Preparation method of oxygen-nitrogen heterocyclic organic matter

Abstract

The invention discloses a preparation method of an oxygen-nitrogen heterocyclic organic matter, and the preparation method comprises the following steps: reacting a mixture containing diethylene glycol, liquid ammonia and a solid catalyst to obtain 1, 4-oxazacyclohexane; the solid catalyst is Cu and Ni / r-Al2O3-activated carbon; the Cu, Ni / r-Al2O3-activated carbon comprises an active component and a carrier for loading the active component, the active components comprise Cu and Ni; and the carrier is r-Al2O3-activated carbon. The catalyst provided by the invention is applied to a reaction for preparing 1, 4-oxazacyclohexane through diethylene glycol ammonolysis reaction, so that the conversion rate of diethylene glycol and the selectivity of the generated 1, 4-oxazacyclohexane are improved.

Description

Technical Field

[0001] The present application relates to a preparation method of an oxazacycloalkane organic compound, belonging to the technical field of chemical catalysis. Background Art

[0002] 1,4-Oxazacyclohexane occupies an important position in chemical production. It is an intermediate for manufacturing many fine chemical products and has become one of the fine petrochemical products with important commercial uses at present. It can be used to prepare rubber vulcanization accelerators such as NOBS (N-oxydiethylene 2-benzothiazole sulfenamide) and OTOS (1-oxydiethylcarbamoyl-N-oxydiethylthiuram disulfide), as well as rust inhibitors, preservatives, surfactants, detergents, painkillers, local anesthetics, fruit preservatives, textile printing and dyeing auxiliaries, etc., and is widely used in the fields of rubber, medicine, pesticides, dyes, coatings, etc.

[0003] The synthesis routes of 1,4-oxazacyclohexane can be divided into the diethanolamine dehydration method, the dicyanomethyl ether catalytic hydrogenation method, the ethylene oxide catalytic amination method, the dichloroethyl ether dechlorination amination cyclization method, the amine dehydration cyclization method, the diethylene glycol catalytic ammonolysis cyclization method, etc. according to the different raw materials used. Among them, the diethylene glycol catalytic ammonolysis cyclization method has the advantages of easily available and low-cost raw materials, low toxicity, and less generation of three wastes, and is very suitable for large-scale industrial production. Most domestic manufacturers basically use this method.

[0004] There have been many studies on the catalysts for 1,4-oxazacyclohexane. Air Products and Chemicals, Inc. of the United States disclosed in the patent EP0036331 a 1,4-oxazacyclohexane catalyst with r-Al2O3 as the carrier and Ni, Co, and Cr as the active components; the Research Institute of Jilin Petrochemical Company disclosed in the patent with the publication number CN1316297A a C2-C8 fatty alcohol amination catalyst with synthetic silicon and aluminum oxides as the carrier and Ni and Co as the active components; Jilin Chemical Industry Corporation disclosed in the patent with the publication number CN1569327A a 1,4-oxazacyclohexane catalyst with amorphous SiO2 prepared by acidifying natural bentonite as the carrier and Ni, Co, and Cu as the active components, and the conversion rate of diethylene glycol was 99.1-99.6%, and the yield of 1,4-oxazacyclohexane reached 94.14%; BASF Company of Germany disclosed in the patent with the patent number DE3125662 a synthetic ammoniation catalyst with Al2O3 as the carrier and Co, Ni, and Cu as the active components, and the yield of 1,4-oxazacyclohexane was 86.06%; the patent with the publication number CN1915497A of the Chinese patent disclosed a catalyst with Al2O3 as the carrier and Cu, Zn, and Ni as the active components, and the conversion rate of diethylene glycol was as high as 98.5-99.5%, and the selectivity of 1,4-oxazacyclohexane was as high as 97.7-98.4%.

