CN115772102A - Preparation process of high-purity anhydrous p-toluenesulfonic acid - Google Patents
Preparation process of high-purity anhydrous p-toluenesulfonic acid Download PDFInfo
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- CN115772102A CN115772102A CN202211704384.6A CN202211704384A CN115772102A CN 115772102 A CN115772102 A CN 115772102A CN 202211704384 A CN202211704384 A CN 202211704384A CN 115772102 A CN115772102 A CN 115772102A
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 62
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims description 72
- 238000005406 washing Methods 0.000 claims description 59
- 238000002425 crystallisation Methods 0.000 claims description 55
- 230000008025 crystallization Effects 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 53
- 239000002244 precipitate Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 39
- 239000012295 chemical reaction liquid Substances 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 25
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003860 storage Methods 0.000 claims description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 16
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 16
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 14
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004807 desolvation Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 abstract 1
- JDQDSEVNMTYMOC-UHFFFAOYSA-N 3-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1 JDQDSEVNMTYMOC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000004064 recycling Methods 0.000 description 17
- 238000001291 vacuum drying Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- PVEFEIWVJKUCLJ-UHFFFAOYSA-N sulfuric acid;toluene Chemical compound OS(O)(=O)=O.CC1=CC=CC=C1 PVEFEIWVJKUCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The invention discloses a preparation process of high-purity anhydrous p-toluenesulfonic acid, belongs to the technical field of organic matter purification, and particularly relates to SO 3 On the basis of preparing p-toluenesulfonic acid by sulfonation, the method for preparing high-purity anhydrous p-toluenesulfonic acid by three-stage series recrystallization comprises the following steps: through adjusting the ratio of toluene and alkane and the recrystallization temperature, three-stage series recrystallization is carried out, the ortho-toluenesulfonic acid, the meta-toluenesulfonic acid and the over-sulfonated product are effectively separated, and the high-purity anhydrous p-toluenesulfonic acid product is obtained.
Description
Technical Field
The invention belongs to the technical field of organic matter purification, and particularly relates to a preparation process of high-purity anhydrous p-toluenesulfonic acid.
Background
Para-toluenesulfonic acid (PTS) is an important fine chemical raw material and an acid catalyst commonly used in organic synthesis, is a main raw material for synthesizing para-toluenesulfonyl chloride, para-cresol and para-toluenesulfonamide, is used as an organic reaction catalyst, and is mainly used for esterification, acetal, dehydration, alkylation, beckmann rearrangement, polymerization, depolymerization and the like.
The main 2 kinds of industrial p-toluenesulfonic acid processes are a toluene-sulfuric acid sulfonation method, when toluene is sulfonated by concentrated sulfuric acid, a large amount of water is generated, the concentration of the concentrated sulfuric acid is reduced, and when the concentration is lower than a certain value, the reaction is difficult to continue, so that a large amount of waste acid is generated, and the environment is not favorable. The second one is a toluene-sulfur trioxide sulfonation method, which is an advanced sulfonation process, can realize stoichiometric reaction, theoretically, no waste acid or waste water is generated, but sulfur trioxide directly sulfonates toluene, the reaction is violent, so that ortho-position and meta-position sulfonation and over-sulfonation products and the like are generated, a certain amount of water is added into a system in general post-treatment, p-toluenesulfonic acid forms p-toluenesulfonic acid monohydrate, and crystallization and separation are realized, so that the purpose of purification is achieved. At present, the bulk sales of the p-toluenesulfonic acid monohydrate in the market are all p-toluenesulfonic acid monohydrate, but in the organic catalytic reaction in which the p-toluenesulfonic acid participates, anhydrous p-toluenesulfonic acid is more needed to participate in the reaction, so that a preparation method and industrial equipment for high-purity anhydrous p-toluenesulfonic acid are developed, and the method has certain market value.
