CN109836353A - The method of optimization manufacture cyclohexanone oxime - Google Patents

Abstract

The present invention relates to a kind of methods of optimization manufacture cyclohexanone oxime, this method includes the following steps: that carrying out acid-base reaction with ammonium phosphate and nitric acid forms ammonium nitrate and phosphoric acid, again by phosphoric acid and ammonium nitrate plus hydrogen be raw material under catalyst catalysis by nitrate reduction at phosphatic hydroxylamine, ammonium phosphate and water, wherein, phosphatic hydroxylamine carries out oximation reaction with cyclohexanone again and forms cyclohexanone oxime；It is characterized by: adjusting a certain proportion of phosphate radical (PO in the manufacturing process₄ ^‑)And nitrate anion (NO₃ ^‑)) concentration, and make phosphate radical (PO₄ ^‑)) concentration be greater than nitrate anion (NO₃ ^‑)) concentration, phosphatic hydroxylamine production capacity can be made to be promoted.

Description

The method of optimization manufacture cyclohexanone oxime

Technical field

The present invention is about a kind of method for manufacturing cyclohexanone oxime；In more detail, particularly relating to one kind has preferable life The method for producing the optimization manufacture cyclohexanone oxime of efficiency.

Background technique

In production caprolactam processing procedure, cyclohexanone oxime is one of them indispensable intermediate product, and utilizes hexamethylene It is the major technique for preparing cyclohexanone oxime at present that ketone and phosphatic hydroxylamine reaction, which generate corresponding oxime, therefore, the manufacture of cyclohexanone oxime The production cost and yield of caprolactam will be directly affected.

In general, the processing procedure of cyclohexanone oxime with phosphate as buffer, be that raw material is catalyzed in catalyst using nitric acid, hydrogen It is lower by nitrate reduction at azanol, aforementioned process is known as azanol reaction, and be formed by azanol again with cyclohexanone carry out oxime To change reaction and forms cyclohexanone oxime, nitric acid is added in the phosphate inorganic processing procedure liquid after oximation reaction or absorption nitrous gas forms nitric acid, To increase the content of required nitrate ion, azanol reaction is then added to prepare azanol, reaction is shown below:

1) reaction equation of general azanol reaction manufacture azanol are as follows:

NH₄NO₃+2H₃PO₄+3H₂→NH₃OH.H₂PO₄+NH₄H₂PO₄+2H₂O

2) if azanol reaction is indicated with ionic reaction formula are as follows:

NO₃ ^-+2H⁺+3H₂→NH₃OH.+2H₂O

3) oximation reaction manufactures cyclohexanone oxime

NH₃OH.H₂PO₄+C₆H₁₀O→C₆H₁₀NOH+H₂O+H₃PO₄

4) nitrate ion of phosphate inorganic processing procedure liquid is supplemented

HNO₃+H₂PO₄ ^-→NO₃ ^-+H₃PO₄

So, in known cyclohexanone oxime processing procedure, often by phosphoric acid (H₃PO₄) buffer is regarded as, therefore ignore phosphoric acid (H₃PO₄) be manufacture azanol reaction in main reactant one, there is no be directed to phosphoric acid (H₃PO₄) concentration regulated and controled, Therefore lead to the phosphatic hydroxylamine (NH generated₃OH.H₂PO) concentration is insufficient, and then leads to not carry out phosphatic hydroxylamine fully reacting, Finally, the generation of phosphatic hydroxylamine is unstable, cause cyclohexanone concentration during oximation reaction higher, the cyclohexanone oxime ultimately produced Concentration is relatively fewer, causes the production efficiency of the processing procedure bad, or even causes many losses.

Summary of the invention

In view of this, the purpose of the present invention is to provide a kind of, the optimization with preferable production efficiency manufactures cyclohexanone oxime Method.

To achieve the above object, the present invention provides a kind of method of optimization manufacture cyclohexanone oxime, under this method includes Column step: acid-base reaction is carried out with ammonium phosphate and nitric acid and forms ammonium nitrate and phosphoric acid, then is plus hydrogen by phosphoric acid and ammonium nitrate Raw material carries out azanol reaction under catalyst catalysis, by nitrate reduction at phosphatic hydroxylamine, ammonium phosphate and water, wherein phosphoric acid Azanol carries out oximation reaction with cyclohexanone again and forms cyclohexanone oxime；It is characterized by: being adjusted a certain proportion of in the manufacturing process Phosphate radical (PO₄ ^-) and nitrate anion (NO₃ ^-) concentration, and make phosphate radical (PO₄ ^-) concentration be greater than nitrate anion (NO₃ ^-) concentration, phosphoric acid can be made Azanol production capacity is promoted.

