Method for catalytically synthesizing tert-butylaminoethoxyethanol

Abstract

The present invention belongs to the technical field of the preparation of tert-butylaminoethoxyethanol, and particularly relates to a method for catalytically synthesizing tert-butylaminoethoxyethanol. The process method comprises the following steps: (1) preparing an aluminum-cerium composite sol; (2) preparing a CeO 2 -Al 2 O 3 support; (3) preparing a Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst; (4) feeding the reaction raw materials composed of tert-butylamine and diethylene glycol into a preheating vaporizer, mixing with hydrogen, preheating and vaporizing, and then entering a fixed-bed reactor for reaction. The fixed-bed reactor is filled with Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst. After the reaction, the reaction materials are condensed and subjected to gas-liquid separation, and the obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol. The method for catalytically synthesizing tert-butylaminoethoxyethanol according to the present invention has mild reaction conditions and high raw material conversion rate, and can realize industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of tert-butylaminoethoxyethanol, and particularly relates to a method for catalytically synthesizing tert-butylaminoethoxyethanol. Background Art

[0002] Tert-butylaminoethoxyethanol (TBEE) is a secondary amino ether alcohol with a strong steric hindrance effect and is a particularly effective selective desulfurization solvent. It is widely used in the selective desulfurization of petroleum, natural gas, associated gas in oil fields, liquid hydrocarbons, and synthesis gas, especially in the desulfurization of high-acidity CO 2 / H 2 S mixed gas, and has remarkable effects. The relative selectivity of TBEE to H 2 S is 3 times that of methyldiethanolamine (MDEA) to H 2 S. During the gas purification process, the energy consumption of TBEE is only 70% of that of MDEA, and the energy-saving effect is very remarkable. There is no phenomenon of equipment corrosion during use, and it has good application prospects.

[0003] At present, a variety of reaction methods and catalyst preparation methods have been applied to the production of TBEE, including: (1) In patent CN1623978A, using tert-butylamine and 2-chloroethoxyethanol as raw materials, methanol, ethanol, etc. as reaction media, heating and self-pressurizing treatment in a reaction kettle without adding a catalyst, followed by adding alkali for neutralization treatment, condensing and recovering excessive tert-butylamine, and subjecting the filtrate to operations such as rough distillation and rectification to prepare the target product tert-butylaminoethoxyethanol. This method uses excessive alkali, has a complex process, and is difficult for subsequent treatment; (2) In patent US4487967, using diethylene glycol and tert-butylamine as reaction raw materials, and using transition metals Ni, Co, and Pt, Ru, Rh, Pd as active components. Single-metal catalysts or multi-metal catalysts are used for activity evaluation. Among all catalysts, when Ni is used as the active component and the loading amount is as high as 65%, the highest yield of TBEE only reaches 54%. There is a large waste caused by the loss of active species during the reaction process, and the utilization rate of active components is low; (3) In patent US453452, using haloalkyl alcohol and primary amine as raw materials for amination reaction, in which more by-products such as halides are generated, and halides will seriously affect the service life of equipment. During the later treatment process, it is necessary to use alkali solution to absorb halides to achieve the purification purpose, and the reaction cost is significantly increased; (4) In patent CN108906061A, using diethylene glycol and tert-butylamine as reaction raw materials, and using single-metal Ni as the active component, exploring the influence of different carriers on the reaction activity. Among them, when using Al 2 O 3 as the carrier, in a batch stirred tank reactor, the best yield of the reaction can only reach 54.3%.

[0004] It can be seen from this that the existing synthesis methods or post-treatment processes of tert-butylaminoethoxyethanol are either difficult, or the catalyst has low activity, 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 object of the present invention is to provide a synthesis method of tert-butylaminoethoxyethanol. This synthesis method has a high raw material conversion rate, a high yield of the prepared tert-butylaminoethoxyethanol, and few by-products.

[0006] The method for catalytically synthesizing tert-butylaminoethoxyethanol according to the present invention comprises the following steps:

[0007] (1) Dissolve the triblock copolymer P123 in a mixed solution of absolute ethanol and isopropanol. Under stirring, add hydrochloric acid and mix evenly, then add cerium oxalate and react for 15 - 20 min, and then add aluminum isopropoxide and stir to react for 4.5 - 4.7 h to prepare a sol.

[0008] (2) Age the sol prepared in step (1) to obtain a wet sol, then dry the wet sol to obtain a dry gel, and finally calcine the dry gel at high temperature to prepare a CeO 2 -Al 2 O 3 support.

