A method for removing impurities from hydroxylamine aqueous solution

Abstract

The present invention belongs to the technical field of chemical separation and purification, and specifically relates to a method for removing impurities from a hydroxylamine aqueous solution. The method for removing impurities from a hydroxylamine aqueous solution provided by the present invention comprises the following steps: mixing a hydroxylamine aqueous solution and an alkaline compound for sedimentation and then performing solid-liquid separation to obtain a liquid phase; the alkaline compound comprises barium hydroxide or calcium hydroxide; the liquid phase is passed through an ion exchange column for ion exchange to obtain a purified hydroxylamine aqueous solution; the resin in the ion exchange column is a resin containing phenolic hydroxyl groups. The phenolic hydroxyl-containing resin used in the present invention is easy to obtain, has a wide range of sources, and has low cost. The present invention first uses an alkaline solution to remove sulfate or phosphate in a hydroxylamine aqueous solution, and then uses a phenolic hydroxyl-containing resin to efficiently, quickly, and conveniently remove metal ions in the hydroxylamine aqueous solution without reacting with hydroxylamine. The impurity removal method provided by the present invention has the advantages of simple operation and obvious purification effect, and has good industrial prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical separation and purification, and particularly relates to a method for removing impurities from a hydroxylamine aqueous solution. Background Art

[0002] Hydroxylamine and its salts are widely used in industry, for example, as raw materials for intermediates of drugs or agricultural chemicals, as surface treatment agents for metal, fiber treatment or dyeing, etc. Free hydroxylamine has very unstable properties, for example, it is easy to decompose under the action of metal ions under high temperature conditions. Therefore, relatively stable hydroxylamine salts are usually produced and used.

[0003] However, in many applications, hydroxylamine has better application effects than hydroxylamine salts, and the purity of hydroxylamine will also affect the application effect. For example, in the field of electronics industry, higher purity hydroxylamine is required to ensure the quality of electronic products.

[0004] In order to meet the market demand for hydroxylamine purity, methods for purifying hydroxylamine have emerged, but existing purification methods are relatively complex and difficult to apply industrially. Summary of the invention

[0005] In view of this, the present invention provides a method for removing impurities from a hydroxylamine aqueous solution. The method provided by the present invention is simple and easy to operate. By treating the hydroxylamine aqueous solution according to the method provided by the present invention, a hydroxylamine aqueous solution with a higher purity can be obtained.

[0006] In order to solve the above technical problems, the present invention provides a method for removing impurities from a hydroxylamine aqueous solution, comprising the following steps:

[0007] The hydroxylamine aqueous solution and the alkaline compound are mixed and precipitated to separate the solid and the liquid, and the liquid phase is obtained; the alkaline compound comprises barium hydroxide or calcium hydroxide;

[0008] The liquid phase is passed through an ion exchange column for ion exchange to obtain a purified hydroxylamine aqueous solution; the resin in the ion exchange column is a resin containing phenolic hydroxyl groups.

[0009] Preferably, the resin containing phenolic hydroxyl groups includes PHS resin.

[0010] Preferably, the ion exchange further comprises:

[0011] sequentially introducing water and a first hydrochloric acid solution into the ion exchange column for washing;

[0012] The washed resin is immersed in a second hydrochloric acid solution and then washed with water to obtain an activated resin.

[0013] Preferably, the flow rate of water into the ion exchange column is 15-40 m / h.

[0014] Preferably, the mass concentration of the first hydrochloric acid solution is 3-5%; and the volume ratio of the first hydrochloric acid solution to the resin is 1.8-2.2:1.

[0015] Preferably, the flow rate of the first hydrochloric acid solution into the ion exchange column is 3-5 m / h.

[0016] Preferably, the mass concentration of the second hydrochloric acid solution is 3-5%; the volume ratio of the second hydrochloric acid solution to the resin is 0.8-1.2:1;

[0017] The soaking time is 4 to 8 hours.

[0018] Preferably, the flow rate of the liquid phase passing into the ion exchange column is 5-25 m / h.

[0019] Preferably, the hydroxylamine aqueous solution is a hydroxylamine aqueous solution prepared using ammonia water and hydroxylamine salt as raw materials;

[0020] The hydroxylamine salt includes hydroxylamine sulfate or hydroxylamine phosphate.

