Method for preparing morphine by adopting solid catalyst

Abstract

The invention discloses a method for preparing morphine by adopting a solid catalyst, which comprises the following steps: reacting a raw material containing liquid ammonia and diethylene glycol with the solid catalyst to obtain morphine, the solid catalyst is a Cu, Ni / r-Al2O3-pure silicon molecular sieve; the Cu, Ni / r-Al2O3-pure silicon molecular sieve is prepared by impregnating an r-Al2O3-pure silicon molecular sieve with a raw material containing an active component through an excessive impregnation method. The catalyst provided by the invention is applied to a reaction for preparing morphine through diethylene glycol ammonolysis reaction, so that the conversion rate of diethylene glycol and the selectivity of the generated morphine are improved.

Description

Technical Field

[0001] The present application relates to a method for preparing morpholine using a solid catalyst, belonging to the field of chemical engineering technology. Background Art

[0002] Morpholine, as an important oxygen-nitrogen heterocyclic organic compound, has a wide range of applications in multiple fields such as rubber, pesticides, pharmaceuticals, and dyes, and is regarded as one of the most critical cyclic amine substances in the industry. In the international market, morpholine is mainly used to manufacture products such as rubber vulcanization accelerators. However, due to the toxicity problems of these accelerators, many countries have gradually prohibited their use, resulting in a decreasing consumption of morpholine year by year. Nevertheless, new uses of morpholine continue to be developed, and the research and application of its downstream products are constantly expanding, indicating the active development of the morpholine market.

[0003] N-Methyloxymorpholine has been explored as an environmentally friendly solvent for man-made fibers and also plays an important role in the development of new drugs. With the development of these new applications, the demand for pharmaceutical-grade morpholine in the domestic and international markets continues to rise. In addition, the metal gas rust inhibitor products of morpholine have been widely used in fields such as instruments and meters. In order to more comprehensively explore the application fields of morpholine, in-depth research on the current catalysts used for synthesizing morpholine is crucial. Through technological innovation of the device, continuous optimization of process conditions, and implementation of energy-saving and consumption-reducing measures, the market application potential of morpholine can be released more greatly.

[0004] There are relatively many studies on morpholine catalysts. Air Products and Chemicals, Inc. in the United States disclosed a morpholine catalyst with r-Al2O3 as the carrier and Ni, Co, and Cr as the active components in patent EP0036331; the Research Institute of Jilin Petrochemical Company disclosed a C2-C8 fatty alcohol amination catalyst with synthetic silicon and aluminum oxides as the carrier and Ni and Co as the active components in the patent with the publication number CN1316297A; Jilin Chemical Industry Corporation disclosed a morpholine catalyst with amorphous SiO2 prepared by acidifying natural bentonite as the carrier and Ni, Co, and Cu as the active components in the patent with the publication number CN1569327A, and the conversion rate of diethylene glycol was 99.1-99.6%, and the yield of morpholine reached 94.14%; BASF Company in Germany disclosed a synthetic ammonia catalyst with Al2O3 as the carrier and Co, Ni, and Cu as the active components in the patent with the patent number DE3125662, and the yield of morpholine was 86.06%; a catalyst with Al2O3 as the carrier and Cu, Zn, and Ni as the active components was disclosed in the patent with the publication number CN1915497A in China, and the conversion rate of diethylene glycol was as high as 98.5-99.5%, and the selectivity of morpholine 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 reports in the literature on solid catalysts used for the catalytic ammoniation reaction of diethylene glycol. With the progress of technology and the improvement of people's environmental protection awareness, in chemical production, a solid catalyst with advantages such as recyclability and reusability. Summary of the Invention

[0006] The application of the catalyst in the preparation process of morpholine in this application is of great significance. The catalyst has good activity, high conversion rate of diethylene glycol and high selectivity of morpholine, and good stability.

[0007] According to one aspect of this application, a method for preparing morpholine using a solid catalyst is provided, and the method includes:

[0008] Reacting a raw material containing liquid ammonia and diethylene glycol with a solid catalyst to obtain morpholine;

[0009] The solid catalyst is Cu,Ni / r-Al2O3-pure silica molecular sieve;

[0010] The Cu,Ni / r-Al2O3-pure silica molecular sieve is prepared by impregnating r-Al2O3-pure silica molecular sieve with a raw material containing active components by the excess impregnation method;

[0011] The active components are Cu and Ni.

