CN101781172B - Novel process for efficiently and continuously synthesizing 2-naphthol - Google Patents

Novel process for efficiently and continuously synthesizing 2-naphthol Download PDF

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CN101781172B
CN101781172B CN 201010039101 CN201010039101A CN101781172B CN 101781172 B CN101781172 B CN 101781172B CN 201010039101 CN201010039101 CN 201010039101 CN 201010039101 A CN201010039101 A CN 201010039101A CN 101781172 B CN101781172 B CN 101781172B
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naphthols
reaction
naphthol
sulfonation
alkali
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CN101781172A (en
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李桂成
罗国林
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QUJIN ZHONGYI FINECHEMICAL CO Ltd
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QUJIN ZHONGYI FINECHEMICAL CO Ltd
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Abstract

The invention discloses a novel process for efficiently and continuously synthesizing 2-naphthol, which comprises the following steps of: (A) putting refined naphthol from a naphthol-melting tank (1) into a prime kettle of a sulfonation reaction kettle, respectively putting sulphuric acid into various levels of the sulfonation reaction kettle from a sulphuric acid-weighting tank (2) for a sulfonation reaction for 2-6h and reducing the pressure of the sulfonation reaction kettle so as to remove water generated by the reaction; (B) guiding a sulfonated product in the step (A) into a neutralizing tank (7), directly neutralizing with diluted alkali, keeping impurities in the sulfonation reaction, primarily evaporating to dewater and directly guiding into an alkali melting pot (9) for an alkali-melting reaction; (C) acidifying an alkali-melting reaction product in an acidifying tank (11) and extracting 2-naphthol and 1-naphthol from the alkali-melting reaction product in an extracting tower (13) with an extracting agent; and (D) rectifying an organic phase after extracting the naphthol in a rectification tower to recycle the extracting agent and rectifying and separating the 2-naphthol, the 1-naphthol and naphthol without participating the reaction. The invention adopts continuous reaction process design, has simple and convenient process, stable performance and high yield, overcomes the detects of intermittent operation, low synthesis effect, multiple steps for separating 2-naphthol from other impurities, low separation efficiency and much three-waste generation in a sulfonation alkali-melting 2-naphthol synthesis process of the prior art, realizes continuous process, greatly reduces three-waste emission, lessens wastewater by 20 percent than that of the traditional process, greatly improves the 2-naphthol synthesis efficiency and obtains the 1-naphthol as a byproduct.

