A method for preparing hydroxylamine solution by catalysis of ferrocene-based molecular sieve

Abstract

The present invention discloses a method for catalytically preparing hydroxylamine solution by ferrocene-based molecular sieve, belonging to the technical field of hydroxylamine solution preparation. The method uses hydrogen peroxide solution, alcohol solution and ammonia water solution as raw materials, stirs them evenly in a reactor, adds a ferrocene-based molecular sieve catalyst for catalytic reaction to obtain a hydroxylamine solution. This method catalyzes the preparation of hydroxylamine solution from hydrogen peroxide and ammonia water by ferrocene-based molecular sieve, and the by-product is water, which is environmentally friendly. At the same time, the ferrocene-based molecular sieve prepared by this method has high catalytic efficiency, high raw material conversion rate, good product selectivity, and the molecular sieve catalyst can be recycled, with good economic benefits.

Description

Technical Field

[0001] The present invention relates to the technical field of hydroxylamine solution preparation, and in particular to a method for preparing hydroxylamine solution by catalysis of ferrocene-based molecular sieve. Background Art

[0002] Hydroxylamine is an important chemical raw material. As a reducing agent in organic synthesis, it condenses with carbonyl compounds to form oximes, and is mainly used for synthesizing caprolactam (for producing nylon-6), the pharmaceutical intermediate hydroxylamine-O-sulfonic acid, as well as synthesizing pesticides, medicines, spices, fuels, etc. In the semiconductor industry, hydroxylamine is also used as a component in photoresist solvents, and can also be used for selectively cleaving asparaginyl-glycine peptide bonds. In the leather manufacturing industry, hydroxylamine is also an important hair remover.

[0003] The published patent document PCT / EP1998 / 003714 provides a method for preparing an aqueous solution of free hydroxylamine with high purity, in which a dilute aqueous solution of hydroxylamine is concentrated in a tower, and the steam containing hydroxylamine is withdrawn from the bottom of the tower through a side stream, and high-purity hydroxylamine is obtained by condensing the steam.

[0004] The published patent document CN104129765B provides a method for preparing hydroxylamine salt / hydroxylamine by coupling an oxime hydrolysis reaction with solvent extraction in one step. Its characteristics are taking oxime (ketoxime or aldoxime) as the raw material, coupling the hydrolysis reaction of oxime in an acidic solution with the extraction and separation of an organic solvent phase. During the hydrolysis reaction, the extractant extracts the corresponding generated ketone or aldehyde into the organic phase, thereby breaking the limitation of the chemical equilibrium of the oxime hydrolysis reaction under relatively mild conditions, and enabling the reaction to proceed in the direction of generating hydroxylamine salt / hydroxylamine, so as to achieve the purpose of improving the reaction conversion rate and the yield of hydroxylamine salt / hydroxylamine.

[0005] The published patent document CN110983370A provides a method for preparing a free hydroxylamine solution by electrolytic electrodialysis. The device used in the method includes four compartments, namely an anode compartment, a raw material compartment, a product compartment and a cathode compartment separated by partitions. The partitions of the four compartments are clamped and fixed in turn in pairs. The clamped partitions in pairs are of a hollow frame structure, and a first anion exchange membrane, a cation exchange membrane and a second anion exchange membrane are respectively fixed in the middle of the three groups of clamped partitions; an anode plate is fixed in the anode compartment, and a cathode plate is fixed in the cathode compartment; the method is as follows: continuously introduce ultrapure water into the anode compartment; continuously introduce a mixed solution of one or several of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine nitrate or hydroxylamine phosphate solution into the raw material compartment; continuously introduce ultrapure water into the product compartment; continuously introduce ultrapure water into the cathode compartment; apply a constant voltage for electrolysis.

[0006] The methods for preparing hydroxylamine solution in the above and existing published technologies generally have disadvantages such as long process flow, many by-products, and large three-waste emissions. Summary of the Invention

[0007] In view of the above problems, the object of the invention of this patent application is to provide a method for catalytically preparing hydroxylamine solution with ferrocene-based molecular sieve. By using ferrocene-based molecular sieve to catalyze hydrogen peroxide and ammonia water to prepare hydroxylamine solution, the by-product is water, which is environmentally friendly. At the same time, the ferrocene-based molecular sieve prepared by this method has high catalytic efficiency and can be recycled, with good economic benefits.

