat for 2 hours at 95 ℃ after the dripping of the formaldehyde is finished.
Example 7
According to one embodiment of the preparation method for synthesizing the aminobenzene sulfonic acid formaldehyde condensate by using the cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 100 parts of cyclohexanone production wastewater and 280 parts of clean water into a reaction kettle with a condenser, heating to 40 ℃, adding 165 parts of sodium sulfanilate (97%), stirring and mixing uniformly, then continuously heating to 60 ℃, adding 98 parts of phenol, detecting the pH value, adding 10 parts of liquid sodium hydroxide (32%), continuously heating while stirring and mixing uniformly, dropwise adding 165 parts of formaldehyde solution (35-37%) after stirring uniformly, heating to 95 ℃, keeping the temperature for 2.5 hours after dropwise adding 78 ℃, and after keeping the temperature, supplementing 180 parts of clean water and cooling.
Example 8
According to one embodiment of the preparation method for synthesizing the aminobenzene sulfonic acid formaldehyde condensate by using the cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 200 parts of cyclohexanone production wastewater and 180 parts of clean water into a reaction kettle with a condenser, heating to 40 ℃, adding 170 parts of sodium sulfanilate (97%), stirring uniformly, then continuously heating to 60 ℃, adding 98 parts of phenol, detecting the pH value of 9.1, dropwise adding 160 parts of formaldehyde solution (35-37%) after stirring uniformly, heating to 95 ℃ after dropwise adding is finished, keeping the temperature for 3 hours, and after the heat preservation is finished, supplementing 180 parts of clean water and cooling.
Example 9
According to one embodiment of the preparation method for synthesizing the aminobenzene sulfonic acid formaldehyde condensate by using the cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 300 parts of cyclohexanone production wastewater and 80 parts of clear water into a reaction kettle with a condenser, heating to 40 ℃, adding 150 parts of sodium sulfanilate (97%) and 20 parts of sulfanilic acid, stirring uniformly, then continuously heating to 60 ℃, adding 100 parts of phenol, detecting the pH value of 9, dropwise adding 165 parts of formaldehyde solution (35-37%) after uniformly stirring, heating to 95 ℃ after dropwise adding 80 ℃, keeping the temperature for 2.5 hours, and after keeping the temperature, supplementing 180 parts of clear water and cooling.
Example 10
According to one embodiment of the preparation method for synthesizing the aminobenzene sulfonic acid formaldehyde condensate by using the cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 380 parts of cyclohexanone production wastewater into a reaction kettle with a condenser, heating to 40 ℃, adding 140 parts of sodium sulfanilate (97%) and 28 parts of sulfanilic acid, stirring uniformly, then continuously heating to 60 ℃, adding 100 parts of phenol, detecting the pH value to be 9.2, dropwise adding 165 parts of formaldehyde solution (35-37%) after stirring uniformly, heating to 95 ℃ after dropwise adding 80 ℃, keeping the temperature for 2.5 hours, and after keeping the temperature, supplementing 180 parts of clear water and cooling.
Example 11
According to one embodiment of the preparation method for synthesizing the aminobenzene sulfonic acid formaldehyde condensate by using the cyclohexanone wastewater, the preparation method comprises the following steps of:
adding 380 parts of cyclohexanone production wastewater into a reaction kettle with a condenser, heating to 40 ℃, adding 140 parts of sodium sulfanilate (97%) and 28 parts of sulfanilic acid, stirring uniformly, then continuously heating to 60 ℃, adding 96 parts of phenol, detecting the pH value to be 9.4, dropwise adding 150 parts of formaldehyde solution (35-37%) after stirring uniformly, heating to 95 ℃ after dropwise adding 80 ℃, keeping the temperature for 2.5 hours, and after the heat preservation is finished, supplementing 160 parts of clean water and cooling.