[0021] Preferably, the mass concentration of the hydroxylamine aqueous solution is 18-22%.

[0022] The present invention provides a method for removing impurities from a hydroxylamine aqueous solution, comprising the following steps: mixing a hydroxylamine aqueous solution and an alkaline compound, performing solid-liquid separation after sedimentation, and taking a liquid phase; the alkaline compound comprises barium hydroxide or calcium hydroxide; passing the liquid phase into an ion exchange column for ion exchange to obtain a purified hydroxylamine aqueous solution; the resin in the ion exchange column is a resin containing phenolic hydroxyl groups. The phenolic hydroxyl-containing resin used in the present invention is easy to obtain, has a wide source, and is low in cost. The present invention first uses an alkaline compound to remove sulfate or phosphate in the hydroxylamine aqueous solution, and then uses the phenolic hydroxyl-containing resin to efficiently, quickly, and conveniently remove metal ions in the hydroxylamine aqueous solution without reacting with hydroxylamine. The impurity removal method provided by the present invention has the advantages of simple operation and obvious purification effect, and has good industrial prospects. DETAILED DESCRIPTION

[0023] The present invention provides a method for removing impurities from a hydroxylamine aqueous solution, comprising the following steps:

[0024] The hydroxylamine aqueous solution and the alkaline compound are mixed and precipitated to separate the solid and the liquid, and the liquid phase is obtained; the alkaline compound comprises barium hydroxide or calcium hydroxide;

[0025] The liquid phase is passed through an ion exchange column for ion exchange to obtain a purified hydroxylamine aqueous solution; the resin in the ion exchange column is a resin containing phenolic hydroxyl groups.

[0026] The present invention mixes a hydroxylamine aqueous solution and an alkaline compound, performs solid-liquid separation after sedimentation, and obtains a liquid phase. As a specific embodiment of the present invention, the hydroxylamine aqueous solution can be a hydroxylamine aqueous solution prepared with ammonia water and a hydroxylamine salt as raw materials; the hydroxylamine salt can include hydroxylamine sulfate or hydroxylamine phosphate. As a specific embodiment of the present invention, when the hydroxylamine salt is hydroxylamine sulfate, the molar ratio of the ammonia water to the hydroxylamine sulfate can be 2-3:1; when the hydroxylamine salt is hydroxylamine phosphate, the molar ratio of the ammonia water to the hydroxylamine phosphate can be 3-4:1; the present invention can first put the hydroxylamine salt aqueous solution into a reactor with a rotor, then drop ammonia water, and react at 0-40°C for 0.5-2h to obtain a hydroxylamine aqueous solution.

[0027] As a specific embodiment of the present invention, the mass concentration of the hydroxylamine aqueous solution can be 18-22%, and can be specifically 20%. As a specific embodiment of the present invention, the impurities in the hydroxylamine aqueous solution include one or more of residual sulfate, phosphate and metal ions; the metal ions include K + 、Na + , Ca 2+ , Ba 2+ , Li + Mg 2+ and Sr 2+ One or more of .

[0028] As a specific embodiment of the present invention, the alkaline compound may include barium hydroxide or calcium hydroxide; the alkaline compound may be added in the form of a suspension. The present invention has no particular limitation on the amount of the alkaline compound, as long as the residual sulfate or phosphate in the hydroxylamine aqueous solution can be removed.

[0029] As a specific embodiment of the present invention, the sedimentation time can be 0.5-2 hours, or 1-1.5 hours; the solid-liquid separation can be filtration. The metal cations in the alkaline compound of the present invention react with the sulfate ions or phosphate ions in the hydroxylamine aqueous solution to form a precipitate which is removed by sedimentation separation.