[0008] The main technical content of the present invention is as follows:

[0009] A method for catalytically preparing hydroxylamine solution with ferrocene-based molecular sieve, and its operation steps are as follows:

[0010] A1: By mass, add 5-10 parts of hydrogen peroxide solution, 75-100 parts of alcohol solution and 20-30 parts of ammonia water solution into the reactor, and stir evenly;

[0011] A2: Add 0.5-2 parts of ferrocene-based molecular sieve catalyst into the reactor, keep the reactor in a water bath for heat preservation, react for 2-6 h, filter and recycle the ferrocene-based molecular sieve after the reaction, and the filtrate is the hydroxylamine solution.

[0012] As a further supplement, in the step A1, the concentration of the hydrogen peroxide solution is 20-30%, and the concentration of the ammonia water solution is 25-28%.

[0013] As a further supplement, in the step A1, the alcohol solution is selected from at least one of methanol, ethylene glycol and trimethyl methanol.

[0014] As a further supplement, in the step A1, the concentration of the alcohol solution is 75-90%.

[0015] As a further supplement, in the step A2, the water bath temperature is 45-85 °C.

[0016] As a further supplement, the recycled ferrocene-based molecular sieve in the step A2 can be reused.

[0017] As a further supplement, the preparation method of the ferrocene-based molecular sieve in the step A2:

[0018] By weight parts, under the condition of 55 - 70 °C, 7 - 14 parts of an organic template agent and 80 - 92 parts of deionized water are successively added into a reactor, stirred evenly, then 100 - 150 parts of a hydrochloric acid solution with a molar concentration of 0.1 - 0.5 mol / L, 1.4 - 2.8 parts of N,N - dimethyldodecylamine are added. After continuing to stir at 57 - 70 °C for 40 - 80 minutes, 4 - 10 parts of an organic titanium metal modifier are added, and 10 - 20 parts of tetraethyl orthosilicate are slowly added dropwise. The obtained mixture is transferred to a crystallization kettle, heated to 70 - 85 °C, and crystallized at a constant temperature for 20 - 40 h; then through separation, washing, and drying, an amino molecular sieve can be obtained.

[0019] As a further supplement, the organic template agent is one or more of F127(EO106PO70EO106), P123(EO20PO70EO20), P104(EO27PO61EO27).

[0020] As a further supplement, the preparation method of the organic titanium metal modifier is as follows:

[0021] By mass parts, 2 - 6 parts of 2 - vinylcyclopropane - 1,1 - dicarboxylic acid, 3 - 8 weight parts of titanium tetrachloride, 100 - 200 parts of chloroform are weighed, mixed and stirred at 70 - 80 °C for 50 - 100 min, then 5 - 10 parts of octavinylcage - type oligosilsesquioxane, 0.005 - 0.03 parts of vinylferrocene, 2 - 4 parts of azobisisobutyronitrile are added, and stirred at 60 - 70 °C for 17 - 22 h. After the reaction ends, chloroform is distilled off and dried to obtain the organic titanium metal modifier.

[0022] Technical effects:

[0023] A method for catalytically preparing hydroxylamine solution with a ferrocene - based molecular sieve of the present invention, compared with the prior art, has the following remarkable effects:

[0024] 1) 2 - vinylcyclopropane - 1,1 - dicarboxylic acid reacts with titanium tetrachloride to form an organometallic precursor, then octavinylcage - type oligosilsesquioxane and vinylferrocene are added for polymerization, which is used as a modification material in the preparation of molecular sieves. The prepared ferrocene - based molecular sieve catalyst has excellent catalytic activity, can be recycled, greatly reduces the production cost and improves the production efficiency;

[0025] 2) The method for preparing hydroxylamine solution in this system has the technical effects of being green, environmentally friendly, energy - saving and economical. It has a high atom utilization rate, excellent reaction stability, and good product selectivity. Specific embodiments

[0026] The essential features and remarkable effects of the present invention can be embodied in the following embodiments, but they do not impose any limitations on the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the present invention. The present invention will be further described below through specific embodiments.

