CN100494050C - Method for preparing hydroxylamine - Google Patents
Method for preparing hydroxylamine Download PDFInfo
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- CN100494050C CN100494050C CNB2006100752583A CN200610075258A CN100494050C CN 100494050 C CN100494050 C CN 100494050C CN B2006100752583 A CNB2006100752583 A CN B2006100752583A CN 200610075258 A CN200610075258 A CN 200610075258A CN 100494050 C CN100494050 C CN 100494050C
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- buffer solution
- acidic buffer
- azanol
- phenyl
- treatment
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Abstract
The invention discloses a making method of hydroxylamine, which comprises the following steps: (1) forming acid buffer to predispose; (2) utilizing hydrogen to reduce nitrate radical in the acid buffer into hydroxylamine under catalyst condition; adopting the compound with functional group as formula (I) to predispose to separate metal impurity from the acid buffer. The method uses acid buffer without metal impurity after predisposing to do hydroxylamine reaction, which can improve the selecting rate of the hydroxylamine reaction obviously.
Description
Technical field
The present invention relates to a kind of method of making azanol, particularly a kind of hydrogen reducing nitrate ion that utilizes is to make the method for azanol.
Background technology
The manufacturing of industrial relevant azanol normally recycles in conjunction with other manufacturing process, hydroxylamine-oximation circulatoing system for example, be exactly as inorganic treating liquid with phosphoric acid salt, with nitric acid, hydrogen is that raw material becomes azanol with nitrate reduction under catalyst, and formed azanol carries out oximation reaction with pimelinketone again and forms cyclohexanone-oxime.Phosphoric acid salt inorganic treating liquid behind the oximation reaction adds nitric acid or absorption nitrous acid gas body forms nitric acid, to increase the content of needed nitrate ion, enters hydroxylamine reactor again and prepares azanol, and its reaction is shown below:
Azanol reaction is made phosphatic hydroxylamine
NH
4NO
3+2H
3PO
4+3H
2→NH
3OH.H
2PO
4+NH
4H
2PO
4+2H
2O
Oximation reaction is made cyclohexanone-oxime
NH
3OH.H
2PO
4+C
6H
10O→C
6H
10NOH+H
2O+H
3PO
4
Replenish the nitrate ion of phosphoric acid salt inorganic treating liquid
HNO
3+H
2PO
4 -→NO
3 -+H
3PO
4
Use circularly in this manufacturing processed and contain phosphatic inorganic treating liquid, therefore, the quality of this inorganic treating liquid quality will directly influence the quality of the azanol of manufacturing with composition.Because this inorganic treating liquid is to use phosphoric acid salt as the acidic buffer solvent, form acidic buffer solution.This acidic buffer solution is meeting corroding metal equipment or facility in working cycle, and metal is dissolved in this acidic buffer solution, forms metallic impurity, causes the selection rate of azanol reaction to descend.
For example, the U.S. the 3rd, 767, No. 758 patents, disclosed content promptly point out to use the inorganic treating liquid that contains molybdenum, rhodium, ruthenium metal can cause the selection rate of azanol reaction to descend.Again, the U.S. the 4th, 062, No. 927 patent is disclosed, by nitrate radical or nitrogen protoxide in acidic liquid, when producing azanol reaction via hydro-reduction, thereby this acidic liquid meeting etching apparatus or facility contain heavy metal contaminants, and especially the molybdenum pollution can make selection rate descend 5～15%.This patent is to be that metal ion in precipitation agent and the acidic solution produces precipitation with the ammonium phosphate molysite, in order to remove this metal pollutant.
But this precipitin reaction must could generate throw out under the condition more than the pH3.5, with regard to employed acid inorganic treating liquid in the hydroxylamine-oximation circulatoing system, must use alkali lye to regulate the pH value, cause the cost increase, make technology complicated more, and selection rate only has been promoted to 83%.
Therefore, still need a kind of technology simple, and can effectively improve the method for azanol selection rate.
Summary of the invention
The object of the present invention is to provide a kind of method of making azanol, can improve the selection rate of azanol reaction.
Another object of the present invention is to provide a kind of method of making azanol, can remove the copper metal in this acidic buffer solution effectively.
Another purpose of the present invention is to provide a kind of method of making azanol, can remove the nickel metal in this acidic buffer solution effectively.