[0009] (3) Dissolve nickel nitrate, ammonium molybdate, and cobalt nitrate in deionized water to prepare a mixed solution. Perform equal-volume impregnation on the CeO 2 -Al 2 O 3 support. After impregnation, evaporate the water, then dry and calcine to obtain a Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor. Finally, reduce the Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor to prepare a Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst.

[0010] (4) Pump the reaction raw materials composed of tert-butylamine and diethylene glycol into a preheating vaporizer through a flow meter for quantitative control, mix with hydrogen, preheat and vaporize, and then enter a fixed-bed reactor for reaction. The fixed-bed reactor is filled with Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst. After the reaction, the reaction materials are condensed and separated by gas-liquid separation. The obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0011] Among them: in step (1), the volume ratio of absolute ethanol to isopropanol in the mixed solution of absolute ethanol and isopropanol is 3:1.

[0012] In step (1), the mass ratio of the triblock copolymer P123 to the volume of the mixed solution of absolute ethanol and isopropanol is 1:20, with the unit of g / mL.

[0013] In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the volume of the mixed solution of absolute ethanol and isopropanol is 1:13.

[0014] In step (1), the addition amounts of cerium oxalate and aluminum isopropoxide are in accordance with the CeO 2 -Al 2 O 3 in the carrier, and the mass of cerium oxide accounts for 2-3% of the sum of the masses of cerium oxide and aluminum oxide and is added.

[0015] In step (2), the aging temperature is room temperature, and the aging time is 22-23h.

[0016] In step (2), the drying temperature is 80-85 °C, and the drying time is 9.5-10h.

[0017] In step (2), for high-temperature calcination, first heat up to 350 °C at a rate of 2.5 °C / min and hold for 4.5h, and finally heat up to 800 °C at a rate of 6 °C / min and hold for 1.2h.

[0018] In step (3), the isovolumetric impregnation time is 2.3-2.5h.

[0019] 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 calcination temperature is 485-490 °C, and the calcination time is 6h.

[0020] In step (3), the reduction is carried out under a hydrogen atmosphere, with a pressure of 0.05 MPa, a temperature of 460 °C, and a space velocity of 1000h -1 for 24h under the condition of.

[0021] In step (3), for the Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst prepared, 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 CeO 2 -Al 2 O 3 accounts for 66-70% of the total mass of the catalyst.

[0022] In step (4), the molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials is 1.5 - 1.7:1.

[0023] In step (4), the feed rate of the fixed-bed reactor is 3.5 - 5 mL / h of the reaction raw materials per 1 liter of Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst.

[0024] In step (4), hydrogen is used as the recycle gas to maintain the reaction pressure in the fixed-bed reactor at 2 - 2.3 MPa and the reaction temperature at 240 - 245 °C.

[0025] In step (4), the distillation temperature is 195 °C and the distillation pressure is 0.05 MPa.

[0026] In step (4), the hydrogen gas obtained after gas-liquid separation is pressurized by a recycle compressor and returned to the preheating vaporizer for recycling.

[0027] In the method for catalytic synthesis of tert-butylaminoethoxyethanol according to the present invention, Co-Ni-Mo / CeO 2 -Al 2 O 3 is used as the catalyst, tert-butylamine and diethylene glycol are used as the reaction raw materials, and hydrogen is used as the recycle gas for gas-solid phase reaction. In Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst, CeO 2 -Al 2 O 3 is used as the catalyst support. The introduced CeO 2 is effectively combined with alumina to improve the pore structure characteristics of the catalyst support, enabling the catalyst support to have both acid and base active sites, which promotes the catalytic activity of Co and thus improves the distribution pattern of the active components. CeO 2 plays an important promoting role in the dehydration condensation reaction of carbonyl compounds and tert-butylamine. Using Co-Ni-Mo as the catalyst active components, 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 carbon adjacent to the hydroxyl group of the alcohol, promoting the cleavage of the O-H bond and the C-H bond. The addition of Mo can improve the dispersion of the active components Ni and Co, thereby improving the activity and selectivity of the prepared catalyst. The three active components act synergistically to improve the utilization rate of the active components while reducing the metal loading. It can be seen that the prepared Co-Ni-Mo / CeO 2 -Al 2 O 3The synergistic effect between the carrier and the active component in the catalyst exhibits excellent catalytic activity for the synthesis of tert-butylaminoethoxyethanol.

