Process method for efficient catalytic synthesis of tert-butylamine ethoxyethanol

Abstract

The invention belongs to the technical field of preparation of tert-butylamine ethoxyethanol, and particularly relates to a process method for efficient catalytic synthesis of tert-butylamine ethoxyethanol. The process method comprises the following steps: (1) preparing aluminum-cerium composite sol; (2) preparing a CeO2-Al2O3 carrier; (3) preparing a Co-Ni-Mo / CeO2-Al2O3 catalyst; and (4) preparing the catalyst. And (4) pumping a reaction raw material consisting of tert-butylamine and diethylene glycol into a preheating gasifier, mixing with hydrogen, preheating and gasifying, then feeding into a fixed bed reactor for reaction, filling the fixed bed reactor with a Co-Ni-Mo / CeO2-Al2O3 catalyst, condensing the reacted material, carrying out gas-liquid separation, and carrying out rectification separation and purification on the obtained liquid phase to prepare the tert-butylamine ethoxyethanol. The process method for efficient catalytic synthesis of tert-butylamine ethoxyethanol is mild in reaction condition and high in raw material conversion rate, and industrial production can be realized.

Description

Technical Field

[0001] The invention belongs to the technical field of tert-butylaminoethoxyethanol preparation, and specifically relates to a process for efficiently catalyzing and synthesizing tert-butylaminoethoxyethanol. Background Art

[0002] Tert-butylaminoethoxyethanol (TBEE) is a secondary amino ether alcohol with a strong steric hindrance effect. It is a particularly effective selective desulfurization solvent and is widely used in the selective desulfurization of petroleum, natural gas, oilfield associated gas, liquid hydrocarbons and synthesis gas, especially in the treatment of highly acidic CO2 / H2S mixed gas desulfurization. The relative selectivity of TBEE to H2S is three times that of methyldiethanolamine (MDEA) to H2S. In the process of gas purification, the energy consumption of TBEE is only 70% of that of MDEA, and the energy-saving effect is very significant. There is no corrosion of equipment during use, and it has a good application prospect.

[0003] At present, it is known that a variety of reaction methods and catalyst preparation methods are used in the production of TBEE, including: (1) Patent CN1623978A uses tert-butylamine and 2-chloroethoxyethanol as raw materials, methanol, ethanol, etc. as reaction medium, and heats and presses the reactor without adding a catalyst. After adding alkali for neutralization and condensation to recover excess tert-butylamine, the filtrate is subjected to crude distillation, rectification and other operations to prepare the target product tert-butylaminoethoxyethanol. This method uses excess alkali, has a complicated procedure, and is difficult to handle later; (2) Patent US4487967 also uses diethylene glycol and tert-butylamine as reaction raw materials, and uses transition metals Ni, Co, and Pt, Ru, Rh, and Pd as active components. Using a single metal catalyst or a multi-metal catalyst for activity evaluation, among all the catalysts, when Ni is used as the active component and the loading amount is as high as 65%, the highest TBEE yield is only 54%. During the reaction, there is a loss of active species, resulting in a large waste, and the utilization rate of active components is low; (3) Patent US453452 uses halogenated alkanols and primary amines as raw materials for amination reaction. In this reaction, a large number of by-products such as halides will be generated, and the halides will seriously affect the service life of the equipment. In the later treatment process, alkali solution is needed to absorb the halides to achieve the purpose of purification, and the reaction cost is significantly increased; (4) Patent CN108906061A uses diethylene glycol and tert-butylamine as reaction raw materials and single metal Ni as active component to explore the effect of different carriers on reaction activity. Among them, when Al2O3 is used as the carrier, the best yield of the reaction in an intermittent reactor can only reach 54.3%.

[0004] It can be seen that the existing tert-butylaminoethoxyethanol synthesis method or post-processing process is difficult, or the catalyst activity is low, or the yield of tert-butylaminoethoxyethanol is low. Therefore, it is urgent to explore a new synthesis method of tert-butylaminoethoxyethanol. Summary of the invention

[0005] The purpose of the present invention is to provide a method for synthesizing tert-butylaminoethoxyethanol. The method has high raw material conversion rate, high yield of the prepared tert-butylaminoethoxyethanol and few by-products.

