A method for synthesizing electronic grade hydroxylamine salt based on high-purity butanone oxime and electronic grade acid

Abstract

The application discloses a method for synthesizing electronic-grade hydroxylamine salt based on high-purity butanone oxime and electronic-grade acid, and relates to the field of chemical synthesis. Specifically, high-purity butanone oxime is reacted with electronic-grade inorganic acid to generate hydroxylamine salt and butanone; after butanone is evaporated under reduced pressure, the water solution is concentrated and cooled to crystallize; then, vacuum heat treatment is performed, and small molecular impurities are removed through membrane separation of a thienyl carboxylic acid plasma grafting modified membrane, so that electronic-grade hydroxylamine salt is obtained. The method has high efficiency and is easy to popularize on an industrial scale.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis, and in particular to a method for synthesizing electronic-grade hydroxylamine salts based on high-purity butanone oxime and electronic-grade acids. Background Technology

[0002] Hydroxylamine salts (especially hydroxylamine hydrochloride and hydroxylamine sulfate) are widely used in the electronics industry, fine chemicals, electroplating, and photovoltaics, and the demand for extremely high purity and low impurity levels is becoming increasingly stringent. Currently, commonly used preparation methods include nitromethane reduction and oxime hydrolysis, with the latter being the mainstream choice due to its simple process and readily available raw materials.

[0003] Traditional methods often involve reacting butanone oxime (≥99%) with concentrated hydrochloric acid to hydrolyze it into hydroxylamine salt and the byproduct butanone, followed by separation steps such as distillation and crystallization to obtain the final product. However, the following key problems exist:

[0004] Residual methyl ethyl ketone (MEK) oxime acid salt impurities: Due to the high solubility of oxime salts, conventional crystallization is insufficient for complete removal, resulting in excessive residual organic impurities in the product, failing to meet electronic grade specifications. Limited purification methods: Excessive distillation temperatures easily degrade hydroxylamine salts, while extraction requires organic solvents, increasing risks and costs. Incomplete resource utilization: MEK byproducts generated from the oxime process are often discharged or degraded, failing to be fully recovered and utilized, resulting in resource waste.

[0005] To improve purification efficiency and environmental friendliness, some patented technologies have introduced methods such as vacuum heat treatment and molecular sieve catalytic oxidation and recycling of butanone oxime, but they still rely on thermal separation and chemical purification, lacking the auxiliary enhancement of membrane separation technology.

[0006] In recent years, membrane material technology has made breakthroughs in the separation, antifouling, and selective retention of small organic molecules. In particular, plasma-induced grafting polymerization technology can graft monomers with specific functional groups (such as carboxyl groups, thiophene ring structures, etc.) onto the membrane surface under low temperature or atmospheric pressure conditions.

[0007] Typical studies have shown that monomers such as acrylic acid, methacrylic acid, and polyvinyl alcohol are grafted onto PVDF or PES membranes, successfully reducing the average pore size of the original membrane from about 0.97 μm to 0.15 μm, thereby improving the filtration performance for small molecules with molecular weights of several hundred to several thousand Da by nearly 80%.

[0008] Thiophene carboxylic acid molecules possess an aromatic sulfur structure, which can significantly enhance impurity retention by interacting with organic impurities (such as butanone oxime and butanone) through π-π interactions, hydrophobic interactions, or hydrogen bonding. Assuming the use of polyethersulfone, PVDF, or polyamide membranes, and surface activation via low-pressure plasma (such as DC, RF, or dielectric barrier discharge), followed by grafting thiophene carboxylic acid monomers, highly cross-linked, functionalized films with thicknesses ranging from nanometers to micrometers can be formed.

[0009] If this grafted modified membrane is placed in the concentration or vacuum treatment stage and before evaporation and drying stage of the hydroxylamine salt purification process, it can efficiently remove trace amounts of residual methyl ethyl ketone, methyl ethyl ketone oxime and other polar / nonpolar small molecules, improve the purity of the final product and reduce the heat treatment load. Summary of the Invention

[0010] To overcome the limitations of existing oxime hydrolysis purification processes and leverage the superior performance of modern membrane technology, this invention proposes a method for synthesizing electronic-grade hydroxylamine salts based on high-purity butanone oxime and electronic-grade acids. Introducing a thiophene carboxylic acid plasma-grafted modified membrane as a membrane separation enhancement unit into the hydroxylamine salt process not only meets the practical needs of the industry but also possesses potential industrial feasibility and innovative advantages.