It connects aforementioned, wherein the acid-base reaction is as follows:

HNO₃+NH₄H₂PO₄→NH₄NO₃+H₃PO₄

And azanol reaction is as follows:

NH₄NO₃+2H₃PO₄+3H₂→NH₃OH.H₂PO₄+NH₄H₂PO₄+2H₂O

Finally, the oximation reaction carried out again is as follows:

NH₃OH.H₂PO₄+C₆H₁₀O→C₆H₁₀NOH+H₂O+H₃PO₄

Further, in the phosphate radical and nitrate anion ratio, respectively nitrate concentration reduces 1.35mole/kg and phosphorus It is that ratio carries out processing procedure that acid group concentration, which reduces 0.5mole/kg,.

The invention has the following advantages:

Method provided by the present invention is mixed with ammonium nitrate and hydrogen by improving phosphoric acid concentration, hydrogen can be solved The problem of ion insufficient supply, and then the generation concentration of phosphatic hydroxylamine can be improved, then by enough phosphatic hydroxylamine and cyclohexanone into Row oximation reaction can be reacted completely, so can effectively reduce cyclohexanone concentration, improve production cyclohexanone oxime efficiency, And without increasing equipment, production cost can be combined, the purpose for improving production efficiency can be also reached.

Specific embodiment

The following example will be further illustrated the embodiments such as other features and advantages of the present invention, but this it is merely illustrative and With not limitation of the present invention.

Present pre-ferred embodiments optimization manufacture cyclohexanone oxime method, this method include the following steps: by ammonium phosphate with Nitric acid carries out acid-base reaction and forms ammonium nitrate and phosphoric acid, then by phosphoric acid and ammonium nitrate plus hydrogen be raw material under catalyst catalysis into Row azanol reaction, by nitrate reduction at phosphatic hydroxylamine, ammonium phosphate and water, wherein phosphatic hydroxylamine is carried out with cyclohexanone again Oximation reaction forms cyclohexanone oxime, and the ammonium phosphate after oximation reaction adds nitric acid or absorption nitrous gas to generate nitric acid, to increase The content of nitrate ion required for adding, is then added to azanol reaction to supplement and prepares phosphatic hydroxylamine, and processing procedure is allowed to continue reaction forever； It is characterized by: promoting a certain proportion of phosphate radical (PO in the processing procedure₄ ^-) concentration, and make phosphate radical (PO₄ ^-) concentration be greater than nitre Acid group (NO₃ ^-) concentration, phosphatic hydroxylamine production capacity can be made to be promoted.

Wherein, the phosphate radical and nitrate anion ratio, respectively nitrate concentration reduce 1.35mole/kg and phosphate concentration Reducing 0.5mole/kg is that ratio carries out processing procedure.

Continue aforementioned, relative in known cyclohexanone oxime preparation process, by azanol reaction with molecule structure change, and leads to Experimental data after crossing actual measurement confirms that it is described in detail the reason of it causes loss and please refers to table 1,2, and table 1 is known The ion concentration table of reactant and product in azanol reaction, table 2 are the molecular structure concentration table promoted after production capacity.

The chemical equation of known manufacture cyclohexanone oxime are as follows:

1) acid-base reaction: HNO₃+NH₄H₂PO₄→NH₄NO₃+H₃PO₄

2) redox reaction: NH₄NO₃+2H₃PO₄+3H₂→NH₃OH.H₂PO₄+NH₄H₂PO₄

+2H₂O

3) buffer function dissociates phosphoric acid (H₃PO₄): 2H₃PO₄→2H₂PO₄ ^-+2H⁺

4) oximation reaction: C₆H₁₀O+NH₃OH.H₂PO₄→C₆H₁₀NOH+H₃PO₄+H₂O

5) buffer function synthesizes phosphoric acid (H₃PO₄): H₂PO₄ ^-+H⁺→H₃PO₄

And the main reactant of its process and the ion of product are hydrogen ion (H⁺), oxyammonia radical ion (NH₃OH⁺)、 Phosphate anion (PO₄ ^3-), amine radical ion (NH₄ ⁴⁺), nitrate ion (NO₃ ^-), as shown in table 1.

Table 1

And the essential molecular structure concentration in its processing procedure is hydrogen ion (H⁺), nitrate anion (NO₃ ^-), phosphate radical (PO₄ ^-), hydrogen-oxygen Change amine (NH₃OH), phosphatic hydroxylamine (NH₄H₂PO₄), as shown in table 2:

Table 2

The table of comparisons 1,2 simultaneously, to survey 1~5 average value nitrate ion (NO₃ ^-) concentration be 2.88mole/kg from the point of view of, Oxyammonia radical ion (the NH of 1.2mole/kg can not be generated in table 1₃OH⁺), because of phosphate anion (PO₄ ^3-) only 2.484mole/kg can only catch the oxyammonia radical ion (NH of 1.09mole/kg reluctantly₃OH⁺), it is caught to reach in table 2 Oxyammonia radical ion (the NH of 1.2mole/kg₃OH⁺) then need phosphate anion (PO₄ ^3-) reach 3.23mole/kg, therefore table 1 In can not generate the oxyammonia radical ion (NH of 1.2mole/kg₃OH⁺), and in the oxyammonia root for generating 1.09mole/kg Ion (NH₃OH⁺) during completely depleted phosphate anion (PO₄ ^3-), therefore the production capacity of known processing procedure reaction can not have Effect generates enough oxyammonia radical ion (NH₃OH⁺)。

Therefore, as shown in table 2, the present invention is by molecular structure concentration phosphate radical (PO₄) concentration is promoted to greater than nitrate anion (NO₃) concentration, and it sets concentration ratio as nitrate anion (NO₃) concentration reduction 1.35mole/kg, while also by phosphate radical (PO₄) concentration reduces 0.5mole/kg, while experiment is stepped up hydrogen (H₂) uptake reduce free nitric acid, and with this Proportional concentration is reacted, and phosphate radical (PO can be made₄) there are also residues after the reaction, therefore azanol reaction carries out reaction completely simultaneously Yield can be improved.

Connect aforementioned, the phosphate radical (PO known to reaction equation₄) it in processing procedure is buffer, therefore increasing its concentration can't It causes to be lost, instead via A~H confirmation is surveyed in table 2, as long as nitrate anion (NO in processing procedure₃) concentration is sufficient, phosphate buffer is dense Degree, hydrogen cooperation increase, that is, may achieve the purpose of azanol reaction production capacity promotion.

In other words, the present embodiment is specific by phosphoric acid molecules structure (PO₄) concentration is promoted to 2.68mole/kg or more, this When phosphoric acid (H₃PO₄) although it is the role of buffer, and its concentration is improved, and adjustment nitrate anion (NO₃) concentration and hydrogen, i.e., Enough hydrogen ion (H can be dissociateed⁺), as hydrogen ion (H⁺) needed for concentration enough provides in azanol reaction, that is, produce enough phosphorus Sour azanol (NH₃OH.H₂PO₄), and then mixed with cyclohexanone, generate enough cyclohexanone oximes.

Therefore, as long as passing through the phosphate concentration and nitrate concentration for improving special ratios, hydrogen ion supply can be solved Insufficient problem, and then the generation concentration of phosphatic hydroxylamine can be improved, then enough phosphatic hydroxylamines and cyclohexanone progress oximate is anti- It answers, can be reacted completely, so can effectively reduce cyclohexanone concentration, improve production cyclohexanone oxime efficiency, and be not necessarily to Increase equipment, production cost can be combined, can also reach the purpose for improving production efficiency.

In conclusion the present invention optimize manufacture cyclohexanone oxime method have the advantages that it is following:

1. the present invention only needs to promote phosphoric acid (H₃PO₄) content, and phosphorus can be improved to be reacted with nitric acid with special ratios The production capacity of sour azanol, that is, can be improved production efficiency.

2. promoting phosphoric acid (H₃PO₄) content, and to be reacted the production that phosphatic hydroxylamine can be improved with special ratios with nitric acid Can, without increasing manufacturing facilities, production cost can be reduced.

In conclusion the foregoing is merely presently preferred embodiments of the present invention, not thereby limits patent of the invention and protect Shield range, therefore description of the invention and the made equivalence changes of attached drawing etc. such as, should all be included in protection scope of the present invention.

Claims (2)

1. a kind of method of optimization manufacture cyclohexanone oxime, this method includes the following steps: anti-with ammonium phosphate and nitric acid progress soda acid Should form ammonium nitrate and phosphoric acid, then by phosphoric acid and ammonium nitrate plus hydrogen be raw material under catalyst catalysis by nitrate reduction At phosphatic hydroxylamine, ammonium phosphate and water, wherein phosphatic hydroxylamine carries out oximation reaction with cyclohexanone again and forms cyclohexanone oxime；Its feature It is, in the manufacturing process, adjusts a certain proportion of phosphate radical (PO₄ ^-) and nitrate anion (NO₃ ^-) concentration, and make phosphate radical (PO₄ ^-) Concentration is greater than nitrate anion (NO₃ ^-) concentration, phosphatic hydroxylamine production capacity can be made to be promoted, and then increase the generation of cyclohexanone oxime.

2. the method for optimization manufacture cyclohexanone oxime as described in claim 1, which is characterized in that the phosphate radical and nitrate anion ratio Example, respectively nitrate concentration reduce 1.35mole/kg and phosphate concentration reduces 0.5mole/kg and carries out processing procedure for ratio.