CN114933675B - Comprehensive utilization method of 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate - Google Patents
Comprehensive utilization method of 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate Download PDFInfo
- Publication number
- CN114933675B CN114933675B CN202210877426.XA CN202210877426A CN114933675B CN 114933675 B CN114933675 B CN 114933675B CN 202210877426 A CN202210877426 A CN 202210877426A CN 114933675 B CN114933675 B CN 114933675B
- Authority
- CN
- China
- Prior art keywords
- filtrate
- acrylamide
- water
- distillation concentrate
- methylpropanesulfonic acid
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a comprehensive utilization method of 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate, which comprises the following steps: adding the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate into water with the temperature of 30-60 ℃, and performing solid-liquid separation to obtain a wet product A and a filtrate B; the wet product A is leached by purified water and then dried to obtain N-tert-butyl acrylamide; adding active carbon into the filtrate B twice, and filtering to remove impurities to obtain filtrate C; heating, distilling and concentrating the filtrate C, and performing solid-liquid separation on concentrated precipitates to obtain a wet product D and a filtrate E; drying the wet product D to obtain 2-acrylamide-2-methyl propanesulfonate; transferring part of the filtrate E to a reaction kettle and heating; mixing the residual part of filtrate E with a polymerization monomer to obtain a mixed solution F; and (3) when the temperature in the kettle reaches 80-90 ℃, dropwise adding an initiator and the mixed solution F, carrying out heat preservation reaction, cooling and discharging to obtain the polycarboxylic acid scale inhibition and dispersion agent. The method can obtain three types of products, and has high resource utilization rate.
Description
Technical Field
The invention belongs to the technical field of chemical waste utilization, and particularly relates to a comprehensive utilization method of a 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate.
Background
The 2-acrylamido-2-methylpropanesulfonic acid (abbreviated as AMPS in English) has a carbon-carbon double bond, a carboxyl group and a sulfonic acid group in the molecule, and is endowed with excellent unique properties. The carbon-carbon double bond can enable the molecule to be homopolymerized and copolymerized with other molecules to form a high polymer; carboxyl enables molecules to have excellent adsorbability and complexation; the sulfonic acid group enables molecules to have excellent water solubility and salt resistance, and has excellent stability; the stability of 2-acrylamido-2-methylpropanesulfonic acid and its copolymers or homopolymers to hydrolysis, temperature and divalent cations makes its use as an irreplaceable monomer and polymer in certain fields. 2-acrylamido-2-methylpropanesulfonic acid has been widely used in industrial production of cement additives, water treatment agents, water retention agents, fillers, and the like.
At present, the typical production process of AMPS is to obtain crude product of AMPS by mixing acrylonitrile, sulfuric acid and isobutene for reaction, then refine the crude product to obtain high-purity AMPS, and then perform other processing and application.
In the AMPS production, after the crude product synthesis filtrate and the recrystallization filtrate are recovered by a rectification solvent, a certain amount of distillation concentrate can be generated, and the main components of the distillation concentrate are a byproduct N-tert-butyl acrylamide, a residual product 2-acrylamide-2-methyl propanesulfonic acid and a very small amount of other sulfonic acid impurities. The prior art mainly adopts an external payment incineration method for treatment, which not only increases the production cost and wastes resources, but also easily causes the environmental protection problem.
Chinese patents CN104250218B and CN105481714A both refer to the treatment of 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate, and each extract a part of substances in the distillation concentrate separately, so that on one hand, there are problems of complicated equipment, complex operation and large energy consumption, on the other hand, organic solvent is needed, secondary pollution exists, the purity of the obtained product is not high, and the overall utilization rate and economic benefit are not high.
CN112047855A is extracted by water to obtain a crude product of tert-butyl acrylamide, and the crude product is further purified by sublimation and refining through special equipment. Complex operation and equipment, limited improvement of the purity of the final product and low resource utilization rate. CN104926697A mentions a co-production method, which also uses water as solvent to extract tert-butyl acrylamide, but the process design has defects, and the purity of the final product is not high.
CN110857325B discloses a preparation process of a polymer scale inhibitor for solving the problem of distillation concentrate, only one product is finally obtained, the application range is limited, and the additional value is not high.
Disclosure of Invention
The invention aims to provide a comprehensive utilization method of a 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate, which can realize the complete utilization of the AMPS distillation concentrate, has high resource utilization rate, can obtain three types of products, and has multiple varieties, high purity and good performance.
