Preparation of nano nickel-based catalyst and application of nano nickel-based catalyst in preparation of tert-butylamine ethoxyethanol

Abstract

The invention discloses preparation of a nano nickel-based catalyst and application of the nano nickel-based catalyst in preparation of tert-butylamine ethoxyethanol (TBEE). The catalyst is prepared by combining an ammonia distillation method with a direct reduction process: taking a nano metal oxide (MO, selected from SnO2, ZrO2, Al2O3 and SiO2) as a carrier, reacting a nickel salt, an auxiliary agent salt (auxiliary agents are Fe, Co, Ce and La) and an ammonia source (ammonia water or urea) at 50-150 DEG C for 5-48 hours to form a precursor, washing and drying, and directly reducing in a hydrogen atmosphere at 250-550 DEG C for 2-6 hours to obtain the catalyst. According to the catalyst, the interaction of nickel-auxiliary-carrier interface electrons is enhanced through the ammonia distillation effect, nickel electron distribution is regulated and controlled, and high-dispersion nano active sites are formed. When the catalyst is applied to a reaction for synthesizing TBEE from diethylene glycol and tert-butylamine, under the conditions of a solvent-free system, the hydrogen pressure of 1-4 MPa and the temperature of 140-180 DEG C, the conversion rate of diethylene glycol is greater than or equal to 77%, the selectivity of TBEE is greater than or equal to 89%, and the selectivity is improved by more than 25% compared with that of a catalyst prepared by a traditional precipitation method.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalysts, and particularly relates to preparation of a nano nickel-based catalyst and application of the catalyst in preparation of tert-butyl amine ethoxy ethanol. BACKGROUND

[0002] When the H2S content in the raw material gas is low, and the CO2 concentration is lower than 2% stipulated in the national standard (GB 17820-2012), if the CO2 / H2S ratio is significantly higher than 10, the importance of selective desulfurization technology is highlighted. As a kind of alcohol amine compound, steric hindrance amine has been widely concerned since the 1980s due to its high selective desulfurization performance. Its structural feature is that there is one or more non-linear substituent groups on the alpha-carbon connected to the amino group, which significantly improves the desulfurization efficiency through the steric hindrance effect. Compared with conventional desulfurization solvents, steric hindrance amine has the following comprehensive advantages: higher boiling point and water solubility; faster desulfurization rate and selectivity; excellent corrosion resistance and low foaming property. These characteristics effectively reduce the solvent circulation amount, and have outstanding value in energy saving and process optimization. Tert-butyl amine ethoxy ethanol (TBEE) is a high-performance steric hindrance amine desulfurization solvent. The traditional process uses tert-butyl amine and 2-chloroethoxy ethanol as raw materials, which has the problems of serious equipment corrosion, high production cost and great environmental risk. In comparison, the route of synthesizing TBEE from diethylene glycol, a water hydration by-product of ethylene oxide, and tert-butyl amine has the significant advantages of high efficiency, cleanness and greenness. However, this route is currently less studied, and the yield of the target product is not ideal. Therefore, developing an efficient catalyst system to improve the reaction yield has important application value for promoting the industrialization of the process. SUMMARY

[0003] The purpose of the present application is to provide a cheap and efficient nano nickel-based catalyst and the application of the catalyst in catalyzing diethylene glycol to prepare tert-butyl amine ethoxy ethanol. The efficient nickel-based catalyst of the present application shows high activity and high selectivity in catalyzing diethylene glycol conversion, which is different from traditional catalysts.

[0004] To achieve the above-mentioned purpose, the present application adopts the following technical solutions: 1. Preparation of a nano nickel-based catalyst (a) mixing a nano metal oxide carrier MO, a nickel salt, an additive salt, water and an ammonia source under the condition of 50-150℃ for 5-48 hours to form a catalyst precursor by the ammonia evaporation method; (b) filtering, washing and drying the product obtained in step (a); (c) directly reducing the dried precursor in a hydrogen atmosphere at 250-550℃ for 2-6 hours to obtain a nano nickel-based catalyst; The nano metal oxide carrier MO is selected from at least one of molybdenum oxide, aluminum oxide, rhenium oxide, silicon oxide, zirconium oxide, tin oxide, zinc oxide and lanthanide metal oxide; The nickel salt is selected from at least one of nitrate, sulfate, acetate, oxalate, chloride and bromide of nickel; The assistant salt is selected from at least one of nitrate, acetate or oxalate of iron, cobalt, titanium, silver, copper, zirconium, vanadium, yttrium, lanthanide metal and alkaline earth metal; The ammonia source is selected from at least one of ammonia water, ammonium carbonate, ammonium bicarbonate, urea and liquid ammonia, and the molar ratio of ammonia in the ammonia source to the metal in the nickel salt and the assistant salt is (0.5-10):1.

