High-efficiency green synthesis method of alkylol amine and catalyst
By designing a bifunctional catalyst of zinc chloride supported on Hβ molecular sieve, the side reaction and waste liquid problems caused by traditional catalysts were solved, and the synthesis of alcoholamines with high selectivity and high yield was achieved, simplifying the process and reducing production costs.
Patent Information
- Application Number
- CN202511003546.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-21
- Publication Date
- 2025-11-07
AI Technical Summary
The existing process for synthesizing monoethanol diisopropanolamine suffers from problems such as side reactions easily caused by traditional alkaline catalysts, low product selectivity, complex post-treatment, and high salt content in waste liquid.
A bifunctional catalyst of zinc chloride supported on Hβ molecular sieve was used to synthesize diisopropanolamine of monoethanol via a multi-step catalytic condensation reaction. The solid acid provided Brønsted acid sites to promote the ring opening of propylene oxide, and the supported ZnCl2 acted as a Lewis acid to regulate the directional addition of amino groups. The pore structure of Hβ molecular sieve was combined to suppress side reactions.
The selectivity of monoethanol diisopropanolamine was increased to over 97%, saline wastewater discharge was reduced, the catalyst can be recycled more than 10 times, the reaction steps were simplified, and the product yield and purity were improved.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of organic synthesis, and relates to a Hbeta molecular sieve loaded zinc chloride bifunctional catalyst and a high-efficiency green synthesis method of an alcohol amine, in particular to a preparation process of ethanol diisopropanolamine (EDIPA), and especially to a method for efficiently synthesizing EDIPA by a multi-step catalytic condensation reaction using the Hbeta molecular sieve loaded zinc chloride bifunctional catalyst. BACKGROUND
[0002] Ethanol diisopropanolamine (EDIPA) is an alcohol amine compound containing one ethanol group and two isopropanolamine groups, and the structure is shown as formula I.
[0003]
[0004] Ethanol diisopropanolamine has dual reactivity of amino and hydroxyl groups, and has good emulsifying, dispersing, corrosion inhibiting and pH adjusting capabilities. EDIPA can be widely applied to metal degreasing agents, cutting fluids, rust inhibitors, oil field chemicals, corrosion inhibitors, gas desulfurization, cement grinding aids, water-based paint dispersants and the like. The soap compound generated by the reaction of EDIPA and fatty acid can effectively remove oil and oxides on the surface of metal, and is suitable for alkaline cleaning agents for automobile parts and machined parts. The corrosion resistance of EDIPA can protect the surface of tools and workpieces, and at the same time, the lubricity can reduce friction heat and prolong tool life. The adsorption film formed by the complex of EDIPA, boric acid and organic acid can inhibit the electrochemical corrosion of metal in a humid environment; the amide surfactant generated by the reaction of EDIPA and carboxylic acid can reduce the oil-water interfacial tension and improve the tertiary oil recovery efficiency. In a CO2 / H2S acidic environment, EDIPA can form a protective film on the surface of metal by adsorption, thereby inhibiting pipeline corrosion (corrosion efficiency ≥ 85%). In the natural gas desulfurization process, EDIPA can react with H2S to generate reversible sulfide, thereby reducing equipment corrosion. EDIPA can reduce the grinding energy consumption and improve the early strength of cement by adsorbing on the surface of cement particles (can reduce the power consumption by 10-15%). In water-based latex paint, the amino group of EDIPA can bind to the surface of pigment particles to prevent agglomeration, thereby improving the gloss and uniformity of the coating. The complex of EDIPA and organophosphorus pesticides can improve the stability of emulsion formulations and reduce the delamination phenomenon. EDIPA can promote the wetting and absorption of fertilizers or pesticides on the surface of plant leaves, thereby increasing the utilization rate by more than 20%.
[0005] At present, there are mainly two synthesis routes for ethanol diisopropanolamine:
[0006] 1. Diisopropanolamine reacts with ethylene oxide to generate ethanol diisopropanolamine, but the price of diisopropanolamine is relatively high, which leads to an increase in the production cost of the product, and the content of ethanol diisopropanolamine in the synthesized product is less than 85%.
[0007] 2, Monoethanolamine and epoxy propane reaction to generate a monoethanolamine diisopropanolamine, the process production cost is lower, process route is simple, product yield is higher. At present, the domestic industrialization device all uses this process, but still has following problems:
[0008] (1), the traditional basic catalyst (such as NaOH) is easy to cause side reaction, and the selectivity of product is low;(2), the post-processing is complex, and multiple neutralization, distillation, waste liquid salt content is high.(3), the side reaction is inhibited by using polymerization inhibitor, and the post-processing is complex, and the production cost is increased. SUMMARY
[0009] The purpose of the present application is to solve the problems in the synthesis process of monoethanolamine diisopropanolamine, provide a bifunctional supported catalyst, and a method for efficiently synthesizing EDIPA by multi-step catalytic condensation reaction using the bifunctional supported catalyst.