[0005] Solid catalysts have become the focus of researchers due to many advantages such as high activity, high selectivity, and easy separation. There are still relatively few solid catalysts reported in the literature for the catalytic ammoniation reaction of diethylene glycol. With the progress of technology and the improvement of people's environmental awareness, in chemical production, a solid catalyst with advantages such as recyclability and reusability. Summary of the Invention

[0006] This application has great significance in the preparation process of 1,4-oxazepane. The catalyst has good activity, high conversion rate of diethylene glycol and high selectivity of 1,4-oxazepane, and good stability.

[0007] According to one aspect of this application, a method for preparing an oxazepane organic compound is provided, and the preparation method includes:

[0008] Reacting a mixture containing diethylene glycol, liquid ammonia, and a solid catalyst to obtain 1,4-oxazepane;

[0009] The solid catalyst is Cu,Ni / r-Al2O3-activated carbon;

[0010] The Cu,Ni / r-Al2O3-activated carbon includes an active component and a carrier for supporting the active component;

[0011] The active component includes Cu and Ni;

[0012] The carrier is r-Al2O3-activated carbon.

[0013] Optionally, in the r-Al2O3-activated carbon, the molar ratio of C to Al is 1:3 to 7.

[0014] Optionally, in the r-Al2O3-activated carbon, the molar ratio of C and Al independently selects any value from 1:3, 1:4, 1:5, 1:6, 1:7 or the range value between any two of the above.

[0015] Optionally, in the Cu,Ni / r-Al2O3-activated carbon, the active component accounts for 20 to 40 wt.% of the Cu,Ni / r-Al2O3-activated carbon.

[0016] Optionally, in the Cu,Ni / r-Al2O3-activated carbon, the active component accounts for the Cu,Ni / r-Al2O3-activated carbon independently selects any value from 20 wt.%, 22 wt.%, 24 wt.%, 26 wt.%, 28 wt.%, 30 wt.%, 32 wt.%, 34 wt.%, 36 wt.%, 38 wt.%, 40 wt.% or the range value between any two of the above.

[0017] Optionally, the preparation method of the r-Al2O3-activated carbon includes:

[0018] Mix raw material I containing activated carbon and pseudoboehmite, and calcine I to obtain r-Al2O3-activated carbon;

[0019] Among them, the mixing method is selected from one or more of rolling into balls, tabletting, and extrusion.

[0020] Optionally, the calcination I temperature is 400-600 °C, and the calcination I time is 4-8 h.

[0021] Optionally, the calcination I temperature is independently selected from any value or the range value between any two of 400 °C, 420 °C, 450 °C, 480 °C, 500 °C, 520 °C, 550 °C, 580 °C, 600 °C.

[0022] Optionally, the calcination I time is selected from any value or the range value between any two of 4 h, 4.2 h, 4.5 h, 4.8 h, 5 h, 5.4 h, 5.8 h, 6 h, 6.8 h, 7 h, 7.8 h, 8 h.

[0023] Optionally, the preparation method of the Cu,Ni / r-Al2O3-activated carbon includes:

[0024] Mix raw material II containing a copper precursor, a nickel precursor, r-Al2O3-activated carbon, and a solvent, stir, dry, and calcine II to obtain Cu,Ni / r-Al2O3-activated carbon.

[0025] Optionally, the copper precursor is selected from one or more of copper nitrate, copper sulfate, and copper chloride.

[0026] Optionally, the nickel precursor is selected from one or more of nickel nitrate, nickel sulfate, and nickel chloride.

[0027] Optionally, the solvent is selected from ethanol and / or water.

[0028] Optionally, the molar ratio of the nickel precursor to the copper precursor is 1:1-3,

[0029] Among them, the molar amount of the nickel precursor is based on the molar amount of the nickel element, and the molar amount of the copper precursor is based on the molar amount of the copper element.

[0030] Optionally, the molar ratio of the nickel precursor to the copper precursor is independently selected from any value or the range value between any two of 1:1, 1:1.4, 1:1.8, 1:2, 1:2.4, 1:2.8, 1:3.

[0031] Optionally, the stirring temperature is 60-80 °C, and the stirring time is 5-10 h.

[0032] Optionally, the stirring temperature is selected from any value among 60°C, 70°C, and 80°C or a range value between any two of them.