[0005] Preferably, the nano metal oxide carrier MO is at least one of tin oxide, zirconium oxide, aluminum oxide or silicon oxide.

[0006] Preferably, the nickel salt is at least one of nickel nitrate, nickel acetate or nickel chloride.

[0007] Preferably, the assistant salt is nitrate of iron, cobalt, holmium, silver or zirconium.

[0008] Preferably, the ammonia source is ammonia water or urea.

[0009] 2. Application of the nano nickel-based catalyst The catalytic reaction of diethylene glycol and tert-butylamine to prepare tert-butylamine ethoxyl ethanol: The reaction is carried out in a batch kettle reactor, and the reaction conditions include: The hydrogen pressure is 0.1-4 MPa; The reaction temperature is 120-200℃; The reaction system is a solvent-free system or a solvent-containing system, and the solvent is selected from at least one of toluene, water, 1,4-dioxane and tetrahydrofuran.

[0010] Preferably, the reaction temperature is 140-180℃, the hydrogen pressure is 1-4 MPa, and the reaction system is a solvent-free system.

[0011] The nano nickel-based catalyst has the characteristics of high activity and high selectivity in preparing tert-butylamine ethoxyl ethanol, can utilize the interface electron interaction between nickel, assistant metal and carrier, promote the selective adsorption of -OH in diethylene glycol by regulating the electron distribution of nickel, and obtain high-selectivity tert-butylamine ethoxyl ethanol.

[0012] The present application has the following advantages compared with the prior art: 1. The application builds the interface interaction between nickel, additives and carriers through the ammonia evaporation method, regulates the electronic distribution of nickel, and solves the problems of poor selectivity of tert-butyl amine ethoxy ethanol, unstable catalyst and the like in the prior art. 2. The application realizes efficient preparation of tert-butyl amine ethoxy ethanol under relatively mild and environmentally friendly conditions, reduces the generation cost, and further promotes the recovery of carbon dioxide and the application of natural gas, and promotes carbon neutralization. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 TPR-MS hydrogen consumption spectrum of the Ni / Fe / SnO2 catalyst prepared in Example 1 of the application.

[0014] Figure 2 TPR-MS water generation spectrum of the Ni / Fe / SnO2 catalyst prepared in Example 1 of the application.

[0015] Figure 3 TPR-MS ammonia generation spectrum of the Ni / Fe / SnO2 catalyst prepared in Example 1 of the application.

[0016] Figure 4 XPS spectrum of the Ni / Fe / SnO2 catalyst prepared in Example 1 of the application and the Ni / Fe / SnO2 catalyst prepared in Comparative Example 3.

[0017] Figure 5 Circulation and reuse results of the Ni / Co / Al2O3 catalyst prepared in Example 4 of the application. DETAILED DESCRIPTION

[0018] The application will be further described in detail through specific examples, but the protection scope of the application is not limited to these examples. The experimental methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used in the examples can be obtained from commercial channels unless otherwise specified.

[0019] Example 1 Preparation of the Ni / Fe / SnO2 catalyst: 10g of Ni(NO3)2·6H2O and 1.5g of Fe(NO3)3·9H2O were dissolved in 150ml of deionized water under vigorous stirring, and stirring was continued for 1h, 10g of SnO2 powder was added to the above solution, and stirring was continued for 1h, 40ml of ammonia water was slowly added to the above solution, and stirring was continued at room temperature for 1h, and then the solution was refluxed at 100℃ until the PH of the solution was less than 7, and then it was filtered, washed with water, and dried, and then reduced in hydrogen at 350℃ for 4h to obtain the Ni / Fe / SnO2 catalyst.