Comparing a conventional aliphatic water reducer produced by Anhuixin solid environment with a conventional sulfamic acid water reducer in the water reducer, and when the mixing amount is 1.3%, analyzing the experimental results of each group by detecting the slump of the neat paste and the concrete, wherein the experimental results are as shown in the following table 1:
TABLE 1
The coal blending of three coal samples, namely, the nakeus coal, the black douglas coal, the sammonte coal, the Xinjiang coal and the inner Mongolian coal, is selected for analyzing the experimental results of each group, the conventional sulfonated acetone-formaldehyde condensate, the conventional sulfamic acid formaldehyde condensate, the lignin dispersant and the composite dispersant (the conventional sulfonated acetone-formaldehyde condensate, the sulfamic acid formaldehyde condensate and the lignin dispersant are 1:1: 1). The coal quality characteristics and the experimental results are shown in the following tables 2 to 4:
TABLE 2
TABLE 3
TABLE 4
As shown in tables 1-4, some of the dispersants of the invention have better dispersibility, low viscosity, improved adaptability and stability and higher cost performance compared with lignin dispersants, amino sulfonic formaldehyde condensates, sulfonated acetone-formaldehyde condensates and composite dispersants, and can treat a large amount of cyclohexanone production wastewater, thereby realizing the resource utilization of cyclohexanone wastewater and being worthy of popularization.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A method for recycling cyclohexanone wastewater is characterized by comprising a method for preparing a sulfonated acetone-formaldehyde condensate and an aminosulfonic acid-formaldehyde condensate by using the cyclohexanone wastewater as a raw material, and specifically comprises the following steps:
preparation of sulfonated acetone-formaldehyde condensate: adding cyclohexanone wastewater and a sulfonating agent into a reaction kettle with a condensing device, stirring and mixing uniformly, adding clear water/liquid sodium hydroxide, and continuously stirring and mixing uniformly to obtain a mixed solution; then slowly dripping acetone into the mixed solution, naturally sulfonating and preserving heat, slowly dripping a formaldehyde solution after heat preservation is finished, and continuously preserving heat for 1.5-3 hours after the dripping of the formaldehyde solution is finished to obtain a sulfonated acetone-formaldehyde condensate;
preparation of aminosulfonic acid Formaldehyde condensate: adding cyclohexanone wastewater into a reaction kettle with a condenser, heating to 40 ℃, adding sodium sulfanilate/sulfanilic acid, stirring and mixing uniformly, then continuing to heat to 60 ℃, adding phenol, detecting the pH value, adding clear water or liquid alkali according to the pH value condition, continuing to stir and mix uniformly, beginning to dropwise add a formaldehyde solution, heating and preserving heat after dropwise adding is finished, finishing the heat preservation, supplementing water and cooling to obtain the aminosulfonic acid formaldehyde condensation compound.
2. The method as claimed in claim 1, wherein the amount of the cyclohexanone waste water used in the preparation of the sulfonated acetone-formaldehyde condensate is not more than 50% of the total amount.
3. The method for recycling cyclohexanone waste water according to claim 1, wherein in the preparation process of the sulfonated acetone-formaldehyde condensate, the pH value of the mixed solution before acetone is added dropwise is 8-10.
4. The method for recycling cyclohexanone waste water according to claim 1, wherein in the preparation process of the sulfonated acetone-formaldehyde condensate, the temperature of acetone dropping and the sulfonation heat preservation temperature are not more than 55 ℃, the time of acetone dropping is 20-40min, and the time of sulfonation heat preservation is 20-60 min; the temperature of the formaldehyde is between 30 and 96 ℃, and the dripping time is 1.5 to 6 hours.
5. The method for recycling cyclohexanone waste water according to claim 1, wherein in the preparation process of the sulfonated acetone-formaldehyde condensate, the sulfonating agent is one or more of sodium metabisulfite, sodium bisulfite and sulfur trioxide, or is mixed with sodium sulfite for use; the mass ratio of the sulfonating agent to the acetone is 1.2:1-1.49: 1; the mass ratio of the formaldehyde solution to the acetone is 2.4:1-2.9: 1.
6. The method as claimed in claim 1, wherein the amount of cyclohexanone waste water used in the preparation of the amino sulfonic acid formaldehyde condensate is not more than 60% of the total amount.