[0028] Compared with the prior art, it has the following beneficial effects:

[0029] In the method for catalytic synthesis of tert-butylaminoethoxyethanol according to the present invention, tert-butylamine and diethylene glycol are used as raw materials, hydrogen is used as the recycle gas, and Co-Ni-Mo / CeO 2 -Al 2 O 3 is used as the catalyst for 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 implementation methods

[0030] Example 1

[0031] The method for catalytic synthesis of tert-butylaminoethoxyethanol described in this Example 1 consists of the following steps:

[0032] (1) Dissolve the triblock copolymer P123 in a mixed solution of anhydrous ethanol and isopropanol. Under stirring, add hydrochloric acid and mix evenly, then add cerium oxalate and react for 17 minutes. Then add aluminum isopropoxide and stir to react for 4.6 hours to prepare a sol.

[0033] (2) Age the sol prepared in step (1) to obtain a wet sol, then dry the wet sol to obtain a dry gel, and finally calcine the dry gel at high temperature to prepare CeO 2 -Al 2 O 3 carrier.

[0034] (3) Dissolve nickel nitrate, ammonium molybdate, and cobalt nitrate in deionized water to prepare a mixed solution. Perform equal-volume impregnation on the CeO 2 -Al 2 O 3 carrier. After impregnation, evaporate the water, then dry and calcine to obtain the Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor. Finally, reduce the Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor to prepare Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst.

[0035] (4) The reaction raw materials composed of tert-butylamine and diethylene glycol are quantitatively pumped into the preheating vaporizer by a pump controlled by a flow meter, mixed with hydrogen, preheated and vaporized, and then enter the fixed bed reactor for reaction. The fixed bed reactor is filled with Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst. After the reaction, the material is condensed and separated into gas and liquid. The obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0036] Among them:

[0037] In the mixed solution of absolute ethanol and isopropanol described in step (1), the volume ratio of absolute ethanol to isopropanol is 3:1.

[0038] In step (1), the mass of the triblock copolymer P123 and the volume of the mixed solution of absolute ethanol and isopropanol are in a ratio of 1:20, with the unit of g / mL.

[0039] In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the mixed solution of absolute ethanol and isopropanol is 1:13.

[0040] In step (1), the addition amounts of cerium oxalate and aluminum isopropoxide are added according to the mass of cerium oxide in the CeO 2 -Al 2 O 3 support accounting for 2.5% of the sum of the masses of cerium oxide and aluminum oxide.

[0041] In step (2), the aging temperature is room temperature and the aging time is 22.5 h.

[0042] In step (2), the drying temperature is 83 °C and the drying time is 9.7 h.

[0043] In step (2), the high-temperature calcination is first heating to 350 °C at a rate of 2.5 °C / min and holding for 4.5 h, and finally heating to 800 °C at a rate of 6 °C / min and holding for 1.2 h.

[0044] In step (3), the equal-volume impregnation time is 2.4 h.

[0045] In step (3), the temperature for evaporating water is 81 °C, the drying temperature is 97 °C, the drying time is 24 h, the calcination temperature is 487 °C, and the calcination time is 6 h.

[0046] In step (3), the reduction 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 for 24 h.

[0047] The Co-Ni-Mo / CeO prepared in step (3)2 -Al 2 O 3 Catalyst, 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 CeO 2 -Al 2 O 3 accounts for 67.5% of the total mass of the catalyst.

[0048] In step (4), the molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials is 1.6:1.

[0049] In step (4), the feed rate of the fixed-bed reactor is 4.3 mL / h of the reaction raw materials per 1 liter of Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst.

[0050] In step (4), hydrogen is used as the recycle gas to maintain the reaction pressure in the fixed-bed reactor at 2.2 MPa and the reaction temperature at 243 °C.

[0051] In step (4), the distillation temperature is 195 °C and the distillation pressure is 0.05 MPa.

[0052] After analysis, the conversion rate of diethylene glycol is 90.34%, the selectivity of tert-butylaminoethoxyethanol is 87.25%, the yield of tert-butylaminoethoxyethanol is 78.82%, and the purity of tert-butylaminoethoxyethanol is 99.5%.

[0053] Example 2

[0054] The method for catalytic synthesis of tert-butylaminoethoxyethanol described in this Example 2 consists of the following steps:

[0055] (1) Dissolve the triblock copolymer P123 in a mixed solution of absolute ethanol and isopropanol. While stirring, add hydrochloric acid and mix evenly, then add cerium oxalate and react for 15 min, and then add aluminum isopropoxide and stir and react for 4.7 h to prepare a sol;

[0056] (2) Age the sol prepared in step (1) to obtain a wet sol, then dry the wet sol to obtain a dry gel, and finally calcine the dry gel at high temperature to prepare CeO 2 -Al 2 O 3 support;

