CN116217445A - Preparation method of dimethyl isophthalate-5-sodium sulfonate - Google Patents
Preparation method of dimethyl isophthalate-5-sodium sulfonate Download PDFInfo
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- CN116217445A CN116217445A CN202211681208.5A CN202211681208A CN116217445A CN 116217445 A CN116217445 A CN 116217445A CN 202211681208 A CN202211681208 A CN 202211681208A CN 116217445 A CN116217445 A CN 116217445A
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- sulfonation
- dimethyl isophthalate
- sodium sulfonate
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 47
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 40
- 239000011734 sodium Substances 0.000 title claims abstract description 40
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 230000032050 esterification Effects 0.000 claims abstract description 30
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000010517 secondary reaction Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 64
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000003054 catalyst Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 21
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 229920002530 polyetherether ketone Polymers 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 claims description 10
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000001994 activation Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002386 leaching Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000005087 graphitization Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000007127 saponification reaction Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 229920000728 polyester Polymers 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 235000012736 patent blue V Nutrition 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 especially fashion Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- 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
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- 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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method of dimethyl isophthalate-5-sodium sulfonate, belonging to dimethyl isophthalate-5-sodium sulfonateThe preparation field. The preparation method comprises the following steps: sulfonation, esterification, neutralization and post-treatment; the sulfonation comprises: primary reaction and secondary reaction. The dimethyl isophthalate-5-sodium sulfonate prepared by the preparation method has the purity of 99.62-99.72 percent, the acid value of 0.17-0.22mgKOH/g, the saponification value of 378.54-378.73mgKOH/g and the sulfate radical content of 41-46mg/kg, and Fe 3+ The content of Cl is 0.72-0.81mg/kg ‑ The content is 3.57-4.19mg/kg, and the yield is 94.35-96.40%; meanwhile, the application amount of sulfuric acid in the sulfonation process is effectively reduced, the procedures of neutralization and waste water post-treatment are simplified, the energy consumption is reduced, and the cost is reduced.
Description
Technical Field
The invention relates to the field of preparation of dimethyl isophthalate-5-sodium sulfonate, in particular to a preparation method of dimethyl isophthalate-5-sodium sulfonate.
Background
Dimethyl isophthalate-5-sodium Sulfonate (SIPM), commonly known as trisomic, molecular formula C 10 H 9 NaO 7 S is an important differentiation modifier and is mainly used in the fields of terylene, films and the like. The terylene is a main application field of the three monomers and is mainly used for synthesizing the third monomer of the cationic modified polyester CDP.
The SIPM is introduced into the polyester chip to produce the cation modified polyester filament yarn, and the appearance of the cation modified polyester filament yarn is not greatly different from that of the common polyester filament yarn, but the cation modification is adopted, so that the color absorption performance of the fiber is greatly improved, the crystallinity is reduced, and the fiber yarn is further suitable for the simulated silk of the polyester fiber. The CDP fiber can be dyed under normal pressure by the imitated silk, the pollution to the fiber is small in the dyeing process, the diffusion rate to the inside of the fiber is high, and no environmental pollution phenomenon exists. And the dyed fiber has the characteristics of bright color, high color fastness and difficult fading, and simultaneously has good antistatic, hygroscopic, anti-pilling and air permeability properties.
In recent years, the cationic dye dyeable polyester prepared by taking dimethyl isophthalate-5-sodium sulfonate as a raw material has breakthrough progress in the following fields of application: (1) Sea-island fiber, especially fashion, artificial leather, high-performance filter material, high-performance paper, biomedical material, etc.; (2) synthesizing water-soluble polyester; (3) Polyester blend additives to improve the dyeability of polypropylene fibers; (4) substituting acrylic fibers to produce cation modified polyester blanket, etc.
At present, in the domestic tri-monomer industry, isophthalic acid is adopted as a raw material, and the method for preparing dimethyl isophthalate-5-sodium sulfonate mainly comprises the following steps: (1) The sulfoacid crystallization method is to sulfonate isophthalic acid by sulfur trioxide or fuming sulfuric acid, and then the product SIPM is prepared through the steps of crystallization, acid removal, esterification, neutralization and refining; (2) Chlorosulfonic acid is sulfonated, namely chlorosulfonic acid is taken as a sulfonating agent to be sulfonated, then isophthalic acid-5-sodium sulfonate is prepared through neutralization, filtration and drying, and then the product SIPM is prepared through esterification and neutralization; (3) The fuming sulfuric acid one-pot method is that fuming sulfuric acid with different concentrations is adopted to sulfonate isophthalic acid, the sulfonate is not separated, and the residual waste acid is used as a catalyst to directly carry out esterification, synthesis and refining, so that the product SIPM is prepared. (4) The esterification and sulfonation method is that methyl alcohol is added into isophthalic acid to carry out esterification to prepare dimethyl isophthalate, then the dimethyl isophthalate is mixed with isophthalic acid, and after sulfonation is carried out by sulfur trioxide or fuming sulfuric acid, esterification, neutralization and refining are carried out to prepare the product SIPM.
In the prior art, the main preparation process of each main production enterprise is to firstly adopt concentrated sulfuric acid with different concentrations for sulfonation, and then adopt a process route of excessive methanol esterification. The applicant finds that in order to ensure the sulfonation effect, the product purity and other indexes, excessive concentrated sulfuric acid is often adopted for sulfonation, so that the production safety is affected, a large amount of waste acid liquid is generated, the treatment pressure of the subsequent step is high, particularly, a large amount of alkaline substances are required to neutralize the waste acid liquid in the neutralization step, the operation is complex, and the production cost, the time cost and the labor cost are high.
Chinese patent CN102633693a discloses a method for synthesizing dimethyl isophthalate-5-sodium sulfonate, which divides the sulfonation step into three temperature intervals, and adopts different catalytic substances (cadmium sulfate, silicon dioxide, mercury sulfate) to catalyze the sulfonation reaction while raising the temperature and keeping the temperature in stages. However, the technical scheme has the defects that the multistage sulfonation operation adopting different catalytic substances is complex in operation and low in fault tolerance in the actual production process, and cannot meet the requirement of large-scale industrial production; meanwhile, the adopted catalytic substances cause the content of heavy metals in the reaction mother solution to be gradually increased, and the SIPM product performance can be influenced after long-term application; and the environmental friendliness of each heavy metal is poor, and the waste liquid treatment difficulty is high.
Chinese patent CN102633693a discloses a method for synthesizing dimethyl isophthalate-5-sodium sulfonate, which divides the sulfonation step into two temperature intervals, and adopts a supported catalyst to catalyze the sulfonation reaction. However, the technical proposal has the defects of unsatisfactory catalyst activity and large catalyst addition amount; and after the catalyst is reused for a plurality of times, the prepared SIPM product cannot obtain ideal purity and yield indexes, and the actual service life of the catalyst is required to be improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of dimethyl isophthalate-5-sodium sulfonate, so as to achieve the purposes of simple operation, high environmental friendliness, high sulfonation reaction yield, few side reactions and high purity of SIPM products.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing dimethyl isophthalate-5-sodium sulfonate, comprising the following steps: sulfonation, esterification, neutralization and post-treatment.
The sulfonation comprises: primary reaction and secondary reaction.
The primary reaction is carried out, a predetermined part of fuming sulfuric acid is put into a sulfonation kettle, and then a sulfonation catalyst is put into the kettle; controlling the temperature of the materials in the sulfonation kettle to 80-90 ℃ at a heating rate of 1-3 ℃/min, preserving heat, adding 35-45% of the total consumption of isophthalic acid, and uniformly stirring; then heating to 100-110 ℃, adding the rest isophthalic acid, and reacting for a period of time with heat preservation.
And (3) under the condition of stirring, controlling the temperature of materials in the sulfonation kettle to be raised to 130-135 ℃ at the temperature rising rate of 0.2-0.5 ℃/min, and carrying out heat preservation reaction for a period of time to obtain the sulfonate.
Preferably, the isophthalic acid: fuming sulfuric acid: the weight ratio of the sulfonation catalyst to the catalyst is 1:0.77-0.82:0.06-0.1.
Further, the sulfonation catalyst is prepared by the following preparation method: pretreatment, modification, granulation and activation.
The pretreatment, namely putting the activated carbon after ball milling into ethanol solution, stirring for a period of time, and filtering out solid matters; then putting the solid into phosphoric acid solution, heating to 35-45 ℃, keeping the temperature, stirring for a period of time, and filtering out the solid; then leaching with deionized water to neutrality; vacuum drying to obtain pretreated activated carbon.
Preferably, the specification of the activated carbon is that the particle size is 40-60 meshes and the specific surfaceThe product is 1000-1200m 2 and/G, the average pore diameter is 4-8nm, and the graphitization degree G value measured by XRD is 60-70%.
The modification, namely mixing predetermined parts of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon, and carrying out reflux reaction for 18-24 hours to obtain a reactant; then placing the reactant in an environment with the vacuum degree of 0.01-0.03MPa, and carrying out heat preservation distillation at the temperature of 112-120 ℃ until no gas phase is generated, thus obtaining distillate; adding the distilled liquid into deionized water with 15-20 times of volume, carrying out ultrasonic vibration for 3-8 hours, filtering out solid matters, and then carrying out freeze-drying treatment to obtain the modified activated carbon.
Preferably, the weight ratio of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon is 140-200:10-12:0.5-0.8:4-5:15-25.
The granulation is carried out, the activated carbon, antimony pentoxide, dibutyl tin oxide and copper chloride which are prepared by modification are mixed, and grinding is carried out for 3-5 hours under the condition of the rotating speed of 300-400rpm, so as to prepare a grinding material; and uniformly mixing a predetermined part of grinding material, N-methyl pyrrolidone and PEEK adhesive, and granulating to obtain pre-granulating.
Preferably, the weight ratio of the grinding material to the N-methyl pyrrolidone to the PEEK adhesive is 100:2-3:3-5.
