阅读说明：本技术 一种制药过程中产生的废甲苯溶剂的资源化利用方法 (Resource utilization method of waste toluene solvent generated in pharmaceutical process ) 是由 董翠平 马丽涛 乔琼琼 彭城 徐培洋 刘子恒 杨道顺 于 2020-10-27 设计创作，主要内容包括：本发明公开了一种制药过程中产生的废甲苯溶剂的资源化利用方法,包括如下步骤：1)称取废甲苯溶剂于四口烧瓶I中,边搅拌边缓慢加入SO-3,将四口烧瓶I至于冰水浴中,通完SO-3继续磺化备用；2)将另一有冷凝器、恒压漏斗的四口烧瓶II放入加热套中,加入质量份的萘,开始加热升温,将萘熔融完全后,开始缓慢滴加浓硫酸,滴加完毕后保温；3)萘磺化结束后降温,将步骤1)所得磺化混合物混入四口烧瓶II中,继续降温,开始缓慢滴加甲醛,滴毕后保温。本发明能够防止废甲苯溶剂对环境、对人体造成污染与损害,同时不用对废甲苯溶剂进行精馏或其他物理、化学等任何处理,可直接循环利用,节省能耗。(The invention discloses a resource utilization method of a waste toluene solvent generated in a pharmaceutical process, which comprises the following steps: 1) weighing waste toluene solvent in a four-neck flask I, and slowly adding SO while stirring 3 Putting the four-neck flask I into an ice-water bath, and introducing SO 3 Continuing sulfonation for standby; 2) putting another four-neck flask II with a condenser and a constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating, starting to slowly dropwise add concentrated sulfuric acid after the naphthalene is completely molten, and keeping the temperature after the dropwise addition is finished; 3) cooling after the naphthalene sulfonation is finished, and mixing the sulfonation mixture obtained in the step 1)Mixing the mixture into a four-neck flask II, continuously cooling, slowly dripping formaldehyde, and keeping the temperature after dripping. The invention can prevent the waste toluene solvent from polluting and damaging the environment and the human body, does not need to carry out rectification or other physical and chemical treatments on the waste toluene solvent, can be directly recycled, and saves energy consumption.)

1. A resource utilization method of a waste toluene solvent generated in a pharmaceutical process is characterized by comprising the following steps:

1) weighing waste toluene solvent in a four-neck flask I, and slowly adding SO while stirring₃And SO₃Controlling the adding speed to be within 30-60min, putting the four-neck flask I into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and introducing SO₃Continuing sulfonation for 1h for standby;

2) putting the other four-neck flask II with a condenser and a constant pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to raise the temperature to 140-;

3) cooling after the naphthalene sulfonation is finished, cooling to 130 ℃, starting to mix the sulfonated mixture obtained in the step 1) into a four-neck flask II, continuing to cool to 90-110 ℃, starting to slowly dropwise add formaldehyde, controlling the dropwise adding speed to be within 1.5-3h, controlling the temperature to be 110-130 ℃ after dropwise adding, and keeping the temperature for 1.5-5 h;

4) and after condensation heat preservation is finished, continuously cooling to 80 ℃, and slowly adding liquid sodium hydroxide while stirring to ensure that the final pH value is 7-10.

2. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 1, characterized in that: the components are mixed according to the mass portion, wherein, the waste toluene solvent is 10 to 35 portions, and SO₃1-55 parts of naphthalene, 220-320 parts of naphthalene, 100-360 parts of concentrated sulfuric acid, 90-180 parts of formaldehyde, 400-600 parts of liquid sodium hydroxide and 50-300 parts of dilution water.

3. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 2, characterized in that: the components are mixed according to the mass portion, wherein, the waste toluene solvent is 10 to 35 portions, and SO₃25 parts of naphthalene 240 parts, 98% concentrated sulfuric acid 180 parts, 110% concentrated sulfuric acid 90 parts, formaldehyde 120 parts, liquid sodium hydroxide 486 parts and dilution water 80 parts.

4. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 2, characterized in that: the components are mixed according to the mass portion, wherein the waste toluene solvent is 30 portions, and SO₃50 parts of naphthalene, 260 parts of 98% concentrated sulfuric acid, 160 parts of formaldehyde, 460 parts of liquid sodium hydroxide and 120 parts of dilution water.

5. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 1, characterized in that: the concentration of the concentrated sulfuric acid is 98-114%.

6. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 1, characterized in that: the mass fraction of the formaldehyde is 36-37%.

7. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 1, characterized in that: the mass fraction of the liquid sodium hydroxide is 32%.

8. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 1, characterized in that: in the step 3), a small amount of dilution water is added for many times when the viscosity of the material is high in the heat preservation process.

9. The resource utilization method of the waste toluene solvent generated in the pharmaceutical process according to claim 1, characterized in that: the dilution water is tap water.

Technical Field

The invention relates to the technical field of chemical industry, in particular to a resource utilization method of a waste toluene solvent generated in a pharmaceutical process.

Background

Naphthalene sulfonate formaldehyde condensates are anionic surfactants with excellent performance, and people divide the condensates into low molecular weight condensates, intermediate molecular weight condensates and high molecular weight condensates according to the difference of polymerization degrees of the condensates, and the application fields of the condensates are also different. Due to the existence of hydrophobic groups such as naphthalene ring, methylene and hydrophilic group sulfonic group in polycondensate molecules, the polycondensate has good dispersion performance and is mainly widely applied to the industries of water reducing agents and water-coal-slurry dispersing agents.

The sodium 2-naphthalenesulfonate formaldehyde condensate with medium and high polymerization degree is mainly used in application research of super strong concrete and compounding oil-substituting fuel coal water slurry, and compared with polycondensate with low polymerization degree, the polycondensate with medium and high polymerization degree has better dispersivity and suspension property. According to the catalytic action of transition metal compounds on condensation reaction, Schonin, Li Shifu and the like screen catalysts, then prepare the catalysts by a precipitation method, and prepare the catalysts MA for condensation through steps of separation, activation and the like, and synthesize products with high polymerization degree of 16-21 by the catalyst catalysis method. In 2008, people in Tao et al use industrial naphthalene as raw material and select SO₃The formaldehyde is taken as a sulfonating agent, the formaldehyde is taken as a condensation raw material, and the anionic surfactant of the high-polymerization-degree 2-sodium naphthalenesulfonate formaldehyde condensate with the polymerization degree of 18-23 is synthesized through the steps of classical sulfonation, hydrolysis, condensation and the like, and when the anionic surfactant is used as a cement water reducing agent, the water reducing effect is ideal.

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 with the largest amount is used in China as a second-generation water reducer, but compared with a third-generation polycarboxylate water reducer, the naphthalene water reducer has poor water reducing and collapse keeping performances due to structural defects of the naphthalene water reducer, but has the characteristics of high water reducing rate, basically no air entraining, no delayed coagulation, relatively low cost, variable polymerization degree, adjustable molecular weight and the like, and is widely applied.

The coal water slurry is highly regarded as a novel oil-replacing fuel, and is generally prepared by physically mixing 55-70% of coal powder, 30-45% of water and a small amount of additives, so that the coal water slurry has good economic, environment-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. 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.

In the modern society, people are suffering from cardiovascular diseases more and more, and good treatment effect is difficult to achieve. With the clinical application of endothelin converting enzyme inhibitors, the hope of patients is brought. The research and synthesis of the endothelin converting enzyme inhibitor intermediate are significant from the aspects of the current research situation at home and abroad and the like. The synthesis method of the 2-acetyl cyclohexanone is that cyclohexanone and morpholine use organic solvent toluene as an entrainer and p-toluenesulfonic acid as a catalyst to prepare enamine, the enamine is heated and distilled to remove the toluene entrainer and other impurities, then enamine acylation reaction is carried out, and the product is acidified and hydrolyzed to obtain the target product 2-acetyl cyclohexanone. When the toluene solvent is removed by distillation after the first-step acylation reaction, the obtained toluene waste solvent contains a small amount of cyclohexanone, morpholine, p-toluenesulfonic acid enamine and other substances due to the fact that the molecular structures and molecular weights of toluene, cyclohexanone, morpholine and p-toluenesulfonic acid enamine are close to each other, so that a large amount of environmental pollution is caused by direct discharge, energy consumption is large when separation and purification are continued, and secondary pollution and resource waste are easily caused.

