A method for preparing hydroxylamine aqueous solution through ion exchange of hydroxylamine salt

Abstract

The invention discloses a method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt, and belongs to the technical field of preparing a hydroxylamine aqueous solution. In this method, ultrapure water is continuously introduced into the anode chamber in an electrolysis dialysis device, a hydroxylamine salt is continuously introduced into a raw material chamber, ultrapure water is continuously introduced into a product chamber, ultrapure water is continuously introduced into a cathode chamber, a constant voltage is applied for electrolysis, and the four chambers are in a self-circulating state, and a hydroxylamine aqueous solution is prepared in the product chamber. In the present invention, the modified hydroxylamine-type porphyrin-based anion exchange membrane effectively removes metal ions in the solution through coordination reaction and molecular recognition mechanism, and further purifies the hydroxylamine solution.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of hydroxylamine aqueous solution, in particular to a method for preparing hydroxylamine aqueous solution through ion exchange of hydroxylamine salt. Background Art

[0002] Hydroxylamine has many uses in various industries. It has wide applications in the pharmaceutical industry and in the field of stripping photoresist compositions. In the pharmaceutical industry and photoresist processing, it is very important that the product does not contain impurities such as anions and cations.

[0003] At present, hydroxylamine is mainly produced by the following methods:

[0004] Raschig method, nitromethane hydrolysis method, acetone oxime method, nitric oxide reduction method, calcium oxide method, double decomposition method, etc.

[0005] Publication PCT / EP1999 / 000993 provides a method for preparing a hydroxylamine aqueous solution substantially free of metal ions, wherein the hydroxylamine solution is treated at least once with a hydroxyl-type anion exchanger, at least once with an acidic cation exchanger, and a stabilizer is added to the hydroxylamine solution to prepare the hydroxylamine aqueous solution.

[0006] Publication PCT / US1998 / 010445 provides a method for purifying hydroxylamine so that cations and anions are significantly reduced. The method comprises passing a hydroxylamine solution through at least one strong acid ion exchange bed and then through at least one strong base anion exchange resin bed, the strong acid ion exchange bed being pretreated with dilute hydrochloric acid to further purify the hydroxylamine solution.

[0007] However, the existing public technology for preparing hydroxylamine aqueous solution has the following technical defects: high cost, large amount of "three wastes" discharged, high content of metal ions in hydroxylamine aqueous solution, difficult to apply on a large scale in the electronics industry, limiting its market. Summary of the invention

[0008] In view of the above problems, the invention of this patent application aims to reduce the metal ion content in the hydroxylamine aqueous solution, improve atom economy, reduce production costs, and reduce the discharge of "three wastes". A method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt is proposed.

[0009] The main technical contents of the present invention are:

[0010] A method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt, the operating steps of which are:

[0011] Ultrapure water is continuously introduced into the anode chamber of the electrolytic dialysis device, hydroxylamine salt is continuously introduced into the raw material chamber, ultrapure water is continuously introduced into the product chamber, and ultrapure water is continuously introduced into the cathode chamber. A constant voltage is applied for electrolysis. The four chambers are in a self-circulating state, and a hydroxylamine aqueous solution is prepared in the product chamber.

[0012] One of the preferred technical means of the above-mentioned overall technical solution is that the electrolytic dialysis device has four compartments from left to right, namely, an anode chamber, a raw material chamber, a product chamber and a cathode chamber.

[0013] One of the preferred technical means of the above overall technical solution is that the four compartments are composed of a first anion exchange membrane, a cation exchange membrane and a second anion exchange membrane in sequence; an anode plate is fixed in the anode chamber, and a cathode plate is fixed in the cathode chamber.

[0014] One of the preferred technical means of the above overall technical solution is that the hydroxylamine salt is selected from at least one of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate or hydroxylamine phosphate.

[0015] One of the preferred technical means of the above overall technical solution is that the mass concentration of the hydroxylamine salt is 18-36%.