[0012] Optionally, in the r-Al2O3-pure silica molecular sieve, the molar ratio of Si and Al elements is 1:3 to 7.

[0013] Optionally, in the r-Al2O3-pure silica molecular sieve, the upper limit of the molar ratio of Si and Al elements is selected from 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7; the lower limit is selected from 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5.

[0014] Optionally, in the Cu,Ni / r-Al2O3-pure silica molecular sieve, Cu and Ni account for 20 to 40 wt.% of the weight of the Cu,Ni / r-Al2O3-pure silica molecular sieve.

[0015] Optionally, in the Cu,Ni / r-Al2O3-pure silica molecular sieve, the upper limit of the weight of Cu and Ni accounting for the Cu,Ni / r-Al2O3-pure silica molecular sieve is selected from 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%; the lower limit is selected from 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%.

[0016] Optionally, the preparation method of the Cu,Ni / r-Al2O3-pure silica molecular sieve comprises:

[0017] Mixing a mixture containing a copper salt, a nickel salt, an r-Al2O3-pure silica molecular sieve, and a solvent, stirring, drying, and calcining to obtain the Cu,Ni / r-Al2O3-pure silica molecular sieve.

[0018] Optionally, the preparation method of the r-Al2O3-pure silica molecular sieve comprises:

[0019] Mixing pseudoboehmite and a pure silica molecular sieve, and calcining to obtain the r-Al2O3-pure silica molecular sieve.

[0020] Optionally, the pure silica molecular sieve is selected from at least one of pure silica MCM-41, pure silica SBA-15, and pure silica Silicalite-1.

[0021] Optionally, the mixing method is selected from at least one of extrusion, pelletizing, and tabletting.

[0022] Optionally, the calcination temperature is 400-600 °C, and the calcination time is 4-8 hours.

[0023] Optionally, the upper limit of the calcination temperature is selected from 450 °C, 500 °C, 550 °C, and 600 °C; the lower limit is selected from 400 °C, 450 °C, 500 °C, and 550 °C.

[0024] Optionally, the upper limit of the calcination time is selected from 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, and 8 hours; the lower limit is selected from 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, and 7.5 hours.

[0025] Optionally, the copper salt is selected from at least one of copper chloride, copper nitrate, and copper sulfate.

[0026] Optionally, the solvent is selected from ethanol and / or water.

[0027] Optionally, the nickel salt is selected from at least one of nickel chloride, nickel nitrate, and nickel sulfate.

[0028] Optionally, in the nickel salt and the copper salt, the molar ratio of nickel element to copper element is 1:1-3.

[0029] Optionally, in the nickel salt and the copper salt, the upper limit of the molar ratio of nickel element to copper element is selected from 1:1.5, 1:2, 1:2.5, and 1:3; the lower limit is selected from 1:1, 1:1.5, 1:2, and 1:2.5.

[0030] Optionally, the stirring temperature is 60 to 80 °C, and the stirring time is 5 to 10 hours.

[0031] Optionally, the upper limit of the stirring temperature is selected from 65 °C, 70 °C, 75 °C, 80 °C; the lower limit is selected from 60 °C, 65 °C, 70 °C, 75 °C.

[0032] Optionally, the upper limit of the stirring time is selected from 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours; the lower limit is selected from 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours.

[0033] Optionally, the drying temperature is 80 to 120 °C, and the drying time is 1 to 10 hours.

[0034] Optionally, the upper limit of the drying temperature is selected from 90 °C, 100 °C, 110 °C, 120 °C; the lower limit is selected from 80 °C, 90 °C, 100 °C, 110 °C.

[0035] Optionally, the upper limit of the drying time is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours; the lower limit is selected from 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours.

[0036] Optionally, the roasting temperature is 400 to 600 °C, and the roasting time is 4 to 8 hours.

[0037] Optionally, the upper limit of the roasting temperature is selected from 450 °C, 500 °C, 550 °C, 600 °C; the lower limit is selected from 400 °C, 450 °C, 500 °C, 550 °C.