[0010] A kind of bifunctional supported catalyst, it is with the pretreatment Hβ molecular sieve as carrier, with ZnCl2 (zinc chloride) as active component, ZnCl2 is loaded on Hβ molecular sieve by impregnation method to prepare Hβ molecular sieve supported zinc chloride bifunctional catalyst.
[0011] In order to further improve the adsorption capacity and dispersion capacity of the carrier to the active component, the SiO2 / Al2O3 molar ratio of the Hβ molecular sieve is 25-30, and the specific surface area is greater than or equal to 500m 2 / g.
[0012] The pretreatment of the Hβ molecular sieve includes dilute acid soaking and calcination.
[0013] The dilute acid is one or more of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, and the concentration of dilute acid is 0.5-1.5mol / L.
[0014] The solid-liquid ratio of the Hβ molecular sieve and dilute acid is 1:5-1:15g / mL.
[0015] The dilute acid soaking temperature is 60-100℃, the dilute acid soaking time is 4-8 hours, and the dilute acid soaking is carried out under stirring.
[0016] The present application pretreats the molecular sieve Hβ molecular sieve with dilute acid, further improves the adsorption capacity of Hβ molecular sieve.
[0017] The calcination temperature is 200-350℃, and the calcination time is 3-10 hours.
[0018] In the bifunctional catalyst, the loading amount of ZnCl2 is 3.5-15wt%.
[0019] A preparation method of the bifunctional catalyst, comprising:
[0020] Step (1), carrier pretreatment: the Hβ molecular sieve carrier is soaked in dilute acid, stirred at 60-100℃ for 4-8 hours, solid-liquid separation, washed with deionized water until neutral, dried at 100-130℃ for 8-14 hours, calcined at 200-350℃ for 3-10 hours, and cooled;
[0021] Step (2), active component impregnation: the pretreated Hβ molecular sieve is immersed in a ZnCl2 alcohol solution at room temperature for 10-24 hours, and the alcohol solution is recovered under reduced pressure;
[0022] Step (3), drying and calcination: the impregnated material is dried at 100-120℃ for 6-15 hours, and then calcined at 300-450℃ for 4-10 hours under nitrogen protection in a tube furnace to obtain a bifunctional catalyst.
[0023] In step (1), the drying is carried out in an oven.
[0024] The calcination is carried out in a muffle furnace.
[0025] Preferably, the calcination is carried out at a temperature rising rate of 2-5℃ / min from room temperature to 200-350℃, and calcined at 200-350℃ for 3-10 hours.
[0026] In step (2), in order to avoid hydrolysis of the active component ZnCl2, preferably, the ZnCl2 alcohol solution is prepared by using anhydrous alcohol solvent, and the anhydrous alcohol solvent is one or more of anhydrous methanol, anhydrous ethanol or anhydrous isopropyl alcohol.
[0027] The concentration of the ZnCl2 alcohol solution is 3.5%-15%, preferably 3.5%-12%.
[0028] The alcohol solution is recovered under reduced pressure by using a rotary evaporator.
[0029] The alcohol solution is recovered under reduced pressure at 60℃ and -0.08MPa.
[0030] The end point of the alcohol solution recovered under reduced pressure is that the solid is in a semi-dry state.
[0031] In step (3), the drying is carried out in an oven.
[0032] Preferably, the calcination is carried out in a tube furnace under nitrogen protection at a temperature rising rate of 2-5℃ / min from room temperature to 300-450℃, and calcined at 300-450℃ for 4-10 hours.
[0033] Another object of the present application is to provide an efficient and green synthesis method of alcohol amine, comprising the following steps:
[0034] Step (1), under nitrogen protection, ethanolamine and the bifunctional supported catalyst are added into a reaction device, and the temperature is increased to 40-50°C under stirring;
[0035] The propylene oxide (PO) is pressurized from a storage tank into the reaction device using nitrogen by positive pressure method, and 45-55% of the total amount of PO is slowly added dropwise. After the dropwise addition is completed, the reaction temperature is controlled at 45-55°C, the reaction pressure is 0.4-0.55 MPa, and the reaction is kept for 1-2 h. Then the remaining PO is slowly added dropwise, the reaction temperature is increased to 70-75°C, the reaction pressure is 0.4-0.55 MPa, and the reaction is kept for 2-4 h.