For achieving the above object, the invention provides a kind of method of making azanol, comprising: (1) forms acidic buffer solution and carries out pre-treatment; And (2) utilize hydrogen that the reducing nitrate radical in this acidic buffer solution is become azanol under the condition that catalyzer exists; This pre-treatment is to use compound separating metal impurity in this acidic buffer solution of the functional group shown in (I) that has following formula:
(in the formula, each symbol defines in the following description).Method of the present invention is to use the acidic buffer solution through pre-treatment removal metallic impurity to carry out azanol reaction, thereby can improve the selection rate of azanol reaction significantly.
Embodiment
Below by specific specific examples embodiments of the present invention are described, those of ordinary skills can understand other advantage of the present invention and effect easily by the disclosed content of this specification sheets.The present invention also can implement or uses by other different specific examples, and the every details in this specification sheets also can be based on different viewpoints and application, carries out various modifications and change under the spirit of the present invention not breaking away from.
Method of the present invention is under the condition that catalyzer exists, and utilizes hydrogen that the nitrate reduction in the pretreated acidic buffer solution is become azanol.This acidic buffer solution comprises acid buffer agent, nitric acid or nitrate and metallic impurity, and the example of this acid buffer agent comprises sulfuric acid, phosphoric acid and acid salt thereof.
In one embodiment, method of the present invention is to use the acidic buffer solution of the phosphoric acid salt inorganic treating liquid of hydroxylamine-oximation circulatoing system as synthetic phosphatic hydroxylamine, with total restatement of this acidic buffer solution, this acidic buffer solution comprises the nitrate ion of the ammonium radical ion of the phosphate anion of the hydrogen ion of about 0.15 to 0.18 weight %, about 21.4 to 23.7 weight %, about 4.6 to 5.3 weight %, the azanol ion of about 0.033 to 0.16 weight %, about 8.6 to 10.7 weight % and tens of ppb copper metallic impurity and the nickel metallic impurity to tens of ppm.Because the metallic impurity in this acidic buffer solution can cause the selection rate of azanol reaction to descend, and must carry out pre-treatment earlier it is removed.In specification sheets of the present invention, this azanol selection rate is defined as follows:
Azanol selection rate=azanol quantum of output/hydrogen ion consumption * 100%.
In the method for the invention, this pre-treatment is to use compound separating metal impurity in this acidic buffer solution of the functional group shown in (I) that has following formula:
In the formula, R
1, R
2, and R
3The phenyl that is the phenyl that is independently selected from hydrogen, phenyl, replaces through the C1-6 alkyl, replaces through nitro, the phenyl that replaces through amido, the phenyl that replaces through halogen, have 1 to 3 heteroatomic heteroaryl ,-XR
4, and cohort that polymkeric substance constituted; Wherein, this heteroatoms be selected from N, O, and S atom cohort, this heteroaryl of being constituted be meant that aromatic group, X with 6 to 18 carbon atoms are the alkylidene groups with 1 to 6 carbon atom, R
4Be to be selected from hydrogen, phenyl, to have 1 to 3 cohort that heteroatomic heteroaryl and polymkeric substance constituted, and R
1, R
2, and R
3Have at least one not to be hydrogen.Preferably, this polymkeric substance is polystyrene divinylbenzene multipolymer, this R
2With R
3Be-XR
4And X is expression methylene radical and R
4Be pyridyl.
In this specific embodiment, this pre-treatment is to make this acidic buffer solution by having the resin bed of the functional group of structure shown in the formula (I).Usually, this flow is in 0.1 to 40BV/ hour scope, and is preferred in 0.1 to 12BV/ hour scope, preferred in 0.5 to 4BV/ hour scope, preferred again in 1 to 3.5BV/ hour scope.This pre-treatment can be carried out under in 0 to 50 ℃ the temperature condition, carries out under preferred in 10 to 40 ℃ the temperature condition, carry out under preferred in 10 to the 25 ℃ temperature condition, but not limited thereto.
In this specific embodiment, be to use phosphoric acid salt inorganic treating liquid in this hydroxylamine-oximation circulatoing system as the acidic buffer solution of making phosphatic hydroxylamine.Therefore this acidic buffer solution is before preparing to carry out the building-up reactions of azanol through pre-treatment, the step that can replenish nitrate ion earlier.With total restatement of this acidic buffer solution, the nitrate ion content in this acidic buffer solution preferably is adjusted in the scope of 13 to 18 weight %, in the preferred scope that is adjusted to 14 to 16.5 weight %.