[0038] Optionally, the upper limit of the roasting time is selected from 5 hours, 6 hours, 7 hours, 8 hours; the lower limit is selected from 4 hours, 5 hours, 6 hours, 7 hours.

[0039] Optionally, the temperature of the reaction is 100 to 300 °C.

[0040] Optionally, the upper limit of the reaction temperature is selected from 120 °C, 140 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °C, 300 °C; the lower limit is selected from 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °C.

[0041] Optionally, the pressure of the reaction is 1 to 3 MPa.

[0042] Optionally, the upper limit of the pressure of the reaction is selected from 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa; the lower limit is selected from 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa.

[0043] Optionally, the mass space velocity of the reaction is 0.1 - 1 h -1 .

[0044] Optionally, the upper limit of the mass space velocity of the reaction is selected from 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 ; the lower limit is selected from 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 .

[0045] Optionally, the molar ratio of the liquid ammonia to the diethylene glycol is 1 - 6:1.

[0046] Optionally, the upper limit of the molar ratio of the liquid ammonia to the diethylene glycol is selected from 2:1, 3:1, 4:1, 5:1, 6:1; the lower limit is selected from 1:1, 2:1, 3:1, 4:1, 5:1.

[0047] As an optional implementation manner, the present application is achieved through the following technical solutions:

[0048] The preparation method of the Cu,Ni / r - Al2O3 - pure silica molecular sieve comprises the following steps:

[0049] (1) Mix pseudo - boehmite and pure silica molecular sieve and then calcine I to obtain r - Al2O3 - pure silica molecular sieve;

[0050] (2) Mix copper salt, nickel salt and r - Al2O3 - pure silica molecular sieve in a solvent;

[0051] (3) Stir at high temperature until dry, dry, and calcine II to obtain Cu,Ni / r - Al2O3 - pure silica molecular sieve.

[0052] In this application, diethylene glycol is contacted with a catalyst to obtain morpholine; the catalyst is Cu,Ni / r - Al2O3 - pure silica molecular sieve, where Cu and Ni are active components and r - Al2O3 - pure silica molecular sieve is the carrier.

[0053] The beneficial effects that can be produced by this application include:

[0054] 1) The catalyst Cu,Ni / r - Al2O3 - pure silica molecular sieve provided by this application can be applied to the reaction of preparing morpholine by the ammoniation of diethylene glycol, and can improve the conversion rate of diethylene glycol and the selectivity of the produced morpholine.

[0055] 2) The preparation method of the catalyst Cu,Ni / r - Al2O3 - pure silica molecular sieve provided by this application is stable, controllable and has good reproducibility.

[0056] 3) The solid acid catalyst provided in the method for preparing morpholine by ammoniation of diethylene glycol provided by this application has a fast reaction rate and a high yield, and can be applied to large - scale production. Detailed implementation manners

[0057] The following describes this application in detail with reference to the embodiments, but this application is not limited to these embodiments.

[0058] Unless otherwise specified, the raw materials in the embodiments of this application are all purchased through commercial channels.

[0059] Among them, the gas chromatograph is the 7890B type gas chromatograph of Agilent Corporation.

[0060] The conversion rate and selectivity in the embodiments of this application are calculated as follows:

[0061] 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):

[0062] Diethylene glycol conversion rate = (Initial carbon number of diethylene glycol - Carbon number of diethylene glycol in the product) * 100 / Initial mole number of diethylene glycol

[0063] Morpholine selectivity = Carbon number of morpholine * 100 / ∑(Carbon number of morpholine + Carbon number of other products).

[0064] Example 1 Preparation of the catalyst

[0065] Pseudoboehmite and pure silica SBA-15 (molar ratio of Si to Al elements is 1:7) are mixed by extrusion and then calcined at 500 °C for 6 hours to obtain γ-Al2O3-pure silica SBA-15. Copper nitrate and nickel nitrate are dissolved in deionized water, poured into γ-Al2O3-pure silica SBA-15 (copper salt and nickel salt account for 30% of the catalyst weight, nickel:copper molar ratio = 1:2), stirred at 70 °C for 6 hours, dried at 100 °C for 8 hours, and then calcined in a muffle furnace at 500 °C for 6 hours to obtain Catalyst 1 # 。

[0066] According to the following steps, the types, dosages of various raw materials and reaction parameters are adjusted to obtain a series of Catalysts No. 2 to 28, which are respectively denoted as Catalyst 2 # ~Catalyst 28 # as shown in Table 1 below:

[0067] Table 1

[0068]

[0069]

[0070] The descriptions of each column in Table 1 above are as follows:

[0071] Copper salts: copper nitrate (Cu1), copper sulfate (Cu2), copper chloride (Cu3).