[0016] One of the preferred technical means of the above overall technical solution is that the electrolysis temperature is 15-50°C and the constant voltage is 1-12V.

[0017] One of the preferred technical means of the above overall technical solution is that the four-chamber self-circulation flow rate is 10-100 ml / min.

[0018] One of the preferred technical means of the above overall technical solution is that the anion exchange membrane is a modified hydroxyl-porphyrin-based anion exchange membrane, and the modification method is:

[0019] H1: Place the dried hydroxyl anion exchange membrane into a plasma surface treatment instrument, introduce steam heated by ethyl 3-mercaptopropionate, set the power to 150-250W, and the treatment time to 80-150S to obtain a mercapto-modified anion exchange membrane;

[0020] H2: by weight, 0.02-0.6 parts of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 0.3-3 parts of 1,5-diaminobiuret, 300-500 parts of ethanol, 50-100 parts of mercapto-modified anion exchange membrane, and 3-6 parts of diethylenetriamine are stirred at 60-70° C. for 100-160 minutes, filtered, and washed with water to obtain a modified anion exchange membrane;

[0021] H3: The modified anion exchange membrane is loaded into an ion exchange column, and 5-10 times the volume of a 10-20% by mass sodium hydroxide solution is passed through the column, filtered, and dried to obtain a hydroxy-porphyrin-based anion exchange membrane.

[0022] The principle of the modified hydroxyl-porphyrin-based anion exchange membrane is as follows:

[0023] The thiol groups of the thiol-modified anion exchange membrane undergo thiol-ene addition reaction with 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin and undergo thiol-amino addition reaction with 1,5-diaminobiuret to obtain grafted biuret functional groups and porphyrin functional groups on the modified anion exchange membrane.

[0024] Technical effects:

[0025] The method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt of the present invention has the following significant effects compared with the prior art:

[0026] 1: After grafting biuret functional groups and porphyrin functional groups, the ion exchange capacity of the membrane is enhanced, and the metal ions in the solution can be removed more effectively. Both biuret functional groups and porphyrin functional groups have coordination ability and can form stable complexes with metal ions. Through the coordination reaction, the metal ions are fixed on the membrane, thereby achieving separation and purification.

[0027] 2: Porphyrin functional groups have molecular recognition functions and can identify specific metal ions. Through the mechanism of molecular recognition, the selective removal of specific metal ions can be achieved, thereby improving the purity of other ions in the solution. DETAILED DESCRIPTION

[0028] The essential features and significant effects of the present invention can be reflected from the following embodiments, but they do not limit the present invention in any way, and those skilled in the art can make some non-essential improvements and adjustments based on the content of the present invention. The present invention is further described below through specific implementation methods.

[0029] Example 1

[0030] A method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt, the operating steps of which are:

[0031] Ultrapure water is continuously introduced into the anode chamber of the electrolytic dialysis device, hydroxylamine salt is continuously introduced into the raw material chamber, ultrapure water is continuously introduced into the product chamber, and ultrapure water is continuously introduced into the cathode chamber. A constant voltage is applied for electrolysis. The four chambers are in a self-circulating state, and a hydroxylamine aqueous solution is prepared in the product chamber.

[0032] The electrolytic dialysis device has four compartments from left to right, namely, an anode chamber, a raw material chamber, a product chamber and a cathode chamber.

[0033] The four compartments are composed of a first anion exchange membrane, a cation exchange membrane and a second anion exchange membrane in sequence; an anode plate is fixed in the anode chamber, and a cathode plate is fixed in the cathode chamber.

[0034] The hydroxylamine salt is selected from hydroxylamine sulfate.

[0035] The mass concentration of the hydroxylamine salt is 18%.

[0036] The electrolysis temperature is 15°C and the constant voltage is 4V.

[0037] The four-chamber self-circulation flow rate is 25 ml / min.

[0038] The cation exchange membrane model is GCCM-S.

