CN1641071A - Alkyl hydroxylamine and its salt electrochemical synthesis method - Google Patents
Alkyl hydroxylamine and its salt electrochemical synthesis method Download PDFInfo
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Abstract
The present invention relates to the electrochemical synthesis process of C1-C6 alkyl hydroxylamine, especially isopropyl hydroxylamine, and its salt. By adopting corresponding nitro group substituted alkane as main material, and plate-frame diaphragm electrolytic bath with homogeneous cationic diaphragm and electrolyte of 5-35 % concentration sulfuric acid or hydrochloric acid aqua, alkyl hydroxylamine salt as electrolytic product is synthesized through electrolytic reduction reaction. The electrolytic product is separated and purified to obtain the alkyl hydroxylamine salt, which is further produced into alkyl hydroxylamine through neutralizing reaction. The said process has short synthesis path, less production links, low production cost, Faraday efficiency up to 90 %, mild reaction condition, simple control, no pollution basically, high product purity and other advantages.
Description
(I) technical field
The invention relates to an electrochemical synthesis method of alkyl hydroxylamine containing 1-6 carbon atoms and salts thereof, in particular to an electrochemical synthesis method of isopropyl hydroxylamine salt.
(II) background of the invention
Alkyl hydroxylamine containing 1 to 6 carbon atoms and salts thereof, especially isopropyl hydroxylamine salt, are important organic synthesis intermediates and are widely used for synthesis of pesticides, medicines, cosmetics and the like or as additives.
In the prior art, isopropyl hydroxylamine and salts thereof are generally prepared by reducing 2-nitropropane by a chemical oxidation 2-propylamine oxidation method and a catalytic hydrogenation method, and the 2-propylamine oxidation method has the disadvantages of difficult reaction control, complex side reaction, low yield and poor product quality; the catalytic hydrogenation method needs to adopt noble metal as a catalyst, the catalyst is easy to be poisoned in the reaction process, the cost of industrial production is increased, the two methods have great difficulty in industrialization, no relevant research report is seen in China, no factory is available for production, the product depends on import for a long time, the price is high, and the wide application of the product is limited. The above problems are also present in the preparation of alkylhydroxylamine salts having 1 to 6 carbon atoms.
Disclosure of the invention
In order to solve the defects of high production cost, poor product quality and complex synthesis process of synthesizing the isopropyl hydroxylamine salt by the existing chemical method, the invention provides the electrochemical synthesis method of the isopropyl hydroxylamine salt with high efficiency, low cost and low pollution, and the method is also suitable for the synthesis of alkyl hydroxylamine salt containing 1-6 carbon atoms and the preparation of alkyl hydroxylamine containing 1-6 carbon atoms.
The technical scheme adopted by the invention for achieving the aim of the invention is as follows:
an electrochemical synthesis method of alkyl hydroxylamine salt with the following general formula,
RNHOH·Y
wherein R is an alkyl group having 1 to 6 carbon atoms, Y is sulfuric acid or hydrochloric acid,
the method comprises the steps of taking corresponding nitro-substituted alkane as a raw material, adopting a plate-frame diaphragm type electrolytic cell, taking a cation homogeneous membrane as a diaphragm, taking a sulfuric acid or hydrochloric acid aqueous solution with the concentration of 5-35% as an electrolyte at a cathode or an anode, synthesizing an electrolytic product containing alkyl hydroxylamine salt through an electrolytic reduction reaction by taking nitro-substituted alkane added in a cathode chamber and the electrolyte sulfuric acid or hydrochloric acid in a molar ratio of 1: 1-5, and separating and purifying the electrolytic product to obtain the alkyl hydroxylamine salt.
The nitro-substituted alkane containing 1-6 carbon atoms is subjected to the following reaction on the surface of the cathode:
wherein R is an alkyl group having 1 to 6 carbon atoms;
the anode reaction is as follows:
The electrolytic reduction reaction is carried out under the following conditions: the electrolyte temperature is 10-90 ℃, and the current density is 100-3000A/m2The electrolytic voltage is 3.0-7.0V, when the concentration of the alkyl hydroxylamine salt in the catholyte reaches 15-25 wt%, or the electrolysis is stopped until the added alkyl nitro compound is 50-100% of the required electric quantity calculated according to the faradaic electric quantity.
