CN106748899B - A kind of naphthalenedisulfonic acid and its preparation process - Google Patents
A kind of naphthalenedisulfonic acid and its preparation process Download PDFInfo
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- CN106748899B CN106748899B CN201611204506.XA CN201611204506A CN106748899B CN 106748899 B CN106748899 B CN 106748899B CN 201611204506 A CN201611204506 A CN 201611204506A CN 106748899 B CN106748899 B CN 106748899B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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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
- C07C303/22—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 from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- 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
Abstract
The present invention relates to a kind of naphthalenedisulfonic acid and its preparation processes, the raw material for preparing the naphthalenedisulfonic acid is made of the support type strong acid catalyst of major ingredient, the auxiliary material of major ingredient weight 95%, the water treatment agent of major ingredient weight 80% and major ingredient weight 0.5-1%, wherein, according to weight ratio, major ingredient is made of the sulfuric acid of 100-150 parts of refined naphthalenes and 150-230 parts of mass fractions 98%, according to weight ratio, the auxiliary material is made of 100-120 parts of sodium chloride and 80-100 parts of anhydrous sodium sulphate, and the water treatment agent is made of 40-80 parts of caustic soda, 20-50 parts of milk of limes；The support type strong acid catalyst is made of according to mass fraction 40-50 parts of zirconium tert-butoxides, 70-90 parts of inclined ammonium tungstophosphates, 30-50 parts of ethyl alcohol, the nitric acid of 30-40 parts of mass fractions 68% and 10-20 parts of mesoporous carbons；Naphthalenedisulfonic acid of the present invention and its preparation process increase the yield of 2,7- naphthalenedisulfonic acids, increase the utilization rate of waste liquid, liquid waste processing effect is good, saves entreprise cost when by the way that support type strong acid catalyst is added being prepared by naphthalenedisulfonic acid.
Description
Technical field
The present invention relates to organic synthesis technical field more particularly to a kind of naphthalenedisulfonic acid and its preparation processes.
Background technology
Production is all made of the batch process that refined naphthalene sulfonation is purified, dried, crushing again to naphthalenedisulfonic acid both at home and abroad at present.Naphthalene two
The process for sulfonation of sulfonic acid is divided into：98% sulfuric acid sulfonation, oleum sulfonation, three kinds of oleum solubilizer sulfonation.Wherein oleum
Although sour solubilizer process for sulfonation can greatly improve yield, because its equipment requirement is very high, the dangerous reasons such as big of production process,
Industrialized production seldom uses.Oleum method of sulfonation is higher than 98% sulfuric acid sulfonation method product harvest rate, and sulfuric acid dosage is also than 98%
Sulfuric acid sulfonation is less slightly, and the waste water of generation is less, but the method equipment investment is higher than 98% sulfuric acid sulfonation method, production process danger
More much bigger than 98% sulfuric acid sulfonation method, safety guarantee input and operating cost are higher, and comprehensive production cost is than 98% sulfuric acid sulfonation method
Height, under the pressure of wastewater treatment pressure, often most of enterprise uses this technique.98% sulfuric acid sulfonation method equipment requirement is not high, produces
Journey danger is relatively low, although yield is relatively low, sulfuric acid dosage is larger, overall cost is relatively low, the disadvantage is that wastewater flow rate is big, generates big
The acid solution of amount, liquid waste processing is difficult, and discharge costs greatly increase.
Naphthalenedisulfonic acid product of gained in preparation process has the isomers such as 2,6- naphthalenedisulfonic acids, 2,7- naphthalenedisulfonic acids, but
It is when practical application, 2,7- naphthalenedisulfonic acids are applied than wide, and it is important to prepare fuel, organic pigment and pesticide etc.
Intermediate, how to increase in naphthalenedisulfonic acid preparation process the yield of 2,7- naphthalenedisulfonic acids be in naphthalenedisulfonic acid preparation process urgently
It solves the problems, such as.
Invention content
To solve the above-mentioned problems, the purpose of the present invention is to propose to a kind of naphthalenedisulfonic acid and its preparation processes, pass through addition
Support type strong acid catalyst increases the yield of 2,7- naphthalenedisulfonic acids when prepared by naphthalenedisulfonic acid, increase the utilization of waste liquid
Rate, liquid waste processing effect is good, saves entreprise cost.