[0020] TPR-MS characterization (see Figure 1 , 2and 3) the decomposition of the prepared Ni / Fe / SnO2 catalyst precursor and the reduction of the metal are carried out simultaneously, the interface electronic interaction between the promoter and nickel is improved, the electronic distribution of the active site nickel is adjusted, nickel forms smaller nanoparticles, the number of active sites of the catalyst is increased, and a high-activity catalyst is obtained. Figure 4 The XPS spectrum of Ni can be seen from the figure, and the diffraction peak of the nickel of the Ni / Fe / SnO2 catalyst prepared by the ammonia evaporation method is obviously shifted. The main reason is that the nickel forms a strong interface interaction with the promoter and the carrier, the electronic distribution of the nickel is changed, and then the generation of the target product is facilitated.

[0021] Example 2 Preparation of Ni / Ho / ZrO2 catalyst: 20 grams of Ni(NO3)2·6H2O and 1.0 grams of Ho(NO3)3·6H2O were dissolved in 150 ml of deionized water, and stirring was continued for 1 hour. 10 grams of ZrO2 powder were added to the above solution, and stirring was continued for 1 hour. 30 grams of ammonium carbonate were added to the above solution, and stirring was continued at room temperature for 1 hour. The temperature was increased to 100°C and refluxed until the solution PH was less than 7. Filtration, water washing, and drying were carried out, and then reduction was carried out in hydrogen at 450°C for 3h to obtain the Ni / Ho / ZrO2 catalyst.

[0022] Example 3 Preparation of Ni / Ag / SiO2 catalyst: 20 grams of Ni(CH3COO)2·6H2O and 1.0 grams of AgNO3 were dissolved in 150 ml of deionized water, and stirring was continued for 1 hour. 10 grams of SiO2 powder were added to the above solution, and stirring was continued for 1 hour. 30 ml of ammonia water was slowly added to the above solution, and stirring was continued at room temperature for 1 hour. The temperature was increased to 100°C and refluxed until the solution PH was less than 7. Filtration, water washing, and drying were carried out, and then reduction was carried out in hydrogen at 450°C for 3h to obtain the Ni / Ag / SiO2 catalyst.

[0023] Example 4 Preparation of Ni / Co / Al2O3 catalyst: 10 grams of NiCl2·6H2O and 2.0 grams of CoSO4·7H2O were dissolved in 150 ml of deionized water under vigorous stirring, and stirring was continued for 1 hour. 10 grams of Al2O3 powder were added to the above solution, and stirring was continued for 1 hour. 20 grams of urea were added to the above solution, and stirring was continued at room temperature for 1 hour. The temperature was increased to 100°C and refluxed until the solution PH was less than 7. Filtration, water washing, and drying were carried out, and then reduction was carried out in hydrogen at 450°C for 3h to obtain the Ni / Co / Al2O3 catalyst.

[0024] Example 5 Preparation of Ni / Zr / CeO2 catalyst: 10 g of NiCl2-6H2O and 2.0 g of Zr(NO3)2-5H2O were dissolved in 150 ml of deionized water under vigorous stirring, and stirring was continued for 1 h. 10 g of CeO2 powder was added to the above solution, and stirring was continued for 1 h. 20 g of ammonium bicarbonate was added to the above solution, and stirring was continued for 1 h at room temperature. The solution was heated to reflux at 100°C until the pH of the solution was less than 7. The solution was filtered, washed with water, and dried. The dried product was reduced in hydrogen at 450°C for 3 h to obtain the Ni / Zr / CeO2 catalyst.

[0025] Example 6 The Ni / Fe / SnO2 catalyst prepared in Example 1 was used in the reaction of diethylene glycol and t-butylamine to prepare t-butylaminoethoxyethanol. The reaction was carried out as follows: In a 100 ml stainless steel autoclave, 0.25 g of catalyst, 20 g of diethylene glycol, and 20 g of t-butylamine were added. The autoclave was closed, and the gas in the autoclave was replaced with inert gas or hydrogen. Hydrogen was charged at 4 MPa at room temperature. The autoclave was heated to 160°C, and the reaction was started. After 12 h of reaction, the autoclave was cooled, and the liquid product was separated and analyzed by gas chromatography. The conversion of diethylene glycol was 77%, and the selectivity of t-butylaminoethoxyethanol was 89%.