The cathode of the electrolytic cell is one of the following:
① copper ② copper-zinc alloy ③ lead ④ lead-silver alloy ⑥ monel ⑦ copper amalgam ⑧ graphite;
the anode of the electrolytic cell is one of the following:
① electrode ② titanium iridium electrode ③ glassy carbon electrode ④ lead ⑤ lead-silver alloy ⑥ graphite ⑦ titanium-based metal oxide coated electrode (DSA);
the cation homogeneous membrane is one of the following:
① polystyrene sulfonic acid membrane ② perfluorosulfonic acid membrane ③ perfluorocarboxylic acid membrane.
The reactant nitro-substituted alkane is one of the following:
① Nitro-methane ② Nitro-ethane ③ 1-Nitro-propane ④ 2-Nitro-propane ⑤ 1-Nitro-butane ⑥ Nitro-pentane ⑦ Nitro-hexane ⑧ Nitro-cyclohexane
Further, the method for synthesizing the alkyl hydroxylamine salt refers to the synthesis of isopropyl hydroxylamine salt, and 2-nitropropane is used as a reactant.
The most suitable temperature of the electrolyte for the electrolytic reduction reaction is 30-60 ℃, and the most suitable current density is 1000-2000A/m2The optimum electrolytic voltage is 3.5-5.0V.
The separation and purification of the electrolysis product generated by the electrolytic reduction reaction can be carried out according to the following steps: and (3) distilling the reacted electrolysis product under reduced pressure, wherein the boiling point is 30-70 ℃, freezing and crystallizing the product after the reduced pressure distillation, the crystallization temperature is-10-20 ℃, and performing centrifugal separation or vacuum filtration on the crystallized product, and then performing vacuum drying to obtain the high-purity alkyl hydroxylamine salt.
Specifically, the electrochemical synthesis method of the more preferred alkyl hydroxylamine salt is carried out according to the following steps:
(1) adding 5-35% of sulfuric acid or hydrochloric acid aqueous solution into a cathode chamber and an anode chamber of an electrolytic cell in a pump circulation mode, and adding nitro-substituted alkane into the cathode chamber in a continuous dropwise or intermittent feeding mode, wherein the molar ratio of the nitro-substituted alkane in the cathode chamber to the sulfuric acid or hydrochloric acid is 1: 1-5;
(2) controlling the temperature of the cathode chamber and the anode chamber to be 10-90 ℃, and adjusting the reaction working current to be 100-3000A/m2The voltage of the reaction tank is 3.0-7.0V;
(3) controlling the electrolysis time to stop the electrolysis when the concentration of the alkyl hydroxylamine salt in the catholyte reaches 15-25 wt%; or the electrolysis is stopped until 50-100% of the required electric quantity of the added alkyl nitro compound is calculated according to the faradaic electric quantity.
(4) And (3) distilling the reacted electrolysis product under reduced pressure, wherein the boiling point is 30-70 ℃, freezing and crystallizing the product after the reduced pressure distillation, the crystallization temperature is-10-20 ℃, and performing centrifugal separation or vacuum filtration on the crystallized product, and then performing vacuum drying to obtain the high-purity alkyl hydroxylamine salt.
Particularly, when the nitro-substituted alkane is 2-nitropropane, the synthesis method of the alkyl hydroxylamine salt refers to the synthesis method of isopropyl hydroxylamine salt, and the synthesis method comprises the following steps:
(1) adding 5-35% of sulfuric acid or hydrochloric acid aqueous solution into a cathode chamber and an anode chamber of an electrolytic cell in a pump circulation mode, adding 2-nitropropane into the cathode chamber in a continuous dropwise adding or intermittent feeding mode, wherein the molar ratio of the 2-nitropropane to the sulfuric acid or hydrochloric acid in the cathode chamber is 1: 1-5;
(2) controlling the temperature of the cathode chamber and the anode chamber to be 30-60 ℃, and adjusting the reaction working current to be 1000-2000A/m2The voltage of the reaction tank is 3.0-5.0V;
(3) controlling the electrolysis time to stop the electrolysis when the concentration of the isopropyl hydroxylamine salt in the catholyte reaches 15-25 wt%;
(4) and (3) distilling the reacted electrolyte under reduced pressure, wherein the boiling point is 30-70 ℃, freezing and crystallizing the product after the reduced pressure distillation, the crystallization temperature is-10-20 ℃, and performing centrifugal separation or vacuum filtration on the crystallized product, and then performing vacuum drying to obtain the high-purity isopropyl hydroxylamine salt.