In order to solve the technical problems, the technical scheme of the invention is as follows: the comprehensive utilization method of the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate comprises the following steps:
s1, adding the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate into water at the temperature of 30-60 ℃, carrying out heat preservation and stirring, cooling to normal temperature, and carrying out solid-liquid separation to obtain a wet product A and a filtrate B; before the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate is added into water, maintaining the temperature at 30-60 ℃;
s2, leaching the wet product A for 1-3 times by using purified water, wherein the first leaching water is converged into the filtrate B, and the subsequent leaching water is separately collected to be used as water for the subsequent distillation concentrate extraction reaction; drying the wet product A after washing to obtain a first product N-tert-butyl acrylamide;
s3, adding activated carbon into the filtrate B for the first time, and filtering to remove impurities; adding alkali into the filtrate, adjusting the pH value to 7-10, adding active carbon for the second time, and filtering again to remove impurities to obtain filtrate C; in the step, active carbon is added into the filtrate B twice, the first time is to adsorb some colored or colorless impurities which show acidity in the filtrate to avoid the impurities from reacting with subsequently added alkali to become soluble impurities, and simultaneously, the loss of the alkali is reduced; the second time is to absorb and remove colored or colorless impurities generated after the reaction of the filtrate and alkali;
s4, heating, distilling and concentrating the filtrate C, collecting distilled produced liquid to be used as subsequent distilled concentrate extraction reaction, adding water, and carrying out solid-liquid separation on concentrated precipitates to obtain a wet product D and a filtrate E;
s5, drying the wet product D to obtain a second product 2-acrylamide-2-methyl propanesulfonate, or directly dissolving the wet product D in purified water to obtain a 2-acrylamide-2-methyl propanesulfonate solution product;
s6, transferring a part of the filtrate E into a polymerization reaction kettle, and starting heating to raise the temperature; mixing the other part of the remaining filtrate E with a polymerization monomer to obtain a mixed solution F; and (3) when the temperature in the kettle reaches 80-90 ℃, starting to dropwise add the initiator and the mixed solution F, finishing dropwise adding the initiator, carrying out heat preservation reaction, cooling and discharging to obtain a third product, namely the polycarboxylic acid scale inhibition and dispersion agent.
Wherein, the distillation concentrate of the 2-acrylamido-2-methylpropanesulfonic acid can be a distillation concentrate of a synthetic filtrate or a distillation concentrate of a recrystallization filtrate or a mixture of the two in any proportion.
In step S1, the temperature of the 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate is maintained at 30-60 ℃ before adding the concentrate to water. It can be realized by heating, and also can adopt a newly prepared rectification thermal distillation concentrate; the heating mode can adopt any realizable forms such as hot water, steam, heat conduction oil, electric heating air blast and the like. The 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate and water are maintained at the temperature of 30-60 ℃, so that the problem of caking caused by direct contact of the concentrate with cold water can be avoided, the product purification purity can be improved, the influence of the cold water on the product crystal form can be reduced, and solid-liquid separation can be facilitated.
Preferably, in the step S1, the mass ratio of the 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate to water is 1 to 3, and the 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate is added while stirring. The temperature of the water is preferably 40-50 ℃, and the heat preservation stirring time is more than 30 min.
Preferably, in step S2, the wet product A is leached by purified water for 1 to 3 times, and the mass of the leaching water is 0.1 to 0.2 times of that of the distilled concentrate of the 2-acrylamido-2-methylpropanesulfonic acid. The more the leaching times, the higher the product purity, and the product purity is not increased after reaching a certain number of times. And the leaching has unexpected effects on improving the drying effect, shortening the drying time and improving the melting point of the product.
In the step S3, the alkali is any one of flake alkali, liquid alkali, sodium carbonate, ammonia water and potassium hydroxide.
In step S4, the filtrate C is heated, distilled and concentrated, the distillation and concentration is carried out by the conventional concentration technology, preferably, reduced pressure distillation and concentration is adopted, and the filtrate E obtained after the solid-liquid separation of the concentrated precipitate contains a small amount of 2-acrylamide-2-methylpropanesulfonic acid salt which is not completely precipitated and a small amount of other sulfonic acid or amide impurities containing unsaturated bonds. The sulfonic acid group can improve the calcium tolerance, has obvious scale inhibition effect on calcium phosphate, calcium carbonate, zinc scale and the like in water, prevents the deposition of ferric oxide, and particularly has high scale inhibition rate on the calcium phosphate. And the sulfonic acid group and the amide group polymer have good high temperature resistance, and the substances are excellent and are commonly used as monomer raw materials for preparing the polycarboxylic acid copolymer water treatment agent.
In step S6, the polymerized monomer is selected from one or a mixture of two of acrylic acid and acrylic ester in any proportion. The acrylic ester comprises methyl acrylate, ethyl acrylate, hydroxypropyl acrylate and the like, and the weight ratio of solid content to polymerized monomer in the filtrate E is 1.
In the step S6, the initiator is sodium persulfate or ammonium persulfate, and the adding amount of the initiator is 1.5-2.5% of the total mass of the obtained product.
Preferably, in step S6, the mass ratio of the part of filtrate E transferred into the polymerization reaction kettle to the rest of filtrate E is 1.
The solid-liquid separation in the present invention can be any method capable of realizing solid-liquid classification, including but not limited to centrifugation, suction filtration, filter pressing and the like.
Due to the adoption of the technical scheme, the invention has at least the following beneficial effects: the process method can realize the complete utilization of the distillation concentrate produced by the 2-acrylamide-2-methylpropanesulfonic acid, zero emission, no pollution and high resource utilization rate. The adopted raw materials are cheap and easy to obtain, and the environment-friendly effect is achieved without secondary pollution. The method can be used for obtaining three types of products, namely N-tert-butyl acrylamide, 2-acrylamide-2-methylpropanesulfonate or salt solution and polycarboxylic acid dirt dispersion agent, and has the advantages of multiple varieties, high purity, good performance and high added value, thereby really realizing the waste recycling, realizing the green, environment-friendly and pollution-free treatment process, simple equipment, simple operation and easy industrial production.
