CN108586256A - A kind of method of continuous flow upstream nitrification production dinitrobenzene - Google Patents
A kind of method of continuous flow upstream nitrification production dinitrobenzene Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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Abstract
The present invention provides a kind of method of continuous flow upstream nitrification production dinitrobenzene, is related to dinitrobenzene production field, preparation method is as follows：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitrification machine, itrated compound flow into 1 with spent acid adverse current, acid dinitrobenzene by platform#Prewasher, pre- wash water is by 2#Prewasher is added, and itrated compound flows into 1 with prewashing waste water adverse current, acid dinitrobenzene#Neutralization machine, sodium hydroxide solution is together with washes by 2#Neutralization machine is added, dinitrobenzene and waste water adverse current, from 1#The waste water and NaHS of neutralization machine outflow continuously flow into 1#Wastewater reduction kettle, then flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction, and production method of the invention is easy to operate, and source control effectively reduces the security risk that nitrophenols is brought in dinitrobenzene production process plus the technical solution that end treatment is combined, and improves essential safety.
Description
Technical field
The present invention relates to dinitrobenzene production fields, and in particular to a kind of side of continuous flow upstream nitrification production dinitrobenzene
Method.
Background technology
Nitrobenzene is the general name of m-dinitrobenzene, paradinitrobenzene and o-dinitrobenzene, is manufacture dyestuff, pigment, pesticide
And the important source material of polyimides functional material.The production of dinitrobenzene at present has interval nitrification process and continuous flow upstream nitrification
Method, interval nitrification process compare, and continuous flow upstream nitrification process advantage is apparent：(1) techniques such as reaction temperature, inventory, reactant concentration
Parameter stability, not time to time change, therefore reaction can carry out under conditions of advantageous, be conducive to improve and stable prod
Rate and quality；(2) since process conditions variation is small, operation is convenient, is conducive to keep the safety in production, and control easy to automate
System.
Dinitrobenzene can occur to generate the oxidation side reaction of nitrophenols in process of production, and nitrophenols, which neutralizes, becomes nitrophenols
Property is unstable after salt, and the generation easily burnt, exploded, therefore reduce nitrophenols in nitration reaction is critically important, one side
It is to remove the nitrophenols of generation from system, while to prevent nitro phenates from accumulating and overheating in systems, it is most of
Explosion be all nitro phenates accumulate in the drying process encounter overheat and occur.Thus stringent in dinitrobenzene production process
The generation of nitrophenols is controlled, and prevents nitrophenols accumulation of salts and overheat.But it in existing production technology, tends not to
Effect controls side reaction and generates excessive nitrophenols, not only reduces product quality but also has some potential safety problems.
Invention content
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of method that continuous flow upstream nitrifies production dinitrobenzene, knots
The example for closing industrialization continuous flow upstream nitrification process production dinitrobenzene, inquires into the factor that nitrophenols generates that influences, while proposing two
The separation of nitrophenols and processing method in nitrobenzene reduce the security risk that nitrophenols is brought, improve essential safety.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs：
A kind of method of continuous flow upstream nitrification production dinitrobenzene, preparation method are as follows：
(1) it nitrifies：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and controls raw material sulphuric acid
Volume ratio with raw material nitrobenzene is 0.65-0.75, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitre
Change machine is serially connected between each nitrification machine, and controlling reaction temperature is 83-87 DEG C, and itrated compound is flowed to spent acid adverse current, spent acid by platform
1#Nitrification machine is simultaneously flowed out from separator, recycled after waste acid concentration, control the nitric acid content in spent acid be 2-3%, spent acid and
The volume ratio of organic phase is 3-4, and acid dinitrobenzene flows to 4 by platform#Nitrification machine is simultaneously flowed out from separator；