The 2-nitropropane reacts on the cathode surface as follows:
The anode reaction is as follows:
An electrochemical synthesis method of alkyl hydroxylamine with the following general formula,
RNHOH
wherein R is alkyl containing 1-6 carbon atoms, the alkyl hydroxylamine salt is prepared by the method, and the alkyl hydroxylamine salt and strong base are subjected to neutralization reaction to generate corresponding alkyl hydroxylamine. The strong base is usually sodium hydroxide, potassium hydroxide or the like, and may be a strong base capable of neutralizing the alkylhydroxylamine salt.
The electrochemical synthesis method of the alkyl hydroxylamine salt has the following beneficial effects: (1) the synthesis route is short, the process flow is simple, the product can be synthesized in one step, the production links are reduced, and the production cost is reduced; (2) the Faraday efficiency in the synthesis process can reach more than 90 percent, the reaction condition is mild, the control is simple, and the production process is basically pollution-free; (3) the product has high purity, easily obtained raw materials and low price, and the isopropyl hydroxylamine hydrochloride or sulfate produced by the process has the cost of 1/5-1/10 synthesized by a chemical method, so that the method is a green electrosynthesis method with great development prospect.
(IV) detailed description of the preferred embodiments
The invention is further described below with reference to specific examples, but the methods and technical parameters involved in the schemes should not be construed as limiting the invention.
Examples 1 to 7: preparation of isopropylhydroxylamine hydrochloride
In an ionic membrane electrolytic cell, a pure copper sheet is used as a cathode, the area is 5.0cm multiplied by 6.0cm, large-area graphite is used as an anode, a catholyte is 300mL of 18 wt% industrial grade hydrochloric acid solution added with 30mL of industrial grade 2-nitropropane, an anolyte is 400mL of 18 wt% industrial grade hydrochloric acid solution, the cathode is separated by a polystyrene sulfonic acid membrane homogeneous ionic membrane, and the catholyte and the anolyte are respectively circulated by a magnetic pump. And then, electrifying direct current to the electrolytic cell for electrolysis, wherein the reaction conditions and the yield are shown in table 1, the temperature of the cathode chamber and the anode chamber is controlled to be 10-90 ℃ in the reaction process, the cell voltage is 3.0-7.0V, and chlorine generated in the reaction process is absorbed by NaOH solution. After the reaction is finished, the electrolyte is taken out, reduced pressure distillation is carried out in a water bath at 90 ℃, most of water in the electrolyte is removed, then freezing crystallization is carried out in a water bath at-5 ℃ for 12 hours, solid isopropylhydroxylamine hydrochloride crystal is separated out, and vacuum drying is carried out, so that the purity is over 98 percent. The experimental data are shown in Table 1, and more than 90% of the unreacted 2-nitropropane can be recovered in the distillation process.
TABLE 1 examples 1-7 Experimental data
Examples 8 to 14: preparation of isopropylhydroxylamine hydrochloride
In an ion-exchange membrane electrolyzer, copper-zinc alloy, lead-silver alloy, monel, amalgam copper sheet or graphite is used as a cathode, the area is 5.0cm multiplied by 6.0cm, a large-area DSA electrode is used as an anode, a catholyte is 300mL of 18 wt% industrial grade hydrochloric acid solution and 30mL of industrial grade 2-nitropropane, an anolyte is 400mL of 18 wt% industrial grade hydrochloric acid solution, a cathode and an anode are separated by a perfluorosulfonic acid ion membrane, and the catholyte and the anolyte are respectively circulated by a magnetic pump. Then the direct current is supplied to the electrolytic cell for electrolysis, and the current density is 2000A/m2The reaction time is 3 hours, the temperature of the cathode chamber and the anode chamber in the reaction process is controlled to be 30-70 ℃, the voltage of the tank is 3.5-7.0V, and chlorine generated in the reaction process isabsorbed by NaOH solution. And after the reaction is finished, taking out the electrolyte, carrying out reduced pressure distillation in a water bath at 50-90 ℃ to remove most of water, and then carrying out freeze crystallization in a water bath at 0 ℃ for 12 hours to separate out solid isopropylhydroxylamine hydrochloride crystals with the purity of more than 98%. The experimental conditions and yield are shown in Table 2, and the unreacted 2-nitropropane can be recovered in the distillation process.
