CN100540532C - The preparation method of a kind of 1-naphthalene sulfonic aicd and 1-naphthalene sulfonic aicd sodium salt - Google Patents
The preparation method of a kind of 1-naphthalene sulfonic aicd and 1-naphthalene sulfonic aicd sodium salt Download PDFInfo
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- CN100540532C CN100540532C CNB2006100968060A CN200610096806A CN100540532C CN 100540532 C CN100540532 C CN 100540532C CN B2006100968060 A CNB2006100968060 A CN B2006100968060A CN 200610096806 A CN200610096806 A CN 200610096806A CN 100540532 C CN100540532 C CN 100540532C
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Abstract
The synthetic method of a kind of 1-naphthalene sulfonic aicd and/or 1-naphthalene sulfonic aicd sodium salt with naphthalene dissolving fully in solvent, adds an amount of 1-naphthalene sulfonic aicd crystal seed, is cooled to 0 ± 5 ℃, drips chlorsulfonic acid under the negative pressure while stirring, drips off in 1-2 hour, keeps 1.5-3 hour at-2～8 ℃ again; Naphthalene: chlorsulfonic acid: solvent=1: 1.01～1.10: 3.0～3.5 (mol ratio); Be cooled to 0 ± 2 ℃ of filtration, filter cake is 1-naphthalene sulfonic aicd; Be separated after the filtrate water washing, obtain solvent and washing acid, washing acid can be produced naphthalene series high-efficiency water-reducing agent.1-naphthalene sulfonic aicd and the solvent of washing after separating are neutralized with 5%～15% NaOH, kept 10～30 minutes for 90 ± 5 ℃, neutralizer is separated and obtains the 1-naphthalene sulfonic aicd sodium water solution, is cooled to≤35 ℃ of following crystallizations filtrations, and filter cake is a 1-naphthalene sulfonic aicd sodium; Filtrate is as preparation NaOH solution.Sulfonation reaction selectivity height of the present invention, the product content of isomer is low, and operation is more easy to control, produces no waste water generation in the process.
Description
Technical field
The present invention relates to the preparation method of a kind of naphthene sulfonic acid and sodium salt thereof, particularly relate to the preparation method of a kind of 1-naphthalene sulfonic aicd and 1-naphthalene sulfonic aicd sodium salt.
Background technology
1-naphthalene sulfonic aicd or 1-naphthalene sulfonic aicd sodium salt are mainly used to produce the 1-naphthols, generally raw naphthalene material are made 1-naphthalene sulfonic aicd through sulfonation reaction, and saltouing through neutralization obtains the 1-naphthalene sulfonic aicd sodium salt again; The 1-naphthalene sulfonic aicd sodium salt makes the 1-naphthols after alkali fusion, acidifying.Prior preparation method mainly contains low-temperature sulfonation method, chlorsulfonic acid sulfonation method etc. by used sulphonating agent branch.
The low-temperature sulfonation method is raw material with the naphthalene, makes sulphonating agent with 98% sulfuric acid, 0～40 ℃ of sulfonation reaction temperature, and it is about 83%～85% that the sulfonated bodies that obtains contains 1-naphthalene sulfonic aicd, 2-naphthene sulfonic acid 15%～17%.There is following shortcoming in this processing method: 1, acid, quantity of alkali consumption is big, can produce a large amount of spent acid waste water, and the three wastes are handled and comprehensive utilization is a difficult problem; 2, in sulfonated products, isomer 2-naphthene sulfonic acid 〉=15%, its difficulty of separating purification of mixing naphthols that makes through alkali fusion, acidifying is very big; 3, inorganic salt Na
2SO
4Be difficult to control, cause follow-up alkali fusion material mobile poor, easily the knot pot.
Make sulphonating agent with chlorsulfonic acid, when the consumption of chlorsulfonic acid is excessive slightly than theoretical amount, generation be the compound of sulfonic acid.In order to make reaction evenly, generally to make releasing agent with oil of mirbane, o-nitroethylbenzene, orthodichlorobenzene or ethylene dichloride etc.Use the chlorsulfonic acid sulfonation, can under relatively mild condition, react, obtain purer product, and do not produce spent acid basically.The hydrogenchloride of by-product can be discharged under negative pressure, and water absorbs makes hydrochloric acid.In order to reduce waste liquid, to avoid environmental pollution, more existing products are used the chlorsulfonic acid sulfonation method instead.
The chlorsulfonic acid sulfonation method prepares 1-naphthalene sulfonic aicd, be to replace the vitriol oil as sulphonating agent with chlorsulfonic acid, with the o-nitroethylbenzene is solvent, make the naphthalene sulfonation at 0～5 ℃, the proportioning raw materials of sulfonation reaction is a naphthalene: chlorsulfonic acid: o-nitroethylbenzene=1: 1.1: 3 (mol ratio), the purity of gained 1-naphthalene sulfonic aicd product is 97%.This method need consume solvent, the difficult control of reaction process, and alkali charge is very big in alkali fusion process thereafter, and there is a serious etching problem, this method was done many researchs and improvement at home, but failed ordinary production, and the relevant technologies scheme is not seen public publish.
The present invention has done improvement to the processing method that the chlorsulfonic acid legal system is equipped with 1-naphthalene sulfonic aicd, determines the related process parameter, and the replenishment of process flow process can be applied in the suitability for industrialized production the inventive method.
Summary of the invention
Technical problem
The object of the present invention is to provide the synthetic method of a kind of 1-naphthalene sulfonic aicd and/or 1-naphthalene sulfonic aicd sodium salt, it is sulphonating agent that this method adopts chlorsulfonic acid, carries out sulfonation reaction at low temperatures with preparation 1-naphthalene sulfonic aicd and/or 1-naphthalene sulfonic aicd sodium salt.Overcome that available technology adopting sulfuric acid is big as the spent acid wastewater flow rate that low-temperature sulfonation technology was difficult to overcome of sulphonating agent, isomer is difficult to defectives such as separation, operability difference; Overcome chlorsulfonic acid sulfonation method technology instability in the prior art, operability is poor, reacts unmanageable shortcoming, and the 1-naphthalene sulfonic aicd of the inventive method preparation and/or the contained isomer of 1-naphthalene sulfonic aicd sodium salt are still less, the 1-naphthols purity height that obtains behind the sulfonation alkali fusion, contained impurity beta naphthal is few.
Technical scheme
It is sulphonating agent that the present invention adopts chlorsulfonic acid, carries out sulfonation reaction at low temperatures with preparation 1-naphthalene sulfonic aicd and/or 1-naphthalene sulfonic aicd sodium salt.
One of purpose of the present invention is to provide a kind of preparation method of 1-naphthalene sulfonic aicd, and concrete technical scheme is as follows:
A kind of preparation method of 1-naphthalene sulfonic aicd, this method may further comprise the steps:
Sulfonation: add naphthalene in the organic solvent and it dissolved fully, add the 1-naphthalene sulfonic aicd crystal seed, be cooled to 0 ℃ ± 5 ℃ after, under negative pressure, drip chlorsulfonic acid while stirring, drip off in 1-2 hour, be added dropwise to complete the back and under-2 ℃～8 ℃, keep reaction 1.5-3 hour; Count naphthalene: chlorsulfonic acid: solvent=1: 1.01～1.10: 3.0～3.5 in molar ratio; The quantity that adds the 1-naphthalene sulfonic aicd crystal seed accounts for 0.5%～1.5% (weight percent) of naphthalene;
Filter: above-mentioned sulfonated liquid is cooled to below 0 ± 2 ℃ filters, the gained filter cake is 1-naphthalene sulfonic aicd.
In described sulfonation procedure, organic solvent can adopt common solvent such as oil of mirbane, o-nitroethylbenzene, orthodichlorobenzene or ethylene dichloride.Why adding an amount of crystal seed in the sulfonation reaction raw material, is in order to make the resulting 1-naphthalene sulfonic aicd of sulfonation can be in reaction process, and limit coronite crystallization is separated out reposefully.Existing chlorsulfonic acid sulfonation prepares in the method for 1-naphthalene sulfonic aicd, carrying out along with sulfonation reaction, 1-naphthalene sulfonic aicd constantly generates, when the concentration of the 1-naphthalene sulfonic aicd in the solvent reaches a threshold value, can concentrate and separate out, the hurried heat release of 1-naphthalene sulfonic aicd crystallisation process meeting, the fluctuation of the temperature that induces reaction, cause the sulfonation reaction selectivity to descend, 2-naphthene sulfonic acid isomer increases, and a large amount of 1-naphthalene sulfonic aicd crystal is concentrated and separated out, can influence the flowability of sulfonation reaction material, under extreme case, even cause sulfonation reaction material ramming material, make this reaction to carry out.After adding the 1-naphthalene sulfonic aicd crystal seed, the 1-naphthalene sulfonic aicd that sulfonation generates can progressively be separated out reposefully, helps the control reaction temperature fluctuation, improve the selectivity of 1-naphthalene sulfonic aicd, and operation is more easy to control.For guaranteeing that sulfonation reaction carries out at low temperatures, the sulfonation reaction still can adopt cryosel to bathe or the chilled brine cooling; In the dropping process,, make temperature of reaction maintain-2 ℃～8 ℃ by the rate of addition of control chlorsulfonic acid.The hydrogen chloride gas that reaction is generated excludes in the reaction system by vacuum, and a pair product hydrochloric acid is made in absorption.Chlorsulfonic acid and organism under optimum conditions almost can quantitative reactions, so the present invention carries out sulfonation reaction with excessive slightly chlorsulfonic acid and naphthalene, count naphthalene: chlorsulfonic acid=1: 1.01～1.10 in molar ratio; Preferable range is a naphthalene: chlorsulfonic acid=1: 1.01～1.05.
Filtering method is isolated 1-naphthalene sulfonic aicd under the inventive method employing low temperature.Sulfonated liquid is cooled to 0 ± 2 ℃ of filtration, and the filter cake that obtains is purpose product 1-naphthalene sulfonic aicd.Gained filtrate can recycling, and method is: gained filtrate is added water, be warming up to 80 ℃, and after keeping 5-15 minute under 80 ℃ ± 5 ℃, standing demix is 30～60 minutes in phase splitter; Lower floor is washing acid, can be used for producing naphthalene series high-efficiency water-reducing agent after the concentrated transposition that heats up; Upper organic phase is a solvent, contain the naphthalene of complete reaction not and do not wash most naphthene sulfonic acid on a small quantity, can be used as the recovery solvent and apply mechanically in sulfonation reaction, or be used for neutralization procedure in producing the 1-naphthalene sulfonic aicd sodium salt thereafter, naphthene sulfonic acid wherein can generate 1-naphthalene sulfonic aicd sodium with alkali generation neutralization reaction.
Can further prepare the 1-naphthalene sulfonic aicd sodium salt as the prepared 1-naphthalene sulfonic aicd of above-mentioned method, be used for the production of 1-naphthols.The invention still further relates to a kind of preparation method of 1-naphthalene sulfonic aicd sodium salt, this method may further comprise the steps:
Make and from sulfonated liquid, isolate 1-naphthalene sulfonic aicd as stated above;
Separated from solvent: sulfonated liquid is filtered gained filtrate add water, be warming up to 80 ℃, and stirring is after 5-15 minute down at 80 ℃ ± 5 ℃, standing demix is 30～60 minutes in phase splitter, and upper organic phase is a solvent, and lower floor is washing acid;
Neutralization: it is in 5%～15% the NaOH solution that the filter cake that sulfonated liquid is filtered gained is dissolved in concentration, add the resulting upper organic phase of separated from solvent step, stirring is warming up to 90 ℃ and keep at 90 ℃ ± 5 ℃ and to carry out neutralization reaction in 10～30 minutes, neutralized reaction product leaves standstill after 5-30 minute and separates in phase splitter under 90 ℃ ± 5 ℃ heat-retaining conditions; The upper strata is an organic layer, and lower floor is the 1-naphthalene sulfonic aicd sodium-salt aqueous solution;
Crystallization Separation: lower floor's 1-naphthalene sulfonic aicd sodium-salt aqueous solution is cooled to≤35 ℃ of following crystallizations, separates after the crystallization, obtain the 1-naphthalene sulfonic aicd sodium salt.
Prepare the 1-naphthalene sulfonic aicd sodium salt by the present invention, not that sulfonated liquid is directly carried out neutralization reaction, but earlier the sulfonated liquid crystallization is filtered, isolate 1-naphthalene sulfonic aicd and go processing such as neutralization again, can effectively remove the impurity in the sulfonation reaction liquid, the 1-naphthalene sulfonic aicd sodium salt impurity that obtains is few, and purity is higher, can improve the quality of products in order to produce the 1-naphthols.And the filtrate behind the separation 1-naphthalene sulfonic aicd can be recycled after the separated from solvent step process, filter 1-naphthalene sulfonic aicd institute filtrate, add the water back of heating up and stir, the consumption of recommendation water is that by chlorsulfonic acid, mol ratio is a water: chlorsulfonic acid=3～5: 1; Isolated upper strata solvent behind the standing demix neutralizes in the adding NaOH solution in neutralization procedure in the lump, and naphthene sulfonic acid wherein can generate 1-naphthalene sulfonic aicd sodium with alkali generation neutralization reaction; Lower floor's washing acid after the separation is used to produce naphthalene series high-efficiency water-reducing agent.5%～15% NaOH solution is adopted in neutralization, can add the water preparation by NaOH, or adds NaOH and water preparation by the mother liquor that next step Crystallization Separation produced.Neutralized reaction product is after separating, and upper organic phase is the solvent that contains a small amount of naphthalene, can add anhydrous Na
2SO
4After carrying out processed, recycled in the sulfonation reaction step.Behind lower floor's 1-naphthalene sulfonic aicd sodium-salt aqueous solution crystallisation by cooling, separate with methods such as vacuum suction filter or centrifugations, the gained filter cake is the 1-naphthalene sulfonic aicd sodium salt, can produce the 1-naphthols through alkali fusion, acidifying; The mother liquor of filtration gained can add alkali and/or water is mixed with NaOH solution, at the neutralization procedure recycled.
Beneficial effect
It is sulphonating agent that the present invention adopts chlorsulfonic acid, in the process of preparation 1-naphthalene sulfonic aicd and/or 1-naphthalene sulfonic aicd sodium salt, no waste water produces, and the hydrogen chloride gas physical efficiency of generation is absorbed well, make to pay and produce technical hydrochloric acid, a spot of washing acid can be used to make high-quality and efficient naphthalene water reducer.
Sulfonation reaction of the present invention is steady, and is easy to control, can ramming material; And 1-naphthalene sulfonic aicd selectivity height, in 1-naphthalene sulfonic aicd of making and/or the 1-naphthalene sulfonic aicd sodium salt, isomer 2-naphthene sulfonic acid and/or 2-sodium naphthalene sulfonate salts contg are low, 1-naphthol content 〉=99% that makes after alkali fusion, acidifying, beta naphthal content≤1%; And according to processing method of the present invention, solvent for use can be recycled effectively, has improved yield, has saved solvent load, can realize suitability for industrialized production.
Describe the present invention below in conjunction with embodiment.Scope of the present invention is not exceeded with embodiment, but is limited by the scope of claim.
Embodiment
Embodiment 1
Embodiment 1 produces 1-naphthalene sulfonic aicd by the present invention.
100 gram (0.78 mole) refined naphthalenes and 380 gram (2.52 moles) o-nitroethylbenzenes are added have in the 500mL ground four-hole boiling flask of stirring, flask places cryosel to bathe cooling, after starting agitator refined naphthalene being dissolved fully, adds 1 gram 1-naphthalene sulfonic aicd crystal seed.92 gram (0.79 mole) chlorsulfonic acids are added in the dropping funnel, and place on the charging opening of four-hole boiling flask.Flask is connected water towards pump and open, make to be negative pressure state in the flask.When solution temperature in the flask reaches 0 ℃, begin to drip chlorsulfonic acid, in 1-2 hour, drip off.In the dropping process by the rate of addition of control chlorsulfonic acid, keep temperature be-2--3 ℃ between.Keep temperature of reaction-2 ℃ after being added dropwise to complete--3 ℃, keep reaction 2-3 hour.The hydrogen chloride gas that produces in the reaction process is taken out of towards the negative pressure that pump produces by water, and water absorbs.
After reaction finishes, be cooled to filter below 0 ℃.Obtain filter cake 156 grams (containing a small amount of solvent), be 1-naphthalene sulfonic aicd, can be used for further neutralizing, produce the 1-naphthalene sulfonic aicd sodium salt.
Filtrate places the 500mL flask, adds 50mL water, heats to 80 ℃ while stirring, keep 5-15 minute after, in the 500mL separating funnel, leave standstill layering in 30 minutes, tell the upper strata organic solvent mutually and lower floor's washing sour.
Embodiment 2
Embodiment 2 usefulness embodiment 1 resulting-naphthene sulfonic acid is produced the 1-naphthalene sulfonic aicd sodium salt.
In flask, it is dissolving in 10% NaOH solution 400 grams that 1-naphthalene sulfonic aicd filter cake among the embodiment 1 is added the concentration prepare, add above-mentioned sulfonated liquid and filter the resulting organic phase of rear filtrate layering, stirring is warming up to 90 ℃, and keep at 90 ℃～95 ℃ and to carry out neutralization reaction in 10 minutes, neutralizer is poured in the 1000mL separating funnel.
Neutralizer in the separating funnel 90 ℃ of insulations, leaves standstill after 10 minutes and separates; Lower floor is the 1-naphthalene sulfonic aicd sodium-salt aqueous solution, divides to go in the 1000mL beaker; The upper strata is an organic layer, divides to go in the beaker, adds 25 gram anhydrous Na
2SO
4Carry out processed, reclaim o-nitroethylbenzene 367 grams, can be at the sulfonation procedure recycled.
The beaker that the 1-naphthalene sulfonic aicd sodium-salt aqueous solution is housed is put into cryosel bathe, be cooled to 30 ℃ of crystallizations, the 1-naphthalene sulfonic aicd sodium salt is separated out the final vacuum suction strainer, and the gained filter cake is the 1-naphthalene sulfonic aicd sodium salt, 203 grams (moisture) of weighing.
Embodiment 3
Embodiment 3 other conditions are identical with embodiment 1, and different is, in embodiment 3, drip 95.5 gram (0.82 mole) chlorsulfonic acids and carry out sulfonation reaction, and in the dropping process and during reaction keeps, controlled temperature is between 3--8 ℃.Obtain 1-naphthalene sulfonic aicd filter cake 162 grams (containing a small amount of solvent).
Embodiment 4
Take by weighing refined naphthalene 87 grams, o-nitroethylbenzene solvent 367 grams that o-nitroethylbenzene 20 grams and embodiment 2 are reclaimed, adding has in the 500mL ground four-hole boiling flask of stirring together, and other processes obtain 1-naphthalene sulfonic aicd filter cake 185 grams (containing a small amount of solvent) with embodiment 1.
The 1-naphthalene sulfonic aicd filter cake is added that sulfonated liquid filters the resulting organic phase of rear filtrate layering and adds in the lump in the NaOH solution and neutralize, described NaOH strength of solution is 7%, consumption is 580 grams, with the mother liquor preparation of gained behind the 1-naphthalene sulfonic aicd sodium-salt aqueous solution vacuum suction filter among the embodiment 2.Press embodiment 2 described methods, 90 ℃～95 ℃ keep carried out neutralization reaction in 15 minutes after, isolate water, be cooled to 25 ℃ of crystallizations, vacuum suction filter gets 1-naphthalene sulfonic aicd sodium salt 236 gram (moisture).
Embodiment 5
With embodiment 2 and 4 resulting 1-naphthalene sulfonic aicd sodium salt meter 439 grams (moisture), carry out alkali fusion, acidifying by existing method, make 1-naphthols 169 grams.By analysis, its purity of finished product 1-naphthols is 99.2%, and beta naphthal content is 0.70%.
Claims (6)
1, a kind of preparation method of 1-naphthalene sulfonic aicd, this method may further comprise the steps:
Sulfonation: add naphthalene in the organic solvent and it dissolved fully, add the 1-naphthalene sulfonic aicd crystal seed, be cooled to 0 ℃ ± 5 ℃ after, under negative pressure, drip chlorsulfonic acid while stirring, drip off in 1-2 hour, be added dropwise to complete the back and under-2 ℃～8 ℃, keep reaction 1.5-3 hour; Count naphthalene: chlorsulfonic acid: solvent=1: 1.01～1.10: 3.0～3.5 in molar ratio; Add the quantity of 1-naphthalene sulfonic aicd crystal seed, by weight percentage, account for 0.5%～1.5% of naphthalene;
Filter: above-mentioned sulfonated liquid is cooled to 0 ± 2 ℃ of filtration, and the gained filter cake is 1-naphthalene sulfonic aicd.
2, the preparation method of 1-naphthalene sulfonic aicd according to claim 1 is characterized in that counting in molar ratio naphthalene: chlorsulfonic acid=1: 1.01～1.05.
3, the preparation method of 1-naphthalene sulfonic aicd according to claim 1 and 2 is characterized in that described organic solvent is an o-nitroethylbenzene.
4, a kind of preparation method of 1-naphthalene sulfonic aicd sodium salt, this method may further comprise the steps:
Produce and from sulfonated liquid, isolate 1-naphthalene sulfonic aicd by the described method of claim 1;
Separated from solvent: sulfonated liquid is filtered gained filtrate add water and be warming up to 80 ℃, and stirring is after 5-15 minute down at 80 ℃ ± 5 ℃, standing demix is 30～60 minutes in phase splitter, and upper organic phase is a solvent, and lower floor is washing acid;
Neutralization: it is in 5%～15% the NaOH solution that the filter cake that sulfonated liquid is filtered gained is dissolved in concentration, add the resulting upper organic phase of separated from solvent step, stirring is warming up to 90 ℃ and keep at 90 ℃ ± 5 ℃ and to carry out neutralization reaction in 10～30 minutes, neutralized reaction product leaves standstill after 5-30 minute and separates in phase splitter under 90 ℃ ± 5 ℃ heat-retaining conditions; The upper strata is an organic layer, and lower floor is the 1-naphthalene sulfonic aicd sodium-salt aqueous solution;
Crystallization Separation: lower floor's 1-naphthalene sulfonic aicd sodium-salt aqueous solution is cooled to≤35 ℃ of following crystallizations, separates after the crystallization, obtain the 1-naphthalene sulfonic aicd sodium salt.
5, the preparation method of 1-naphthalene sulfonic aicd sodium salt according to claim 4 is characterized in that neutralized reaction product after separating, and upper organic phase adds anhydrous Na
2SO
4After carrying out processed, in the sulfonation reaction step, use as solvent cycle.
6, the preparation method of 1-naphthalene sulfonic aicd sodium salt according to claim 4 is characterized in that the crystallization of 1-naphthalene sulfonic aicd sodium-salt aqueous solution filters the mother liquor of gained, adds alkali and/or water and is mixed with NaOH solution, recycles at neutralization procedure.
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| CN102993060B (en) * | 2012-07-30 | 2014-07-30 | 枣庄市泰瑞精细化工有限公司 | Preparation method of 1,6-naphthalenedisulfonic acid disodium salt |
| CN103304450A (en) * | 2013-06-14 | 2013-09-18 | 杨锌荣 | Alkyl naphthalene polysulfonate and preparation method thereof |
| CN106146356B (en) * | 2016-07-01 | 2018-07-20 | 宁夏紫光川庆化工有限公司 | The method of continuous production 1-naphthalene sulfonic aicd |
| CN107674006A (en) * | 2017-09-11 | 2018-02-09 | 天津大学 | A kind of preparation method of 2 sodium naphthalene sulfonate |
| 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 |
| CN113698323B (en) * | 2021-09-02 | 2023-09-05 | 昌邑瑞新化学工业有限公司 | Method for producing tobias acid by reducing yield of acid precipitation mother liquor wastewater |
| CN115626883A (en) * | 2022-09-30 | 2023-01-20 | 安徽生源化工有限公司 | Microwave preparation method of naphthalene sulfonic acid |
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