[0006] The process for efficiently catalyzing the synthesis of tert-butylaminoethoxyethanol of the present invention comprises the following steps: (1) dissolving the triblock copolymer P123 in a mixture of anhydrous ethanol and isopropanol, adding hydrochloric acid while stirring and mixing evenly, adding cerium oxalate and reacting for 15-20 minutes, and then adding aluminum isopropoxide and stirring and reacting for 4.5-4.7 hours to prepare a sol; (2) aging the sol prepared in step (1) to obtain a wet sol, then drying the wet sol to obtain a dry gel, and finally calcining the dry gel at a high temperature to obtain a CeO2-Al2O3 carrier; (3) nickel nitrate, ammonium molybdate and cobalt nitrate are dissolved in deionized water to prepare a mixed solution, and an equal volume of CeO2-Al2O3 carrier is impregnated. After the impregnation, the water is evaporated, and then dried and calcined to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst precursor. Finally, the Co-Ni-Mo / CeO2-Al2O3 catalyst precursor is reduced to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst; (4) The reaction raw materials consisting of tert-butylamine and diethylene glycol are quantitatively pumped into a preheating gasifier by a pump through a flow meter and mixed with hydrogen for preheating and gasification, and then enter a fixed bed reactor for reaction. The fixed bed reactor is filled with a Co-Ni-Mo / CeO2-Al2O3 catalyst. After the reaction, the materials are condensed and separated into gas and liquid, and the obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0007] in: The volume ratio of anhydrous ethanol to isopropanol in the mixed solution of anhydrous ethanol and isopropanol in step (1) is 3:1.

[0008] The volume ratio of the mass of the triblock copolymer P123 to the mixed solution of anhydrous ethanol and isopropanol in step (1) is 1:20, expressed in g / mL.

[0009] In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the mixed solution of anhydrous ethanol and isopropanol is 1:13.

[0010] The amount of cerium oxalate and aluminum isopropoxide added in step (1) is such that the mass of cerium oxide in the CeO2-Al2O3 carrier prepared in step (2) accounts for 2-3% of the total mass of cerium oxide and aluminum oxide.

[0011] In step (2), the aging temperature is room temperature and the aging time is 22-23 hours.

[0012] In step (2), the drying temperature is 80-85°C and the drying time is 9.5-10h.

[0013] In step (2), the high temperature calcination is firstly to increase the temperature to 350°C at a rate of 2.5°C / min and keep it at that temperature for 4.5h, and finally to increase the temperature to 800°C at a rate of 6°C / min and keep it at that temperature for 1.2h.

[0014] The medium volume immersion time in step (3) is 2.3-2.5 h.

[0015] In step (3), the temperature for evaporating water is 80-83°C, the drying temperature is 95-100°C, the drying time is 24h, the roasting temperature is 485-490°C, and the roasting time is 6h.

[0016] The reduction in step (3) is carried out under a hydrogen atmosphere at a pressure of 0.05 MPa, a temperature of 460°C and a space velocity of 1000 h -1 Reduction under the conditions of 24h.

[0017] In the Co-Ni-Mo / CeO2-Al2O3 catalyst prepared in step (3), the mass of Ni accounts for 5-8% of the total mass of the catalyst, the mass of Mo accounts for 2-4% of the total mass of the catalyst, the mass of Co accounts for 20-25% of the total mass of the catalyst, and the mass of CeO2-Al2O3 accounts for 66-70% of the total mass of the catalyst.

[0018] The molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials of step (4) is 1.5-1.7:1.

[0019] The feed rate of the fixed bed reactor in step (4) is 3.5-5 mL / h of the reaction raw material per 1 liter of Co-Ni-Mo / CeO2-Al2O3 catalyst.

[0020] In step (4), hydrogen is used as circulating gas to maintain the reaction pressure in the fixed bed reactor at 2-2.3 MPa and the reaction temperature at 240-245°C.

[0021] In step (4), the distillation temperature is 195° C. and the distillation pressure is 0.05 MPa.

[0022] The gaseous hydrogen obtained after gas-liquid separation in step (4) is pressurized by a circulating compressor and returned to the preheating gasifier for recycling.