Description

The continuous Synthetic 2 of high-level efficiency-naphthols technology
Technical field
The invention belongs to the organic chemistry synthesis technical field, be specifically related to a kind of novel process that can the continuous Synthetic 2-naphthols of high-level efficiency.
Background technology
Beta naphthal is claimed ethyl naphthol, β-Nai Fen again, is important Organic Chemicals and synthetic intermediate, reaches kind more than 130 by its direct synthetic dyestuff, pigment variety, more than 20 of dyestuff intermediates.Also be widely used at aspects such as medicine, agricultural chemicals, rubber ingredients, spices, leather tanning, textile auxiliary and dressing agents.Aspect dyestuff, the synthetics of mainly spreading out of beta naphthal has 2, and 3-acid, TOBIAS ACID 97MIN.& 98MIN., diazonium sulfonaphthol, G acid, R is sour, Y is sour, J is sour, 2,6 acid etc.; Aspect medicine, agricultural chemicals, beta naphthal is mainly used in synthetic analgesic agent Naproxen Base, weedicide naproanilide, plant modifying agent 2-naphthyloxy ethamine etc.In recent years, the naphthols derived product is used for the synthetic of sensitive materials and liquid crystal material, like hydroxyl-1-naphthoic acid, naphthols benzylic ether, 2 hydroxy naphthalene-6-formic acid etc., very extensive market prospects is arranged.The main method of comparatively sophisticated synthetic naphthols has sulfonated alkali fusion method and the different third naphthalene method in the industry.In recent years; Rise along with green synthetic chemistry thought; The investigator reduces the synthesis technique scheme of three waste discharge, like technical matters such as biological synthesis process, direct catalysis synthesis process, superacid catalysis, heteropoly acid catalysis, transition metal oxide catalysis, transition metal oxide catalysis, high-energy radiation catalysis to synthetic some the minimizing synthesis paths that proposed of naphthols; Though obtained some achievements, also had very long distance from industrial applications.The major industry method of synthetic naphthols still is a sulfonated alkali fusion method both at home and abroad at present, its technological comparative maturity, but sulfonated alkali fusion method exists technical process long; Synthesis technique is interrupted, and labor condition is poor, and equipment corruption property is serious; Three waste discharge is many, the more high shortcoming of synthetic cost.For this reason, the inventor is through secular experimental study, melts at prior art sulfonation alkali to have developed a kind of novel process that can the continuous Synthetic 2-naphthols of high-level efficiency on the basis of technology, and the evidence technique effect is good.
Summary of the invention
The object of the present invention is to provide a kind of technology easy, stable work in work, novel process that can the continuous Synthetic 2-naphthols of high-level efficiency.
The objective of the invention is to realize like this, comprise following operation:
A, refined naphthalene put into the prime still of sulfonation reaction still from naphthalene melting slot, and sulfuric acid is put into the at different levels of sulfonation reaction still respectively from the sulphur acid meter measuring tank and was used for sulfonation reaction 2 to 6 hours, simultaneously to the decompression of sulfonation reaction still to remove the water that dereaction was generated;
B, the sulfonated products in the A operation imported direct join connects with the diluted alkaline neutralization in the neutralizing well, and keep the impurity of by-product in the sulfonation reaction, pre-evaporation dehydration back directly imports alkali and melts and carry out alkali in the pot and melt reaction;
C, alkali melt reaction product after the acidifying of acidifying groove, in extraction tower, extract wherein beta naphthal, 1-naphthols with extraction agent;
D, the organic phase of extraction behind the naphthols reclaim extraction agent through rectifying tower rectifying, rectifying separation beta naphthal wherein simultaneously, 1-naphthols and have neither part nor lot in the naphthalene of reaction.
In the naphthalene sulfonation process, adopted many stills formula continuous reaction process, and the moisture content that adopts pressure reducing mode to remove in the reaction process to be produced, carry out to the direction of Synthetic 2-naphthols to help sulfonation reaction.Blow decomposition 1-naphthols and blow down naphthalene without steaming (vapour) for the product after the naphthalene sulfonation, melt but concentrate the direct alkali in back; Alkali melts product naphthols with the SX aqueous phase after acidifying, improves the yield of naphthols; Use highly efficient distilling to separate 1-naphthols and beta naphthal in the organic phase, accomplish the synthetic two kinds of products of a cover processing unit.
The present invention has adopted the continuous reaction process design, and technology is easy, stable performance, and yield is high, has overcome the batch operation that prior art sulfonation alkali fusion Synthetic 2-naphthols technology exists, and combined coefficient is low; Beta naphthal is many with other separate impurities process steps, and separation efficiency is low, produces the many drawbacks of the three wastes; Realization technology is continuous, has significantly reduced three waste discharge, and waste water is merely 20% of former technology; And the combined coefficient of beta naphthal greatly improves, and can obtain the 1-naphthols as sub product simultaneously.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Among the figure: the 1-naphthalene melting slot, 2-sulphur acid meter measuring tank, 3-one-level sulfonation groove, 4-secondary sulfonation groove, three grades of sulfonation grooves of 5-, 6-diluted alkaline groove, the 7-neutralizing well, 8-concentrated base groove, 9-alkali melt a pot 10-dilute acid bath, 11-acidifying groove, 12-solvent oil groove, 13-extraction tower, 14-rectifying tower.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described, but never in any form the present invention is limited, any improvement of doing based on training centre of the present invention is all within protection scope of the present invention.
As shown in the figure, the present invention includes following operation:
A, refined naphthalene put into the prime still of sulfonation reaction still from naphthalene melting slot 1, and sulfuric acid is put into the at different levels of sulfonation reaction still respectively from sulphur acid meter measuring tank 2 and was used for sulfonation reaction 2 to 6 hours, simultaneously to the decompression of sulfonation reaction still to remove the water that dereaction was generated;
B, the sulfonated products in the A operation imported direct join connects with the diluted alkaline neutralization in the neutralizing well 7, and keep the impurity of by-product in the sulfonation reaction, pre-evaporation dehydration back directly imports alkali and melts and carry out alkali in the pot 9 and melt reaction;
C, alkali melt reaction product after 11 acidifyings of acidifying groove, in extraction tower 13, extract wherein beta naphthal, 1-naphthols with extraction agent;
D, the organic phase of extraction behind the naphthols reclaim extraction agent through rectifying tower 14 rectifying, rectifying separation beta naphthal wherein simultaneously, 1-naphthols and have neither part nor lot in the naphthalene of reaction.
Described sulfonation reaction still is a multi-stage reacting kettle, comprises one-level sulfonation groove 3, secondary sulfonation groove 4/ and three grades of sulfonation grooves 5 at least.
Described sulfonation reaction temperature is 140 ℃-170 ℃, is preferably 160 ℃.
Can be any one or more than one mixed base in sodium hydroxide, yellow soda ash, the S-WAT with used diluted alkaline in the described B operation.
Used extraction agent is any one or more than one the combination in tributyl phosphate, toluene, the trioctylamine in the described C operation.
The used souring agent of described acidifying is sulfurous gas or dilute sulphuric acid.
The consumption of said extraction agent is a reaction mass: extraction agent=1: 2 (weight ratio).
It is 250 ℃-350 ℃ that described C operation alkali melts temperature, is preferably 320 ℃.
Embodiment 1
Naphthalene sulfuric acid with 96% in the time of 155~165 ℃ carries out sulfonation, mainly obtains 2-naphthene sulfonic acid (content 85%), and 1-naphthalene sulfonic aicd (content 10%) adds S-WAT (by product during alkali fusion) and makes it to separate out, and heating obtains the 2-naphthalene sulfonate salt after concentrating.In cast iron that stirring is arranged or zinc steel still, the 2-sodium naphthalene sulfonate being carried out alkali then melts.At first add 50% sodium hydroxide solution, be heated to 300 ℃, the dehydration back adds the 2-sodium naphthalene sulfonate, keeps 320 ℃ of about 3h.After melts is dissolved in water, adds sulfurous gas and carry out acidifying, be neutralized to weakly alkaline (pH=8); After the phase-splitting; Organic phase is thick naphthols, and water is extracted naphthols with the mixed solvent of tributyl phosphate, toluene 1: 1 (v/v), and with organic phase rectifying together; Reclaim solvent, obtain product and beta naphthal and 1-naphthols.The purity of beta naphthal is greater than 99%; Beta naphthal whole process yield is greater than more than 85%; The purity of 1-naphthols is greater than 99%; 1-naphthols whole process yield is greater than more than 10%; Three waste discharge is merely 20% of former technology.
Embodiment 2
Naphthalene with 96% sulfuric acid sulfonation, mainly obtains 2-naphthene sulfonic acid (content 85%) in the time of 140~155 ℃, 1-naphthalene sulfonic aicd (content 10%) adds S-WAT (by product during alkali fusion) and makes it to separate out, and heating obtains the 2-naphthalene sulfonate salt after concentrating.In cast iron that stirring is arranged or zinc steel still, 2-naphthene sulfonic acid soda is melted then.At first add 50% sodium carbonate solution, be heated to 250 ℃, the dehydration back adds the 2-sodium naphthalene sulfonate, keeps 300 ℃ of about 3h.After melts is dissolved in water, adds dilute sulphuric acid and carry out acidifying, be neutralized to weakly alkaline (pH=8), after the phase-splitting; Organic phase is thick naphthols, water is extracted with the trioctylamine solvent, to improve the yield of naphthols; With organic phase rectifying together, reclaim solvent, obtain product and beta naphthal and 1-naphthols.The beta naphthal purity that obtains is greater than 99%; Beta naphthal whole process yield is greater than more than 83%; The 1-naphthols purity that obtains is greater than 99%; 1-naphthols whole process yield is greater than more than 8%; Three waste discharge is merely 20% of former technology.
Embodiment 3
Naphthalene with 96% sulfuric acid sulfonation, mainly obtains 2-naphthene sulfonic acid (content 85%) in the time of 160~170 ℃, 1-naphthalene sulfonic aicd (content 10%) adds sodium hydroxide solution and makes it to separate out, and heating obtains the 2-naphthalene sulfonate salt after concentrating.In cast iron that stirring is arranged or zinc steel still, 2-naphthene sulfonic acid soda is melted then.At first add 50% sodium sulfite solution, be heated to 300 ℃, the dehydration back adds the 2-sodium naphthalene sulfonate, keeps 350 ℃ of about 3h.After melts is dissolved in water, adds dilute sulphuric acid and carry out acidifying, be neutralized to weakly alkaline (pH=8); After the phase-splitting, organic phase is thick naphthols, and the mixed solvent of water with tributyl phosphate, toluene 1: 1 (v/v) extracted; To improve the yield of naphthols; With organic phase rectifying together, reclaim solvent, obtain product and beta naphthal and 1-naphthols.The beta naphthal purity that obtains is greater than 99%; Beta naphthal whole process yield is greater than more than 86%; The 1-naphthols purity that obtains is greater than 99%; 1-naphthols whole process yield is greater than more than 9%; Three waste discharge is merely 25% of former technology.
Characteristics of the present invention:
1, the process for sulfonation combined coefficient is high continuously;
2, the solvent dehydration process for sulfonation improves the selectivity and the transformation efficiency of sulfonation process;
3, shorten the step of sulfonation N-process, reduce three waste discharge;
4, the naphthols bullion after solvent extraction and separation alkali fusion, the acidifying improves the naphthols yield;
5, the thick naphthols of rectifying separation improves naphthols yield and purity.

Claims (10)

1. the continuous Synthetic 2 of high-level efficiency-naphthols technology is characterized in that comprising following operation:
A, refined naphthalene put into the prime still of sulfonation reaction still from naphthalene melting slot (1), and sulfuric acid is put into the at different levels of sulfonation reaction still respectively from sulphur acid meter measuring tank (2) and was used for sulfonation reaction 2 to 6 hours, simultaneously to the decompression of sulfonation reaction still to remove the water that dereaction was generated;
B, import in the neutralizing well (7) sulfonated products in the A operation and directly with the diluted alkaline neutralization, and keep the impurity of by-product in the sulfonation reaction, pre-evaporation dehydration back directly imports alkali and melts and carry out alkali in the pot (9) and melt reaction;
C, alkali melt reaction product after acidifying groove (11) acidifying, in extraction tower (13), extract wherein beta naphthal, 1-naphthols with extraction agent;
D, the organic phase of extraction behind the naphthols reclaim extraction agent through rectifying tower (14) rectifying, rectifying separation beta naphthal wherein simultaneously, 1-naphthols and have neither part nor lot in the naphthalene of reaction.
2. the continuous Synthetic 2 of high-level efficiency as claimed in claim 1-naphthols technology is characterized in that described sulfonation reaction still is a multi-stage reacting kettle, comprises that at least one-level sulfonation groove (3), secondary sulfonation groove (4) are or/and three grades of sulfonation grooves (5).
3. the continuous Synthetic 2 of high-level efficiency as claimed in claim 1-naphthols technology is characterized in that described sulfonation reaction temperature is 140 ℃-170 ℃.
4. the continuous Synthetic 2 of high-level efficiency as claimed in claim 1-naphthols technology is characterized in that in the said B operation and used diluted alkaline is any one or more than one the mixed base in sodium hydroxide, yellow soda ash, the S-WAT.
5. the continuous Synthetic 2 of high-level efficiency as claimed in claim 1-naphthols technology is characterized in that extraction agent used in the said C operation is any one or more than one the combination in tributyl phosphate, toluene, the trioctylamine.
6. the continuous Synthetic 2 of high-level efficiency as claimed in claim 1-naphthols technology is characterized in that the used souring agent of described acidifying is sulfurous gas or dilute sulphuric acid.
7. like claim 1 or the continuous Synthetic 2 of 5 described high-level efficiency-naphthols technology, the consumption that it is characterized in that said extraction agent is the weight ratio reaction mass: extraction agent=1: 2.
8. the continuous Synthetic 2 of high-level efficiency as claimed in claim 1-naphthols technology is characterized in that it is 250 ℃-350 ℃ that described C operation alkali melts temperature of reaction.
9. like claim 1 or the continuous Synthetic 2 of 3 described high-level efficiency-naphthols technology, it is characterized in that described sulfonation reaction temperature is 160 ℃.
10. like claim 1 or the continuous Synthetic 2 of 8 described high-level efficiency-naphthols technology, it is characterized in that it is 320 ℃ that said alkali melts temperature of reaction.
CN 201010039101 2010-01-04 2010-01-04 Novel process for efficiently and continuously synthesizing 2-naphthol Active CN101781172B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102850190A (en) * 2011-06-28 2013-01-02 北京石油化工学院 Method for preparing mixed naphthol
CN102503752B (en) * 2011-10-08 2014-04-02 大连理工大学 Method for preparing polysubstituted 2-naphthol
CN104447215B (en) * 2014-10-29 2016-01-20 绍兴奇彩化工有限公司 A kind of continuously acidizing technique of synthesizing beta naphthal
CN104628605B (en) * 2015-02-16 2016-05-25 曲靖众一合成化工有限公司 A kind of naphthalene continuous catalysis method of sulfonating and device thereof
CN108822006A (en) * 2018-05-31 2018-11-16 山西豪仑科化工有限公司 A kind of naphthalene sulfonation continuous reaction process
CN108821950A (en) * 2018-05-31 2018-11-16 山西豪仑科化工有限公司 A kind of continuous neutralization reaction method of bisnaphthol production

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237323A (en) * 1979-06-08 1980-12-02 Aliev Sakhib M O Method for preparing α-naphthol
CN1513824A (en) * 2003-08-18 2004-07-21 常州市华达化工厂 Preparation method of joint production of alpha maphthol and beta naphthol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237323A (en) * 1979-06-08 1980-12-02 Aliev Sakhib M O Method for preparing α-naphthol
CN1513824A (en) * 2003-08-18 2004-07-21 常州市华达化工厂 Preparation method of joint production of alpha maphthol and beta naphthol

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Application publication date: 20100721

Assignee: The many synthesis Chemical Co., Ltd.s in Qujing

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