CN106674062B - A method of catalysis sulfonation prepares m-nitrobenzene sodium sulfonate - Google Patents
A method of catalysis sulfonation prepares m-nitrobenzene sodium sulfonate Download PDFInfo
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- CN106674062B CN106674062B CN201611224094.6A CN201611224094A CN106674062B CN 106674062 B CN106674062 B CN 106674062B CN 201611224094 A CN201611224094 A CN 201611224094A CN 106674062 B CN106674062 B CN 106674062B
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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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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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 present invention relates to the production method of m-nitrobenzene sodium sulfonate, specifically a kind of method that catalysis sulfonation prepares m-nitrobenzene sodium sulfonate.Sodium tungstate catalyst is added into nitrobenzene, then sulfur trioxide is added drop-wise at 80-100 DEG C in nitrobenzene, then 2~4 hours are kept the temperature at 100-120 DEG C carries out sulfonating reaction, sulfonated liquid is diluted into the water after reaction, it is filtered after dilution, filtrate is through alkali neutralization, through extractant extraction, the remaining nitro benzene raw materials of precipitation recycling, it is concentrated to wait for that material moisture reaches 40% 50% again through being dried to get to the m-nitrobenzene sodium sulfonate dry product of 98% or more content.The present invention is using sodium tungstate as catalyst, sulfur trioxide is as sulfonating agent, by-product 3 can be greatly reduced, 3 ' diphenylsulfone dinitros, at the same it is remaining without sulfur trioxide, there is no sulfuric acid generation in reaction system, also it is generated without waste residue, excessive nitrobenzene is recycled and recycled simultaneously, the generation three wastes is can effectively avoid, reaches clean manufacturing purpose.
Description
Technical field
The present invention relates to the production method of m-nitrobenzene sodium sulfonate, specifically a kind of catalysis sulfonation prepares m-nitro
The method of sodium sulfonate.
Background technology
M-nitrobenzene sodium sulfonate alias 3- nitrobenzene sodium sulfonates, are an important chemical intermediates, can be used as reducing dye,
The orange protective agent of sulfur dye resist agent and dyestuff also serves as the rust remover and plating nickel stripper of ship.
M-nitrobenzene sodium sulfonate production technology mainly uses Sulphurex process and oleum sulfonation nitrobenzene at present
Method.Sulfur trioxide or oleum are added drop-wise in nitrobenzene at a certain temperature, then held for some time keeps nitrobenzene complete
Full conversion, generates m-nitrobenzene sulfonic acid, 3,3 '-diphenylsulfone dinitro of by-product, m-nitrobenzene sulfonic acid through alkali neutralization generate between nitro
Benzene sulfonic acid sodium salt.
SO 3 sulfonated nitrobenzene main reaction equation
Side reaction equation
CN102786445 describes SO 3 sulfonated nitrobenzene, using microreactor plus stirring process integration, shortens anti-
It answers the period, yield 92%, the 3 of by-product 8%, 3 '-diphenylsulfone dinitros.CN103752336 is described with vanadium catalyst, uses smoke
Sulfuric acid sulfonation nitro benzene process, yield 87-93.5%.It is old after new etc., the Study on Preparation of m-nitrobenzene sodium sulfonate, Jilin
Chemical engineering institute's journal, volume 2004,21 (second phase), it is 110-115 DEG C to describe nitrobenzene sulfonation reaction temperature, sulfur trioxide
With nitrobenzene molar ratio 3.2-3.8：1, liquid phase sulphonation recovery 72-82%, gas phase xanthation yield 90-92.5%.(the rivers such as Wu Yinsu
Northern chemical industry, 1999,4.24-26, sulfuric acid is added to reduce sulfur trioxide oxidisability.
Prior art data introduces different synthesis technologies, between can only shortening inverse time using microreactor, with oleum sulphur
Sulfur trioxide oxidisability is reduced, but removes residual sulfuric acid and necessarily leads to a large amount of solid slags.It is not process for cleanly preparing.
Due to the strong oxidizing property of sulfur trioxide and high dehydrated, m-nitrobenzene sodium sulfonate production technology, is all by three at present
Sulfur oxide is excessive, and nitrobenzene is allowed to react completely, at this moment unavoidably generates 3,3 '-diphenylsulfone dinitro of by-product and sulfuric acid, does not have
There is the sulfur trioxide for participating in reaction to be also converted to sulfuric acid after water dilutes, is filtered to remove by-product sulfone, excess sulfuric acid hydroxide
Calcium neutralizes, and Waste Sulfuric Acid calcium waste residue is obtained by filtration, then generate m-nitrobenzene sodium sulfonate with alkali neutralization m-nitrobenzene sulfonic acid.Wang Zhenchuan,
M-nitrobenzene sodium sulfonate process for cleanly preparing is studied, (Hebei chemical industry, 2004,6.37-39), in sodium hydroxide and excess sulfuric acid
Anhydrous sodium sulphate is generated, makees salting-out agents with anhydrous sodium sulphate, wherein m-nitrobenzene sulfonic acid is reacted with sodium sulphate can not possibly generate sulfuric acid, in addition use
30% liquid caustic soda neutralisation of sulphuric acid, material sealing cycle, system material are uneven, it is impossible to the three wastes are completely eliminated, from high-concentration sulfuric acid
M-nitrobenzene sodium sulfonate content be obtained by filtration in sodium solution reach 98.6% and be also not easily accomplished, in addition generates solid waste sodium sulphate,
Clean manufacturing purpose is not achieved.
Invention content
There are waste residues and wastewater problem in the existing production technology of the object of the invention solution, provide a kind of catalysis sulfonation system
The method of standby m-nitrobenzene sodium sulfonate.
To achieve the above object, the invention adopts a technical scheme as：
Sodium tungstate catalyst is added into nitrobenzene, is then added drop-wise to sulfur trioxide in nitrobenzene at 80-100 DEG C, so
2~4 hours are kept the temperature at 100-120 DEG C afterwards and carries out sulfonating reaction, sulfonated liquid is diluted into the water after reaction, is filtered after dilution,
Extractant extraction is added through alkali neutralization, to reaction solution in filtrate, and precipitation, recycling remains in nitrobenzene in neutralizer, concentrated to wait for object
Material moisture reaches 40%-60% again through being dried to get to the m-nitrobenzene sodium sulfonate dry product of 98% or more content；
Wherein, sulfur trioxide and nitrobenzene mol ratio are 0.5-1：1, catalyst input amount is nitrobenzene weight
0.001%-10%；Dilute 0.5-5 times that water is sulfonated liquid weight.
The catalyst input amount is the 0.05%-0.5% of nitrobenzene weight；It is sulfonated liquid weight to dilute water
1.3-1.5 times.
The alkali is sodium hydroxide, sodium carbonate or sodium bicarbonate, preferably sodium carbonate.
In the filtrate and extractant extraction, precipitation is added in backward reaction solution, and recycling remains in nitrobenzene in neutralizer, will
Gained nitrobenzene recycles after drying.
The extractant is ethyl acetate, butyl acetate, n-butanol or methyl iso-butyl ketone (MIBK), preferably methyl-isobutyl
Ketone.
Concentration of the present invention is normal pressure or steaming water is concentrated under reduced pressure, and is conveyed into when material moisture reaches 40%-60% dry
Dry machine is dried, condensed water, is used as sulfonated liquid dilution water.
Drying of the present invention be concentrate be sent into drying machine drying, m-nitrobenzene sodium sulfonate dry product content 98% with
On, 98% or more yield, product is by chemical industry standard HG/T 2591-1994 detections.
Advantage for present invention：
For the present invention using sodium tungstate as catalyst, by-product 3,3 '-two can be greatly reduced as sulfonating agent in sulfur trioxide
Nitro diphenylsulfone, at the same it is remaining without sulfur trioxide, there is no sulfuric acid generation in reaction system, after alkali neutralization m-nitrobenzene sulfonic acid
There is no waste residue generation, while excessive nitrobenzene is recycled and being recycled, can effectively avoid the generation three wastes, reach clean manufacturing
Purpose；It embodies：
(1) present invention effectively reduces the production quantity of by-product sulfone by the way that sodium tungstate catalyst is added.
(2) present invention is matched by reducing sulfur trioxide with nitrobenzene, is avoided generating excess sulfuric acid, is eliminated waste water, waste residue
Reach clean manufacturing purpose.
(3) in reaction system of the present invention in the presence of catalyst, sulfur trioxide is in shortage, not only effectively reduces by-product 3,
3 '-diphenylsulfone dinitro production quantities improve product selectivity, dilution water consumption are reduced, to reduce energy consumption and production cost.
Specific implementation mode
In order to be best understood from the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the content of present invention
It is not limited solely to following example.
Embodiment 1
248 grams of nitrobenzenes are added to equipped in thermometer, electric stirring, addition funnel 500ml four-hole bottles, are added 0.2
Gram sodium tungstate, is heated to 80 DEG C, starts that 112 grams of sulfur trioxides are added dropwise, dropping temperature is controlled at 80-100 DEG C, drips three oxygen
Change sulphur, be warming up to 100-110 DEG C, keeps the temperature 1 hour, keep the temperature 2 hours at 110-120 DEG C, reaction solution is poured into 500ml water,
Filtering, washing, 3,3 '-diphenylsulfone dinitro of filter cake, filtrate are neutralized to pH=7 with natrium carbonicum calcinatum, and first is added to reaction solution
Base isobutyl ketone, extraction, precipitation, recycling remain in nitrobenzene in neutralizer, recycle 77 grams of nitrobenzene altogether, obtain by-product 3,3 '-
0.3 gram of diphenylsulfone dinitro, filtrate is concentrated to water content 50%, is dried, and obtains 307 grams of dry product m-nitrobenzene sodium sulfonate,
Content：99.2%, sodium sulphate, content：0.2%, yield 98.5% (to consume in terms of nitrobenzene).
Embodiment 2
248 grams of nitrobenzenes are added to equipped in thermometer, electric stirring, addition funnel 500ml four-hole bottles, are added 0.3
Gram sodium tungstate, is heated to 80 DEG C, starts that 142 grams of sulfur trioxides are added dropwise, dropping temperature is controlled at 80-100 DEG C, drips three oxygen
Change sulphur, be warming up to 100-110 DEG C, keeps the temperature 1 hour, keep the temperature 2 hours at 110-120 DEG C, reaction solution is poured into 500ml water,
Filtering, washing, 3,3 '-diphenylsulfone dinitro of filter cake, filtrate are neutralized to pH=7 with natrium carbonicum calcinatum, first is added to reaction solution
Base isobutyl ketone, extraction, precipitation, recycling remain in nitrobenzene in neutralizer, recycle 29 grams of nitrobenzene altogether, obtain by-product 3,3 '-
0.15 gram of diphenylsulfone dinitro, filtrate is concentrated to water content 50%, is dried, and obtains dry product m-nitrobenzene sodium sulfonate 395.0
Gram, content：99.0%, sodium sulphate content：0.3%, yield 98.6% (to consume in terms of nitrobenzene).
Embodiment 3
248 grams of recycling nitrobenzenes are added to equipped in thermometer, electric stirring, addition funnel 500ml four-hole bottles, are added
0.3 gram of sodium tungstate, is heated to 80 DEG C, starts that 142 grams of sulfur trioxides are added dropwise, dropping temperature is controlled at 80-100 DEG C, drips three
Sulfur oxide is warming up to 100-110 DEG C, keeps the temperature 1 hour, keeps the temperature 2 hours at 110-120 DEG C, reaction solution is poured into 500ml water
In, filtering, washing, 3,3 '-diphenylsulfone dinitro of filter cake, filtrate is neutralized to pH=7 with natrium carbonicum calcinatum, to reaction solution plus
Enter methyl iso-butyl ketone (MIBK), extract, precipitation, recycling remains in nitrobenzene in neutralizer, and recycling remains in nitrobenzene in neutralizer, altogether
29 grams of nitrobenzene to be recycled, 0.15 gram of 3,3 '-diphenylsulfone dinitro of by-product is obtained, filtrate is concentrated to water content 50%, is dried,
Obtain 395.3 grams of dry product m-nitrobenzene sodium sulfonate, content：99.1%, sodium sulphate content：0.4%, yield 98.6% is (with consumption
Nitrobenzene meter).
Embodiment 4
500 kilograms of nitrobenzenes are added to equipped with thermometer, stirring, 1m3In enamel still, 0.6 kilogram of sodium tungstate is added, adds
284 kilograms of sulfur trioxides are pressed by heat to 80 DEG C, with nitrogen, measuring tank, and sulfur trioxide is added dropwise into kettle, and dropping temperature control exists
80-100 DEG C, sulfur trioxide is dripped, is warming up to 100-110 DEG C, 1 hour is kept the temperature, 2 hours is kept the temperature at 110-120 DEG C,
Reaction solution is put into equipped with being diluted in kettle in 1000L water, and filtering, washing, 3,3 '-diphenylsulfone dinitro of filter cake, filtrate is with anhydrous
Sodium carbonate is neutralized to pH=7,300L methyl iso-butyl ketone (MIBK)s, extraction is added to reaction solution, precipitation recycles and remains in nitre in neutralizer
Base benzene recycles 60 kilograms of nitrobenzene, obtains 0.15 kilogram of 3,3 '-diphenylsulfone dinitro of by-product, filtrate is concentrated to water content altogether
50%, it is dried, obtains 790 kilograms of dry product m-nitrobenzene sodium sulfonate, content：99.1%, sodium sulphate content：0.3%, yield
98.6% (to consume in terms of nitrobenzene).
Comparing embodiment
500 kilograms of nitrobenzenes are added to equipped with thermometer, stirring, 1m3In enamel still, 80 DEG C are heated to, it will with nitrogen
410 kilograms of sulfur trioxides are pressed into measuring tank, and sulfur trioxide is added dropwise into kettle, and dropping temperature is controlled at 80-100 DEG C, drips three
Sulfur oxide is warming up to 100-110 DEG C, keeps the temperature 1 hour, keeps the temperature 2 hours at 110-120 DEG C, reaction solution is put into equipped with 1600L
It is diluted in kettle in water, filtering, washing are dry, obtain 25 kilogram 3,210 kilograms of nothings are added in 3 '-diphenylsulfone dinitro dry products, filtrate
Aqueous sodium carbonate is neutralized to pH=7 with calcium hydroxide, obtains 190 kilograms of waste residues calcium sulfate, and filtrate is concentrated to water content 50%, into
Row drying obtains 790 kilograms of dry product m-nitrobenzene sodium sulfonate, content：95.0%, yield 83.3% (to consume in terms of nitrobenzene).
By the various embodiments described above and comparative example as it can be seen that the embodiment of the present invention is using sodium tungstate as catalyst, sulfur trioxide conduct
3,3 '-diphenylsulfone dinitro of by-product can be greatly reduced in sulfonating agent, while remaining without sulfur trioxide, in reaction system
Raw sulfuric acid is at not having waste residue generation after alkali neutralization m-nitrobenzene sulfonic acid, while recycling excessive nitrobenzene and recycle
It uses, can effectively avoid the generation three wastes, reach clean manufacturing purpose；Pair and since sulfur trioxide excessively causes system in comparative example
In have excess sulfuric acid, will generate a large amount of waste residue in removal process.
Claims (7)
1. a kind of method that catalysis sulfonation prepares m-nitrobenzene sodium sulfonate, it is characterised in that：Sodium tungstate is added into nitrobenzene to urge
Then sulfur trioxide is added drop-wise at 80-100 DEG C in nitrobenzene by agent, 2~4 hours are then kept the temperature at 100-120 DEG C and is carried out
Sulfonated liquid is diluted after reaction, is filtered after dilution by sulfonating reaction into the water, and filtrate is added to reaction solution and extracts through alkali neutralization
Agent extracts, precipitation, and recycling remains in nitrobenzene in neutralizer, concentrated to wait for that material moisture reaches 40%-60% again through at dry
Reason is to get to the m-nitrobenzene sodium sulfonate dry product of 98% or more content；
Wherein, sulfur trioxide and nitrobenzene mol ratio are 0.5-1：1 does not include 1:1, catalyst input amount is nitrobenzene weight
0.001%-10%；Dilute 0.5-5 times that water is sulfonated liquid weight.
2. the method that catalysis sulfonation as described in claim 1 prepares m-nitrobenzene sodium sulfonate, it is characterised in that：The catalyst
Input amount is the 0.05%-0.5% of nitrobenzene weight；Dilute 1.3-1.5 times that water is sulfonated liquid weight.
3. the method that catalysis sulfonation as described in claim 1 prepares m-nitrobenzene sodium sulfonate, it is characterised in that：The alkali is hydrogen
Sodium oxide molybdena, sodium carbonate or sodium bicarbonate.
4. the method that catalysis sulfonation as described in claim 3 prepares m-nitrobenzene sodium sulfonate, it is characterised in that：The alkali is carbon
Sour sodium.
5. the method that catalysis sulfonation as described in claim 1 prepares m-nitrobenzene sodium sulfonate, it is characterised in that：In the filtrate
Extractant extraction, precipitation is added with backward reaction solution, recycling remains in nitrobenzene in neutralizer, after drying by gained nitrobenzene
It recycles.
6. the method for preparing m-nitrobenzene sodium sulfonate by the catalysis sulfonation described in claim 1 or 5, it is characterised in that：The extraction
It is ethyl acetate, butyl acetate, n-butanol or methyl iso-butyl ketone (MIBK) to take agent.
7. the method that catalysis sulfonation as described in claim 6 prepares m-nitrobenzene sodium sulfonate, it is characterised in that：The extractant
For methyl iso-butyl ketone (MIBK).
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| CN108997175B (en) * | 2018-06-28 | 2021-03-26 | 金华双宏化工有限公司 | Method for preparing sodium m-nitrobenzenesulfonate and derivatives thereof by sulfonating chlorosulfonic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1052484A (en) * | 1964-05-23 | |||
| DE2328574C3 (en) * | 1972-06-14 | 1982-02-18 | Witco Chemical Corp., New York, N.Y. | Process for the sulfonation of nitroaromatic compounds |
| CN101585789A (en) * | 2009-06-26 | 2009-11-25 | 河北建新化工股份有限公司 | Method for preparing 3-nitrophenyl sulphone |
| CN102188942B (en) * | 2011-04-01 | 2013-04-24 | 沈阳化工大学 | Production method for preparing m-nitrobenzenesulfonic acid by tubular sulfonation reactor |
| CN102786445B (en) * | 2011-05-19 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method and device for producing m-nitrobenzenesulphonic acid |
| CN103752336B (en) * | 2014-01-07 | 2015-12-09 | 南京云高新型材料有限公司 | A kind of vanadium catalyst for nitrobenzene sulfonation and preparation method thereof |
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