[0057] (3) Dissolve nickel nitrate, ammonium molybdate, and cobalt nitrate in deionized water to prepare a mixed solution, and for CeO 2 -Al 2 O 3The carrier was impregnated with an equal volume, and after the impregnation was completed, the water was evaporated to dryness, and then dried and calcined to obtain a Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor. Finally, the Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor was reduced to prepare Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst;

[0058] (4) The reaction raw materials composed of tert-butylamine and diethylene glycol were quantitatively pumped into a preheating vaporizer by a pump controlled by a flow meter, mixed with hydrogen, preheated and vaporized, and then entered a fixed-bed reactor for reaction. The fixed-bed reactor was filled with Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst. After the reaction, the material was condensed and separated into gas and liquid. The obtained liquid phase was separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0059] Among them:

[0060] In the mixed solution of absolute ethanol and isopropanol described in step (1), the volume ratio of absolute ethanol to isopropanol is 3:1.

[0061] In step (1), the mass ratio of the triblock copolymer P123 to the volume of the mixed solution of absolute ethanol and isopropanol is 1:20, with the unit of g / mL.

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

[0063] In step (1), the addition amounts of cerium oxalate and aluminum isopropoxide are added according to the mass of cerium oxide in the CeO 2 -Al 2 O 3 support accounting for 2% of the sum of the masses of cerium oxide and aluminum oxide.

[0064] In step (2), the aging temperature is room temperature and the aging time is 22 h.

[0065] In step (2), the drying temperature is 80 °C and the drying time is 9.5 h.

[0066] In step (2), the high-temperature calcination is first to raise the temperature to 350 °C at a rate of 2.5 °C / min and hold for 4.5 h, and finally to raise the temperature to 800 °C at a rate of 6 °C / min and hold for 1.2 h.

[0067] In step (3), the medium-volume impregnation time is 2.3 h.

[0068] In step (3), the temperature for evaporating water is 80 °C, the drying temperature is 95 °C, the drying time is 24 h, the calcination temperature is 485 °C, and the calcination time is 6 h.

[0069] In step (3), the reduction 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 for 24 h under the conditions of.

[0070] The Co-Ni-Mo / CeO prepared in step (3) 2 -Al 2 O 3 catalyst, 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 CeO 2 -Al 2 O 3 accounts for 70% of the total mass of the catalyst.

[0071] In step (4), the molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials is 1.5:1.

[0072] In step (4), the feed rate of the fixed-bed reactor is 3.5 mL / h of the reaction raw materials per 1 liter of Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst.

[0073] In step (4), hydrogen is used as the recycle gas to maintain the reaction pressure in the fixed-bed reactor at 2.0 MPa and the reaction temperature at 240 °C.

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

[0075] After analysis, the conversion rate of diethylene glycol is 88.23%, the selectivity of tert-butylaminoethoxyethanol is 84.51%, the yield of tert-butylaminoethoxyethanol is 74.56%, and the purity of tert-butylaminoethoxyethanol is 99.4%.

[0076] Example 3

[0077] The method for catalytic synthesis of tert-butylaminoethoxyethanol described in this Example 3 consists of the following steps:

[0078] (1) Dissolve the triblock copolymer P123 in a mixed solution of anhydrous ethanol and isopropanol, add hydrochloric acid under stirring and mix evenly, then add cerium oxalate and react for 20 min, and then add aluminum isopropoxide and stir and react for 4.5 h to prepare a sol;

[0079] (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 subjecting the dry gel to high-temperature calcination to prepare CeO 2 -Al 2 O 3 support;

[0080] (3) Dissolving nickel nitrate, ammonium molybdate, and cobalt nitrate in deionized water to prepare a mixed solution, and subjecting the CeO 2 -Al 2 O 3 support to equal-volume impregnation. After the impregnation is completed, the moisture is evaporated, and then dried and calcined to obtain a Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor. Finally, reducing the Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst precursor to prepare Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst;

[0081] (4) Pumping the reaction raw materials composed of tert-butylamine and diethylene glycol into a preheating vaporizer through a flowmeter for quantitative control, mixing with hydrogen, preheating and vaporizing, and then entering a fixed-bed reactor for reaction. The fixed-bed reactor is filled with Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst. After the reaction, the material is condensed and subjected to gas-liquid separation, and the obtained liquid phase is separated and purified by distillation to prepare tert-butylaminoethoxyethanol.

[0082] Among them:

[0083] In the mixed solution of absolute ethanol and isopropanol in step (1), the volume ratio of absolute ethanol to isopropanol is 3:1.

[0084] In step (1), the mass ratio of the triblock copolymer P123 to the volume of the mixed solution of absolute ethanol and isopropanol is 1:20, with the unit of g / mL.