[0023] The process method for efficiently catalyzing the synthesis of tert-butylaminoethoxyethanol of the present invention uses Co-Ni-Mo / CeO2-Al2O3 as a catalyst, tert-butylamine and diethylene glycol as reaction raw materials, and hydrogen as a circulating gas to carry out a gas-solid phase reaction. In the Co-Ni-Mo / CeO2-Al2O3 catalyst, CeO2-Al2O3 is used as a catalyst carrier, and the introduced CeO2 is effectively combined with alumina to improve the pore structure characteristics of the catalyst carrier, so that the catalyst carrier has acid-base active sites at the same time, which promotes the catalytic activity of Co, thereby improving the distribution morphology of the active component. CeO2 plays an important role in promoting the dehydration condensation reaction of carbonyl compounds and tert-butylamine. With Co-Ni-Mo as the active component of the catalyst, Ni and Co cooperate with each other, with Co as the main component and Ni as the auxiliary component, reducing the activation energy of the carbon-hydrogen bond on the adjacent carbon of the hydroxyl group of the alcohol, promoting the breaking of the OH bond and the CH bond, and the addition of Mo can improve the dispersibility of the active components Ni and Co, thereby improving the activity and selectivity of the prepared catalyst. The three active components act synergistically, reducing the metal loading while improving the utilization of the active components. It can be seen that the carrier and the active components in the prepared Co-Ni-Mo / CeO2-Al2O3 catalyst act synergistically, and have good catalytic activity for the synthesis of tert-butylaminoethoxyethanol.

[0024] Compared with the prior art, the present invention has the following beneficial effects: The process method for efficiently catalytically synthesizing tert-butylaminoethoxyethanol of the present invention adopts tert-butylamine and diethylene glycol as raw materials, hydrogen as circulating gas, and Co-Ni-Mo / CeO2-Al2O3 as catalyst to carry out gas-solid phase continuous reaction. The catalyst has high catalytic activity, mild reaction conditions, high raw material conversion rate, and can realize industrial production. DETAILED DESCRIPTION

[0025] Example 1 The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol described in Example 1 is composed of the following steps: (1) The triblock copolymer P123 was dissolved in a mixture of anhydrous ethanol and isopropanol, hydrochloric acid was added under stirring and mixed evenly, cerium oxalate was added and reacted for 17 minutes, and then aluminum isopropoxide was added and stirred for 4.6 hours to prepare a sol; (2) aging the sol prepared in step (1) to obtain a wet sol, then drying the wet sol to obtain a dry gel, and finally calcining the dry gel at a high temperature to obtain a CeO2-Al2O3 carrier; (3) nickel nitrate, ammonium molybdate and cobalt nitrate are dissolved in deionized water to prepare a mixed solution, and an equal volume of CeO2-Al2O3 carrier is impregnated. After the impregnation, the water is evaporated, and then dried and calcined to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst precursor. Finally, the Co-Ni-Mo / CeO2-Al2O3 catalyst precursor is reduced to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst; (4) The reaction raw materials consisting of tert-butylamine and diethylene glycol are quantitatively pumped into a preheating gasifier by a pump through a flow meter and mixed with hydrogen for preheating and gasification, and then enter a fixed bed reactor for reaction. The fixed bed reactor is filled with a Co-Ni-Mo / CeO2-Al2O3 catalyst. After the reaction, the materials are condensed and separated into gas and liquid, and the obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0026] in: The volume ratio of anhydrous ethanol to isopropanol in the mixed solution of anhydrous ethanol and isopropanol in step (1) is 3:1.

[0027] The volume ratio of the mass of the triblock copolymer P123 to the mixed solution of anhydrous ethanol and isopropanol in step (1) is 1:20, expressed in g / mL.

[0028] In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the mixed solution of anhydrous ethanol and isopropanol is 1:13.

[0029] The amount of cerium oxalate and aluminum isopropoxide added in step (1) is such that the mass of cerium oxide in the CeO2-Al2O3 carrier prepared in step (2) accounts for 2.5% of the total mass of cerium oxide and aluminum oxide.

[0030] In step (2), the aging temperature is room temperature and the aging time is 22.5 h.