[0027] In the embodiments of the present invention, hydroxylamine is analyzed by potassium permanganate redox titration; hydrogen peroxide is analyzed by iodometry.

[0028] Example 1

[0029] A method for catalytically preparing a hydroxylamine solution using a ferrocene-based molecular sieve, the operating steps of which are as follows:

[0030] A1: Add 5 kg of hydrogen peroxide solution, 75 kg of alcohol solution, and 20 kg of ammonia water solution into the reactor, and stir evenly;

[0031] A2: Add 0.5 kg of ferrocene-based molecular sieve catalyst into the reactor, keep the reactor warm in a water bath, react for 2 h, filter and recover the ferrocene-based molecular sieve after the reaction, and the filtrate is the hydroxylamine solution.

[0032] In step A1, the concentration of the hydrogen peroxide solution is 20%, and the concentration of the ammonia water solution is 25%.

[0033] In step A1, the alcohol solution is selected from methanol.

[0034] In step A1, the concentration of the alcohol solution is 75%.

[0035] In step A2, the water bath temperature is 45 °C.

[0036] The recovered ferrocene-based molecular sieve in step A2 can be reused.

[0037] The preparation method of the ferrocene-based molecular sieve in step A2:

[0038] Under the condition of 55 °C, add 70 g of organic template agent and 800 g of deionized water into the reactor in sequence, stir evenly, then add 1000 g of hydrochloric acid solution with a molar concentration of 0.1 mol / L, 14 g of N,N-dimethyldodecylamine, continue to stir at 57 °C for 40 minutes, add 40 g of organic titanium metal modifier, slowly add 100 g of tetraethyl orthosilicate drop by drop, transfer the obtained mixture to a crystallization kettle, heat up to 70 °C, and crystallize at a constant temperature for 20 h; then through separation, washing, and drying, the amino molecular sieve can be obtained.

[0039] The organic template agent is F127 (EO106PO70EO106).

[0040] The preparation method of the organic titanium metal modifier:

[0041] Weigh 20 g of 2-vinylcyclopropane-1,1-dicarboxylic acid, 30 g of titanium tetrachloride, and 1000 g of chloroform. Mix and stir at 70 °C for 50 min. Then add 50 g of octavinylcage oligomeric silsesquioxane, 0.1 g of vinylferrocene, and 20 g of azobisisobutyronitrile. Stir at 60 °C for 17 h. After the reaction is completed, distill off the chloroform and dry to obtain the organotitanium metal modifier.

[0042] Through analysis and calculation, the conversion rate of hydrogen peroxide in this example is 99.3%, and the selectivity of hydroxylamine is 97.8%.

[0043] Example 2

[0044] A method for catalytically preparing hydroxylamine solution with ferrocene-based molecular sieve, and its operation steps are as follows:

[0045] A1: Add 6.5 kg of hydrogen peroxide solution, 80 kg of alcohol solution, and 25 kg of ammonia water solution into the reactor, and stir evenly.

[0046] A2: Add 1 kg of ferrocene-based molecular sieve catalyst into the reactor. Keep the reactor in a water bath for heat preservation and react for 3 h. After the reaction is completed, filter to recover the ferrocene-based molecular sieve, and the filtrate is the hydroxylamine solution.

[0047] In the step A1, the concentration of the hydrogen peroxide solution is 25%, and the concentration of the ammonia water solution is 26%.

[0048] In the step A1, the alcohol solution is selected from ethylene glycol.

[0049] In the step A1, the concentration of the alcohol solution is 80%.

[0050] In the step A2, the water bath temperature is 55 °C.

[0051] The recovered ferrocene-based molecular sieve in the step A2 can be reused.

[0052] The preparation method of the ferrocene-based molecular sieve in the step A2:

[0053] Under the condition of 60 °C, add 100 g of organic template agent and 850 g of deionized water into the reactor in sequence, stir evenly, then add 1200 g of hydrochloric acid solution with a molar concentration of 0.25 mol / L, 18 g of N,N-dimethyldodecylamine. Continue to stir at 62 °C for 50 minutes, then add 60 g of organotitanium metal modifier, and slowly add 130 g of tetraethyl orthosilicate drop by drop. Transfer the obtained mixture to a crystallization kettle, heat up to 75 °C, and keep the temperature constant for crystallization for 30 h; then through separation, washing, and drying, the amino molecular sieve can be obtained.