[0085] In step (1), the mass concentration of hydrochloric acid is 37%, and the volume ratio of hydrochloric acid to the volume of the mixed solution of absolute ethanol and isopropanol is 1:13.

[0086] In step (1), the addition amounts of cerium oxalate and aluminum isopropoxide are based on the CeO 2 -Al 2 O 3The cerium oxide in the carrier is added at 3% of the sum of the masses of cerium oxide and alumina.

[0087] In step (2), the aging temperature is room temperature and the aging time is 23 h.

[0088] In step (2), the drying temperature is 85 °C and the drying time is 10 h.

[0089] In step (2), the high-temperature calcination is first heating to 350 °C at a rate of 2.5 °C / min and holding for 4.5 h, and finally heating to 800 °C at a rate of 6 °C / min and holding for 1.2 h.

[0090] In step (3), the equal-volume impregnation time is 2.5 h.

[0091] In step (3), the temperature for evaporating water is 83 °C, the drying temperature is 100 °C, the drying time is 24 h, the calcination temperature is 490 °C, and the calcination time is 6 h.

[0092] In step (3), the reduction is carried out under a hydrogen atmosphere, with a pressure of 0.05 MPa, a temperature of 460 °C, and a space velocity of 1000 h -1 for 24 h.

[0093] In step (3), the prepared Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst, 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 CeO 2 -Al 2 O 3 accounts for 66% of the total mass of the catalyst.

[0094] In step (4), the molar ratio of tert-butylamine to diethylene glycol in the reaction raw materials is 1.7:1.

[0095] In step (4), the feed rate of the fixed-bed reactor is 5 mL / h of the reaction raw materials per 1 L of Co-Ni-Mo / CeO 2 -Al 2 O 3 catalyst.

[0096] In step (4), hydrogen is used as the recycle gas to maintain the reaction pressure in the fixed-bed reactor at 2.3 MPa and the reaction temperature at 245 °C.

[0097] In step (4), the distillation temperature is 195 °C and the distillation pressure is 0.05 MPa.

[0098] After 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%.

[0099] Comparative Example 1

[0100] The process for catalytic synthesis of tert-butylaminoethoxyethanol described in this Comparative Example 1 was the same as that in Example 1. The only difference was that in step (1), cerium oxalate was not added, and alumina sol was directly prepared. Thus, in step (2), Al 2 O 3 support was directly prepared. After analysis, the conversion rate of diethylene glycol was 54.55%, the selectivity of tert-butylaminoethoxyethanol was 75.31%, the yield of tert-butylaminoethoxyethanol was 41.08%, and the purity of tert-butylaminoethoxyethanol was 80.9%.

[0101] Comparative Example 2

[0102] The process for catalytic synthesis of tert-butylaminoethoxyethanol described in this Comparative Example 2 was the same as that in Example 1. The only difference was that in step (3), cobalt nitrate was not added. Thus, the catalyst prepared in step (3) was Ni-Mo / CeO 2 -Al 2 O 3 catalyst. After analysis, the conversion rate of diethylene glycol was 59.24%, the selectivity of tert-butylaminoethoxyethanol was 65.49%, the yield of tert-butylaminoethoxyethanol was 38.80%, and the purity of tert-butylaminoethoxyethanol was 84.2%.

[0103] Comparative Example 3

[0104] The process for catalytic synthesis of tert-butylaminoethoxyethanol described in this Comparative Example 3 was the same as that in Example 1. The only difference was that in step (3), cobalt nitrate was not added. Thus, the catalyst prepared in step (3) was Co-Ni / CeO 2 -Al 2 O 3 catalyst. After analysis, the conversion rate of diethylene glycol was 77.36%, the selectivity of tert-butylaminoethoxyethanol was 75.19%, the yield of tert-butylaminoethoxyethanol was 58.17%, and the purity of tert-butylaminoethoxyethanol was 95.4%.

[0105] Comparative Example 4

[0106] The process for catalytic synthesis of tert-butylaminoethoxyethanol described in this Comparative Example 4 was the same as that in Example 1. The only difference was that in step (3), nickel nitrate was not added. Thus, the catalyst prepared in step (3) was Co-Mo / CeO2 -Al 2 O 3 Catalyst. After analysis, the conversion rate of diethylene glycol was 67.17%, the selectivity of tert-butylaminoethoxyethanol was 65.10%, the yield of tert-butylaminoethoxyethanol was 43.73%, and the purity of tert-butylaminoethoxyethanol was 89.2%.

Claims

1. A method for catalytic 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 method for 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 method for 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 method for 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 method for 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 method for 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 method for 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 method for 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 method for 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 method for 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.