CN108707094A - A kind of synthesis of 2,6- naphthalenedisulfonic acids and the method for purification - Google Patents
A kind of synthesis of 2,6- naphthalenedisulfonic acids and the method for purification Download PDFInfo
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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
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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Abstract
The method of the synthesis and purification of one kind 2,6- naphthalenedisulfonic acids, includes the following steps：1) sulfonation, dissolved：Refined naphthalene and concentrated sulfuric acid heating are subjected to sulfonating reaction, generate 2,6- naphthalenedisulfonic acids and 2,7- naphthalenedisulfonic acids add water-soluble analysis, filtering, obtain 2,6- naphthalenedisulfonic acids filter cake and 2,7- naphthalenedisulfonic acid mother liquors；2) it washs：It is the ammonium hydroxide of 8-20%% or the ammonium sulfate solution of 15-28%% as washing reagent using mass fraction, to 2,6- naphthalenedisulfonic acid filter cakes are washed, obtain 1 grade 2,6- naphthalenedisulfonic acids filter cake and 1 grade of refined filtrate so recycle 2,6- naphthalenedisulfonic acids filter cake washing 2~4 times, obtain 2, the 6- naphthalenedisulfonic acid products that purity is more than 99%；3) cleaning solution is applied mechanically：1 grade of refined filtrate returns to set for the dissolved process of step 1) and/or the washing procedure of step 2), remaining refined filtrate returns to washing procedure of the set for step 2).The present invention realizes separation and purification purification and obtains high-quality 2,6- naphthalenedisulfonic acids, improves the yield of 2,7- naphthalenedisulfonic acids and reduce the purpose of discharge of wastewater.
Description
(1) technical field
The invention belongs to organic synthesis fields, and in particular to one kind synthesis of 2,6- naphthalenedisulfonic acids and the side of purification
Method.
(2) background technology
2,6- naphthalenedisulfonic acids are a kind of important chemical intermediates, are mainly used in dyestuff, medicine and concrete additive.
For example, it synthesizes 2,6- naphthalenedisulfonic acid dihydroxy naphthlenes by alkali fusion, the added value of product is high and wide market, fiber,
Packing container, electronic component, dyestuff and medicine and other fields have a wide range of applications, and especially prepare various polyester materials and liquid
The important monomer of brilliant polyester resin.For another example, part alkali fusion can be carried out by controlling reaction condition and generates Xue Shi salt, and Xue Shi salt
It is a kind of raw material mainly for the manufacture of dyestuffs such as acid blue, acid bordeaux, edible bright red, food coloring sunset yellows.For another example, exist
In naphthalene water reducer production process, it is proportionally added into 2,6- naphthalenedisulfonic acids and formaldehyde progress condensation reaction is added dropwise, because it carries two
A sulfonic acid group and all at β is easily condensed with formaldehyde and beta-naphthalenesulfonic-acid, and synthesized water-reducing agent is made to have higher diminishing
Rate.
The preparation method of current 2,6- naphthalenedisulfonic acids is mainly addition water and p-phenylenediamine after naphthalene and concentrated sulfuric acid heating reaction
So that its precipitation is obtained solid, 2,6- naphthalenes two are obtained after the sequence of operations such as being further dried, grind, being filtered, washed and recrystallizing
Sulfonic acid finished product, but the method production technology is more complex.Patent CN101412685A is disclosed using sodium chloride crystallization 2,6- naphthalenes two
The method of sulfonic acid, but sodium chloride is higher to process equipment requirement；Patent CN101412686A is disclosed using sodium sulphate essence
The method for making 2,6- naphthalenedisulfonic acids, but sodium sulphate solubility in room temperature is relatively low；And the 2,6- naphthalenedisulfonic acids in above-mentioned technique
Solid purity about 90% (liquid chromatogram purity) cannot all reach the requirement of high-quality product, and be used in above-mentioned technique big
The inorganic salts of amount saltout refined, and the wastewater flow rate of generation is big, difficult.
