CN106995392A - A kind of method of catalytic hydrogenation production M acid - Google Patents
A kind of method of catalytic hydrogenation production M acid Download PDFInfo
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- CN106995392A CN106995392A CN201610041489.6A CN201610041489A CN106995392A CN 106995392 A CN106995392 A CN 106995392A CN 201610041489 A CN201610041489 A CN 201610041489A CN 106995392 A CN106995392 A CN 106995392A
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- acid
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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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed herein is a kind of method of catalytic hydrogenation method production M acid.Will dissolved with the tri-methyl p-toluenesulfonate of 3,5 dinitro 2,4,6 the aqueous solution, add hydriding reactor, add catalyst, be passed through after hydrogen, hydrogenation, filter, filtrate is acidified, crystallizing and drying obtain M acid.Feed stock conversion 100% of the present invention, products obtained therefrom is white powder, chromatographic purity：More than 99%, yield is up to more than 95%.
Description
Technical field
The present invention relates to a kind of production method of organic acid, specifically a kind of method of catalytic hydrogenation production M acid.
Background technology
M acid is important dyestuff, medicine intermediate, is mainly used in synthesis Australia ammonia indigo plant 3R and reactive brilliant bule K-3R etc., external
Demand is larger.It is related to 3,5- dinitro -2,4,6- tri-methyl p-toluenesulfonates reduction preparation M acid in document and has three kinds of approach：I.e.
Iron powder reducing, hydrazine reduction and three routes of hydrogenating reduction.Using iron powder reducing method production M acid, cost is relatively low, production compared with into
It is ripe, but working condition is poor, and the environmental pollution that iron cement is caused is serious, does not use typically.India's scholar Gowda hydrazine formates
As reducing agent, success is also achieved with iron powder reducing, but is simply tested in the lab so far, be further in industrial big rule
Mould production application still needs time.Consider that hydrogenating reduction is preferred route from product quality and environmental angle.
The content of the invention
There is provided a kind of method of catalytic hydrogenation method production M acid for present situation sour country M by the present invention.The method has
Technique is simple, pollution-free, by 3,5- dinitros -2,4, and 6- tri-methyl p-toluenesulfonates prepare the features such as sour added values of M are high.
The present invention is the technique developed according to catalytic hydrogenation method, and its feature is that this method uses catalytic hydrogenation, institute
Obtain product quality to improve, yield increases, cost reduction, production is stable, suitable industrialized production, and this method is using environment friend
Good reaction medium, can be achieved recycling for catalysts and solvents, no waste discharge alleviates environmental pressure.
The technical scheme for realizing the object of the invention is specifically described below：
(1) 3,5- dinitros -2,4,6- tri-methyl p-toluenesulfonates are dissolved with alkali lye, configuration quality percentage composition is 5-30% 3,5- bis-
Nitro -2,4,6- tri-methyl p-toluenesulfonate solution.
(2) solution is added in hydrogenation reaction cauldron, adds 3,5- dinitros -2,4,6- tri-methyl p-toluenesulfonate quality 0.5-
5% catalyst, is passed through hydrogen, Stress control is in 0.3-1.0Mpa, and temperature control is in 50-100 DEG C, speed of agitator 150-200r/
Min, carries out hydrogenation reaction.
(3), by reacting liquid filtering, it is 4-5 that filtrate, which adds acid regulation ph values, is cooled to normal temperature, and finished product is dried to obtain in centrifugation.
Gained finished product M acid of the invention, outward appearance is presented white, nondiscolouring is placed for a long time, content more than 99%, yield 95% with
On.
The invention provides a kind of temperature and pressure is relatively low, and conversion ratio is of a relatively high, catalyst can be achieved continuous
The method applied mechanically, can be greatly reduced cost, improve yield, safe, it is adaptable to industrialization large-scale production, and without three
Useless pollution, belongs to environmentally friendly technology.Using water as solvent, wide material sources, cost is low, and pollution, security will not be produced again
Height, and water can and material mix completely under certain condition, have significant economic benefit and social benefit.With noble-metal-supported
As catalyst, a kind of metal is only loaded, the use of metal is reduced, cost is reduced, catalyst can promote instead in water
The progress answered, makes reaction condition gentle, products obtained therefrom quality is good.The equal reusable edible of water and catalyst used, is substantially reduced
Production cost, and three-waste free pollution.
The present invention is by the improvement to technique, using water-metal/activated-carbon catalyst system, although carried metal ratio
Traditional Raney nickel is expensive, but passes through repetition test, it is found that catalyst is recycled in the reaction and apply mechanically, apply mechanically number of times up to tens of
More than secondary, after catalyst is applied mechanically in the present invention, the catalyst newly added is only 1/10 of original amount or so, is substantially reduced, so
The usage amount of catalyst is much smaller than the amount of being intended for single use on the whole, and cost reduction is suitable with traditional catalyst price, overcomes expensive
Metal is as the high technical barrier of catalyst cost, and solvent used is water, and wide material sources are also recycled and applied mechanically, will not be dirty
Environment is contaminated, is environmentally friendly solvent.
Specific implementation measure：
Below by specific embodiment, the present invention will be further elaborated, it should be appreciated that, the description below merely to
The present invention is explained, its content is not limited.
Following embodiments elaborate the technical process of the present invention, master used by taking our company's continuous production device as an example
The raw material is wanted to be：3,5- dinitro -2,4,6- tri-methyl p-toluenesulfonates（Technical grade, 99%）, hydrogen（Technical grade, 99.9%）, metal/C
Catalyst（Self-control）；Capital equipment used is：Refining kettle（5m³）；Hydriding reactor（5m³）, measuring tank（5m³）, it is acidified kettle（5m³）,
Filter（It is accurate）.
Water used in the present invention is deionized water, metal of the used catalyst for load on the activated carbon（Self-control）.Though should
Catalyst series price is slightly expensive, but due to activity it is higher, consumption is less, industrially commonly used, but 3,5- dinitros-
Report is but had no in the technique of 2,4,6- tri-methyl p-toluenesulfonates production M acid.
Embodiment 1：
With 400 kilograms of 3,5- dinitros -2,4, exemplified by 6- tri-methyl p-toluenesulfonates, used catalyst is that carried noble metal makes catalysis by oneself
The 0.1-5% that the total amount of catalyst is raw material is used in agent, production process（0.4-20 kilograms）, water inventory is 3-10 times of raw material
（1200-4000 kilograms）, before hydrogenation, 3,5- dinitros -2,4,6- tri-methyl p-toluenesulfonates, water and catalyst put into the order of kettle
It is as follows：
1st, 3,5- dinitros -2,4,400 kilograms of 6- tri-methyl p-toluenesulfonates, 1200-4000 kilograms of addition reactor of water, by adding
Enter sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate etc., regulation reaction solution ph values are 7-8, gas displacement.
2nd, hydrogen is passed through, hydrogenation starts, controlling reaction temperature is 50-100 DEG C, it is 0.3- to control reaction pressure
1.0Mpa。
3rd, reaction terminates filtration catalytic agent, and filtrate adjusts its ph value for 4-5, had by adding the acidulants such as hydrochloric acid, sulfuric acid
Mass crystallization is separated out, after crystal is all separated out, filtering, filter cake drying, obtains finished product M acid.
4th, obtained product is analyzed according to the method described above, 3,5- dinitros -2,4, the conversion of 6- tri-methyl p-toluenesulfonates
Rate is that the selectivity of 100%, M acid is that 99.6%, M acid contents are 99.9%, and yield is 96.5%.
Embodiment 2：
With 3,5- dinitros -2,4 between 400 kilograms, exemplified by 6- tri-methyl p-toluenesulfonates production M is sour, the catalysis used in production process
Agent is the self-control catalyst of carried noble metal, and consumption is 3,5- dinitros -2,4,6- tri-methyl p-toluenesulfonates 0.1-5%（0.4-20
Kilogram）, water inventory is 3-10 times of raw material（1200-4000 kilograms）, in continuous production, 3,5- dinitros -2,4,6- front threes
Base benzene sulfonic acid, water and catalyst be according to（One）Order add, for investigate technique stability, be carried out continuously five experiments,
Its result is that table 1 is as follows：
Reaction condition：50-100 DEG C of temperature, pressure 0.3-1.0Mpa, ph7-8.
Find out from table, 3,5- dinitros -2,4,6- tri-methyl p-toluenesulfonates conversion ratio is that the selectivity of 100%, M acid exists
More than 99.5%, finished product content is more than 99.7%, and yield is more than 97%.
Embodiment 3：
With 400 kilograms of 3,5- dinitros -2,4, exemplified by 6- tri-methyl p-toluenesulfonates production M is sour, it is using catalyst in production process
Carried noble metal makes catalyst by oneself, and consumption is 3,5- dinitros -2,4, the 0.1-5% of 6- tri-methyl p-toluenesulfonates（0.4-10 kilograms）,
Water inventory is 3-10 times of raw material（1200-4000 kilograms）, in continuous production, carried out according to the production technology of embodiment 1
Reaction, the difference is that catalyst carries out recycled.Each kettle reaction terminates, and after the complete catalyst of press filtration, catalyst blowback is entered
In reactor, 0.1-1.0 kilograms of catalyst is added, the recycled through row catalyst.Catalyst starts after applying mechanically, new catalysis
The addition of agent is greatly reduced, only original 5%-25%, greatly reduces cost, and through a large amount of productive experiments, this catalyst can
Continuously apply mechanically more than ten times.
It is cost-effective in order to reduce catalyst amount, now carry out catalyst according to the method for embodiment 2 and apply mechanically experiment,
The amount for adding raw catelyst every time is the 0.1% of nitro compounds（The 10% of i.e. original catalyst usage amount）, continuously apply mechanically five times, as a result
It is shown in Table 2.
Reaction condition：50-100 DEG C of temperature, pressure 0.3-1.0Mpa, ph7-8.
Find out from table, 3,5- dinitros -2,4,6- tri-methyl p-toluenesulfonates conversion ratio is that the selectivity of 100%, M acid exists
More than 99.5%, finished product content is more than 99.7%, and yield is basically identical with the result do not applied mechanically more than 97%, but catalyst
Consumption and production cost but can significantly decline.
Apply example 4：
With 400 kilograms of 3,5- dinitros -2,4, exemplified by 6- tri-methyl p-toluenesulfonates, used catalyst is that carried noble metal makes catalysis by oneself
The 0.1-5% that the total amount of catalyst is raw material is used in agent, production process（0.4-20 kilograms）, water inventory is 3-10 times of raw material
（1200-4000 kilograms）, before hydrogenation, 3,5- dinitros -2,4,6- tri-methyl p-toluenesulfonates, water and catalyst put into the order of kettle
It is as follows：
1st, 3,5- dinitros -2,4,400 kilograms of 6- tri-methyl p-toluenesulfonates, 1200-4000 kilograms of addition reactor of water, by adding
Enter sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate etc., regulation reaction solution ph values are 7-8, gas displacement.
2nd, hydrogen is passed through, hydrogenation starts, controlling reaction temperature is 50-100 DEG C, it is 0.3- to control reaction pressure
1.0Mpa。
3rd, reaction terminates, and catalyst is recovered by filtration, and the catalyst of recovery is recycled.
4th, filtrate adjusts its ph value for 4-5, has mass crystallization precipitation, treat crystal by adding the acidulants such as hydrochloric acid, sulfuric acid
After all separating out, filtering, filter cake drying obtain finished product M acid.