[0011] The technical solution is as follows:

[0012] A method for synthesizing electronic-grade hydroxylamine salts based on high-purity butanone oxime and electronic-grade acid includes the following steps, in parts by mass:

[0013] Step A: Mix 100 parts of high-purity butanone oxime with 100-200 parts of electronic-grade inorganic acid;

[0014] Step B: Stir the reaction at the set temperature and pressure for 6–12 hours to produce a mixture of butanone oxime salt and acidic hydroxylamine salt;

[0015] Step C: Reduce the pressure of the reaction mixture and distill off the byproduct butanone at 70–95°C until the mass of the solution decreases by 15%–30%;

[0016] Step D: Concentrate the aqueous solution to 60-78 wt%, then cool to 5-10°C and stir for 0.5-3 hours to crystallize crude hydroxylamine salt;

[0017] Step E: The obtained crude hydroxylamine salt solution is subjected to vacuum heat treatment at 55-65℃ and -0.02--0.04MPa for 1-3 hours to degrade residual butanone oxime salt. The resulting concentrated solution containing crude hydroxylamine salt is then subjected to impurity removal operation through a modified membrane.

[0018] Step F: Continue to evaporate volatile organic compounds under reduced pressure at 25–70°C, and obtain dry hydroxylamine salt solid.

[0019] Furthermore, in step A, the purity of the high-purity butanone oxime is not less than 99.9%, and the content of electronic-grade inorganic acid metal ions is not higher than 5 ppb.

[0020] Furthermore, in step A, the electronic-grade inorganic acid is selected from hydrochloric acid, sulfuric acid, or phosphoric acid.

[0021] Furthermore, the temperature set in step B is 70–95°C and the pressure is 0.1–1.0 MPa.

[0022] Further, in step C, the pressure is reduced to 0.06–0.10 MPa.

[0023] Furthermore, the cooling rate in step D is controlled to be 1–5 °C / min.

[0024] Furthermore, the modified membrane in step E is a thiophene carboxylic acid plasma-grafted modified membrane, and its preparation method is as follows:

[0025] Pretreatment: Soak 100 parts of polysulfone membrane in 300-450 parts of anhydrous ethanol for 2-4 hours, and then dry in a vacuum drying oven at 60-80℃ for 1-2 hours;

[0026] Grafting reaction: 5-15 parts glycidyl methacrylate (GMA), 0.1-0.5 parts benzoyl peroxide (BPO), 30-50 parts anhydrous ethanol, 1-3 parts 2-dihydroxyboron-3-thiophenic acid, and 0.1-0.3 parts triethylamine were added to a reaction vessel and mixed evenly. The pretreated polysulfone membrane was then immersed in the mixed solution and reacted at 60-80°C for 3-6 hours.

[0027] Curing: The grafted membrane is taken out and placed in a vacuum drying oven at 80-100℃ for heat treatment for 2-4 hours to obtain the modified membrane.

[0028] Furthermore, the filtration conditions for the modified membrane in step E are: temperature of 20 to 40°C and pressure of 0.1 to 0.5 MPa.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] 1) The dihydroxyboronic group in thiophene carboxylic acid undergoes specific coordination with the hydroxyl group of hydroxylamine to form a borate ester coordination structure, which significantly improves the membrane's adsorption or permeation selectivity for hydroxylamine, effectively reduces co-permeation of impurities, and results in high purity hydroxylamine after purification, reaching electronic grade.

[0031] 2) Functional groups are grafted onto the membrane surface through covalent bonds. Combined with curing treatment, the bonding force between the functional layer and the polysulfone substrate is enhanced. The functional group shedding rate is low, the membrane performance decays slowly, and the service life is long. Detailed Implementation

[0032] The features of the present invention are further illustrated below through embodiments, but the scope of protection of this patent is not limited to the embodiments.