The literature (j. Phys. Chem. A2018, 122, 3, 762-772) studies the interaction hydrogen bonding of p-toluenesulfonic acid with water molecules by the stretching movement of sulfonate-OH by infrared absorption spectroscopy, and the literature indicates that the crystal water of p-toluenesulfonic acid is independent in organic solvent, and when the hydrogen bonding of water molecules and pi electrons exists in aqueous solution, the report only studies the intermolecular interaction of p-toluenesulfonic acid monohydrate, and has no specific preparation method for preparing anhydrous p-toluenesulfonic acid. The literature (org. Process res. Dev. 2021, 25, 1383-1390) reports a Process for the dehydration of methyl tert-butyl ether to para-toluenesulfonic acid monohydrate in yields of 65% which is low and provides only one set of data, without involving the screening and comparison of other solvents, and without complete description of the isolation Process. The document (research on production technology of anhydrous p-toluenesulfonic acid [ J ]. Zhejiang chemical industry, 2015,46 (08)) reports a preparation method of anhydrous p-toluenesulfonic acid, wherein the anhydrous p-toluenesulfonic acid is obtained by directly concentrating dichloromethane in a reaction solution and then cooling and crystallizing. None of the above reports relate to a complete process scheme for the preparation of high purity anhydrous p-toluenesulfonic acid.
Disclosure of Invention
Aiming at the problems of low purity and low yield existing in the existing anhydrous paratoluenesulfonic acid preparation technology, the invention aims to provide a preparation process of high-purity anhydrous paratoluenesulfonic acid.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation process of high-purity anhydrous p-toluenesulfonic acid comprises the following steps:
1) Solvent removal: transferring the sulfonation reaction liquid to a desolventizing kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid by a liquid phase method, adding toluene to obtain a concentrated reaction liquid G 0 ；
2) Three-stage series crystallization:
(1) alkane L 1 Adding the mixture into a first-stage crystallization kettle through a liquid storage tank 1, stirring, heating to 40 ℃, and adding the concentrated reaction solution G obtained in the step 1) 0 Adding the mixture into a first-stage crystallization kettle, continuously stirring for 30 to 40 minutes after the material is added, cooling to 25 to 35 ℃, and centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With alkanes W 1 Washing twice to obtain a solid 1, and drying the solid 1 in vacuum at 30 to 70 ℃ for 1 to 6h to obtain the anhydrous p-toluenesulfonic acid D 1 Centrifugal liquid G 1 Standby;
(2) alkane L 2 Adding into a secondary crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding the mixture into a secondary crystallization kettle, continuously stirring for 30 to 40 minutes after the addition is finished, cooling to 15 to 25 ℃, and centrifuging to obtain precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 With alkanes W 2 Washing twice to obtain a solid 2, and drying the solid 2 in vacuum at 30 to 70 ℃ for 1 to 6h to obtain the anhydrous p-toluenesulfonic acid D 2 Centrifugate G 2 Standby;
(3) alkane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding the mixture into a three-stage crystallization kettle, continuously stirring for 30 to 40 minutes after the material is added, cooling to 5 to 15 ℃, and centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 With alkanes W 3 Washing twice to obtain a solid 3, and drying the solid 3 in vacuum at 30 to 70 ℃ for 1 to 6 hours to obtain the anhydrous p-toluenesulfonic acid D 3 Centrifugal liquid G 3 Transferring to a distillation kettle to recover the solvent;
3) The anhydrous p-toluenesulfonic acid D obtained in the step (1) 1 The anhydrous p-toluenesulfonic acid D obtained in the step (2) 2 And the anhydrous p-toluenesulfonic acid D obtained in the step (3) 3 And mixing by a double-cone mixer to obtain the anhydrous p-toluenesulfonic acid.
Further, the mass ratio of the toluene to the p-toluenesulfonic acid in the sulfonation reaction liquid is 3-1: 1.
further, the alkane L 1 Of an alkane L 2 C, an alkane L 3 Alkane W 1 Alkane W 2 And an alkane W 3 Cyclohexane, methylcyclohexane, n-heptane or isooctane.
