CN100500641C - Method for manufacturing hydroxylamine - Google Patents
Method for manufacturing hydroxylamine Download PDFInfo
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- CN100500641C CN100500641C CNB2006100759811A CN200610075981A CN100500641C CN 100500641 C CN100500641 C CN 100500641C CN B2006100759811 A CNB2006100759811 A CN B2006100759811A CN 200610075981 A CN200610075981 A CN 200610075981A CN 100500641 C CN100500641 C CN 100500641C
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Abstract
The invention discloses a preparing method of hydroxylamine, which comprises the following steps: leading water-based reaction medium with acid buffer, nitrate radical and little iron-copper metallic impurity into hydroxylamine synthetic zone; proceeding hydroxylamine synthetic reaction under the condition of activator; deacidizing nitrate radical of water-based reaction medium to hydroxylamine with hydrogen gas. This method make the water-based reaction medium proceed hydroxylamine synthetic reaction, which can increase selective ratio of reaction.
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 aqueous reaction medium 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.Behind the oximation reaction, restock nitric acid or absorption nitrous acid gas body form nitric acid, to increase the content of needed nitrate ion, enter hydroxylamine reactor again and prepare azanol, and its reaction is shown below:
Azanol reaction is made phosphatic hydroxylamine
NH
4NO
3+2H
3PO
4+3H
2→NH
3OHH
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
In this manufacturing processed, aqueous reaction medium is to synthesize circulation between the district in azanol reaction district and cyclohexanone-oxime, and the quality of reaction medium is good and bad will directly to influence the efficient of azanol reaction with composition.The U.S. the 3rd, 767, No. 758 patents, disclosed content promptly point out to use the aqueous reaction medium that contains molybdenum, rhodium, ruthenium metal can cause the selection rate of azanol reaction to descend.The U.S. the 4th, 062, No. 927 patent is also disclosed, thus heavy metal contaminants, especially molybdenum pollution that acidic liquid meeting etching apparatus or facility increase in the reaction medium can make the reaction selection rate descend 5 to 15%.This patent is to be that metal ion in precipitation agent and the reaction medium produces co-precipitation with the ammonium phosphate molysite, and in order to removing this metal pollutant, yet in the content disclosed in this patent, the selection rate of azanol reaction surpasses 87% yet.
Therefore, still need a kind of technology simple, and can effectively improve the method for azanol reaction selection rate.
Summary of the invention
The object of the present invention is to provide a kind of azanol manufacture method, to overcome the above-mentioned defective of existing in prior technology with high selectivity.
For achieving the above object, the invention provides a kind of method of making azanol, this method is to contain acid buffer agent and nitrate radical and only to contain small amounts of iron or the aqueous reaction medium of copper metallic impurity importing hydroxylammonium synthesis zone, under the condition that catalyzer exists, carry out the azanol building-up reactions, utilize hydrogen to make that reducing nitrate radical becomes azanol in the aqueous reaction medium.Method of the present invention is to use metals content impurity aqueous reaction medium low or not even containing metal impurity to advance shape azanol building-up reactions, to improve the selection rate of azanol reaction.
The object of the present invention is achieved like this: a kind of method of making azanol, this method is that the aqueous reaction medium that will contain acid buffer agent and nitrate radical imports hydroxylammonium synthesis zone, under the condition that catalyzer exists, carry out the azanol building-up reactions, make this reducing nitrate radical become azanol, wherein, the iron metal contents in this aqueous reaction medium is below the 100ppm.
Method of the present invention, the iron metal contents in the wherein said aqueous reaction medium is below the 75ppm.
Method of the present invention, the iron metal contents in the wherein said aqueous reaction medium is below the 55ppm.
Purpose of the present invention also can realize like this: a kind of method of making azanol, this method is that the aqueous reaction medium that will contain acid buffer agent and nitrate radical imports hydroxylammonium synthesis zone, under the condition that catalyzer exists, carry out the azanol building-up reactions, make this reducing nitrate radical become azanol, wherein, the copper metal content in this aqueous reaction medium is below the 0.9ppm.
Method of the present invention, the copper metal content in the wherein said aqueous reaction medium is below the 0.09ppm.
Method of the present invention, the copper metal content in the wherein said aqueous reaction medium is below the 0.05ppm.
Method of the present invention, wherein said acid buffer agent are sulfuric acid, phosphoric acid or its acid salt.
Method of the present invention, wherein said acid buffer agent is a phosphoric acid salt.
Method of the present invention, wherein said method is to be used for hydroxylamine-oximation circulatoing system.
Method of the present invention, wherein said azanol building-up reactions are to carry out under 20 to 100 ℃ temperature condition.
Method of the present invention, wherein said azanol building-up reactions are to carry out under 10 to 30 kilograms/square centimeter pressure condition.