[0033] Example 1

[0034] Raw material formula:

[0035] High-purity methyl ethyl ketone oxime (purity not less than 99.9%): 100g

[0036] Electronic grade inorganic acid (hydrochloric acid): 100g

[0037] Preparation steps:

[0038] Raw material mixing (step A): Mix 100g of high-purity methyl ethyl ketone oxime with 100g of electronic-grade hydrochloric acid.

[0039] Reaction (Step B): The reaction was stirred for 6 hours at a reaction temperature of 70°C and a reaction pressure of 0.1 MPa to produce a mixture of butanone oxime hydrochloride and acidic hydroxylamine salt.

[0040] Distillation of byproducts (Step C): Reduce the pressure of the reaction mixture to 0.06 MPa and distill off the byproduct methyl ethyl ketone at 70°C until the mass of the solution is reduced by 15%.

[0041] Crystallization (Step D): Concentrate the aqueous solution to 60 wt%, then cool to 5 °C at a cooling rate of 1 °C / min, and stir for 0.5 hours to crystallize crude hydroxylamine salt.

[0042] Impurity removal (step E): The obtained crude hydroxylamine salt solution was subjected to vacuum heat treatment at 55°C and -0.02MPa for 1 hour to degrade residual butanone oxime hydrochloride. The resulting concentrated solution containing crude hydroxylamine salt was then subjected to impurity removal through a modified membrane. The modified membrane filtration conditions were 20°C and 0.1MPa.

[0043] Drying (Step F): Continue to evaporate volatile organic compounds under reduced pressure at 25°C and obtain dry hydroxylamine salt solid.

[0044] Preparation of modified membranes:

[0045] Pretreatment: Soak 100g of polysulfone membrane in 300g of anhydrous ethanol for 2 hours, and then dry it in a vacuum drying oven at 60℃ for 1 hour.

[0046] Grafting reaction: 5g glycidyl methacrylate (GMA), 0.1g benzoyl peroxide (BPO), 30g anhydrous ethanol, 1g 2-dihydroxyboryl-3-thiophenic acid, and 0.1g triethylamine were added to a reaction vessel and mixed evenly. The pretreated polysulfone membrane was then immersed in the mixed solution and reacted at 60°C for 3 hours.

[0047] Curing: The membrane after the grafting reaction was taken out and placed in a vacuum drying oven at 80°C for heat treatment for 2 hours to obtain a thiophene carboxylic acid plasma grafted modified membrane.

[0048] Example 2

[0049] Raw material formula:

[0050] High-purity methyl ethyl ketone oxime (purity not less than 99.9%): 100g

[0051] Electronic grade inorganic acid (sulfuric acid): 130g

[0052] Preparation steps:

[0053] Raw material mixing (step A): Mix 100g of high-purity methyl ethyl ketone oxime with 130g of electronic-grade sulfuric acid.

[0054] Reaction (Step B): The reaction was stirred for 8 hours at a reaction temperature of 78°C and a reaction pressure of 0.3 MPa to produce a mixture of butanone oxime sulfate and acidic hydroxylamine salt.

[0055] Distillation of byproducts (Step C): Reduce the pressure of the reaction mixture to 0.07 MPa and distill off the byproduct methyl ethyl ketone at 80°C until the mass of the solution is reduced by 20%.

[0056] Crystallization (Step D): Concentrate the aqueous solution to 65 wt%, then cool to 7 °C at a cooling rate of 2 °C / min, and stir for 1.5 hours to crystallize crude hydroxylamine salt.

[0057] Impurity removal (step E): The obtained crude hydroxylamine salt solution was subjected to vacuum heat treatment at 58°C and -0.03MPa for 2 hours to degrade residual butanone oxime sulfate. The resulting concentrated solution containing crude hydroxylamine salt was then subjected to impurity removal through a modified membrane. The modified membrane filtration conditions were 25°C and 0.2MPa.

[0058] Drying (Step F): Continue to evaporate volatile organic compounds under reduced pressure at 40°C and obtain dry hydroxylamine salt solid.

[0059] Preparation of modified membranes:

[0060] Pretreatment: Soak 100g of polysulfone membrane in 350g of anhydrous ethanol for 3h, and then dry it in a vacuum drying oven at 70℃ for 1.5h.