Detailed Description
The invention is further illustrated by the following examples. In the following detailed description, certain exemplary embodiments of the present invention have been described by way of illustration only. Needless to say, a person skilled in the art realizes that the described embodiments can be modified in various different ways without departing from the spirit and scope of the present invention. Accordingly, the following description is illustrative in nature and is not intended to limit the scope of the claims.
Example 1
(1) After the distillation of the mother liquor for producing the 2-acrylamide-2-methylpropanesulfonic acid is finished, the temperature in the distillation kettle is about 60 ℃, and the weight of the concentrate measured on line is 980kg in total. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. And (3) pressing the concentrate into an extraction kettle by opening compressed air, adding 1960kg of water with the temperature of 50 ℃ into the kettle in advance, keeping the temperature and stirring for 30min, cooling to 26 ℃, performing solid-liquid separation to obtain a wet product A and a filtrate B, leaching the wet product A with purified water for 3 times, wherein 98kg of the first leaching water is converged into the filtrate B each time, and separately collecting the later leaching water as the subsequent distilled concentrate extraction reaction water. The wet product A after washing is dried under reduced pressure at 50 ℃ for 4 hours to obtain 435kg of N-tert-butylacrylamide, white crystalline powder with the liquid phase purity of 99.83 percent, the melting point of 128.5 ℃ and the water content of 0.23 percent.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1) for the first time, filtering to remove impurities, then adding sodium hydroxide into the remaining filtrate, adjusting the pH to 9.60, and controlling the temperature to 20 ℃. Then 2.5kg of active carbon is added for the second time, and the filtration and the impurity removal are carried out to obtain filtrate C. And starting heating, distilling and concentrating the filtrate C, collecting distilled produced liquid to be used as subsequent distillation concentrate extraction reaction, adding water, carrying out solid-liquid separation on the concentrated precipitate to obtain a wet product D and a filtrate E, drying the wet product D to obtain 480kg of white 2-acrylamide-2-methylpropanesulfonic acid sodium salt, wherein the liquid phase purity is 98.3%.
(3) Transferring 134.5kg of part of filtrate E (with the solid content of 23.42%) obtained in the step (2) to a polymerization reaction kettle, adding 67kg of purified water, heating, mixing the other part of filtrate E with 63kg of acrylic acid to obtain a mixed solution F, and dissolving 11kg of sodium persulfate in 40kg of purified water to obtain a sodium persulfate solution (initiator). After the temperature in the kettle reaches 88 ℃, dropwise adding a sodium persulfate solution and the mixed solution F, and after the dropwise adding of the mixed solution F is finished for 20min, finishing the dropwise adding of the initiator; keeping the temperature for reaction for 4 hours, cooling to normal temperature, and discharging to obtain a light reddish brown scale inhibition and dispersion agent product with the solid content of 30.42 percent, the free monomer of 0.33 percent and the limit viscosity of 0.07dl/g.
Example 2
(1) After the distillation of the mother liquor for producing the 2-acrylamide-2-methylpropanesulfonic acid is finished, the temperature in the distillation kettle is about 60 ℃, and the weight of the concentrate measured on line is 980kg in total. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. And (3) compressed air is started to press the concentrate into an extraction kettle, 980kg of water with the temperature of 40 ℃ is added into the extraction kettle in advance, the temperature is kept and the stirring is carried out for 30min, the temperature is reduced to 25 ℃, the solid-liquid separation is carried out to obtain a wet product A and a filtrate B, purified water of the wet product A is leached for 3 times, 98kg of purified water is leached every time, the first leaching water is converged into the filtrate B, and the later leaching water is separately collected to be used as the subsequent water for the extraction reaction of the distillation concentrate. The wet product A after washing was dried under reduced pressure at 50 ℃ for 4 hours to obtain 439kg of N-t-butylacrylamide as white crystalline powder with a liquid phase purity of 99.78%, a melting point of 128.2 ℃ and a moisture content of 0.25%.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1) for the first time, filtering to remove impurities, then adding sodium hydroxide into the remaining filtrate, adjusting the pH to 9.50, and controlling the temperature to 23 ℃. Then 2.5kg of active carbon is added for the second time, and the filtrate C is obtained after filtration and impurity removal. And (3) starting heating, distilling and concentrating the filtrate C, and collecting distilled produced liquid as subsequent distilled concentrate extraction reaction water. And (3) performing solid-liquid separation on the precipitate to obtain a wet product D and a filtrate E, and drying the wet product D to obtain 480kg of white 2-acrylamide-2-methylpropanesulfonic acid sodium salt with the liquid phase purity of 98.1 percent.
(3) And (3) transferring 88kg of part of filtrate E (with the solid content of 22.35%) obtained in the step (2) to a polymerization reaction kettle, adding 68kg of purified water, heating, mixing the other part of filtrate E with 67kg of acrylic acid to obtain a mixed solution F, and dissolving 11kg of sodium persulfate in 40kg of purified water to obtain a sodium persulfate solution (initiator). And after the temperature in the kettle reaches 87 ℃, dropwise adding a sodium persulfate solution and the mixed solution F, after the dropwise adding of the mixed solution F is finished for 20min, finishing the dropwise adding of an initiator, carrying out heat preservation reaction for 3h, cooling to normal temperature, and discharging to obtain a light reddish brown scale inhibition and dispersion agent product, wherein the solid content is 30.37%, the free monomer is 0.30%, and the limit viscosity is 0.075dl/g.