The technical solution that the present invention is taken to solve the above-mentioned problems is：A kind of naphthalenedisulfonic acid prepares the naphthalenedisulfonic acid
Raw material by major ingredient, the support type of the auxiliary material of major ingredient weight 95%, the water treatment agent of major ingredient weight 80% and major ingredient weight 0.5-1%
Strong acid catalyst forms, wherein according to weight ratio, major ingredient by 100-150 parts of refined naphthalenes and 150-230 parts of mass fractions 98% sulphur
Acid composition, according to weight ratio, the auxiliary material is made of 100-120 parts of sodium chloride and 80-100 parts of anhydrous sodium sulphate, at the water
Reason agent is made of 40-80 parts of caustic soda, 20-50 parts of milk of limes；The support type strong acid catalyst is according to mass fraction by 40-50
Part zirconium tert-butoxide, 70-90 part inclined ammonium tungstophosphates, 30-50 parts of ethyl alcohol, the nitric acid of 30-40 parts of mass fractions 68% and 10-20 parts are situated between
Hole charcoal is constituted, which is first prepared before, and concrete operations are：First by inclined ammonium tungstophosphate and ethyl alcohol
Mixed with the nitric acid of mass fraction 68%, backward mixed liquor in be added zirconium tert-butoxide and mesoporous carbon mixing, adjusting reaction temperature to
60-70 DEG C and insulation reaction 1-2h, residue is obtained after being later dried in vacuo reactant, residue is baked into 12- at 360-380 DEG C
It is crushed after 14h and can be prepared by the support type strong acid catalyst；
A kind of preparation process of naphthalenedisulfonic acid weighs each raw material first, in accordance with the ratio of claim 1, and backward quality is divided
Refined naphthalene is added in the sulfuric acid of number 98% and support type strong acid catalyst forms sulfonating reaction system, by the sulfonating reaction body after reaction
System is added in the water of 5 times of weight of sulfonating reaction system and is diluted, and adds sodium chloride and anhydrous sodium sulphate carries out reaction analysis of saltouing
Go out naphthalenedisulfonic acid, naphthalenedisulfonic acid, which is carried out refined purification, later can be prepared by product, is eventually adding water treatment agent and is carried out to waste liquid
Preparation process can be completed after processing, the liquid waste processing is directed to that caustic soda, milk of lime progress are added in waste reaction solution instead
Ying Hou by reaction product precipitation, purification & isolation and neutralizes residual sulfuric acid, and specific operation process is：First in a kettle
Waste liquid is concentrated into the 40% of original volume, then caustic soda is added and is stirred continuously into waste liquid and dissolves and be cooled to 20-30 DEG C of reaction 2-
3h, be precipitated sodium sulfate crystal, sodium sulfate crystal filter and is dried, backward remaining filtered fluid in be added milk of lime stir
It is even, and 80-85 DEG C of reaction 2-3h is adjusted the temperature to, press filtration simultaneously dries to obtain calcium sulfate, and filtrate obtained by press filtration replaces thinned water again
It recycles；
During the sulfonating reaction of the refined naphthalene, refined naphthalene is slowly added dropwise while stirring into the sulfuric acid of mass fraction 98%
With support type strong acid catalyst, time for adding 1-2h then heats to 170-190 DEG C of reaction 5-6h and obtains sulfonated liquid；
The chlorination of 50% weight of dilution is first added in the reaction process of saltouing into the dilution of sulfonating reaction system
Sodium is heated up to 90-95 DEG C and keeps the temperature 1-2h, then anhydrous sodium sulphate is added while stirring and dissolves postcooling to 23-25 DEG C, and filters and get rid of
It is dry to obtain naphthalenedisulfonic acid crude product；
First naphthalenedisulfonic acid crude product is added in the water of its 3 times of weight in the refined purification process of the naphthalenedisulfonic acid,
It is beaten and is added the sodium chloride of 1.5 times of slurries, be warming up to 90-95 DEG C and filters to take supernatant after keeping the temperature 1-2h, is cooled to
23-25 DEG C and drying is filtered, is finally warming up to 95-100 DEG C of drying naphthalenedisulfonic acid.
Beneficial effects of the present invention：
1, the present invention in preparation process by being added support type strong acid catalyst, and the support type strong acid catalyst makes
It is first pre-processed with preceding, inclined ammonium tungstophosphate and zirconium tert-butoxide reaction, obtained strong acid catalyst catalytic is good, and is not easy
Corrosion pipeline, simultaneously because mesoporous carbon is added thereto, the special cage structure absorption strong acid catalyst of mesoporous carbon forms more steady
Fixed structure, excellent catalytic effect, acid group not facile hydrolysis, catalyst durability is good, and 2,6- naphthalenedisulfonic acids can be promoted to be converted into 2,
7- naphthalenedisulfonic acids increase effectively the yield of 2,7- naphthalenedisulfonic acids in sulfonic acid reaction, save entreprise cost；
2, the present invention carries out press filtration and gets rid of by the processed waste liquid of milk of lime addition caustic soda, will produce calcium sulfate
It can be sold as finished product after dry, also can further prepare water-reducing agent, antifreezing agent etc., in the simple and practical waste liquid of processing procedure
Sulfuric acid treatment effect is good, increases production efficiency, saves entreprise cost；
3, the present invention is reacted with the acid waste liquid in naphthalenedisulfonic acid production process, is added by the way that water treatment agent is added
Caustic soda can generate sodium sulphate, it is anti-that sodium sulphate can be used as precipitation agent to be precipitated in naphthalenedisulfonic acid with the sulfuric acid reaction in waste liquid
It is applied mechanically again in answering, saves entreprise cost, while extra sodium sulphate is also used as product and is sold, it also can be further
Antifreezing agent, water-reducing agent etc. are prepared, waste water utilization rate is increased, saves liquid waste processing expense；
4, the liquid after liquid waste processing of the present invention can also be further used as diluent and realize recycled, save water money
Source, environmental protection and energy saving solve the problems, such as discharging of waste liquid, save the cost of enterprise.