Method of the present invention, wherein said azanol building-up reactions is to carry out under the condition of pH0.5 to 6.
Method of the present invention, wherein said catalyzer are palladium or palladium-platinum noble metals catalyzer.
Embodiment
Below by specific examples characteristics of the present invention and effect are described.
Method of the present invention is to contain acid buffer agent, for example sulfuric acid, phosphoric acid or its acid salt, with nitrate radical and only contain on a small quantity or not the aqueous reaction medium of containing metal impurity import hydroxylammonium synthesis zone, under the condition that catalyzer exists, carry out the azanol building-up reactions, utilize hydrogen to make the reducing nitrate radical in the aqueous reaction medium become azanol.This method improves the selection rate of azanol reaction by the metals content impurity in the reduction aqueous reaction medium.In specification sheets of the present invention, this azanol selection rate is defined as follows:
Azanol selection rate=2 times azanol quantum of output/hydrogen ion consumption * 100%.
In a specific examples, method of the present invention is to use the aqueous reaction medium of the phosphoric acid salt inorganic treating liquid of hydroxylamine-oximation circulatoing system as synthetic phosphatic hydroxylamine, the composition of this aqueous reaction medium comprises phosphate anion, ammonium radical ion, nitrate ion and metallic impurity, for example iron, molybdenum, nickel, bismuth, cobalt, copper, manganese, tin, tungsten, zinc etc.For avoiding the metallic impurity in this aqueous reaction medium to cause the selection rate of azanol reaction to descend, in this specific examples, be to carry out pre-treatment earlier, reduce the metals content impurity in this aqueous reaction medium, particularly the content of ferrous metal impurity imports hydroxylammonium synthesis zone with this aqueous reaction medium again and carries out the azanol building-up reactions.This pretreated mode, for example adding precipitation agent forms complex compound and separates this metal complex with metallic impurity, or utilize the filtering mode of resin absorption to remove metallic impurity, but be not limited to this, the mode of various suitable reductions or removal metallic impurity all can be used.
The method according to this invention, this hydroxylammonium synthesis zone are carried out the content of the metallic impurity iron in the aqueous reaction medium of azanol reaction preferably below the 100ppm, below the preferred 75ppm, below the preferred again 55ppm, below the preferred again 30ppm.The selection rate of this azanol reaction is preferably more than 87%, and is preferred more than 90%, preferred again more than 91.5%, preferred again more than 94%.
In this specific examples, be to use phosphoric acid salt inorganic treating liquid in this hydroxylamine-oximation circulatoing system as the aqueous reaction medium of making phosphatic hydroxylamine.This aqueous reaction medium before the building-up reactions of carrying out azanol, can replenish the step of nitrate ion earlier after ferrous metal impurity is removed in pre-treatment.With total restatement of this aqueous reaction medium, the nitrate ion content in this acidic buffer solution preferably is adjusted in the scope of 13 to 18 weight %, preferred 14 to the 16.5 weight % that are adjusted to.
In the method for the present invention, the condition of carrying out azanol reaction at this hydroxylammonium synthesis zone there is no special restriction, 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; And in the pH value in 0.5 to 6 scope, preferably the pH value is carried out in 1 to 3.5 scope.The air inlet of this azanol reaction is formed, and with total total of hydrogen and nitrogen, this hydrogen is normally in 30 to 70% scope, preferably in 45 to 55% scope.The example of the employed catalyzer of this azanol reaction includes but not limited to contain the noble metal catalyst of palladium, or palladium-platinum catalyst.The example of this support of the catalyst includes but not limited to carbon or aluminum oxide.Usually, with total restatement of this support of the catalyst and catalyzer, the amount of this noble metal catalyst 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 %.
Using in phosphoric acid salt inorganic treating liquid another specific examples as the aqueous reaction medium of synthetic phosphatic hydroxylamine of hydroxylamine-oximation circulatoing system, is to utilize the filtering mode of resin absorption to remove copper metallic impurity in the aqueous reaction medium.In this specific examples, this hydroxylammonium synthesis zone carries out the content of the metallic impurity copper in the aqueous reaction medium of azanol reaction preferably below the 0.9ppm, below the preferred 0.09ppm, below the preferred again 0.05ppm.The selection rate of this azanol reaction is preferably more than 90%, and is preferred more than 91.5%, preferred again more than 94%.