Example 3
(1) After the distillation of the mother liquor for producing the 2-acrylamide-2-methylpropanesulfonic acid is finished, the temperature in the distillation kettle is about 60 ℃, and the weight of the concentrate measured on line is 980kg in total. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. And (3) compressed air is started to press the concentrate into an extraction kettle, 2940kg of water with the temperature of 50 ℃ is added into the extraction kettle in advance, the temperature is kept and the stirring is carried out for 30min, the temperature is reduced to 25 ℃, the solid-liquid separation is carried out to obtain a wet product A and a filtrate B, the wet product A is leached for 2 times by adopting purified water, 147kg of first-time leaching water is converged into the filtrate B every time, and the later leaching water is separately collected to be used as the subsequent distilled concentrate extraction reaction water. The wet product A after washing is dried under reduced pressure at 50 ℃ for 4 hours to obtain 430kg of N-tert-butylacrylamide, white crystalline powder with the liquid phase purity of 99.82%, the melting point of 128.2 ℃ and the water content of 0.28 percent.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1) for the first time, filtering to remove impurities, then adding sodium hydroxide into the remaining filtrate, adjusting the pH to 9.60, and controlling the temperature to be 20 ℃. Then 2.5kg of active carbon is added for the second time, and the filtration and the impurity removal are carried out to obtain filtrate C. Heating, distilling and concentrating the filtrate C, collecting distilled produced liquid as subsequent distilled concentrate extraction reaction, adding water, performing solid-liquid separation on the concentrated precipitate to obtain a wet product D and a filtrate E, drying the wet product D to obtain 479kg of white 2-acrylamido-2-methylpropanesulfonic acid sodium salt, wherein the liquid phase purity is 98.2%.
(3) 69.5kg of the filtrate E (with the solid content of 24.82%) obtained in the step (2) is transferred to a polymerization reaction kettle, 240.5kg of purified water is added, the temperature is raised by heating, the other part of the filtrate E, 208.5kg of the filtrate E, is mixed with 138kg of acrylic acid to obtain a mixed solution F, and 16kg of sodium persulfate is dissolved in 57.5kg of purified water to obtain a sodium persulfate solution (initiator). After the temperature in the kettle reaches 88 ℃, dropwise adding a sodium persulfate solution and the mixed solution F, and after the dropwise adding of the mixed solution F is finished for 20min, finishing the dropwise adding of the initiator; keeping the temperature for reaction for 4 hours, cooling to normal temperature, and discharging to obtain a light reddish brown scale inhibition and dispersion agent product with the solid content of 30.53 percent, the free monomer of 0.31 percent and the limit viscosity of 0.073dl/g.
Example 4
(1) After the distillation of the mother liquor for producing the 2-acrylamide-2-methylpropanesulfonic acid is finished, the temperature in the distillation kettle is about 60 ℃, and the weight of the concentrate measured on line is 980kg in total. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. And (3) compressed air is started to press the concentrate into an extraction kettle, 1960kg of water with the temperature of 50 ℃ is added into the kettle in advance, the temperature is kept and stirred for 30min, the temperature is reduced to 27 ℃, solid-liquid separation is carried out to obtain a wet product A and a filtrate B, the wet product A is leached by purified water for 2 times, 98kg of first-time leaching water is converged into the filtrate B every time, and the later leaching water is separately collected to be used as the subsequent distilled concentrate extraction reaction water. The wet product A after washing is dried under reduced pressure at 50 ℃ for 4 hours to obtain 436kg of N-tert-butylacrylamide, white crystalline powder with the liquid phase purity of 99.81 percent, the melting point of 128.6 ℃ and the water content of 0.28 percent.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1) for the first time, filtering to remove impurities, adding sodium carbonate into the remaining filtrate, adjusting the pH to 9.30, and controlling the temperature to be 21 ℃. And then 2.5kg of active carbon is added for the second time, and the filtrate C is obtained after filtration and impurity removal. And starting heating, distilling and concentrating the filtrate C, collecting distilled produced liquid as subsequent distillation concentrate extraction reaction, adding water, performing solid-liquid separation on concentrated precipitates to obtain a wet product D and a filtrate E, drying the wet product D to obtain 479kg of white 2-acrylamide-2-methylpropanesulfonic acid sodium salt, wherein the purity of a liquid phase is 98.1%.
(3) Transferring 135kg of part of filtrate E (with the solid content of 22.96%) obtained in the step (2) to a polymerization reaction kettle, adding 66kg of purified water, heating to raise the temperature, mixing the other part of filtrate E with 63kg of methyl acrylate to obtain a mixed solution F, and dissolving 11kg of sodium persulfate in 40kg of purified water to obtain a sodium persulfate solution (initiator). After the temperature in the kettle reaches 88 ℃, dropwise adding the sodium persulfate solution and the mixed solution F, and after the dropwise adding of the mixed solution F is finished for 20min, finishing the dropwise adding of the initiator; the reaction is kept for 4 hours, the temperature is reduced to normal temperature, and the light reddish brown scale inhibition and dispersion agent product with the solid content of 30.24 percent, the free monomer of 0.32 percent and the limit viscosity of 0.068dl/g is obtained.