Specific implementation mode
In conjunction with following specific examples, the present invention is described in further detail, and protection scope of the present invention is not limited to
In following embodiment.Process, condition, reagent, the experimental method etc. for implementing the present invention, in addition to the following content specially referred to,
It is among the general principles and common general knowledge in the art, content is not particularly limited in the present invention.
Embodiment 1
The technical solution that the present invention is taken to solve the above-mentioned problems is：A kind of naphthalenedisulfonic acid prepares the naphthalenedisulfonic acid
Raw material it is strong by the support type of major ingredient, the auxiliary material of major ingredient weight 95%, the water treatment agent of major ingredient weight 80% and major ingredient weight 0.5%
Acid catalyst forms, wherein and according to weight ratio, major ingredient is made of the sulfuric acid of 100 parts of refined naphthalenes and 150 parts of mass fractions 98%, according to
Weight ratio, the auxiliary material are made of 100 parts of sodium chloride and 80 parts of anhydrous sodium sulphate, the water treatment agent by 40 parts of caustic soda, 20 parts
Milk of lime forms；The support type strong acid catalyst is according to mass fraction by 40 parts of zirconium tert-butoxides, 70 parts of inclined ammonium tungstophosphate, 30
Part ethyl alcohol, the nitric acid of 30 parts of mass fractions 68% and 10 parts of mesoporous carbons are constituted, which first carries out before
It prepares, concrete operations are：First inclined ammonium tungstophosphate is mixed with the nitric acid of ethyl alcohol and mass fraction 68%, backward mixed liquor in plus
Enter zirconium tert-butoxide and mesoporous carbon mixing, adjusts reaction temperature to 60-70 DEG C and insulation reaction 1-2h, later do reactant vacuum
After dry residue, after residue to be baked at 360-380 DEG C to 12-14h crushing can be prepared by the support type strong acid catalyst.
A kind of preparation process of naphthalenedisulfonic acid weighs each raw material first, in accordance with the ratio of claim 1, and backward quality is divided
Refined naphthalene is added in the sulfuric acid of number 98% and support type strong acid catalyst forms sulfonating reaction system, by the sulfonating reaction body after reaction
System is added in the water of 5 times of weight of sulfonating reaction system and is diluted, and adds sodium chloride and anhydrous sodium sulphate carries out reaction analysis of saltouing
Go out naphthalenedisulfonic acid, naphthalenedisulfonic acid, which is carried out refined purification, later can be prepared by product, is eventually adding water treatment agent and is carried out to waste liquid
Preparation process can be completed after processing, the liquid waste processing is directed to that caustic soda, milk of lime progress are added in waste reaction solution instead
Ying Hou by reaction product precipitation, purification & isolation and neutralizes residual sulfuric acid, and specific operation process is：First in a kettle
Waste liquid is concentrated into the 40% of original volume, then caustic soda is added and is stirred continuously into waste liquid and dissolves and be cooled to 20-30 DEG C of reaction 2-
3h, be precipitated sodium sulfate crystal, sodium sulfate crystal filter and is dried, backward remaining filtered fluid in be added milk of lime stir
It is even, and 80-85 DEG C of reaction 2-3h is adjusted the temperature to, press filtration simultaneously dries to obtain calcium sulfate, and filtrate obtained by press filtration replaces thinned water again
It recycles.
During the sulfonating reaction of the refined naphthalene, refined naphthalene is slowly added dropwise while stirring into the sulfuric acid of mass fraction 98%
With support type strong acid catalyst, time for adding 1-2h then heats to 170-180 DEG C of reaction 5-6h and obtains sulfonated liquid.
The chlorination of 50% weight of dilution is first added in the reaction process of saltouing into the dilution of sulfonating reaction system
Sodium is heated up to 90-95 DEG C and keeps the temperature 1-2h, then anhydrous sodium sulphate is added while stirring and dissolves postcooling to 23-25 DEG C, and filters and get rid of
It is dry to obtain naphthalenedisulfonic acid crude product.