Shenyang Chemical Engineering Inst proposes that the fuming acid of the fuming acid of naphthalene and the concentrated sulfuric acid/20%/65% generates under certain conditions
2,6- naphthalenedisulfonic acids and 2,7- naphthalenedisulfonic acids obtain the filter cake based on 2,6- naphthalenedisulfonic acids and 2,7- naphthalenes two by adding water-soluble analysis
Mother liquor based on sulfonic acid, wherein 2,7- naphthalenedisulfonic acids can be used for preparing important color-forming intermediate H acids, but the filter cake 2 of gained,
6- naphthalenedisulfonic acid purity is relatively low, and impurity is more, and wherein main residues are 2,7- naphthalenedisulfonic acids, are unfavorable for opening for subsequent product
Hair.
Therefore, how efficiently to detach, purify 2,6- naphthalenedisulfonic acids and 2 in filter cake, 7- naphthalenedisulfonic acids increase 2,7- naphthalenes
The yield of disulfonic acid, it is the key factor of this technique to reduce discharge of wastewater and produce 2, the 6- naphthalenedisulfonic acid products of high-quality.
(3) invention content
The technical problem to be solved in the present invention is to provide the method for the synthesis and purification of one kind 2,6- naphthalenedisulfonic acids, with
Reach separation and purification purification to obtain high-quality 2,6- naphthalenedisulfonic acids, improve the yield of 2,7- naphthalenedisulfonic acids and reduce discharge of wastewater
Purpose.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
The method of the synthesis and purification of one kind 2,6- naphthalenedisulfonic acids, includes the following steps：
1) sulfonation, dissolved
Refined naphthalene and concentrated sulfuric acid heating are subjected to sulfonating reaction, generate 2,6- naphthalenedisulfonic acids and 2,7- naphthalenedisulfonic acids add water-soluble
Analysis, filtering, obtain 2,6- naphthalenedisulfonic acids filter cake and 2,7- naphthalenedisulfonic acid mother liquors；
2) it washs
It is the ammonium hydroxide of 8-20%% or the ammonium sulfate solution of 15-28%% as washing reagent using mass fraction, to 2,
6- naphthalenedisulfonic acid filter cakes are washed, and 1 grade of 2,6- naphthalenedisulfonic acids filter cake and 1 grade of refined filtrate are obtained, and are filtered to 2,6- naphthalenedisulfonic acids
Cake so recycles washing 2~4 times, obtains 2, the 6- naphthalenedisulfonic acid products that purity is more than 99%；
3) cleaning solution is applied mechanically
1 grade of refined filtrate returns to set for the dissolved process of step 1) and/or the washers of step 2) as washing reagent
Sequence, remaining refined filtrate returns to washing procedure of the set for step 2) as washing reagent, to recycle 2,6- naphthalenes, two sulphur therein
Acid and 2,7- naphthalenedisulfonic acids；
Further, in step 1), refined naphthalene is 1 with sulfuric acid molar ratio:3.5~6.5 (preferably 1:4.5~5.5), reaction temperature
Degree is 130~190 DEG C (preferably 150~180 DEG C), and soaking time is 5~15h (preferably 5~8h), and liquid chromatographic detection is aobvious
Show that raw material refined naphthalene reacts completely.
Further, step 1) after the sulfonation reaction is complete, recommends to operate as follows：System temperature is down to 40~
120 DEG C (preferably 50~100 DEG C), add water regulation system acidity (acidity of the present invention is in terms of the mass fraction of sulfuric acid) to 30~60%
(preferably 35~50%), and further 0.5~4h of heat preservation (preferably 1~2h) are then separated by filtration to obtain the filter of 2,6- naphthalenedisulfonic acids
Cake and 2,7- naphthalenedisulfonic acid mother liquors.2,7- naphthalenedisulfonic acid mother liquors can be used for subsequently nitrifying, hydrogen and hydrolysis added to prepare H acid.
Further, in step 2), the mass ratio of 2,6- naphthalenedisulfonic acid filter cakes and washing reagent is 1:1~5, preferably 1:3~
5。
Further, in step 3), 1 grade of refined filtrate returns to set and is used for 2 in the dissolved process and/or step 2) of step 1),
The washing procedure of 6- naphthalenedisulfonic acid filter cakes, N grades of refined filtrates return to set and are used for N-1 grades 2 in step 2), 6- naphthalenedisulfonic acid filter cakes
Washing procedure, wherein N >=2, final stage refine filter cake and use mass fraction water-soluble for the ammonium sulfate of the ammonium hydroxide of 8-20% or 15-28%
Liquid is washed.
Further, in step 2), washing 3 times is preferably so recycled to 2,6- naphthalenedisulfonic acids filter cake.