[0054] The organic template agent is P123(EO20PO70EO20).

[0055] Preparation method of the organotitanium metal modifier:

[0056] Weigh 40 g of 2-vinylcyclopropane-1,1-dicarboxylic acid, 50 g of titanium tetrachloride, 1350 g of chloroform, mix and stir at 75 °C for 75 min, then add 65 g of octavinylcage oligomeric silsesquioxane, 0.2 g of vinylferrocene, 30 g of azobisisobutyronitrile, stir at 65 °C for 20 h. After the reaction is completed, distill off chloroform and dry to obtain the organotitanium metal modifier.

[0057] Through analysis and calculation, in this example, the conversion rate of hydrogen peroxide is 99.6% and the selectivity of hydroxylamine is 98.6%.

[0058] Example 3

[0059] A method for catalytically preparing hydroxylamine solution with ferrocene-based molecular sieve, and its operation steps are as follows:

[0060] A1: Add 8.5 kg of hydrogen peroxide solution, 90 kg of alcohol solution and 27 kg of ammonia water solution into the reactor, and stir evenly;

[0061] A2: Add 1.5 kg of ferrocene-based molecular sieve catalyst into the reactor, keep the reactor in a water bath for heat preservation, react for 5 h, after the reaction is completed, filter and recover the ferrocene-based molecular sieve, and the filtrate is the hydroxylamine solution.

[0062] In the step A1, the concentration of the hydrogen peroxide solution is 25% and the concentration of the ammonia water solution is 27%.

[0063] In the step A1, the alcohol solution is selected from trimethylcarbinol.

[0064] In the step A1, the concentration of the alcohol solution is 85%.

[0065] In the step A2, the water bath temperature is 70 °C.

[0066] The recovered ferrocene-based molecular sieve in the step A2 can be reused.

[0067] Preparation method of the ferrocene-based molecular sieve in the step A2:

[0068] Under the condition of 65 °C, add 120 g of organic template agent and 890 g of deionized water into the reactor in sequence, stir evenly, then add 1400 g of hydrochloric acid solution with a molar concentration of 0.4 mol / L, 24 g of N,N-dimethyldodecylamine, continue to stir at 68 °C for 60 minutes, then add 80 g of organotitanium metal modifier, slowly add 180 g of tetraethyl orthosilicate drop by drop, transfer the obtained mixture to a crystallization kettle, heat up to 75 °C, and crystallize at a constant temperature for 30 h; then through separation, washing and drying, the amino molecular sieve can be obtained.

[0069] The organic template agent is P104(EO27PO61EO27).

[0070] The preparation method of the organic titanium metal modifier:

[0071] Weigh 50 g of 2-vinylcyclopropane-1,1-dicarboxylic acid, 65 g of titanium tetrachloride, 1800 g of chloroform, mix and stir at 75 °C for 80 min, then add 80 g of octavinylcage oligomeric silsesquioxane, 0.2 g of vinylferrocene, 30 g of azobisisobutyronitrile, stir at 65 °C for 20 h. After the reaction is completed, distill off the chloroform and dry to obtain the organic titanium metal modifier.

[0072] Through analysis and calculation, the conversion rate of hydrogen peroxide in this example is 99.5%, and the selectivity of hydroxylamine is 99.0%.

[0073] Example 4

[0074] A method for catalytically preparing hydroxylamine solution with ferrocene-based molecular sieve, and its operation steps are as follows:

[0075] A1: Add 10 kg of hydrogen peroxide solution, 100 kg of alcohol solution and 30 kg of ammonia water solution into the reactor, and stir evenly;

[0076] A2: Add 2 kg of ferrocene-based molecular sieve catalyst into the reactor, keep the reactor in a water bath for heat preservation, react for 6 h, after the reaction is completed, filter and recycle the ferrocene-based molecular sieve, and the filtrate is the hydroxylamine solution.

[0077] In the step A1, the concentration of the hydrogen peroxide solution is 30%, and the concentration of the ammonia water solution is 28%.