7. The method for recycling cyclohexanone waste water according to claim 1, wherein the pH value is detected after phenol is added in the preparation process of the amino sulfonic acid group formaldehyde condensate, and if the pH value is more than 8.5, clear water is added; if the pH value is less than 8.5, adding liquid alkali to make the pH value between 8.5 and 10.
8. The method for recycling cyclohexanone waste water according to claim 1, wherein the speed of dripping formaldehyde is controlled in the preparation process of the sulfamic acid formaldehyde condensate, the temperature in the dripping process is not more than 80 ℃, the dripping time is 2-6h, the temperature is raised to 90-95 ℃ after dripping, and the temperature is kept for 1.5-3 h.
9. The method for recycling cyclohexanone waste water according to claim 1, wherein a mass ratio of sodium sulfanilate/sulfanilic acid to phenol in the preparation process of the sulfamic acid-based formaldehyde condensate is 1.55:1-1.85: 1.
10. The method for recycling cyclohexanone waste water as claimed in claim 1, wherein the mass fraction of the formaldehyde solution is 35-37%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010871585.XA CN111994975A (en) | 2020-08-26 | 2020-08-26 | Recycling method of cyclohexanone wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010871585.XA CN111994975A (en) | 2020-08-26 | 2020-08-26 | Recycling method of cyclohexanone wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111994975A true CN111994975A (en) | 2020-11-27 |
Family
ID=73471419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010871585.XA Pending CN111994975A (en) | 2020-08-26 | 2020-08-26 | Recycling method of cyclohexanone wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111994975A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106189A (en) * | 2022-06-08 | 2022-09-27 | 淮南矿业(集团)有限责任公司 | Method and system for realizing benefit maximization of coal preparation plant |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB871923A (en) * | 1954-04-22 | 1961-07-05 | Dasher Rubber And Chemical Com | Improvements in the production of powdered vulcanized rubber |
| GB1334718A (en) * | 1970-09-14 | 1973-10-24 | Union Carbide Corp | Recovery of rubber |
| US4162045A (en) * | 1976-05-19 | 1979-07-24 | The Dow Chemical Company | Ore grinding process |
| US4406411A (en) * | 1979-09-10 | 1983-09-27 | Ford Motor Company | Reclamation and rejuvenation of plastic and metal from metallized plastic |
| EP0318027A1 (en) * | 1987-11-26 | 1989-05-31 | Daikin Industries, Limited | Fluororubber-containing powder coating composition |
| CA2507335A1 (en) * | 2002-12-02 | 2004-06-17 | Pirelli & C. S.P.A. | Pulverization process of a vulcanized rubber material |
| CN101346311A (en) * | 2005-12-23 | 2009-01-14 | 索尔维公司 | Milling process |
| CN102295965A (en) * | 2010-06-28 | 2011-12-28 | 中国石油化工股份有限公司 | Method for treating waste alkali liquor of cyclohexanone device |
| DE102015101506A1 (en) * | 2015-02-03 | 2016-08-04 | Daniel Schrempf | System and method for the recovery of secondary raw materials |
| CN108503253A (en) * | 2018-05-18 | 2018-09-07 | 萧县沃德化工科技有限公司 | The method that the spent lye of mercerization prepares modified amido sulfoacid series high-efficiency water reducer |
| CN111250252A (en) * | 2019-12-30 | 2020-06-09 | 浙江瑞堂塑料科技股份有限公司 | Grinding aid for thermoplastic grinding process and grinding equipment |
-
2020
- 2020-08-26 CN CN202010871585.XA patent/CN111994975A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB871923A (en) * | 1954-04-22 | 1961-07-05 | Dasher Rubber And Chemical Com | Improvements in the production of powdered vulcanized rubber |
| GB1334718A (en) * | 1970-09-14 | 1973-10-24 | Union Carbide Corp | Recovery of rubber |
| US4162045A (en) * | 1976-05-19 | 1979-07-24 | The Dow Chemical Company | Ore grinding process |
| US4406411A (en) * | 1979-09-10 | 1983-09-27 | Ford Motor Company | Reclamation and rejuvenation of plastic and metal from metallized plastic |