Further, the alkane L 1 Of an alkane L 2 Of an alkane L 3 The mass ratio of the toluene to the toluene is 0.5-1: 0.2 to 0.6:0.2 to 0.6:1.
further, the alkane W 1 Alkane W 2 Alkane W 3 The mass ratio of the p-toluenesulfonic acid to the p-toluenesulfonic acid in the sulfonation reaction liquid is 0.1-0.5: 0.1 to 0.5:0.1 to 0.5:1.
preferably, the mass ratio of the toluene to the p-toluenesulfonic acid in the sulfonation reaction liquid is 1.5:1.
preferably, said alkane L 1 C, an alkane L 2 Of an alkane L 3 Alkane W 1 Alkane W 2 And an alkane W 3 Is cyclohexane.
Preferably, the alkane L 1 C, an alkane L 2 Of an alkane L 3 Mass ratio to toluene 0.8:0.5:0.5:1.
preferably, said alkane W 1 Alkane W 2 Alkane W 3 The mass ratio of the p-toluenesulfonic acid to the sulfonation reaction liquid is 0.2:0.2:0.2:1.
preferably, the drying temperature of the solid 1, the solid 2 and the solid 3 is 50 ℃, and the drying time is 3h.
Compared with the prior art, the invention has the following advantages:
the invention relates to a preparation process of anhydrous p-toluenesulfonic acid, and provides a method for preparing anhydrous p-toluenesulfonic acid in SO 3 A method for preparing high-purity anhydrous p-toluenesulfonic acid on the basis of preparing p-toluenesulfonic acid by sulfonation. By utilizing a dissolution equilibrium principle, adopting a dissolution-crystallization process, carrying out three-stage series crystallization by using the solubility difference of p-toluenesulfonic acid and impurities in a toluene/alkane mixed solvent and adjusting the proportion of a polar solvent and an inert solvent and the crystallization temperature, and effectively separating ortho-sulfonated products, meta-sulfonated products and para-sulfonated products to obtain the high-purity anhydrous p-toluenesulfonic acid. The method has the advantages of simple equipment, strong operability and small solvent indiscriminate application loss, and is suitable for large-scale production.
Drawings
FIG. 1 is a flow chart of a three-stage series crystallization process for preparing anhydrous p-toluenesulfonic acid according to the present invention.
Detailed Description
The above-mentioned aspects of the present invention will be further described in detail by the following embodiments in the form of examples for better understanding of the technical solutions of the present invention, but it should not be construed that the scope of the above-mentioned subject matter of the present invention is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
The sulfonation reaction liquid of the invention is a sulfonation product or liquid material obtained in the step (1) of the method disclosed in patent CN 114839310.
Example 1
Transferring the sulfonation reaction liquid to a desolventizing kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid to be 0.79kg by a liquid phase method, and adding 1.18kg of toluene to obtain concentrated reaction liquid G 0 。
0.95kg of cyclohexane L 1 Adding into a first-stage crystallization kettle via a liquid storage tank 1, stirring, heating to 40 deg.C to obtain concentrated reaction solution G 0 Adding into a first-stage crystallization kettle, stirring for 30 min after the addition, cooling to 30 deg.C, and centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With 0.16kg of cyclohexane W 1 Washing twice to obtain solid 1 and washing liquid, and vacuum drying the solid 1 at 50 deg.C for 3 hr to obtain 0.38kg anhydrous p-toluenesulfonic acid D 1 Centrifugal liquid G 1 For standby, the washing liquid is used as a solvent for recycling;
0.59kg of cyclohexane L 2 Adding into a second-stage crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding into a second-stage crystallization kettle, stirring for 30 min after the addition, cooling to 20 deg.C, and centrifuging to obtain precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 With 0.16kg of cyclohexane W 2 Washing twice to obtain solid 2 and washing liquid, and vacuum drying the solid 2 at 50 deg.C for 3 hr to obtain 0.24kg anhydrous p-toluenesulfonic acid D 2 Centrifugal liquid G 2 For standby, the washing liquid is used as a solvent for recycling;
0.59kg of cyclohexane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding into a three-stage crystallization kettle, stirring for 30 min after the material addition, cooling to 10 deg.C, and centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 With 0.16kg of cyclohexane W 3 Washing twice to obtain solid 3 and washing liquid, and vacuum drying the solid 3 at 50 deg.C for 3 hr to obtain 0.13kg anhydrous p-toluenesulfonic acid D 3 Centrifugate G 3 Transferring into distillation still to recover solvent, washingRecycling the solution as solvent, D 1 、D 2 And D 3 The product is mixed by a double cone mixer to obtain the anhydrous paratoluenesulfonic acid, the purity of the product is 99.8 percent, and the water content is 0.11 percent.
Example 2
Transferring the sulfonation reaction liquid to a desolventizing kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid to be 0.92kg by a liquid phase method, adding 2.76kg of toluene to obtain concentrated reaction liquid G 0 ；
2.76kg of methylcyclohexane L 1 Adding into a first-stage crystallization kettle via a liquid storage tank 1, stirring, heating to 40 deg.C to obtain concentrated reaction solution G 0 Adding into a first-stage crystallization kettle, stirring for 30 min after the addition, cooling to 25 deg.C, and centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With 0.46kg of methylcyclohexane W 1 Washing twice to obtain solid 1 and washing liquid, and vacuum drying the solid 1 at 70 ℃ for 6h to obtain 0.38kg of anhydrous p-toluenesulfonic acid D 1 Centrifugate G 1 For standby, the washing liquid is used as a solvent for recycling;
1.66kg of methylcyclohexane L 2 Adding into a second-stage crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding into a second-stage crystallization kettle, stirring for 30 min after the addition, cooling to 15 deg.C, and centrifuging to obtain precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 With 0.46kg of methylcyclohexane W 2 Washing twice to obtain solid 2 and washing liquid, and vacuum drying the solid 2 at 70 deg.C for 6 hr to obtain 0.28kg of anhydrous p-toluenesulfonic acid D 2 Centrifugal liquid G 2 For standby, the washing liquid is used as a solvent for recycling;
1.66kg of methylcyclohexane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding into a three-stage crystallization kettle, stirring for 30 min after the material is added, cooling to 5 deg.C, centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 With 0.46kg of methylcyclohexane W 3 Washing twice to obtain solid 3 and washing liquid, and vacuum drying the solid 3 at 70 ℃ for 6h to obtain 0.14kg of anhydrous p-toluenesulfonic acid D 3 Centrifugal liquid G 3 Transferring into a distillation still to recover solvent, recycling washing liquid as solvent, and D 1 、D 2 And D 3 The product is mixed by a double cone mixer to obtain the anhydrous p-toluenesulfonic acid, the purity of the product is 99.7%, and the water content is 0.12%.
Example 3
Transferring the sulfonation reaction liquid to a desolventizing kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid to be 0.9kg by a liquid phase method, and adding 0.9kg of toluene to obtain concentrated reaction liquid G 0 ；
0.45kg of isooctane L 1 Adding into a first-stage crystallization kettle via a liquid storage tank 1, stirring, heating to 40 deg.C to obtain concentrated reaction solution G 0 Adding into a first-stage crystallization kettle, stirring for 40 min after the material is added, cooling to 35 deg.C, centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With 0.09kg of isooctane W 1 Washing twice to obtain solid 1 and washing liquid, and vacuum drying the solid 1 at 30 ℃ for 1h to obtain 0.39kg of anhydrous p-toluenesulfonic acid D 1 Centrifugal liquid G 1 For standby, the washing liquid is used as a solvent for recycling;
0.18kg of isooctane L 2 Adding into a secondary crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding into a second-stage crystallization kettle, stirring for 40 min after the addition, cooling to 25 deg.C, and centrifuging to obtain precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 With 0.09kg of isooctane W 2 Washing twice to obtain solid 2 and washing liquid, and vacuum drying the solid 2 at 30 deg.C for 1 hr to obtain 0.3kg anhydrous p-toluenesulfonic acid D 2 Centrifugal liquid G 2 For standby, the washing liquid is used as a solvent for recycling;
0.18kg of isooctane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding into a three-stage crystallization kettle, stirring for 40 min after the addition, cooling to 15 deg.C, centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 With 0.09kg of isooctane W 3 Washing twice to obtain solid 3 and washing solution, vacuum drying the solid 3 at 30 deg.C for 1 hr to obtain 0.14kgWater p-toluenesulfonic acid D 3 Centrifugate G 3 Transferring into a distillation still to recover solvent, recycling washing liquid as solvent, and D 1 、D 2 And D 3 The product is mixed by a double cone mixer to obtain the anhydrous p-toluenesulfonic acid, the purity of the product is 99.6%, and the water content is 0.15%.
Example 4
Transferring the sulfonation reaction liquid to a desolventizing kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid to be 0.79kg by a liquid phase method, adding 2kg of toluene to obtain concentrated reaction liquid G 0 ；
1.8kg of isooctane L 1 Adding into a first-stage crystallization kettle via a liquid storage tank 1, stirring, heating to 40 deg.C to obtain concentrated reaction solution G 0 Adding into a first-stage crystallization kettle, stirring for 30 min after the material is added, cooling to 32 deg.C, centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With 0.3kg of isooctane W 1 Washing twice to obtain solid 1 and washing liquid, and vacuum drying the solid 1 at 60 deg.C for 2 hr to obtain 0.35kg of anhydrous p-toluenesulfonic acid D 1 Centrifugal liquid G 1 For standby, the washing liquid is used as a solvent for recycling;
1kg of isooctane L 2 Adding into a second-stage crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding into a secondary crystallization kettle, stirring for 30 min after the addition, cooling to 22 deg.C, centrifuging to obtain precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 Using 0.35kg of isooctane W 2 Washing twice to obtain solid 2 and washing liquid, and vacuum drying the solid 2 at 60 deg.C for 2 hr to obtain 0.25kg anhydrous p-toluenesulfonic acid D 2 Centrifugal liquid G 2 For standby, the washing liquid is used as a solvent for recycling;
1kg of isooctane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding into a three-stage crystallization kettle, stirring for 30 min after the material is added, cooling to 12 deg.C, centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 Using 0.32kg of isooctane W 3 Washing twice to obtain solid 3 and washing liquid, and vacuum drying solid 3 at 60 deg.C0.14kg of anhydrous p-toluenesulfonic acid D is obtained in 2h 3 Centrifugate G 3 Transferring into a distillation still to recover solvent, recycling washing liquid as solvent, and recovering solvent 1 、D 2 And D 3 The product is mixed by a double cone mixer to obtain the anhydrous p-toluenesulfonic acid, the purity of the product is 99.8 percent, and the water content is 0.14 percent.
Example 5
Transferring the sulfonation reaction liquid to a desolventizing kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid to be 0.79kg by a liquid phase method, adding 1.6kg of toluene to obtain concentrated reaction liquid G 0 ；
1.1kg of n-heptane L 1 Adding into a first-stage crystallization kettle via a liquid storage tank 1, stirring, heating to 40 deg.C to obtain concentrated reaction solution G 0 Adding into a first-stage crystallization kettle, stirring for 35 min after the addition, cooling to 27 deg.C, centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With 0.24kg of n-heptane W 1 Washing twice to obtain solid 1 and washing liquid, and vacuum drying the solid 1 at 40 deg.C for 4 hr to obtain 0.36kg anhydrous p-toluenesulfonic acid D 1 Centrifugate G 1 For standby, the washing liquid is used as a solvent for recycling;
0.64kg of n-heptane L 2 Adding into a second-stage crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding into a second-stage crystallization kettle, stirring for 35 min after the addition, cooling to 18 deg.C, and centrifuging to obtain precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 With 0.20kg of n-heptane W 2 Washing twice to obtain solid 2 and washing liquid, and vacuum drying the solid 2 at 40 deg.C for 4 hr to obtain 0.24kg of anhydrous p-toluenesulfonic acid D 2 Centrifugal liquid G 2 For standby, the washing liquid is used as a solvent for recycling;
0.64kg of n-heptane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding into a three-stage crystallization kettle, stirring for 35 min after the material is added, cooling to 8 deg.C, centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 With 0.22kg of n-heptane W 3 Washing twice to obtain solid 3 and washing liquid, solidThe body 3 was dried under vacuum at 40 ℃ for 4 hours to give 0.14kg of anhydrous p-toluenesulfonic acid D 3 Centrifugal liquid G 3 Transferring into a distillation still to recover solvent, recycling washing liquid as solvent, and D 1 、D 2 And D 3 The product is mixed by a double cone mixer to obtain the anhydrous paratoluenesulfonic acid, the purity of the product is 99.7 percent, and the water content is 0.11 percent.
Example 6
Transferring the sulfonation reaction liquid to a desolventizing kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid to be 0.79kg by a liquid phase method, adding 1.2kg of toluene to obtain concentrated reaction liquid G 0 ；
0.72kg of cyclohexane L 1 Adding into a first-stage crystallization kettle via a liquid storage tank 1, stirring, heating to 40 deg.C to obtain concentrated reaction solution G 0 Adding into a first-stage crystallization kettle, stirring for 30 min after the material is added, cooling to 30 deg.C, centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With 0.16kg of cyclohexane W 1 Washing twice to obtain solid 1 and washing liquid, and vacuum drying the solid 1 at 50 deg.C for 5 hr to obtain 0.35kg of anhydrous p-toluenesulfonic acid D 1 Centrifugate G 1 For standby, the washing liquid is used as a solvent for recycling;
0.36kg of cyclohexane L 2 Adding into a second-stage crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding into a second-stage crystallization kettle, stirring for 30 min after the addition, cooling to 20 deg.C, and centrifuging to obtain precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 With 0.16kg of cyclohexane W 2 Washing twice to obtain solid 2 and washing liquid, and vacuum drying the solid 2 at 40 deg.C for 4 hr to obtain 0.25kg of anhydrous p-toluenesulfonic acid D 2 Centrifugate G 2 For standby, the washing liquid is used as a solvent for recycling;
0.40kg of cyclohexane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding into a three-stage crystallization kettle, stirring for 30 min after the material is added, cooling to 10 deg.C, centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 With 0.16kg of cyclohexane W 3 Washing twice to obtainTo solid 3 and the washings, the solid 3 was dried under vacuum at 50 ℃ for 5h to give 0.13kg of anhydrous p-toluenesulfonic acid D 3 Centrifugate G 3 Transferring into a distillation still to recover solvent, recycling washing liquid as solvent, and recovering solvent 1 、D 2 And D 3 The product is mixed by a double cone mixer to obtain the anhydrous p-toluenesulfonic acid, the purity of the product is 99.8 percent, and the water content is 0.12 percent.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Claims (10)
1. A preparation process of high-purity anhydrous p-toluenesulfonic acid is characterized by comprising the following steps: the method comprises the following steps:
1) Desolventizing: transferring the sulfonation reaction liquid to a desolvation kettle, removing the solvent, measuring the mass of p-toluenesulfonic acid in the sulfonation reaction liquid by a liquid phase method, adding toluene to obtain concentrated reaction liquid G 0 ；
2) Three-stage series crystallization:
(1) alkane L 1 Adding the mixture into a first-stage crystallization kettle through a liquid storage tank 1, starting stirring, heating to 40 ℃, and adding the concentrated reaction liquid G obtained in the step 1) 0 Adding the mixture into a first-stage crystallization kettle, continuously stirring for 30 to 40 minutes after the material is added, cooling to 25 to 35 ℃, and centrifuging to obtain precipitate C 1 And centrifugate G 1 The obtained precipitate C 1 With alkanes W 1 Washing twice to obtain a solid 1, and drying the solid 1 in vacuum at 30 to 70 ℃ for 1 to 6h to obtain anhydrous p-toluenesulfonic acid D 1 Centrifugal liquid G 1 Standby;
(2) alkane L 2 Adding into a second-stage crystallization kettle via a liquid storage tank 2, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 1 Adding the mixture into a secondary crystallization kettle, continuing stirring for 30 to 40 minutes after the charging is finished, cooling to 15 to 25 ℃, and centrifuging to obtain a precipitate C 2 And centrifugate G 2 The obtained precipitate C 2 With alkanes W 2 Washing twice to obtain a solid 2, and drying the solid 2 in vacuum at 30 to 70 ℃ for 1 to 6 hours to obtainAnhydrous p-toluenesulfonic acid D 2 Centrifugal liquid G 2 Standby;