In this specific examples, aqueous reaction medium before the building-up reactions of carrying out azanol, can replenish the step of nitrate ion earlier after the copper metallic impurity are removed in pre-treatment.With total restatement of this aqueous reaction medium, the nitrate ion content in this acidic buffer solution preferably is adjusted in the scope of 13 to 18 weight %, preferred 14 to the 16.5 weight % that are adjusted to.The condition of this azanol reaction there is no special restriction, 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; And in the pH value in 0.5 to 6 scope, preferably the pH value is carried out in 1 to 3.5 scope.The air inlet of this azanol reaction is formed, and with total total of hydrogen and nitrogen, this hydrogen is normally in 30 to 70% scope, preferably in 45 to 55% scope.The example of the employed catalyzer of this azanol reaction includes but not limited to contain the noble metal catalyst of palladium, or palladium-platinum catalyst.The example of this support of the catalyst includes but not limited to carbon or aluminum oxide.Usually, with total restatement of this support of the catalyst and catalyzer, the amount of this noble metal catalyst 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 low aqueous reaction medium of metals content impurity to carry out the building-up reactions of azanol, particularly the content of the ferrous metal impurity content that is lower than 100ppm or copper metallic impurity is lower than 0.9ppm, the selection rate of azanol reaction is promoted to more than 87%, or more than 90%, even more than 94%.
By the following examples, further describe characteristics of the present invention and effect.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
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 98ppm, the selection rate 87.20% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.292 weight %
[H
2PO
4 -] 20.13 weight %
[NH
4 +] 4.17 weight %
[NH
3OH
+] 0.082 weight %
[NO
3 -] 15.7 weight %.
Embodiment 2
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 91ppm, the selection rate 88.50% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises;
[H
+] 0.305 weight %
[H
2PO
4 -] 20.17 weight %
[NH
4 +] 4.14 weight %
[NH
3OH
+] 0.077 weight %
[NO
3 -] 16.2 weight %.
Embodiment 3
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 85ppm, the selection rate 89.21% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.297 weight %
[H
2PO
4 -] 20.13 weight %
[NH4
+] 4.14 weight %
[NH
3OH
+] 0.078 weight %
[NO
3 -] 15.25 weight %.
Embodiment 4
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 72ppm, the selection rate 90.50% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.298 weight %
[H
2PO
4 -] 20.13 weight %
[NH
4 +] 4.19 weight %
[NH
3OH
+] 0.082 weight %
[NO
3 -] 15.6 weight %.
Embodiment 5
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 34ppm, the selection rate 91.50% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.301 weight %
[H
2PO
4 -] 20.15 weight %
[NH
4 +] 4.12 weight %
[NH
3OH
+] 0.073 weight %
[NO
3 -] 16.38 weight %.
Embodiment 6
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 25ppm, the selection rate 94.20% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.304 weight %
[H
2PO
4 -] 20.18 weight %
[NH
4 +] 4.08 weight %
[NH
3OH
+] 0.064 weight %
[NO
3 -] 16.4 weight %.
Comparative example 1
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 116ppm, the selection rate 85.21% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.290 weight %
[H
2PO
4 -] 20.11 weight %
[NH
4 +] 4.17 weight %
[NH
3OH
+] 0.079 weight %
[NO
3 -] 14.34 weight %.
Comparative example 2
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 105ppm, the selection rate 86.80% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.293 weight %
[H
2PO
4 -] 20.13 weight %
[NH
4 +] 4.15 weight %
[NH
3OH
+] 0.074 weight %
[NO
3 -] 15.2 weight %.
Comparative example 3
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, ferrous metal impurity 143ppm, the selection rate 84.35% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.295 weight %
[H
2PO
4 -] 20.13 weight %
[NH
4 +] 4.14 weight %
[NH
3OH
+] 0.074 weight %
[NO
3 -] 15.24 weight %.
Table 1 be explanation in the aqueous reaction medium iron metal contents and the selection rate of azanol building-up reactions.
Table 1
| Ferrous metal impurity (ppm) | Selection rate (%) | |
| Embodiment 1 | 98 | 87.20 |
| Embodiment 2 | 91 | 88.50 |
| Embodiment 3 | 85 | 89.21 |
| Embodiment 4 | 72 | 90.50 |
| Embodiment 5 | 34 | 91.50 |
| Embodiment 6 | 25 | 94.20 |
| Comparative example 1 | 116 | 85.21 |
| Comparative example 2 | 105 | 86.80 |
| Comparative example 3 | 143 | 84.35 |
Embodiment 7
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, copper metallic impurity 0.83ppm, the selection rate 90.50% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.298 weight %
[H
2PO
4 -] 20.13 weight %
[NH
4 +] 4.19 weight %
[NH
3OH
+] 0.082 weight %
[NO
3 -] 15.6 weight %.
Embodiment 8
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, copper metallic impurity 0.08ppm, the selection rate 91.50% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.295 weight %
[H
2PO
4 -] 20.13 weight %
[NH
4 +] 4.15 weight %
[NH
3OH
+] 0.082 weight %
[NO
3 -] 15.8 weight %.
Embodiment 9
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, copper metallic impurity 0.03ppm, the selection rate 94.20% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.304 weight %
[H
2PO
4 -] 20.18 weight %
[NH
4 +] 4.08 weight %
[NH
3OH
+] 0.064 weight %
[NO
3 -] 16.4 weight %.