Example 5
(1) After the distillation of the mother liquor for producing 2-acrylamido-2-methylpropanesulfonic acid was completed, the temperature in the distillation still was about 55 ℃, and the total weight of the on-line metered concentrate was 980kg. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. And (3) compressed air is started to press the concentrate into an extraction kettle, 2940kg of water with the temperature of 50 ℃ is added into the extraction kettle in advance, the temperature is kept and the stirring is carried out for 30min, the temperature is reduced to 25 ℃, solid-liquid separation is carried out to obtain a wet product A and a filtrate B, the wet product A is leached for 3 times by adopting purified water, 147kg of first-time leaching water is converged into the filtrate B every time, and the later leaching water is separately collected to be used as the subsequent distilled concentrate extraction reaction water. The wet product A after washing is dried under reduced pressure at 50 ℃ for 4 hours to obtain 431kg of N-tert-butylacrylamide, white crystalline powder with the liquid phase purity of 99.90 percent, the melting point of 128.5 ℃ and the water content of 0.21 percent.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1) for the first time, filtering to remove impurities, then adding potassium hydroxide into the remaining filtrate, adjusting the pH to 9.45, and controlling the temperature to be 19 ℃. Then 2.5kg of active carbon is added for the second time, and the filtration and the impurity removal are carried out to obtain filtrate C. And starting heating, distilling and concentrating the filtrate C, collecting distilled produced liquid to be used as subsequent distilled concentrate extraction reaction, adding water, carrying out solid-liquid separation on concentrated precipitates to obtain a wet product D and a filtrate E, drying the wet product D to obtain 478kg of white 2-acrylamide-2-methylpropanesulfonic acid potassium salt, wherein the liquid phase purity is 98.0%.
(3) 70kg of part of filtrate E (with the solid content of 24.29%) obtained in the step (2) is transferred to a polymerization reaction kettle, 230.5kg of purified water is added, the temperature is raised by heating, the other part of filtrate E, 210kg of filtrate E, is mixed with 136kg of hydroxypropyl acrylate to obtain mixed solution F, and 16kg of sodium persulfate is dissolved in 57.5kg of purified water to obtain a sodium persulfate solution (initiator). After the temperature in the kettle reaches 88 ℃, dropwise adding the sodium persulfate solution and the mixed solution F, and after the dropwise adding of the mixed solution F is finished for 20min, finishing the dropwise adding of the initiator; keeping the temperature for reaction for 4 hours, cooling to normal temperature, and discharging to obtain a light red brown scale inhibition and dispersion agent product with the solid content of 30.58 percent, the free monomer of 0.29 percent and the limit viscosity number of 0.071dl/g.
Comparative example 6
(1) After the distillation of the mother liquor for producing the 2-acrylamide-2-methylpropanesulfonic acid is finished, the temperature in the distillation kettle is about 60 ℃, and the weight of the concentrate measured on line is 980kg in total. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. And (3) compressed air is started to press the concentrate into an extraction kettle, 1960kg of water with the temperature of 40 ℃ is added into the kettle in advance, the temperature is kept and stirred for 30min, the temperature is reduced to 25 ℃, solid-liquid separation is carried out to obtain a wet product A and a filtrate B, purified water of the wet product A is leached for 1 time and 98kg, and leaching water is converged into the filtrate B. The wet product A after washing was dried under reduced pressure at 50 ℃ for 4 hours to obtain 437kg of N-t-butylacrylamide in the form of white crystalline powder with a liquid phase purity of 99.75%, a melting point of 128.0 ℃ and a moisture content of 0.35%.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1), filtering to remove impurities, then adding sodium hydroxide into the remaining filtrate, adjusting the pH to 9.50, and controlling the temperature to 23 ℃ to obtain filtrate C. And (3) starting heating, distilling and concentrating the filtrate C, and collecting distilled produced liquid as subsequent distilled concentrate extraction reaction water. And performing solid-liquid separation on the precipitate to obtain a wet product D and a filtrate E, and drying the wet product D to obtain 481.5kg of white 2-acrylamide-2-methylpropanesulfonic acid sodium salt with the liquid phase purity of 97.2%.
(3) 132.5kg of the filtrate E (with the solid content of 22.45%) obtained in the step (2) is transferred to a polymerization reaction kettle, 102kg of purified water is additionally added, the temperature is raised by heating, the other part of the filtrate E, 132.5kg of the filtrate E and 83kg of acrylic acid are mixed to obtain a mixed solution F, and 10kg of sodium persulfate is dissolved in 40kg of purified water to obtain a sodium persulfate solution (initiator). And after the temperature in the kettle reaches 87 ℃, dropwise adding a sodium persulfate solution and the mixed solution F, after 15min of dropwise adding of the mixed solution F, finishing dropwise adding of an initiator, carrying out heat preservation reaction for 3h, cooling to normal temperature, and discharging to obtain a light reddish brown scale inhibition and dispersion agent product, wherein the solid content is 30.51%, the free monomer content is 0.35%, and the limiting viscosity is 0.065dl/g.
Comparative example 7
(1) After the distillation of the mother liquor for producing 2-acrylamido-2-methylpropanesulfonic acid was completed, the temperature in the distillation still was about 60 ℃, and the total weight of the on-line metered concentrate was 980kg. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. Introducing compressed air to the concentrate, adding water (1960 kg) at 50 deg.C into the extraction kettle, stirring for 30min, cooling to 25 deg.C, and performing solid-liquid separation to obtain wet product A and filtrate B. The wet product A is dried under reduced pressure at 50 ℃ for 5 hours to obtain 440kg of N-tert-butyl acrylamide, white crystalline powder with the liquid phase purity of 99.33 percent, the melting point of 127.1 ℃ and the water content of 0.53 percent.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1) for the first time, filtering to remove impurities, then adding sodium hydroxide into the remaining filtrate, adjusting the pH to 9.50, and controlling the temperature to 20 ℃. Then 2.5kg of active carbon is added for the second time, and the filtrate C is obtained after filtration and impurity removal. And (4) starting heating, distilling and concentrating the filtrate C, and collecting distilled produced liquid to be used as subsequent distilled concentrate extraction reaction and adding water. And (3) performing solid-liquid separation on the precipitate to obtain a wet product D and a filtrate E, and drying the wet product D to obtain 477kg of white 2-acrylamide-2-methylpropanesulfonic acid sodium salt with the liquid phase purity of 98.2 percent.
(3) 258kg of the total filtrate E (with the solid content of 22.09%) obtained in the step (2) is transferred to a polymerization reaction kettle, 45kg of purified water is additionally added, the temperature is raised by heating, and 10kg of sodium persulfate is dissolved in 40kg of purified water to obtain a sodium persulfate solution (initiator). And after the temperature in the kettle reaches 88 ℃, dropwise adding a sodium persulfate solution and 57kg of acrylic acid, keeping the temperature for reaction for 4 hours after the dropwise adding is finished, and discharging at normal temperature to obtain a light reddish brown scale inhibition and dispersion agent product with the solid content of 30.24 percent, the free monomer content of 0.45 percent and the limit viscosity number of 0.05dl/g.
Comparative example 8
(1) After the distillation of the mother liquor for producing the 2-acrylamide-2-methylpropanesulfonic acid is finished, the temperature in the distillation kettle is about 25 ℃, and the weight of the concentrate measured on line is 980kg in total. The concentrate contained 45% N-t-butylacrylamide, 50% AMPS and 5% others. Compressed air is started to press the concentrate into an extraction kettle, 1960kg of water with the temperature of 25 ℃ is added into the kettle in advance, then the kettle is heated to 40 ℃, the temperature is kept and the stirring is carried out for 30min, the temperature is reduced to 25 ℃, solid-liquid separation is carried out to obtain a wet product A and a filtrate B, the wet product A is leached for 3 times by adopting purified water, 98kg of purified water is added into the filtrate B every time, and later leaching water is separately collected to be used as subsequent water for the extraction reaction of the distillation concentrate. The wet product A after washing was dried under reduced pressure at 50 ℃ for 4 hours to obtain 438kg of N-t-butylacrylamide, white crystalline powder (containing fine agglomerates), liquid phase purity 98.63%, melting point 126.7 ℃ and water content 0.33%.
(2) Adding 2.5kg of activated carbon into the filtrate B obtained in the step (1) for the first time, filtering to remove impurities, then adding sodium hydroxide into the remaining filtrate, adjusting the pH to 9.60, and controlling the temperature to 20 ℃. Then 2.5kg of active carbon is added for the second time, and the filtration and the impurity removal are carried out to obtain filtrate C. And starting heating, distilling and concentrating the filtrate C, collecting distilled produced liquid to be used as subsequent distilled concentrate extraction reaction, adding water, carrying out solid-liquid separation on concentrated precipitates to obtain a wet product D and a filtrate E, drying the wet product D to obtain 478kg of white 2-acrylamide-2-methylpropanesulfonic acid sodium salt, wherein the liquid phase purity is 98.2%.
(3) Transferring 132kg of part of filtrate E (with the solid content of 23.48%) obtained in the step (2) to a polymerization reaction kettle, adding 71kg of purified water, heating, mixing the other part of filtrate E with 65kg of acrylic acid to obtain a mixed solution F, and dissolving 10kg of sodium persulfate in 40kg of purified water to obtain a sodium persulfate solution (initiator). After the temperature in the kettle reaches 88 ℃, dropwise adding the sodium persulfate solution and the mixed solution F, and after the dropwise adding of the mixed solution F is finished for 20min, finishing the dropwise adding of the initiator; the reaction is kept for 4 hours, the temperature is reduced to normal temperature, and the light reddish brown scale inhibition and dispersion agent product with the solid content of 30.43 percent, the free monomer of 0.33 percent and the limit viscosity of 0.07dl/g is obtained.
In conclusion, the process method can realize the complete utilization of the distillation concentrate produced by the 2-acrylamide-2-methylpropanesulfonic acid, and has the advantages of zero emission, no pollution and high resource utilization rate. The method can be used for obtaining three types of products, namely N-tert-butyl acrylamide, 2-acrylamide-2-methylpropanesulfonate or salt solution and polycarboxylic acid dirt dispersion agent, and the products have high purity and good performance.
In addition, it can be seen from examples 1 to 5 and comparative examples 6 to 8 that:
(1) When the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate is contacted with water, the temperature is required to be maintained at 30-60 ℃, but the temperature cannot be raised to the temperature only after the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate is completely mixed, otherwise, the purity, the melting point and the form of the obtained N-tert-butyl acrylamide product are influenced; as comparative example 8, 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate was initially in cold contact with water, and even if the temperature was raised later, the effect was not good, and there were still small lumps in the product obtained and the melting point (126.7 ℃ C.) was low; if the heating temperature is too high, the product is easily degraded by polymerization.