[0078] In the step A1, the alcohol solution is selected from methanol.

[0079] In the step A1, the concentration of the alcohol solution is 90%.

[0080] In the step A2, the water bath temperature is 85 °C.

[0081] The recycled ferrocene-based molecular sieve in the step A2 can be reused.

[0082] The preparation method of the ferrocene-based molecular sieve in the step A2:

[0083] Under the condition of 70 °C, 140 g of an organic template agent and 920 g of deionized water were successively added to a reactor, stirred evenly, then 1500 g of a hydrochloric acid solution with a molar concentration of 0.5 mol / L, 28 g of N,N-dimethyldodecylamine were added, and stirring was continued at 70 °C for 80 minutes. Then, 100 g of an organic titanium metal modifier was added, and 200 g of tetraethyl orthosilicate was slowly added dropwise. The resulting mixture was transferred to a crystallization kettle, heated to 85 °C, and crystallized at a constant temperature for 40 h; then, through separation, washing, and drying, an amino molecular sieve could be obtained.

[0084] The organic template agent is F127 (EO106PO70EO106).

[0085] The preparation method of the organic titanium metal modifier:

[0086] Weigh 60 g of 2-vinylcyclopropane-1,1-dicarboxylic acid, 80 g of titanium tetrachloride, 2000 g of chloroform, mix and stir at 80 °C for 100 min, then add 100 g of octavinylcage-like oligosilsesquioxane, 0.3 g of vinylferrocene, 40 g of azobisisobutyronitrile, and stir at 70 °C for 22 h. After the reaction is completed, chloroform is removed by distillation and dried to obtain the organic titanium metal modifier.

[0087] Through analysis and calculation, the conversion rate of hydrogen peroxide in this example was 99.4%, and the selectivity of hydroxylamine was 98.5%.

[0088] Comparative Example 1

[0089] A method for catalytically preparing a hydroxylamine solution with a ferrocene-based molecular sieve, and its operation steps are as follows:

[0090] A1: Add 5 kg of a hydrogen peroxide solution, 75 kg of an alcohol solution, and 20 kg of an ammonia water solution into a reactor, and stir evenly;

[0091] A2: Add 0.5 kg of a ferrocene-based molecular sieve catalyst into the reactor, keep the reactor in a water bath for heat preservation, react for 2 h, after the reaction is completed, filter and recover the ferrocene-based molecular sieve, and the filtrate is the hydroxylamine solution.

[0092] In the step A1, the concentration of the hydrogen peroxide solution is 20%, and the concentration of the ammonia water solution is 25%.

[0093] In the step A1, the alcohol solution is selected from methanol.

[0094] In the step A1, the concentration of the alcohol solution is 75%.

[0095] In the step A2, the water bath temperature is 45 °C.

[0096] The recovered ferrocene-based molecular sieve in the step A2 can be reused.

[0097] The preparation method of ferrocenyl molecular sieve in step A2:

[0098] Under the condition of 55 °C, 70 g of organic template agent and 800 g of deionized water are successively added into the reactor and stirred evenly. Then 1000 g of hydrochloric acid solution with a molar concentration of 0.1 mol / L, 14 g of N,N-dimethyldodecylamine are added. After continuing to stir at 57 °C for 40 minutes, 40 g of organic titanium metal modifier is added, and 100 g of tetraethyl orthosilicate is slowly added drop by drop. The obtained mixture is transferred to a crystallization kettle, heated to 70 °C, and crystallized at a constant temperature for 20 h; then through separation, washing, and drying, amino molecular sieve can be obtained.

[0099] The organic template agent is F127(EO106PO70EO106).

[0100] The preparation method of the organic titanium metal modifier:

[0101] Weigh 30 g of titanium tetrachloride and 1000 g of chloroform, mix and stir at 70 °C for 50 min, then add 50 g of octavinylcage oligomeric silsesquioxane, 0.1 g of vinylferrocene, and 20 g of azobisisobutyronitrile, stir at 60 °C for 17 h. After the reaction ends, chloroform is removed by distillation and dried to obtain the organic titanium metal modifier.

[0102] Through analysis and calculation, the conversion rate of hydrogen peroxide in this example is 95.6%, and the selectivity of hydroxylamine is 87.9%.

[0103] Comparative Example 2

[0104] A method for catalytically preparing hydroxylamine solution with ferrocenyl molecular sieve, and its operation steps are as follows:

[0105] A1: Add 5 kg of hydrogen peroxide solution, 75 kg of alcohol solution, and 20 kg of ammonia water solution into the reactor and stir evenly;

[0106] A2: Add 0.5 kg of ferrocenyl molecular sieve catalyst into the reactor, keep the temperature of the reactor water bath constant, react for 2 h. After the reaction ends, filter and recover the ferrocenyl molecular sieve, and the filtrate is the hydroxylamine solution.

[0107] In step A1, the concentration of the hydrogen peroxide solution is 20%, and the concentration of the ammonia water solution is 25%.

[0108] In step A1, the alcohol solution is selected from methanol.

[0109] In step A1, the concentration of the alcohol solution is 75%.

[0110] In step A2, the water bath temperature is 45 °C.

[0111] The recovered ferrocenyl molecular sieve in step A2 can be reused.

[0112] The preparation method of ferrocenyl molecular sieve in step A2:

[0113] Under the condition of 55 °C, 70 g of organic template agent and 800 g of deionized water are successively added into the reactor, stirred evenly, then 1000 g of hydrochloric acid solution with a molar concentration of 0.1 mol / L, 14 g of N,N-dimethyldodecylamine are added. After stirring at 57 °C for 40 minutes, 40 g of organic titanium metal modifier is added, and 100 g of tetraethyl orthosilicate is slowly added dropwise. The obtained mixture is transferred to a crystallization kettle, heated to 70 °C, and crystallized at a constant temperature for 20 h; then through separation, washing, and drying, amino molecular sieve can be obtained.

[0114] The organic template agent is F127 (EO106PO70EO106).

[0115] The preparation method of the organic titanium metal modifier:

[0116] Weigh 20 g of 2-vinylcyclopropane-1,1-dicarboxylic acid, 30 g of titanium tetrachloride, 1000 g of chloroform, mix and stir at 70 °C for 50 min, 0.1 g of vinylferrocene, 20 g of azobisisobutyronitrile, stir at 60 °C for 17 h. After the reaction is completed, chloroform is removed by distillation and dried to obtain the organic titanium metal modifier.

[0117] Through analysis and calculation, in this example, the conversion rate of hydrogen peroxide is 96.7%, and the selectivity of hydroxylamine is 89.2%.

[0118] Comparative Example 3

[0119] A method for catalytically preparing hydroxylamine solution with ferrocenyl molecular sieve, and its operation steps are as follows:

[0120] A1: Add 5 kg of hydrogen peroxide solution, 75 kg of alcohol solution, and 20 kg of ammonia water solution into the reactor, and stir evenly;

[0121] A2: Add 0.5 kg of ferrocenyl molecular sieve catalyst into the reactor, keep the reactor warm in a water bath, react for 2 h. After the reaction is completed, filter and recover the ferrocenyl molecular sieve, and the filtrate is the hydroxylamine solution.

[0122] In step A1, the concentration of the hydrogen peroxide solution is 20%, and the concentration of the ammonia water solution is 25%.

[0123] In step A1, the alcohol solution is selected from methanol.

[0124] In step A1, the concentration of the alcohol solution is 75%.

[0125] In step A2, the water bath temperature is 45 °C.

[0126] The ferrocene-based molecular sieve recovered in step A2 can be reused.

[0127] The preparation method of the ferrocene-based molecular sieve in step A2:

[0128] Under the condition of 55 °C, 70 g of organic template agent and 800 g of deionized water are successively added into the reactor, stirred evenly, then 1000 g of hydrochloric acid solution with a molar concentration of 0.1 mol / L is added. After continuing to stir at 57 °C for 40 minutes, 40 g of organic titanium metal modifier is added, and 100 g of tetraethyl orthosilicate is slowly added dropwise. The obtained mixture is transferred to a crystallization kettle, heated to 70 °C, and crystallized at a constant temperature for 20 h; then through separation, washing, and drying, the amino molecular sieve can be obtained.