[0026] Example 7 The Ni / Fe / SnO2 catalyst prepared in Example 1 was used in the reaction of diethylene glycol and t-butylamine to prepare t-butylaminoethoxyethanol. The reaction was carried out as follows: In a 100 ml stainless steel autoclave, 0.25 g of catalyst, 10 g of diethylene glycol, 8 g of t-butylamine, and 20 g of 1,4-dioxane were added. The autoclave was closed, and the gas in the autoclave was replaced with hydrogen five times. Hydrogen was charged at 0.1 MPa at room temperature. The autoclave was heated to 100°C, and the reaction was started. After 10 h of reaction, the autoclave was cooled in an ice water bath. The hydrogen was released, and the liquid was separated by centrifugation and analyzed by gas chromatography. The conversion of diethylene glycol was 75%, and the selectivity of t-butylaminoethoxyethanol was 90%.

[0027] Example 8 The Ni / Ho / ZrO2 catalyst prepared in Example 2 was used in the reaction of diethylene glycol and t-butylamine to prepare t-butylaminoethoxyethanol. The reaction was carried out as follows: In a 100 ml stainless steel autoclave, 0.5 g of catalyst, 10 g of diethylene glycol, 8 g of t-butylamine, and 20 g of water were added. The autoclave was closed, and the gas in the autoclave was replaced with hydrogen five times. Hydrogen was charged at 1 MPa at room temperature. The autoclave was heated to 180°C, and the reaction was started. After 10 h of reaction, the autoclave was cooled in an ice water bath. The hydrogen was released, and the liquid was separated by centrifugation and analyzed by gas chromatography. The conversion of diethylene glycol was 55%, and the selectivity of t-butylaminoethoxyethanol was 88%.

[0028] Example 9 The Ni / Co / Al203 catalyst prepared in Example 4 was used in the reaction of diethylene glycol and t-butylamine to prepare t-butylaminoethoxyethanol. The detailed reaction procedure was as follows: In a 100 mL stainless steel autoclave, 0.5 g catalyst, 20 g diethylene glycol and 15 g t-butylamine were added. The autoclave was closed and the gas in the autoclave was replaced with hydrogen five times. Before the reaction, 3 MPa hydrogen was charged at room temperature. The autoclave was heated to 140 °C and the reaction was started. After 10 hours of reaction, the autoclave was cooled in an ice water bath. The hydrogen was released. After centrifugal separation, the liquid was analyzed by gas chromatography. The conversion of diethylene glycol was 62% and the selectivity of t-butylaminoethoxyethanol was 91%.

[0029] Example 10 The catalyst of Example 9 was recycled and used. The detailed results were as follows: Figure 5 . Figure 5 It can be seen that the catalyst can be used for 8 times without deactivation, indicating that the catalyst has very good stability.

[0030] Comparative Example 1 Preparation of traditional supported Ni / Fe / Sn02: 10 g of Ni(N03)2·6H20 and 1.5 g of Fe(N03)3·9H20 were dissolved in 150 ml of deionized water under vigorous stirring. The stirring was continued for 1 hour. 10 g of Sn02 powder was added to the above solution and the stirring was continued for 10 hours in a 60 °C water bath. The water was removed by rotary evaporation and the dried product was reduced in hydrogen at 350 °C for 4 h to obtain the supported Ni / Fe / Sn02 catalyst.

[0031] Comparative Example 2 The supported Ni / Fe / Sn02 catalyst prepared in Comparative Example 1 was used in the reaction of diethylene glycol and t-butylamine to prepare t-butylaminoethoxyethanol. The detailed reaction procedure was as follows: In a 100 mL stainless steel autoclave, 0.25 g catalyst, 20 g diethylene glycol and 20 g t-butylamine were added. The autoclave was closed and the gas in the autoclave was replaced with hydrogen five times. Before the reaction, 4 MPa hydrogen was charged at room temperature. The autoclave was heated to 160 °C and the reaction was started. After 12 hours of reaction, the autoclave was cooled in an ice water bath. The hydrogen was released. After centrifugal separation, the liquid was analyzed by gas chromatography. The conversion of diethylene glycol was 73% and the selectivity of t-butylaminoethoxyethanol was 65%.

[0032] Comparative Example 3 Preparation of NaOH precipitated Ni / Fe / SnO2: 10 g of Ni(NO3)2·6H2O and 1.5 g of Fe(NO3)3·9H2O were dissolved in 150 ml of deionized water under vigorous stirring, and stirring was continued for 1 hour. 10 g of SnO2 powder was added to the above solution, and stirring was continued for 1 hour. 5 mol / L sodium hydroxide solution was slowly added to the above solution until the solution pH was 12, and stirring was continued for 5 hours. After filtration, water washing, and drying, the NaOH precipitated Ni / Fe / SnO2 catalyst was reduced in hydrogen at 350°C for 4 hours.