Disclosure of Invention

The invention aims to reuse the waste toluene solvent, prevent the waste toluene solvent from polluting and damaging the environment and the human body, simultaneously, the waste toluene solvent does not need rectification or any other physical and chemical treatment, can be directly recycled, and saves energy consumption.

The second purpose of the invention is to utilize toluene in the waste toluene solvent to pass through SO₃The method comprises the steps of sulfonating to obtain p-toluenesulfonic acid, then modifying a naphthalene sulfonate formaldehyde condensate through formaldehyde condensation, and introducing active groups such as benzene rings, methyl groups, more sulfonic groups and the like into a molecular chain of the naphthalene sulfonate formaldehyde condensate, so that the dispersing agent is environment-friendly, low in cost, wide in adaptability and better in dispersibility, and can be used as a coal water slurry dispersing agent or a concrete water reducing agent according to different polymers.

The third purpose of the invention is to utilize the condensation of a small amount of residual cyclohexanone, p-toluenesulfonic acid enamine and formaldehyde in the waste toluene solvent to modify the naphthalenesulfonate formaldehyde condensate, and introduce carbonyl and cycloalkyl to further increase the dispersibility of the naphthalenesulfonate formaldehyde condensate.

The fourth purpose of the invention is to utilize a small amount of residual morpholine in the waste toluene solvent as a metal corrosion inhibitor to slow down the corrosion influence of the naphthalene water reducer on the reinforced concrete due to the alkalinity thereof.

The invention aims to utilize the waste toluene solvent as a raw material of the modified sodium naphthalenesulfonate formaldehyde condensate, thereby not only increasing the dispersibility of the condensate, but also reducing the usage amount of naphthalene and lowering the production and use costs.

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

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following steps:

1) weighing waste toluene solvent in a four-neck flask I, and slowly adding SO while stirring₃And SO₃Controlling the adding speed to be within 30-60min, putting the four-neck flask I into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and introducing SO₃Continuing sulfonation for 1h for standby;

2) putting the other four-neck flask II with a condenser and a constant pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to raise the temperature to 140-;

3) cooling after the naphthalene sulfonation is finished, cooling to 130 ℃, starting to mix the sulfonated mixture obtained in the step 1) into a four-neck flask II, continuing to cool to 90-110 ℃, starting to slowly dropwise add formaldehyde, controlling the dropwise adding speed to be within 1.5-3h, controlling the temperature to be 110-130 ℃ after dropwise adding, and keeping the temperature for 1.5-5 h;

4) and after condensation heat preservation is finished, continuously cooling to 80 ℃, and slowly adding liquid sodium hydroxide while stirring to ensure that the final pH value is 7-10.

Further, in the resource utilization method of the waste toluene solvent generated in the pharmaceutical process, the components are proportioned according to the parts by mass, wherein the waste toluene solvent accounts for 10-35 parts, and SO₃1-55 parts of naphthalene, 220-320 parts of naphthalene, 100-360 parts of concentrated sulfuric acid, 90-180 parts of formaldehyde, 400-600 parts of liquid sodium hydroxide and 50-300 parts of dilution water.

Further, in the resource utilization method of the waste toluene solvent generated in the pharmaceutical process, the components are proportioned according to the parts by mass, wherein the waste toluene solvent accounts for 10-35 parts, and SO₃25 parts of naphthalene 240 parts, 98% concentrated sulfuric acid 180 parts, 110% concentrated sulfuric acid 90 parts, formaldehyde 120 parts, liquid sodium hydroxide 486 parts and dilution water 80 parts.

Further, the waste toluene generated in the pharmaceutical process is dissolvedIn the resource utilization method of the agent, the components are proportioned according to the mass parts, wherein the waste toluene solvent accounts for 30 parts, and SO₃50 parts of naphthalene, 260 parts of 98% concentrated sulfuric acid, 160 parts of formaldehyde, 460 parts of liquid sodium hydroxide and 120 parts of dilution water.

Further, in the resource utilization method of the waste toluene solvent generated in the pharmaceutical process, the concentration of the concentrated sulfuric acid is 98-114%.