(3) alkane L 3 Adding into a three-stage crystallization kettle via a liquid storage tank 3, stirring, heating to 35 deg.C, and centrifuging to obtain centrifugate G 2 Adding the mixture into a three-stage crystallization kettle, continuously stirring for 30 to 40 minutes after the material is added, cooling to 5 to 15 ℃, and centrifuging to obtain precipitate C 3 And centrifugate G 3 The obtained precipitate C 3 With alkanes W 3 Washing twice to obtain solid 3, and drying the solid 3 in vacuum at 30 to 70 ℃ for 1 to 6h to obtain anhydrous p-toluenesulfonic acid D 3 Centrifugal liquid G 3 Transferring to a distillation kettle to recover the solvent;
3) The anhydrous p-toluenesulfonic acid D obtained in the step (1) 1 And (3) obtaining anhydrous p-toluenesulfonic acid D in step (2) 2 And the anhydrous p-toluenesulfonic acid D obtained in the step (3) 3 And mixing by a double-cone mixer to obtain the anhydrous p-toluenesulfonic acid.
2. The process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the mass ratio of the toluene to the p-toluenesulfonic acid in the sulfonation reaction liquid is 3-1: 1.
3. the process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the alkane L 1 Of an alkane L 2 C, an alkane L 3 Alkane W 1 Alkane W 2 And an alkane W 3 Cyclohexane, methylcyclohexane, n-heptane or isooctane.
4. The process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the alkane L 1 C, an alkane L 2 C, an alkane L 3 The mass ratio of the toluene to the toluene is 0.5-1: 0.2 to 0.6:0.2 to 0.6:1.
5. the process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the alkane W 1 Alkane W 2 Alkane W 3 With p-toluenesulfonic acid in the sulfonation reaction liquidThe mass ratio of (A) to (B) is 0.1-0.5: 0.1 to 0.5:0.1 to 0.5:1.
6. the process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the mass ratio of the toluene to the p-toluenesulfonic acid in the sulfonation reaction liquid is 1.5:1.
7. the process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the alkane L 1 Of an alkane L 2 C, an alkane L 3 Alkane W 1 Alkane W 2 And an alkane W 3 Is cyclohexane.
8. The process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the alkane L 1 C, an alkane L 2 C, an alkane L 3 Mass ratio to toluene 0.8:0.5:0.5:1.
9. the process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the alkane W 1 Alkane W 2 Alkane W 3 The mass ratio of the p-toluenesulfonic acid to the sulfonation reaction liquid is 0.2:0.2:0.2:1.
10. the process for preparing high-purity anhydrous p-toluenesulfonic acid according to claim 1, characterized in that: the drying temperature of the solid 1, the solid 2 and the solid 3 is 50 ℃, and the drying time is 3h.
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| CN101845004A (en) * | 2010-04-16 | 2010-09-29 | 苏州市兴业化工有限公司 | Method for preparing p-toluenesulfonic acid by toluene sulfonation |
| CN109651262A (en) * | 2019-01-24 | 2019-04-19 | 安徽广信农化股份有限公司 | A kind of intermediate prepares the synthetic method of Fluoxastrobin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845004A (en) * | 2010-04-16 | 2010-09-29 | 苏州市兴业化工有限公司 | Method for preparing p-toluenesulfonic acid by toluene sulfonation |
| CN109651262A (en) * | 2019-01-24 | 2019-04-19 | 安徽广信农化股份有限公司 | A kind of intermediate prepares the synthetic method of Fluoxastrobin |
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| 王宏亮等: "无水对甲苯磺酸生产技术研究", 《精细化工》, pages 32 - 33 * |
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