TABLE 2 Experimental data for examples 8-14
The DSA electrode in Table 2 is a titanium-based metal oxide coating electrode
Examples 15 to 17: preparation of isopropylhydroxylamine hydrochloride
In an ionic membrane electrolytic cell, a ruthenium-titanium electrode, glassy carbon and a graphite electrode are respectively used as anodes, a copper sheet is used as a cathode, the area is 5.0cm multiplied by 6.0cm, a catholyte is 300mL of 18 wt% industrial grade hydrochloric acid solution and 30mL of industrial grade 2-nitropropane are added, an anolyte is 400mL of 18 wt% industrial grade hydrochloric acid solution, cathodes and anodes are separated by perfluorocarboxylic acid type ionic membranes, and catholyte and anolyte are respectively circulated by a magnetic pump. Then the direct current is supplied to the electrolytic cell for electrolysis, and the current density is 2000A/m2The reaction time is 3 hours, the temperature of the cathode chamber and the anode chamber in the reaction process is controlled to be 30-70 ℃, the voltage of the tank is 3.8-7.0V, and chlorine generated in the reaction process is absorbed by NaOH solution. And after the reaction is finished, taking out the electrolyte, carrying out reduced pressure distillation in a water bath at 50-90 ℃ to remove most of water, and then carrying out freeze crystallization in a water bath at 0 ℃ for 12 hours to separate out solid isopropylhydroxylamine hydrochloride crystals with the purity of more than 98%. The experimental conditions and yields are shown in Table 3, and unreacted 2-nitropropane can be recovered in the distillation process.
TABLE 3 Experimental data for examples 15-17
Examples 18 to 20: preparation of isopropyl hydroxylamine sulphate
In the ionic membrane electrolytic cell, a pure copper sheet is used as a cathode, the area is 5.0cm multiplied by 6.0cm, lead-silver alloy and titanium iridium alloy electrodes are respectively used as anodes, the catholyte is 150mL of 15 wt% industrial-grade sulfuric acid solution and 25mL of industrial-grade 2-nitropropane, the anolyte is 150mL of 15 wt% industrial-grade sulfuric acid solution, the cathode and the anode are separated by a homogeneous ionic membrane, and the catholyte and the anolyte are respectively circulated by a magnetic pump. Then the direct current is supplied to the electrolytic cell for electrolysis, and the current density is 2500A/m2The reaction time is 3.0 hours, the temperature of the cathode chamber and the anode chamber in the reaction process is controlled to be 20-30 ℃, and the voltage of the tank is 3.8-4.1V. After the reaction is finishedTaking out the electrolyte, distilling at 90 deg.C in water bath under reduced pressure to remove most of water, and freezing and crystallizing at 10 deg.C in water bath for 12 hr to separate out solid crystalline isopropyl hydroxylamine sulfate with purity over 98%. The experimental conditions and yields are shown in Table 4.