[0033] Comparative Example 4 The NaOH precipitated Ni / Fe / SnO2 catalyst prepared in Comparative Example 3 was used in the reaction of diethylene glycol and tert-butylamine to prepare tert-butylamine ethoxy ethanol. The specific reaction method was as follows: In a 100 mL stainless steel reaction kettle, 0.25 g of catalyst, 20 g of diethylene glycol, and 20 g of tert-butylamine were added, and the reaction kettle was closed. The gas in the kettle was replaced with hydrogen five times, and 4 MPa of hydrogen was charged at room temperature before the reaction. The reaction kettle was heated to 160°C, and the reaction was started. After 12 hours of reaction, the reaction kettle was cooled in an ice water bath, and the hydrogen was vented. After centrifugal separation, the liquid was analyzed in a gas chromatograph. The conversion rate of diethylene glycol was 71%, and the selectivity of tert-butylamine ethoxy ethanol was 63%.

[0034] From the comparison of Comparative Example 2, Comparative Example 4, and Example 6, the performance of the ammonia evaporation catalyst is much higher than that of the traditional catalyst. The reason is that the ammonia evaporation catalyst improves the interface electronic interaction between the additive and nickel, thereby adjusting the electronic distribution of the active site nickel, improving the selectivity of tert-butylamine ethoxy ethanol, and saving costs by directly reducing the precursor. At the same time, the nickel forms smaller nanoparticles, increasing the number of active sites of the catalyst, and obtaining a high-activity catalyst.

Claims

1. A method for preparing a nano-nickel-based catalyst, characterized in that, Includes the following steps: (a) At 50-150℃, the nano-metal oxide support MO, nickel salt, auxiliary salt, water and ammonia source are mixed and reacted for 5-48 hours to form a catalyst precursor by ammonia stripping. (b) Filter, wash and dry the product obtained in step (a); (c) The dried precursor was directly reduced in a hydrogen atmosphere at 250-550℃ for 2-6 hours to obtain a nano-nickel-based catalyst; The nano-metal oxide carrier MO is selected from at least one of molybdenum oxide, aluminum oxide, rhenium oxide, silicon oxide, zirconium oxide, tin oxide, zinc oxide, and lanthanide metal oxides. The nickel salt is selected from at least one of nickel nitrates, sulfates, acetates, oxalates, chlorides, and bromides; The auxiliary salt is selected from at least one of the nitrates, acetates or oxalates of iron, cobalt, titanium, silver, copper, zirconium, vanadium, yttrium, lanthanides and alkaline earth metals; The ammonia source is selected from at least one of ammonia water, ammonium carbonate, ammonium bicarbonate, urea, and liquid ammonia, and the molar ratio of ammonia in the ammonia source to the metal in the nickel salt and auxiliary salt is (0.5-10):

1.

2. The preparation method according to claim 1, characterized in that: The nano-metal oxide carrier MO is preferably at least one of tin oxide, zirconium oxide, aluminum oxide, or silicon oxide.

3. The preparation method according to claim 1, characterized in that: The nickel salt is preferably at least one of nickel nitrate, nickel acetate, or nickel chloride.

4. The preparation method according to claim 1, characterized in that: The auxiliary salt is preferably a nitrate of iron, cobalt, holmium, silver, or zirconium.

5. The preparation method according to claim 1, characterized in that: The ammonia source is ammonia water or urea.

6. The application of a nano-nickel-based catalyst prepared by the method of any one of claims 1-5 in the catalytic reaction of diethylene glycol with tert-butylamine to prepare tert-butylamine ethoxyethanol.

7. The application according to claim 6, characterized in that: The reaction was carried out in a batch reactor under the following conditions: Hydrogen pressure: 0.1-4 MPa; Reaction temperature 120-200℃; The reaction system is a solvent-free system or a solvent-containing system, wherein the solvent is selected from at least one of toluene, water, 1,4-dioxane, and tetrahydrofuran.

8. The application according to claim 7, characterized in that: The reaction temperature is 140-180℃, the hydrogen pressure is 1-4 MPa, and the reaction system is a solvent-free system.

Images