(2) prewashing：Acid dinitrobenzene is from 4#Nitrification machine flows into 1#Prewasher, pre- wash water is by 2#Prewasher is added, and two pre-
It is serially connected between washing machine, controlling reaction temperature is 83-87 DEG C, and itrated compound is flowed to prewashing waste water adverse current, prewashing waste water by platform
1#Prewasher then flows into 1#Nitrification machine, recycles nitric acid, sulfuric acid in waste water, and acid dinitrobenzene flows to 2 by platform#Prewasher；
(3) it neutralizes：Acid dinitrobenzene is from 2#Prewasher flows into 1#Neutralization machine, raw material sodium hydroxide solution are useless together with washing
Water is by 2#Neutralization machine is added, and is serially connected between two neutralization machines, and controlling reaction temperature is 83-87 DEG C, dinitrobenzene and waste water
Adverse current carries out neutralization reaction, and waste water flows to 1 by platform#Neutralization machine, and from 1#Neutralization machine flows out, and dinitrobenzene is from 2#Neutralization machine flows out；
(4) it washs：Dinitrobenzene is from 2#Neutralization machine flows into 1#Rinsing maching, washings are by 2#Rinsing maching is added, and controls washings
Volume ratio with dinitrobenzene is 1.5-2.0:1, it is serially connected between two rinsing machings, controlling reaction temperature is 83-87 DEG C, nitre
Compound is fully washed with washings adverse current, and waste water flows to 1 by platform#Rinsing maching, and from 1#Rinsing maching flow to 2#Neutralization machine, is washed
Qualified dinitrobenzene is washed from 2#Rinsing maching flows into pan tank；
(5) Wastewater Pretreatment：From 1#The waste water of neutralization machine outflow and the NaHS by metering continuously flow into 1#Waste water is also
Former kettle, then flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction.
Preferably, the structure of the nitrification machine include autoclave body, blender, lifter, heat exchange coil, guide shell, separator,
The compositions such as transmission device, feed and exhaust tube.
Preferably, the structure of the prewasher, the neutralization machine and the rinsing maching is identical, includes autoclave body, stirring
The compositions such as device, lifter, heat exchange jacket, guide shell, separator, transmission device, feed and exhaust tube.
Preferably, nitrification installation is connected in series by 4 nitrification machines, two prewashers, two neutralization machines, two rinsing machings.
Preferably, the mass fraction of sodium hydrate aqueous solution described in step (3) is 8%.
Preferably, waste water described in step (3) is alkalinity, pH value 8-9.
(3) advantageous effect
Acid and water-solubility impurity in denitration object are washed with water by prewashing first, are beneficial to reduce hydrogen-oxygen in N-process
Change sodium dosage, secondly during continuous flow upstream is antacid, nitrophenols and sodium hydroxide effect generated into nitrophenols sodium salt,
After be dissolved in water, realize the separation of dinitrobenzene and nitrophenols, be beneficial to the content of nitrophenols in control system, and for it is subsequent into
The processing of one step safe is prepared, and is washed after neutralization, by remaining hydrogen-oxygen in dinitrobenzene and sodium, sodium sulphate, sodium nitrate and nitre
The impurity such as base sodium phenolate remove, and are beneficial to improve product quality, reduction with sodium bisulfide nitrophenols is selected when wastewater treatment, due to useless
In liquid contain excessive sodium hydroxide, react with NaHS generate the stronger vulcanized sodium of reducing power, and vulcanized sodium and
NaHS belongs to akali sulphide, and the reaction condition of akali sulphide is mild, can make the nitro step-by-step reduction in more nitro compounds, from
And ensure that nitrophenols sodium salt is converted into the amino sodium phenolate of safety and stability, it is beneficial to the content of nitrophenols in effective reduction system,
Ensure the safety of waste water post-processing, is finally parallel with the oxidation side reaction of generation nitrophenols due to the nitration reaction of dinitrobenzene
Reaction, therefore control washings by reducing reaction temperature, improving nitric acid content and increasing modulus in sulfuric acid ratio, increase spent acid
Amount effectively reduces the advantage of nitrophenols generation, while ensureing that nitration reaction is smoothed out, inhibits oxidation side reaction,
It is beneficial to the content of the nitrophenols from reduction system on source.
Description of the drawings
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.
Fig. 1 is the flow chart of continuous flow upstream of the present invention nitrification production dinitrobenzene；
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.