[0129] The organic template agent is F127 (EO106PO70EO106).

[0130] The preparation method of the organic titanium metal modifier:

[0131] Weigh 20 g of 2-vinylcyclopropane-1,1-dicarboxylic acid, 30 g of titanium tetrachloride, 1000 g of chloroform, mix and stir at 70 °C for 50 min, then add 50 g of octavinylcage oligomeric silsesquioxane, 0.1 g of vinylferrocene, and 20 g of azobisisobutyronitrile, stir at 60 °C for 17 h. After the reaction is completed, chloroform is removed by distillation and dried to obtain the organic titanium metal modifier.

[0132] Through analysis and calculation, the conversion rate of hydrogen peroxide in this example is 94.2%, and the selectivity of hydroxylamine is 85.5%.

[0133] The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and variations according to the concept of the present invention without creative labor. Therefore, all technical solutions that can be obtained by those skilled in the art in the technical field of the present invention 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 protection scope determined by the claims.

Claims

1. A method for preparing a hydroxylamine solution using a ferrocenyl molecular sieve as catalyst, characterized in that: The operation steps are: A1: Add 5-10 parts of hydrogen peroxide solution, 75-100 parts of alcohol solution and 20-30 parts of ammonia solution into the reactor by mass and stir evenly; A2: Add 0.5-2 parts of ferrocenyl molecular sieve catalyst into the reactor, keep the reactor warm in a water bath, and react for 2-6 hours. After the reaction is completed, filter and recover the ferrocenyl molecular sieve, and the filtrate is the hydroxylamine solution; The preparation method of ferrocenyl molecular sieve in step A2: According to weight, at 55-70°C, 7-14 parts of organic template and 80-92 parts of deionized water are added to the reactor in sequence, stirred evenly, and then 100-150 parts of 0.1-0.5 mol / L hydrochloric acid solution and 1.4-2.8 parts of N,N-dimethyldodecylamine are added, and stirring is continued at 57-70°C for 40-80 minutes, and then 4-10 parts of organic titanium metal modifier are added, and 10-20 parts of tetraethyl orthosilicate are slowly added dropwise, and the obtained mixture is transferred to a crystallization kettle, heated to 70-85°C, and crystallized at a constant temperature for 20-40 hours; and then separated, washed, and dried to obtain an amino molecular sieve; The preparation method of the organic titanium metal modifier: Weigh 2-6 parts of 2-vinylcyclopropane-1,1-dicarboxylic acid, 3-8 parts of titanium tetrachloride, and 100-200 parts of chloroform by mass, stir at 70-80° C. for 50-100 min, then add 5-10 parts of octavinyl cage-type oligomeric silsesquioxane, 0.005-0.03 parts of vinyl ferrocene, and 2-4 parts of azobisisobutyronitrile, stir at 60-70° C. for 17-22 h, and after the reaction is completed, distill off the chloroform and dry to obtain an organic titanium metal modifier.

2. The method for preparing hydroxylamine solution by catalysis of ferrocenyl molecular sieve according to claim 1, characterized in that: In step A1, the concentration of the hydrogen peroxide solution is 20-30%, and the concentration of the ammonia solution is 25-28%.

3. The method for preparing hydroxylamine solution by catalysis of ferrocenyl molecular sieve according to claim 1, characterized in that: In the step A1, the alcohol solution is selected from at least one of methanol, ethylene glycol and trimethyl carbinol.

4. The method for preparing hydroxylamine solution by catalysis of ferrocenyl molecular sieve according to claim 1, characterized in that: The concentration of the alcohol solution in step A1 is 75-90%.

5. The method for preparing hydroxylamine solution by catalysis of ferrocenyl molecular sieve according to claim 1, characterized in that: The water bath temperature in step A2 is 45-85°C.

6. The method for preparing hydroxylamine solution by catalysis of ferrocenyl molecular sieve according to claim 1, characterized in that: The ferrocenyl molecular sieve recovered in step A2 can be reused.

7. The method for preparing hydroxylamine solution by catalysis of ferrocenyl molecular sieve according to claim 1, characterized in that: The organic template is one or more of F127 (EO106PO70EO106), P123 (EO20PO70EO20), and P104 (EO27PO61EO27).