[0061] Grafting reaction: 8g glycidyl methacrylate (GMA), 0.2g benzoyl peroxide (BPO), 35g anhydrous ethanol, 1.5g 2-dihydroxyboryl-3-thiophenic acid, and 0.15g triethylamine were added to a reaction vessel and mixed evenly. The pretreated polysulfone membrane was then immersed in the mixed solution and reacted at 65°C for 4 hours.

[0062] Curing: The membrane after the grafting reaction was taken out and placed in a vacuum drying oven at 85°C for heat treatment for 2.5 h to obtain a thiophene carboxylic acid plasma grafted modified membrane.

[0063] Example 3

[0064] Raw material formula:

[0065] High-purity methyl ethyl ketone oxime (purity not less than 99.9%): 100g

[0066] Electronic grade inorganic acid (phosphoric acid): 170g

[0067] Preparation steps:

[0068] Raw material mixing (step A): Mix 100g of high-purity methyl ethyl ketone oxime with 170g of electronic-grade phosphoric acid.

[0069] Reaction (Step B): The reaction was stirred for 10 hours at a reaction temperature of 85℃ and a reaction pressure of 0.6MPa to produce a mixture of butanone oxime phosphate and acidic hydroxylamine salt.

[0070] Distillation of byproducts (Step C): Reduce the pressure of the reaction mixture to 0.08 MPa and distill off the byproduct methyl ethyl ketone at 85°C until the mass of the solution is reduced by 25%.

[0071] Crystallization (Step D): Concentrate the aqueous solution to 70 wt%, then cool to 8 °C at a cooling rate of 3 °C / min, and stir for 2 hours to crystallize crude hydroxylamine salt.

[0072] Impurity removal (step E): The obtained crude hydroxylamine salt solution was subjected to vacuum heat treatment at 62°C and -0.03MPa for 2.5 hours to degrade residual butanone oxime phosphate. The resulting concentrated solution containing crude hydroxylamine salt was then subjected to impurity removal through a modified membrane. The modified membrane filtration conditions were 35°C and 0.4MPa.

[0073] Drying (Step F): Continue to evaporate volatile organic compounds under reduced pressure at 50°C and obtain dry hydroxylamine salt solid.

[0074] Preparation of modified membranes:

[0075] Pretreatment: 100g of polysulfone membrane was soaked in 400g of anhydrous ethanol for 3.5h, and then dried in a vacuum drying oven at 75℃ for 1.8h.

[0076] Grafting reaction: 12g glycidyl methacrylate (GMA), 0.4g benzoyl peroxide (BPO), 45g anhydrous ethanol, 2g 2-dihydroxyboryl-3-thiophenic acid, and 0.2g triethylamine were added to a reaction vessel and mixed evenly. The pretreated polysulfone membrane was then immersed in the mixed solution and reacted at 75°C for 5 hours.

[0077] Curing: The grafted membrane was taken out and placed in a vacuum drying oven at 95°C for heat treatment for 3.5 h to obtain a thiophene carboxylic acid plasma grafted modified membrane.

[0078] Example 4

[0079] Raw material formula:

[0080] High-purity methyl ethyl ketone oxime (purity not less than 99.9%): 100g

[0081] Electronic grade inorganic acid (sulfuric acid): 200g

[0082] Preparation steps:

[0083] Raw material mixing (step A): Mix 100g of high-purity methyl ethyl ketone oxime with 200g of electronic-grade sulfuric acid.

[0084] Reaction (Step B): The reaction was stirred for 12 hours at a reaction temperature of 95℃ and a reaction pressure of 1.0MPa to produce a mixture of butanone oxime sulfate and acidic hydroxylamine salt.

[0085] Distillation of byproducts (Step C): Reduce the pressure of the reaction mixture to 0.10 MPa and distill off the byproduct methyl ethyl ketone at 95°C until the mass of the solution is reduced by 30%.

[0086] Crystallization (Step D): Concentrate the aqueous solution to 78 wt%, then cool to 10 °C at a cooling rate of 5 °C / min and stir for 3 hours to crystallize crude hydroxylamine salt.

