CN104016835B - Sulfonation and alkali fusion optimized production process for 2- naphthol - Google Patents
Sulfonation and alkali fusion optimized production process for 2- naphthol Download PDFInfo
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- CN104016835B CN104016835B CN201410285410.5A CN201410285410A CN104016835B CN 104016835 B CN104016835 B CN 104016835B CN 201410285410 A CN201410285410 A CN 201410285410A CN 104016835 B CN104016835 B CN 104016835B
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- sulfonation
- beta naphthal
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- alkali fusion
- alkali
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
Abstract
The invention relates to a sulfonation and alkali fusion optimized production process for 2-naphthol, and belongs to the field of organic chemical industry. By taking refined naphthalene as a material, 2-naphthol is prepared through processes such as sulfonating by 98% sulfuric acid, salting-out, alkali-fusing, acidifying, distilling, and the like. Defects of sulfonating, hydrolyzing and naphthalene-blowing, neutralizing, cold-separating, drying, alkali-fusing, acidifying and distilling in the convention process are overcome, the process is optimized, process flow is shortened, production cost is lowered, and no wastewater is produced; besides, the sulfonation and alkali fusion optimized production process for 2-naphthol has positive meaning for environment protection, and is especially applicable to production and usage of 2-naphthol.
Description
Technical field
The present invention relates to a kind of beta naphthal sulfonation alkali fusion optimized production process, belong to organic chemical industry field.
Background technology
Beta naphthal is a kind of dyestuff intermediate, is widely used in the industry products such as dyestuff, pigment, spices, sterilant, antioxidant.Its derivative G salt, K are sour, γ is sour, R salt etc. is applied in dyestuffs industries in large quantities, and beta naphthal derived product is used for the production of sensitive materials and liquid crystal material in recent years, has market outlook widely.Current industrial beta naphthal production method take refined naphthalene as raw material, blows the processes such as naphthalene, neutralization, cold analysis, suction strainer, drying, alkali fusion, acidifying, distillation obtain beta naphthal through 98% sulfuric acid sulfonation, hydrolysis.This technique weak point: naphthalene is blown in hydrolysis in process of production, neutralization, cold analysis produce a large amount of waste water, this waste water height salt, high COD, high chroma, and intractability is larger; And complicated component to human body and environmental hazard larger.
Summary of the invention
The object of the invention is to: overcome sulfonation in above-mentioned traditional technology, be hydrolyzed the deficiency of blowing naphthalene, neutralization, cold analysis, drying, alkali fusion, acidifying, distillation, Optimization Dept.'s division technique, thus shortened process, reduce production cost, and without the beta naphthal sulfonation alkali fusion optimized production process that waste water generates.
The present invention realizes above-mentioned purpose by the following technical solutions:
A kind of beta naphthal sulfonation alkali fusion optimized production process, is characterized in that: it comprises the following steps:
1) sulfonation: refined naphthalene was carried out sulfonation reaction at 160 DEG C, 150 minutes under condition through 98% sulfuric acid sulfonation, control total acidity 24-26%, after qualified, be cooled to 88-90 DEG C, put in suction filtration tank, continue to be cooled to 40 DEG C, vacuum filtration dewaters, require that free acid controls to apply mechanically to acidifying at 5%(sour water), obtain solid-state 2-naphthene sulfonic acid;
2) saltout: in horizontal auger device, add solid-state 2-naphthene sulfonic acid, dripping quality is while stirring the liquid caustic soda of 50%, mixing speed 15 revs/min, liquid caustic soda rate of addition is first slow rear fast, rate of addition control 5L/ minute, and reaction generates 2-naphthalene sulfonate salt, water content 14.5-15.5%, pH value 6-7;
3) alkali fusion: the 2-naphthalene sulfonate salt wet product about moisture about 15% of generation, directly add in alkali fusion reactor and carry out high temperature alkali fuse reaction, NaOH under 2-naphthalene sulfonate salt and molten state reacts at 320 ~ 340 DEG C, 2 hours reaction times, generates beta naphthal sodium crude product;
4), acidifying: the beta naphthal sodium that alkali fusion generates and the sour water that sulfonation is dewatered react and generate beta naphthal crude product; And neutralizing unreacted sodium hydroxide in alkali fusion reaction process, reaction is held time 60 minutes, terminates rear washing, with by the partial impurities eccysis in beta naphthal crude product.
5), distillation: through washing after crude phenols be depressed into still pot, be heated to 300 DEG C, distill under negative pressure-0.09Mpa condition, obtain conform to quality requirements finished product beta naphthal.
The invention has the advantages that:
Present invention process is simple, take refined naphthalene as raw material, through 98% sulfuric acid sulfonation, saltout, alkali fusion, acidifying, the operation such as distillation obtain beta naphthal.Overcome sulfonation in traditional technology, be hydrolyzed the deficiency of blowing naphthalene, neutralization, cold analysis, drying, alkali fusion, acidifying, distillation, optimize technique, shorten technical process, reduce production cost, and generate without waste water; To environment protection, there is positive meaning, be specially adapted to beta naphthal production and application.
Embodiment
Embodiment 1:
1000 kilograms of refined naphthalenes, 950 kilograms of sulfuric acid are added in sulfonation reaction still, reaction 150 minutes are maintained under 160 DEG C of conditions, sampling analysis total acidity is qualified 25.2%, open temperature lowering water system, be cooled to 90 DEG C, be discharged in ramp pan, continue to be cooled to 40 DEG C, vacuum leaches sour water, requires that free acid controls 5%; It is for subsequent use that the sour water leached is evacuated to acidifying post, obtains solid-state 2-naphthene sulfonic acid.Solid-state 2-naphthene sulfonic acid is added in horizontal auger device, while stirring drip quality be 50% liquid caustic soda 30L carry out neutralization reaction, rate of addition controls at 5L/ minute, and mixing speed is 15 revs/min, reaction generates 2-naphthalene sulfonate salt sampling analysis pH value 6.5, and moisture content 15.2% is qualified.Directly added in alkali fusion reactor by the 2-naphthalene sulfonate salt that neutralization reaction generates and under 320 DEG C of conditions, carry out high temperature alkali fuse reaction with the NaOH under molten state, 2 hours reaction times, generate beta naphthal sodium, it is qualified 2-3% that sampling detects free alkali.Beta naphthal sodium is discharged to acidifying still and the sour water 500L adding sulfonation suction filtration carries out acidification reaction, to neutralize unreacted sodium hydroxide in alkali fusion reaction process, it is qualified that the beta naphthal crude product sampling that reaction generates detects pH value 7, then qualified beta naphthal crude product is washed, with by the partial impurities eccysis in beta naphthal crude product.Beta naphthal crude product after washing is depressed into still pot, is heated to 300 DEG C, vacuum distillation-0.09Mpa, distills to obtain beta naphthal finished product.Distillation residue after distillation drain into the cooling of deslagging pot, and cooled residue is pitch.
Embodiment 2:
1500 kilograms of refined naphthalenes, 1420 kilograms of sulfuric acid are added in sulfonation reaction still, reaction 150 minutes are maintained under 160 DEG C of conditions, sampling analysis total acidity is qualified 25%, open temperature lowering water system, be cooled to 88 DEG C, be discharged in ramp pan, continue to be cooled to 40 DEG C, vacuum leaches sour water, requires that free acid controls 5%; It is for subsequent use that the sour water leached is evacuated to acidifying post, obtains solid-state 2-naphthene sulfonic acid.Solid-state 2-naphthene sulfonic acid is added in horizontal auger device, while stirring drip quality be 50% liquid caustic soda 46L carry out neutralization reaction, rate of addition controls at 5L/ minute, and mixing speed is 15 revs/min, reaction generates 2-naphthalene sulfonate salt sampling analysis pH value 6.8, and moisture content 14.8% is qualified.Directly added in alkali fusion reactor by the 2-naphthalene sulfonate salt that neutralization reaction generates and under 330 DEG C of conditions, carry out high temperature alkali fuse reaction with the NaOH under molten state, 2 hours reaction times, generate beta naphthal sodium, it is qualified 2-3% that sampling detects free alkali.Beta naphthal sodium is discharged to acidifying still and the sour water 720L adding sulfonation suction filtration carries out acidification reaction, to neutralize unreacted sodium hydroxide in alkali fusion reaction process, it is qualified that the beta naphthal crude product sampling that reaction generates detects pH value 7, then qualified beta naphthal crude product is washed, with by the partial impurities eccysis in beta naphthal crude product.Beta naphthal crude product after washing is depressed into still pot, is heated to 300 DEG C, vacuum distillation-0.09Mpa, distills to obtain beta naphthal finished product.Distillation residue after distillation drain into the cooling of deslagging pot, and cooled residue is pitch.
Embodiment 3:
2000 kilograms of refined naphthalenes, 1900 kilograms of sulfuric acid are added in sulfonation reaction still, reaction 150 minutes are maintained under 160 DEG C of conditions, sampling analysis total acidity is qualified 24.9%, open temperature lowering water system, be cooled to 88 DEG C, be discharged in ramp pan, continue to be cooled to 40 DEG C, vacuum leaches sour water, requires that free acid controls 5%; It is for subsequent use that the sour water leached is evacuated to acidifying post, obtains solid-state 2-naphthene sulfonic acid.Solid-state 2-naphthene sulfonic acid is added in horizontal auger device, while stirring drip quality be 50% liquid caustic soda 62L carry out neutralization reaction, rate of addition controls at 5L/ minute, and mixing speed is 15 revs/min, reaction generates 2-naphthalene sulfonate salt sampling analysis pH value 6.6, and moisture content 15.1% is qualified.Directly added in alkali fusion reactor by the 2-naphthalene sulfonate salt that neutralization reaction generates and under 340 DEG C of conditions, carry out high temperature alkali fuse reaction with the NaOH under molten state, 2 hours reaction times, generate beta naphthal sodium, it is qualified 2-3% that sampling detects free alkali.Beta naphthal sodium is discharged to acidifying still and the sour water 980L adding sulfonation suction filtration carries out acidification reaction, to neutralize unreacted sodium hydroxide in alkali fusion reaction process, it is qualified that the beta naphthal crude product sampling that reaction generates detects pH value 7, then qualified beta naphthal crude product is washed, with by the partial impurities eccysis in beta naphthal crude product.Beta naphthal crude product after washing is depressed into still pot, is heated to 300 DEG C, vacuum distillation-0.09Mpa, distills to obtain beta naphthal finished product.Distillation residue after distillation drain into the cooling of deslagging pot, and cooled residue is pitch.
Claims (1)
1. a beta naphthal sulfonation alkali fusion production technique, is characterized in that: it comprises the following steps:
1), sulfonation: refined naphthalene was carried out sulfonation reaction at 160 DEG C, 150 minutes under condition through 98% sulfuric acid sulfonation, control total acidity 24-26%, after qualified, be cooled to 88-90 DEG C, put in suction filtration tank, continue to be cooled to 40 DEG C, vacuum filtration dewaters, require that free acid controls 5%, sour water is applied mechanically to acidifying, obtains solid-state 2-naphthene sulfonic acid;
2), saltout: in horizontal auger device, add solid-state 2-naphthene sulfonic acid, dripping mass percent concentration is while stirring the liquid caustic soda of 50%, mixing speed 15 revs/min, liquid caustic soda rate of addition is first slow rear fast, rate of addition control 5L/ minute, reaction generates 2-naphthalene sulfonate salt, water content 14.5-15.5%, pH value 6-7;
3), alkali fusion: the 2-naphthalene sulfonate salt wet product moisture 14.5-15.5% of generation, directly add in alkali fusion reactor and carry out high temperature alkali fuse reaction, NaOH under 2-naphthalene sulfonate salt and molten state reacts at 320 ~ 340 DEG C, 2 hours reaction times, generates beta naphthal sodium crude product;
4), acidifying: the beta naphthal sodium that alkali fusion generates and the sour water that sulfonation is dewatered react and generate beta naphthal crude product; And neutralizing unreacted sodium hydroxide in alkali fusion reaction process, reaction is held time 60 minutes, terminates rear washing, with by the partial impurities eccysis in beta naphthal crude product;
5), distillation: the crude phenols after washing are depressed into still pot, are heated to 300 DEG C, distill under negative pressure-0.09Mpa condition, obtain the finished product beta naphthal conformed to quality requirements.
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| CN104016835B true CN104016835B (en) | 2015-07-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104592062B (en) * | 2015-02-16 | 2016-09-28 | 曲靖众一合成化工有限公司 | A kind of beta-naphthalenesulfonic-acid neutralizes and waste gas recovery method of comprehensive utilization and device thereof continuously |
| CN108003068A (en) * | 2016-10-31 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method of synthesis 2- naphthalene sulfonic acids |
| CN108002984B (en) * | 2017-09-14 | 2021-02-19 | 重庆紫光化工股份有限公司 | Production system and method for continuously preparing (alpha, beta) sodium naphthol from naphthalene |
| CN112961034B (en) * | 2021-02-23 | 2023-07-25 | 上海东庚化工技术有限公司 | Clean naphthol production process taking sulfur trioxide as raw material |
| CN112979427B (en) * | 2021-02-23 | 2023-07-25 | 上海东庚化工技术有限公司 | Process for synthesizing naphthol through sulfur trioxide indirect sulfonation reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442888A (en) * | 2011-11-10 | 2012-05-09 | 丹东深兰化工有限公司 | Method for producing 1,5-dihydroxy naphthalene |
| CN103626637A (en) * | 2013-12-11 | 2014-03-12 | 青岛奥盖克化工股份有限公司 | Environment-friendly production process of 2-naphthol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0672932A (en) * | 1992-06-25 | 1994-03-15 | Sumikin Chem Co Ltd | Production of beta-naphthol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442888A (en) * | 2011-11-10 | 2012-05-09 | 丹东深兰化工有限公司 | Method for producing 1,5-dihydroxy naphthalene |
| CN103626637A (en) * | 2013-12-11 | 2014-03-12 | 青岛奥盖克化工股份有限公司 | Environment-friendly production process of 2-naphthol |
Non-Patent Citations (1)
| Title |
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| 梁诚.2-萘酚及其衍生产品合成工艺进展.《染料工业》.2001,第38卷(第5期),17-19. * |
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