Comparative example 4
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, copper metallic impurity 1.05ppm, the selection rate 85.21% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.290 weight %
[H
2PO
4 -] 20.11 weight %
[NH
4 +] 4.17 weight %
[NH
3OH
+] 0.079 weight %
[NO
3 -] 14.34 weight %.
Comparative example 5
Aqueous reaction medium, hydrogen and nitrogen are imported hydroxylammonium synthesis zone, under the condition that palladium-platinum catalyst exists, under the pressure of 50 ℃ temperature and 24 kilograms/square centimeter, carry out the azanol building-up reactions.Utilize inductive couple plasma atomic radiations spectrum (ICP-OES) to analyze metal content, copper metallic impurity 0.97ppm, the selection rate 86.80% of azanol building-up reactions.With total restatement of this aqueous reaction medium, the composition that imports the aqueous reaction medium of hydroxylammonium synthesis zone comprises:
[H
+] 0.293 weight %
[H
2PO
4 -] 20.13 weight %
[NH
4 +] 4.15 weight %
[NH
3OH
+] 0.074 weight %
[NO
3 -] 15.2 weight %.
Table 2 be explanation in the aqueous reaction medium the copper metal content and the selection rate of azanol building-up reactions.
Table 2
| Copper metallic impurity (ppm) | Selection rate (%) | |
| Embodiment 7 | 0.83 | 90.50 |
| Embodiment 8 | 0.08 | 91.50 |
| Embodiment 9 | 0.03 | 94.20 |
| Comparative example 4 | 1.05 | 85.21 |
| Comparative example 5 | 0.97 | 86.80 |
The result of comparative examples and comparative example as can be known, method of the present invention is to use the low aqueous reaction medium of metals content impurity to carry out the building-up reactions of azanol, when particularly the content of the ferrous metal impurity content that is lower than 100ppm or copper metallic impurity is lower than 0.9ppm, can obviously promote the selection rate of azanol reaction.
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 rights protection of the present invention should be as described in claims.
Claims (10)
1. method of making azanol, this method is to import hydroxylammonium synthesis zone with containing the acid buffer agent of sulfuric acid, phosphoric acid or its acid salt and the aqueous reaction medium of nitrate radical, under the condition that the catalyzer that is selected from palladium or palladium-platinum noble metals exists, carry out the azanol building-up reactions, make this reducing nitrate radical become azanol, wherein, the iron metal contents in this aqueous reaction medium is below the 100ppm.
2. the method for claim 1, the iron metal contents in the wherein said aqueous reaction medium is below the 75ppm.
3. method as claimed in claim 2, the iron metal contents in the wherein said aqueous reaction medium is below the 55ppm.
4. method of making azanol, this method is to import hydroxylammonium synthesis zone with containing the acid buffer agent of sulfuric acid, phosphoric acid or its acid salt and the aqueous reaction medium of nitrate radical, under the condition that the catalyzer that is selected from palladium or palladium-platinum noble metals exists, carry out the azanol building-up reactions, make this reducing nitrate radical become azanol, wherein, the copper metal content in this aqueous reaction medium is below the 0.9ppm.
5. method as claimed in claim 4, the copper metal content in the wherein said aqueous reaction medium is below the 0.09ppm.
6. method as claimed in claim 5, the copper metal content in the wherein said aqueous reaction medium is below the 0.05ppm.
7. as claim 1 or 4 described methods, wherein said method is to be used for hydroxylamine-oximation circulatoing system.
8. method as claimed in claim 7, wherein said azanol building-up reactions are to carry out under 20 to 100 ℃ temperature condition.
9. method as claimed in claim 7, wherein said azanol building-up reactions are to carry out under 10 to 30 kilograms/square centimeter pressure condition.
10. method as claimed in claim 7, wherein said azanol building-up reactions is to carry out under the condition of pH0.5 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100759811A CN100500641C (en) | 2006-04-26 | 2006-04-26 | Method for manufacturing hydroxylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100759811A CN100500641C (en) | 2006-04-26 | 2006-04-26 | Method for manufacturing hydroxylamine |
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| Publication Number | Publication Date |
|---|---|
| CN101062902A CN101062902A (en) | 2007-10-31 |
| CN100500641C true CN100500641C (en) | 2009-06-17 |
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|---|---|---|---|
| CNB2006100759811A Expired - Fee Related CN100500641C (en) | 2006-04-26 | 2006-04-26 | Method for manufacturing hydroxylamine |
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|---|---|
| CN (1) | CN100500641C (en) |
-
2006
- 2006-04-26 CN CNB2006100759811A patent/CN100500641C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 催化还原羟胺. 程永钢.陕西化工，第3期. 1994 |
| 催化还原羟胺. 程永钢.陕西化工，第3期. 1994 * |
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