The present invention is based on the characteristic of different solubility of the naphthalene sulfonated bodies in different inorganic salt solutions, using being easy to industry
The weak aqua ammonia or ammonium sulfate pair 2 of change, 6- naphthalenedisulfonic acid filter cakes carry out multi-stage countercurrent washing, obtain high-quality 2, two sulphur of 6- naphthalenes
Acid, and 2, the 7- naphthalenedisulfonic acids in filter cake have effectively been recycled, the once through yield of 2,7- naphthalenedisulfonic acids is improved, and realize useless
Water zero discharge reduces sewage disposal expense, to achieve the purpose that substance efficiently, clean separation.Specifically, the present invention
Advantage is as follows：
1, the high-quality 2,6- naphthalenes that purity is more than 99% are refining to obtain the washing of filter cake by inorganic salt solution or ammonium hydroxide
Disulfonic acid product.
2, during washing is refined, safe and non-toxic, cheap inorganic salt solution or ammonia solvent 2,6- naphthalenedisulfonic acids are selected
Crude product stirs evenly, and 2,6- naphthalenedisulfonic acids are precipitated in the form of recrystallization, and this method is easy to operate, easily realizes industrialization, increases
Production efficiency, saves entreprise cost.
3,2,6- naphthalenedisulfonic acids refine filtrate set for naphthalene sulfonated products (2,6- naphthalenedisulfonic acids and 2,7- naphthalenes in dissolved process
Disulfonic acid) separation, effectively recycled 2, the 7- naphthalenedisulfonic acids in filter cake, improved its once through yield, increase enterprise profit.
4,2,6- naphthalenedisulfonic acids multistage, which refines filtrate, realizes recycled, has saved water resource, and additional without generating
Waste water, solve the problems, such as discharging of waste liquid, save treatment cost of waste liquor, realize the environmentally protective purpose of technique.
(4) it illustrates
Fig. 1 is a kind of process flow chart of the synthesis of 2,6- naphthalenedisulfonic acids of the present invention and the method for purification.
(5) specific implementation mode
With reference to embodiment, the invention will be further described, and but this invention is by no means limited to this.
Embodiment 1：
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 175 DEG C, heat preservation is anti-
5h is answered, is cooled to 80 DEG C after reaction.
805.80Kg water is added into sulfonation material, controls time for adding 1.5h, stirs 2h after being added dropwise, be separated by filtration
To hundred weight 647.61Kg 2 of folding, the filter cake based on 6- naphthalenedisulfonic acids, wherein in filter cake containing 79.21% 2,6- naphthalenedisulfonic acids and
13.29% 2,7- naphthalenedisulfonic acids.
2) it washs
The ammonium sulfate (ammonium sulfate mass content 27.27%) of 2609.46Kg is added in reaction kettle, stirring is lower to be added
Enter hundred weight 647.61Kg 2 of folding, the filter cake based on 6- naphthalenedisulfonic acids, mixing time 2h is separated by filtration to obtain 1 grade of 2,6- naphthalenes, two sulphur
Filter cake based on acid, rolls over hundred heavy 632.18Kg, and 1 grade of refined filtrate 1488.69Kg set is produced for dissolved process naphthalene sulfonation next time
The separation of object.Continue ammonium sulfate (the ammonium sulfate mass content of filter cake and 1000Kg based on 1 grade of 2,6- naphthalenedisulfonic acid
15%) it is mixed evenly, mixing time 2h, is separated by filtration to obtain the filter cake based on 2 grades of 2,6- naphthalenedisulfonic acids, 2 grades of refined filters
Liquid 1192.26Kg continues set for 1 grade of washing of 2,6- naphthalenedisulfonic acids next time；Continue 2 grades of 2,6- naphthalenedisulfonic acids filter cakes and
The ammonium sulfate (ammonium sulfate mass content 15%) of 925.24Kg carries out 3 grades of washings, 3 grades of 2,6- naphthalenedisulfonic acids production after separation
Product pass through liquid-phase chromatographic analysis (area normalization method), and content 99.76% rolls over hundred heavy 621.37Kg, 3 grades of refined filtrates
1018.49Kg continues set for 2 grades of washings of 2,6- naphthalenedisulfonic acids filter cake next time.
Embodiment 1a
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 175 DEG C, heat preservation is anti-
5h is answered, is cooled to 80 DEG C after reaction.The level-one that embodiment 1 obtains is added into sulfonation material and refines filtrate 1488.69Kg (its
In 2, the 7- naphthalenedisulfonic acids containing 20.65% 2,6- naphthalenedisulfonic acids and 60.23%), control time for adding 1.5h, be added dropwise
After stir 2h, be separated by filtration to obtain hundred weight 654.94Kg 2 of folding, the filter cake based on 6- naphthalenedisulfonic acids wherein contains in filter cake
81.12% 2,6- naphthalenedisulfonic acids and 10.76% 2,7- naphthalenedisulfonic acids, level-one of the set for sulfonated products separation refine filtrate
51.52% 2,7- naphthalenedisulfonic acids, make 2,7- naphthalenedisulfonic acid ultimate yields improve 5.24% effectively in recycling filter cake.
2) it washs
The level-one obtained according to 1 method of embodiment is refined into filtrate 1120.77Kg, two level refines filtrate 1192.26Kg and
Ammonium sulfate 296.43Kg after mixing, is added in reaction kettle, is added with stirring 2,6- naphthalenes, two sulphur of hundred weight 654.94Kg of folding
Filter cake based on acid, mixing time 2h are separated by filtration to obtain the filter cake based on 1 grade of 2,6- naphthalenedisulfonic acid, roll over hundred heavy 643.46Kg,
1 grade of refined filtrate 1488.69Kg continues separation of the set for naphthalene sulfonated products in next dissolved process.Continue 1 grade of 2,6- naphthalene
The three-level that disulfonic acid filter cake and embodiment 1 obtain refines filtrate 1018.49Kg and is mixed evenly, mixing time 2h, filtering point
From the filter cake based on 2 grades of 2,6- naphthalenedisulfonic acids is obtained, 2 grades of refined filtrate 1192.26Kg continue set for 2,6- naphthalenes two next time
1 grade of washing of sulfonic acid；Continue 2 grades of 2,6- naphthalenedisulfonic acid filter cakes carrying out 3 grades of washings, the ammonium sulfate of three-level washing 1192.26Kg
Solution (ammonium sulfate mass content 15%), 3 grades of 2,6- naphthalenedisulfonic acid products after separation pass through liquid-phase chromatographic analysis (area normalization
Method), content 99.54% rolls over hundred heavy 639.75Kg, and 3 grades of refined filtrate 1018.49Kg continue to apply mechanically 2,6- naphthalenes, two sulphur next time
The 2 grades of washings of acidleach cake.
Embodiment 2：
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 165 DEG C, heat preservation is anti-
6.5h is answered, is cooled to 90 DEG C after reaction.
805.80Kg water is added into sulfonation material, controls time for adding 2h, stirs 2h after being added dropwise, be separated by filtration to obtain
Roll over the filter cake based on hundred heavy 651.22Kg 2,6- naphthalenedisulfonic acids.Wherein in filter cake containing 78.88% 2,6- naphthalenedisulfonic acids and
13.49% 2,7- naphthalenedisulfonic acids.
2) it washs
The ammonia spirit (mass content 17%) of 2544.30Kg is added in reaction kettle, hundred weights of folding are added with stirring
Filter cake based on 651.22Kg 2,6- naphthalenedisulfonic acid, mixing time 2h are separated by filtration to obtain based on 1 grade of 2,6- naphthalenedisulfonic acid
Filter cake rolls over hundred heavy 634.52Kg, point of 1 grade of refined filtrate 1160.60Kg set for naphthalene sulfonated products in dissolved process next time
From.Continue the ammonia spirit (mass content 10%) of 1 grade of 2,6- naphthalenedisulfonic acids filter cake and 1000Kg being mixed evenly, stir
Time 2h, is separated by filtration to obtain the filter cake based on 2 grades of 2,6- naphthalenedisulfonic acids, and 2 grades of refined filtrate 1058.26Kg continue set and are used for down
The 1 grade of washing of 2,6- naphthalenedisulfonic acid；Continue the ammonia spirit (content by 2 grades of 2,6- naphthalenedisulfonic acids filter cakes and 946.17Kg
10%) 3 grades of washings are carried out, 3 grades of 2,6- naphthalenedisulfonic acid products after separation pass through liquid-phase chromatographic analysis (area normalization method), content
It is 99.57%, rolls over hundred heavy 630.14Kg, 3 grades of refined filtrate 1098.59Kg continues set for 2,6- naphthalenedisulfonic acids filter cake next time
2 grades of washings.
Embodiment 2a
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 165 DEG C, heat preservation is anti-
6.5h is answered, is cooled to 90 DEG C after reaction.The level-one that embodiment 2 obtains is added into sulfonation material and refines filtrate 1160.60Kg
(wherein 2, the 7- naphthalenedisulfonic acids containing 19.46% 2,6- naphthalenedisulfonic acids and 61.26%) controls time for adding 2h, drips
2h is stirred after finishing, is separated by filtration to obtain hundred weight 655.45Kg 2 of folding, the filter cake based on 6- naphthalenedisulfonic acids wherein contains in filter cake
80.05% 2,6- naphthalenedisulfonic acids and 11.87% 2,7- naphthalenedisulfonic acids, level-one of the set for sulfonated products separation refine filtrate
42.57% 2,7- naphthalenedisulfonic acids, make 2,7- naphthalenedisulfonic acid ultimate yields improve 4.68% effectively in recycling filter cake.
2) it washs
The level-one obtained according to 2 method of embodiment is refined into filtrate 1547.19Kg, two level refines filtrate 1058.26Kg and
Ammonium hydroxide (mass content 17%) 104.96Kg after mixing, is added in reaction kettle, is added with stirring hundred heavy 655.45Kg of folding
Filter cake based on 2,6- naphthalenedisulfonic acids, mixing time 2h are separated by filtration to obtain the filter cake based on 1 grade of 2,6- naphthalenedisulfonic acid, folding hundred
Weight 644.14Kg, 1 grade of refined filtrate 1160.60Kg continue separation of the set for naphthalene sulfonated products in next dissolved process.Continue
The three-level that 1 grade of 2,6- naphthalenedisulfonic acids filter cake and embodiment 2 obtain is refined filtrate 1098.59Kg to be mixed evenly, when stirring
Between 2h, be separated by filtration to obtain the filter cake based on 2 grades of 2,6- naphthalenedisulfonic acids, 2 grades of refined filtrate 1058.26Kg continue set for next
The 1 grade of washing of secondary 2,6- naphthalenedisulfonic acids；Continue 2 grades of 2,6- naphthalenedisulfonic acid filter cakes carrying out 3 grades of washings, three-level washing is used
The ammonia spirit (mass content 15%) of 1055.64Kg, 3 grades of 2,6- naphthalenedisulfonic acid products after separation pass through liquid-phase chromatographic analysis
(area normalization method), content 99.43% roll over hundred heavy 640.21Kg, and 3 grades of refined filtrate 1098.59Kg continue set for next
The 2 grades of washings of secondary 2,6- naphthalenedisulfonic acids filter cake.
Embodiment 3：
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 155 DEG C, heat preservation is anti-
8h is answered, is cooled to 100 DEG C after reaction.
805.80Kg water is added into sulfonation material, controls time for adding 1.5h, stirs 2h after being added dropwise, be separated by filtration
To hundred weight 650.72Kg 2 of folding, the filter cake based on 6- naphthalenedisulfonic acids, wherein in filter cake containing 82.12% 2,6- naphthalenedisulfonic acids and
10.48% 2,7- naphthalenedisulfonic acids.
2) it washs
The ammonium sulfate (mass content 22%) of 3057.00Kg is added in reaction kettle, hundred weights of folding are added with stirring
Filter cake based on 650.72Kg 2,6- naphthalenedisulfonic acid, mixing time 2h are separated by filtration to obtain based on 1 grade of 2,6- naphthalenedisulfonic acid
Filter cake, rolls over hundred heavy 631.46Kg, and 1 grade of refined filtrate 2029.82Kg set is detached for naphthalene sulfonated products next time.Continue 1 grade
The ammonium sulfate (mass content 17%) of 2,6- naphthalenedisulfonic acid filter cakes and 1000Kg are mixed evenly, mixing time 2h, mistake
The filter cake based on isolated 2 grades of 2,6- naphthalenedisulfonic acids is filtered, 2 grades of refined filtrate 1142.31Kg continue set for next time 2,6-
1 grade of washing of naphthalenedisulfonic acid；Continue the ammonium sulfate (mass content 17%) by 2 grades of 2,6- naphthalenedisulfonic acids filter cakes and 901.46Kg
3 grades of washings are carried out, 3 grades of 2,6- naphthalenedisulfonic acid products after separation pass through liquid-phase chromatographic analysis (area normalization method), and content is
99.72%, hundred heavy 627.46Kg are rolled over, 3 grades of refined filtrate 1118.49Kg continue set for 2,6- naphthalenedisulfonic acids filter cake 2 next time
Grade washing.
Embodiment 3a
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 155 DEG C, heat preservation is anti-
8h is answered, is cooled to 100 DEG C after reaction.The level-one that embodiment 3 obtains is added into sulfonation material and refines filtrate 2029.82Kg
(wherein 2, the 7- naphthalenedisulfonic acids containing 21.23% 2,6- naphthalenedisulfonic acids and 59.46%) controls time for adding 1.5h, is added dropwise
After stir 2h, be separated by filtration to obtain hundred weight 653.68Kg 2 of folding, the filter cake based on 6- naphthalenedisulfonic acids wherein contains in filter cake
81.94% 2,6- naphthalenedisulfonic acids and 10.11% 2,7- naphthalenedisulfonic acids, level-one of the set for sulfonated products separation refine filtrate
63.69% 2,7- naphthalenedisulfonic acids, make 2,7- naphthalenedisulfonic acid ultimate yields improve 5.89% effectively in recycling filter cake.
2) it washs
The level-one obtained according to 3 method of embodiment is refined into filtrate 1057.17Kg, two level refine filtrate 1142.31Kg and
Ammonium sulfate 379.59Kg after mixing, is added in reaction kettle, is added with stirring hundred weight 653.68Kg 2 of folding, 6- naphthalenedisulfonic acids
Based on filter cake, mixing time 2h is separated by filtration to obtain the filter cake based on 1 grade of 2,6- naphthalenedisulfonic acid, rolls over hundred heavy 642.46Kg, 1
Grade refines filtrate 2029.82Kg and continues separation of the set for naphthalene sulfonated products in next dissolved process.Continue 1 grade of 2,6- naphthalene two
The three-level that sulfonic acid filter cake and embodiment 3 obtain refines filtrate 1118.49Kg and is mixed evenly, and mixing time 2h is separated by filtration
The filter cake based on 2 grades of 2,6- naphthalenedisulfonic acids is obtained, 2 grades of refined filtrate 1142.31Kg continue set for 2,6- naphthalenes, two sulphur next time
1 grade of washing of acid；Continue 2 grades of 2,6- naphthalenedisulfonic acid filter cakes carrying out 3 grades of washings, three-level washing is molten with the ammonium sulfate of 1650.23Kg
Liquid (content 17%), 3 grades of 2,6- naphthalenedisulfonic acid products after separation pass through liquid-phase chromatographic analysis (area normalization method), and content is
99.25%, hundred heavy 640.45Kg are rolled over, 3 grades of refined filtrate 1118.49Kg continue set for 2,6- naphthalenedisulfonic acids filter cake 2 next time
Grade washing.
Embodiment 4：
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 170 DEG C, heat preservation is anti-
6h is answered, is cooled to 70 DEG C after reaction.
805.80Kg water is added into sulfonation material, controls time for adding 3h, stirs 2h after being added dropwise, be separated by filtration to obtain
Roll over hundred weight 645.53Kg 2, the filter cake based on 6- naphthalenedisulfonic acids, wherein in filter cake containing 82.13% 2,6- naphthalenedisulfonic acids and
11.76% 2,7- naphthalenedisulfonic acids.
2) it washs
The ammonia spirit (mass content 20%) of 2162.65Kg is added in reaction kettle, hundred weights of folding are added with stirring
Filter cake based on 645.53Kg 2,6- naphthalenedisulfonic acid, mixing time 2h are separated by filtration to obtain based on 1 grade of 2,6- naphthalenedisulfonic acid
Filter cake rolls over hundred heavy 626.52Kg, separation of 1 grade of refined filtrate 900.04Kg set for naphthalene sulfonated products in next dissolved process.
Continue the ammonia spirit (mass content 8%) of 1 grade of 2,6- naphthalenedisulfonic acids filter cake and 1000Kg being mixed evenly, mixing time
2h, is separated by filtration to obtain the filter cake based on 2,6- naphthalenedisulfonic acids, and 2 grades of refined filtrate 975.85Kg continue set for next time 2,6-
1 grade of washing of naphthalenedisulfonic acid；Continue by the ammonia spirit (mass content 8%) of 2 grades of 2,6- naphthalenedisulfonic acids filter cakes and 1182.71Kg into
3 grades of washings of row, 3 grades of 2,6- naphthalenedisulfonic acid products after separation pass through liquid-phase chromatographic analysis (area normalization method), and content is
99.79%, hundred heavy 621.45Kg are rolled over, 3 grades of refined filtrate 1182.71Kg continue set for 2,6- naphthalenedisulfonic acids filter cake 2 next time
Grade washing.
Embodiment 4a
1) sulfonation, dissolved
1000Kg refined naphthalenes are added in reaction kettle, the 3828.13Kg concentrated sulfuric acids are slowly added to, are warming up to 170 DEG C, heat preservation is anti-
6h is answered, is cooled to 70 DEG C after reaction.The level-one that embodiment 4 obtains is added into sulfonation material and refines filtrate 900.04Kg (its
In 2, the 7- naphthalenedisulfonic acids containing 20.56% 2,6- naphthalenedisulfonic acids and 60.72%), control time for adding 3h, after being added dropwise
2h is stirred, is separated by filtration to obtain hundred weight 649.56Kg 2 of folding, the filter cake based on 6- naphthalenedisulfonic acids wherein contains in filter cake
80.24% 2,6- naphthalenedisulfonic acids and 10.57% 2,7- naphthalenedisulfonic acids, level-one of the set for sulfonated products separation refine filtrate
44.41% 2,7- naphthalenedisulfonic acids, make 2,7- naphthalenedisulfonic acid ultimate yields improve 4.74% effectively in recycling filter cake.
2) it washs
The level-one obtained according to 4 method of embodiment is refined into filtrate 1342.65Kg, two level refines filtrate 975.85Kg and ammonia
Water (mass content 20%) 129.22Kg after mixing, is added in reaction kettle, is added with stirring hundred weight 649.56Kg 2 of folding,
Filter cake based on 6- naphthalenedisulfonic acids, mixing time 2h are separated by filtration to obtain the filter cake based on 1 grade of 2,6- naphthalenedisulfonic acid, roll over hundred weights
639.53Kg, 1 grade of refined filtrate 900.04Kg continue separation of the set for naphthalene sulfonated products in next dissolved process.Continue 1
Grade 2,6- naphthalenedisulfonic acids filter cake and three-level refine filtrate 1182.71Kg and are mixed evenly, and mixing time 2h is separated by filtration to obtain
Filter cake based on 2 grades of 2,6- naphthalenedisulfonic acids, 2 grades of refined filtrate 975.85Kg continue set for 1 grade of 2,6- naphthalenedisulfonic acids next time
Washing；Continue 2 grades of 2,6- naphthalenedisulfonic acid filter cakes carrying out 3 grades of washings, with the ammonia spirit of 855.64Kg, (quality contains for three-level washing
8%), 3 grades of 2,6- naphthalenedisulfonic acid products after separation pass through liquid-phase chromatographic analysis (area normalization method) to amount, content 99.71%,
Hundred heavy 637.79Kg are rolled over, 3 grades of refined filtrate 1182.71Kg continue to apply mechanically 2,6- naphthalenedisulfonic acids filter cake, 2 grades of washings next time.
Claims (9)
1. one kind 2, the synthesis of 6- naphthalenedisulfonic acids and the method for purification, include the following steps：
1) sulfonation, dissolved
Refined naphthalene and concentrated sulfuric acid heating are subjected to sulfonating reaction, generate 2,6- naphthalenedisulfonic acids and 2,7- naphthalenedisulfonic acids add water-soluble analysis, mistake
Filter, obtains 2,6- naphthalenedisulfonic acids filter cake and 2,7- naphthalenedisulfonic acid mother liquors；
2) it washs
It is the ammonium hydroxide of 8-20%% or the ammonium sulfate solution of 15-28%% as washing reagent using mass fraction, to 2,6- naphthalenes
Disulfonic acid filter cake is washed, and 1 grade of 2,6- naphthalenedisulfonic acids filter cake and 1 grade of refined filtrate are obtained, such as to 2,6- naphthalenedisulfonic acids filter cake
This cycle washing 2~4 times, obtains 2, the 6- naphthalenedisulfonic acid products that purity is more than 99%；
3) cleaning solution is applied mechanically
1 grade of refined filtrate returns to set and returns to set for step 2) for the dissolved process of step 1) and/or as washing reagent
Washing procedure, remaining refined filtrate returns to washing procedure of the set for step 2) as washing reagent, to recycle therein 2,6-
Naphthalenedisulfonic acid and 2,7- naphthalenedisulfonic acids；
2. the method as described in claim 1, it is characterised in that：In step 1), refined naphthalene is 1 with sulfuric acid molar ratio:3.5~6.5,
Reaction temperature is 130~190 DEG C, and soaking time is 5~15h.
3. the method as described in claim 1, it is characterised in that：In step 1), refined naphthalene is 1 with sulfuric acid molar ratio:4.5~5.5,
Reaction temperature is 150~180 DEG C, and soaking time is 5~8h.
4. the method as described in one of claims 1 to 3, it is characterised in that：Step 1) after the sulfonation reaction is complete, according to as follows
It is operated：System temperature is down to 40~120 DEG C, adds water regulation system acidity to 30~60%, and further heat preservation 0.5~
4h is then separated by filtration to obtain 2,6- naphthalenedisulfonic acids filter cake and 2,7- naphthalenedisulfonic acid mother liquors.
5. method as claimed in claim 4, it is characterised in that：Step 1) after the sulfonation reaction is complete, proceeds as follows behaviour
Make：System temperature is down to 50~100 DEG C, adds water regulation system acidity to 35~50%, and further keeps the temperature 1~2h, then
It is separated by filtration to obtain 2,6- naphthalenedisulfonic acids filter cake and 2,7- naphthalenedisulfonic acid mother liquors.
6. the method as described in one of claims 1 to 3, it is characterised in that：In step 2), 2,6- naphthalenedisulfonic acid filter cakes and washing
The mass ratio of reagent is 1:1~5.
7. method as claimed in claim 6, it is characterised in that：In step 2), 2,6- naphthalenedisulfonic acid filter cakes and washing reagent
Mass ratio is 1:3~5.
8. the method as described in one of claims 1 to 3, it is characterised in that：In step 3), 1 grade of refined filtrate returns to set and is used for
The dissolved process of step 1) and/or the washers that 2,6- naphthalenedisulfonic acid filter cakes in step 2) are used for as washing reagent return set
Sequence, N grades of refined filtrates return to set for N-1 grades 2 in step 2), the washing procedure of 6- naphthalenedisulfonic acid filter cakes, wherein N >=2, final stage
Refined filter cake uses mass fraction to be washed for the ammonium sulfate solution of the ammonium hydroxide of 8-20% or 15-28%.
9. the method as described in one of claims 1 to 3, it is characterised in that：In step 2), 2,6- naphthalenedisulfonic acid filter cakes are recycled
Washing 3 times.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324742A (en) * | 1978-06-15 | 1982-04-13 | Sugai Chemical Industry Co., Ltd. | Process for separation of naphthalenedisulfonic acids |
| JPS63280055A (en) * | 1987-05-12 | 1988-11-17 | Kawasaki Steel Corp | Production of 2,6-naphthalenedisulfonic acid |
| CN101717355A (en) * | 2009-11-25 | 2010-06-02 | 泰兴市锦鸡染料有限公司 | Method for synthesizing dyestuff intermediate H acid by naphthalene |
| CN102391161A (en) * | 2011-12-28 | 2012-03-28 | 湖北鑫慧化工有限公司 | Process for preparing amino G acid |
-
2018
- 2018-06-27 CN CN201810679358.XA patent/CN108707094B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324742A (en) * | 1978-06-15 | 1982-04-13 | Sugai Chemical Industry Co., Ltd. | Process for separation of naphthalenedisulfonic acids |
| JPS63280055A (en) * | 1987-05-12 | 1988-11-17 | Kawasaki Steel Corp | Production of 2,6-naphthalenedisulfonic acid |
| CN101717355A (en) * | 2009-11-25 | 2010-06-02 | 泰兴市锦鸡染料有限公司 | Method for synthesizing dyestuff intermediate H acid by naphthalene |
| CN102391161A (en) * | 2011-12-28 | 2012-03-28 | 湖北鑫慧化工有限公司 | Process for preparing amino G acid |
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