[0031] In step (2), the drying temperature is 83°C and the drying time is 9.7h.

[0032] In step (2), the high temperature calcination is firstly to increase the temperature to 350°C at a rate of 2.5°C / min and keep it at that temperature for 4.5h, and finally to increase the temperature to 800°C at a rate of 6°C / min and keep it at that temperature for 1.2h.

[0033] The medium volume immersion time in step (3) is 2.4 h.

[0034] In step (3), the temperature for evaporating water is 81°C, the drying temperature is 97°C, the drying time is 24h, the roasting temperature is 487°C, and the roasting time is 6h.

[0035] The reduction in step (3) is carried out under a hydrogen atmosphere at a pressure of 0.05 MPa, a temperature of 460°C and a space velocity of 1000 h -1 Reduction under the conditions of 24h.

[0036] In the Co-Ni-Mo / CeO2-Al2O3 catalyst prepared in step (3), the mass of Ni accounts for 6.5% of the total mass of the catalyst, the mass of Mo accounts for 3% of the total mass of the catalyst, the mass of Co accounts for 23% of the total mass of the catalyst, and the mass of CeO2-Al2O3 accounts for 67.5% of the total mass of the catalyst.

[0037] The molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials of step (4) is 1.6:1.

[0038] The feed rate of the fixed bed reactor in step (4) is 4.3 mL / h of the reaction raw material per 1 liter of Co-Ni-Mo / CeO2-Al2O3 catalyst.

[0039] In step (4), hydrogen is used as circulating gas to maintain the reaction pressure in the fixed bed reactor at 2.2 MPa and the reaction temperature at 243°C.

[0040] In step (4), the distillation temperature is 195° C. and the distillation pressure is 0.05 MPa.

[0041] According to the analysis, the conversion rate of diethylene glycol was 90.34%, the selectivity of tert-butylaminoethoxyethanol was 87.25%, the yield of tert-butylaminoethoxyethanol was 78.82%, and the purity of tert-butylaminoethoxyethanol was 99.5%.

[0042] Example 2 The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol described in Example 2 is composed of the following steps: (1) The triblock copolymer P123 was dissolved in a mixture of anhydrous ethanol and isopropanol, hydrochloric acid was added under stirring and mixed evenly, cerium oxalate was added and reacted for 15 minutes, and then aluminum isopropoxide was added and stirred for 4.7 hours to prepare a sol; (2) aging the sol prepared in step (1) to obtain a wet sol, then drying the wet sol to obtain a dry gel, and finally calcining the dry gel at a high temperature to obtain a CeO2-Al2O3 carrier; (3) nickel nitrate, ammonium molybdate and cobalt nitrate are dissolved in deionized water to prepare a mixed solution, and an equal volume of CeO2-Al2O3 carrier is impregnated. After the impregnation, the water is evaporated, and then dried and calcined to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst precursor. Finally, the Co-Ni-Mo / CeO2-Al2O3 catalyst precursor is reduced to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst; (4) The reaction raw materials consisting of tert-butylamine and diethylene glycol are quantitatively pumped into a preheating gasifier by a pump through a flow meter and mixed with hydrogen for preheating and gasification, and then enter a fixed bed reactor for reaction. The fixed bed reactor is filled with a Co-Ni-Mo / CeO2-Al2O3 catalyst. After the reaction, the materials are condensed and separated into gas and liquid, and the obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0043] in: The volume ratio of anhydrous ethanol to isopropanol in the mixed solution of anhydrous ethanol and isopropanol in step (1) is 3:1.

[0044] The volume ratio of the mass of the triblock copolymer P123 to the mixed solution of anhydrous ethanol and isopropanol in step (1) is 1:20, expressed in g / mL.

[0045] In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the mixed solution of anhydrous ethanol and isopropanol is 1:13.

[0046] The amount of cerium oxalate and aluminum isopropoxide added in step (1) is such that the mass of cerium oxide in the CeO2-Al2O3 carrier prepared in step (2) accounts for 2% of the total mass of cerium oxide and aluminum oxide.

[0047] In step (2), the aging temperature is room temperature and the aging time is 22 h.