[0039] The anion exchange membrane is a modified hydroxyl-porphyrin-based anion exchange membrane, and the modification method is as follows:

[0040] H1: Place the dried hydroxyl anion exchange membrane into a plasma surface treatment instrument, introduce steam heated by ethyl 3-mercaptopropionate, set the power to 150 W, and treat for 150 seconds to obtain a mercapto-modified anion exchange membrane;

[0041] H2: 2 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 3 g of 1,5-diaminobiuret, 3000 g of ethanol, 500 g of thiol-modified anion exchange membrane, and 30 g of diethylenetriamine were stirred at 60° C. for 160 minutes, filtered, and washed with water to obtain a modified anion exchange membrane;

[0042] H3: The modified anion exchange membrane is loaded into an ion exchange column, and 5 volumes of a 10% by mass sodium hydroxide solution are passed through the column, filtered, and dried to obtain a hydroxy-porphyrin-based anion exchange membrane.

[0043] Example 2

[0044] A method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt, the operating steps of which are:

[0045] Ultrapure water is continuously introduced into the anode chamber of the electrolytic dialysis device, hydroxylamine salt is continuously introduced into the raw material chamber, ultrapure water is continuously introduced into the product chamber, and ultrapure water is continuously introduced into the cathode chamber. A constant voltage is applied for electrolysis. The four chambers are in a self-circulating state, and a hydroxylamine aqueous solution is prepared in the product chamber.

[0046] The electrolytic dialysis device has four compartments from left to right, namely, an anode chamber, a raw material chamber, a product chamber and a cathode chamber.

[0047] The four compartments are composed of a first anion exchange membrane, a cation exchange membrane and a second anion exchange membrane in sequence; an anode plate is fixed in the anode chamber, and a cathode plate is fixed in the cathode chamber.

[0048] The hydroxylamine salt is selected from hydroxylamine hydrochloride.

[0049] The mass concentration of the hydroxylamine salt is 24%.

[0050] The electrolysis temperature is 30°C and the constant voltage is 6V.

[0051] The four-chamber self-circulation flow rate is 50 ml / min.

[0052] The cation exchange membrane model is GCCM-S.

[0053] The anion exchange membrane is a modified hydroxyl-porphyrin-based anion exchange membrane, and the modification method is as follows:

[0054] H1: Place the dried hydroxyl anion exchange membrane into a plasma surface treatment instrument, introduce steam heated by ethyl 3-mercaptopropionate, set the power to 200 W, and the treatment time to 125 s to obtain a mercapto-modified anion exchange membrane;

[0055] H2: 4 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 12 g of 1,5-diaminobiuret, 4000 g of ethanol, 700 g of thiol-modified anion exchange membrane, and 40 g of diethylenetriamine were stirred at 65° C. for 145 minutes, filtered, and washed with water to obtain a modified anion exchange membrane;

[0056] H3: The modified anion exchange membrane is loaded into an ion exchange column, and 7 volumes of a 15% by mass sodium hydroxide solution are passed through the column, filtered, and dried to obtain a hydroxy-porphyrin-based anion exchange membrane.

[0057] Example 3

[0058] A method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt, the operating steps of which are:

[0059] Ultrapure water is continuously introduced into the anode chamber of the electrolytic dialysis device, hydroxylamine salt is continuously introduced into the raw material chamber, ultrapure water is continuously introduced into the product chamber, and ultrapure water is continuously introduced into the cathode chamber. A constant voltage is applied for electrolysis. The four chambers are in a self-circulating state, and a hydroxylamine aqueous solution is prepared in the product chamber.

[0060] The electrolytic dialysis device has four compartments from left to right, namely, an anode chamber, a raw material chamber, a product chamber and a cathode chamber.

[0061] The four compartments are composed of a first anion exchange membrane, a cation exchange membrane and a second anion exchange membrane in sequence; an anode plate is fixed in the anode chamber, and a cathode plate is fixed in the cathode chamber.

[0062] The hydroxylamine salt is selected from hydroxylamine nitrate.