[0030] After obtaining the liquid phase, the present invention passes the liquid phase into an ion exchange column for ion exchange to obtain a purified hydroxylamine aqueous solution. As a specific embodiment of the present invention, the resin in the ion exchange column is a resin containing phenolic hydroxyl groups; the resin containing phenolic hydroxyl groups may include PHS resin (poly-p-hydroxystyrene); the PHS resin may be purchased from Xi'an Lanxiao Technology New Materials Co., Ltd. or Beijing Bayi Space-Time Liquid Crystal Technology Co., Ltd. In the present invention, the PHS resin is a weakly acidic cationic resin, and its functional group is a phenolic hydroxyl group; the acidity of the phenolic hydroxyl group is weaker than the acidity generated by the hydrolysis of the product ammonium radical, so it does not react with hydroxylamine. The present invention uses a resin containing phenolic hydroxyl groups to remove metal ions in a hydroxylamine aqueous solution, which is simple to operate and has an obvious purification effect.

[0031] As a specific embodiment of the present invention, the method may further include:

[0032] sequentially introducing water and a first hydrochloric acid solution into the ion exchange column for washing;

[0033] The washed resin is immersed in a second hydrochloric acid solution and then washed with water to obtain an activated resin.

[0034] The present invention sequentially introduces water and a first hydrochloric acid solution into the ion exchange column for washing. As a specific embodiment of the present invention, the water may be deionized water; the flow rate of water introduced into the ion exchange column may be 15-40 m / h, or may be 20-30 m / h. The present invention washes with water until the effluent is clear, so that the resin settles into a bed.

[0035] As a specific embodiment of the present invention, the mass concentration of the first hydrochloric acid solution can be 3-5%, specifically 3%, 4% or 5%; the volume ratio of the first hydrochloric acid solution to the resin can be 1.8-2.2:1, specifically 2:1; the flow rate of the first hydrochloric acid solution introduced into the ion exchange column of the present invention can be 3-5m / h, specifically 3m / h, 4m / h or 5m / h.

[0036] After washing, the present invention soaks the washed resin in a second hydrochloric acid solution and then washes it with water to obtain an activated resin. As a specific embodiment of the present invention, the mass concentration of the second hydrochloric acid solution can be 3-5%, specifically 3%, 4% or 5%; the volume ratio of the second hydrochloric acid solution to the resin can be 0.8-1.2:1, specifically 1:1; the soaking time can be 4-8 hours, and can also be 5-7 hours.

[0037] As a specific embodiment of the present invention, the soaked resin can be washed with water after the soaking, and the water used for the washing can be pure water; the present invention has no special requirements on the number of times of the washing, as long as the pH of the water after the washing can be 6~7.

[0038] As a specific embodiment of the present invention, the flow rate of the liquid phase passing into the ion exchange column can be 5-25 m / h, specifically 5 m / h, 10 m / h, 15 m / h, 20 m / h or 25 m / h. In the present invention, the flow rate is the volume of hydroxylamine solution flowing through the empty tower cross-sectional area per hour.

[0039] As a specific embodiment of the present invention, the ion exchange can be repeated, and the number of repetitions can be 2 to 4. The present invention can further reduce the metal ions in the hydroxylamine aqueous solution and improve its purity by repeatedly performing ion exchange.

[0040] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0041] Example 1

[0042] A hydroxylamine aqueous solution with a mass concentration of 20% is prepared using ammonia water and hydroxylamine sulfate as raw materials, and the concentration of sulfate in the hydroxylamine aqueous solution is 24%;

[0043] Add 51.4 g of Ba(OH)2 to the hydroxylamine aqueous solution, let the mixture settle for 2 hours, and then filter to obtain a liquid phase and barium sulfate precipitate;

[0044] The liquid phase is pumped into an ion exchange column filled with an activated PHS resin at a flow rate of 25 m / h for ion exchange, and the ion exchange is repeated 3 times to obtain a purified hydroxylamine aqueous solution; the PHS resin is activated according to the following method: first, deionized water is passed into the ion exchange column at a flow rate of 30 m / h until the effluent is clear; then, a hydrochloric acid solution with a mass concentration of 4% twice the volume of the resin is passed at a flow rate of 4 m / h; the resin is soaked in a hydrochloric acid solution with a mass concentration of 4% once the volume of the resin for 6 hours, and then washed with pure water until the pH of the effluent is 6, to obtain an activated PHS resin.

[0045] Example 2

[0046] The impurity removal treatment of the 20% hydroxylamine aqueous solution was carried out according to the method of Example 1, except that the liquid phase was pumped into the ion exchange column filled with activated PHS resin at a flow rate of 15 m / h for ion exchange.