[0033] Optionally, the stirring time is selected from any value among 5 h, 6 h, 7 h, 8 h, 9 h, and 10 h or a range value between any two of them.

[0034] Optionally, the calcination II temperature is 400 - 600°C and the calcination II time is 4 - 8 h.

[0035] Optionally, the calcination II temperature is independently selected from any value among 400°C, 450°C, 500°C, 550°C, and 600°C or a range value between any two of them.

[0036] Optionally, the calcination II time is independently selected from any value among 4 h, 5 h, 6 h, 7 h, and 8 h or a range value between any two of them.

[0037] Optionally, the drying temperature is 80 - 120°C and the drying time is 1 - 10 h.

[0038] Optionally, the drying temperature is independently selected from any value among 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, and 120°C or a range value between any two of them.

[0039] Optionally, the drying time is independently selected from any value among 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, and 10 h or a range value between any two of them.

[0040] Optionally, the molar ratio of liquid ammonia to diethylene glycol is 1 - 6:1.

[0041] Optionally, the molar ratio of liquid ammonia to diethylene glycol is independently selected from any value among 1:1, 2:1, 3:1, 4:1, 5:1, and 6:1 or a range value between any two of them.

[0042] Optionally, the mass space velocity of the reaction is 0.1 - 1 h -1 。

[0043] Optionally, the mass space velocity of the reaction is 0.1 h -1 、0.2 h -1 、0.3 h -1 、0.4 h -1 、0.5 h -1 、0.6 h -1 、0.7 h -1 、0.8 h -1 、0.9 h -1 、1 h-1 Any value within or any range value between any two of them.

[0044] Optionally, the temperature of the reaction is 100 - 300 °C.

[0045] Optionally, the temperature of the reaction is selected from any value of 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °C, 300 °C or any range value between any two of them.

[0046] Optionally, the pressure of the reaction is 1 - 3 MPa.

[0047] Optionally, the pressure of the reaction is selected from any value of 1 MPa, 2 MPa, 3 MPa or any range value between any two of the above;

[0048] The beneficial effects that can be produced by this application include:

[0049] 1) The catalyst Cu,Ni / r - Al2O3 - activated carbon provided by this application can be applied to the reaction of preparing 1,4 - oxazacyclohexane by the ammoniation of diethylene glycol, and can improve the conversion rate of diethylene glycol and the selectivity of the produced 1,4 - oxazacyclohexane.

[0050] 2) The preparation method of the catalyst Cu,Ni / r - Al2O3 - activated carbon provided by this application is stable, controllable, and has good reproducibility.

[0051] 3) The method for preparing 1,4 - oxazacyclohexane by the ammoniation of diethylene glycol provided by this application uses the solid catalyst provided in this application, has a fast reaction rate and a high yield, and can be applied to large - scale production. Detailed implementation manners

[0052] The following describes this application in detail with reference to the embodiments, but this application is not limited to these embodiments.

[0053] Unless otherwise specified, the raw materials in the embodiments of this application are all purchased through commercial channels.

[0054] Among them, the gas chromatograph is the 7890B type gas chromatograph of Agilent Corporation.

[0055] The conversion rate and selectivity in the embodiments of this application are calculated as follows:

[0056] The calculation formulas for the conversion rate and selectivity in the embodiments of this application are as follows (taking the conversion rate of diethylene glycol as the evaluation index):

[0057] Conversion rate of diethylene glycol = (Initial carbon number of diethylene glycol - Carbon number of diethylene glycol in the product) * 100 / Initial mole number of diethylene glycol

[0058] 1,4 - oxazacyclohexane selectivity = number of carbon atoms of 1,4 - oxazacyclohexane * 100 / ∑(number of carbon atoms of 1,4 - oxazacyclohexane + number of carbon atoms of other products).