[0063] The mass concentration of the hydroxylamine salt is 30%.

[0064] The electrolysis temperature is 40°C and the constant voltage is 8V.

[0065] The four-chamber self-circulation flow rate is 75 ml / min.

[0066] The cation exchange membrane model is GCCM-S.

[0067] The anion exchange membrane is a modified hydroxyl-porphyrin-based anion exchange membrane, and the modification method is as follows:

[0068] H1: Place the dried hydroxyl anion exchange membrane into a plasma surface treatment instrument, introduce steam heated by ethyl 3-mercaptopropionate, set the power to 200 W, and the treatment time to 100 s to obtain a mercapto-modified anion exchange membrane;

[0069] H2: 5 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 24 g of 1,5-diaminobiuret, 4000 g of ethanol, 850 g of thiol-modified anion exchange membrane, and 50 g of diethylenetriamine were stirred at 65° C. for 120 minutes, filtered, and washed with water to obtain a modified anion exchange membrane;

[0070] H3: The modified anion exchange membrane is loaded into an ion exchange column, and 8.5 times the volume of a 15% by mass sodium hydroxide solution is passed through the column, filtered, and dried to obtain a hydroxy-porphyrin-based anion exchange membrane.

[0071] Example 4

[0072] A method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt, the operating steps of which are:

[0073] Ultrapure water is continuously introduced into the anode chamber of the electrolytic dialysis device, hydroxylamine salt is continuously introduced into the raw material chamber, ultrapure water is continuously introduced into the product chamber, and ultrapure water is continuously introduced into the cathode chamber. A constant voltage is applied for electrolysis. The four chambers are in a self-circulating state, and a hydroxylamine aqueous solution is prepared in the product chamber.

[0074] The electrolytic dialysis device has four compartments from left to right, namely, an anode chamber, a raw material chamber, a product chamber and a cathode chamber.

[0075] The four compartments are composed of a first anion exchange membrane, a cation exchange membrane and a second anion exchange membrane in sequence; an anode plate is fixed in the anode chamber, and a cathode plate is fixed in the cathode chamber.

[0076] The hydroxylamine salt is selected from hydroxylamine phosphate.

[0077] The mass concentration of the hydroxylamine salt is 36%.

[0078] The electrolysis temperature is 50°C and the constant voltage is 12V.

[0079] The four-chamber self-circulation flow rate is 100 ml / min.

[0080] The cation exchange membrane model is GCCM-S.

[0081] The anion exchange membrane is a modified hydroxyl-porphyrin-based anion exchange membrane, and the modification method is as follows:

[0082] H1: Place the dried hydroxyl anion exchange membrane into a plasma surface treatment instrument, introduce steam heated by ethyl 3-mercaptopropionate, set the power to 250 W, and treat for 150 seconds to obtain a mercapto-modified anion exchange membrane;

[0083] H2: 6 g of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 30 g of 1,5-diaminobiuret, 5000 g of ethanol, 1000 g of thiol-modified anion exchange membrane, and 60 g of diethylenetriamine were stirred at 70° C. for 160 minutes, filtered, and washed with water to obtain a modified anion exchange membrane;

[0084] H3: The modified anion exchange membrane is loaded into an ion exchange column, and 10 volumes of a 20% by mass sodium hydroxide solution are passed through the column, filtered, and dried to obtain a hydroxy-porphyrin-based anion exchange membrane.

[0085] Comparative Example 1

[0086] The anion exchange membrane in this example is a hydroxyl anion exchange membrane, and the remaining steps and processes are consistent with those in Example 1.

[0087] Comparative Example 2

[0088] In the modification process of the modified hydroxy-porphyrin-based anion exchange membrane in this example, 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin is not added in step H2, and the remaining steps and processes are consistent with those in Example 1.

[0089] Comparative Example 3

[0090] In the modification process of the modified hydroxy-porphyrin-based anion exchange membrane in this example, 1,5-diaminobiuret is not added in step H2, and the remaining steps and processes are consistent with those in Example 1.

