CN115403490B - Refining method of sodium methallyl sulfonate - Google Patents
Refining method of sodium methallyl sulfonate Download PDFInfo
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- CN115403490B CN115403490B CN202210980658.8A CN202210980658A CN115403490B CN 115403490 B CN115403490 B CN 115403490B CN 202210980658 A CN202210980658 A CN 202210980658A CN 115403490 B CN115403490 B CN 115403490B
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- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000007670 refining Methods 0.000 title claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 95
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims abstract description 77
- 239000000047 product Substances 0.000 claims abstract description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 49
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012043 crude product Substances 0.000 claims abstract description 30
- 239000012452 mother liquor Substances 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000012065 filter cake Substances 0.000 claims abstract description 25
- 238000004537 pulping Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000012047 saturated solution Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 239000010413 mother solution Substances 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims description 23
- 238000005119 centrifugation Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000010009 beating Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- VRAHSRHQTRYBJV-UHFFFAOYSA-M sodium;2-methyl-1-oxoprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)C(=O)S([O-])(=O)=O VRAHSRHQTRYBJV-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a refining method of sodium methallyl sulfonate, which belongs to the technical field of aliphatic sulfonate and comprises the following steps: s1, centrifuging sodium methallyl sulfonate crystal slurry containing sodium chloride to obtain a sodium methallyl sulfonate wet solid filter cake; s2, washing the wet solid filter cake with a saturated solution of sodium methallyl sulfonate containing chloride ions to obtain a crude sodium methallyl sulfonate product; s3, crushing the sodium methallyl sulfonate crude product, putting the crushed sodium methallyl sulfonate crude product into a refining kettle, adding deionized water, pulping and centrifuging to obtain sodium methallyl sulfonate refined product, and collecting a centrifuging mother solution; s4, circularly pulping the centrifugal mother liquor for multiple times, and recycling the centrifugal mother liquor in the washing of the step S2 when the chloride ion content exceeds 0.3%; s5, crushing, mixing and drying the refined sodium methacrylate sulfonate. The invention obviously improves the washing speed and effect of the sodium methallyl sulfonate, and has the advantages of less product loss, good product quality, low chloride ion content, small batch-to-batch difference and stable quality in the washing process.
Description
Technical Field
The invention relates to the technical field of aliphatic sulfonate, in particular to a refining method of sodium methallyl sulfonate.
Background
Sodium methallyl sulfonate has high water reducing rate and good retarder, and is generally used as a polycarboxylic acid high-performance water reducing agent. Meanwhile, trace sodium methacrylate can improve the dyeing property of ternary polymerization acrylic fiber with acrylonitrile as a main component, so that the ternary polymerization acrylic fiber has the advantages of quick color absorption, strong fastness and bright color, and can improve the heat resistance and elasticity of the fiber. Besides, the sodium methacrylate sulfonate can be used as a monomer of a water treatment corrosion and scale inhibitor, a coating auxiliary agent, a drying strengthening agent in a papermaking auxiliary agent and the like.