First naphthalenedisulfonic acid crude product is added in the water of its 3 times of weight in the refined purification process of the naphthalenedisulfonic acid,
It is beaten and is added the sodium chloride of 1.5 times of slurries, be warming up to 90-95 DEG C and filters to take supernatant after keeping the temperature 1-2h, is cooled to
23-25 DEG C and drying is filtered, is finally warming up to 95-100 DEG C of drying naphthalenedisulfonic acid.
Embodiment 2
The technical solution that the present invention is taken to solve the above-mentioned problems is：A kind of naphthalenedisulfonic acid prepares the naphthalenedisulfonic acid
Raw material it is strong by the support type of major ingredient, the auxiliary material of major ingredient weight 95%, the water treatment agent of major ingredient weight 80% and major ingredient weight 0.7%
Acid catalyst forms, wherein and according to weight ratio, major ingredient is made of the sulfuric acid of 125 parts of refined naphthalenes and 180 parts of mass fractions 98%, according to
Weight ratio, the auxiliary material are made of 110 parts of sodium chloride and 85 parts of anhydrous sodium sulphate, the water treatment agent by 50 parts of caustic soda, 35 parts
Milk of lime forms；The support type strong acid catalyst is according to mass fraction by 45 parts of zirconium tert-butoxides, 80 parts of inclined ammonium tungstophosphate, 35
Part ethyl alcohol, the nitric acid of 34 parts of mass fractions 68% and 13 parts of mesoporous carbons are constituted, which first carries out before
It prepares, concrete operations are：First inclined ammonium tungstophosphate is mixed with the nitric acid of ethyl alcohol and mass fraction 68%, backward mixed liquor in plus
Enter zirconium tert-butoxide and mesoporous carbon mixing, adjusts reaction temperature to 60-70 DEG C and insulation reaction 1-2h, later do reactant vacuum
After dry residue, after residue to be baked at 360-380 DEG C to 12-14h crushing can be prepared by the support type strong acid catalyst.
A kind of preparation process of naphthalenedisulfonic acid weighs each raw material first, in accordance with the ratio of claim 1, and backward quality is divided
Refined naphthalene is added in the sulfuric acid of number 98% and support type strong acid catalyst forms sulfonating reaction system, by the sulfonating reaction body after reaction
System is added in the water of 5 times of weight of sulfonating reaction system and is diluted, and adds sodium chloride and anhydrous sodium sulphate carries out reaction analysis of saltouing
Go out naphthalenedisulfonic acid, naphthalenedisulfonic acid, which is carried out refined purification, later can be prepared by product, is eventually adding water treatment agent and is carried out to waste liquid
Preparation process can be completed after processing, the liquid waste processing is directed to that caustic soda, milk of lime progress are added in waste reaction solution instead
Ying Hou by reaction product precipitation, purification & isolation and neutralizes residual sulfuric acid, and specific operation process is：First in a kettle
Waste liquid is concentrated into the 40% of original volume, then caustic soda is added and is stirred continuously into waste liquid and dissolves and be cooled to 20-30 DEG C of reaction 2-
3h, be precipitated sodium sulfate crystal, sodium sulfate crystal filter and is dried, backward remaining filtered fluid in be added milk of lime stir
It is even, and 80-85 DEG C of reaction 2-3h is adjusted the temperature to, press filtration simultaneously dries to obtain calcium sulfate, and filtrate obtained by press filtration replaces thinned water again
It recycles.
During the sulfonating reaction of the refined naphthalene, refined naphthalene is slowly added dropwise while stirring into the sulfuric acid of mass fraction 98%
With support type strong acid catalyst, time for adding 1-2h then heats to 180-190 DEG C of reaction 5-6h and obtains sulfonated liquid.
The chlorination of 50% weight of dilution is first added in the reaction process of saltouing into the dilution of sulfonating reaction system
Sodium is heated up to 90-95 DEG C and keeps the temperature 1-2h, then anhydrous sodium sulphate is added while stirring and dissolves postcooling to 23-25 DEG C, and filters and get rid of
It is dry to obtain naphthalenedisulfonic acid crude product.
First naphthalenedisulfonic acid crude product is added in the water of its 3 times of weight in the refined purification process of the naphthalenedisulfonic acid,
It is beaten and is added the sodium chloride of 1.5 times of slurries, be warming up to 90-95 DEG C and filters to take supernatant after keeping the temperature 1-2h, is cooled to
23-25 DEG C and drying is filtered, is finally warming up to 95-100 DEG C of drying naphthalenedisulfonic acid.