Embodiment 1：
A kind of method of continuous flow upstream nitrification production dinitrobenzene, preparation method are as follows：
(1) it nitrifies：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and controls raw material sulphuric acid
Volume ratio with raw material nitrobenzene is 0.65, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitrification machine,
It is serially connected between each nitrification machine, controlling reaction temperature is 83 DEG C, and itrated compound flows to 1 with spent acid adverse current, spent acid by platform#Nitrification machine
And flowed out from separator, recycled after waste acid concentration, control the body that the nitric acid content in spent acid is 2%, spent acid and organic phase
For product than being 3, acid dinitrobenzene flows to 4 by platform#Nitrification machine is simultaneously flowed out from separator；
(2) prewashing：Acid dinitrobenzene is from 4#Nitrification machine flows into 1#Prewasher, pre- wash water is by 2#Prewasher is added, and two pre-
It is serially connected between washing machine, controlling reaction temperature is 83 DEG C, and itrated compound flows to 1 with prewashing waste water adverse current, prewashing waste water by platform#In advance
Washing machine then flows into 1#Nitrification machine, recycles nitric acid, sulfuric acid in waste water, and acid dinitrobenzene flows to 2 by platform#Prewasher；
(3) it neutralizes：Acid dinitrobenzene is from 2#Prewasher flows into 1#Neutralization machine, raw material sodium hydroxide solution are useless together with washing
Water is by 2#Neutralization machine is added, and is serially connected between two neutralization machines, and controlling reaction temperature is 83 DEG C, dinitrobenzene and waste water adverse current
Neutralization reaction is carried out, waste water flows to 1 by platform#Neutralization machine, and from 1#Neutralization machine flows out, and dinitrobenzene is from 2#Neutralization machine flows out；
(4) it washs：Dinitrobenzene is from 2#Neutralization machine flows into 1#Rinsing maching, washings are by 2#Rinsing maching is added, and controls washings
Volume ratio with dinitrotouene is 1.5:1, be serially connected between two rinsing machings, controlling reaction temperature is 83 DEG C, itrated compound with
Washings adverse current is fully washed, and waste water flows to 1 by platform#Rinsing maching, and from 1#Rinsing maching flow to 2#Neutralization machine, washing are qualified
Dinitrobenzene from 2#Rinsing maching flows into pan tank；
(5) Wastewater Pretreatment：From 1#The waste water of neutralization machine outflow and the NaHS by metering continuously flow into 1#Waste water is also
Former kettle, then flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction.
Embodiment 2：
A kind of method of continuous flow upstream nitrification production dinitrobenzene, preparation method are as follows：
(1) it nitrifies：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and controls raw material sulphuric acid
Volume ratio with raw material nitrobenzene is 0.75, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitrification machine,
It is serially connected between each nitrification machine, controlling reaction temperature is 87 DEG C, and itrated compound flows to 1 with spent acid adverse current, spent acid by platform#Nitrification machine
And flowed out from separator, recycled after waste acid concentration, control the body that the nitric acid content in spent acid is 3%, spent acid and organic phase
For product than being 4, acid dinitrobenzene flows to 4 by platform#Nitrification machine is simultaneously flowed out from separator；
(2) prewashing：Acid dinitrobenzene is from 4#Nitrification machine flows into 1#Prewasher, pre- wash water is by 2#Prewasher is added, and two pre-
It is serially connected between washing machine, controlling reaction temperature is 87 DEG C, and itrated compound flows to 1 with prewashing waste water adverse current, prewashing waste water by platform#In advance
Washing machine then flows into 1#Nitrification machine, recycles nitric acid, sulfuric acid in waste water, and acid dinitrobenzene flows to 2 by platform#Prewasher；
(3) it neutralizes：Acid dinitrobenzene is from 2#Prewasher flows into 1#Neutralization machine, raw material sodium hydroxide solution are useless together with washing
Water is by 2#Neutralization machine is added, and is serially connected between two neutralization machines, and controlling reaction temperature is 87 DEG C, dinitrobenzene and waste water adverse current
Neutralization reaction is carried out, waste water flows to 1 by platform#Neutralization machine, and from 1#Neutralization machine flows out, and dinitrobenzene is from 2#Neutralization machine flows out；
(4) it washs：Dinitrobenzene is from 2#Neutralization machine flows into 1#Rinsing maching, washings are by 2#Rinsing maching is added, and controls washings
Volume ratio with dinitrotouene is 2.0:1, be serially connected between two rinsing machings, controlling reaction temperature is 87 DEG C, itrated compound with
Washings adverse current is fully washed, and waste water flows to 1 by platform#Rinsing maching, and from 1#Rinsing maching flow to 2#Neutralization machine, washing are qualified
Dinitrobenzene from 2#Rinsing maching flows into pan tank；
(5) Wastewater Pretreatment：From 1#The waste water of neutralization machine outflow and the NaHS by metering continuously flow into 1#Waste water is also
Former kettle, then flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction.