The chloride ion content in sodium methacrylate is a very important indicator, and high quality sodium methacrylate is required to contain less chloride ion (less than or equal to 300 ppm). However, in the production process of sodium methallyl sulfonate, a large amount of sodium chloride is contained in the reaction solution in addition to sodium methallyl sulfonate, which causes entrainment during the crystallization and purification process, and therefore, it is necessary to reduce the chloride ion content in the crystals by washing or the like. In the prior art, chinese patent CN 101492399A (a preparation method of sodium methacrylate sulfonate) discloses a washing method of sodium methacrylate sulfonate, which comprises the steps of placing a crude product obtained by crystallization in a washing kettle, adding methanol with water content of 5% -15%, stirring, dissolving, filtering, repeatedly washing for 2-3 times, and drying the separated crystal to obtain a finished product of sodium methacrylate sulfonate. According to the method, methanol is added in the washing process, so that the dissolution loss of the product in the washing process is reduced, the yield is improved, but more solvent is added in each washing (the ratio of the solvent to the crude product is about 1.5:1), the effective utilization rate of the washing kettle is reduced, the product loss is about 1/4 due to repeated washing, the toxicity of the solvent methanol is high, and potential safety hazards exist. Chinese patent CN 1172800A (sodium methacrylate sulfonate production process and equipment) discloses a centrifugal washing method of sodium methacrylate sulfonate, which reduces the loss of products by a method of recycling washing liquid in the process of washing the products, but in the process of collecting the washing liquid in a grading manner, the problems of overhigh chloride ion content (sodium chloride content is 0.1%) and poor washing effect in the washing liquid which is received in a grading manner, which are easily caused by the problems of accumulated liquid in a pipeline of a centrifugal machine and the like, are solved, and meanwhile, the process of collecting the washing liquid in a grading manner is complex in operation and low in washing efficiency. Chinese patent CN 1462741A, a method for producing sodium methallyl sulfonate, discloses a method for washing sodium methallyl sulfonate, which comprises the steps of adding a crude product obtained by crystallization into a washing kettle for washing for four times, washing liquid for four times in a grading manner, wherein the fourth washing mode is repeated crystallization, the quality of the product is improved by the washing method, but the difficulty of transferring solid materials among a plurality of washing kettles is high, the energy consumption in the recrystallization process is increased, the product is more lost after washing, and the yield is only 50.6%. Chinese patent CN112851555B, "a method for synthesizing and refining sodium methacrylate sulfonate", discloses a method for preparing sodium methacrylate sulfonate by increasing the crystal grain size of sodium methacrylate sulfonate through gradient cooling crystallization and washing with water in a centrifuge for a small amount of multiple times, the method significantly improves the washing effect and reduces the amount of washing water, but the method is difficult to control the gradient cooling crystallization process, thereby affecting the washing effect, and the gradient cooling crystallization process consumes a long time and affects the production efficiency; meanwhile, the processing capacity of the centrifugal machine is relatively small, the process of detecting the quality of products after centrifugal washing is long, and the phenomenon of uneven washing occasionally occurs in the washing process, so that the productivity is affected.
In summary, the existing sodium methallyl sulfonate washing process has the problems of complex operation, serious product loss in the washing process, low production efficiency, difficult control of the crystallization process, influence on the washing effect and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a refining method of sodium methacrylate sulfonate, which obviously improves the washing speed and the washing effect of sodium methacrylate sulfonate, has less product loss, and the obtained product has good quality, low chloride ion content, small batch-to-batch difference and stable quality.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for refining sodium methallyl sulfonate, comprising the following steps:
s1, centrifuging sodium methallyl sulfonate crystal slurry containing sodium chloride to obtain a sodium methallyl sulfonate wet solid filter cake;
s2, washing the wet solid filter cake with a saturated solution of sodium methallyl sulfonate containing chloride ions to obtain a crude sodium methallyl sulfonate product;
s3, crushing the sodium methallyl sulfonate crude product, putting the crushed sodium methallyl sulfonate crude product into a refining kettle, adding deionized water, pulping and centrifuging to obtain a sodium methallyl sulfonate refined product, and collecting a centrifuging mother solution;
s4, circularly pulping the centrifugal mother liquor for multiple times, and recycling the centrifugal mother liquor into washing of the wet solid filter cake of sodium methacrylate sulfonate in the step S2 when the chloride ion content in the centrifugal mother liquor exceeds 0.3%;
s5, crushing and mixing the refined sodium methacrylate sulfonate, and drying to obtain a finished product with high sodium methacrylate sulfonate content and low chloride ion content (less than or equal to 300 ppm).
