CN104016835A - 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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- CN104016835A CN104016835A CN201410285410.5A CN201410285410A CN104016835A CN 104016835 A CN104016835 A CN 104016835A CN 201410285410 A CN201410285410 A CN 201410285410A CN 104016835 A CN104016835 A CN 104016835A
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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
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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
- C07C37/64—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 acid, γ are sour, R salt etc. is applied in dyestuffs industries in large quantities, and beta naphthal derived product, for the production of sensitive materials and liquid crystal material, has market outlook very widely in recent years.Current industrial beta naphthal production method, is to take refined naphthalene as raw material, and the processes such as naphthalene, neutralization, cold analysis, suction strainer, dry, alkali fusion, acidifying, distillation of blowing through 98% sulfuric acid sulfonation, hydrolysis make beta naphthal.This technique weak point: hydrolysis is blown naphthalene, neutralization, cold analysis and produced a large amount of waste water in process of production, the high salt of this waste water, high COD, high chroma, intractability is larger; And complicated component is larger to human body and environmental hazard.
Summary of the invention
The object of the invention is to: overcome the deficiency that naphthalene, neutralization, cold analysis, dry, alkali fusion, acidifying, distillation are blown in sulfonation in above-mentioned traditional technology, hydrolysis, Optimization Dept.'s division technique, thereby shortened process, reduces production costs, and the beta naphthal sulfonation alkali fusion optimized production process generating without waste water.
The present invention realizes above-mentioned purpose by the following technical solutions:
A beta naphthal sulfonation alkali fusion optimized production process, is characterized in that: it comprises the following steps:
1) sulfonation: refined naphthalene was carried out to sulfonation reaction at 160 ℃, 150 minutes under condition through 98% sulfuric acid sulfonation, control total acidity 24-26%, after qualified, be cooled to 88-90 ℃, put to suction filtration tank, continue to be cooled to 40 ℃, vacuum filtration dehydration, requiring free acid to be controlled at 5%(sour water applies mechanically to acidifying), obtain solid-state 2-naphthene sulfonic acid;
2) saltout: in horizontal auger device, add solid-state 2-naphthene sulfonic acid, drip while stirring quality and be 50% liquid caustic soda, 15 revs/min of mixing speed, liquid caustic soda rate of addition is first slow rear fast, and rate of addition is controlled 5L/ minute, and reaction generates 2-naphthalene sulfonate salt, water content 14.5-15.5%, pH value 6-7;
3) alkali fusion: approximately moisture 15% left and right of 2-naphthalene sulfonate salt wet product of generation, directly add and in alkali fusion reactor, carry out high temperature alkali fuse reaction, 2-naphthalene sulfonate salt reacts at 320～340 ℃ with the NaOH under molten state, in 2 hours reaction times, generates beta naphthal sodium crude product;
4), acidifying: the beta naphthal sodium that alkali fusion generates reacts and generates beta naphthal crude product with the sour water of sulfonation dehydration; And neutralizing unreacted sodium hydroxide in alkali fusion reaction process, reaction is held time 60 minutes, finishes 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 ℃, under negative pressure-0.09Mpa condition, distill, obtain conform to quality requirements finished product beta naphthal.
The invention has the advantages that:
Technique of the present invention is simple, take refined naphthalene as raw material, through 98% sulfuric acid sulfonation, saltout, the operation such as alkali fusion, acidifying, distillation makes beta naphthal.Overcome sulfonation in traditional technology, hydrolysis and blown the deficiency of naphthalene, neutralization, cold analysis, dry, alkali fusion, acidifying, distillation, optimized technique, shortened technical process, reduced production cost, and generate without waste water; Environment protection is had to 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, under 160 ℃ of conditions, maintain reaction 150 minutes, sampling analysis total acidity is qualified 25.2%, open temperature lowering water system, be cooled to 90 ℃, be discharged in ramp pan, continue to be cooled to 40 ℃, vacuum leaches sour water, requires free acid to be controlled at 5%; It is standby that the sour water leaching is evacuated to acidifying post, obtains solid-state 2-naphthene sulfonic acid.In horizontal auger device, add solid-state 2-naphthene sulfonic acid, drip while stirring quality and be 50% liquid caustic soda 30L and carry out neutralization reaction, rate of addition is controlled 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.The 2-naphthalene sulfonate salt that neutralization reaction is generated directly adds in alkali fusion reactor and under 320 ℃ of conditions, to carry out high temperature alkali fuse with NaOH under molten state and react, 2 hours reaction times, generate beta naphthal sodium, and it is qualified 2-3% that sampling detects free alkali.Beta naphthal sodium is discharged to acidifying still and adds the sour water 500L of sulfonation suction filtration to carry 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 ℃, vacuum distillation-0.09Mpa, distills to obtain beta naphthal finished product.It is cooling that distillation residue after distillation drain into 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, under 160 ℃ of conditions, maintain reaction 150 minutes, sampling analysis total acidity is qualified 25%, open temperature lowering water system, be cooled to 88 ℃, be discharged in ramp pan, continue to be cooled to 40 ℃, vacuum leaches sour water, requires free acid to be controlled at 5%; It is standby that the sour water leaching is evacuated to acidifying post, obtains solid-state 2-naphthene sulfonic acid.In horizontal auger device, add solid-state 2-naphthene sulfonic acid, drip while stirring quality and be 50% liquid caustic soda 46L and carry out neutralization reaction, rate of addition is controlled 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.The 2-naphthalene sulfonate salt that neutralization reaction is generated directly adds in alkali fusion reactor and under 330 ℃ of conditions, to carry out high temperature alkali fuse with NaOH under molten state and react, 2 hours reaction times, generate beta naphthal sodium, and it is qualified 2-3% that sampling detects free alkali.Beta naphthal sodium is discharged to acidifying still and adds the sour water 720L of sulfonation suction filtration to carry 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 ℃, vacuum distillation-0.09Mpa, distills to obtain beta naphthal finished product.It is cooling that distillation residue after distillation drain into 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, under 160 ℃ of conditions, maintain reaction 150 minutes, sampling analysis total acidity is qualified 24.9%, open temperature lowering water system, be cooled to 88 ℃, be discharged in ramp pan, continue to be cooled to 40 ℃, vacuum leaches sour water, requires free acid to be controlled at 5%; It is standby that the sour water leaching is evacuated to acidifying post, obtains solid-state 2-naphthene sulfonic acid.In horizontal auger device, add solid-state 2-naphthene sulfonic acid, drip while stirring quality and be 50% liquid caustic soda 62L and carry out neutralization reaction, rate of addition is controlled 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.The 2-naphthalene sulfonate salt that neutralization reaction is generated directly adds in alkali fusion reactor and under 340 ℃ of conditions, to carry out high temperature alkali fuse with NaOH under molten state and react, 2 hours reaction times, generate beta naphthal sodium, and it is qualified 2-3% that sampling detects free alkali.Beta naphthal sodium is discharged to acidifying still and adds the sour water 980L of sulfonation suction filtration to carry 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 ℃, vacuum distillation-0.09Mpa, distills to obtain beta naphthal finished product.It is cooling that distillation residue after distillation drain into deslagging pot, and cooled residue is pitch.
Claims (1)
1. a beta naphthal sulfonation alkali fusion optimized production process, is characterized in that: it comprises the following steps:
1) sulfonation: refined naphthalene was carried out to sulfonation reaction at 160 ℃, 150 minutes under condition through 98% sulfuric acid sulfonation, control total acidity 24-26%, after qualified, be cooled to 88-90 ℃, put to suction filtration tank, continue to be cooled to 40 ℃, vacuum filtration dehydration, requiring free acid to be controlled at 5%(sour water applies mechanically to acidifying), obtain solid-state 2-naphthene sulfonic acid;
2) saltout: in horizontal auger device, add solid-state 2-naphthene sulfonic acid, drip while stirring quality and be 50% liquid caustic soda, 15 revs/min of mixing speed, liquid caustic soda rate of addition is first slow rear fast, and rate of addition is controlled 5L/ minute, and reaction generates 2-naphthalene sulfonate salt, water content 14.5-15.5%, pH value 6-7;
3) alkali fusion: approximately moisture 15% left and right of 2-naphthalene sulfonate salt wet product of generation, directly add and in alkali fusion reactor, carry out high temperature alkali fuse reaction, 2-naphthalene sulfonate salt reacts at 320～340 ℃ with the NaOH under molten state, in 2 hours reaction times, generates beta naphthal sodium crude product;
4), acidifying: the beta naphthal sodium that alkali fusion generates reacts and generates beta naphthal crude product with the sour water of sulfonation dehydration; And neutralizing unreacted sodium hydroxide in alkali fusion reaction process, reaction is held time 60 minutes, finishes 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 ℃, under negative pressure-0.09Mpa condition, distill, obtain conform to quality requirements finished product beta naphthal.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592062A (en) * | 2015-02-16 | 2015-05-06 | 曲靖众一合成化工有限公司 | Method and device for continuously neutralizing beta-naphthalene sulfonic acid and comprehensively recycling waste gas |
| 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 |
| CN108002984A (en) * | 2017-09-14 | 2018-05-08 | 重庆紫光化工股份有限公司 | Continuously prepared from naphthalene（α、β）The production system and method for sodium naphtholate |
| CN112961034A (en) * | 2021-02-23 | 2021-06-15 | 上海东庚化工技术有限公司 | Clean production process of naphthol by taking sulfur trioxide as raw material |
| CN112979427A (en) * | 2021-02-23 | 2021-06-18 | 上海东庚化工技术有限公司 | Process for synthesizing naphthol through sulfur trioxide indirect sulfonation reaction |
Citations (3)
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| JPH0672932A (en) * | 1992-06-25 | 1994-03-15 | Sumikin Chem Co Ltd | Production of beta-naphthol |
| 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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2014
- 2014-06-24 CN CN201410285410.5A patent/CN104016835B/en not_active Expired - Fee Related
Patent Citations (3)
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|---|---|---|---|---|
| JPH0672932A (en) * | 1992-06-25 | 1994-03-15 | Sumikin Chem Co Ltd | Production of beta-naphthol |
| 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》, vol. 38, no. 5, October 2001 (2001-10-01), pages 17 - 19 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592062A (en) * | 2015-02-16 | 2015-05-06 | 曲靖众一合成化工有限公司 | Method and device for continuously neutralizing beta-naphthalene sulfonic acid and comprehensively recycling waste gas |
| 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 |
| CN108002984A (en) * | 2017-09-14 | 2018-05-08 | 重庆紫光化工股份有限公司 | Continuously prepared from naphthalene（α、β）The production system and method for sodium naphtholate |
| 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 |
| CN112961034A (en) * | 2021-02-23 | 2021-06-15 | 上海东庚化工技术有限公司 | Clean production process of naphthol by taking sulfur trioxide as raw material |
| CN112979427A (en) * | 2021-02-23 | 2021-06-18 | 上海东庚化工技术有限公司 | Process for synthesizing naphthol through sulfur trioxide indirect sulfonation reaction |
| 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 |
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