(2) When the wet product A is treated, purified water is preferably adopted for leaching for 1-3 times, and the more leaching times, the higher the product purity, and the product purity is not increased after a certain number of times. And the leaching has unexpected effects on improving the drying effect, shortening the drying time and improving the melting point of the product. As in comparative example 7, wet product A was not rinsed with purified water, and the melting point of the resulting N-t-butylacrylamide product (127.1 ℃ C.) was lower.
(3) When the filtrate B is treated, active carbon is added to the filtrate B twice, so that the purity of the 2-acrylamide-2-methyl propanesulfonate can be effectively improved. As comparative example 6, the liquid phase purity of the obtained 2-acrylamido-2-methylpropanesulfonic acid salt was only 97.2% by adding activated carbon to the filtrate B only once, which was significantly lower than that of the activated carbon added twice in examples and other comparative examples.
(4) When the filtrate E is treated, transferring a part of the filtrate E into a polymerization reaction kettle, and starting heating to raise the temperature; mixing the other part of the remaining filtrate E with a polymerization monomer to obtain a mixed solution F; and (3) after the temperature in the kettle reaches a set requirement, beginning to dropwise add the initiator and the mixed solution F, finishing dropwise adding the mixed solution F, and finishing dropwise adding the initiator, so that the obtained scale inhibition and dispersion agent product has moderate viscosity and good performance. As comparative example 7, the whole filtrate E was transferred to a polymerization reactor and the limiting viscosity (0.05 dl/g) of the resulting dispersion product was lower without reacting according to the above process.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
- The comprehensive utilization method of the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate is characterized by comprising the following steps:s1, adding the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate into water at the temperature of 30-60 ℃, carrying out heat preservation and stirring, cooling to normal temperature, and carrying out solid-liquid separation to obtain a wet product A and a filtrate B; before the 2-acrylamide-2-methylpropanesulfonic acid distillation concentrate is added into water, maintaining the temperature at 30-60 ℃;s2, leaching the wet product A for 1-3 times by using purified water, wherein the first leaching water is converged into the filtrate B, and the subsequent leaching water is separately collected to be used as water for the subsequent distillation concentrate extraction reaction; drying the wet product A after the washing to obtain a first product N-tertiary butyl acrylamide;s3, adding activated carbon into the filtrate B for the first time, and filtering to remove impurities; adding alkali into the filtrate, adjusting the pH value to 7-10, adding active carbon for the second time, and filtering again to remove impurities to obtain filtrate C;s4, heating, distilling and concentrating the filtrate C, collecting distilled produced liquid as subsequent distillation concentrate extraction reaction, adding water, and performing solid-liquid separation on concentrated precipitates to obtain a wet product D and a filtrate E;s5, drying the wet product D to obtain a second product 2-acrylamide-2-methyl propanesulfonate, or directly dissolving the wet product D in purified water to obtain a 2-acrylamide-2-methyl propanesulfonate solution product;s6, transferring a part of the filtrate E into a polymerization reaction kettle, and starting heating to raise the temperature; mixing the other part of the residual filtrate E with a polymerization monomer to obtain a mixed solution F; and (3) when the temperature in the kettle reaches 80-90 ℃, starting to dropwise add the initiator and the mixed solution F, finishing dropwise adding the initiator, performing heat preservation reaction, cooling and discharging to obtain a third product, namely the polycarboxylic acid scale inhibition and dispersion agent.
- 2. The process for the comprehensive utilization of the distillation concentrate of 2-acrylamido-2-methylpropanesulfonic acid according to claim 1, wherein: the 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate is a synthetic filtrate distillation concentrate or a recrystallization filtrate distillation concentrate or a mixture of the two in any proportion.
- 3. The process for the integrated utilization of 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate according to claim 1, wherein: in the step S1, the mass ratio of the 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate to water is 1 to 3.
- 4. The process for the comprehensive utilization of the distillation concentrate of 2-acrylamido-2-methylpropanesulfonic acid according to claim 1, wherein: in the step S2, the mass of the rinsing water each time is 0.1 to 0.2 time of the mass of the 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate.
- 5. The process for the integrated utilization of 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate according to claim 1, wherein: in the step S3, the alkali is any one of flake alkali, liquid alkali, sodium carbonate, ammonia water and potassium hydroxide.
- 6. The process for the integrated utilization of 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate according to claim 1, wherein: in the step S6, the polymerization monomer is selected from one or a mixture of two of acrylic acid and acrylic ester in any proportion, and the weight ratio of the solid content in the filtrate E to the polymerization monomer is 1.
- 7. The process for the integrated utilization of 2-acrylamido-2-methylpropanesulfonic acid distillation concentrate according to claim 1, wherein: in step S6, the initiator is sodium persulfate or ammonium persulfate.