[0072] Nickel salts: nickel nitrate (Ni1), nickel sulfate (Ni2), nickel chloride (Ni3).

[0073] Mixing method: extrusion (Method 1), rolling (Method 2), tabletting (Method 3).

[0074] Pure silica molecular sieves: pure silica SBA-15 (Si1), pure silica Silicalite-1 (Si2), pure silica MCM-41 (Si3).

[0075] Comparative Example 1

[0076] Take pure silica SBA-15 (molar ratio of Si to Al elements is 1:7), dissolve copper nitrate and nickel nitrate in deionized water, pour into pure silica SBA-15 (copper salt and nickel salt 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 then calcine in a muffle furnace at 500 °C for 6 hours to obtain the catalyst of Comparative Example 1 # Catalyst.

[0077] Comparative Example 2

[0078] Pseudoboehmite was calcined at 500 °C for 6 hours to obtain γ-Al2O3. Copper nitrate and nickel nitrate were dissolved in deionized water, and then poured onto γ-Al2O3 (the copper salt and nickel salt accounted for 30% of the catalyst weight, and the molar ratio of nickel to copper was 1:2). After stirring at 70 °C for 6 hours, it was dried at 100 °C for 8 hours and then calcined in a muffle furnace at 500 °C for 6 hours to obtain Comparative Example 2 # catalyst.

[0079] Comparative Example 3

[0080] Pseudoboehmite and pure silica SBA-15 (the molar ratio of Si to Al elements was 1:7) were mixed by extrusion and then calcined at 500 °C for 6 hours to obtain γ-Al2O3-pure silica SBA-15. Copper nitrate was dissolved in deionized water, and then poured onto γ-Al2O3-pure silica SBA-15 (the copper salt and nickel salt accounted for 30% of the catalyst weight, and the molar ratio of nickel to copper was 1:2). After stirring at 70 °C for 6 hours, it was dried at 100 °C for 8 hours and then calcined in a muffle furnace at 500 °C for 6 hours to obtain Comparative Example 3 # catalyst.

[0081] Comparative Example 4

[0082] Pseudoboehmite and pure silica SBA-15 (the molar ratio of Si to Al elements was 1:7) were mixed by extrusion and then calcined at 500 °C for 6 hours to obtain γ-Al2O3-pure silica SBA-15. Nickel nitrate was dissolved in deionized water, and then poured onto γ-Al2O3-pure silica SBA-15 (the copper salt and nickel salt accounted for 30% of the catalyst weight, and the molar ratio of nickel to copper was 1:2). After stirring at 70 °C for 6 hours, it was dried at 100 °C for 8 hours and then calcined in a muffle furnace at 500 °C for 6 hours to obtain Comparative Example 4 # catalyst.

[0083] Example 2

[0084] The catalyst was used for the reaction of ammoniaation of diethylene glycol to prepare morpholine.

[0085] The catalysts 1 numbered 1 to 28 prepared in Example 1 # ~catalyst 28 # were used for the ammoniaation of diethylene glycol to prepare morpholine. At a reaction temperature of 230 °C, a reaction time of 4 hours, a reaction pressure of 1.8 MPa, and a mass space velocity of 0.15 h -1 , and an ammonia-alcohol molar ratio of 5:1. The raw materials were introduced into a fixed-bed reactor loaded with 3 g of the catalyst, and morpholine was produced by the ammoniation reaction.

[0086] After the reaction was stable, both the reaction raw materials and products were analyzed by gas-phase online chromatography. The reaction results are shown in Table 2.

[0087] Gas chromatography characterization:

[0088] The composition of the reaction product of diethylene glycol amination was analyzed using an Agilent 7890B gas chromatograph (FID detector, FFAP capillary column).

[0089] Table 2

[0090] Serial number Conversion rate of diethylene glycol (%) Morpholine selectivity (%) 1 77.9 90.1 2 74.3 83.2 3 72.5 86.5 4 68.5 87.7 5 67.4 82.4 6 62.3 85.5 7 66.8 79.5 8 70.1 80.3 9 72.5 81.4 10 76.4 82.6 11 70.3 80.3 12 71.2 78.2 13 75.2 70.4 14 68.5 72.6 15 64.2 77.9 16 66.9 85.4 17 63.2 86.4 18 59.5 81.2 19 58.7 84.4 20 62.3 80.1 21 64.2 79.8 22 68.9 75.8 23 70.1 72.4 24 72.3 76.9 25 75.2 77.1 26 73.4 79.9 27 72.4 80.3 28 70.5 82.6 Comparative example 1 58.9 71.2 Comparative example 2 56.4 74.3 Comparative example 3 51.3 69.5 Comparative example 4 49.2 65.4

[0091] As can be seen from Table 2, the Cu,Ni / r-Al2O3-pure silica molecular sieve catalyst applied in the amination reaction for preparing morpholine has higher conversion rate and selectivity than the catalysts prepared with r-Al2O3, pure silica molecular sieve or single active substance.

[0092] Example 3

[0093] Use the catalyst 1 prepared in Table 1 # Carry out the reaction of preparing morpholine by diethylene glycol amination, change each reaction parameter. After the reaction is stable, both the reaction raw materials and products are analyzed by gas online chromatography. The reaction results are shown in Table 3.

[0094] Table 3

[0095]

[0096] 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.

[0097] The above 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 above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, within the scope of the technical solution of the present application, making some changes or modifications using the disclosed technical content is equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. A method for preparing morpholine using a solid catalyst, characterized in that, The method includes: Reacting a raw material containing liquid ammonia and diethylene glycol with a solid catalyst to obtain morpholine; The solid catalyst is Cu,Ni / r-Al2O3-pure silica molecular sieve; The Cu,Ni / r-Al2O3-pure silica molecular sieve is prepared by impregnating r-Al2O3-pure silica molecular sieve with a raw material containing active components through an excess impregnation method; The active components are Cu and Ni.

2. The method according to claim 1, characterized in that, In the r-Al2O3-pure silica molecular sieve, the molar ratio of Si to Al elements is 1:3 to 7; Preferably, in the Cu,Ni / r-Al2O3-pure silica molecular sieve, Cu and Ni account for 20 to 40 wt.% of the weight of the Cu,Ni / r-Al2O3-pure silica molecular sieve.

3. The method according to claim 1, characterized in that, The preparation method of the Cu,Ni / r-Al2O3-pure silica molecular sieve includes: Mixing a mixture containing copper salt, nickel salt, r-Al2O3-pure silica molecular sieve, and solvent, stirring, drying, and calcining to obtain Cu,Ni / r-Al2O3-pure silica molecular sieve.

4. The method according to claim 3, characterized in that, The preparation method of the r-Al2O3-pure silica molecular sieve includes: Mixing pseudoboehmite and pure silica molecular sieve and calcining to obtain the r-Al2O3-pure silica molecular sieve.

5. The method according to claim 4, characterized in that, The pure silica molecular sieve is selected from at least one of pure silica MCM-41, pure silica SBA-15, and pure silica Silicalite-1; Preferably, the mixing method is selected from at least one of extrusion, pelletizing, and tableting; Preferably, the calcination temperature is 400 to 600 °C, and the calcination time is 4 to 8 hours.

6. The method according to claim 3, characterized in that, The copper salt is selected from at least one of copper chloride, copper nitrate, and copper sulfate; Preferably, the solvent is selected from ethanol and / or water; Preferably, the nickel salt is selected from at least one of nickel chloride, nickel nitrate, and nickel sulfate.

7. The method according to claim 3, characterized in that, In the nickel salt and the copper salt, the molar ratio of nickel element to copper element is 1:1 to 3.

8. The method according to claim 3, characterized in that, The stirring temperature is 60 to 80 °C, and the stirring time is 5 to 10 hours; Preferably, the drying temperature is 80 to 120 °C, and the drying time is 1 to 10 hours; Preferably, the calcination temperature is 400 to 600 °C, and the calcination time is 4 to 8 hours.

9. The 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.

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

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