Preferably, the sodium methacrylate crystal mush in the step S1 comprises the following components in percentage by mass: 5.0-15.0% of sodium chloride, 20.0-40.0% of sodium methacrylate sulfonate crystal, 15.0-25.0% of dissolved sodium methacrylate sulfonate and the balance of water.
Further preferably, the sodium chloride content in the sodium methallyl sulfonate crystal slurry is 8.0-12.0%. The excessive sodium chloride content can cause precipitation and influence the washing effect; the too low concentration of sodium chloride can increase the solubility of sodium methallyl sulfonate, so that the crystallization products are reduced, and the production efficiency is affected.
Further preferably, the sodium methallyl sulfonate crystal content in the sodium methallyl sulfonate crystal slurry is 25.0-35.0%. The crystal content is too low, which affects the production efficiency; the crystal content is too high, which is easy to cause pipeline blockage.
Preferably, the centrifugal speed in the step S1 is 1000-2000 rpm, the centrifugal time is 15-20 minutes, the mass percentage content of water in the obtained sodium methacrylate wet solid filter cake is 5.0-10.0%, and the mass percentage content of chloride ions is 0.5-1.0%.
Preferably, the chloride ion content in the saturated solution of sodium methacrylate sulfonate in the step S2 is 0.3-0.4% by mass.
Preferably, step S2 sprays a saturated solution of sodium methacrylate onto the wet solid cake of sodium methacrylate sulfonate during centrifugation. Further preferably, the spraying is performed for 3-4 times, the mass of the saturated solution of sodium methacrylate sulfonate sprayed each time is 5.0-15.0% of that of the wet solid filter cake of sodium methacrylate sulfonate, the next spraying is started after the solution is centrifuged at a rotational speed of 1000-2000 rpm for 5-10 minutes after each spraying, and the solution is centrifuged at a rotational speed of 1000-2000 rpm for 10-15 minutes after the last spraying is finished.
Preferably, in the step S3, the mass ratio of the sodium methacrylate crude product to the deionized water is 10:6-10:10, and more preferably 10:6.5-10:7.5. Too little deionized water is added, the sodium methallyl sulfonate is washed unevenly, and the discharging process is easy to cause pipeline blockage; too much deionized water is added, so that the loss of products is increased, and the yield is reduced.
Preferably, in the step S3, the pulping time is 1-2 hours, the centrifugal speed is 1000-2000 rpm, and the centrifugal time is 10-15 minutes.
Preferably, the chloride ion content of the centrifugal mother liquor of the refining kettle in the step S4 is lower than 0.3% in the cyclic pulping process.
Preferably, in step S5, the refined sodium methacrylate sulfonate is dried by using steam, and the steam pressure is 0.02-0.06 mpa, more preferably 0.025-0.04 mpa. The steam pressure is too low, the drying effect is poor, the drying time is long, and the production efficiency is affected; the steam pressure is too high, the drying effect is good, but the deterioration of the product is easy to cause, and the quality of the product is affected. The drying time is 20-60 minutes.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, through combining two washing methods of coarse washing in the centrifugal machine and pulping washing in the refining kettle, the problems of uneven washing in the centrifugal machine and difference in washing effect of different batches of products are effectively solved, the operation flow is simplified, the washing speed and the production efficiency are obviously improved, and the product quality is uniform and stable.
(2) The centrifugal mother liquor in the refining kettle is reused for a plurality of times, and is reused for washing the crude product in the centrifuge after the chloride ion content is increased to a certain concentration, so that the consumption of fresh deionized water is obviously reduced, the loss of the product in the washing process is reduced, the product yield is improved, and the energy consumption for dehydration in the washing liquid application process is reduced.
Drawings
FIG. 1 is a process flow diagram of the refining method of the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
A method for refining sodium methallyl sulfonate, comprising the following steps:
s1, centrifuging sodium methacrylate crystal slurry containing sodium chloride (the sodium chloride content is 5.0-15.0%) at a speed of 1000-2000 rpm for 15-20 minutes to obtain a sodium methacrylate wet solid filter cake with the water content of 5.0-10.0% and the chloride ion content of 0.5-1.0%, and enabling filtrate to enter a mother liquid tank;
s2, washing the wet solid filter cake with a sodium methallyl sulfonate saturated solution with chloride ion content lower than 0.4% to obtain a sodium methallyl sulfonate crude product, and allowing filtrate to enter a mother liquor tank;
s3, crushing the sodium methallyl sulfonate crude product, putting the crushed sodium methallyl sulfonate crude product into a refining kettle, adding deionized water, pulping and centrifuging to obtain a sodium methallyl sulfonate refined product, and collecting a centrifuging mother solution; the chloride ion content of the product is measured before and after each pulping and centrifugation, and the results are shown in Table 2;
s4, circularly pulping the centrifugal mother liquor for multiple times, and recycling the centrifugal mother liquor into washing of the wet solid filter cake of sodium methacrylate sulfonate in the step S2 after the chloride ion content in the centrifugal mother liquor exceeds 0.3%;
s5, crushing and mixing the refined sodium methacrylate sulfonate, and drying to obtain a finished product with high main content and low chloride ion content (less than or equal to 300 ppm).
Wherein, the washing specific operation of the step S2 is as follows: and S1, after centrifugation is finished, in the process of keeping the high-speed operation of the centrifuge, spraying sodium methacrylate wet solid filter cake with the chloride ion mass percentage content of 0.3-0.4% to 3-4 times through a spray washing pipe, wherein the mass of the sodium methacrylate saturated solution sprayed each time is 5.0-15.0% of that of the sodium methacrylate wet solid filter cake, centrifuging at a rotating speed of 1000-2000 rpm for 5-10 minutes after each spraying, and then starting next spraying, and centrifuging at a rotating speed of 1000-2000 rpm for 10-15 minutes after the last spraying is finished, thereby obtaining a sodium methacrylate crude product.
The specific operation of step S3 is: and (3) crushing the sodium methacrylate crude product, putting the crushed sodium methacrylate crude product into a refining kettle, adding deionized water, and stirring for 1-2 hours. And discharging the mixture to a centrifugal machine after stirring, and carrying out high-speed centrifugation at a speed of 1000-2000 rpm for 10-15 minutes to obtain a sodium methacrylate essence.
The specific operation of step S5 is: the refined sodium methacrylate is crushed and mixed and then enters a disc dryer for drying, a heating medium in the dryer is steam, the steam pressure is 0.02-0.06 mpa, and the retention time of materials in the dryer is 20-60 minutes in the drying process. And (5) after the drying is finished, obtaining a sodium methacrylate finished product.
Example 1
A method for refining sodium methallyl sulfonate, comprising the following steps:
s1, 5000kg of sodium methacrylate crystal slurry with the crystal concentration of 25% is centrifugally washed in batches to obtain a sodium methacrylate crude product. The centrifugal washing operation conditions of each batch are as follows: after the distribution of the crystal slurry in the centrifuge is finished, centrifuging for 15 minutes at the speed of 1200 revolutions per minute to obtain a wet solid filter cake with the water content of 6.5%, and feeding the centrifugate filtrate into a mother liquor tank.
S2, spraying sodium methacrylate saturated solution with chloride ion content of 0.3% to the surface of the wet solid filter cake through a spray washing pipe four times in the high-speed running process of the centrifugal machine, wherein the spraying amount is 15kg each time. And after the previous three spraying processes are finished, dewatering for 5 minutes at the speed of 1200 rpm, continuing the next spraying process, and after the fourth spraying process is finished, dewatering for 10 minutes at the speed of 1200 rpm, so as to obtain 1320kg of crude sodium methacrylate product with the water content of 5.3%, and feeding the washing filtrate into a mother liquor tank. The chloride ion content of the product was measured before and after each wash and the results are shown in Table 1:
TABLE 1 coarse washing Effect of step S2
As can be seen from Table 1, the chloride ion content in the crude sodium methacrylate sulfonate product can be effectively reduced by performing crude washing on the wet solid filter cake by using a saturated solution of sodium methacrylate sulfonate with the chloride ion content of 0.3%.
S3, crushing a sodium methacrylate crude product (the chloride ion content is 210ppm-389 ppm), adding the crushed sodium methacrylate crude product into a refining kettle, adding 924kg of deionized water, and stirring for 2 hours. And after stirring, centrifuging in batches to obtain a sodium methacrylate refined product. The centrifugation conditions were: after the material is distributed in the centrifuge, the material is centrifuged for 15 minutes at the speed of 1200 revolutions per minute, and 594kg of sodium methacrylate refined product and 1650kg of centrifugal mother liquor are obtained. After pulping and centrifugation, the chloride ion content of the product is measured, and the result is shown in Table 2:
TABLE 2 deionized water beating centrifugal effect of product in refining kettle in step S3
As can be seen from table 2, the pulping and centrifuging of the sodium methallyl sulfonate crude product by deionized water can effectively reduce the chloride ion content in the sodium methallyl sulfonate refined product, and the chloride ion content of the products centrifuged in different batches is uniform, and the chloride ion content of the products centrifuged in different positions in the same centrifuging process is uniform.
S4, crushing and mixing sodium methacrylate refined products of different batches, drying in a disc dryer, setting the steam pressure in the dryer to be 0.035Mpa, and keeping the material in the dryer for 45 minutes to obtain 557kg of sodium methacrylate finished product.
S5, the chloride ion content in the centrifugal mother liquor obtained by centrifugation after the first pulping is 0.016%, and the chloride ion content reaches 0.32% after the centrifugal mother liquor is circularly pulped for 7 times and is used for washing the wet solid filter cake in the step S2. In the pulping process of the mother liquor circulation, 9107kg of sodium methacrylate finished product is obtained, and the average yield is 91.07%. The chloride ion content of the product is measured after each mother liquor beating and centrifugation, and the result is shown in Table 3:
TABLE 3 mother liquor beating centrifugal effect of products in refining kettle in step S5 with chloride ion content of 0.3%
Note that: the chloride ion content of the crude product before pulping is 210ppm-389ppm.
As can be seen from table 3, the mother liquor with 0.3% of chloride ion content is recycled to pulp and centrifuge the crude sodium methallyl sulfonate product prepared in step S2, so that the chloride ion content in sodium methallyl sulfonate can be effectively reduced, the chloride ion content of products centrifuged in different batches is uniform, and the chloride ion content of products centrifuged in different positions in the same centrifuging process is uniform.
Example 2
A method for refining sodium methallyl sulfonate, comprising the following steps:
s1, 5000kg of sodium methallyl sulfonate crystal slurry with the crystal concentration of 30% is centrifugally washed in batches to obtain a sodium methallyl sulfonate crude product. The centrifugal washing operation conditions of each batch are as follows: after the distribution of the crystal slurry in the centrifuge is finished, centrifuging for 20 minutes at the speed of 1200 revolutions per minute to obtain a wet solid filter cake with the water content of 4.5%, and feeding the centrifugate filtrate into a mother liquor tank.
S2, spraying sodium methallyl sulfonate saturated solution with low chloride ion content to the surface of the wet solid filter cake for three times through a spray washing pipe in the high-speed running process of the centrifugal machine, wherein the spraying amount is 20kg each time. And after the previous three spraying processes are finished, dewatering for 5 minutes at the speed of 1200 rpm, continuing the next spraying process, and after the fourth spraying process is finished, dewatering for 10 minutes at the speed of 1200 rpm, so as to obtain 1585kg of crude sodium methacrylate product with the water content of 5.4%, and feeding the washing filtrate into a mother liquor tank.
S3, crushing the sodium methacrylate crude product, putting the crushed sodium methacrylate crude product into a refining kettle, adding 1189kg of deionized water, and stirring for 2 hours. And after stirring, centrifuging in batches to obtain a sodium methacrylate refined product. The centrifugation conditions were: after the material is distributed in the centrifuge, the material is centrifuged for 15 minutes at the speed of 1200 revolutions per minute, so as to obtain 925kg of sodium methacrylate refined product and 1849kg of centrifugal mother liquor.
S4, crushing and mixing sodium methacrylate refined products of different batches, drying in a disc dryer, setting the steam pressure in the dryer to be 0.04Mpa, and keeping the material in the dryer for 40 minutes to obtain 879kg of sodium methacrylate finished products.
S5, the content of chloride ions in the centrifugal mother liquor obtained by centrifugation after the first pulping is 0.018%, and the chloride ions reach 0.31% after the centrifugal mother liquor is circularly pulped for 6 times and are used for washing wet solid filter cakes. In the pulping process of mother liquor circulation, 9580kg of sodium methacrylate finished product is obtained, and the average yield is 91.2%.
Comparative example 1
The preparation method of the sodium methallyl sulfonate in Chinese patent CN 1462741A is taken as comparative example 1, and the specific operation is as follows:
after centrifugal separation, obtaining 850kg of crude crystal, putting the crude crystal into a primary washing kettle, washing and stirring for 30 minutes, and centrifugally separating washing materials; about 500 kg of separation liquid is returned to a concentration storage tank, about 800 kg of primary semi-finished product is obtained, the primary semi-finished product is put into a secondary washing kettle, stirring is carried out for 30 minutes, centrifugal separation is carried out on materials, and about 500 kg of secondary separation liquid is returned to the primary washing kettle to be used as primary washing liquid; and returning the third separating liquid to the second washing kettle, and returning the fourth separating liquid to the third washing kettle.
About 700 kg of the crystal finished product obtained after three times of washing is put into a fourth washing kettle, 350 kg of deionized water is added for washing, and the temperature is raised to 80+/-2 ℃; and cooling and crystallizing the circulating liquid, separating by a centrifugal machine, conveying the crystallized product to a drying oven for drying to obtain 430 kg of finished products, cooling and packaging, wherein the yield is 50.6%.
As can be seen from the product yields of comparative examples 1-2 and comparative example 1, the product yield of the invention is remarkably improved, the deionized water used in the whole washing process is less, the cost is saved, the energy consumption in the next dehydration crystallization process is reduced, and the operation is simpler and more convenient.
Comparative example 2
The method for synthesizing and refining sodium methacrylate sulfonate in Chinese patent CN112851555B is taken as comparative example 2, and the specific operation is as follows:
and (3) dehydrating and separating out sodium chloride from the sodium methallyl sulfonate reaction solution, and carrying out gradient cooling crystallization to obtain sodium methallyl sulfonate crystal slurry. And (3) centrifuging the crystal slurry to obtain 324kg of sodium methacrylate crude product. The crude product is washed by water for 4 times, centrifuged (the dosage of deionized water is 5% of the mass of the crude product, namely 16.2 kg) and immediately sampled after each centrifugation, and the chloride ion content of the washing liquid is measured, and the result is shown in Table 4; after drying 281kg of sodium methallyl sulfonate fine product is obtained. The yield of the product in the centrifugal washing process is 86.7%, but the phenomenon of uneven washing occasionally occurs in the centrifugal washing process, and the difficulty in controlling the quality of the product is increased.
TABLE 4 centrifugal washing Effect of comparative example 2
As can be seen from the product yields of comparative examples 1 to 2 and comparative example 2, the product yield of the present invention is significantly higher than that of comparative example 2. As can be seen from comparison of tables 1 to 4, the method provided by the invention has the advantages of more uniform washing, small difference in washing effect among different batches, and more uniform washing effect at different positions in the same batch of washing process.
The quality of the sodium methallyl sulfonate finished products obtained in examples 1 and 2 and comparative examples 1 and 2 was measured, and the results are shown in Table 5.
TABLE 5 quality detection results of sodium Methacrylsulfonate finished product
As can be seen from Table 5, the method provided by the invention has higher yield of the product in the washing process.
From the above, the refining method of the invention reduces the consumption of washing water, reduces the loss of products in the washing process, improves the yield of products in the washing process, and has good quality, uniform and stable chloride ion content, small batch-to-batch difference and stable quality.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (6)
1. A refining method of sodium methacrylate sulfonate is characterized in that: the method comprises the following steps:
s1, centrifuging sodium methallyl sulfonate crystal slurry containing sodium chloride to obtain a sodium methallyl sulfonate wet solid filter cake; wherein, the sodium methacrylate crystal slurry comprises the following components in percentage by mass: 5.0-15.0% of sodium chloride, 20.0-40.0% of sodium methacrylate sulfonate crystal, 15.0-25.0% of dissolved sodium methacrylate sulfonate and the balance of water;
s2, washing the wet solid filter cake by using a saturated solution of sodium methallyl sulfonate containing chloride ions, wherein the washing specific operation is as follows: spraying a sodium methacrylate saturated solution to a sodium methacrylate wet solid filter cake in the centrifugation process, wherein the spraying is performed for 3-4 times to obtain a sodium methacrylate crude product; wherein the mass percentage content of chloride ions in the sodium methallyl sulfonate saturated solution is 0.3-0.4%;
s3, crushing the sodium methallyl sulfonate crude product, putting the crushed sodium methallyl sulfonate crude product into a refining kettle, adding deionized water, pulping and centrifuging to obtain a sodium methallyl sulfonate refined product, and collecting a centrifuging mother solution; wherein the mass ratio of the sodium methacrylate crude product to the deionized water is 10:6-10:10;
s4, circularly pulping the centrifugal mother liquor for multiple times, and recycling the centrifugal mother liquor into washing of the wet solid filter cake of sodium methacrylate sulfonate in the step S2 when the chloride ion content in the centrifugal mother liquor exceeds 0.3%;
s5, crushing and mixing the sodium methallyl sulfonate refined product, and drying to obtain a finished product.
2. The method for purifying sodium methallyl sulfonate according to claim 1, wherein: the centrifugal speed in the step S1 is 1000-2000 rpm, the centrifugal time is 15-20 minutes, and the mass percentage content of water in the obtained sodium methacrylate wet solid filter cake is 5.0-10.0% and the mass percentage content of chloride ions is 0.5-1.0%.
3. The method for purifying sodium methallyl sulfonate according to claim 1, wherein: in the step S2, the mass of the saturated solution of sodium methacrylate sulfonate sprayed each time is 5.0-15.0% of that of the wet solid filter cake of sodium methacrylate sulfonate, the next spraying is started after the solution is centrifuged at a rotational speed of 1000-2000 rpm for 5-10 minutes after each spraying, and the solution is centrifuged at a rotational speed of 1000-2000 rpm for 10-15 minutes after the last spraying is finished.
4. The method for purifying sodium methallyl sulfonate according to claim 1, wherein: and in the step S3, the pulping time is 1-2 hours, the centrifugal speed is 1000-2000 rpm, and the centrifugal time is 10-15 minutes.
5. The method for purifying sodium methallyl sulfonate according to claim 1, wherein: and (3) circularly applying the centrifugal mother liquor of the refining kettle in the step (S4) to the pulping process, wherein the chloride ion content is lower than 0.3%.
6. The method for purifying sodium methallyl sulfonate according to claim 1, wherein: in the step S5, the dryer is a disc dryer, the dryer is heated by steam, the steam pressure is 0.02-0.06 Mpa, and the drying time is 20-60 minutes.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1244074A (en) * | 1968-10-19 | 1971-08-25 | Bayer Ag | Process for the production of sodium methallyl sulphonate |
| JPS6097950A (en) * | 1983-10-12 | 1985-05-31 | ヘミツシエ・ウエルケ・ヒユールス・アクチエンゲゼルシヤフト | Post-treatment of sodium methallylsulfonate aqueous solution |
| CN1172800A (en) * | 1997-05-22 | 1998-02-11 | 南开大学新技术集团公司丹阳分厂 | Preparation technology and equipment for sodium salt of methyl propenyl sulfonic acid |
| CN1398852A (en) * | 2001-07-24 | 2003-02-26 | 奥克森诺奥勒芬化学股份有限公司 | Prepn of methallyl sulfonate |
| CN1462741A (en) * | 2003-06-23 | 2003-12-24 | 余姚市东泰精细化工有限公司 | Method for preparing sodium methallyl sulfonic acid |
| CN101492399A (en) * | 2009-03-04 | 2009-07-29 | 太仓市新毛涤纶化工有限公司 | Method for preparing methylpropene sodium sulfonate |
| CN101805275A (en) * | 2010-03-20 | 2010-08-18 | 陆豪杰 | Method for synthesizing sodium methyl allylsulfonate |
| CN108929062A (en) * | 2018-07-04 | 2018-12-04 | 穆琳瑛 | A kind of polycarboxylate water-reducer and its preparation process |
| CN112851555A (en) * | 2021-01-18 | 2021-05-28 | 浙江皇马科技股份有限公司 | Synthesis and refining method of sodium methallyl sulfonate |
| CN113825553A (en) * | 2019-05-15 | 2021-12-21 | Spcm股份公司 | Novel method for filtering 2-acrylamide-2-methylpropanesulfonic acid |
-
2022
- 2022-08-16 CN CN202210980658.8A patent/CN115403490B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1244074A (en) * | 1968-10-19 | 1971-08-25 | Bayer Ag | Process for the production of sodium methallyl sulphonate |
| JPS6097950A (en) * | 1983-10-12 | 1985-05-31 | ヘミツシエ・ウエルケ・ヒユールス・アクチエンゲゼルシヤフト | Post-treatment of sodium methallylsulfonate aqueous solution |
| CN1172800A (en) * | 1997-05-22 | 1998-02-11 | 南开大学新技术集团公司丹阳分厂 | Preparation technology and equipment for sodium salt of methyl propenyl sulfonic acid |
| CN1398852A (en) * | 2001-07-24 | 2003-02-26 | 奥克森诺奥勒芬化学股份有限公司 | Prepn of methallyl sulfonate |
| CN1462741A (en) * | 2003-06-23 | 2003-12-24 | 余姚市东泰精细化工有限公司 | Method for preparing sodium methallyl sulfonic acid |
| CN101492399A (en) * | 2009-03-04 | 2009-07-29 | 太仓市新毛涤纶化工有限公司 | Method for preparing methylpropene sodium sulfonate |
| CN101805275A (en) * | 2010-03-20 | 2010-08-18 | 陆豪杰 | Method for synthesizing sodium methyl allylsulfonate |
| CN108929062A (en) * | 2018-07-04 | 2018-12-04 | 穆琳瑛 | A kind of polycarboxylate water-reducer and its preparation process |
| CN113825553A (en) * | 2019-05-15 | 2021-12-21 | Spcm股份公司 | Novel method for filtering 2-acrylamide-2-methylpropanesulfonic acid |
| CN112851555A (en) * | 2021-01-18 | 2021-05-28 | 浙江皇马科技股份有限公司 | Synthesis and refining method of sodium methallyl sulfonate |
Non-Patent Citations (1)
| Title |
|---|
| 甲代烯丙基磺酸钠的合成;陆豪杰;《化学工程师》;第183卷(第12期);63-64、72 * |
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