TABLE 4 Experimental data for examples 18-20
Example 21: preparation of isopropylhydroxylamine hydrochloride
Copper is used as a cathode, DSA and graphite are used as an anode, catholyte is respectively 20 wt% of industrial hydrochloric acid 6L and 7L, anolyte is 20 wt% of industrial hydrochloric acid 30L, and the feeding amount of 2-nitropropane is 2000 g. And in the electrolysis process, the temperature of the cathode region is controlled to be 30-60 ℃, the temperature of the anode region is controlled to be 30-60 ℃, the cathode region and the anode region are respectively circulated by a mechanical pump (20L/min), and the electrolysis energization amount is 2000 Ah. The average cell voltage in the electrolytic process is 4.0-5.5V at 2000A/m2The current density of 4 batches of electrolysis, 200g of 2-nitropropane are recovered from each batch on average, average 1845g of crude isopropyl hydroxylamine hydrochloride is obtained, the average current efficiency is 88.7 percent, the average molar reaction yield is 81.8 percent, and the product is light yellow to white crystals with the purity of more than 98 percent. The current density is 1000A/m2The average current efficiency was 89.2% and the average molar reaction yield was 82.3%. Chlorine generated in the reaction process is absorbed by NaOH solution, and unreacted 2-nitropropane is recycled in the distillation process.
Examples 22 to 29: preparation of alkylhydroxylamine salts
In an ion membrane electrolytic cell, red copper is used as a cathode, the area is 5.0cm multiplied by 6.0cm, a large-area DSA electrode is used as an anode, the catholyte is 300mL of 18 wt% industrial grade hydrochloric acid solution, 2-nitropropane (30mL), nitromethane (20mL), nitroethane (25mL), 1-nitropropane (30mL), 1-nitrobutane (35mL), nitropentane (40mL), nitrohexane (45mL) and nitrocyclohexane (45mL) are respectively added, the anolyte is 400mL of 18 wt% industrial grade hydrochloric acid solution, and perfluorosulfonic acid type ion membrane is used for a cathode and an anodeSeparately, the catholyte and anolyte were circulated separately with magnetic pumps. Then the direct current is supplied to the electrolytic cell for electrolysis, and the current density is 2000A/m2The reaction time is 3 hours, the temperature of the cathode chamber and the anode chamber in the reaction process is controlled to be 30-70 ℃, the voltage of the tank is 3.5-7.0V, and chlorine generated in the reaction process is absorbed by NaOH solution. After the reaction is finished, taking out the electrolyte, carrying out reduced pressure distillation in a water bath at 50-90 ℃ to remove most of water, then freezing and crystallizing in a water bath at 0 ℃ for 12 hours to separate out solid isopropyl hydroxylamine hydrochloride, methyl hydroxylamine hydrochloride, ethyl hydroxylamine hydrochloride, n-propyl hydroxylamine hydrochloride and n-butyl hydroxyl hydroxylamine hydrochlorideThe amine hydrochloride, amyl hydroxylamine hydrochloride, hexyl hydroxylamine hydrochloride and cyclohexyl hydroxylamine hydrochloride crystals all have a purity of over 92 percent. The experimental data are shown in Table 5, and the unreacted nitro compound can be recovered in the distillation process. The alkyl hydroxylamine salt and sodium hydroxide are neutralized to obtain corresponding hydroxylamine.
TABLE 5 Experimental data for examples 22-29
| Reaction substrate | Product of | Current efficiency | Yield of | |
| Example 22 | 30mL of 2-nitropropane | Isopropyl hydroxylamine hydrochloride | 93.6％ | 91.2％ |
| Example 23 | Nitromethane 20mL | Methylhydroxylamine hydrochloride | 96.76％ | 95.2％ |
| Example 24 | Nitroethane 25mL | Ethylhydroxylamine hydrochloride | 91.5％ | 87.1％ |
| Example 25 | 30mL of 1-nitropropane | N-propylhydroxylamine hydrochloride | 90.5％ | 88.3％ |
| Example 26 | 35mL of 1-nitrobutane | N-butylhydroxylamine hydrochloride | 88.8％ | 87.4％ |
| Example 27 | Nitropentane 40mL | Pentylhydroxylamine hydrochloride | 89.4％ | 85.2％ |
| Example 28 | 45mL of nitrohexane | Hexylhydroxylamine hydrochloride | 90.5％ | 86.1％ |
| Example 29 | 45mL of nitrocyclohexane | Cyclohexyl hydroxylamine hydrochloride | 88.6％ | 83.5％ |
Claims (10)
1. An electrochemical synthesis method of alkyl hydroxylamine salt with the following general formula,
RNHOH·Y
wherein R is alkyl containing 1-6 carbon atoms, Y is sulfuric acid or hydrochloric acid, and the method is characterized in that: the method comprises the steps of taking corresponding nitro-substituted alkane as a raw material, adopting a plate-frame diaphragm type electrolytic cell, taking a cation homogeneous membrane as a diaphragm, taking a sulfuric acid or hydrochloric acid aqueous solution with the concentration of 5-35% as an electrolyte at a cathode or an anode, synthesizing an electrolytic product containing alkyl hydroxylamine salt through an electrolytic reduction reaction by taking nitro-substituted alkane added in a cathode chamber and the electrolyte sulfuric acid or hydrochloric acid in a molar ratio of 1: 1-5, and separating and purifying the electrolytic product to obtain the alkyl hydroxylamine salt.