[0091] The metal content results of the hydroxylamine solutions (all 50 wt%) prepared in the above examples are shown in the following table, in mg / kg: Analysis accuracy: 0.1 mg / kg:

[0092] Table test results

[0093] Fe3+ Na+ K+ Total Metal Example 1 ＜0.1 ＜0.1 ＜0.1 ＜0.1 Example 2 ＜0.1 ＜0.1 ＜0.1 ＜0.1 Example 3 ＜0.1 ＜0.1 ＜0.1 ＜0.1 Example 4 ＜0.1 ＜0.1 ＜0.1 ＜0.1 Comparative Example 1 0.3 0.3 0.2 0.8 Comparative Example 2 0.2 0.2 0.1 0.5 Comparative Example 3 0.1 0.2 ＜0.1 0.4

[0094] In the embodiment, a modified hydroxyl-porphyrin-based anion exchange membrane is used to lock and remove metal ions in the solution through coordination ability and molecular recognition mechanism, thereby effectively reducing the metal ion content in the hydroxylamine solution.

[0095] The preferred specific embodiments of the present invention are described in detail above. It should be understood that ordinary technicians in the field can make many modifications and changes based on the concept of the present invention without creative work. Therefore, all technical solutions that can be obtained by technicians in the technical field based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt, the operating steps of which are: Ultrapure water is continuously introduced into the anode chamber of the electrolytic dialysis device, hydroxylamine salt is continuously introduced into the raw material chamber, ultrapure water is continuously introduced into the product chamber, and ultrapure water is continuously introduced into the cathode chamber, and a constant voltage is applied to perform electrolysis, so that the four chambers are in a self-circulating state, and a hydroxylamine aqueous solution is prepared in the product chamber; There is a first anion exchange membrane between the anode chamber and the raw material chamber, there is a cation exchange membrane between the raw material chamber and the product chamber, and there is a second anion exchange membrane between the product chamber and the cathode chamber; The anion exchange membrane is a modified hydroxyl-porphyrin-based anion exchange membrane, and the modification method is as follows: H1: Place the dried hydroxyl anion exchange membrane into a plasma surface treatment instrument, introduce steam heated by ethyl 3-mercaptopropionate, set the power to 150-250W, and the treatment time to 80-150S to obtain a mercapto-modified anion exchange membrane; H2: by weight, 0.02-0.6 parts of 5,10,15,20-tetrakis(4-vinylphenyl)porphyrin, 0.3-3 parts of 1,5-diaminobiuret, 300-500 parts of ethanol, 50-100 parts of mercapto-modified anion exchange membrane, and 3-6 parts of diethylenetriamine are stirred at 60-70° C. for 100-160 minutes, filtered, and washed with water to obtain a modified anion exchange membrane; H3: The modified anion exchange membrane is loaded into an ion exchange column, and 5-10 times the volume of a 10-20% by mass sodium hydroxide solution is passed through the column, filtered, and dried to obtain a hydroxy-porphyrin-based anion exchange membrane.

2. The method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt according to claim 1, characterized in that: The electrolytic dialysis device has four compartments from left to right, namely, an anode chamber, a raw material chamber, a product chamber and a cathode chamber.

3. The method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt according to claim 2, characterized in that: An anode plate is fixed in the anode chamber, and a cathode plate is fixed in the cathode chamber.

4. The method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt according to claim 1, characterized in that: The hydroxylamine salt is selected from at least one of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate or hydroxylamine phosphate.

5. The method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt according to claim 4, characterized in that: The mass concentration of the hydroxylamine salt is 18-36%.

6. The method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt according to claim 1, characterized in that: The electrolysis temperature is 15-50°C, and the constant voltage is 1-12V.

7. The method for preparing a hydroxylamine aqueous solution by ion exchange of a hydroxylamine salt according to claim 1, characterized in that: The four-chamber self-circulation flow rate is 10-100 ml / min.