CN109320421A - A kind of new method preparing paranitrobenzoic acid with para-nitrotoluene raw material - Google Patents
A kind of new method preparing paranitrobenzoic acid with para-nitrotoluene raw material Download PDFInfo
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- CN109320421A CN109320421A CN201811292193.7A CN201811292193A CN109320421A CN 109320421 A CN109320421 A CN 109320421A CN 201811292193 A CN201811292193 A CN 201811292193A CN 109320421 A CN109320421 A CN 109320421A
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- nitrotoluene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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Abstract
The invention discloses a kind of new methods that paranitrobenzoic acid is prepared with para-nitrotoluene raw material, in air system, using para-nitrotoluene and dust technology as raw material, using aluminium powder or iron powder or zinc powder as catalyst, 2 ~ 6h, isolated paranitrobenzoic acid are reacted under the conditions of 60 ~ 95 DEG C.The present invention utilizes metallic catalyst-nitric acid-air system, has the advantages that production cost waste liquid that is low, small to equipment corrosion, generating is few, low to the pollution of environment.
Description
Technical field
It with para-nitrotoluene is original more particularly to one kind the present invention relates to a kind of preparation method of paranitrobenzoic acid
Material, the new method of paranitrobenzoic acid is prepared by metal activation-nitric acid-air oxidation process.
Background technique
Paranitrobenzoic acid is a kind of important intermediate for synthesizing the pharmaceuticals such as anesthetic, and production pesticide, dyestuff etc.
The important source material of common chemical products.Para-nitrotoluene oxidation is to prepare one of main method of paranitrobenzoic acid, commonly
Chemical reagent and method have: potassium permanganate oxidation method, sodium dichromate oxidizing process, nitric acid oxidation method, air oxidation process etc..(1) high
Potassium manganate oxidizing process is that the method for measuring oxidation PNT PNBA is reacted its advantage is that yield is higher (being greater than 90%) earliest
Condition requirement is low, and the reaction time is shorter, but higher cost, and can generate the by-product of a large amount of high pollutions, is only used for productive experiment
Reagent PNBA, is not suitable for large-scale industrial production, is not suitable for the processing of nitro-aromatic pollutant yet；(2) sodium dichromate is made
It can also make PNT the efficient oxidation PNBA for oxidant, the efficiency and cost for aoxidizing PNT are below KMnO4, since nitro exists
Sucting electronic effect on PNT aromatic ring, so that this legal system takes the effect of PNBA preferable, but environmental pollution caused by heavy metal chromium is difficult
In processing, it is not suitable for modern industry；(3) nitric acid oxidation PNT will not generate heavy metallic salt pollution, and byproduct of reaction is to hold
Segregative gas, product purity is higher, is suitble to industrial production, but need to keep higher concentration when nitric acid as oxidant, otherwise right
Container corrosion is more serious, in addition, high concentration nitric acid is also easy to produce nitrification side reaction, and generates NOx, cause atmosphere pollution and HNO3
Utilization rate is not high, low concentration nitric acid is such as selected, although cost can be reduced to a certain degree, to the more demanding of reaction vessel；(4)
Sodium hypochlorite oxidization, Sasson has been delivered and has been used PTC-RuO within 19864- NaClO method carries out the research of the liquid phase oxidation of PNT, phase
Transfer catalyst (PTC) is Bu4N+Br-(tetrabutylammonium bromide), PNBA yield is up to 92% or more, but PTC-RuO4-
NaClO oxidizing process is because using expensive RuCl3Keep cost too high with PTC, therefore, it is difficult to fairly large uses；(5) empty
Gas oxidizing process utilizes cheap air oxidation PNT PNBA, U.S. Amoco(A Moke) company develops and uses lower fatty acid
(such as acetic acid, propionic acid) is toluene-air oxidation in liquid phase method (hereinafter referred to as Amoco process) that solvent, Co-Mn-Br etc. are catalyst
Later, people start to produce PNBA using Amoco process oxidation PNT.