- 8. The process for the comprehensive utilization of the distillation concentrate of 2-acrylamido-2-methylpropanesulfonic acid according to claim 1, wherein: in step S6, the mass ratio of the part of the filtrate E transferred into the polymerization reactor to the other part of the filtrate E is 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210877426.XA CN114933675B (en) | 2022-07-25 | 2022-07-25 | Comprehensive utilization method of 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210877426.XA CN114933675B (en) | 2022-07-25 | 2022-07-25 | Comprehensive utilization method of 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114933675A CN114933675A (en) | 2022-08-23 |
| CN114933675B true CN114933675B (en) | 2022-10-04 |
Family
ID=82868566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210877426.XA Active CN114933675B (en) | 2022-07-25 | 2022-07-25 | Comprehensive utilization method of 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114933675B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1566639A (en) * | 1976-05-18 | 1980-05-08 | Merck & Co Inc | Additive for compositions used in oil recovery |
| EP0068038A1 (en) * | 1981-06-29 | 1983-01-05 | Merck & Co. Inc. | (+)-(4R,6S)-(E)-6-(2-(4'-fluoro-3,3',5-trimethyl-(1,1'-biphenyl)-2-yl)ethenyl)-3,4,5,6-tetrahydro-4-hydroxy-2H-pyran-2-one, a process for preparing and a pharmaceutical composition containing the same |
| CA2252941A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Detergent compositions comprising modified polyamines as dye transfer inhibitors |
| JP2005029476A (en) * | 2003-07-08 | 2005-02-03 | Toagosei Co Ltd | METHOD FOR PRODUCING tert-BUTYLACRYLAMIDE |
| JP2005154740A (en) * | 2003-10-29 | 2005-06-16 | Nippon Shokubai Co Ltd | Polymer, method for producing the same, and use of the same |
| CN104395834A (en) * | 2012-06-29 | 2015-03-04 | 富士胶片株式会社 | Method for concentrating processing waste liquid and method for recycling processing waste liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101783494B1 (en) * | 2009-11-04 | 2017-09-29 | 바스프 에스이 | Process for producing aqueous polyacrylic acid solutions |
-
2022
- 2022-07-25 CN CN202210877426.XA patent/CN114933675B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1566639A (en) * | 1976-05-18 | 1980-05-08 | Merck & Co Inc | Additive for compositions used in oil recovery |
| EP0068038A1 (en) * | 1981-06-29 | 1983-01-05 | Merck & Co. Inc. | (+)-(4R,6S)-(E)-6-(2-(4'-fluoro-3,3',5-trimethyl-(1,1'-biphenyl)-2-yl)ethenyl)-3,4,5,6-tetrahydro-4-hydroxy-2H-pyran-2-one, a process for preparing and a pharmaceutical composition containing the same |
| CA2252941A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Detergent compositions comprising modified polyamines as dye transfer inhibitors |
| JP2005029476A (en) * | 2003-07-08 | 2005-02-03 | Toagosei Co Ltd | METHOD FOR PRODUCING tert-BUTYLACRYLAMIDE |
| JP2005154740A (en) * | 2003-10-29 | 2005-06-16 | Nippon Shokubai Co Ltd | Polymer, method for producing the same, and use of the same |
| CN104395834A (en) * | 2012-06-29 | 2015-03-04 | 富士胶片株式会社 | Method for concentrating processing waste liquid and method for recycling processing waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114933675A (en) | 2022-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101580464B (en) | Method for producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct | |
| CN102910676B (en) | Preparation method of high-purity vanadium pentoxide | |
| CN112707808A (en) | Preparation process of 2-hydroxy-6-naphthoic acid | |
| CN115403019A (en) | Preparation method of iron phosphate | |
| CN114933675B (en) | Comprehensive utilization method of 2-acrylamide-2-methyl propanesulfonic acid distillation concentrate | |
| CN101168543A (en) | Process for producing glucurolactone | |
| CN107032981B (en) | A kind of method recycled containing sodium formate and sodium chloride mixing solid wastes recycling | |
| CN101955233A (en) | Method for producing ferrous sulphate monohydrate | |
| CN110857325B (en) | Method for treating 2-acrylamide-2-methylpropanesulfonic acid kettle residue | |
| CN113307774B (en) | Method for recovering imidazole from imidazole hydrochloride wastewater | |
| CN105271406B (en) | A kind of preparation method of sodium metavanadate | |
| CN109694049B (en) | Treatment method of phosphated slag containing zinc, calcium and iron | |
| CN110040698B (en) | Method for treating titanium dioxide waste acid by using magnesium sulfate | |
| CN101219802A (en) | Method for producing basic magnesium carbonate with boric sludge | |
| CN103421043A (en) | Hydrosis process improvement method for synthesizing glyphosate by alkyl ester process | |
| CN101987737A (en) | Method for preparing spectrum pure calcium carbonate | |
| CN111574387A (en) | P-aminomethyl benzoic acid and preparation method thereof | |
| CN110451550A (en) | One-step method prepares the method and semi-hydrated gypsum of semi-hydrated gypsum co-production Aluminum Chloride Hexahydrate | |
| CN115073302B (en) | Method for extracting tetrabutylammonium bromide from byproduct mother liquor | |
| CN1052962C (en) | New method for producing potassium sulfate | |
| CN115323181B (en) | Method for recovering vanadium from calcified vanadium extraction tailings | |
| CN115057568B (en) | Method for treating ammonium paratungstate crystallization mother liquor | |
| CN113980175A (en) | Preparation method of modified hydrolyzed polymaleic anhydride | |
| CN117210971A (en) | Method for preparing high-water-holding capacity and high-oil-holding capacity nano citrus fiber | |
| CN1240195A (en) | Process for preparing potassium sulfate by using potassium chloride and aminium sulfate |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |