CN109593054B - Method for preparing tri-monomer by neutralizing esterification material containing dimethyl isophthalate-5-sulfonic acid - Google Patents
Method for preparing tri-monomer by neutralizing esterification material containing dimethyl isophthalate-5-sulfonic acid Download PDFInfo
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Abstract
The invention provides a method for preparing a tri-monomer by neutralizing an esterification material containing dimethyl isophthalate-5-sulfonic acid, which comprises the steps of adding process water and the esterification material, adding part of soda ash, transferring the material and controlling a reaction end point. When the method is applied to an industrial device, the conversion rate of the isophthalic acid-dimethyl ester 5-sulfonic acid exceeds 97 percent and reaches 97.15 to 97.65 percent, the yield of the crude product of the three monomers in the neutralization process (calculated by the isophthalic acid dimethyl ester-5-sulfonic acid) is 96.09 to 96.77 percent, and the yield of the product of the three monomers prepared by the subsequent refining and drying processes exceeds 84 percent; the neutralization reaction period is shortened to 435-475 min; due to the effective control of the neutralization end point and the combination of other neutralization process parameters, the side reaction is reduced, particularly the amount of the tri-monomer finished product hydrolyzed into the m-phthalic acid monomethyl ester-5-sodium sulfonate is reduced, and the amount and quantity of other byproducts are reduced.
Description
Technical Field
The present invention belongs to the field of organic synthesis technology, and is especially suitable for preparing tri-monomer with esterification product (dimethyl isophthalate-5-sulfonic acid as main component) in the production process of inorganic alkaline compound and tri-monomer (chemical name: dimethyl isophthalate-5-sodium sulfonate, abbreviated as SIPM).
Background
The existing tri-monomer production process adopts any process route, takes dimethyl isophthalate-5-sulfonic acid which is a main component in an esterified material as an initial raw material, and prepares the tri-monomer through alkali liquor neutralization, wherein the used alkali generally comprises sodium carbonate, sodium hydroxide, sodium sulfite and the like. Because numerous side reactions are inevitable when the dimethyl isophthalate-5-sulfonic acid is synthesized, a certain amount of by-products such as monomethyl isophthalate-5-sulfonic acid and the like exist in a system, when neutralization is carried out, the reaction degree of each component and alkali is different, and different neutralization process parameters have larger influence on the conversion rate of the dimethyl isophthalate-5-sulfonic acid, hydrolysis reaction, subsequent refining of a neutralization product and the like. Because of more components generated in the neutralization process, the intensive research on the neutralization process of the three monomers, the improvement of the conversion rate of the dimethyl isophthalate-5-sulfonic acid and the yield of the three monomers is a subject which is always concerned and regarded by the three-monomer industry at home and abroad. The prior main research results for producing the three monomers by neutralizing the m-phthalic acid dimethyl ester-5-sulfonic acid comprise:
yanglin, a chemical auxiliary factory, Yanyang, in Shaanxi province, in the fine chemical industry, 1998, 3 rd published article, 5-dimethyl isophthalate sodium sulfonate, synthetic research, proposes a method for preparing SIPM by using isophthalic acid as a raw material and silicon dioxide as a catalyst through the processes of sulfonation, esterification, neutralization and the like, wherein the total yield is 76%, and the purity is 99.5%.
Li Shiwu proposed a process for preparing SIPM by sulfonation, esterification and neutralization using 30% fuming sulfuric acid as a sulfonating agent and isophthalic acid as a reaction raw material in the study of synthesis and industrial scale-up research and analysis of low-cost cationic dyeable polyester (2002) of Master thesis at Hunan university. Wherein, NaOH with the concentration of 30 percent is used in the neutralization reaction, the pH value of the neutralization end point is controlled to be less than or equal to 7, and the neutralization later stage needs to be frozen. The final SIPM average yield was only 61.9%.
The great Lizhong university of Qingdao science and technology, Li nationality et al, published in spectral laboratory 2003, 4 th phase, paper HPLC analysis of improved preparation Process of sodium Dimethoate 5-Isophthalate, determined that the temperature is 25 ℃, the optimum pH =5, and the waste liquid SIPM and Na are neutralized2The SO4 content determination confirms that the product yield reaches 83 percent.
A process for preparing SIPM by sulfonating, esterifying and neutralizing reaction between 50% fuming sulfuric acid as sulfonating agent and phthalic acid as reaction raw materials in the synthesis and process condition optimization of cation dyeable polyester modified additive (2004) of Shuichi treatise of Qingdao university of technology in Qingdao, Tangxuli. The proposed neutralization process conditions are: neutralizing with liquid NaOH at 25 deg.C to obtain final product SIPM with yield of 78.7%;
weifanwa volter chemical Limited Wang Xinpeng, et al, published in Shandong chemical engineering, stage 2, 2012, of the study on neutralization process in sodium dimethyl isophthalate-5-sulfonate production, conducted intensive studies on the neutralization process, analyzed the purity of the neutralized material, and the contents of SIPM and sodium sulfate in the neutralized and centrifuged waste liquid by liquid chromatography, and determined the optimal neutralization conditions, that is, at 30 ℃, the optimal pH value of the neutralization reaction is 6.5, the product purity can reach more than 99.5%, but the yield of SIPM is only about 80%.
Plum ice is a small-scale process for synthesizing isophthalic acid-5-sulfonic acid by using 1, 3-phthalic acid and 22% fuming sulfuric acid, then re-esterifying, neutralizing, refining and crystallizing in a research study on the synthesis and performance of 1, 3-dimethyl phthalate-5-sodium sulfonate (2012, 5 month) of a Master thesis of Petroleum university (east China), wherein liquid NaOH is adopted for neutralization, the reaction temperature is 10-35 ℃, the end-point pH value is controlled to be 7, and the yield of SIPM is 84.3%;
the prior method for producing the tri-monomer by using alkali inorganic salt to neutralize the esterified material mainly has the following problems:
1. the conversion rate of the dimethyl isophthalate-5-sulfonic acid is low, and the yield of the finished product of the tri-monomer is low because the conversion rate of the dimethyl isophthalate-5-sulfonic acid is generally not more than 92% in domestic and the same industry (because the parameter for controlling the reaction end point during adding alkali only depends on one index of pH value); and in the neutralization step, the yield of the crude product of the three monomers is not more than 92 percent based on the dimethyl isophthalate-5-sulfonic acid.
2. The neutralization reaction time is long, and the neutralization process of some industrial devices only adds alkali (sodium carbonate solution) for 8 hours; the neutralization reaction time of the existing small test is 2-4h, and the time of industrial production is generally 8-12 h.
The addition of alkali is an exothermic reaction, and too fast addition of sodium carbonate solution can cause flooding (i.e., the carbon dioxide produced carries material out of the neutralization kettle and causes loss).
3. The reaction end point is determined only by one parameter of pH value, so that the accuracy is poor, the repeatability is poor, the error is large, and the reaction end point cannot be correctly judged.
4. The side reactions are more, a large amount of foams are generated on materials in the kettle in the neutralization process, the centrifuged materials sometimes form red, yellow, brown yellow and other materials, the subsequent refining process is difficult, the purity of the three monomers is low, the impurities are more and high, and even the final product with the three monomers is unqualified.
Disclosure of Invention
Aiming at the problems of low conversion rate of dimethyl isophthalate-5-sulfonic acid, more side reactions, low yield of finished products of the tri-monomers, long reaction time, high cost of the finally prepared products of the tri-monomers, low purity, more impurities, high content and the like in the neutralization process in the existing production of synthesizing the tri-monomers by neutralizing an esterified material with an alkali liquor, the invention improves the prior process and forms a new production process. The main purposes of the invention are as follows:
1. the conversion rate of the dimethyl isophthalate-5-sulfonic acid and the yield of the tri-monomer are improved;
2. the reaction time is shortened;
3. side reactions are reduced, the purity of the three monomers is improved, and the impurity content is reduced;
4. the accuracy of determining the reaction end point is improved;
5. the solid sodium carbonate is directly added into the neutralization kettle without preparing the sodium carbonate solution in advance, so that the operation is simplified, the cost is reduced, and the economic benefit of the product is improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a tri-monomer by neutralizing an esterification material containing dimethyl isophthalate-5-sulfonic acid comprises the steps of adding process water and the esterification material, adding part of soda ash, transferring the materials and controlling the reaction end point.
The method specifically comprises the following steps:
1. adding process water and an esterification material
Adding process water into a neutralization kettle, starting stirring, introducing cooling water into a jacket of the first neutralization kettle, and completely putting all the lactone materials in the esterification kettle into the first neutralization kettle.
2. Adding part of soda ash
When the temperature of the materials in the first neutralization kettle is reduced to 16-20 ℃, starting a spiral feeder, starting to add solid sodium carbonate into the neutralization kettle, opening a discharge valve at the bottom of the first neutralization kettle when 23.5-27% of the total amount of the sodium carbonate is added, and starting a circulating pump of the first neutralization kettle to start circulation; the temperature of the first neutralization kettle is controlled to be 35-40 ℃ in the operation process.
3. Transferring material
When 47-53% of the total amount of the soda is added, switching a discharge valve of a circulating pump of a first neutralization kettle, pumping materials of the first neutralization kettle into a second neutralization kettle, introducing cooling water into a jacket of the second neutralization kettle, pumping the materials of the first neutralization kettle into the second neutralization kettle for 10-15 minutes, then starting the circulating pump of the second neutralization kettle, pumping the materials in the second neutralization kettle into the first neutralization kettle, and controlling the temperature in the second neutralization kettle to be 35-40 ℃; and at the moment, the change situation of the pH value of the neutralization material displayed by the on-line digital display pH meter at the outlet of the circulating pump of the first neutralization kettle is observed.
4. Control of the end of the reaction
When 90.4-95% of the total amount of the soda is added and the pH value of the neutralization material is 6.9 as shown by an online digital display pH meter, 2.3-5.5% of the total amount of the soda is continuously added into the neutralization kettle, the observed pH value data is 7.0, and the sample can be sampled after about 10 minutes, and the saponification value of the sample (liquid material) can be rapidly sampled and analyzed. And when the saponification value of the sample (liquid material) is higher than 95mgKOH/g, adding all metered sodium carbonate into the first neutralization kettle, adding the rest sodium carbonate, continuing stirring for 15-30 minutes, wherein the digital display pH meter displays that the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation is finished. Sampling, analyzing and obtaining saponification value not less than 97.5mgKOH/g and reaching 97.28-99.94KOH/g, centrifuging the neutralized material, drying by spinning, and carrying out post-treatment and refining to obtain the finished product of the tri-monomer.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the conversion rate of the dimethyl isophthalate-5-sulfonic acid and the yield of the tri-monomer are improved;
when the method is applied to an industrial device, the conversion rate of the isophthalic acid-dimethyl ester 5-sulfonic acid exceeds 97 percent and reaches 97.15 to 97.65 percent, the yield of the crude product of the three monomers in the neutralization process (calculated by the isophthalic acid dimethyl ester-5-sulfonic acid) is 96.09 to 96.77 percent, the yield of the product of the three monomers prepared by the subsequent refining and drying processes exceeds 84 percent, and the product quality reaches the high-grade product standard in the industry.
2. The reaction time is shortened;
the neutralization reaction period is shortened to 435-475 minutes. After the neutralization temperature is increased to 35-40 ℃, except that the reaction speed is accelerated, Na is in a set temperature range2CO3Has the highest solubility, solid Na2CO3Adding into a neutralization kettle, adding a stirrer and a forced circulation liquid to act synergistically, and adding Na2CO3Has an accelerated solubility and a high solubility of sodium sulphate, Na2CO3The speed of participating in the neutralization reaction is also increased.
3. Side reactions are reduced, the purity of the three monomers is improved, and the impurity content is reduced;
due to the effective control of the neutralization end point and the combination of other neutralization process parameters, the side reaction is reduced, particularly the amount of the tri-monomer finished product hydrolyzed into the m-phthalic acid monomethyl ester-5-sodium sulfonate is reduced, and the amount and quantity of other byproducts are reduced.
The acid value of the prepared three-monomer finished product is 0.23-0.56 mgKOH/g, the saponification value is 377.65-379.73 mgKOH/g, the sulfate radical content is 70.82-98.202 mg/kg, and Fe3+The content of Cl is 2.65-4.21 mg/kg-The content is 3.56-9.25 mg/kg, the chroma is No. 20-25, and the water content is 0.35-0.47%.
4. Determining a neutralization reaction end point, and improving the accuracy of determining the reaction end point;
in the neutralization reaction, besides the reaction of soda ash with sulfuric acid, dimethyl isophthalate-5-sulfonic acid, monomethyl isophthalate-5-sulfonic acid and isophthalic acid-5-sulfonic acid, there are many side reactions. The determination of the reaction end point of the prior art is generally as follows: firstly, sampling and analyzing the pH value, stopping adding alkali after the pH value reaches 7, continuing to react for 30 minutes, then sampling and analyzing the pH value, stopping the neutralization reaction if the pH value is maintained at 7, and carrying out next refining operation on the neutralized material; if the pH value is maintained to be less than 7, adding a certain amount of soda ash, continuing to operate and test until the pH value is maintained to be 7, and stopping the neutralization reaction; firstly, sampling and carrying out liquid chromatography analysis, and determining whether the neutralization reaches the end point according to the content of the tri-monomer obtained by the liquid chromatography analysis. Because the neutralization sample needs to be treated in the early stage before liquid chromatography detection, the sample treatment steps are complicated, the requirement is high, otherwise inorganic salts such as sodium sulfate in the sample can block a liquid chromatography separation column to influence normal use.
Combining the characteristics of the neutralization reaction, the process provides a method for rapidly analyzing and determining the reaction endpoint. Except that an online digital display pH meter is arranged on a circulating pump pipeline to display the change condition of the pH value of the neutralization material at any time, the online digital display pH meter displays that the pH value of the neutralization material reaches 6.9, the data is stable for 10 minutes, and then the sample can be sampled, and the saponification value of the obtained sample (liquid material) is rapidly analyzed by taking the data that the pH value reaches 7.0 as the assistance. When the saponification value of the sample (liquid material) is higher than 95mgKOH/g, a certain amount of soda ash is added into the neutralization kettle and stirring is continued for 15-30 minutes, and the digital display pH meter shows that the pH value of the neutralized material is stabilized at 7.0. The saponification value of the sample is analyzed to be not less than 97.5mgKOH/g, and the neutralization operation can be finished.
5. Solid sodium carbonate is directly added into the neutralization kettle without preparing a sodium carbonate solution in advance, so that the operation is simplified, the cost is reduced, and the economic benefit of the product is improved;
using solid Na2CO3Without using Na dissolved in water2CO3Adding sodium carbonate into a neutralization kettle and solid Na by using a spiral feeder by taking solution or liquid NaOH as a neutralizer2CO3After dissolution, the sodium hydroxide immediately takes part in the neutralization reaction, thereby omitting Na2CO3The preparation process of the solution reduces the water adding amount of neutralization operation by 850Kg/t compared with the prior art, and simplifies the operation process.
6. Two neutralization kettles are used, one neutralization kettle is used for adding alkali, and the other neutralization kettle is used for carrying out deep neutralization reaction. And circulating the materials in the neutralization kettle by using a circulating pump in the alkali adding process. Because solid Na is added from the upper part of the neutralization kettle2CO3Addition of a baseThen a dissolving and re-reacting process is carried out, which can cause the local alkali concentration of the materials at the upper part of the neutralization kettle to be too high and can cause hydrolysis reaction. The bottom of the neutralization kettle is provided with a circulating pump to circulate the materials, and the compositions of the materials at the top, the middle and the bottom of the neutralization kettle are basically consistent under the condition of forced circulation, so that the excessive alkalinity of the local part in the neutralization kettle is avoided, meanwhile, the forced circulation of the materials also promotes the heat transfer and mass transfer, and the neutralization reaction speed is accelerated.
7. The neutralization temperature was increased to 35-40 ℃. The neutralization temperature adopted by the prior art is generally 10-33 ℃, the neutralization reaction is an exothermic reaction, low-temperature cooling water is required to be used for forced circulation to remove heat generated by the reaction in time, and especially cooling water with the temperature lower than 10 ℃ needs to be prepared by a water cooler for circulation in summer, so that the energy consumption is large. The process sets the neutralization temperature to be 35-40 ℃, so that the neutralization reaction speed is accelerated, the temperature requirement in the neutralization kettle can be met by using circulating water even when the environmental temperature is higher in summer, low-temperature water is not needed for cooling, and the energy-saving effect is obvious.
Detailed Description
The formula for calculating the yield of the three monomers in the neutralization step is as follows: the amount of the tri-monomer (calculated value, calculated according to saponification value) in the neutralization solution is divided by the total amount of dimethyl isophthalate-5-sulfonic acid to calculate the theoretical amount of the tri-monomer, and the result is multiplied by 100%;
the calculation formula of the conversion rate of the dimethyl isophthalate-5-sulfonic acid is as follows: the amount of the tri-monomer in the neutralized liquid (calculated, calculated from the saponification value) was multiplied by the molecular weight of dimethyl isophthalate-5-sulfonic acid, divided by the molecular weight of the tri-monomer, and divided by the total amount of dimethyl isophthalate-5-sulfonic acid, and the result was multiplied by 100%.
Example 1
The weight of the esterification material used in this example was 2285kG, and the contents (weight ratio) of the main components of the esterification material were as follows: dimethyl isophthalate-5-sulfonic acid, 80.21%; isophthalic acid monomethyl ester-5-sulfonic acid, 1.32%; isophthalic acid, 0.053%; sulfuric acid, 15.51%; methanol, 12.45%; the balance of sulfonated organic impurities, esterified organic impurities and impurities brought by raw materials.
1. Adding process water and an esterification material
4920Kg of process water after metering is added into the neutralization kettle, stirring is started, cooling water is introduced into a first neutralization kettle jacket, and all the lactone materials in the esterification kettle are put into the first neutralization kettle.
2. Adding part of soda ash
When the temperature of the materials in the first neutralization kettle is reduced to 18 ℃, starting a spiral feeder, starting to add solid soda into the neutralization kettle, opening a discharge valve at the bottom of the first neutralization kettle when 150Kg of soda is added, and starting a circulating pump of the first neutralization kettle to start circulation; soda ash is continuously added. Controlling the temperature of the first neutralization kettle to be 35 ℃ in the operation process; the total amount of the added soda ash is 300 Kg.
3. Transferring material
When the total amount of the added soda is 300Kg, switching a discharge valve of a circulating pump of a first neutralization kettle, pumping a material of the first neutralization kettle into a second neutralization kettle, introducing cooling water into a jacket of the second neutralization kettle, pumping the material of the first neutralization kettle into the second neutralization kettle for 10-15 minutes, then starting the circulating pump of the second neutralization kettle, pumping the material in the second neutralization kettle into the first neutralization kettle, and controlling the temperature in the second neutralization kettle to be 35 ℃;
and at the moment, the change situation of the pH value of the neutralization material displayed by the on-line digital display pH meter at the outlet of the circulating pump of the first neutralization kettle is observed.
4. Control of the end of the reaction
When the total amount of the soda added into the first neutralization kettle is 570Kg, the online digital display pH meter displays that the pH value of the neutralization material is 6.9, 30Kg of soda is continuously added into the neutralization kettle, the pH value data is 7.0 at the moment, the sample can be sampled after being stabilized for about 10 minutes, and the saponification value of a rapid analysis sample (liquid material) is 96.32 mgKOH/g. And adding 20Kg of soda ash into the first neutralization kettle, and continuing to stir for 20 minutes, wherein the digital display pH meter shows that the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation is finished. Sampling and analyzing the saponification value to 97.84mgKOH/g, centrifuging the neutralized material, drying, carrying out post-treatment refining, and drying to obtain the finished product of the tri-monomer.
According to the sampling analysis that the saponification value of the neutralized material was 97.84mgKOH/g, the conversion rate of dimethyl isophthalate-5-sulfonic acid was calculated to be 97.23%, and the yield of the crude product of the tri-monomer in the neutralization step (based on dimethyl isophthalate-5-sulfonic acid) was 96.54%.
The production period (the time from the beginning of the first addition of the metered process water to the end of the last addition of the base to the neutralization solution pH of 7.0) was 465 minutes.
The quality indexes of the prepared SIPM product are shown in the following table 1.
TABLE 1
Example 2
The weight of the esterification material used in this example was 2285kG, and the contents (weight ratio) of the main components of the esterification material were as follows: dimethyl isophthalate-5-sulfonic acid, 80.21%; isophthalic acid monomethyl ester-5-sulfonic acid, 1.32%; isophthalic acid, 0.053%; sulfuric acid, 15.51%; methanol, 12.45%; the balance of sulfonated organic impurities, esterified organic impurities and impurities brought by raw materials.
Exactly the same process parameters as in example 1, steps 1-3, except for step 4.
And 4, when the total amount of the added soda is 570Kg, displaying the pH value of the neutralization material to be 6.9 by an online digital display pH meter, continuously adding 35Kg of soda into the neutralization kettle, displaying the pH value to be 7.0 at the moment, sampling after stabilizing for about 10 minutes, and quickly analyzing the saponification value of a sample (liquid material) to be 97.16 mgKOH/g. And adding 25Kg of soda ash into the first neutralization kettle, and continuing to stir for 25 minutes, wherein the digital display pH meter shows that the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation is finished. Sampling and analyzing the saponification value to be 99.94mgKOH/g, centrifuging the neutralized material, drying, carrying out post-treatment refining, and drying to obtain the finished product of the tri-monomer.
According to the sampling analysis that the saponification value of the neutralized material was 99.94mgKOH/g, the conversion rate of dimethyl isophthalate-5-sulfonic acid was calculated to be 97.65%, and the yield of the crude product of the tri-monomer in the neutralization step (based on dimethyl isophthalate-5-sulfonic acid) was 96.77%.
The production cycle (time from the start of the first addition of metered process water to the end of the last addition of base to pH 7.0 of the neutralization liquor) was 435 minutes.
The quality index of the prepared SIPM product is shown in the following table 2.
TABLE 2
Example 3
The weight of the esterified material used in this example was 2360kG, and the contents (weight ratio) of the main components of the esterified material were as follows: 80.78 percent of m-phthalic acid dimethyl ester-5-sulfonic acid; isophthalic acid monomethyl ester-5-sulfonic acid, 1.02%; isophthalic acid, 0.047%; sulfuric acid, 14.72%; methanol, 11.48%; the balance of sulfonated organic impurities, esterified organic impurities and impurities brought by raw materials.
1. Adding process water and an esterification material
5200Kg of metered process water is added into the neutralization kettle, stirring is started, cooling water is introduced into the jacket of the first neutralization kettle, and all the lactone materials in the esterification kettle are put into the first neutralization kettle.
2. Adding part of soda ash
When the temperature of the materials in the first neutralization kettle is reduced to 20 ℃, starting a spiral feeder, starting to add solid soda into the neutralization kettle, opening a discharge valve at the bottom of the first neutralization kettle when 175Kg of soda is added, and starting a circulating pump of the first neutralization kettle to start circulation; soda ash is continuously added. Controlling the temperature of the first neutralization kettle to be 37 ℃ in the operation process;
3. transferring material
When the total amount of the added soda is 325Kg, switching a discharge valve of a circulating pump of a first neutralization kettle, pumping a material of the first neutralization kettle into a second neutralization kettle, introducing cooling water into a jacket of the second neutralization kettle, pumping the material of the first neutralization kettle into the second neutralization kettle for 10-15 minutes, then starting the circulating pump of the second neutralization kettle, pumping the material in the second neutralization kettle into the first neutralization kettle, and controlling the temperature in the second neutralization kettle to be 37 ℃; at the moment, the change situation of the pH value of the neutralization material displayed by the on-line digital display pH meter at the outlet of the circulating pump of the first neutralization kettle is observed;
4. control of the end of the reaction
When the total amount of the added soda is 600Kg, an online digital display pH meter shows that the pH value of the neutralization material is 6.9, 25Kg of soda is continuously added into the neutralization kettle, the pH value data shows 7.0 at the moment, the sample can be sampled after about 10 minutes of stabilization, and the saponification value of a sample (liquid material) for rapid analysis is 95.29 mgKOH/g. And adding 25Kg of soda ash into the first neutralization kettle, and continuing to stir for 15 minutes, wherein the digital display pH meter shows that the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation is finished. Sampling and analyzing the saponification value to be 96.55mgKOH/g, centrifuging the neutralized material, drying, carrying out post-treatment refining, and drying to obtain the finished product of the tri-monomer.
According to the sampling analysis that the saponification value of the neutralized material was 97.75mgKOH/g, the conversion of dimethyl isophthalate-5-sulfonic acid was calculated to be 97.15%, and the yield of the crude product of the tri-monomer in the neutralization step (based on dimethyl isophthalate-5-sulfonic acid) was 96.25%.
The production cycle (time from the beginning of the first addition of the metered process water to the end of the last addition of the base to the neutralization solution pH 7.0) was 470 minutes.
The quality index of the prepared SIPM product is shown in the following table 3.
TABLE 3
Example 4
The weight of the esterified material used in this example was 2360kG, and the contents (weight ratio) of the main components of the esterified material were as follows: 80.78 percent of m-phthalic acid dimethyl ester-5-sulfonic acid; isophthalic acid monomethyl ester-5-sulfonic acid, 1.02%; isophthalic acid, 0.047%; sulfuric acid, 14.72%; methanol, 11.48%; the balance of sulfonated organic impurities, esterified organic impurities and impurities brought by raw materials.
Exactly the same process parameters as in example 3, steps 1-3, except for step 4.
And 4, when the total amount of the added soda is 610Kg, displaying the pH value of the neutralization material to be 6.9 by an online digital display pH meter, continuously adding 20Kg of soda into the neutralization kettle, wherein the pH value data is 7.0, sampling can be carried out after about 10 minutes of stabilization, and the saponification value of a sample (liquid material) for rapid analysis is 96.11 mgKOH/g. And adding 30Kg of soda ash into the first neutralization kettle, and continuing to stir for 20 minutes, wherein the digital display pH meter shows that the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation can be finished. Sampling and analyzing the saponification value to be 97.28mgKOH/g, centrifuging the neutralized material, drying, carrying out post-treatment refining, and drying to obtain the finished product of the tri-monomer.
According to the sampling analysis that the saponification value of the neutralized material was 97.28mgKOH/g, the conversion rate of dimethyl isophthalate-5-sulfonic acid was 97.31%, and the yield of the crude product of the tri-monomer in the neutralization step (based on dimethyl isophthalate-5-sulfonic acid) was 96.29%.
The production cycle (time from the beginning of the first addition of the metered process water to the end of the last addition of the base to the neutralization solution pH 7.0) was 450 minutes.
The quality index of the prepared SIPM product is shown in the following table 4.
TABLE 4
Example 5
The weight of the esterified material used in this example was 2415kG, and the contents (weight ratio) of the main components of the esterified material were as follows: dimethyl isophthalate-5-sulfonic acid, 80.62%; isophthalic acid monomethyl ester-5-sulfonic acid, 1.15%; isophthalic acid, 0.051%; sulfuric acid, 15.06%; methanol, 12.17%; the balance of sulfonated organic impurities, esterified organic impurities and impurities brought by raw materials.
1. Adding process water and an esterification material
5380Kg of metered process water is firstly added into a neutralization kettle, stirring is started, cooling water is introduced into a first neutralization kettle jacket, and all esterification materials in an esterification kettle are put into the first neutralization kettle.
2. Adding part of soda ash
When the temperature of the materials in the first neutralization kettle is reduced to 16 ℃, starting a spiral feeder, starting to add solid soda into the neutralization kettle, opening a discharge valve at the bottom of the first neutralization kettle when 160Kg of soda is added, and starting a circulating pump of the first neutralization kettle to start circulation; soda ash is continuously added. Controlling the temperature of the first neutralization kettle to be 39 ℃ in the operation process;
3. transferring material
When the total amount of the added soda is 350Kg, switching a discharge valve of a circulating pump of a first neutralization kettle, pumping a material of the first neutralization kettle into a second neutralization kettle, introducing cooling water into a jacket of the second neutralization kettle, pumping the material of the first neutralization kettle into the second neutralization kettle for 10-15 minutes, then starting the circulating pump of the second neutralization kettle, pumping the material in the second neutralization kettle into the first neutralization kettle, and controlling the temperature in the second neutralization kettle to be 39 ℃; at the moment, the change situation of the pH value of the neutralization material displayed by the on-line digital display pH meter at the outlet of the circulating pump of the first neutralization kettle is observed;
4. control of the end of the reaction
When the total amount of the added soda is 625Kg, an online digital display pH meter shows that the pH value of the neutralization material is 6.9, 15Kg of soda is continuously added into the neutralization kettle, the pH value data shows 7.0 at the moment, the sample can be sampled after about 10 minutes of stabilization, and the saponification value of a sample (liquid material) for rapid analysis is 96.44 mgKOH/g. And adding 20Kg of soda ash into the first neutralization kettle, and continuing to stir for 20 minutes, wherein the digital display pH meter shows that the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation is finished. Sampling and analyzing the saponification value to 97.25mgKOH/g, centrifuging the neutralized material, drying, performing post-treatment refining, and drying to obtain the finished product of the tri-monomer.
According to the sampling analysis that the saponification value of the neutralized material was 97.25mgKOH/g, the conversion of dimethyl isophthalate-5-sulfonic acid was calculated to be 97.47%, and the yield of the crude product of the tri-monomer in the neutralization step (based on dimethyl isophthalate-5-sulfonic acid) was 96.18%.
The production cycle (time from the start of the first addition of metered process water to the end of the last addition of base to pH 7.0 of the neutralization liquor) was 475 minutes.
The quality index of the prepared SIPM product is shown in the following table 5.
TABLE 5
Example 6
The weight of the esterified material used in this example was 2415kG, and the contents (weight ratio) of the main components of the esterified material were as follows: dimethyl isophthalate-5-sulfonic acid, 80.62%; isophthalic acid monomethyl ester-5-sulfonic acid, 1.15%; isophthalic acid, 0.051%; sulfuric acid, 15.06%; methanol, 12.17%; the balance of sulfonated organic impurities, esterified organic impurities and impurities brought by raw materials.
Exactly the same process parameters as in example 5, steps 1-3, except for step 4.
And 4, when the total amount of the added soda is 625Kg, displaying the pH value of the neutralization material to be 6.9 by an online digital display pH meter, continuously adding 20Kg of soda into the neutralization kettle, displaying the pH value to be 7.0 at the moment, sampling after stabilizing for about 10 minutes, and quickly analyzing the saponification value of a sample (liquid material) to be 96.45 mgKOH/g. And adding 15Kg of soda ash into the first neutralization kettle, and continuing to stir for 20 minutes, wherein the digital display pH meter shows that the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation can be finished. Sampling and analyzing the saponification value to be 97.58mgKOH/g, centrifuging the neutralized material, drying, carrying out post-treatment refining, and drying to obtain the finished product of the tri-monomer.
According to the sampling analysis that the saponification value of the neutralized material was 97.58mgKOH/g, the conversion rate of dimethyl isophthalate-5-sulfonic acid was 97.29%, and the yield of the crude product of the tri-monomer in the neutralization step (based on dimethyl isophthalate-5-sulfonic acid) was 96.09%.
The production cycle (time from the start of the first addition of metered process water to the end of the last addition of base to the neutralization solution pH 7.0) was 455 minutes.
The quality index of the prepared SIPM product is shown in the following table 6.
TABLE 6
Selection and determination of the technical solution of the invention
1. Determination of reaction temperature and reaction time
Because the neutralization reaction of the dimethyl isophthalate-5-sulfonic acid and the soda ash is an exothermic reaction, the heat generated by the reaction must be removed in time to control reasonable reaction temperature, and when the temperature is high, the neutralization reaction speed is accelerated, but side reactions such as hydrolysis of tri-monomer homologues are promoted; the temperature in the reaction kettle is low, the dissolution speed of the sodium carbonate is low, the neutralization speed is low, the reaction time is long, the yield is influenced, and the final three-monomer product is unqualified due to the fact that the reaction end point is not easy to control. The process selects proper reaction temperature and time by combining the reaction characteristics of the dimethyl isophthalate-5-sulfonic acid and the soda ash, so that the neutralization reaction is more sufficient, and the conversion rate of the dimethyl isophthalate-5-sulfonic acid is over 98.7 percent in the industrial scale production time.
2. Effect of pH on the Process during neutralization
When the pH of the material in the neutralization kettle exceeds 7.0, the SIPM begins to hydrolyze along with the gradual reduction of the acidic environment to generate various organic byproducts such as monomethyl ester-5-sodium sulfonate and the like, and the SIPM content in the material is reduced and the saponification value is increased along with the occurrence of a plurality of side reactions. The SIPM finished product prepared under the condition of high PH value is easy to cause the blockage of a fiber spray head after being used in the synthesis of downstream polyester fiber, and a series of problems of unbalanced chromaticity, difficult coloring and the like can be generated when the cloth is subjected to a dyeing process.
3. Determination of the end-point of the reaction
Combining the characteristics of the neutralization reaction, the process provides a method for rapidly analyzing and determining the reaction endpoint. The saponification value of the obtained sample (liquid material) was quickly analyzed with the aid of the data that the pH reached 7.0. When the saponification value of the sample (liquid material) is higher than 95mgKOH/g, a certain amount of soda ash is added into the neutralization kettle, the stirring is continued for 15-30 minutes, and the neutralization operation is finished, and the digital display pH meter shows that the pH value of the neutralization material is stabilized at 7.0.
Claims (2)
1. A method for preparing a tri-monomer by neutralizing an esterification material containing dimethyl isophthalate-5-sulfonic acid is characterized in that: the method comprises the steps of adding process water and an esterification material, adding part of soda ash, transferring the material and controlling a reaction end point; the mass ratio of the esterification material to the process water is as follows: 2.1-2.3: 1; the mass ratio of the total dosage of the esterified material to the sodium carbonate is as follows: 3.5-3.7: 1; the esterification material comprises 80.2-80.8% of dimethyl isophthalate-5-sulfonic acid by mass; 1.02-1.32% of m-phthalic acid monomethyl ester-5-sulfonic acid; isophthalic acid, 0.045-0.055%; 14.7 to 15.6 percent of sulfuric acid; 11.48 to 12.45 percent of methanol;
adding part of soda ash, adding solid soda ash when the temperature of the materials in the first neutralization kettle is reduced to 16-20 ℃, opening a discharge valve at the bottom of the first neutralization kettle when the adding amount is 23.5-27% of the total amount of the soda ash, and starting a circulating pump of the first neutralization kettle to start circulation; controlling the temperature of the first neutralization kettle to be 35-40 ℃;
when the amount of the added soda ash is 47-53% of the total amount, the materials in the first neutralization kettle are pumped into a second neutralization kettle, the temperature in the second neutralization kettle is 35-40 ℃, and after the materials stay for 10-15 minutes, the materials in the second neutralization kettle are pumped into the first neutralization kettle;
controlling the reaction end point, wherein the amount of the soda added into the first neutralization kettle reaches 90.4-95% of the total amount, when the pH value of the neutralization material is 6.9, the soda is continuously added into the neutralization kettle, the addition amount is 2.3-5.5% of the total amount of the soda, the pH value data is observed to be 7.0, and the sample can be taken after 9-12 minutes, and the saponification value of the sample is analyzed; when the saponification value of the sample is higher than 95mgKOH/g, adding the rest soda ash, and continuing stirring for 15-30 minutes, wherein the pH value of the neutralization material is stabilized at 7.0, and the neutralization operation can be finished; after the neutralization operation, sampling analysis shows that the saponification value is not less than 97.5 mgKOH/g.
2. The method for preparing the tri-monomer by neutralizing the ester stock containing the isophthalic acid dimethyl ester-5-sulfonic acid as set forth in claim 1, wherein: the conversion rate of the isophthalic acid-dimethyl ester 5-sulfonic acid is 97.15-97.65%, and the yield of the crude product of the three monomers in the neutralization process is 96.09-96.77% based on the isophthalic acid-dimethyl ester 5-sulfonic acid.
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