| EP0318027A1 (en) * | 1987-11-26 | 1989-05-31 | Daikin Industries, Limited | Fluororubber-containing powder coating composition |
| CA2507335A1 (en) * | 2002-12-02 | 2004-06-17 | Pirelli & C. S.P.A. | Pulverization process of a vulcanized rubber material |
| CN101346311A (en) * | 2005-12-23 | 2009-01-14 | 索尔维公司 | Milling process |
| CN102295965A (en) * | 2010-06-28 | 2011-12-28 | 中国石油化工股份有限公司 | Method for treating waste alkali liquor of cyclohexanone device |
| DE102015101506A1 (en) * | 2015-02-03 | 2016-08-04 | Daniel Schrempf | System and method for the recovery of secondary raw materials |
| CN108503253A (en) * | 2018-05-18 | 2018-09-07 | 萧县沃德化工科技有限公司 | The method that the spent lye of mercerization prepares modified amido sulfoacid series high-efficiency water reducer |
| CN111250252A (en) * | 2019-12-30 | 2020-06-09 | 浙江瑞堂塑料科技股份有限公司 | Grinding aid for thermoplastic grinding process and grinding equipment |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115106189A (en) * | 2022-06-08 | 2022-09-27 | 淮南矿业(集团)有限责任公司 | Method and system for realizing benefit maximization of coal preparation plant |
| CN115106189B (en) * | 2022-06-08 | 2024-04-30 | 淮南矿业(集团)有限责任公司 | Implementation method and implementation system for maximizing benefits of coal preparation plant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101805144B (en) | Low-cost modified amino-sulfonic acid-based high-efficiency water reducer and preparation method thereof | |
| CN106279705B (en) | A kind of anti-mud sacrifice agent of lignin and preparation method thereof and the application in concrete | |
| CN104560248A (en) | Coal water slurry prepared from industrial wastewater and preparation technique thereof | |
| CN100465123C (en) | Method of preparing poly carboxylic acid series water reducer using maleic anhydride | |
| CN111994975A (en) | Recycling method of cyclohexanone wastewater | |
| CN110042128A (en) | A method of it improving changing food waste into resources and utilizes | |
| CN105967536B (en) | Red mud and flyash geology polymer material formula and preparation method thereof under a kind of room temperature | |
| CN103045317B (en) | Lignin serial coal water slurry dispersing agent and preparation method thereof | |
| CN112625765A (en) | CMN type coal water slurry additive | |
| CN104478280B (en) | Concrete synergist and preparation method thereof | |
| CN112374786B (en) | Resource utilization method of salicylic acid production wastewater | |
| CN112592452A (en) | Method for resource utilization of resorcinol distillation residues | |
| CN111848890A (en) | Resource utilization method of 3-methyl-2-nitrobenzoic acid wastewater | |
| CN112028528A (en) | Resource utilization method of 1-aminoanthraquinone production wastewater | |
| CN110819407A (en) | Coal water slurry dispersing agent prepared by dinaphthol production wastewater and preparation method thereof | |
| CN112574072A (en) | Method for synthesizing dispersant by using acid tar | |
| CN112662443A (en) | Method for synthesizing coal water slurry dispersing agent by utilizing concentrated solution of landfill leachate | |
| CN111849569A (en) | Device for preparing coal water slurry by using 1-aminoanthraquinone production wastewater and using method thereof | |
| CN104829792B (en) | A kind of preparation method of polyether-modified polycarboxylic acids grinding aid | |
| CN111792868A (en) | Environment-friendly naphthalene-based high-efficiency water reducing agent and preparation method thereof | |
| CN111825816A (en) | Resource utilization method of 1-aminoanthraquinone and DSD acid production wastewater | |
| CN102311242B (en) | Water-soluble polymer grinding aid prepared from papermaking waste liquor and preparation method thereof | |
| CN110819402A (en) | Starch modified comb-type coal water slurry dispersing agent and preparation method thereof | |
| CN112480343A (en) | Method for resource utilization of phenol tar | |
| CN112574373A (en) | Resource utilization method of waste toluene solvent generated in pharmaceutical process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |