CN1044808C - Technology for industrialized production of 1-naphthol-4-sulfonic-acid and sodium salt thereof - Google Patents
Technology for industrialized production of 1-naphthol-4-sulfonic-acid and sodium salt thereof Download PDFInfo
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- CN1044808C CN1044808C CN97104183A CN97104183A CN1044808C CN 1044808 C CN1044808 C CN 1044808C CN 97104183 A CN97104183 A CN 97104183A CN 97104183 A CN97104183 A CN 97104183A CN 1044808 C CN1044808 C CN 1044808C
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- 238000005516 engineering process Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title abstract description 17
- 159000000000 sodium salts Chemical class 0.000 title abstract description 8
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000000047 product Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 36
- SRJCJJKWVSSELL-UHFFFAOYSA-N 2-methylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C)=CC=C21 SRJCJJKWVSSELL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012442 inert solvent Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 20
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000967 suction filtration Methods 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 95
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 33
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 29
- 229910052708 sodium Inorganic materials 0.000 claims description 29
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 27
- -1 halogenated aryl hydrocarbon Chemical class 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XILYOLONIFWGMT-UHFFFAOYSA-N benzene;dihydrochloride Chemical compound Cl.Cl.C1=CC=CC=C1 XILYOLONIFWGMT-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 241000792859 Enema Species 0.000 claims description 8
- 239000007920 enema Substances 0.000 claims description 8
- 229940095399 enema Drugs 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 235000011837 pasties Nutrition 0.000 abstract 1
- 238000005185 salting out Methods 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 150000004782 1-naphthols Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000000989 food dye Substances 0.000 description 4
- 239000003317 industrial substance Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229940023462 paste product Drugs 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention belongs to a process for preparing 1-naphthol-4-sulfonic acid and sodium salt thereof. The process comprises the procedures that methyl naphthol is dissolved in an inert solvent, a sulfonating agent is added for reaction, and hydrogen chloride is removed by a coercion method after sulfonation reaction; the carried inert solvent returns to a reaction still via the condensation of a condenser, and 1-naphthol-4-sulphonic acid filter cakes are obtained by suction filtration after the sulfonation reaction. The process for preparing the sodium salt comprises the procedures that materials are separated so as to remove the inert solvent after the sulfonation reaction, the rest materials are added in alkali liquor and sodium chloride, and finished products of the pasty sodium salt are obtained after salting-out and suction filtration. The process has the advantages of thorough sulfonation reaction, low impurity content in products and little three-waste treating capacity.
Description
The present invention relates to a kind of technology for preparing Neville acid and sodium salt thereof.
Neville acid is called for short N.W. Acid, is widely used in organic synthesis, especially as the intermediate of numerous azoic dyestuffs.Because the N.W. Acid instability, thus industrial make stable N.W. Acid sodium salt that is with Neville acid sodium as product export.At present, the preparation method of N.W. Acid has two kinds.A kind of is the method for common preparation of industrialization N.W. Acid.It is a main raw material with 1-amino-4-sulfonate, carries out addition reaction with sodium bisulfite in the presence of hydrochloric acid, further hydrolysis, saltout and finished product.Reaction equation is as follows:
Because this technology is residual in finished product naphthalidine-4-sodium sulfonate and sulfurous gas arranged,, can bring unsafe factor and potential danger for N.W. Acid is further synthetic during as the required dyestuff of medicine, food dye, biology or makeup.Simultaneously, this operational path is long, the acid of consumption alkaline consumption is many, and washing is arranged and the waste water that produces and the discharging of ammonia, easily causes environmental pollution.Have again, during with the N.W. Acid synthetic dyestuff of this technology gained, again Jia Shui, add acid, be heated to 90 ℃, insulation and wasted the more energy to drive away residual sulfurous gas in about 8 hours.
The another kind of method for preparing N.W. Acid is, with the 1-naphthols is main raw material, be dissolved in behind the insensitive organic inert solvent of sulphonating agent, the adding sulphonating agent carries out sulfonation reaction and makes the N.W. Acid crude product, can avoid generating many sulfonic acid thing of 1-naphthols because of using inert solvent, so the productive rate of the monosulfonic acid thing of 1-naphthols is higher, but this method is just let alone to overflow to the hydrogen chloride gas that sulfonation reaction generated, do not take to force elimination methods, so level of response is not thorough, the by product 1-naphthols-2-sulfonic acid of its reaction is more, also has other by product to generate simultaneously, the organic impurity total content is higher to making.Because when Neville acid was used for synthesizing azoic dyestuff as coupling component, Neville acid and unreacted 1-naphthols also can be used as the reaction that the coupling component is participated in synthetic dyestuff.This will have a strong impact on the quality of azoic dyestuff.Be to improve the productive rate of Neville acid, reduce the productive rate of 1-naphthols-2-sulfonic acid simultaneously, often temperature of reaction is controlled at and is higher than 50 ℃.But the content of the 1-naphthols-2-sulfonic acid in the product is still higher.After the process purification step of salt fractionation, the content of 1-naphthols-2-sulfonic acid also has 5～10% (weight), and the content of Neville acid descends simultaneously, and need expend a large amount of salt, and produces the waste water of a large amount of pollutions.This method lacks suitability for industrialized production and is worth.Though US4540525 improves this method, but still the halfway problem of unresolved sulfonation reaction, its improvement is only in the separation to sulfonation reaction gained resultant.Improved foundation is that when temperature was higher than 50 ℃, the solubleness of Neville acid in inert solvent was about 0.01～5.0% (weight).So when adopting filtration method to separate, the temperature of filtering and washing must be higher than 50 ℃, even so, the content of its organic impurity is 1-naphthols-2-sulfonic acid and 1-naphthols-2 only, two of 4-disulfonic acid just reach 1～4%, useful again organic solvent washing filter cake is not only wasted industrial chemicals, and three wastes work of treatment amount is still bigger.
The objective of the invention is, provide a kind of sulfonation reaction comparatively thoroughly, when separating isolating temperature condition do not had particular requirement and the products therefrom foreign matter content is lower and save the less preparation of industrialization 1-naphthols 4-sulfonic acid of industrial chemicals, three wastes treatment capacity and the technology of sodium salt thereof.
The technical scheme that realizes the technology that a kind of preparation of industrialization 1-naphthols 4-sulfonic acid is provided in the object of the invention is, in reactor, methyl naphthol is dissolved in the inert solvent, adding sulphonating agent makes methyl naphthol and sulphonating agent carry out sulfonation reaction, be created on the less Neville acid of solubleness in the inert solvent, be characterized in, remove the hydrogen chloride gas that sulfonation reaction generates at the back segment of sulfonation reaction with vacuum suction method or pressurized air blind enema or compressed nitrogen blind enema, the inert solvent of being taken out of refluxes through condenser and returns in the reactor; After sulfonation reaction is finished, carry out suction filtration, obtain the filter cake of 1-naphthols 4-sulfonic acid, the temperature condition of suction filtration is a room temperature or more than the room temperature.
The above-mentioned time of removing hydrogen chloride gas is 1～4 hour, and during suction filtration, the temperature condition of suction filtration is room temperature or room temperature to 90 ℃.
Above-mentioned methyl naphthol is that industrial goods or content are the highly finished product more than 96%～99.99%; Sulphonating agent is oleum, sulphur trioxide or chlorsulfonic acid; Inert solvent is to be difficult for being sulfonated agent sulfonated organic solvent and inert solvent is a monochlor(in)ate benzene, benzene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin. Ortho Nitro Toluene, halohydrocarbon, halogenated aryl hydrocarbon, or the mixture of monochlor(in)ate benzene and benzene dichloride, the mixture of ethylene dichloride and tetracol phenixin, the mixture of Ortho Nitro Toluene and halohydrocarbon, the mixture of Ortho Nitro Toluene and halogenated aryl hydrocarbon, the mixture of halogenated aryl hydrocarbon and halohydrocarbon, or the mixture of Ortho Nitro Toluene and halohydrocarbon and halogenated aryl hydrocarbon.
Above-mentioned sulphonating agent is a chlorsulfonic acid, and the mol ratio of methyl naphthol and chlorsulfonic acid is: 1: 1-1: 1.5.
The mol ratio of above-mentioned methyl naphthol and chlorsulfonic acid is: 1: 1.2～1: 1.3.
When above-mentioned chlorsulfonic acid as sulphonating agent was added reactor, the method for adding was for dripping, and the temperature of dropping is-25 ℃ to 60 ℃, dripped the back insulation and proceeded reaction, and the temperature of insulation reaction is 40 ℃ to 120 ℃, and the time of insulation reaction is 4～24 hours.
Realize that the technical scheme that a kind of preparation of industrialization Neville acid sodium technology is provided in the object of the invention is, in reactor, methyl naphthol is dissolved in the inert solvent, adding sulphonating agent makes methyl naphthol and sulphonating agent carry out sulfonation reaction, be created on the less Neville acid of solubleness in the inert solvent, be characterized in, remove the hydrogen chloride gas that sulfonation reaction generates at the back segment of sulfonation reaction with vacuum suction method or pressurized air blind enema or compressed nitrogen blind enema, the inert solvent of being taken out of refluxes through condenser and returns in the reactor; After sulfonation reaction is finished, material delivered in the separating device separate, remove inert solvent; Again material is delivered in the aftertreatment still, added alkali lye and sodium-chlor reacts, separate out Neville acid sodium, material is emitted from handle still deliver to strainer and filter, obtain paste Neville acid sodium finished product.
Neville acid sodium is more than 40%～60% by the chemical analysis analysis in the content of acid in the above-mentioned paste finished product.
When separating after the above-mentioned sulfonation reaction, material delivered to carry out suction filtration in the pumping and filtering device, the condition of carrying out suction filtration is a room temperature or more than the room temperature, obtain the Neville acid filter cake, with the centrifugal liquid of further sloughing of filter cake, obtain lumpy material, again lumpy material is delivered to the reaction of saltouing in the aftertreatment still.
When separating after the above-mentioned sulfonation reaction, material is delivered in the separating device of agitator, added water or methyl alcohol or ethanol Neville acid is dissolved in wherein, leave standstill then, divide and remove inert solvent, again material is delivered to the reaction of saltouing in the aftertreatment still.
Above-mentioned methyl naphthol is that industrial goods or content are the highly finished product more than 96%～99.99%; Sulphonating agent is oleum, sulphur trioxide or chlorsulfonic acid; Inert solvent is to be difficult for being sulfonated agent sulfonated organic solvent and inert solvent is a monochlor(in)ate benzene, benzene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, Ortho Nitro Toluene, halohydrocarbon, halogenated aryl hydrocarbon, or the mixture of monochlor(in)ate benzene and benzene dichloride, the mixture of ethylene dichloride and tetracol phenixin, the mixture of Ortho Nitro Toluene and halohydrocarbon, the mixture of Ortho Nitro Toluene and halogenated aryl hydrocarbon, the mixture of halogenated aryl hydrocarbon and halohydrocarbon, or the mixture of Ortho Nitro Toluene and halohydrocarbon and halogenated aryl hydrocarbon.
Above-mentioned sulphonating agent is a chlorsulfonic acid, and the mol ratio of methyl naphthol and chlorsulfonic acid is: 1: 1～1: 1.5.
The mol ratio of above-mentioned methyl naphthol and chlorsulfonic acid is: 1: 1.2～1: 1.3; In the time of will adding reactor as the chlorsulfonic acid of sulphonating agent, the method for adding is for dripping, and the temperature of dropping is-25 ℃ to 60 ℃, drips the back insulation and proceeds reaction, and the temperature of insulation reaction is 40 ℃ to 120 ℃, and the time of insulation reaction is 4～24 hours; After obtaining paste Neville acid sodium, paste is delivered to the centrifugal liquid of further sloughing in the sedimentator, obtain lumpy material, lumpy material is carried out drying, obtain powdery Neville acid sodium finished product.
The content of analyzing in acid by chemical analysis (coupling process) of Neville acid sodium is more than 70%～80% in the above-mentioned powdery finished product, is more than 95%～98.5% by liquid chromatography analysis in the content of acid.
Above-mentioned drying is carried out in two steps, and the first step is predrying, lumpy material is delivered to dried by the fire in the drying room to half-dried; Second step was delivered to drying in the moisture eliminator for drying by the fire to half-dried lumpy material, obtained powdery Neville acid sodium, and moisture eliminator is pneumatic dryer, ebullated dryer or spray-dryer.
From above-mentioned material, divide remove inert solvent after, material is delivered in the reactor, add gac or clorox or hydrogen peroxide and decolour, add hydrogen sulfide or sodium sulphite removal of impurities again, filter the reaction of saltouing again of gained filtrate then.
The mol ratio of above-mentioned methyl naphthol and chlorsulfonic acid is: 1: 1.2～1: 1.3; In the time of will adding reactor as the chlorsulfonic acid of sulphonating agent, the method that adds is for dripping, the temperature that drips is-25 ℃ to 60 ℃, drip the back insulation and proceed reaction, the temperature of insulation reaction is 40 ℃ to 120 ℃, and the time of insulation reaction is 4～24 hours: after obtaining paste Neville acid sodium, paste is delivered to the centrifugal liquid of further sloughing in the sedimentator, obtain lumpy material, lumpy material is carried out drying, obtain powdery Neville acid sodium finished product; Drying is carried out in two steps, and the first step is predrying, lumpy material is delivered to dried by the fire in the drying room to half-dried; Second step was delivered to drying in the moisture eliminator for drying by the fire to half-dried lumpy material, obtained powdery Neville acid sodium, and moisture eliminator is pneumatic dryer, ebullated dryer or spray-dryer.
Relevant reaction equation is as follows:
The present invention has positive effect: 1. the present invention is a kind of method of preparation of industrialization N.W. Acid.At present, find no the report that comes the suitability for industrialized production N.W. Acid with methyl naphthol, chlorsulfonic acid and solvent at home and abroad.The existing method for preparing N.W. Acid with methyl naphthol is the experiment of Laboratory Instruments sample, and the methyl naphthol charging capacity only is 70～100 grams, and industrialized many measures all reckon without as the separation method etc. of forcing to get rid of hydrogen chloride gas, being suitable for industrial ratio etc.If carry out suitability for industrialized production by the method for US4540525, just appoint hydrogen chloride gas to overflow, because of there being more resultant hydrogenchloride in the system, then reaction can not be carried out fully, and not only the 1-naphthols is more, and 1-naphthols-2-sulfonic acid content is also more.When filtering separation, must improve the service temperature when separating, also need filter cake is washed.This method not only consumes energy more, and the industrial chemicals of consumption is also more, and cost is higher by 1/10 than the present invention at least; Though foreign matter content decreases, still be 5～6% through test, institute's synthetic dyestuff can not be used as food dye etc., so no suitability for industrialized production is worth.And applicant of the present invention has finished large-scale industrialization production, and every batch of charging capacity of methyl naphthol is more than 300 kilograms or 300 kilograms, and both differ 3000 times.Because the present invention is at the sulfonation reaction leading portion, react under normal pressure, adopt the measure of forcing to get rid of hydrogen chloride gas at the back segment of sulfonation reaction, thereby sulfonation reaction is comparatively thorough, and foreign matter content is greatly reduced.Just so, when the sulfonation reaction product was separated, the present invention can directly operate at normal temperatures, had saved a large amount of energy; The present invention simultaneously need not the processing step of washing leaching cake, and this not only can significantly reduce three wastes treatment capacity, and has saved industrial chemicals, has improved the yield of product.2. because the present invention has taked the industrialization measure that is suitable for producing, the sulfonation reaction process is more thorough, during separation loss also few, with its dyestuff, meet the specification of quality of food dye fully as intermediate production.US4540525 has exemplified 12 with the example of chlorsulfonic acid as sulphonating agent, only 1-naphthols-2 sulfonic acid and 1-naphthols-2 of the content of organic impurity in the final product, and two of 4-disulfonic acid just reach 1～4%.And the used methyl naphthol of the present invention is 99.5% highly finished product, and used sulphonating agent is a chlorsulfonic acid, and when used inert solvent was chlorobenzene or dichlorobenzene, the content of total organic matter impurity≤1.5% was compared not a halfpenny the worse with the laboratory result of US4540525.3. the present invention compares with the technology of existing suitability for industrialized production Neville acid, and tangible positively effect is also arranged.Because old processing step is many, not only reaction time long, and energy consumption height, productive rate are low.One ton of product of every production, only energy consumption is one, and old technology is 1500 yuan per ton, and the present invention is 800 yuan per ton.Gained N.W. Acid content of the present invention improves 5～15% than the powdery dry product of old technology.Old technology dry product N.W. Acid content (in acid) is 65%, and N.W. Acid content is 70～80% in the gained dry product of the present invention.And dry product water content of the present invention is lower, and prevented from caking between staging life helps prolonged preservation and transportation.Because main content height has not only been saved a large amount of wrapping material and trucking costs, and because of wherein not containing toxic substances such as naphthalidine-4-sodium sulfonate, free naphthylamines, S-WAT, finished product is more safe and reliable.Be particularly suitable as intermediate and synthesize dyestuff and the pigment that is used for medicine, food dye, biology and makeup etc.4. contain sulfurous gas etc. in the N.W. Acid because of old technology generation, so must Jia Shui before using, add acid, heat and drive sulfurous gas considerable time, a large amount of energy and man-hour have been wasted, and do not contain poisonous impurity such as sulfurous gas or organic amine in the N.W. Acid of the present invention, and the strict grinding and processing of finished product process, homogeneous powder is thin, need only during use and directly feed intake, can use after the water-soluble filtration, dissolving is fast, and is easy to use.Gained N.W. Acid content height of the present invention, saliferous and impure few are the desirable intermediates of further synthetic numerous quality productss simultaneously.5. three-waste free discharge of the present invention.The hydrogen chloride gas that is produced can absorb by the water spraying process, generates hydrochloric acid, recycles.After the material that contains Neville acid after to sulfonation reaction carried out suction filtration, centrifugation, surplus materials can be used as the intermediate of producing other dyestuff.After the material that contains Neville acid sodium after to the reaction of saltouing separated, gained liquid carried out pickle change, and N.W. Acid content is 40%, is 65% in the powder-like product in the paste product.
The invention will be further described below in conjunction with embodiment.
Embodiment 1,
2200 kilograms of monochlor(in)ate benzene are fed in the reactor of 3000 liters, open stirring; Drop into 300 kilograms of content when stirring and be 95.5% methyl naphthol industrial goods, the dissolving back ℃ dripped 260 kilograms of chlorsulfonic acids about 3 hours in room temperature to 50.After dropwising, be warming up to 90 ± 20 ℃, insulation reaction is 8 hours under stirring.Afterwards, pressurized air is fed drive about 3 hours of the hydrogen chloride gas that sulfonation reaction generates in the reactor.The monochlor(in)ate benzene that flows out reactor in company with air and hydrogen chloride gas returns in the reactor through the condenser condenses backflow.The hydrogenchloride used water that flows out reactor absorbs to be used as hydrochloric acid.
After reaction is finished material emitted from reactor and at room temperature carry out suction filtration in the vacuum filtration case of delivering to 2000 liters, the whizzer that the gained filter cake is put into SS-800 is the centrifugal solvent of sloughing further, obtains block Neville acid.Organic solvent reclaims and uses.The block Neville acid of gained is put into the aftertreatment still add 25% 500 kilograms of sodium hydroxide lyes (also can be the sodium carbonate aqueous solution or potassium hydroxide aqueous solution), add 485 kilograms in sodium-chlor again, Neville acid sodium is separated out in the reaction that makes it to saltout.Emit material and to the suction filtration case, at room temperature carry out suction filtration, obtain plaster material, again plaster material is put into the at room temperature centrifugal solvent of further sloughing of whizzer and obtained block Neville acid sodium.
Drying treatment.With lumpy material send in the drying room 100 ℃ predrying 2～3 hours down, obtain block half-dried material (promptly the content liquid in material this moment is half of content liquid in the predrying preceding material).The half-dried material of bulk is put into the pneumatic dryer of the throughput of Changzhou model group moisture eliminator factory manufacturing for 2 tons of powdery finished products of daily output, carry out drying, make 450 kilograms of powdery Neville acid sodium finished products.
The gained finished product is carried out chemical analysis, is 80% in the content of Neville acid weight.Use liquid chromatography analysis, total organic impurity content is≤2%.
Embodiment 2,
2200 kilograms of benzene dichlorides are dropped in the 3000 liter reactors, add purity in the time of stirring and be 300 kilograms of 95.5% industrial goods methyl naphthols.After the dissolving, drip 280 kilograms of chlorsulfonic acids down in room temperature to 50 ℃, be warming up to 90 ± 20 ℃ from 50 ℃ after, insulation reaction 6 hours.Compressed nitrogen fed drove hydrogen chloride gas in the reactor about 4 hours, flow out the benzene dichloride of reactor in condenser condenses back flow reaction still in company with nitrogen and hydrogen chloride gas.The hydrogenchloride water that flows out reactor absorbs and uses as hydrochloric acid.
After reaction is finished, material is put into the separator tank of 4000 liters that have agitator from reactor, under the room temperature, when stirring, add 900 kilograms in water, make Neville acid soluble in water, leave standstill half an hour then, make the aqueous solution and benzene dichloride layering, emit the aqueous solution downwards and deliver in the aftertreatment still of 2000 liters of agitator.Benzene dichloride reclaims.Stir that to add concentration down in handling still be 400 kilograms of 30% sodium hydroxide lyes, add 480 kilograms in sodium-chlor again, Neville acid sodium is separated out in the reaction that makes it to saltout.Material emitted from handle still deliver in the vacuum filtration case at room temperature that suction filtration obtains 840 kilograms of paste Neville acid sodium finished products.
Through chemical analysis, wherein the N.W. Acid content in acid is 45%; Through the total organic impurity content of liquid chromatography analysis≤2.5%.
Put into after also can be centrifugal that drying room is predrying to become block half-dried material, carry out drying through pneumatic dryer again and then make powder-like product above-mentioned paste Neville acid sodium.
Used moisture eliminator can also be ebullated dryer or spray-dryer etc.
Embodiment 3,
Repeat the production craft step of example 2, difference is that the employing sulphur trioxide is a sulphonating agent, can get the powdery N.W. Acid of finished product more than 420 kilograms.Through chemical analysis, in the meal in the content of the N.W. Acid of acid more than 75%; Through liquid-phase chromatographic analysis organic impurity content≤4%.
Embodiment 4,
Repeat the production craft step of example 2, difference is that the employing oleum is a sulphonating agent, can get the powdery N.W. Acid of finished product more than 400 kilograms.By analysis, the content of N.W. Acid is more than 72%, organic impurity content≤5%.
Embodiment 5,
Repeat the production craft step of example 2, difference is, adopts the methyl naphthol of 99.5% above purity, can get the powdery N.W. Acid of finished product more than 455 kilograms.By analysis, the content of N.W. Acid is more than 80%, total organic impurity content≤1.5%.
Embodiment 6,
Repeat the production craft step of example 2, difference is, drips the chlorsulfonic acid more than 265 kilograms.Can get the powdery finished product at last more than 450 kilograms.By analysis, the content of N.W. Acid is more than 75%.
Embodiment 7,
Repeat the production craft step of example 2, difference is that adopting tetracol phenixin or chloroform etc. is solvent, can get the powdery finished product more than 440 kilograms.By analysis, the content of N.W. Acid is more than 77%, and total organic impurity content is 4%～5%.
Embodiment 8,
To be in 2200 kilograms of adding reactors of mixture of 1: 1 monochlor(in)ate benzene and benzene dichloride by volume, stir the industrial methyl naphthol that adds 300 kilograms down, after the dissolving, at 5～50 ℃ of industrial chlorsulfonic acids that drip 260 kilograms, be warming up to 90 ± 20 ℃, insulation continued reaction after 2 hours, continued to remove about 8 hours of the hydrogen chloride gas that dereaction generates with retouching vacuum method.Then material is put into separator tank, under the room temperature, add water or ethanol and also can add methyl alcohol Neville acid is dissolved in wherein, divide and remove inert solvent and reclaim.The aqueous solution or alcoholic solution are delivered in the reactor, with gac or clorox or hydrogen peroxide decolouring more than 1 hour, added hydrogen sulfide or sodium sulphite again and stir and sloughed relative substance in 1 hour.Under the room temperature, material is put into vacuum filtration case suction filtration again.Gained filtrate is sent into and is handled in the still, adds 300 kilograms of 30% alkali lye in the stirring, adds 400 kilograms in sodium-chlor again, and the reaction of saltouing generates Neville acid sodium.Material delivered in the vacuum filtration case to filter again obtain 675 kilograms of paste finished products.
In the paste finished product in N.W. Acid content 〉=50% of acid, total organic impurity content≤2.5%.
Also can carry out above-mentioned paste finished product centrifugal and drying treatment obtains the powdery finished product, wherein N.W. Acid content 〉=75%.
Claims (17)
1, a kind of technology of preparation of industrialization Neville acid, in reactor, methyl naphthol is dissolved in the inert solvent, adding sulphonating agent makes methyl naphthol and sulphonating agent carry out sulfonation reaction, be created on the less Neville acid of solubleness in the inert solvent, it is characterized in that, remove the hydrogen chloride gas that sulfonation reaction generates at the back segment of sulfonation reaction with vacuum suction method or pressurized air blind enema or compressed nitrogen blind enema, the inert solvent of being taken out of refluxes through condenser and returns in the reactor; After sulfonation reaction is finished, carry out suction filtration, obtain the filter cake of Neville acid, the temperature condition of suction filtration is a room temperature to 90 ℃.
2, technology according to claim 1 is characterized in that, the time of removing hydrogen chloride gas is 1-4 hour.
3, technology according to claim 2 is characterized in that, methyl naphthol is that industrial goods or content are the highly finished product more than 96%～99.99%; Sulphonating agent is oleum, sulphur trioxide or chlorsulfonic acid; Inert solvent is the mixture of mixture, halogenated aryl hydrocarbon and halohydrocarbon of mixture, Ortho Nitro Toluene and halogenated aryl hydrocarbon of mixture, Ortho Nitro Toluene and halohydrocarbon of mixture, halogenated aryl hydrocarbon of Ortho Nitro Toluene, halohydrocarbon, halogenated aryl hydrocarbon, halohydrocarbon or Ortho Nitro Toluene and halohydrocarbon and halogenated aryl hydrocarbon three's mixture.
4, technology according to claim 3 is characterized in that, sulphonating agent is a chlorsulfonic acid; The mol ratio of methyl naphthol and chlorsulfonic acid is: 1: 1-1: 1.5; Halohydrocarbon is ethylene dichloride, trichloromethane or tetracol phenixin; Halogenated aryl hydrocarbon is monochlor(in)ate benzene or benzene dichloride; The mixture of halohydrocarbon is the mixture of ethylene dichloride and tetracol phenixin; The mixture of halogenated aryl hydrocarbon is the mixture of monochlor(in)ate benzene and benzene dichloride.
5, technology according to claim 4 is characterized in that, the mol ratio of methyl naphthol and chlorsulfonic acid is: 1: 1.2～1: 1.3.
According to each described technology of claim 3～5, it is characterized in that 6, in the time of will adding reactor as the chlorsulfonic acid of sulphonating agent, the method for adding is for dripping, the temperature of dropping is-25 ℃ to 60 ℃; Drip the back insulation and proceed reaction, the temperature of insulation reaction is 40 ℃ to 120 ℃, and the time of insulation reaction is 4～24 hours.
7, a kind of technology of preparation of industrialization Neville acid sodium, in reactor, methyl naphthol is dissolved in the inert solvent, adding sulphonating agent makes methyl naphthol and sulphonating agent carry out sulfonation reaction, be created on the less Neville acid of solubleness in the inert solvent, it is characterized in that, remove the hydrogen chloride gas that sulfonation reaction generates at the back segment of sulfonation reaction with vacuum suction method or pressurized air blind enema or compressed nitrogen blind enema, the inert solvent of being taken out of refluxes through condenser and returns in the reactor; After sulfonation reaction is finished, material delivered in the separating device separate, remove inert solvent; Again material is delivered in the aftertreatment still, added alkali lye and sodium-chlor reacts, separate out Neville acid sodium, material is emitted from handle still deliver to strainer and carry out suction filtration, obtain paste Neville acid sodium finished product.
8, technology according to claim 7, it is characterized in that, when separating after the sulfonation reaction, material delivered to carry out suction filtration in the pumping and filtering device, the condition of carrying out suction filtration is a room temperature to 90 ℃, obtains the Neville acid filter cake, with the centrifugal liquid of further sloughing of filter cake, obtain lumpy material, again lumpy material is delivered to the reaction of saltouing in the aftertreatment still.
9, technology according to claim 7, it is characterized in that, when separating after the sulfonation reaction, material is delivered in the separating device of agitator, adding water or methyl alcohol or ethanol is dissolved in wherein Neville acid, leave standstill then, divide and remove inert solvent, again material is delivered to the reaction of saltouing in the aftertreatment still.
According to each described technology of claim 7～9, it is characterized in that 10, methyl naphthol is that industrial goods or content are the highly finished product more than 96%～99.99%; Sulphonating agent is oleum, sulphur trioxide or chlorsulfonic acid; Inert solvent is the mixture of mixture, halogenated aryl hydrocarbon and halohydrocarbon of mixture, Ortho Nitro Toluene and halogenated aryl hydrocarbon of mixture, Ortho Nitro Toluene and halohydrocarbon of mixture, halogenated aryl hydrocarbon of Ortho Nitro Toluene, halohydrocarbon, halogenated aryl hydrocarbon, halohydrocarbon or Ortho Nitro Toluene and halohydrocarbon and halogenated aryl hydrocarbon three's mixture.
11, technology according to claim 10 is characterized in that, sulphonating agent is a chlorsulfonic acid; The mol ratio of methyl naphthol and chlorsulfonic acid is: 1: 1～1: 1.5; Halohydrocarbon is ethylene dichloride, trichloromethane or tetracol phenixin; Halogenated aryl hydrocarbon is monochlor(in)ate benzene or benzene dichloride; The mixture of halohydrocarbon is the mixture of ethylene dichloride and tetracol phenixin; The mixture of halogenated aryl hydrocarbon is the mixture of monochlor(in)ate benzene and benzene dichloride.
12, technology according to claim 11, it is characterized in that, the mol ratio of methyl naphthol and chlorsulfonic acid is: 1: 1.2～1: 1.3: in the time of will adding reactor as the chlorsulfonic acid of sulphonating agent, the method that adds is for dripping, the temperature that drips is-25 ℃ to 60 ℃, drip the back insulation and proceed reaction, the temperature of insulation reaction is 40 ℃ to 120 ℃, and the time of insulation reaction is 4～24 hours; After obtaining paste Neville acid sodium, paste is delivered to the centrifugal liquid of further sloughing in the sedimentator, obtain lumpy material, lumpy material is carried out drying, obtain powdery Neville acid sodium finished product.
13, technology according to claim 12 is characterized in that, drying is carried out in two steps, and the first step is predrying, and second step was dried to and obtains finished product.
14, technology according to claim 13 is characterized in that, when predrying, lumpy material delivered to the content liquid that dries by the fire in the drying room to the material reduce 50%; Second step, dry used moisture eliminator was pneumatic dryer, ebullated dryer or spray-dryer.
15, technology according to claim 11 is characterized in that, after branch removes inert solvent from material, material is delivered in the reactor, added gac or clorox or hydrogen peroxide and decolour, add hydrogen sulfide or sodium sulphite removal of impurities again, filter the reaction of saltouing again of gained filtrate then.
16, technology according to claim 15 is characterized in that, the mol ratio of methyl naphthol and chlorsulfonic acid is: 1: 1.2～1: 1.3; In the time of will adding reactor as the chlorsulfonic acid of sulphonating agent, the method for adding is for dripping, and the temperature of dropping is-25 ℃ to 60 ℃, drips the back insulation and proceeds reaction, and the temperature of insulation reaction is 40 ℃ to 120 ℃, and the time of insulation reaction is 4～24 hours; After obtaining paste Neville acid sodium, paste is delivered to the centrifugal liquid of further sloughing in the sedimentator, obtain lumpy material, lumpy material is carried out drying, obtain powdery Neville acid sodium finished product; Drying is carried out in two steps, and the first step is predrying, and second step was dried to and obtains finished product.
17, technology according to claim 16 is characterized in that, when predrying, lumpy material delivered to the content liquid that dries by the fire in the drying room to the material reduce 50%; Second step, dry used moisture eliminator was pneumatic dryer, ebullated dryer or spray-dryer.
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| CN97104183A CN1044808C (en) | 1997-04-30 | 1997-04-30 | Technology for industrialized production of 1-naphthol-4-sulfonic-acid and sodium salt thereof |
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| CN97104183A CN1044808C (en) | 1997-04-30 | 1997-04-30 | Technology for industrialized production of 1-naphthol-4-sulfonic-acid and sodium salt thereof |
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| CN104725282A (en) * | 2014-07-17 | 2015-06-24 | 叶良梅 | Novel environment-friendly production process of 1-naphthol-4-sulfonic acid |
| CN104829504A (en) * | 2015-04-02 | 2015-08-12 | 湖北鑫慧化工有限公司 | New solvent sulfonation technology of G acid |
| CN106082140A (en) * | 2016-08-23 | 2016-11-09 | 广西联壮科技股份有限公司 | The sodium sulfide knot screen of multi-layer efficient |
| CN108299162B (en) * | 2018-01-22 | 2021-01-12 | 南通柏盛化工有限公司 | Preparation process for synthesizing 2, 6-dihydroxynaphthalene |
| CN108395390A (en) * | 2018-04-16 | 2018-08-14 | 新乡市锦源化工有限公司 | The synthetic method and P-aminobenzene-sulfonamide of the P-aminobenzene-sulfonamide of energy-saving and emission-reduction |
| CN111333585A (en) * | 2020-04-24 | 2020-06-26 | 黄冈美丰化工科技有限公司 | Preparation method of ultraviolet absorbent 2-phenylbenzimidazole-5-sulfonic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5035147A (en) * | 1973-07-26 | 1975-04-03 | ||
| JPS5077353A (en) * | 1973-11-12 | 1975-06-24 | ||
| DE3411058A1 (en) * | 1983-04-05 | 1984-10-11 | Sandoz-Patent-GmbH, 7850 Lörrach | IMPROVED METHOD FOR PRODUCING 1-NAPHTHOL-4-SULPHONIC ACID (NEVILE-WINTHER ACID) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5035147A (en) * | 1973-07-26 | 1975-04-03 | ||
| JPS5077353A (en) * | 1973-11-12 | 1975-06-24 | ||
| DE3411058A1 (en) * | 1983-04-05 | 1984-10-11 | Sandoz-Patent-GmbH, 7850 Lörrach | IMPROVED METHOD FOR PRODUCING 1-NAPHTHOL-4-SULPHONIC ACID (NEVILE-WINTHER ACID) |
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