[0048] In step (2), the drying temperature is 80° C. and the drying time is 9.5 h.

[0049] In step (2), the high temperature calcination is firstly to increase the temperature to 350°C at a rate of 2.5°C / min and keep it at that temperature for 4.5h, and finally to increase the temperature to 800°C at a rate of 6°C / min and keep it at that temperature for 1.2h.

[0050] The medium volume immersion time in step (3) is 2.3 h.

[0051] In step (3), the temperature for evaporating water is 80°C, the drying temperature is 95°C, the drying time is 24h, the roasting temperature is 485°C, and the roasting time is 6h.

[0052] The reduction in step (3) is carried out under a hydrogen atmosphere at a pressure of 0.05 MPa, a temperature of 460°C and a space velocity of 1000 h -1 Reduction under the conditions of 24h.

[0053] In the Co-Ni-Mo / CeO2-Al2O3 catalyst prepared in step (3), the mass of Ni accounts for 8% of the total mass of the catalyst, the mass of Mo accounts for 2% of the total mass of the catalyst, the mass of Co accounts for 20% of the total mass of the catalyst, and the mass of CeO2-Al2O3 accounts for 70% of the total mass of the catalyst.

[0054] The molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials of step (4) is 1.5:1.

[0055] The feed rate of the fixed bed reactor in step (4) is 3.5 mL / h of reaction raw material per liter of Co-Ni-Mo / CeO2-Al2O3 catalyst.

[0056] In step (4), hydrogen is used as circulating gas to maintain the reaction pressure in the fixed bed reactor at 2.0 MPa and the reaction temperature at 240°C.

[0057] In step (4), the distillation temperature is 195° C. and the distillation pressure is 0.05 MPa.

[0058] According to the analysis, the conversion rate of diethylene glycol was 88.23%, the selectivity of tert-butylaminoethoxyethanol was 84.51%, the yield of tert-butylaminoethoxyethanol was 74.56%, and the purity of tert-butylaminoethoxyethanol was 99.4%.

[0059] Example 3 The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol described in Example 3 is composed of the following steps: (1) The triblock copolymer P123 was dissolved in a mixture of anhydrous ethanol and isopropanol, hydrochloric acid was added under stirring and mixed evenly, cerium oxalate was added and reacted for 20 minutes, and then aluminum isopropoxide was added and stirred for 4.5 hours to prepare a sol; (2) aging the sol prepared in step (1) to obtain a wet sol, then drying the wet sol to obtain a dry gel, and finally calcining the dry gel at a high temperature to obtain a CeO2-Al2O3 carrier; (3) nickel nitrate, ammonium molybdate and cobalt nitrate are dissolved in deionized water to prepare a mixed solution, and an equal volume of CeO2-Al2O3 carrier is impregnated. After the impregnation, the water is evaporated, and then dried and calcined to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst precursor. Finally, the Co-Ni-Mo / CeO2-Al2O3 catalyst precursor is reduced to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst; (4) The reaction raw materials consisting of tert-butylamine and diethylene glycol are quantitatively pumped into a preheating gasifier by a pump through a flow meter and mixed with hydrogen for preheating and gasification, and then enter a fixed bed reactor for reaction. The fixed bed reactor is filled with a Co-Ni-Mo / CeO2-Al2O3 catalyst. After the reaction, the materials are condensed and separated into gas and liquid, and the obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0060] in: The volume ratio of anhydrous ethanol to isopropanol in the mixed solution of anhydrous ethanol and isopropanol in step (1) is 3:1.

[0061] The volume ratio of the mass of the triblock copolymer P123 to the mixed solution of anhydrous ethanol and isopropanol in step (1) is 1:20, expressed in g / mL.

[0062] In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the mixed solution of anhydrous ethanol and isopropanol is 1:13.

[0063] The amount of cerium oxalate and aluminum isopropoxide added in step (1) is such that the mass of cerium oxide in the CeO2-Al2O3 carrier prepared in step (2) accounts for 3% of the total mass of cerium oxide and aluminum oxide.

[0064] In step (2), the aging temperature is room temperature and the aging time is 23 h.

[0065] In step (2), the drying temperature is 85°C and the drying time is 10 hours.