Further, in the resource utilization method of the waste toluene solvent generated in the pharmaceutical process, the mass fraction of the formaldehyde is 36-37%.

Further, in the method for recycling the waste toluene solvent generated in the pharmaceutical process, the mass fraction of the liquid sodium hydroxide is 32%.

Further, in the method for recycling the waste toluene solvent generated in the pharmaceutical process, in the step 3), a small amount of dilution water is added for multiple times when the viscosity of the material is high in the heat preservation process.

Further, in the method for recycling the waste toluene solvent generated in the pharmaceutical process, the dilution water is tap water.

The invention has the beneficial effects that:

1. the invention realizes the reutilization of the waste toluene solvent, prevents the waste toluene solvent from polluting and damaging the environment and the human body, does not need to carry out rectification or other physical and chemical treatments, can be directly recycled, and saves energy consumption.

2. The invention uses toluene in the waste toluene solvent to be firstly treated by concentrated sulfuric acid/SO₃The method comprises the steps of sulfonating to obtain p-toluenesulfonic acid, then modifying a naphthalene sulfonate formaldehyde condensate through formaldehyde condensation, introducing hydrophobic groups such as benzene rings and methyl groups on a molecular chain of the naphthalene sulfonate formaldehyde condensate, and greatly increasing the number of hydrophilic groups such as sulfonic groups, so that the water reducing and collapse protecting effects of the naphthalene sulfonate formaldehyde condensate on concrete and the dispersing effect of coal water slurry are improved. The lipophilicity of benzene ring and methyl and the hydrophilic dispersibility of sulfonic acid group are enhanced, and the benzene ring and the methyl are added, so that the structural composition of the product and coal are more similar, and the water-coal-slurry dispersing agent is increasedThe coal slurry has good dispersibility and stability, and is suitable for various coal types. The invention provides a dispersant with environmental protection, low cost, wide adaptability and better dispersibility, and the product of the invention.

3. The method utilizes a small amount of residual cyclohexanone in the waste toluene solvent to be sulfonated by SO3, the sulfonated cyclohexanone, residual paratoluenesulfonic acid enamine and formaldehyde are condensed to modify the naphthalenesulfonate formaldehyde condensate, and hydrophilic carbonyl, sulfonic group and hydrophobic naphthenic group are introduced to further increase the dispersibility of the naphthalenesulfonate formaldehyde condensate.

4. The invention utilizes a small amount of residual morpholine in the waste toluene solvent as a metal corrosion inhibitor to slow down the corrosion influence of the alkalinity of the naphthalene water reducer on the reinforced concrete.

5. The invention utilizes the waste toluene solvent as a raw material of the modified sodium naphthalenesulfonate formaldehyde condensate, thereby not only increasing the dispersibility of the condensate, but also reducing the usage amount of naphthalene and lowering the production and use cost.

Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.

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.

Comparative tests in the following examples use naphthalene sulphonate formaldehyde condensates from Anhuxin environmental protection technology, Inc. in place of "conventional NX" below.

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

1. laboratory apparatus

The concrete mortar comprises an NJ-160A cement paste stirrer, a glass plate (400 x 400mm, the thickness of 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.

3. Experimental procedure

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. laboratory apparatus

a. Truncated cone circular die: the diameter of the upper opening is 36mm, the diameter of the lower opening is 60mm, the height is 60mm, and the inner wall of the metal product is smooth and has no seam;

b. glass plates (400X 400mm, thickness 5 mm);

c. straightedge in steel, (300 mm);

d. and (4) scraping the blade.

2. Experimental procedure

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.

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:

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

2. 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. laboratory apparatus

LS100Q laser particle size analyzer.

2. Principle of operation

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%).

The relevant examples and comparative examples are as follows:

example 1:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 10 parts of the waste toluene solvent, 312 parts of SO, 290 parts of naphthalene, 300 parts of concentrated sulfuric acid (98%), 120 parts of formaldehyde (36% -37%), 482 parts of liquid sodium hydroxide (32%), and 60 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly adding SO3 (the adding speed is controlled to be about 30 min) while stirring, placing the four-neck flask into an ice-water bath, controlling the reaction temperature to be 0-8 ℃, and continuing to sulfonate for 1h after the SO3 is added.