5th, the filtrate that crystallization and filtration goes out, concentrates through vacuum distillation, further separates out crystallization, adds before it is concentrated inorganic
Class antioxidant, to prevent the M acid oxidases in solution.The water of concentration and the water distilled out, add hydriding reactor, carry out circulating sleeve
With, it is to avoid environmental pollution and the wasting of resources.
6th, obtained product is analyzed according to the method described above, 3,5- dinitros -2,4, the conversion of 6- tri-methyl p-toluenesulfonates
Rate is that the selectivity of 100%, M acid is that 99.6%, M acid contents are 99.9%, and yield is 96.5%.With the repetition of above-mentioned production stage
Carry out, catalyst and water carries out the substantial amounts of work applied mechanically and reused, it is to avoid environmental pollution and the wasting of resources.
Claims (6)
1. a kind of method that catalytic hydrogenation method prepares M acid, it is characterised in that this method comprises the following steps：3,5- is dissolved with alkali lye
Dinitro -2,4,6- tri-methyl p-toluenesulfonates, configuration quality percentage composition is 5-30% 3,5- dinitros -2,4,6- trimethylbenzenes
Sulfonic acid solutions；Filtrate is added in hydrogenation reaction cauldron, catalyst is added, is passed through hydrogen, under certain pressure and temperature, enters
Row hydrogenation；Reacting liquid filtering, filtrate is acidified, and crystallizing and drying obtains finished product.
2. the method that catalytic hydrogenation method according to claim 1 prepares M acid, it is characterised in that (1) described alkali lye is step
Sodium hydroxide, potassium hydroxide, sodium carbonate or solution of potassium carbonate.
3. require that described catalytic hydrogenation prepares the sour methods of M according to right 1, it is characterised in that the addition of the step (1) alkali
For nitro compounds equivalent, water and 3,5- dinitro -2,4,6- tri-methyl p-toluenesulfonates mass ratio are 3-10:1.
4. the method that described catalytic hydrogenation prepares M acid is required according to right 1, it is characterised in that (3) the catalyst is negative to step
It is loaded with the activated carbon of metal（Make catalyst by oneself）.
5. the method that described catalytic hydrogenation prepares M acid is required according to right 1, it is characterised in that (3) the catalyst is added step
Measure as 3,5- dinitros -2,4, the 0.1-3% of 6- tri-methyl p-toluenesulfonate quality, hydrogen intake keeps reduction kettle pressure to be 0.3-
1.0Mpa, reaction temperature is 50-100 DEG C, and speed of agitator turns for 150-200.
6. the method that described catalytic hydrogenation prepares M acid is required according to right 1, it is characterised in that (4) the acidifying adjusts ph to step
It is worth for 4-5, crystallization temperature is normal temperature.
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| CN201610041489.6A CN106995392A (en) | 2016-01-22 | 2016-01-22 | A kind of method of catalytic hydrogenation production M acid |
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| CN201610041489.6A CN106995392A (en) | 2016-01-22 | 2016-01-22 | A kind of method of catalytic hydrogenation production M acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3347452A1 (en) * | 1983-12-29 | 1985-07-11 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING AROMATIC AMINOSULPHONIC ACIDS |
| CS244713B1 (en) * | 1984-11-07 | 1986-08-14 | Frantisek Zdarsa | Production method of brown colouring agents for non textile materials |
| CS259448B1 (en) * | 1986-12-15 | 1988-10-14 | Peter Slosar | Method of 2,6-diaminomesitylene-4-sulphonic acid's preparation |
-
2016
- 2016-01-22 CN CN201610041489.6A patent/CN106995392A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3347452A1 (en) * | 1983-12-29 | 1985-07-11 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING AROMATIC AMINOSULPHONIC ACIDS |
| CS244713B1 (en) * | 1984-11-07 | 1986-08-14 | Frantisek Zdarsa | Production method of brown colouring agents for non textile materials |
| CS259448B1 (en) * | 1986-12-15 | 1988-10-14 | Peter Slosar | Method of 2,6-diaminomesitylene-4-sulphonic acid's preparation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
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