[0066] In step (2), the high temperature calcination is firstly to increase the temperature to 350°C at a rate of 2.5°C / min and keep it at that temperature for 4.5h, and finally to increase the temperature to 800°C at a rate of 6°C / min and keep it at that temperature for 1.2h.

[0067] The medium volume immersion time in step (3) is 2.5 h.

[0068] In step (3), the temperature for evaporating water is 83°C, the drying temperature is 100°C, the drying time is 24h, the roasting temperature is 490°C, and the roasting time is 6h.

[0069] The reduction in step (3) is carried out under a hydrogen atmosphere at a pressure of 0.05 MPa, a temperature of 460°C and a space velocity of 1000 h -1 Reduction under the conditions of 24h.

[0070] In the Co-Ni-Mo / CeO2-Al2O3 catalyst prepared in step (3), the mass of Ni accounts for 5% of the total mass of the catalyst, the mass of Mo accounts for 4% of the total mass of the catalyst, the mass of Co accounts for 25% of the total mass of the catalyst, and the mass of CeO2-Al2O3 accounts for 66% of the total mass of the catalyst.

[0071] The molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials of step (4) is 1.7:1.

[0072] The feed rate of the fixed bed reactor in step (4) is 5 mL / h of the reaction raw material per liter of Co-Ni-Mo / CeO2-Al2O3 catalyst.

[0073] In step (4), hydrogen is used as circulating gas to maintain the reaction pressure in the fixed bed reactor at 2.3 MPa and the reaction temperature at 245°C.

[0074] In step (4), the distillation temperature is 195° C. and the distillation pressure is 0.05 MPa.

[0075] According to the analysis, the conversion rate of diethylene glycol was 86.71%, the selectivity of tert-butylaminoethoxyethanol was 83.19%, the yield of tert-butylaminoethoxyethanol was 72.13%, and the purity of tert-butylaminoethoxyethanol was 99.1%.

[0076] Comparative Example 1 The process for catalytically synthesizing tert-butylaminoethoxyethanol described in this comparative example 1 is the same as that in Example 1, except that cerium oxalate is not added in step (1), and alumina sol is directly prepared, thereby directly preparing Al2O3 carrier in step (2). According to analysis, the conversion rate of diethylene glycol is 54.55%, the selectivity of tert-butylaminoethoxyethanol is 75.31%, the yield of tert-butylaminoethoxyethanol is 41.08%, and the purity of tert-butylaminoethoxyethanol is 80.9%.

[0077] Comparative Example 2 The process for catalytically synthesizing tert-butylaminoethoxyethanol described in this comparative example 2 is the same as that in Example 1, except that cobalt nitrate is not added in step (3), and the catalyst prepared in step (3) is a Ni-Mo / CeO2-Al2O3 catalyst. According to analysis, the conversion rate of diethylene glycol is 59.24%, the selectivity of tert-butylaminoethoxyethanol is 65.49%, the yield of tert-butylaminoethoxyethanol is 38.80%, and the purity of tert-butylaminoethoxyethanol is 84.2%.

[0078] Comparative Example 3 The process for catalytically synthesizing tert-butylaminoethoxyethanol described in this comparative example 3 is the same as that in Example 1, except that cobalt nitrate is not added in step (3), and the catalyst prepared in step (3) is a Co-Ni / CeO2-Al2O3 catalyst. According to analysis, the conversion rate of diethylene glycol is 77.36%, the selectivity of tert-butylaminoethoxyethanol is 75.19%, the yield of tert-butylaminoethoxyethanol is 58.17%, and the purity of tert-butylaminoethoxyethanol is 95.4%.

[0079] Comparative Example 4 The process for catalytically synthesizing tert-butylaminoethoxyethanol described in this comparative example 4 is the same as that in Example 1, except that nickel nitrate is not added in step (3), and the catalyst prepared in step (3) is a Co-Mo / CeO2-Al2O3 catalyst. After analysis, the conversion rate of diethylene glycol is 67.17%, the selectivity of tert-butylaminoethoxyethanol is 65.10%, the yield of tert-butylaminoethoxyethanol is 43.73%, and the purity of tert-butylaminoethoxyethanol is 89.2%.