[0059] Example 1 Preparation of catalyst

[0060] Pseudoboehmite and activated carbon were mixed by extrusion and then calcined at 500 °C for 6 hours to obtain γ - Al2O3 - activated carbon. Copper nitrate, nickel nitrate were dissolved in deionized water and poured into γ - Al2O3 - activated carbon (the copper source and nickel source accounted for 30% of the catalyst weight, nickel:copper molar ratio = 1:2). After stirring at 70 °C for 6 hours, it was dried at 100 °C for 8 hours and then calcined at 500 °C for 6 hours in a muffle furnace to obtain Catalyst 1 # .

[0061] According to the following steps, the types, dosages of each raw material and reaction parameters were adjusted to obtain a series of catalysts numbered 2 - 28, which were respectively marked as Catalyst 2 # ~Catalyst 28 # , as shown in Table 1 below:

[0062] Table 1

[0063]

[0064]

[0065] The explanations of each column in Table 1 above are as follows:

[0066] In Table 1, the copper source corresponds to the copper precursor, and the nickel source corresponds to the nickel precursor.

[0067] Copper precursors: copper nitrate (Cu1), copper sulfate (Cu2), copper chloride (Cu3).

[0068] Nickel precursors: nickel nitrate (Ni1), nickel sulfate (Ni2), nickel chloride (Ni3).

[0069] Mixing methods: extrusion (Method 1), rolling (Method 2), tableting (Method 3).

[0070] Comparative Example 1

[0071] Activated carbon was taken, copper nitrate, nickel nitrate were dissolved in deionized water and poured into activated carbon (the copper source and nickel source accounted for 30% of the catalyst weight, nickel:copper molar ratio = 1:2). After stirring at 70 °C for 6 hours, it was dried at 100 °C for 8 hours and then calcined at 500 °C for 6 hours in a muffle furnace to obtain Comparative Example 1 # catalyst.

[0072] Comparative Example 2

[0073] Take r-Al2O3, dissolve copper nitrate and nickel nitrate in deionized water, pour it into r-Al2O3 (the copper source and nickel source account for 30% of the catalyst weight, nickel:copper molar ratio = 1:2), stir at 70°C for 6 hours, dry at 100°C for 8 hours, and calcine in a muffle furnace at 500°C for 6 hours to obtain Comparative Example 2 # catalyst.

[0074] Comparative Example 3

[0075] Extrude and mix pseudoboehmite and activated carbon, then calcine at 500°C for 6 hours to obtain r-Al2O3-activated carbon. Dissolve copper nitrate in deionized water, pour it into r-Al2O3-activated carbon (the copper source accounts for 30% of the catalyst weight), stir at 70°C for 6 hours, dry at 100°C for 8 hours, and calcine in a muffle furnace at 500°C for 6 hours to obtain Comparative Example 3 # catalyst.

[0076] Comparative Example 4

[0077] Extrude and mix pseudoboehmite and activated carbon, then calcine at 500°C for 6 hours to obtain r-Al2O3-activated carbon. Dissolve nickel nitrate in deionized water, pour it into r-Al2O3-activated carbon (the nickel source accounts for 30% of the catalyst weight), stir at 70°C for 6 hours, dry at 100°C for 8 hours, and calcine in a muffle furnace at 500°C for 6 hours to obtain Comparative Example 4 # catalyst.

[0078] Example 2

[0079] The catalyst is used for the reaction of ammoniating diethylene glycol to prepare 1,4-oxazacyclohexane.

[0080] The catalysts 1 numbered 1 to 28 prepared in Example 1 # ~Catalyst 28 # are used for the ammoniation of diethylene glycol to prepare 1,4-oxazacyclohexane. At a reaction temperature of 230°C, a reaction time of 4 hours, a reaction pressure of 1.8 Mpa, a mass space velocity of 0.15 h -1 , and an ammonia-alcohol molar ratio of 5:1. The raw materials are introduced into a fixed-bed reactor loaded with 3 g of the catalyst, and 1,4-oxazacyclohexane is produced by the ammoniation reaction.

[0081] After the reaction is stable, both the reaction raw materials and products are analyzed using on-line gas chromatography. The reaction results are shown in Table 2.

[0082] Gas chromatography characterization:

[0083] Use an Agilent 7890B gas chromatograph (FID detector, FFAP capillary column) to analyze the composition of the products of the diethylene glycol ammoniation reaction.

[0084] Table 2

[0085]

[0086]

[0087] As can be seen from Table 2, the Cu,Ni / r-Al2O3-activated carbon catalyst has higher conversion rate and selectivity than the catalysts prepared with r-Al2O3, activated carbon or a single active substance in the ammoniation reaction for preparing 1,4-oxazane.

[0088] Example 3

[0089] Use Catalyst 1 prepared in Table 1 # Carry out the ammoniation reaction of diethylene glycol to prepare 1,4-oxazane. Change each reaction parameter. After the reaction is stable, both the reaction raw materials and products are analyzed by gas-phase online chromatography. The reaction results are shown in Table 3.

[0090] Table 3

[0091]

[0092] As can be seen from Table 3, the reaction temperature and mass space velocity have a greater impact on the conversion rate of diethylene glycol.

[0093] As described above, these are only several embodiments of the present application and do not impose any form of limitation on the present application. Although the present application is disclosed with preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, makes some changes or modifications using the disclosed technical content, which are equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. A preparation method of an oxazoline organic compound, characterized in that, The preparation method includes the following steps: Reacting a mixture containing diethylene glycol, liquid ammonia, and a solid catalyst to obtain 1,4-oxazepane; The solid catalyst is Cu,Ni / r-Al2O3-activated carbon; The Cu,Ni / r-Al2O3-activated carbon includes an active component and a carrier for supporting the active component; The active component includes Cu and Ni; The carrier is r-Al2O3-activated carbon.

2. The preparation method according to claim 1, characterized in that, In the r-Al2O3-activated carbon, the molar ratio of C to Al is 1:3 to 7.

3. The preparation method according to claim 1, characterized in that, In the Cu,Ni / r-Al2O3-activated carbon, the active component accounts for 20 to 40 wt.% of the Cu,Ni / r-Al2O3-activated carbon.

4. The preparation method according to claim 1, characterized in that, The preparation method of the r-Al2O3-activated carbon includes the following steps: Mixing raw material I containing activated carbon and pseudo-boehmite, and calcining I to obtain r-Al2O3-activated carbon; Among them, the mixing method is selected from one or more of rolling into balls, tabletting, and extrusion.

5. The preparation method according to claim 4, characterized in that, The calcination I temperature is 400 to 600 °C, and the calcination I time is 4 to 8 h.

6. The preparation method according to claim 1, characterized in that, The preparation method of the Cu,Ni / r-Al2O3-activated carbon includes the following steps: Stirring, drying, and calcining II a raw material II containing a copper precursor, a nickel precursor, r-Al2O3-activated carbon, and a solvent to obtain Cu,Ni / r-Al2O3-activated carbon.

7. The preparation method according to claim 6, characterized in that, The copper precursor is selected from one or more of copper nitrate, copper sulfate, and copper chloride; Preferably, the nickel precursor is selected from one or more of nickel nitrate, nickel sulfate, and nickel chloride; Preferably, the solvent is selected from ethanol and / or water.

8. The preparation method according to claim 6, characterized in that, The molar ratio of the nickel precursor to the copper precursor is 1:1 to 3, wherein, the molar amount of the nickel precursor is calculated based on the molar amount of the nickel element, and the molar amount of the copper precursor is calculated based on the molar amount of the copper element; Preferably, the stirring temperature is 60 to 80 °C, and the stirring time is 5 to 10 h; Preferably, the calcination II temperature is 400 to 600 °C, and the calcination II time is 4 to 8 h; Preferably, the drying temperature is 80 to 120 °C, and the drying time is 1 to 10 h.

9. The preparation method according to claim 1, characterized in that, The molar ratio of the liquid ammonia to the diethylene glycol is 1 to 6:1; Preferably, the mass space velocity of the reaction is 0.1 to 1 h -1 .

10. The preparation method according to claim 1, characterized in that, The reaction temperature is 100 to 300 °C; Preferably, the reaction pressure is 1 to 3 MPa.

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