[0087] Impurity removal (step E): The obtained crude hydroxylamine salt solution was subjected to vacuum heat treatment at 65°C and -0.04MPa for 3 hours to degrade residual butanone oxime sulfate. The resulting concentrated solution containing crude hydroxylamine salt was then subjected to impurity removal through a modified membrane. The modified membrane filtration conditions were 40°C and 0.5MPa.

[0088] Drying (Step F): Continue to evaporate volatile organic compounds under reduced pressure at 70°C and obtain dry hydroxylamine salt solid.

[0089] Preparation of modified membranes:

[0090] Pretreatment: Soak 100g of polysulfone membrane in 450g of anhydrous ethanol for 4 hours, and then dry it in a vacuum drying oven at 80℃ for 2 hours.

[0091] Grafting reaction: 15g glycidyl methacrylate (GMA), 0.5g benzoyl peroxide (BPO), 50g anhydrous ethanol, 3g 2-dihydroxyboryl-3-thiophenic acid, and 0.3g triethylamine were added to a reaction vessel and mixed evenly. The pretreated polysulfone membrane was then immersed in the mixed solution and reacted at 80°C for 6 hours.

[0092] Curing: The membrane after the grafting reaction was taken out and placed in a vacuum drying oven at 100℃ for heat treatment for 4 hours to obtain a thiophene carboxylic acid plasma grafted modified membrane.

[0093] Comparative Example 1

[0094] Raw material formula:

[0095] High-purity methyl ethyl ketone oxime (purity not less than 99.9%): 100g

[0096] Electronic grade inorganic acid (hydrochloric acid): 100g

[0097] Preparation steps:

[0098] Raw material mixing (step A): Mix 100g of high-purity methyl ethyl ketone oxime with 100g of electronic-grade hydrochloric acid.

[0099] Reaction (Step B): The reaction was stirred for 6 hours at a reaction temperature of 70°C and a reaction pressure of 0.1 MPa to produce a mixture of butanone oxime hydrochloride and acidic hydroxylamine salt.

[0100] Distillation of byproducts (Step C): Reduce the pressure of the reaction mixture to 0.06 MPa and distill off the byproduct methyl ethyl ketone at 70°C until the mass of the solution is reduced by 15%.

[0101] Crystallization (Step D): Concentrate the aqueous solution to 60 wt%, then cool to 5 °C at a cooling rate of 1 °C / min, and stir for 0.5 hours to crystallize crude hydroxylamine salt.

[0102] Drying (Step E): Continue to evaporate volatile organic compounds under reduced pressure at 25°C and obtain dry hydroxylamine salt solid.

[0103] Comparative Example 2

[0104] Raw material formula:

[0105] High-purity methyl ethyl ketone oxime (purity not less than 99.9%): 100g

[0106] Electronic grade inorganic acid (hydrochloric acid): 100g

[0107] Preparation steps:

[0108] Raw material mixing (step A): Mix 100g of high-purity methyl ethyl ketone oxime with 100g of electronic-grade hydrochloric acid.

[0109] Reaction (Step B): The reaction was stirred for 6 hours at a reaction temperature of 70°C and a reaction pressure of 0.1 MPa to produce a mixture of butanone oxime hydrochloride and acidic hydroxylamine salt.

[0110] Distillation of byproducts (Step C): Reduce the pressure of the reaction mixture to 0.06 MPa and distill off the byproduct methyl ethyl ketone at 70°C until the mass of the solution is reduced by 15%.

[0111] Crystallization (Step D): Concentrate the aqueous solution to 60 wt%, then cool to 5 °C at a cooling rate of 1 °C / min, and stir for 0.5 hours to crystallize crude hydroxylamine salt.

[0112] Impurity removal (step E): The obtained crude hydroxylamine salt solution was subjected to vacuum heat treatment at 55°C and -0.02MPa for 1 hour to degrade residual butanone oxime hydrochloride. The resulting concentrated solution containing crude hydroxylamine salt was then subjected to impurity removal through a modified membrane. The modified membrane filtration conditions were 20°C and 0.1MPa.