Embodiment 3：
A kind of method of continuous flow upstream nitrification production dinitrobenzene, preparation method are as follows：
(1) it nitrifies：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and controls raw material sulphuric acid
Volume ratio with raw material nitrobenzene is 0.70, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitrification machine,
It is serially connected between each nitrification machine, controlling reaction temperature is 85 DEG C, and itrated compound flows to 1 with spent acid adverse current, spent acid by platform#Nitrification machine
And flowed out from separator, recycled after waste acid concentration, it is 2.2%, spent acid and organic phase to control the nitric acid content in spent acid
Volume ratio is 3.5, and acid dinitrobenzene flows to 4 by platform#Nitrification machine is simultaneously flowed out from separator；
(2) prewashing：Acid dinitrobenzene is from 4#Nitrification machine flows into 1#Prewasher, pre- wash water is by 2#Prewasher is added, and two pre-
It is serially connected between washing machine, controlling reaction temperature is 85 DEG C, and itrated compound flows to 1 with prewashing waste water adverse current, prewashing waste water by platform#In advance
Washing machine then flows into 1#Nitrification machine, recycles nitric acid, sulfuric acid in waste water, and acid dinitrobenzene flows to 2 by platform#Prewasher；
(3) it neutralizes：Acid dinitrobenzene is from 2#Prewasher flows into 1#Neutralization machine, raw material sodium hydroxide solution are useless together with washing
Water is by 2#Neutralization machine is added, and is serially connected between two neutralization machines, and controlling reaction temperature is 85 DEG C, dinitrobenzene and waste water adverse current
Neutralization reaction is carried out, waste water flows to 1 by platform#Neutralization machine, and from 1#Neutralization machine flows out, and dinitrobenzene is from 2#Neutralization machine flows out；
(4) it washs：Dinitrobenzene is from 2#Neutralization machine flows into 1#Rinsing maching, washings are by 2#Rinsing maching is added, and controls washings
Volume ratio with dinitrotouene is 1.8:1, be serially connected between two rinsing machings, controlling reaction temperature is 85 DEG C, itrated compound with
Washings adverse current is fully washed, and waste water flows to 1 by platform#Rinsing maching, and from 1#Rinsing maching flow to 2#Neutralization machine, washing are qualified
Dinitrobenzene from 2#Rinsing maching flows into pan tank；
(5) Wastewater Pretreatment：From 1#The waste water of neutralization machine outflow and the NaHS by metering continuously flow into 1#Waste water is also
Former kettle, then flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction.
Embodiment 4：
A kind of method of continuous flow upstream nitrification production dinitrobenzene, preparation method are as follows：
(1) it nitrifies：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and controls raw material sulphuric acid
Volume ratio with raw material nitrobenzene is 0.71, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitrification machine,
It is serially connected between each nitrification machine, controlling reaction temperature is 86 DEG C, and itrated compound flows to 1 with spent acid adverse current, spent acid by platform#Nitrification machine
And flowed out from separator, recycled after waste acid concentration, it is 2.4%, spent acid and organic phase to control the nitric acid content in spent acid
Volume ratio is 3.9, and acid dinitrobenzene flows to 4 by platform#Nitrification machine is simultaneously flowed out from separator；
(2) prewashing：Acid dinitrobenzene is from 4#Nitrification machine flows into 1#Prewasher, pre- wash water is by 2#Prewasher is added, and two pre-
It is serially connected between washing machine, controlling reaction temperature is 86 DEG C, and itrated compound flows to 1 with prewashing waste water adverse current, prewashing waste water by platform#In advance
Washing machine then flows into 1#Nitrification machine, recycles nitric acid, sulfuric acid in waste water, and acid dinitrobenzene flows to 2 by platform#Prewasher；
(3) it neutralizes：Acid dinitrobenzene is from 2#Prewasher flows into 1#Neutralization machine, raw material sodium hydroxide solution are useless together with washing
Water is by 2#Neutralization machine is added, and is serially connected between two neutralization machines, and controlling reaction temperature is 86 DEG C, dinitrobenzene and waste water adverse current
Neutralization reaction is carried out, waste water flows to 1 by platform#Neutralization machine, and from 1#Neutralization machine flows out, and dinitrobenzene is from 2#Neutralization machine flows out；
(4) it washs：Dinitrobenzene is from 2#Neutralization machine flows into 1#Rinsing maching, washings are by 2#Rinsing maching is added, and controls washings
Volume ratio with dinitrotouene is 1.8:1, be serially connected between two rinsing machings, controlling reaction temperature is 86 DEG C, itrated compound with
Washings adverse current is fully washed, and waste water flows to 1 by platform#Rinsing maching, and from 1#Rinsing maching flow to 2#Neutralization machine, washing are qualified
Dinitrobenzene from 2#Rinsing maching flows into pan tank；
(5) Wastewater Pretreatment：From 1#The waste water of neutralization machine outflow and the NaHS by metering continuously flow into 1#Waste water is also
Former kettle, then flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction.