Wherein, nitric acid oxidation PNT is the method that people study since the beginning of the 1960s, reaction equation are as follows:
Since nitric acid oxidation method does not have pollution caused by heavy metallic salt, and byproduct of reaction is gas, be can be easily separated, product is pure
Degree is higher, therefore is industrially developed quickly.But using nitric acid as oxidant, nitric acid need to be made to keep higher concentration,
Otherwise more serious to container corrosion.However high concentration nitric acid is also also easy to produce nitrification side reaction, and generates NOx, cause atmosphere dirty
Dye and HNO3Utilization rate is not high.Low concentration nitric acid is such as selected, although cost can be reduced to a certain degree, the requirement to reaction vessel
It is higher.
As it can be seen that above-mentioned traditional chemical reagent method is most of highly developed, and once or transporting in the industrial production
With.But these methods have the shortcomings that obvious: high production cost, severe corrosion to equipment generate a large amount of waste liquids, pollution environment
Deng.
Summary of the invention
In order to solve the problems, such as it is existing prepare paranitrobenzoic acid technology, the invention discloses one kind to nitro
Methylbenzene raw material prepares the new method of paranitrobenzoic acid, using metallic catalyst-nitric acid-air system, lower pressure (1 ~
3 atmospheric pressure) and lower temperature (80 ~ 110 DEG C) under can react, with production cost it is low, it is small to equipment corrosion, generate
Waste liquid is few, to the low advantage of the pollution of environment.
The present invention is achieved through the following technical solutions:
The invention discloses a kind of new methods that paranitrobenzoic acid is prepared with para-nitrotoluene raw material, in air system, with
Para-nitrotoluene and dust technology are raw material, and using aluminium powder or iron powder or zinc powder as catalyst, 2 ~ 6h is reacted under the conditions of 60 ~ 95 DEG C,
Isolated paranitrobenzoic acid；Separate mode is all a variety of, can be separated by rectifying, can also be by the way that dilute HNO is first added3Acid
It washes to remove possible remaining metal in product, NaOH solution is then added and is adjusted to alkaline (pH=13), is placed in magnetic stirring apparatus
On, 60 DEG C or so stirring 30min are heated to, product paranitrobenzoic acid is dissolved in aqueous solution in the form of an ion, then by institute
After solution is cooled to room temperature, filtered with Buchner funnel, isolated filter residue and filtrate.
First para-nitrotoluene and catalyst by proportion are mixed as a preferred implementation manner, made at 55 ~ 60 DEG C pair
After nitrotoleune is completely melt, dilute HNO is added3And blowing air simultaneously, after being warming up to 60 ~ 95 DEG C, 2 ~ 6h is reacted, it is isolated right
Nitrobenzoic acid.
The catalyst is aluminium powder as a preferred implementation manner,.
It is analyzed and determined through fusing point and conversion ratio, when other reaction conditions are identical, temperature is increased, and reaction conversion ratio is higher, temperature
After degree rises to 90 DEG C, reaction conversion ratio reaches peak value, continues to increase temperature then conversion ratio slightly reduction, optimal reaction temperature 90
℃；In a certain range, with the extension in reaction time, the conversion ratio of para-nitrotoluene increases, when reacted between increase to
When 4h, conversion ratio is not further added by；Preferably, 4h is reacted in the reaction at 90 DEG C obtains comparatively ideal effect.
The molar ratio of the para-nitrotoluene and catalyst is (82 ~ 84): (1 ~ 5), institute as a preferred implementation manner,
State para-nitrotoluene and dilute HNO3Mass volume ratio be 1g/3mL, dilute HNO3Mass percent be 10 ~ 30%, preferably
Ground, dilute HNO3Mass percent be 10%.
The present invention uses metallic catalyst-nitric acid-air system, using the lesser nitric acid of concentration, carry out under normal pressure pair
The oxidation of nitrotoleune, specifically, the present invention mainly use low concentration nitric acid as oxidant, utilize reducing agent and dust technology
Cause and generate NO, NO is oxidized to NO using air2As oxidation system, nitric acid dosage is reduced, (1 ~ 3 is big in lower pressure
Air pressure) and lower temperature (80 ~ 110 DEG C) under can react, and do not have NOxIt generates, recycles aluminum nitrate after spent acid distillation, make nitre
Acid-utilising rate is high and does not generate spent acid；In addition, improving the bearing capacity of reaction vessel, conversion ratio can be further improved.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other drawings based on these drawings.
Fig. 1 is experimental facilities used in 1-12 of the embodiment of the present invention.
Fig. 2 is the infrared spectrogram of filter residue in embodiment 1-3.
Fig. 3 is the infrared spectrogram of filtrate in embodiment 1-3.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment
A kind of new method preparing paranitrobenzoic acid with para-nitrotoluene raw material, first by para-nitrotoluene and aluminium powder or iron
Powder or the mixing of zinc powder catalyst by proportion, after being completely melt para-nitrotoluene at 55 ~ 60 DEG C, mass percent, which is added, is
Dilute HNO of 10-30%3And blowing air simultaneously, after being warming up to 60 ~ 95 DEG C, 2 ~ 6h of reaction obtains the mixed solution containing product；First
Dilute HNO is added3Then pickling is added NaOH solution and is adjusted to alkaline (pH=13), juxtaposition to remove possible remaining metal in product
In on magnetic stirring apparatus, being heated to 60 DEG C or so stirring 30min, product paranitrobenzoic acid is dissolved in the form of an ion water-soluble
In liquid, then after acquired solution is cooled to room temperature, filtered with Buchner funnel, isolated filter residue and filtrate；After filter residue is dried
Weighing measures fusing point using micro-meldometer and records, while measuring ir data with pellet technique, after measured should
Filter residue is paranitrobenzoic acid；After filtrate is characterized with infrared spectrometer, dilute hydrochloric acid is added and is adjusted to acid (pH=2 ~ 3), if any heavy
Form sediment generate then it is to be precipitated completely after, filter and retain filter residue, the filter residue is also paranitrobenzoic acid, the reaction of embodiment after measured
Condition and interpretation of result are as shown in table 1 and Fig. 1.
The reaction condition and interpretation of result (dilute HNO that mass percent is 10% that table 1 is embodiment 1-123)
Seen from table 1, the melting range of filter residue is concentrated mainly on 51 DEG C or so twice, the literature value with paranitrobenzoic acid fusing point
It coincide substantially for 51.9 DEG C, can tentatively judge that filter residue main component, can be with by the infrared spectrogram of the filter residue of Fig. 2 for PNT
Find out the characteristic peak for still having para-nitrotoluene, demonstrates again that the filter residue is para-nitrotoluene.
As seen from Figure 3: the infrared spectrogram of filtrate obtained by embodiment 1-12 is in 3000 ~ 3600 cm-1Place occurs one
A wide and strong absorption peak, this is-OH in 3200 ~ 3400 cm-1Absorption peak and phenyl ring on C-H in 3030 cm-1Neighbouring stretches
Contracting vibration peak, which is superimposed, to be formed；Positioned at 1500 ~ 1850 cm-1Locate strong and sharp absorption peak, is by-C=O (1600 ~ 1850
cm-1) stretching vibration and-NO2( 1500~1600 cm-1) antisymmetric stretching vibration be formed by stacking.
On the basis of embodiment 8, the dilute HNO for being 10% by mass fraction3Successively be changed to mass fraction be 30%, 25%,
20%, 15%, respectively as embodiment 13,14,15,16, conversion ratio is as shown in table 2:
Reaction condition and the interpretation of result that table 2 is embodiment 13-16
。
When using 25% nitric acid solution, when reacting beginning, there are some brown fogs.After reacting 1h, fog subtracts
Few, solution is in light yellow；After reaction terminates, reaction system is transferred in receiving flask, observing in bottle has apparent layering,
Upper layer is reddish yellow oily liquids, and lower layer is faint yellow turbid.A period of time is stood, finds receiving flask mass sets at the middle and upper levels,
For reddish yellow solid, lower layer is transparency liquid and has colourless acicular crystal precipitation；Product is filtered, is rushed with 1% nitric acid solution
It washes, filter residue is in light yellow.Filter residue is transferred in beaker, addition 10ml distilled water, dropwise addition NaOH solution, adjusting pH to alkalinity,
Stir 30min.It can be seen that solution takes on a red color, filtering obtains lurid filter residue, and red filtrate collects filtrate.To filtrate
30% nitric acid solution of middle dropwise addition adjusts pH to acidity, it can be seen that the color fade of solution after standing a period of time, becomes without obvious
Change.
When using 20%, 30%, 15% nitric acid, reacting phenomenon is same as described above.But, the liquid in receiving flask is cold
But after, the color of upper layer solid is gradually deepened.Through overpickling, alkali cleaning, after pH is adjusted, it can be seen that start to sink in solution
It forms sediment, and is incremented by.
When using 10% nitric acid, reacting phenomenon is same as described above.But, it can be seen that oily liquids exists in receiving flask
Lower layer, upper layer are light yellow turbid.Through pickling, alkali cleaning, after adjusting pH, precipitating generates and is most.
It can be found that the conversion of para-nitrotoluene takes the lead in reducing as concentration of nitric acid increases, it is rear to increase.But 10% nitre
Acid solution is the largest the consumption of para-nitrotoluene.Effect is preferable, and dosage is minimum.As can be seen that using from experimental phenomena
The resulting product of reaction of 30% nitric acid solution is than using the reaction of 10% nitric acid solution few.The reason is that with the increasing of concentration of nitric acid
Height, aluminium and nitric acid reaction generate NO2It is increased with NO than regular meeting, that is, the NO generated2Amount can increase therewith, para-nitrotoluene
Be oxidized to paranitrobenzoic acid can reinforce even hyperoxidation it is excessive.When concentration of nitric acid is lower than 10%, reaction carried out slow.Cause
This concentration of nitric acid 10 ~ 30%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of new method for preparing paranitrobenzoic acid with para-nitrotoluene raw material, it is characterised in that: in air system, with
Para-nitrotoluene and dust technology are raw material, and using aluminium powder or iron powder or zinc powder as catalyst, 2 ~ 6h is reacted under the conditions of 60 ~ 95 DEG C,
Isolated paranitrobenzoic acid.
2. the new method of paranitrobenzoic acid is prepared with para-nitrotoluene raw material as described in claim 1, it is characterised in that: first will
Para-nitrotoluene and catalyst by proportion mixing, after being completely melt para-nitrotoluene at 55 ~ 60 DEG C, are added dilute HNO3And it is same
When blowing air, after being warming up to 60 ~ 95 DEG C, react 2 ~ 6h, isolated paranitrobenzoic acid.
3. the new method of paranitrobenzoic acid is prepared with para-nitrotoluene raw material as described in claim 1, it is characterised in that: described
Catalyst is aluminium powder.
4. the new method of paranitrobenzoic acid is prepared with para-nitrotoluene raw material as described in claim 1, it is characterised in that: 90
4h is reacted at DEG C.
5. the new method of paranitrobenzoic acid, feature are prepared with para-nitrotoluene raw material as described in any in claim 1-4
Be: the molar ratio of the para-nitrotoluene and catalyst is (82 ~ 84): (1 ~ 5), the para-nitrotoluene and dilute HNO3Matter
Amount volume ratio is 1g/3mL, dilute HNO3Mass percent be 10 ~ 30%.
6. the new method of paranitrobenzoic acid is prepared with para-nitrotoluene raw material as claimed in claim 5, it is characterised in that: described
Dilute HNO3Mass percent be 10%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2815373A (en) * | 1954-03-08 | 1957-12-03 | Robert S Aries | Preparation of para-nitrobenzoic acid |
| CN104803815A (en) * | 2015-03-25 | 2015-07-29 | 浙江嘉化能源化工股份有限公司 | Industrial production method of benzoic acid containing electron withdrawing groups on benzene rings |
-
2018
- 2018-11-01 CN CN201811292193.7A patent/CN109320421A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2815373A (en) * | 1954-03-08 | 1957-12-03 | Robert S Aries | Preparation of para-nitrobenzoic acid |
| CN104803815A (en) * | 2015-03-25 | 2015-07-29 | 浙江嘉化能源化工股份有限公司 | Industrial production method of benzoic acid containing electron withdrawing groups on benzene rings |
Non-Patent Citations (3)
| Title |
|---|
| 化学工业出版社组织: "《中国化工产品大全 （第三版）》", 31 December 1994 * |
| 王建忠: "硝酸氧化法生产对硝基苯甲酸的工艺探讨", 《内蒙古石油化工》 * |
| 马世昌: "《化学物质辞典》", 31 December 1999 * |
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