2) And putting the other four-neck flask with the condenser and the constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid, after dropwise adding is completed within 30min, controlling the temperature to be 160 ℃ in the dropwise adding process, and after the dropwise adding is completed, keeping the temperature for 2h at 160 ℃ of 158-.

3) Cooling after the naphthalene sulfonation is finished, cooling to 145 ℃, starting to mix the sulfonated mixture obtained in the step 1) into a four-neck flask, continuing to cool to 120 ℃, starting to slowly dropwise add formaldehyde, controlling the dropwise adding speed to be about 2 hours, finishing dropwise adding, and keeping the temperature at 115 ℃ for 3 hours after dropwise adding. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, wherein the total amount of dilution water is 60g, and continuously preserving the heat until the heat preservation is finished.

4) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 7.

Example 2:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 10 parts of the waste toluene solvent, 310 parts of SO, 280 parts of naphthalene, 100 parts of concentrated sulfuric acid (98%), 178 parts of concentrated sulfuric acid (105%), 170 parts of formaldehyde (36% -37%), 470 parts of liquid sodium hydroxide (32%), and 100 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly adding SO3 (the adding speed is controlled to be about 45 min) while stirring, and heating the four necks into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and continuing to sulfonate for 1h after SO3 is introduced for later use.

2) And putting the other four-neck flask with the condenser and the constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid at 150 ℃, after dropwise adding is completed within 30min, controlling the temperature in the dropwise adding process at 155-160 ℃, and after the dropwise adding is completed, keeping the temperature at 155-160 ℃ for 3 h.

3) Cooling after the naphthalene sulfonation is finished, cooling to 130 ℃, mixing the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, slowly dripping formaldehyde, controlling the dripping speed to be about 2.5 hours, finishing the dripping, and keeping the temperature at 110 ℃ for 3 hours after the dripping is finished. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, keeping the temperature for 100g in total, and continuing to keep the temperature until the temperature is kept.

4) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 7.

Example 3:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 20 parts of the waste toluene solvent, 318 parts of SO, 270 parts of naphthalene, 290 parts of concentrated sulfuric acid (98%), 160 parts of formaldehyde (36% -37%), 470 parts of liquid sodium hydroxide (32%), and 100 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly adding SO3 (the adding speed is controlled to be about 40 min) while stirring, and heating the four necks into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and continuing to sulfonate for 0.5h after SO3 is introduced for later use.

2) And putting the other four-neck flask with the condenser and the constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid at 150 ℃, after dropwise adding is finished for 30min, controlling the temperature in the dropwise adding process at 155-160 ℃, and after the dropwise adding is finished, keeping the temperature at 155-160 ℃ for 2.5 h.

3) Cooling after the naphthalene sulfonation is finished, cooling to 120 ℃, mixing the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, slowly dripping formaldehyde, controlling the dripping speed to be about 2 hours, finishing dripping, and keeping the temperature at 106 ℃ for 3 hours after dripping. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, keeping the temperature for 100g in total, and continuing to keep the temperature until the temperature is kept.

4) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 8.

Example 4:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 20 parts of the waste toluene solvent, 328 parts of SO, 260 parts of naphthalene, 170 parts of concentrated sulfuric acid (98%), 90 parts of concentrated sulfuric acid (110%), 150 parts of formaldehyde (36% -37%), 470 parts of liquid sodium hydroxide (32%) and 120 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly adding SO3 (the adding speed is controlled to be about 40 min) while stirring, and heating the four necks into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and continuing to sulfonate for 1h after SO3 is introduced for later use.

2) Putting the other four-neck flask with the condenser and the constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid (98%) at 150 ℃, then slowly dropwise adding concentrated sulfuric acid (110%), after all the concentrated sulfuric acids are dropwise added for 30min, controlling the temperature at 155-160 ℃ in the dropwise adding process, and keeping the temperature at 155-160 ℃ for 2.5h after the dropwise adding is finished.

3) Cooling after the naphthalene sulfonation is finished, cooling to 120 ℃, mixing the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, slowly dripping formaldehyde, controlling the dripping speed to be about 2 hours, finishing dripping, and keeping the temperature at 106 ℃ for 3 hours after dripping. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, wherein the total amount is 120g, and continuously preserving the heat until the heat preservation is finished.

4) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 8.

Example 5:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 30 parts of the waste toluene solvent, 332 parts of SO, 230 parts of naphthalene, 235 parts of concentrated sulfuric acid (98%), 130 parts of formaldehyde (36% -37%), 410 parts of liquid sodium hydroxide (32%), and 85 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly adding SO3 (the adding speed is controlled to be about 50min to be finished) while stirring, and heating the four necks into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and continuing to sulfonate for 1.5h after the SO3 is added for later use.

2) And putting the other four-neck flask with the condenser and the constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid at 150 ℃, after dropwise adding is completed for 30min, controlling the temperature in the dropwise adding process at 155-160 ℃, and after the dropwise adding is completed, keeping the temperature at 155-160 ℃ for 2 h.

3) Cooling after the naphthalene sulfonation is finished, cooling to 120 ℃, mixing the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, slowly dripping formaldehyde, controlling the dripping speed to be about 2 hours, finishing the dripping, and keeping the temperature at 106 ℃ for 4 hours after the dripping is finished. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, keeping the temperature for 85g in total, and continuing to keep the temperature until the temperature is kept.

After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 7.

Example 6:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 30 parts of the waste toluene solvent, 310 parts of SO, 230 parts of naphthalene, 160 parts of concentrated sulfuric acid (98%), 90 parts of concentrated sulfuric acid (110%), 150 parts of formaldehyde (36% -37%), 460 parts of liquid sodium hydroxide (32%), and 105 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly adding SO3 (the adding speed is controlled to be about 40 min) while stirring, and heating the four necks into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and continuing to sulfonate for 1h after SO3 is introduced for later use.

2) Putting another four-neck flask with a condenser and a constant pressure funnel into a heating sleeve, adding naphthalene by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid (98%) at 150 ℃, continuously dropwise adding (110%) concentrated sulfuric acid after dropwise adding is finished for 30min, controlling the temperature at 155-160 ℃ in the dropwise adding process, and keeping the temperature at 155-160 ℃ for 3h after dropwise adding is finished.

3) Cooling after the naphthalene sulfonation is finished, cooling to 125 ℃, starting to mix the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, starting to slowly dropwise add formaldehyde, controlling the dropwise adding speed to be about 2 hours, finishing dropwise adding, and keeping the temperature at 106 ℃ for 4 hours after dropwise adding. The dilution water was added several times in small amounts, a total of 105g, slowly as the material thickened, and the incubation continued until the incubation was complete.

4) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 7.

Example 7:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 30 parts of the waste toluene solvent, 310 parts of SO, 230 parts of naphthalene, 200 parts of concentrated sulfuric acid (98%), 150 parts of formaldehyde (36% -37%), 390 parts of liquid sodium hydroxide (32%), and 70 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly adding SO3 (the adding speed is controlled to be about 40 min) while stirring, and heating the four necks into an ice water bath, controlling the reaction temperature to be 0-8 ℃, and continuing to sulfonate for 1h after SO3 is introduced for later use.

2) And putting the other four-neck flask with the condenser and the constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid at 150 ℃, after dropwise adding is completed within 30min, controlling the temperature in the dropwise adding process at 155-160 ℃, and after the dropwise adding is completed, keeping the temperature at 155-160 ℃ for 3 h.

3) Cooling after the naphthalene sulfonation is finished, cooling to 125 ℃, starting to mix the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, starting to slowly dropwise add formaldehyde, controlling the dropwise adding speed to be about 2 hours, finishing dropwise adding, and keeping the temperature at 106 ℃ for 4 hours after dropwise adding. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, keeping the temperature for 70g in total, and continuing to keep the temperature until the temperature is kept.

4) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 7.

Example 8:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 20 parts of the waste toluene solvent, 321 parts of SO, 230 parts of naphthalene, 240 parts of concentrated sulfuric acid (98%), 150 parts of formaldehyde (36% -37%), 390 parts of liquid sodium hydroxide (32%), and 70 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) weighing the waste toluene solvent in parts by mass into a four-neck flask, slowly introducing SO3 (the adding speed is controlled to be about 40 min) while stirring, placing the four-neck flask into a water bath, controlling the reaction temperature to be 16-50 ℃, and continuing to sulfonate for 1h after SO3 is introduced for later use.