Embodiment 3
The technical solution that the present invention is taken to solve the above-mentioned problems is：A kind of naphthalenedisulfonic acid prepares the naphthalenedisulfonic acid
Raw material it is strong by the support type of major ingredient, the auxiliary material of major ingredient weight 95%, the water treatment agent of major ingredient weight 80% and major ingredient weight 0.8%
Acid catalyst forms, wherein and according to weight ratio, major ingredient is made of the sulfuric acid of 110 parts of refined naphthalenes and 190 parts of mass fractions 98%, according to
Weight ratio, the auxiliary material are made of 105 parts of sodium chloride and 90 parts of anhydrous sodium sulphate, the water treatment agent by 60 parts of caustic soda, 30 parts
Milk of lime forms；The support type strong acid catalyst is according to mass fraction by 43 parts of zirconium tert-butoxides, 75 parts of inclined ammonium tungstophosphate, 40
Part ethyl alcohol, the nitric acid of 35 parts of mass fractions 68% and 15 parts of mesoporous carbons are constituted, which first carries out before
It prepares, concrete operations are：First inclined ammonium tungstophosphate is mixed with the nitric acid of ethyl alcohol and mass fraction 68%, backward mixed liquor in plus
Enter zirconium tert-butoxide and mesoporous carbon mixing, adjusts reaction temperature to 60-70 DEG C and insulation reaction 1-2h, later do reactant vacuum
After dry residue, after residue to be baked at 360-380 DEG C to 12-14h crushing can be prepared by the support type strong acid catalyst.
A kind of preparation process of naphthalenedisulfonic acid weighs each raw material first, in accordance with the ratio of claim 1, and backward quality is divided
Refined naphthalene is added in the sulfuric acid of number 98% and support type strong acid catalyst forms sulfonating reaction system, by the sulfonating reaction body after reaction
System is added in the water of 5 times of weight of sulfonating reaction system and is diluted, and adds sodium chloride and anhydrous sodium sulphate carries out reaction analysis of saltouing
Go out naphthalenedisulfonic acid, naphthalenedisulfonic acid, which is carried out refined purification, later can be prepared by product, is eventually adding water treatment agent and is carried out to waste liquid
Preparation process can be completed after processing, the liquid waste processing is directed to that caustic soda, milk of lime progress are added in waste reaction solution instead
Ying Hou by reaction product precipitation, purification & isolation and neutralizes residual sulfuric acid, and specific operation process is：First in a kettle
Waste liquid is concentrated into the 40% of original volume, then caustic soda is added and is stirred continuously into waste liquid and dissolves and be cooled to 20-30 DEG C of reaction 2-
3h, be precipitated sodium sulfate crystal, sodium sulfate crystal filter and is dried, backward remaining filtered fluid in be added milk of lime stir
It is even, and 80-85 DEG C of reaction 2-3h is adjusted the temperature to, press filtration simultaneously dries to obtain calcium sulfate, and filtrate obtained by press filtration replaces thinned water again
It recycles.
During the sulfonating reaction of the refined naphthalene, refined naphthalene is slowly added dropwise while stirring into the sulfuric acid of mass fraction 98%
With support type strong acid catalyst, time for adding 1-2h then heats to 170-190 DEG C of reaction 5-6h and obtains sulfonated liquid.
The chlorination of 50% weight of dilution is first added in the reaction process of saltouing into the dilution of sulfonating reaction system
Sodium is heated up to 90-95 DEG C and keeps the temperature 1-2h, then anhydrous sodium sulphate is added while stirring and dissolves postcooling to 23-25 DEG C, and filters and get rid of
It is dry to obtain naphthalenedisulfonic acid crude product.
First naphthalenedisulfonic acid crude product is added in the water of its 3 times of weight in the refined purification process of the naphthalenedisulfonic acid,
It is beaten and is added the sodium chloride of 1.5 times of slurries, be warming up to 90-95 DEG C and filters to take supernatant after keeping the temperature 1-2h, is cooled to
23-25 DEG C and drying is filtered, is finally warming up to 95-100 DEG C of drying naphthalenedisulfonic acid.
Embodiment 4
The technical solution that the present invention is taken to solve the above-mentioned problems is：A kind of naphthalenedisulfonic acid prepares the naphthalenedisulfonic acid
Raw material it is strong by the support type of major ingredient, the auxiliary material of major ingredient weight 95%, the water treatment agent of major ingredient weight 80% and major ingredient weight 0.9%
Acid catalyst forms, wherein and according to weight ratio, major ingredient is made of the sulfuric acid of 150 parts of refined naphthalenes and 210 parts of mass fractions 98%, according to
Weight ratio, the auxiliary material are made of 120 parts of sodium chloride and 95 parts of anhydrous sodium sulphate, the water treatment agent by 80 parts of caustic soda, 40 parts
Milk of lime forms；The support type strong acid catalyst is according to mass fraction by 50 parts of zirconium tert-butoxides, 85 parts of inclined ammonium tungstophosphate, 50
Part ethyl alcohol, the nitric acid of 38 parts of mass fractions 68% and 20 parts of mesoporous carbons are constituted, which first carries out before
It prepares, concrete operations are：First inclined ammonium tungstophosphate is mixed with the nitric acid of ethyl alcohol and mass fraction 68%, backward mixed liquor in plus
Enter zirconium tert-butoxide and mesoporous carbon mixing, adjusts reaction temperature to 60-70 DEG C and insulation reaction 1-2h, later do reactant vacuum
After dry residue, after residue to be baked at 360-380 DEG C to 12-14h crushing can be prepared by the support type strong acid catalyst.