2. The electrochemical synthesis method of alkylhydroxylamine salts according to claim 1, wherein the electrolytic reduction reaction is carried out under the following conditions: the electrolyte temperature is 10-90 ℃, and the current density is 100-3000A/m2The electrolyticvoltage is 3.0-7.0V, when the concentration of the alkyl hydroxylamine salt in the catholyte reaches 15-25 wt%, or the required electric quantity is calculated according to the faradaic electric quantity by electrolyzing the added alkyl nitro compoundAnd when the concentration is 50-100%, stopping electrolysis.
3. The electrochemical synthesis method of an alkylhydroxylamine salt according to claim 2, wherein: the cathode of the electrolytic cell is one of the following:
① copper ② copper-zinc alloy ③ lead ④ lead-silver alloy ⑥ monel ⑦ copper amalgam ⑧ graphite;
the anode of the electrolytic cell is one of the following:
① ruthenium titanium electrode ② titanium iridium electrode ③ glassy carbon electrode ④ lead ⑤ lead-silver alloy ⑥ graphite ⑦ titanium-based metal oxide coated electrode (DSA);
the cation homogeneous membrane is one of the following:
① polystyrene sulfonic acid membrane ② perfluorosulfonic acid membrane ③ perfluorocarboxylic acid membrane.
4. The electrochemical synthesis method of an alkylhydroxylamine salt according to claim 3, wherein the reactant nitro-substituted alkane is one of the following:
① Nitromethane ② Nitroethane ③ 1-Nitropropane ④ 2-Nitropropane
⑤ 1-Nitrobutane ⑥ Nitropentane ⑦ Nitro-Hexane ⑧ Nitro-cyclohexane
5. The electrochemical synthesis method of an alkylhydroxylamine salt according to claim 4, wherein the nitro-substituted alkane is 2-nitropropane.
6. The electrochemical synthesis method of alkyl hydroxylamine salts according to claim 2, wherein the temperature of the electrolyte is 30-60 ℃, and the current density is 1000-2000A/m2The electrolytic voltage is 3.5-5.0V.
7. The electrochemical synthesis method of alkylhydroxylamine salts according to claim 2, wherein the separation and purification are carried out by the following steps:
and (3) distilling the reacted electrolysis product under reduced pressure, wherein the boiling point is 30-70 ℃, freezing and crystallizing the product after the reduced pressure distillation, the crystallization temperature is-10-20 ℃, and performing centrifugal separation or vacuum filtration on the crystallized product, and then performing vacuum drying to obtain the high-purity alkyl hydroxylamine salt.
8. The electrochemical synthesis process of an alkylhydroxylamine salt according to claim 3, wherein said process comprises the steps of:
(1) adding 5-35% of sulfuric acid or hydrochloric acid aqueous solution into a cathode chamber and an anode chamber of an electrolytic cell in a pump circulation mode, and adding nitro-substituted alkane into the cathode chamber in a continuous dropwise or intermittent feeding mode, wherein the molar ratio of the nitro-substituted alkane in the cathode chamber to the sulfuric acid or hydrochloric acid is 1: 1-5;
(2) controlling the temperature of the cathode chamber and the anode chamber to be 10-90 ℃, and adjusting the reaction working current to be 100-3000A/m2The voltage of the reaction tank is 3.0-7.0V;
(3) controlling the electrolysis time to stop the electrolysis when the concentration of the alkyl hydroxylamine salt in the catholyte reaches 15-25 wt%; or the electrolysis is stopped until 50-100% of the required electric quantity of the added alkyl nitro compound is calculated according to the faradaic electric quantity.