2) And putting the other four-neck flask with the condenser and the constant-pressure funnel into a heating sleeve, adding naphthalene in parts by mass, starting heating to 145 ℃, after the naphthalene is completely melted, slowly dropwise adding concentrated sulfuric acid at 150 ℃, after dropwise adding is completed within 30min, controlling the temperature in the dropwise adding process at 155-160 ℃, and after the dropwise adding is completed, keeping the temperature at 155-160 ℃ for 3 h.

3) Cooling after the naphthalene sulfonation is finished, cooling to 125 ℃, starting to mix the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, starting to slowly dropwise add formaldehyde, controlling the dropwise adding speed to be about 2 hours, finishing dropwise adding, and keeping the temperature at 106 ℃ for 4 hours after dropwise adding. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, keeping the temperature for 70g in total, and continuing to keep the temperature until the temperature is kept.

4) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 8.

Example 9:

a resource utilization method of a waste toluene solvent generated in a pharmaceutical process comprises the following components, by mass, 30 parts of the waste toluene solvent, 230 parts of naphthalene, 260 parts of concentrated sulfuric acid (98%), 150 parts of formaldehyde (36% -37%), 390 parts of liquid sodium hydroxide (32%), and 70 parts of dilution water.

A method for resource utilization of waste toluene solvent generated in the pharmaceutical process comprises the following steps:

1) putting a four-neck flask with a condenser and a constant-pressure funnel into a heating sleeve, adding a mass part of waste toluene solvent, starting heating to raise the temperature to 105 ℃, slowly dropwise adding concentrated sulfuric acid (60 parts), after dropwise adding is finished for about 20min, starting adding a mass part of naphthalene, after the dropwise adding is finished, raising the temperature to 140 ℃, completely melting the naphthalene, starting slowly dropwise adding the rest mass part of concentrated sulfuric acid (200 parts), after 30min of dropwise adding is finished, controlling the temperature at 140-160 ℃ in the dropwise adding process, and after the dropwise adding is finished, keeping the temperature at 155-160 ℃ for 2 h.

2) Cooling after the naphthalene sulfonation is finished, cooling to 125 ℃, starting to mix the sulfonated mixture obtained in the step 1) into a four-neck flask, continuously cooling to 110 ℃, starting to slowly dropwise add formaldehyde, controlling the dropwise adding speed to be about 2 hours, finishing dropwise adding, and keeping the temperature at 106 ℃ for 4 hours after dropwise adding. And slowly adding a small amount of dilution water for multiple times with the thickening of the materials, keeping the temperature for 70g in total, and continuing to keep the temperature until the temperature is kept.

3) After the condensation and heat preservation are finished, the temperature is continuously reduced to about 80 ℃, and liquid sodium hydroxide is slowly added while stirring, so that the final pH value is 7.

When the mixing amount of the water reducing agent is 1.2%, analyzing the experimental results of each group by detecting the slump of the neat paste and the concrete, wherein the initial slump is T0, the experimental result detected in 10min is T10, and the experimental results are T20, T30, T40 and T50 in turn, and the detection results are shown in the following table 1:

TABLE 1

The three coal samples selected in the embodiment of the invention are coal blends composed of parts of Shenmu coal, Wuqi Turkey coal, Samontel coal, Xinjiang coal and inner Mongolia coal, and the experimental results of each group are analyzed, and the coal quality characteristics and the practical results are shown in the following tables 2, 3 and 4:

TABLE 2

TABLE 3

TABLE 4

As shown in tables 1 to 4, when the products obtained in examples 3, 4 and 2 are used as water reducing agents, the water reducing rate is higher than that of the conventional NX water reducing agents, and the collapse protection effect is good; compared with the conventional NX, the product obtained in the embodiment 3, the embodiment 4 or the embodiment 5 has better dispersibility, higher adaptability, stability and dispersibility, no hard settling phenomenon in 72 hours, higher cost performance and high popularization value when used as a water-coal-slurry dispersing agent.

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.