Embodiment 5：
A kind of method of continuous flow upstream nitrification production dinitrobenzene, preparation method are as follows：
(1) it nitrifies：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and controls raw material sulphuric acid
Volume ratio with raw material nitrobenzene is 0.69, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitrification machine,
It is serially connected between each nitrification machine, controlling reaction temperature is 84 DEG C, and itrated compound flows to 1 with spent acid adverse current, spent acid by platform#Nitrification machine
And flowed out from separator, recycled after waste acid concentration, it is 2.6%, spent acid and organic phase to control the nitric acid content in spent acid
Volume ratio is 3.7, and acid dinitrobenzene flows to 4 by platform#Nitrification machine is simultaneously flowed out from separator；
(2) prewashing：Acid dinitrobenzene is from 4#Nitrification machine flows into 1#Prewasher, pre- wash water is by 2#Prewasher is added, and two pre-
It is serially connected between washing machine, controlling reaction temperature is 84 DEG C, and itrated compound flows to 1 with prewashing waste water adverse current, prewashing waste water by platform#In advance
Washing machine then flows into 1#Nitrification machine, recycles nitric acid, sulfuric acid in waste water, and acid dinitrobenzene flows to 2 by platform#Prewasher；
(3) it neutralizes：Acid dinitrobenzene is from 2#Prewasher flows into 1#Neutralization machine, raw material sodium hydroxide solution are useless together with washing
Water is by 2#Neutralization machine is added, and is serially connected between two neutralization machines, and controlling reaction temperature is 84 DEG C, dinitrobenzene and waste water adverse current
Neutralization reaction is carried out, waste water flows to 1 by platform#Neutralization machine, and from 1#Neutralization machine flows out, and dinitrobenzene is from 2#Neutralization machine flows out；
(4) it washs：Dinitrobenzene is from 2#Neutralization machine flows into 1#Rinsing maching, washings are by 2#Rinsing maching is added, and controls washings
Volume ratio with dinitrotouene is 1.6:1, be serially connected between two rinsing machings, controlling reaction temperature is 84 DEG C, itrated compound with
Washings adverse current is fully washed, and waste water flows to 1 by platform#Rinsing maching, and from 1#Rinsing maching flow to 2#Neutralization machine, washing are qualified
Dinitrobenzene from 2#Rinsing maching flows into pan tank；
(5) Wastewater Pretreatment：From 1#The waste water of neutralization machine outflow and the NaHS by metering continuously flow into 1#Waste water is also
Former kettle, then flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction.
The nitration reaction of dinitrobenzene and the oxidation side reaction for generating nitrophenols are parallel reactions.It is nitrified in conjunction with continuous flow upstream
Method creation data is found：Reaction temperature, sulfuric acid are the principal elements for influencing nitrophenols and generating than nitric acid content, modulus in, spent acid,
Specific result of study is as follows：
(1) influence that reaction temperature paranitrophenol generates
Influence of the reaction temperature to nitration reaction and oxidation side reaction is that reaction temperature improves 10 DEG C, and nitration reaction speed carries
It is 2.2 times high, and aoxidize side reaction speed and improve four times[4].Therefore the speed of two reactions can be reduced by reducing reaction temperature
Degree, nitration reaction drop are lacked, and aoxidize the fast of side reaction drop.The influence that reaction temperature paranitrophenol generates is as shown in table 1.