In the method for the present invention, there is no particular restriction to carry out the condition of this azanol reaction, and the reaction conditions of general using hydrogen reducing nitrate ion is all applicable.For example, can be 20 to 100 ℃ temperature range, preferably 30 to 90 ℃ temperature range, preferred temperature range at 40 to 65 ℃; And 10 to 30 kilograms/square centimeter pressure range, preferably 18 to 26 kilograms/square centimeter pressure range, preferred pressure range at 18 to 24 kilograms/square centimeter.The example of the employed catalyzer of this azanol reaction comprises, but is not limited only to contain the noble metal catalyst of palladium, or palladium-platinum catalyst GeO
2The example of this support of the catalyst comprises, but is not limited only to carbon or aluminum oxide.Usually, with total restatement of this support of the catalyst and catalyzer, this usage of noble metal catalysts is between 1 to 25 weight %, preferably between 5 to 15 weight %.The amount of the employed catalyzer of this azanol reaction is with total restatement of this acidic buffer solution, normally in the scope of 0.2 to 5 weight %.
Method of the present invention is to use the building-up reactions of carrying out azanol through pretreated acidic buffer solution, because this pre-treatment step can be removed metallic impurity such as copper and nickel effectively in this acidic buffer solution, therefore can obviously improve the selection rate of this azanol reaction.
Below, be described in further detail characteristics of the present invention and effect by specific embodiment.But these implementation details only are in order to characteristics of the present invention to be described, and are not used for limiting the scope of the invention.
Embodiment 1
The phosphoric acid salt inorganic treating liquid of getting hydroxylamine-oximation circulatoing system is as the acidic buffer solution of making phosphatic hydroxylamine.Carry out the composition of this phosphoric acid salt inorganic treating liquid of titrimetry, and utilize inductive couple plasma atomic radiations spectrum (ICP-OES), analyze the metal content of this inorganic treating liquid, and with outcome record in table 1.
This phosphoric acid salt inorganic treating liquid be flow velocity with 2BV per hour by having the resin bed of functional group shown in the following formula, carry out pre-treatment
Then, absorb the step of nitric acid.The phosphoric acid salt inorganic treating liquid of analyzing behind this absorption nitric acid is formed and metal content, and its result is as shown in table 1.
Table 1
Under the condition that the pressure and the catalyzer of 50 ℃ temperature and 24 kilograms/square centimeter exists, import hydrogen and nitrogen, carry out azanol reaction, make phosphatic hydroxylamine, azanol selection rate 91.20%.
Embodiment 2
The phosphoric acid salt inorganic treating liquid of getting hydroxylamine-oximation circulatoing system is as the acidic buffer solution of making phosphatic hydroxylamine.Carry out the composition of this phosphoric acid salt inorganic treating liquid of titrimetry, and utilize inductive couple plasma atomic radiations spectrum (ICP-OES), analyze the metal content of this inorganic treating liquid, and with outcome record in table 2.
This phosphoric acid salt inorganic treating liquid be flow velocity with 2BV per hour by having the resin bed of functional group shown in the following formula, carry out pre-treatment
Then, absorb the step of nitric acid.The phosphoric acid salt inorganic treating liquid of analyzing behind this absorption nitric acid is formed and metal content, and its result is as shown in table 2.
Table 2
Under the condition that the pressure and the catalyzer of 50 ℃ temperature and 24 kilograms/square centimeter exists, import hydrogen and nitrogen, carry out azanol reaction, make phosphatic hydroxylamine, azanol selection rate 91.8%.
Comparative example 1
The phosphoric acid salt inorganic treating liquid of getting hydroxylamine-oximation circulatoing system is as the acidic buffer solution of making phosphatic hydroxylamine.Carry out the composition of this phosphoric acid salt inorganic treating liquid of titrimetry, and utilize inductive couple plasma atomic radiations spectrum (ICP-OES), analyze the metal content of this inorganic treating liquid, and with outcome record in table 3.
Table 3
Under the condition that the pressure and the catalyzer of 50 ℃ temperature and 24 kilograms/square centimeter exists, import hydrogen and nitrogen, carry out azanol reaction, make phosphatic hydroxylamine, azanol selection rate 85.58%.
Comparative example 2
The phosphoric acid salt inorganic treating liquid of getting hydroxylamine-oximation circulatoing system is as the acidic buffer solution of making phosphatic hydroxylamine.Carry out the composition of this phosphoric acid salt inorganic treating liquid of titrimetry, and utilize inductive couple plasma atomic radiations spectrum (ICP-OES), analyze the metal content of this inorganic treating liquid, and with outcome record in table 4.
Table 4
Under the condition that the pressure and the catalyzer of 50 ℃ temperature and 24 kilograms/square centimeter exists, import hydrogen and nitrogen, carry out azanol reaction, make phosphatic hydroxylamine, azanol selection rate 76.49%.
Comparative example 3
The phosphoric acid salt inorganic treating liquid of getting hydroxylamine-oximation circulatoing system is as the acidic buffer solution of making phosphatic hydroxylamine.Carry out the composition of this phosphoric acid salt inorganic treating liquid of titrimetry, and utilize inductive couple plasma atomic radiations spectrum (ICP-OES), analyze the metal content of this inorganic treating liquid, and with outcome record in table 5.
Table 5
Under the condition that the pressure and the catalyzer of 50 ℃ temperature and 24 kilograms/square centimeter exists, import hydrogen and nitrogen, carry out azanol reaction, make phosphatic hydroxylamine, azanol selection rate 51.33%.
The result of comparative examples and comparative example as can be known, method of the present invention can be removed metallic impurity such as the copper of this acidic buffer solution and nickel effectively, carries out azanol reaction again, obviously improves the selection rate of azanol reaction.
The foregoing description is only for example understood principle of the present invention and effect thereof, rather than is used to limit the present invention.Those of ordinary skills all can be under spirit of the present invention and category, and the foregoing description is modified and changed.Therefore, the scope of the present invention should be as described in claims.
Claims (9)
1. method of making azanol, this method comprises the following steps:
(1) form and to comprise the acidic buffer solution of acid buffer agent, nitric acid or nitrate and metallic impurity and to carry out pre-treatment, this pre-treatment is to use compound separating metal impurity in this acidic buffer solution of the functional group shown in (I) that has following formula:
In the formula, R
1, R
2, and R
3Be be independently selected from hydrogen, phenyl, through C
1-6The phenyl that alkyl replaces, the phenyl that replaces through nitro, the phenyl that replaces through amido, the phenyl that replaces through halogen, have 1 to 3 heteroatomic heteroaryl ,-XR
4, and the cohort that constituted of polystyrene divinylbenzene multipolymer; Wherein, this heteroatoms be selected from N, O, and S atom cohort, this heteroaryl of being constituted be meant that aromatic group, X with 6 to 18 carbon atoms are the alkylidene groups with 1 to 6 carbon atom, R4 is selected from hydrogen, phenyl, has the cohort that 1 to 3 heteroatomic heteroaryl and polystyrene divinylbenzene multipolymer are constituted, and R
1, R
2, and R
3Have at least one not to be hydrogen; And
(2) under the condition that catalyzer exists, utilize hydrogen that the reducing nitrate radical in this acidic buffer solution is become azanol.
2. the method for claim 1, wherein said R
2With R
3Be-XR
4, X is expression methylene radical and R
4Be pyridyl.
3. the method for claim 1, wherein said pre-treatment are to carry out under in 0 to 50 ℃ the temperature condition.
4. method as claimed in claim 3, wherein said pre-treatment are to carry out under in 10 to 40 ℃ the temperature condition.
5. method as claimed in claim 4, wherein said pre-treatment are to carry out under in 10 to 25 ℃ the temperature condition.
6. the method for claim 1, wherein said metallic impurity are to comprise copper and nickel.
7. the method for claim 1, wherein said acidic buffer solution is an oximation reaction of taking from the synthesizing cyclohexane 1 ketoxime.
8. the method for claim 1 also comprises the step of replenishing the nitrate ion content in this acidic buffer solution between wherein said step (1) and the step (2).
9. the method for claim 1, the acid buffer agent in the wherein said acidic buffer solution is to be selected from the cohort that sulfuric acid, phosphoric acid and acid salt thereof constitute.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100752583A CN100494050C (en) | 2006-04-17 | 2006-04-17 | Method for preparing hydroxylamine |
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|---|---|---|---|
| CNB2006100752583A CN100494050C (en) | 2006-04-17 | 2006-04-17 | Method for preparing hydroxylamine |
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| CN100494050C true CN100494050C (en) | 2009-06-03 |
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| CN103987658A (en) | 2011-12-29 | 2014-08-13 | 帝斯曼知识产权资产管理有限公司 | Process for the continuous preparation of hydroxylamine |
| EP2682365A1 (en) * | 2012-07-06 | 2014-01-08 | DSM IP Assets B.V. | Process for the production of hydroxylamine by reduction of nitrate or nitrogen monoxide |
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