And (3) activating, namely pre-granulating the granules prepared in the granulating step, and standing for 6-10h at the temperature of 160-180 ℃ to prepare the sulfonation catalyst.
The temperature of the sulfonate is reduced to 90-100 ℃ at the cooling rate of 0.5-1 ℃/min under the condition of esterification and stirring, and 50-60% of the total dosage of methanol is added for natural cooling; when naturally cooling to 70-75 ℃, adding the rest amount of methanol; and (3) when the materials in the esterification kettle are naturally cooled to 65-68 ℃, preserving heat and esterifying for 2-5h to obtain the esterified material.
Preferably, the weight ratio of the isophthalic acid to the methanol is 1:3-4.
And (3) under the condition of neutralization and stirring, after the esterified substance is mixed with deionized water, adjusting the pH value to be neutral by adopting sodium hydroxide, and continuously stirring for a period of time to obtain a neutralized substance.
Further, in the process of adding sodium hydroxide, the temperature is kept within the range of 25-30 ℃.
Preferably, the ratio of the esterified substance to the deionized water in parts by weight is 1:4-5;
and (3) carrying out post-treatment, namely dissolving, decoloring, filtering, crystallizing and drying the neutralized product to obtain the dimethyl isophthalate-5-sodium sulfonate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention relates to a preparation method of dimethyl isophthalate-5-sodium sulfonate, which is used for preparing the dimethyl isophthalate-5-sodium sulfonate and has the main quality indexes that: purity 99.62-99.72%, acid value 0.17-0.22mgKOH/g, saponification value 378.54-378.73mgKOH/g, sulfate content 41-46mg/kg, fe 3+ The content of Cl is 0.72-0.81mg/kg - The content is 3.57-4.19mg/kg, and the yield is 94.35-96.40%.
(2) According to the preparation method of the dimethyl isophthalate-5-sodium sulfonate, a two-step sulfonation method is adopted, and a special sulfonation catalyst is matched, so that the application amount of fuming sulfuric acid in the sulfonation process is effectively reduced, and the problems that the production process has potential safety hazards, the post-treatment difficulty is high, the alkali liquor amount required for neutralization is high, and the generated wastewater amount is large due to the fact that excessive concentrated sulfuric acid is adopted for sulfonation in the prior art are solved. The method not only reduces the usage amount (sulfuric acid and alkali liquor) of the production raw materials, but also simplifies the operation complexity of the procedures of neutralization, waste water post-treatment and the like, reduces the occupied area of relevant procedure devices, and effectively reduces the production cost while reducing the energy consumption.
(3) The preparation method of the dimethyl isophthalate-5-sodium sulfonate adopts a two-step sulfonation method, and can realize ideal sulfonation effect at about 135 ℃ by matching with a special sulfonation catalyst, and meanwhile, the sulfonation reaction time is further shortened, and the sulfonation time is controlled within 150min, so that the excellent reaction effect can be realized with low energy consumption and short time. Furthermore, under the conditions of low reaction temperature and short sulfonation time, the side reaction is effectively reduced, and the purity of the SIPM product is ensured to reach 99.62-99.72%.
(4) According to the preparation method of the dimethyl isophthalate-5-sodium sulfonate, the specially-made sulfonation catalyst has high catalytic activity, and the optimal catalytic effect can be realized under the condition that the addition amount is only 3-5wt%, so that the product yield of single reaction is effectively improved.
(5) According to the preparation method of dimethyl isophthalate-5-sodium sulfonate, the adopted special sulfonation catalyst can be recycled for a plurality of times, and through experiments, the catalysis times of the qualified SIPM product prepared by recycling can reach 82 times, so that the economic benefit is remarkable.
(6) Compared with the prior art, the preparation method of the dimethyl isophthalate-5-sodium sulfonate can improve the yield of the isophthalic acid-5-sulfonic acid by 2-3%, and further ensure the reaction effects of esterification, neutralization and the like in the subsequent reaction.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A method for preparing dimethyl isophthalate-5-sodium sulfonate, comprising the following steps: sulfonation, esterification, neutralization and post-treatment.
The sulfonation method comprises the following steps: primary reaction and secondary reaction.
The operation of the primary reaction is that a predetermined part of fuming sulfuric acid is put into a sulfonation kettle, and then a sulfonation catalyst is put under the stirring condition of 20 rpm; then, heat conduction oil is used as a heating medium, the temperature of the materials in the sulfonation kettle is controlled to rise to 80 ℃ at a heating rate of 1 ℃/min, the temperature is kept, 35% of the total consumption of isophthalic acid is added, and stirring is continued for 5min; then, the temperature is raised to 100 ℃ under the stirring condition of 50rpm, the temperature is kept, the rest amount of isophthalic acid is added, and the reaction is carried out for 70min.
Wherein the isophthalic acid: fuming sulfuric acid: the ratio of the parts by weight of the sulfonation catalyst is 1:0.77:0.06.
The fuming sulfuric acid concentration was 64wt%.
The sulfonation catalyst is prepared by the following preparation method: pretreatment, modification, granulation and activation.
The pretreatment method comprises the steps of putting a predetermined part of activated carbon into a ball mill, and performing ball milling treatment for 20min at a ball milling rotating speed of 400 rpm; then putting the ball-milled active carbon into ethanol solution with the volume of 3 times, stirring at 200rpm for 20min, and filtering out solid matters; then putting the solid into phosphoric acid solution with 3 times of volume, heating to 35 ℃, keeping the temperature and stirring for 40min under the condition of 100rpm, filtering out the solid, and leaching with deionized water to be neutral; and then drying the mixture until the weight is unchanged under the condition that the vacuum degree is 0.04MPa and the temperature is 85 ℃ to prepare the pretreated activated carbon.
The specification of the activated carbon is that the particle size is 40 meshes, the specific surface area is 1000m 2 and/G, average pore diameter of 4nm, graphitization degree G value of 60% by XRD.
The ball milling treatment is carried out by controlling the ball-material ratio in the ball milling to be 5:1.
The concentration of the ethanol solution is 80wt%.
The concentration of the phosphoric acid solution is 10wt%.
The modification method comprises the steps of mixing predetermined parts of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon, and carrying out reflux reaction for 18 hours to obtain a reactant; then placing the reactant in an environment with the vacuum degree of 0.01MPa, and carrying out heat preservation distillation at the temperature of 112 ℃ until no gas phase is generated, so as to obtain distillate; adding the distilled liquid into deionized water with 15 times of volume, carrying out ultrasonic vibration for 3 hours, filtering out solid matters, and then carrying out freeze-drying treatment to obtain the modified activated carbon.
Wherein the polyethylene glycol has a molecular weight of 400.
The weight ratio of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon is 140:10:0.5:4:15.
The ultrasonic vibration is operated with the ultrasonic vibration frequency of 24kHz and the power of 400W.
The granulating method comprises the steps of mixing a predetermined part of modified activated carbon, antimony pentoxide, dibutyl tin oxide and copper chloride, and grinding for 3 hours at a rotating speed of 300rpm to obtain a ground product; and uniformly mixing a predetermined part of grinding material, N-methyl pyrrolidone and PEEK adhesive, and granulating to obtain pre-granulating.
Wherein the weight ratio of the grinding material to the N-methyl pyrrolidone to the PEEK adhesive is 100:2:3.
The granularity of the sulfonation catalyst is 150 meshes.
The PEEK adhesive is manufactured by Guangzhou sky blue chemical technology Co.
The activation method is that the pre-granules are placed in 160 ℃ environment and kept stand for 6 hours, and the sulfonation catalyst is prepared.
The secondary reaction is carried out by controlling the temperature of the materials in the sulfonation kettle to be raised to 130 ℃ at a heating rate of 0.2 ℃/min under the stirring condition of 50rpm, and carrying out heat preservation reaction for 40min; the solids are filtered off and the liquid phase (i.e. the sulphonates) is introduced into the esterifying reactor.
And leaching the solid by using 8 times of deionized water, then placing the solid in an environment with the vacuum degree of 0.01MPa, and performing heat treatment at 110 ℃ for 3 hours to complete the recovery of the sulfonation catalyst.
The esterification method comprises the steps of controlling the temperature of materials in an esterification kettle to be reduced to 90 ℃ at a temperature reduction rate of 0.5 ℃/min under the stirring condition of 20rpm, adding 50% of the total dosage of methanol, and naturally cooling; when the materials in the esterification kettle are naturally cooled to 70 ℃, adding the rest amount of methanol; and (3) when the materials in the esterification kettle are naturally cooled to 65 ℃, preserving heat and esterifying for 2 hours to prepare an esterified material, and introducing the esterified material into the neutralization kettle.
Wherein the weight ratio of isophthalic acid to methanol is 1:3.
The neutralization method comprises the steps of adding a predetermined part of deionized water into a neutralization kettle at a charging rate of 1.5L/min under the stirring condition of 10 rpm; after the completion of the addition, sodium hydroxide was added under stirring at 20rpm, the pH value of the material in the neutralization tank was adjusted to be neutral, and stirring was continued for 30 minutes to obtain a neutralized product.
In the process of adding sodium hydroxide, the temperature of the materials in the neutralization kettle is kept within the range of 25-30 ℃ by controlling the circulating water flow of the jacket of the neutralization kettle.
The weight ratio of the esterified substance to the deionized water is 1:4.
And (3) carrying out post-treatment, namely dissolving, decoloring, filtering, crystallizing and drying the neutralized product to obtain the dimethyl isophthalate-5-sodium sulfonate.
Example 2
A method for preparing dimethyl isophthalate-5-sodium sulfonate, comprising the following steps: sulfonation, esterification, neutralization and post-treatment.
The sulfonation method comprises the following steps: primary reaction and secondary reaction.
The operation of the primary reaction is that a predetermined part of fuming sulfuric acid is put into a sulfonation kettle, and then a sulfonation catalyst is put under the stirring condition of 30 rpm; then, heat conduction oil is used as a heating medium, the temperature of the materials in the sulfonation kettle is controlled to be raised to 85 ℃ at a heating rate of 2 ℃/min, the temperature is kept, and 40% of the total consumption of isophthalic acid is added, and stirring is continued for 8min; then, the temperature is raised to 105 ℃ under the stirring condition of 80rpm, the temperature is kept, the rest amount of isophthalic acid is added for reaction for 80min.
Wherein the isophthalic acid: fuming sulfuric acid: the weight ratio of the sulfonation catalyst to the catalyst is 1:0.8:0.08.
The fuming sulfuric acid concentration is 65wt%.
The sulfonation catalyst is prepared by the following preparation method: pretreatment, modification, granulation and activation.
The pretreatment method comprises the steps of putting a predetermined part of activated carbon into a ball mill, and performing ball milling treatment for 30min at a ball milling rotating speed of 500 rpm; then putting the ball-milled active carbon into an ethanol solution with the volume of 4 times, stirring at 250rpm for 25min, and filtering out solid matters; then putting the solid into phosphoric acid solution with the volume of 4 times, heating to 40 ℃, keeping the temperature and stirring for 50min under the condition of 150rpm, filtering out the solid, and leaching with deionized water to be neutral; and then drying the mixture until the weight is unchanged under the condition that the vacuum degree is 0.05MPa and the temperature is 90 ℃ to prepare the pretreated activated carbon.
The specification of the activated carbon is that the particle size is 50 meshes, the specific surface area is 1100m 2 and/G, average pore diameter of 6nm, graphitization degree G value of 65% by XRD.
The ball milling treatment is carried out by controlling the ball-material ratio in ball milling to be 8:1.
The concentration of the ethanol solution is 90wt%.
The concentration of the phosphoric acid solution is 15wt%.
The modification method comprises the steps of mixing predetermined parts of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon, and carrying out reflux reaction for 20 hours to obtain a reactant; then placing the reactant in an environment with the vacuum degree of 0.02MPa, and carrying out heat preservation distillation at the temperature of 115 ℃ until no gas phase is generated, so as to obtain distillate; adding the distilled liquid into deionized water with the volume of 18 times, carrying out ultrasonic oscillation for 6 hours, filtering out solid matters, and then carrying out freeze-drying treatment to obtain the modified activated carbon.
Wherein the polyethylene glycol has a molecular weight of 500.
The weight ratio of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon is 170:11:0.6:4.5:20.
The ultrasonic vibration is operated with the ultrasonic vibration frequency of 25kHz and the power of 450W.
The granulating method comprises the steps of mixing a predetermined part of modified activated carbon, antimony pentoxide, dibutyl tin oxide and copper chloride, and grinding for 4 hours at a rotating speed of 350rpm to obtain a ground product; and uniformly mixing a predetermined part of grinding material, N-methyl pyrrolidone and PEEK adhesive, and granulating to obtain pre-granulating.
Wherein the weight ratio of the grinding material to the N-methyl pyrrolidone to the PEEK adhesive is 100:2.5:4.
The granularity of the sulfonation catalyst is 160 meshes.
The PEEK adhesive is manufactured by Guangzhou sky blue chemical technology Co.
The activation method is that the pre-granules are placed in a temperature environment of 170 ℃ and kept stand for 8 hours, and the sulfonation catalyst is prepared.
The secondary reaction is carried out by controlling the temperature of the materials in the sulfonation kettle to be raised to 132 ℃ at a heating rate of 0.4 ℃/min under the stirring condition of 90rpm, and carrying out heat preservation reaction for 45min; the solids are filtered off and the liquid phase (i.e. the sulphonates) is introduced into the esterifying reactor.
And leaching the solid by using deionized water with the volume of 9 times, and then placing the solid in an environment with the vacuum degree of 0.02MPa, and performing heat treatment for 4 hours at 120 ℃ to complete the recovery of the sulfonation catalyst.
The esterification method comprises the steps of controlling the temperature of materials in an esterification kettle to be reduced to 95 ℃ at a temperature reduction rate of 0.8 ℃/min under the stirring condition of 40rpm, adding 55% of the total dosage of methanol, and naturally cooling; when the materials in the esterification kettle are naturally cooled to 72 ℃, adding the rest amount of methanol; and (3) when the materials in the esterification kettle are naturally cooled to 66 ℃, preserving heat and esterifying for 4 hours to prepare an esterified material, and introducing the esterified material into the neutralization kettle.
Wherein the weight ratio of isophthalic acid to methanol is 1:3.2.
The neutralization method comprises the steps of adding a predetermined part of deionized water into a neutralization kettle at a charging rate of 2L/min under the stirring condition of 20 rpm; after the completion of the addition, sodium hydroxide was added under stirring at 30rpm, the pH value of the material in the neutralization tank was adjusted to be neutral, and the stirring was continued for 35 minutes, to obtain a neutralized product.
In the process of adding sodium hydroxide, the temperature of the materials in the neutralization kettle is kept within the range of 25-30 ℃ by controlling the circulating water flow of the jacket of the neutralization kettle.
The weight ratio of the esterified substance to the deionized water is 1:4.5.
And (3) carrying out post-treatment, namely dissolving, decoloring, filtering, crystallizing and drying the neutralized product to obtain the dimethyl isophthalate-5-sodium sulfonate.
Example 3
A method for preparing dimethyl isophthalate-5-sodium sulfonate, comprising the following steps: sulfonation, esterification, neutralization and post-treatment.
The sulfonation method comprises the following steps: primary reaction and secondary reaction.
The operation of the primary reaction is that a predetermined part of fuming sulfuric acid is put into a sulfonation kettle, and then a sulfonation catalyst is put under the stirring condition of 50 rpm; then, heat conduction oil is used as a heating medium, the temperature of the materials in the sulfonation kettle is controlled to be increased to 90 ℃ at a heating rate of 3 ℃/min, the temperature is kept, and 45% of the total consumption of isophthalic acid is added, and stirring is continued for 10min; then heating to 110 ℃ under the stirring condition of 100rpm, preserving heat, adding the rest amount of isophthalic acid, and reacting for 90min.
Wherein the isophthalic acid: fuming sulfuric acid: the ratio of the parts by weight of the sulfonation catalyst is 1:0.82:0.1.
The fuming sulfuric acid concentration was 66wt%.
The sulfonation catalyst is prepared by the following preparation method: pretreatment, modification, granulation and activation.
The pretreatment method comprises the steps of putting a predetermined part of activated carbon into a ball mill, and performing ball milling treatment for 40min at a ball milling rotating speed of 600 rpm; then putting the ball-milled active carbon into ethanol solution with the volume of 5 times, stirring at 300rpm for 30min, and filtering out solid matters; then putting the solid into phosphoric acid solution with the volume of 5 times, heating to 45 ℃, keeping the temperature and stirring for 60 minutes under the condition of 200rpm, filtering out the solid, and leaching with deionized water to be neutral; and then drying under the condition that the vacuum degree is 0.06MPa and the temperature is 95 ℃ until the weight is unchanged, and preparing the pretreated activated carbon.
The specification of the activated carbon is that the particle size is 60 meshes, and the specific surface area is 1200m 2 and/G, average pore diameter of 8nm, graphitization degree G value of 70% by XRD.
The ball milling treatment is carried out by controlling the ball-material ratio in ball milling to be 9:1.
The concentration of the ethanol solution is 95wt%.
The concentration of the phosphoric acid solution is 20wt%.
The modification method comprises the steps of mixing predetermined parts of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon, and carrying out reflux reaction for 24 hours to obtain a reactant; then placing the reactant in an environment with the vacuum degree of 0.03MPa, and carrying out heat preservation distillation at the temperature of 120 ℃ until no gas phase is generated, so as to obtain distillate; adding the distilled liquid into deionized water with the volume of 20 times, carrying out ultrasonic oscillation for 8 hours, filtering out solid matters, and then carrying out freeze-drying treatment to obtain the modified activated carbon.
Wherein the polyethylene glycol has a molecular weight of 600.
The weight ratio of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon is 200:12:0.8:5:25.
The ultrasonic vibration is operated with the ultrasonic vibration frequency of 26kHz and the power of 500W.
The granulating method comprises the steps of mixing a predetermined part of modified activated carbon, antimony pentoxide, dibutyl tin oxide and copper chloride, and grinding for 5 hours at a rotating speed of 400rpm to obtain a ground product; and uniformly mixing a predetermined part of grinding material, N-methyl pyrrolidone and PEEK adhesive, and granulating to obtain pre-granulating.
Wherein the weight ratio of the grinding material to the N-methyl pyrrolidone to the PEEK adhesive is 100:3:5.
The granularity of the sulfonation catalyst is 180 meshes.
The PEEK adhesive is manufactured by Guangzhou sky blue chemical technology Co.
The activation method is that the pre-granules are placed in a temperature environment of 170 ℃ and kept stand for 10 hours, and the sulfonation catalyst is prepared.
The secondary reaction is carried out by controlling the temperature of the materials in the sulfonation kettle to be raised to 135 ℃ at a heating rate of 0.5 ℃/min under the stirring condition of 100rpm, and carrying out heat preservation reaction for 60min; the solids are filtered off and the liquid phase (i.e. the sulphonates) is introduced into the esterifying reactor.
And leaching the solid by adopting deionized water with the volume of 10 times, then placing the solid in an environment with the vacuum degree of 0.03MPa, and carrying out heat treatment at 130 ℃ for 5 hours to complete the recovery of the sulfonation catalyst.
The esterification method comprises the steps of controlling the temperature of materials in an esterification kettle to be reduced to 100 ℃ at a temperature reduction rate of 1 ℃/min under the stirring condition of 50rpm, adding 60% of the total dosage of methanol, and naturally cooling; when the materials in the esterification kettle are naturally cooled to 75 ℃, adding the rest amount of methanol; and (3) when the materials in the esterification kettle are naturally cooled to 68 ℃, preserving heat and esterifying for 5 hours to prepare an esterified material, and introducing the esterified material into the neutralization kettle.
Wherein the weight ratio of isophthalic acid to methanol is 1:4.
The neutralization method comprises the steps of adding a predetermined part of deionized water into a neutralization kettle at a charging rate of 3L/min under the stirring condition of 30 rpm; after the completion of the addition, sodium hydroxide was added under stirring at 50rpm, the pH value of the material in the neutralization tank was adjusted to be neutral, and stirring was continued for 40 minutes to obtain a neutralized product.
In the process of adding sodium hydroxide, the temperature of the materials in the neutralization kettle is kept within the range of 25-30 ℃ by controlling the circulating water flow of the jacket of the neutralization kettle.
The weight ratio of the esterified substance to the deionized water is 1:5.
And (3) carrying out post-treatment, namely dissolving, decoloring, filtering, crystallizing and drying the neutralized product to obtain the dimethyl isophthalate-5-sodium sulfonate.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that in the sulfonation step, a one-step reaction is adopted, and the specific method is as follows: adding a predetermined part of fuming sulfuric acid into a sulfonation kettle, and then adding a sulfonation catalyst under the stirring condition of 30 rpm; then, heat conduction oil is used as a heating medium, materials in the sulfonation kettle are controlled to be heated to 85 ℃ at a heating rate of 2 ℃/min, and isophthalic acid is added after heat preservation; then controlling the temperature of the materials in the sulfonation kettle to be raised to 130 ℃ at the heating rate of 0.2 ℃/min, and carrying out heat preservation reaction for 120min.
In comparative example 1, isophthalic acid: fuming sulfuric acid: the weight ratio of the sulfonation catalyst to the catalyst is 1:0.8:0.08.
The sulfonation catalyst was the same as that used in example 2.
The fuming sulfuric acid concentration is 65wt%.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, wherein in the preparation method of the sulfonation catalyst, 1) a pretreatment step is omitted; 2) Omitting the tolyldiphenyl phosphate used in the modification step; 3) N-methylpyrrolidone used in the granulation step was omitted.
Comparative example 3
The technical scheme of example 2 is adopted, which is different in that in the preparation method of the sulfonation catalyst, the modification step is omitted.
The relevant indexes of SIPM products prepared in examples 1-3 and comparative examples 1-3 were tested, and specific results are as follows:
further, the service life of the sulfonation catalysts prepared in examples 1-3 was tested, and the number of times of repeated use of the qualified SIPM products prepared by catalyzing the sulfonation catalysts was recorded, wherein the standard of the qualified SIPM products is as follows: SIPM purity is more than or equal to 97%, SIPM acid value is less than or equal to 0.8mgKOH/g, SIPM saponification value is 378+ -3 mgKOH/g, SIPM sulfate radical content is less than or equal to 80mg/kg, SIPM Fe 3+ The content is less than or equal to 5mg/kg, SIPM Cl - The content is less than or equal to 10mg/kg. The specific results are as follows:
the percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing dimethyl isophthalate-5-sodium sulfonate, which is characterized by comprising the following steps: sulfonation, esterification, neutralization and post-treatment;
the sulfonation comprises: primary reaction and secondary reaction;
the primary reaction is carried out, a predetermined part of fuming sulfuric acid is put into a sulfonation kettle, and then a sulfonation catalyst is put into the kettle; controlling the temperature of the materials in the sulfonation kettle to 80-90 ℃ at a heating rate of 1-3 ℃/min, preserving heat, adding 35-45% of the total consumption of isophthalic acid, and uniformly stirring; then heating to 100-110 ℃, adding the rest isophthalic acid, and reacting for a period of time with heat preservation;
and (3) under the condition of stirring, controlling the temperature of materials in the sulfonation kettle to be raised to 130-135 ℃ at the temperature rising rate of 0.2-0.5 ℃/min, and carrying out heat preservation reaction for a period of time to obtain the sulfonate.
2. The method for producing dimethyl isophthalate-5-sodium sulfonate according to claim 1, characterized in that the isophthalic acid: fuming sulfuric acid: the weight ratio of the sulfonation catalyst to the catalyst is 1:0.77-0.82:0.06-0.1.
3. The method for preparing dimethyl isophthalate-5-sodium sulfonate according to claim 1, wherein the sulfonation catalyst is prepared by the following preparation method: pretreatment, modification, granulation and activation;
the pretreatment, namely putting the activated carbon after ball milling into ethanol solution, stirring for a period of time, and filtering out solid matters; then putting the solid into phosphoric acid solution, heating to 35-45 ℃, keeping the temperature, stirring for a period of time, and filtering out the solid; then leaching with deionized water to neutrality; vacuum drying to obtain pretreated activated carbon.
4. The method for producing dimethyl isophthalate-5-sodium sulfonate according to claim 3, wherein the activated carbon has a particle size of 40 to 60 mesh and a specific surface area of 1000 to 1200m 2 and/G, the average pore diameter is 4-8nm, and the graphitization degree G value measured by XRD is 60-70%.
5. The method for preparing dimethyl isophthalate-5-sodium sulfonate according to claim 3, wherein the modification comprises mixing predetermined parts of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluene sulfonic acid and pretreated activated carbon, and carrying out reflux reaction for 18-24 hours to obtain a reactant; then placing the reactant in an environment with the vacuum degree of 0.01-0.03MPa, and carrying out heat preservation distillation at the temperature of 112-120 ℃ until no gas phase is generated, thus obtaining distillate; adding the distilled liquid into deionized water with 15-20 times of volume, carrying out ultrasonic vibration for 3-8 hours, filtering out solid matters, and then carrying out freeze-drying treatment to obtain the modified activated carbon.
6. The method for preparing dimethyl isophthalate-5-sodium sulfonate according to claim 5, wherein the weight ratio of toluene, polyethylene glycol, toluene diphenyl phosphate, p-toluenesulfonic acid and pretreated activated carbon is 140-200:10-12:0.5-0.8:4-5:15-25.
7. The method for preparing dimethyl isophthalate-5-sodium sulfonate according to claim 3, wherein the granulating comprises mixing the modified activated carbon, antimony pentoxide, dibutyltin oxide and copper chloride, and grinding for 3-5h at a rotation speed of 300-400rpm to obtain a ground product; uniformly mixing a predetermined part of grinding material, N-methyl pyrrolidone and PEEK adhesive, and granulating to obtain pre-granules;
the weight ratio of the grinding material to the N-methyl pyrrolidone to the PEEK adhesive is 100:2-3:3-5.
8. The method for preparing dimethyl isophthalate-5-sodium sulfonate according to claim 3, wherein the activation comprises the steps of pre-granulating the granules obtained in the granulating step, and standing the granules at 160-180 ℃ for 6-10h to obtain the sulfonated catalyst.
9. The method for preparing dimethyl isophthalate-5-sodium sulfonate according to claim 1, wherein the temperature of the sulfonate is reduced to 90-100 ℃ at a temperature reduction rate of 0.5-1 ℃/min under the condition of esterification and stirring, and the sulfonate is added with 50-60% of the total dosage of methanol for natural cooling; when naturally cooling to 70-75 ℃, adding the rest amount of methanol; when the materials in the esterification kettle are naturally cooled to 65-68 ℃, preserving heat and esterifying for 2-5h to obtain esterified materials;
the weight ratio of the isophthalic acid to the methanol is 1:3-4.
10. The method for preparing dimethyl isophthalate-5-sodium sulfonate according to claim 1, wherein the neutralization is carried out, after the esterified substance is mixed with deionized water under the stirring condition, the pH value is adjusted to be neutral by adopting sodium hydroxide, and the stirring is continued for a period of time to obtain a neutralized substance;
in the process of adding sodium hydroxide, keeping the temperature within the range of 25-30 ℃;
the ratio of the esterified substance to the deionized water in parts by weight is 1:4-5;
and (3) carrying out post-treatment, namely dissolving, decoloring, filtering, crystallizing and drying the neutralized product to obtain the dimethyl isophthalate-5-sodium sulfonate.
Priority Applications (1)
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| CN110256301A (en) * | 2019-06-25 | 2019-09-20 | 青岛中科荣达新材料有限公司 | A kind of synthetic method of Sodium Dimethyl Isophthalate-5-sulfonate |
| CN110252396A (en) * | 2019-06-27 | 2019-09-20 | 山东第一医科大学(山东省医学科学院) | A kind of catalyst in Sodium Dimethyl Isophthalate-5-sulfonate synthesis process, preparation method and application |
| CN110302793A (en) * | 2019-07-08 | 2019-10-08 | 山东第一医科大学(山东省医学科学院) | A kind of Sodium Dimethyl Isophthalate-5-sulfonate catalyst for synthesizing and its application |
| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256301A (en) * | 2019-06-25 | 2019-09-20 | 青岛中科荣达新材料有限公司 | A kind of synthetic method of Sodium Dimethyl Isophthalate-5-sulfonate |
| CN110252396A (en) * | 2019-06-27 | 2019-09-20 | 山东第一医科大学(山东省医学科学院) | A kind of catalyst in Sodium Dimethyl Isophthalate-5-sulfonate synthesis process, preparation method and application |
| CN110302793A (en) * | 2019-07-08 | 2019-10-08 | 山东第一医科大学(山东省医学科学院) | A kind of Sodium Dimethyl Isophthalate-5-sulfonate catalyst for synthesizing and its application |
| CN112121817A (en) * | 2020-09-22 | 2020-12-25 | 万华化学集团股份有限公司 | Sulfonic acid modified carrier supported solid acid catalyst and preparation method and application thereof |
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