(4) And (3) distilling the reacted electrolysis product under reduced pressure, wherein the boiling point is 30-70 ℃, freezing and crystallizing the product after the reduced pressure distillation, the crystallization temperature is-10-20 ℃, and performing centrifugal separation or vacuum filtration on the crystallized product, and then performing vacuum drying to obtain the high-purity alkyl hydroxylamine salt.
9. The electrochemical synthesis process of an alkylhydroxylamine salt according to claim 8, wherein said process comprises the steps of:
(1) adding 5-35% of sulfuric acid or hydrochloric acid aqueous solution into a cathode chamber and an anode chamber of an electrolytic cell in a pump circulation mode, adding 2-nitropropane into the cathode chamber in a continuous dropwise adding or intermittent feeding mode, wherein the molar ratio of the 2-nitropropane to the sulfuric acid or hydrochloric acid in the cathode chamber is 1: 1-5;
(2) controlling the temperature of the cathode chamber and the anode chamber to be 30-60 ℃, and adjustingThe reaction operating current is 1000-2000A/m2The voltage of the reaction tank is 3.0-5.0V;
(3) controlling the electrolysis time to stop the electrolysis when the concentration of the isopropyl hydroxylamine salt in the catholyte reaches 15-25 wt%;
(4) and (3) distilling the reacted electrolyte under reduced pressure, wherein the boiling point is 30-70 ℃, freezing and crystallizing the product after the reduced pressure distillation, the crystallization temperature is-10-20 ℃, and performing centrifugal separation or vacuum filtration on the crystallized product, and then performing vacuum drying to obtain the high-purity isopropyl hydroxylamine salt.
10. An electrochemical synthesis method of alkyl hydroxylamine with the following general formula,
RNHOH
wherein R is alkyl containing 1-6 carbon atoms, and is characterized in that: the alkylhydroxylamine salt prepared by the method according to claim 1 to 9, wherein the alkylhydroxylamine salt is neutralized with a strong base to produce the corresponding alkylhydroxylamine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823981A (en) * | 2010-05-18 | 2010-09-08 | 嘉兴市向阳化工厂 | Method for synthesizing N-isopropylhydroxyla |
| CN101660171B (en) * | 2009-09-09 | 2011-01-05 | 淮北煤炭师范学院 | Method for preparing aminopropanol by electrolysis |
| CN102776525A (en) * | 2012-08-20 | 2012-11-14 | 云南天恒通泰腐植酸有限公司 | Method for electrolyzing and recycling chromium containing waste liquid generated during oxidation decoloration of montan wax, deresinated montan wax, peat wax or deresinated peat wax |
| CN113651730A (en) * | 2021-08-20 | 2021-11-16 | 宿迁盛瑞新材料有限公司 | Preparation method of bis (octadecyl) hydroxylamine |
-
2004
- 2004-01-18 CN CN200410016041.6A patent/CN1641071A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101660171B (en) * | 2009-09-09 | 2011-01-05 | 淮北煤炭师范学院 | Method for preparing aminopropanol by electrolysis |
| CN101823981A (en) * | 2010-05-18 | 2010-09-08 | 嘉兴市向阳化工厂 | Method for synthesizing N-isopropylhydroxyla |
| CN101823981B (en) * | 2010-05-18 | 2013-04-10 | 嘉兴市向阳化工厂 | Method for synthesizing N-isopropylhydroxyla |
| CN102776525A (en) * | 2012-08-20 | 2012-11-14 | 云南天恒通泰腐植酸有限公司 | Method for electrolyzing and recycling chromium containing waste liquid generated during oxidation decoloration of montan wax, deresinated montan wax, peat wax or deresinated peat wax |
| CN113651730A (en) * | 2021-08-20 | 2021-11-16 | 宿迁盛瑞新材料有限公司 | Preparation method of bis (octadecyl) hydroxylamine |
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