[0113] Drying (Step F): Continue to evaporate volatile organic compounds under reduced pressure at 25°C and obtain dry hydroxylamine salt solid.

[0114] Preparation of modified membranes:

[0115] Pretreatment: Soak 100g of polysulfone membrane in 300g of anhydrous ethanol for 2 hours, and then dry it in a vacuum drying oven at 60℃ for 1 hour.

[0116] Grafting reaction: 5g glycidyl methacrylate (GMA), 0.1g benzoyl peroxide (BPO), 30g anhydrous ethanol and 0.1g triethylamine were added to the reaction vessel and mixed evenly. The pretreated polysulfone membrane was then immersed in the mixed solution and reacted at 60℃ for 3h.

[0117] Curing: The membrane after the grafting reaction was taken out and placed in a vacuum drying oven at 80°C for heat treatment for 2 hours to obtain a thiophene carboxylic acid plasma grafted modified membrane.

[0118] Comparative Example 3

[0119] Raw material formula:

[0120] High-purity methyl ethyl ketone oxime (purity not less than 99.9%): 100g

[0121] Electronic grade inorganic acid (hydrochloric acid): 100g

[0122] Preparation steps:

[0123] Raw material mixing (step A): Mix 100g of high-purity methyl ethyl ketone oxime with 100g of electronic-grade hydrochloric acid.

[0124] Reaction (Step B): The reaction was stirred for 6 hours at a reaction temperature of 70°C and a reaction pressure of 0.1 MPa to produce a mixture of butanone oxime hydrochloride and acidic hydroxylamine salt.

[0125] Distillation of byproducts (Step C): Reduce the pressure of the reaction mixture to 0.06 MPa and distill off the byproduct methyl ethyl ketone at 70°C until the mass of the solution is reduced by 15%.

[0126] Crystallization (Step D): Concentrate the aqueous solution to 60 wt%, then cool to 5 °C at a cooling rate of 1 °C / min, and stir for 0.5 hours to crystallize crude hydroxylamine salt.

[0127] Impurity removal (step E): The obtained crude hydroxylamine salt solution was subjected to vacuum heat treatment at 55°C and -0.02MPa for 1 hour to degrade residual butanone oxime hydrochloride. The resulting concentrated solution containing crude hydroxylamine salt was then subjected to impurity removal through a modified membrane. The modified membrane filtration conditions were 20°C and 0.1MPa.

[0128] Drying (Step F): Continue to evaporate volatile organic compounds under reduced pressure at 25°C and obtain dry hydroxylamine salt solid.

[0129] Preparation of modified membranes:

[0130] Pretreatment: Soak 100g of polysulfone membrane in 300g of anhydrous ethanol for 2 hours, and then dry it in a vacuum drying oven at 60℃ for 1 hour.

[0131] Grafting reaction: 5g glycidyl methacrylate (GMA), 30g anhydrous ethanol, 1g 2-dihydroxyboryl-3-thiophenic acid, and 0.1g triethylamine were added to a reaction vessel and mixed evenly. The pretreated polysulfone membrane was then immersed in the mixed solution and reacted at 60°C for 3h.

[0132] Curing: The membrane after the grafting reaction was taken out and placed in a vacuum drying oven at 80°C for heat treatment for 2 hours to obtain a thiophene carboxylic acid plasma grafted modified membrane.

[0133] Test method:

[0134] 1) HPLC purity and residual methyl ethyl ketone oxime detection

[0135] Instrumentation: Agilent 1260 HPLC;

[0136] Column: C18, 4.6×250mm, 5µm;

[0137] Mobile phase: 37% propionitrile / 63% water + 0.1% trifluoroacetic acid;

[0138] Flow rate: 1.0 mL / min;

[0139] Detection wavelength: 205nm;

[0140] Sample preparation: Dissolve 0.1 g of hydroxylamine salt solid in 10 mL of mobile phase; filter and load 1 µL of the solution.

[0141] Calculation method: Purity is calculated by dividing the area of ​​the main peak by the total area; methyl ethyl ketone oxime is quantitatively detected based on its retention time.

[0142] 2) Yield calculation

[0143] Calculation formula: Final weight of hydroxylamine salt / theoretical yield × 100%.