Claims

1. A process for efficiently catalyzing the synthesis of tert-butylaminoethoxyethanol, characterized in that: It consists of the following steps: (1) dissolving the triblock copolymer P123 in a mixture of anhydrous ethanol and isopropanol, adding hydrochloric acid while stirring and mixing evenly, adding cerium oxalate and reacting for 15-20 minutes, and then adding aluminum isopropoxide and stirring and reacting for 4.5-4.7 hours to prepare a sol; (2) aging the sol prepared in step (1) to obtain a wet sol, then drying the wet sol to obtain a dry gel, and finally calcining the dry gel at a high temperature to obtain a CeO2-Al2O3 carrier; (3) nickel nitrate, ammonium molybdate and cobalt nitrate are dissolved in deionized water to prepare a mixed solution, and an equal volume of CeO2-Al2O3 carrier is impregnated. After the impregnation, the water is evaporated, and then dried and calcined to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst precursor. Finally, the Co-Ni-Mo / CeO2-Al2O3 catalyst precursor is reduced to obtain a Co-Ni-Mo / CeO2-Al2O3 catalyst; (4) The reaction raw materials consisting of tert-butylamine and diethylene glycol are quantitatively pumped into a preheating gasifier by a pump through a flow meter and mixed with hydrogen for preheating and gasification, and then enter a fixed bed reactor for reaction. The fixed bed reactor is filled with a Co-Ni-Mo / CeO2-Al2O3 catalyst. After the reaction, the materials are condensed and separated into gas and liquid, and the obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

2. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: The volume ratio of anhydrous ethanol to isopropanol in the mixed solution of anhydrous ethanol and isopropanol in step (1) is 3:1; The volume ratio of the mass of the triblock copolymer P123 to the mixed solution of anhydrous ethanol and isopropanol in step (1) is 1:20, expressed in g / mL; In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the mixed solution of anhydrous ethanol and isopropanol is 1:13; The amount of cerium oxalate and aluminum isopropoxide added in step (1) is such that the mass of cerium oxide in the CeO2-Al2O3 carrier prepared in step (2) accounts for 2-3% of the total mass of cerium oxide and aluminum oxide.

3. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: In step (2), the aging temperature is room temperature and the aging time is 22-23 hours; In step (2), the drying temperature is 80-85°C and the drying time is 9.5-10h; In step (2), the high temperature calcination is firstly to increase the temperature to 350°C at a rate of 2.5°C / min and keep it at that temperature for 4.5h, and finally to increase the temperature to 800°C at a rate of 6°C / min and keep it at that temperature for 1.2h.

4. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: Step (3) The medium volume immersion time is 2.3-2.5h; In step (3), the temperature for evaporating water is 80-83°C, the drying temperature is 95-100°C, the drying time is 24h, the roasting temperature is 485-490°C, and the roasting time is 6h.

5. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: The reduction in step (3) is carried out under a hydrogen atmosphere at a pressure of 0.05 MPa, a temperature of 460°C and a space velocity of 1000 h -1 Reduction under the conditions of 24h.

6. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: In the Co-Ni-Mo / CeO2-Al2O3 catalyst prepared in step (3), the mass of Ni accounts for 5-8% of the total mass of the catalyst, the mass of Mo accounts for 2-4% of the total mass of the catalyst, the mass of Co accounts for 20-25% of the total mass of the catalyst, and the mass of CeO2-Al2O3 accounts for 66-70% of the total mass of the catalyst.

7. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: The molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials of step (4) is 1.5-1.7:

1.

8. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: The feed rate of the fixed bed reactor in step (4) is 3.5-5 mL / h of the reaction raw material per 1 liter of Co-Ni-Mo / CeO2-Al2O3 catalyst.

9. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: In step (4), hydrogen is used as circulating gas to maintain the reaction pressure in the fixed bed reactor at 2-2.3 MPa and the reaction temperature at 240-245°C.

10. The process for the efficient catalytic synthesis of tert-butylaminoethoxyethanol according to claim 1, characterized in that: In step (4), the distillation temperature is 195° C. and the distillation pressure is 0.05 MPa.