The influence that 1 reaction temperature paranitrophenol of table generates
| Serial number | Reaction temperature | Nitrophenols (ppm) |
| 2 | (℃98).6 | 1215 |
| 3 | 87.2 | 813 |
| 4 | 85.1 | 810 |
| 5 | 82.5 | 796 |
| 6 | 80.6 | 792 |
As can be seen from Table 1, with the reduction of reaction temperature, nitrophenols production quantity declines, when reaction temperature is to 87.2 DEG C
When, nitrophenols production quantity is no longer decreased obviously, dinitrobenzene be between, it is adjacent, to the mixture of dinitrobenzene, the mixture is in 80-82
DEG C start to crystallize, therefore reaction temperature is unsuitable too low, control is advisable at 83-87 DEG C.
(2) influence that sulfuric acid ratio (referring to the raw material sulphuric acid of input and the volume ratio of nitrobenzene) paranitrophenol generates
Nitric-sulfuric acid nitrifies, and sulfuric acid is activator, and nitric acid is made to be dissociated into Nitronium NO+ 2, for sulfuric acid than small, sulfuric acid is effective
Concentration is low, Nitronium NO+ 2For content with regard to low, nitration reaction is small, and oxidation side reaction is big, and the nitrophenols of generation is more.Sulfuric acid compares
The influence that nitrophenols generates is as shown in table 2.
2 sulfuric acid of table is than the influence that paranitrophenol generates
| Serial number | Sulfuric acid ratio | Nitrophenols (ppm) |
| 1 | 0.85 | 805 |
| 2 | 0.80 | 809 |
| 3 | 0.75 | 810 |
| 4 | 0.65 | 818 |
| 5 | 0.60 | 1092 |
| 6 | 0.55 | 1280 |
As can be seen from Table 2, for the production quantity of nitrophenols as sulfuric acid ratio reduces and increases, oxygen can be reduced by improving sulfuric acid ratio
Change side reaction, controls the generation of nitrophenols, but sulfuric acid, than excessive, sulfuric acid effective concentration becomes larger, and not only increases sulfuric acid consumption, but also
Solubility of the itrated compound in spent acid increases, and causes spent acid and itrated compound to detach unclear, test data shows：1000 kilograms
The sulfuric acid of 94.8% (mass fraction) can dissolve 400 kilograms of dinitrobenzenes.Therefore suitable sulfuric acid than control 0.65-0.75 it
Between.
(3) influence that nitric acid content paranitrophenol generates in spent acid
Nitric acid content improves in spent acid, and Nitronium increases, and oxidation side reaction speed reduces, and nitration reaction speed carries
It is high.The influence that nitric acid content paranitrophenol generates in spent acid is as shown in table 3.
The influence that 3 nitric acid content paranitrophenol of table generates
| Serial number | Nitric acid contains | Nitrophenols (ppm) |
| 2 | Measure %1.5 | 1020 |
| 3 | 2.0 | 812 |
| 4 | 2.5 | 816 |
| 5 | 3.0 | 818 |
| 6 | 3.5 | 817 |
From table 3 it can be seen that with the raising of nitric acid content in spent acid, nitrophenols production quantity declines, and nitric acid content improves
To after 2.0%, nitrophenols production quantity tends towards stability, and no longer declines, then improves nitric acid content in spent acid, the nitric acid that spent acid is taken away
Just more, nitric acid consumption increases, therefore nitric acid content control is between 2-3%.
(4) modulus (also known as compares, refer to the volume ratio of spent acid and organic phase) influence of paranitrophenol generation
Modulus increases, and nitration reaction speed increases, and oxidation side reaction is opposite to be reduced[5].Since nitric acid is in spent acid, organic phase
In distribution coefficient it is different, keep quantitative difference of the nitric acid in spent acid, organic phase very big, nitric acid is for nitrifying in spent acid, and nitre
Nitric acid is for aoxidizing in compound, and spent acid increases in nitrification machine, and organic phase is reduced, and the nitrophenols amount of generation is reduced.Modulus is to nitro
The influence that phenol generates is as shown in table 4.
The influence that 4 modulus paranitrophenol of table generates
| Serial number | Modulus | Nitrophenols (ppm) |
| 1 | 2.0 | 1420 |
| 2 | 2.5 | 1135 |
| 3 | 3.0 | 816 |
| 4 | 3.5 | 814 |
| 5 | 4.0 | 816 |
| 6 | 4.5 | 815 |
From table 4, it can be seen that modulus increases, oxidation side reaction is reduced, and nitrophenols production quantity declines, when modulus increases to
When 3.0, nitrophenols production quantity no longer declines, if continuing increasing modulus, is bound to cause equipment capacity reduction, considers, suitable
Modulus controls between 3-4.
(5) washing separation nitrophenols is neutralized
Nitrophenols is weakly acidic, neutralization reaction can occur with sodium hydroxide, generate nitrophenols sodium salt, Sodium nitrophenolate is dissolved in
Nitrophenols in dinitrobenzene is first neutralized into nitrophenols by water using the property with 8% (mass fraction) sodium hydrate aqueous solution
Sodium salt, then plus water washing detaches.It is found by creation data, washs influence such as 5 institute of table of water p-nitrophenol sodium salt content
Show.
Table 5 washs the influence of water p-nitrophenol sodium salt content
Note：Nitrophenols determined by ultraviolet spectrophotometry, it is nitrophenols meter to neutralize the nitrophenols sodium salt conversion after washing.
As can be seen from Table 5, with the increase of washing water, Sodium nitrophenolate salt content declines in dinitrobenzene, when
Washings：Dinitrobenzene (volume ratio) reaches 1.5:When 1, Sodium nitrophenolate salt content no longer declines in dinitrobenzene, comprehensive wastewater
Processing cost and safety factor consideration, washings：Dinitrobenzene (volume ratio) is controlled in 1.5-2.0:Between 1.
(6) reduction with sodium bisulfide nitrophenols
In dinitrobenzene and washes in alkalinity, pH value 8-9, wherein contain excessive sodium hydroxide, NaHS with
Sodium hydroxide reaction generates the stronger vulcanized sodium of reducing power, and NaHS belongs to akali sulphide with vulcanized sodium, for restoring nitre
Base, sodium sulfide reducing have many advantages, such as that reaction condition is mild, can make the nitro step-by-step reduction in more nitro compounds.This technique is adopted
With the nitrophenols sodium salt in reduction with sodium bisulfide waste water, it is made to be converted into the amino sodium phenolate of safety and stability, table 6 is to randomly select
The different batches dinitrobenzene washes nitrophenols content table of comparisons before and after the processing.
The nitrophenols content table of comparisons before and after the processing in 6 washes of table
Note：Nitrophenols determined by ultraviolet spectrophotometry, the nitrophenols sodium salt conversion in waste water is nitrophenols meter.
By table 6 as it can be seen that can effectively be converted the nitrophenols in dinitrobenzene and in washes to using NaHS
Amino sodium phenolate, it is ensured that waste water post-processing safety.
By upper table 1-6 it is found that the method for continuous flow upstream provided by the invention nitrification production dinitrobenzene, is set by improving
It is standby, using continuous flow upstream nitrification process, Optimizing Technical, such as：Reaction temperature is reduced, sulfuric acid ratio is improved, increases nitric acid in spent acid
Content, increasing modulus can reduce oxidation side reaction, reduce the generation of nitrophenols；Using in continuous flow upstream and washing process
Nitrophenols can be converted to Sodium nitrophenolate, effectively realize the separation of dinitrobenzene and nitrophenols；Sodium nitrophenolate in waste water is adopted
With reduction with sodium bisulfide, amino phenols sodium substance is converted thereof into, danger classes substantially reduces.Source control adds end treatment
The technical solution being combined effectively reduces the security risk that nitrophenols is brought in dinitrobenzene production process, improves essence
Safety.