A kind of preparation process of naphthalenedisulfonic acid weighs each raw material first, in accordance with the ratio of claim 1, and backward quality is divided
Refined naphthalene is added in the sulfuric acid of number 98% and support type strong acid catalyst forms sulfonating reaction system, by the sulfonating reaction body after reaction
System is added in the water of 5 times of weight of sulfonating reaction system and is diluted, and adds sodium chloride and anhydrous sodium sulphate carries out reaction analysis of saltouing
Go out naphthalenedisulfonic acid, naphthalenedisulfonic acid, which is carried out refined purification, later can be prepared by product, is eventually adding water treatment agent and is carried out to waste liquid
Preparation process can be completed after processing, the liquid waste processing is directed to that caustic soda, milk of lime progress are added in waste reaction solution instead
Ying Hou by reaction product precipitation, purification & isolation and neutralizes residual sulfuric acid, and specific operation process is：First in a kettle
Waste liquid is concentrated into the 40% of original volume, then caustic soda is added and is stirred continuously into waste liquid and dissolves and be cooled to 20-30 DEG C of reaction 2-
3h, be precipitated sodium sulfate crystal, sodium sulfate crystal filter and is dried, backward remaining filtered fluid in be added milk of lime stir
It is even, and 80-85 DEG C of reaction 2-3h is adjusted the temperature to, press filtration simultaneously dries to obtain calcium sulfate, and filtrate obtained by press filtration replaces thinned water again
It recycles.
During the sulfonating reaction of the refined naphthalene, refined naphthalene is slowly added dropwise while stirring into the sulfuric acid of mass fraction 98%
With support type strong acid catalyst, time for adding 1-2h then heats to 170-190 DEG C of reaction 5-6h and obtains sulfonated liquid.
The chlorination of 50% weight of dilution is first added in the reaction process of saltouing into the dilution of sulfonating reaction system
Sodium is heated up to 90-95 DEG C and keeps the temperature 1-2h, then anhydrous sodium sulphate is added while stirring and dissolves postcooling to 23-25 DEG C, and filters and get rid of
It is dry to obtain naphthalenedisulfonic acid crude product.
First naphthalenedisulfonic acid crude product is added in the water of its 3 times of weight in the refined purification process of the naphthalenedisulfonic acid,
It is beaten and is added the sodium chloride of 1.5 times of slurries, be warming up to 90-95 DEG C and filters to take supernatant after keeping the temperature 1-2h, is cooled to
23-25 DEG C and drying is filtered, is finally warming up to 95-100 DEG C of drying naphthalenedisulfonic acid.
Embodiment 5
The technical solution that the present invention is taken to solve the above-mentioned problems is：A kind of naphthalenedisulfonic acid prepares the naphthalenedisulfonic acid
Raw material by major ingredient, the auxiliary material of major ingredient weight 95%, the water treatment agent of major ingredient weight 80% and major ingredient weight 1% support type strong acid
Catalyst forms, wherein according to weight ratio, major ingredient is made of the sulfuric acid of 140 parts of refined naphthalenes and 230 parts of mass fractions 98%, according to weight
Ratio is measured, the auxiliary material is made of 115 parts of sodium chloride and 100 parts of anhydrous sodium sulphate, and the water treatment agent is by 70 parts of caustic soda, 50 parts of stones
Grey breast composition；The support type strong acid catalyst according to mass fraction by 48 parts of zirconium tert-butoxides, 90 parts of inclined ammonium tungstophosphates, 45 parts
Ethyl alcohol, the nitric acid of 40 parts of mass fractions 68% and 18 parts of mesoporous carbons are constituted, which is first made before
Standby, concrete operations are：First inclined ammonium tungstophosphate is mixed with the nitric acid of ethyl alcohol and mass fraction 68%, backward mixed liquor in be added
Zirconium tert-butoxide and mesoporous carbon mixing adjust reaction temperature to 60-70 DEG C and insulation reaction 1-2h, are later dried in vacuo reactant
Afterwards residue, after residue to be baked at 360-380 DEG C to 12-14h crushing can be prepared by the support type strong acid catalyst.
A kind of preparation process of naphthalenedisulfonic acid weighs each raw material first, in accordance with the ratio of claim 1, and backward quality is divided
Refined naphthalene is added in the sulfuric acid of number 98% and support type strong acid catalyst forms sulfonating reaction system, by the sulfonating reaction body after reaction
System is added in the water of 5 times of weight of sulfonating reaction system and is diluted, and adds sodium chloride and anhydrous sodium sulphate carries out reaction analysis of saltouing
Go out naphthalenedisulfonic acid, naphthalenedisulfonic acid, which is carried out refined purification, later can be prepared by product, is eventually adding water treatment agent and is carried out to waste liquid
Preparation process can be completed after processing, the liquid waste processing is directed to that caustic soda, milk of lime progress are added in waste reaction solution instead
Ying Hou by reaction product precipitation, purification & isolation and neutralizes residual sulfuric acid, and specific operation process is：First in a kettle
Waste liquid is concentrated into the 40% of original volume, then caustic soda is added and is stirred continuously into waste liquid and dissolves and be cooled to 20-30 DEG C of reaction 2-
3h, be precipitated sodium sulfate crystal, sodium sulfate crystal filter and is dried, backward remaining filtered fluid in be added milk of lime stir
It is even, and 80-85 DEG C of reaction 2-3h is adjusted the temperature to, press filtration simultaneously dries to obtain calcium sulfate, and filtrate obtained by press filtration replaces thinned water again
It recycles.
During the sulfonating reaction of the refined naphthalene, refined naphthalene is slowly added dropwise while stirring into the sulfuric acid of mass fraction 98%
With support type strong acid catalyst, time for adding 1-2h then heats to 170-190 DEG C of reaction 5-6h and obtains sulfonated liquid.
The chlorination of 50% weight of dilution is first added in the reaction process of saltouing into the dilution of sulfonating reaction system
Sodium is heated up to 90-95 DEG C and keeps the temperature 1-2h, then anhydrous sodium sulphate is added while stirring and dissolves postcooling to 23-25 DEG C, and filters and get rid of
It is dry to obtain naphthalenedisulfonic acid crude product.
First naphthalenedisulfonic acid crude product is added in the water of its 3 times of weight in the refined purification process of the naphthalenedisulfonic acid,
It is beaten and is added the sodium chloride of 1.5 times of slurries, be warming up to 90-95 DEG C and filters to take supernatant after keeping the temperature 1-2h, is cooled to
23-25 DEG C and drying is filtered, is finally warming up to 95-100 DEG C of drying naphthalenedisulfonic acid.
For proof load type strong acid catalyst pair 2, the influence of 7- naphthalenedisulfonic acid yields, spy makees following comparative testing：
It is prepared according to the basic mode of embodiment 1 and is free of the product of medium charcoal in support type strong acid catalyst as sample
1, at this point, the ingredient of support type strong acid catalyst is：Tertiary fourth zirconium alcohol and inclined ammonium tungstophosphate；
It is prepared according to the method for embodiment 1 and contains the product of medium charcoal in support type strong acid catalyst as sample 2, this
When, the ingredient of support type strong acid catalyst is：Tertiary fourth zirconium alcohol, ammonium tungstophosphate and mesoporous carbon；
It is prepared in water treatment agent according to the method for embodiment 1 and does not contain the product of support type strong acid catalyst as a comparison
Example.
The yield of the 2,7- naphthalenedisulfonic acids of the different samples of table 1
| Group | The yield of 2,7- naphthalenedisulfonic acids（%） | The conversion ratio of 2,6- naphthalenedisulfonic acids（%） |
| Comparative example | 45% | 5% |
| Sample 1 | 60% | 30% |
| Sample 2 | 75% | 50% |
Before can obtaining non-loading type strong acid catalyst by the data in upper table, the yield of 2,7- naphthalenedisulfonic acids is not high, also
More 2,6- naphthalenedisulfonic acids are generated, the support type strong acid catalyst without medium charcoal are added in sample 1, with comparative example phase
Than the yield of 2,7- naphthalenedisulfonic acids is significantly raised, and the conversion ratio of 2,6- naphthalenedisulfonic acids also increases, and sample 2 is added containing Jie
The support type strong acid catalyst of hole charcoal, hence it is evident that the yield of 2,7- naphthalenedisulfonic acids is increased, while also effectively increasing 2,6- naphthalenes
The conversion ratio of disulfonic acid, the volume production amount highest of the product of obtained 2,7- naphthalenedisulfonic acids.
Claims (4)
1. a kind of preparation process of naphthalenedisulfonic acid, it is characterised in that：Weigh sulfuric acid, the refined naphthalene of mass fraction 98% in proportion first
With support type strong acid catalyst, and refined naphthalene is added in the sulfuric acid of backward mass fraction 98% and support type strong acid catalyst forms sulphur
Change reaction system, the sulfonating reaction system is added in the water of 5 times of weight of sulfonating reaction system after reaction and is diluted, then adds
Enter sodium chloride and anhydrous sodium sulphate carries out reaction precipitation naphthalenedisulfonic acid of saltouing, naphthalenedisulfonic acid, which is carried out refined purification, later can be prepared by producing
Product are eventually adding after water treatment agent handles waste liquid and preparation process can be completed, it is characterised in that：At the waste liquid
Reason is directed to be added in waste reaction solution after caustic soda, milk of lime reacted, and reaction product is precipitated, purification & isolation and neutralizes residue
Sulfuric acid, specific operation process are：Waste liquid is concentrated into the 40% of original volume first, then the stirring of addition caustic soda is molten into waste liquid
Solve and be cooled to 20-30 DEG C reaction 2-3h, be precipitated sodium sulfate crystal, filter and dry, backward remaining filtered fluid in be added
Milk of lime stirs evenly, and adjusts the temperature to 80-85 DEG C of reaction 2-3h, and press filtration simultaneously dries to obtain calcium sulfate, filtrate generation obtained by press filtration
For thinned water recycling；The raw material of the naphthalenedisulfonic acid is prepared by major ingredient, the auxiliary material of major ingredient weight 95%, major ingredient weight
The water treatment agent of amount 80% and the support type strong acid catalyst composition of major ingredient weight 0.5-1%, wherein according to weight ratio, major ingredient by
The sulfuric acid of 100-150 parts of refined naphthalenes and 150-230 parts of mass fractions 98% composition, it is characterised in that：According to weight ratio, described is auxiliary
Material is made of 100-120 parts of sodium chloride and 80-100 parts of anhydrous sodium sulphate, and the water treatment agent is by 40-80 parts of caustic soda, 20-50 parts of stones
Grey breast composition；The support type strong acid catalyst is according to mass fraction by 40-50 parts of zirconium tert-butoxides, 70-90 parts of inclined tungstophosphoric acids
Ammonium, 30-50 part ethyl alcohol, the nitric acid of 30-40 parts of mass fractions 68% and 10-20 parts of mesoporous carbons are constituted, the support type strong acid catalyst
It is first prepared before, concrete operations are：First inclined ammonium tungstophosphate is mixed with the nitric acid of ethyl alcohol and mass fraction 68%, it
Zirconium tert-butoxide and mesoporous carbon mixing is added in backward mixed liquor, adjusts reaction temperature to 60-70 DEG C and insulation reaction 1-2h, later
After reactant is dried in vacuo residue, residue baked at 360-380 DEG C to crush after 12-14h can be prepared by described bear
Load type strong acid catalyst.
2. a kind of preparation process of naphthalenedisulfonic acid as described in claim 1, it is characterised in that：The sulfonating reaction of the refined naphthalene
In the process, refined naphthalene and support type strong acid catalyst are slowly added to while stirring into the sulfuric acid of mass fraction 98%, is then heated to
170-190 DEG C of reaction 5-6h obtains sulfonated liquid.
3. a kind of preparation process of naphthalenedisulfonic acid as described in claim 1, it is characterised in that：In the reaction process of saltouing
The sodium chloride of 50% weight of dilution is first added into the dilution of sulfonating reaction system, is heated up to 90-95 DEG C and keeps the temperature 1-2h,
It adds anhydrous sodium sulphate and dissolves postcooling to 23-25 DEG C, and filter drying and obtain naphthalenedisulfonic acid crude product.
4. a kind of preparation process of naphthalenedisulfonic acid as described in claim 1, it is characterised in that：The naphthalenedisulfonic acid refines
First naphthalenedisulfonic acid crude product is added in the water of its 3 times of weight in purification process, is beaten and is added the sodium chloride of 1.5 times of slurries,
It is warming up to 90-95 DEG C and filters to take supernatant after keeping the temperature 1-2h, be cooled to 23-25 DEG C and filter drying, be finally warming up to
95-100 DEG C of drying naphthalenedisulfonic acid.
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| JPS54163563A (en) * | 1978-06-15 | 1979-12-26 | Sugai Chemical Ind Co Ltd | Method of isolating naphthalenedisulfonic acids |
| JPS63225350A (en) * | 1987-03-12 | 1988-09-20 | Kawasaki Steel Corp | Separation of 2,7-naphthalenedisulfonic acid |
| CN101717355B (en) * | 2009-11-25 | 2012-02-15 | 泰兴锦汇化工有限公司 | Method for synthesizing dyestuff intermediate H acid by naphthalene |
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| CN102993061B (en) * | 2012-07-30 | 2013-09-18 | 枣庄市泰瑞精细化工有限公司 | Preparation method of 2,7-sodium naphthalenedisulfonate product using transforming production of 1,6-naphthalenedisulfonic mother liquid |
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