[0047] Example 3

[0048] The impurity removal treatment of the 20% hydroxylamine aqueous solution was carried out according to the method of Example 1, except that the liquid phase was pumped into the ion exchange column filled with activated PHS resin at a flow rate of 10 m / h for ion exchange.

[0049] Example 4

[0050] The impurity removal treatment of the 20% hydroxylamine aqueous solution was carried out according to the method of Example 1, except that the liquid phase was pumped into the ion exchange column filled with activated PHS resin at a flow rate of 20 m / h for ion exchange.

[0051] Comparative Example 1

[0052] The impurity removal treatment was performed on the 20% hydroxylamine aqueous solution according to the method of Example 4, except that the PHS resin in the ion exchange column was replaced by D113 resin.

[0053] The contents of barium ions, sulfate ions and strontium ions in the liquid phase and the purified hydroxylamine aqueous solution were measured by inductively coupled plasma emission spectrometry or atomic absorption spectrophotometry. The results are listed in Table 1.

[0054] The contents of hydroxylamine in the liquid phase and the purified hydroxylamine aqueous solution were detected by potassium permanganate titration. The results are listed in Table 2.

[0055] Table 1 Content of metal ions in hydroxylamine aqueous solution before and after purification in Examples 1 to 4 and Comparative Example 1

[0056]

[0057] Table 2 The content of hydroxylamine in the hydroxylamine aqueous solution before and after purification in Examples 1 to 4 and Comparative Example 1

[0058]

[0059] It can be seen from Table 1 and Table 2 that the method of the present invention can well remove impurity ions in the hydroxylamine aqueous solution without causing much loss of hydroxylamine in the hydroxylamine aqueous solution.

[0060] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for removing impurities from a hydroxylamine aqueous solution, characterized in that: The following steps are involved: The hydroxylamine aqueous solution and the alkaline compound are mixed and settled, and then the solid-liquid separation is carried out to obtain the liquid phase; the alkaline compound comprises barium hydroxide or calcium hydroxide; The liquid phase is passed through an ion exchange column for ion exchange to obtain a purified hydroxylamine aqueous solution; the resin in the ion exchange column is a resin containing phenolic hydroxyl groups, and the resin containing phenolic hydroxyl groups is a PHS resin.

2. The method for removing impurities from the hydroxylamine aqueous solution according to claim 1, characterized in that: The ion exchange also includes: sequentially introducing water and a first hydrochloric acid solution into the ion exchange column for washing; The washed resin is immersed in a second hydrochloric acid solution and then washed with water to obtain an activated resin.

3. The method for removing impurities from the hydroxylamine aqueous solution according to claim 2, characterized in that: The flow rate of water introduced into the ion exchange column is 15-40 m / h.

4. The method for removing impurities from the hydroxylamine aqueous solution according to claim 2, characterized in that: The mass concentration of the first hydrochloric acid solution is 3-5%; the volume ratio of the first hydrochloric acid solution to the resin is 1.8-2.2:

1.

5. The method for removing impurities from the hydroxylamine aqueous solution according to claim 2 or 4, characterized in that: The flow rate of the first hydrochloric acid solution introduced into the ion exchange column is 3-5 m / h.

6. The method for removing impurities from the hydroxylamine aqueous solution according to claim 2, characterized in that: The mass concentration of the second hydrochloric acid solution is 3-5%; the volume ratio of the second hydrochloric acid solution to the resin is 0.8-1.2:1; The soaking time is 4 to 8 hours.

7. The method for removing impurities from a hydroxylamine aqueous solution according to claim 1, characterized in that: The flow rate of the liquid phase passing into the ion exchange column is 5-25 m / h.

8. The method for removing impurities from the hydroxylamine aqueous solution according to claim 1, characterized in that: The hydroxylamine aqueous solution is a hydroxylamine aqueous solution prepared using ammonia water and hydroxylamine salt as raw materials; The hydroxylamine salt includes hydroxylamine sulfate or hydroxylamine phosphate.

9. The method for removing impurities from the hydroxylamine aqueous solution according to claim 1 or 8, characterized in that: The mass concentration of the hydroxylamine aqueous solution is 18-22%.

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