It should be noted that herein, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also include other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited including sentence "including a ...", it is not excluded that
There is also other identical elements in the process, method, article or apparatus that includes the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations, although with reference to the foregoing embodiments
Invention is explained in detail, it will be understood by those of ordinary skill in the art that:It still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features；And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (6)
1. a kind of method of continuous flow upstream nitrification production dinitrobenzene, which is characterized in that preparation method is as follows：
(1) it nitrifies：By raw material nitrobenzene from 1#Nitrification machine is added, and raw material sulphuric acid is by 4#Nitrification machine is added, and controls raw material sulphuric acid and nitre
The volume ratio of base benzene is 0.65-0.75, and raw material nitric acid is by 2#、3#、4#Nitrification machine is added, and prewashing waste water is added 1#Nitrification machine, each nitre
It is serially connected between change machine, controlling reaction temperature is 83-87 DEG C, and itrated compound flows to 1 with spent acid adverse current, spent acid by platform#Nitrification machine
And flowed out from separator, recycled after waste acid concentration, it is 2-3%, spent acid and organic phase to control the nitric acid content in spent acid
Volume ratio is 3-4, and acid dinitrobenzene flows to 4 by platform#Nitrification machine is simultaneously flowed out from separator；
(2) prewashing：Acid dinitrobenzene is from 4#Nitrification machine flows into 1#Prewasher, pre- wash water is by 2#Prewasher is added, two prewashers
Between be serially connected, controlling reaction temperature is 83-87 DEG C, and itrated compound flows to 1 with prewashing waste water adverse current, prewashing waste water by platform#In advance
Washing machine then flows into 1#Nitrification machine, recycles nitric acid, sulfuric acid in waste water, and acid dinitrobenzene flows to 2 by platform#Prewasher；
(3) it neutralizes：Acid dinitrobenzene is from 2#Prewasher flows into 1#Neutralization machine, raw material sodium hydroxide solution together with washes by
2#Neutralization machine is added, and is serially connected between two neutralization machines, and controlling reaction temperature is 83-87 DEG C, dinitrobenzene and waste water adverse current
Neutralization reaction is carried out, waste water flows to 1 by platform#Neutralization machine, and from 1#Neutralization machine flows out, and dinitrobenzene is from 2#Neutralization machine flows out；
(4) it washs：Dinitrobenzene is from 2#Neutralization machine flows into 1#Rinsing maching, washings are by 2#Rinsing maching is added, and controls washings and two
The volume ratio of nitrobenzene is 1.5-2.0:1, it is serially connected between two rinsing machings, controlling reaction temperature is 83-87 DEG C, itrated compound
It is fully washed with washings adverse current, waste water flows to 1 by platform#Rinsing maching, and from 1#Rinsing maching flow to 2#Neutralization machine, washing are closed
The dinitrobenzene of lattice is from 2#Rinsing maching flows into pan tank；
(5) Wastewater Pretreatment：From 1#The waste water of neutralization machine outflow and the NaHS by metering continuously flow into 1#Wastewater reduction
Then kettle flows into 2 successively#、3#Wastewater reduction kettle carries out reduction reaction.
2. a kind of method of continuous flow upstream nitrification production dinitrobenzene as described in claim 1, which is characterized in that the nitrification machine
Structure include the compositions such as autoclave body, blender, lifter, heat exchange coil, guide shell, separator, transmission device, feed and exhaust tube.
3. a kind of method of continuous flow upstream nitrification production dinitrobenzene as described in claim 1, which is characterized in that the prewashing
The structure of machine, the neutralization machine and the rinsing maching is identical, include autoclave body, blender, lifter, heat exchange jacket, guide shell,
The compositions such as separator, transmission device, feed and exhaust tube.
4. a kind of method of continuous flow upstream nitrification production dinitrobenzene as described in claim 1, which is characterized in that above-mentioned continuous inverse
Device used in stream nitrification production dinitrobenzene is by 4 nitrification machines, two prewashers, two neutralization machines, two rinsing maching strings
Join.
5. a kind of method of continuous flow upstream nitrification production dinitrobenzene as described in claim 1, which is characterized in that in step (3)
The mass fraction of the sodium hydrate aqueous solution is 8%.
6. a kind of method of continuous flow upstream nitrification production dinitrobenzene as described in claim 1, which is characterized in that in step (3)
The waste water is alkalinity, pH value 8-9.
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