[0144] Test results:

[0145]

[0146] The above test methods and results fully demonstrate that the method of the present invention can achieve the preparation of high-purity, high-yield, and low-residue electronic-grade hydroxylamine salts.

[0147] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. Other modifications can be easily made by those skilled in the art. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and examples shown and described herein.

Claims

1. A process for synthesis of electronic grade hydroxylamine salt based on high purity butanone oxime and electronic grade acid characterized in that, It comprises the following steps, according to mass fraction: Step A: mix 100 parts of high-purity butanone oxime with 100-200 parts of electronic-grade inorganic acid; Step B: stir the reaction under the set temperature and pressure for 6-12 hours to generate a butanone oxime salt and acidic hydroxylamine salt mixture; Step C: reduce the pressure and evaporate the byproduct butanone at 70-95℃ until the solution mass is reduced by 15%-30%; Step D: concentrate the aqueous solution to 60-78wt%, then cool to 5-10℃, stir for 0.5-3 hours, and crystallize the crude hydroxylamine salt; Step E: heat treat the obtained crude hydroxylamine salt solution at 55-65℃ under a vacuum of -0.02 to -0.04 MPa for 1-3 hours to degrade the residual butanone oxime salt, and then pass the obtained concentrated solution containing the crude hydroxylamine salt through a modified membrane for impurity removal; Step F: continue to evaporate volatile organic matter under reduced pressure at 25-70℃, and obtain the dry hydroxylamine salt solid; The modified membrane in Step E is a thienecarboxylic acid plasma-grafted modified membrane, which is obtained by immersing a polysulfone membrane into a mixed solution of glycidyl methacrylate, benzoyl peroxide, anhydrous ethanol, 2-dihydroxyboron-3-thienecarboxylic acid, and triethylamine, and then solidifying; The modified membrane in Step E is a thienecarboxylic acid plasma-grafted modified membrane, and its preparation method is as follows: Pre-treatment: immerse 100 parts of a polysulfone membrane in 300-450 parts of anhydrous ethanol for 2-4 hours, and then dry in a vacuum drying oven at 60-80℃ for 1-2 hours; Grafting reaction: add 5-15 parts of glycidyl methacrylate, 0.1-0.5 parts of benzoyl peroxide, 30-50 parts of anhydrous ethanol, 1-3 parts of 2-dihydroxyboron-3-thienecarboxylic acid, and 0.1-0.3 parts of triethylamine into a reaction kettle and mix uniformly, immerse the pre-treated polysulfone membrane into the mixed solution, and react at 60-80℃ for 3-6 hours; Solidification: take out the membrane after the grafting reaction, place it in a vacuum drying oven at 80-100℃ for heat treatment for 2-4 hours, and obtain the modified membrane; The filtration conditions of the modified membrane in Step E are as follows: the temperature is 20-40℃, and the pressure is 0.1-0.5 MPa.

2. A process for synthesis of electronic grade hydroxylamine salt based on high purity butanone oxime and electronic grade acid as claimed in claim 1, wherein: The purity of the high-purity butanone oxime in Step A is not less than 99.9%, and the metal ion content of the electronic-grade inorganic acid is not higher than 5 ppb.

3. A process for synthesis of electronic grade hydroxylamine salt based on high purity butanone oxime and electronic grade acid as claimed in claim 1, wherein: The electronic-grade inorganic acid in Step A is selected from one of hydrochloric acid, sulfuric acid, or phosphoric acid.

4. The process as claimed in claim 1 for synthesis of electronic grade hydroxylamine salt based on high purity butanone oxime and electronic grade acid, wherein: The set temperature in Step B is 70-95℃, and the pressure is 0.1-1.0 MPa.

5. The process as claimed in claim 1 for synthesis of electronic grade hydroxylamine salt based on high purity butanone oxime and electronic grade acid, wherein: The pressure in Step C is reduced to 0.06-0.10 MPa.

6. A process for synthesis of electronic grade hydroxylamine salt based on high purity butanone oxime and electronic grade acid as claimed in claim 1, wherein: The cooling rate in Step D is controlled to be 1-5℃ / min.

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