[0036] Step (2), after the reaction is completed, the temperature is cooled to 60°C, and the unreacted PO is removed under vacuum. The reaction device is opened, and the catalyst is recovered by filtration. The crude product is subjected to vacuum distillation at -0.09 MPa, and the fraction collected at 180-190°C is monoethanol diisopropanolamine.
[0037] In step (1), the reaction device can be a high-pressure reaction kettle.
[0038] Preferably, the gas in the reaction device is replaced with nitrogen using nitrogen.
[0039] The stirring speed is 300-500 rpm.
[0040] In order to improve the yield and purity of monoethanol diisopropanolamine, preferably, the molar ratio of ethanolamine to propylene oxide is 1:2-1:2.2.
[0041] In order to reduce the generation of by-products, preferably, the first dropwise addition speed of propylene oxide is 1-2 mL / min, and the second dropwise addition speed of propylene oxide is 0.5-1.0 mL / min.
[0042] In order to improve the conversion rate of ethanolamine and the selectivity of monoethanol diisopropanolamine, preferably, the addition amount of the bifunctional supported catalyst is 1-5% wt of the total amount of ethanolamine.
[0043] In step (2), preferably, after the reaction is completed, the temperature of the reaction device is cooled to 60°C, and the unreacted PO is removed under vacuum at -0.085 to -0.09 MPa.
[0044] The innovation points of the present application are as follows: (1) a bifunctional catalyst is used, solid acid provides a Bronsted acid site to promote the ring opening of propylene oxide; (2) the supported ZnCl2 acts as a Lewis acid to regulate the directional addition of amine groups and inhibit side reactions, and the selectivity is increased to more than 97%; (3) the catalyst can be recycled to replace traditional acid-base neutralization, reduce salt-containing wastewater discharge, and the catalyst can be used for more than 10 times; (4) the pore size of Hβ molecular sieve is between small-pore molecular sieve (such as erionite and chabazite) and medium-large-pore molecular sieve (such as Y type), and the molecular size and shape are used to inhibit unnecessary side reactions (such as the continuous reaction of product monoethanol diisopropanolamine and propylene oxide into an ether), and the selectivity of monoethanol diisopropanolamine is increased to more than 97%.
[0045] The beneficial effects of the present application are as follows:
[0046] The present application selects a bifunctional catalyst, solid acid provides a Bronsted acid site to promote the ring opening of propylene oxide; the supported ZnCl2 acts as a Lewis acid to regulate the directional addition of amine groups and inhibit side reactions, and the selectivity is increased to more than 97%.
[0047] The special pore structure of Hβ molecular sieve is used to inhibit unnecessary side reactions based on the molecular size and shape, and the selectivity of monoethanol diisopropanolamine is further increased to more than 97%;
[0048] The present application selects a supported catalyst which can be recycled to replace traditional acid-base neutralization, reduce salt-containing wastewater discharge, and the catalyst can be used for more than 10 times.
[0049] The present application has the advantages of short reaction time, simple reaction steps, high product yield and purity. DETAILED DESCRIPTION
[0050] The technical solutions of the present application will be described in detail below through specific examples, but the protection scope of the present application is not limited to the examples. The endpoints and any values of the disclosed ranges are not limited to the precise values or ranges stated, and these ranges should be interpreted as approximately between the endpoints and the individual points within the ranges. For numerical ranges, the endpoints between the individual ranges, the endpoints between the individual ranges and the individual points, and the individual points can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0051] Hβ molecular sieve (Beijing Huanye Universe Chemical Co., Ltd., industrial grade).
[0052] ZnCl2 (Araldine, analytical pure).
[0053] Methanol (Nanjing Chemical Reagent Co., Ltd., analytical pure).
[0054] Ethanol (Nanjing Chemical Reagent Co., Ltd., analytical pure).
[0055] Isopropyl alcohol (Nanjing Chemical Reagent Co., Ltd., analytical pure).
[0056] Nitrogen (Nanjing Ruier Special Gas Co., Ltd., purity 99.999%).
[0057] High-pressure reaction kettle (Weihai Chemical Machinery Factory, volume 500 mL).
[0058] Propylene oxide (Shandong Binzhou Chemical Co., Ltd., industrial grade).
[0059] Ethanolamine (Nanjing Hongbaoli Co., Ltd., industrial grade).
[0060] Product determination:
[0061] Agilent 6890A gas chromatograph was used for determination, chromatographic column: Agilent DB-1701 (30 m x 0.32 mm x 0.25 μm), product serial number 123-0732;
[0062] Carrier gas: He, constant flow mode, flow rate: 1.5 mL / min; Injection port: split mode, temperature 270℃, split ratio: 20:1, injection volume: 1.0 μL;
[0063] Liner: deactivated glass wool liner;
[0064] Column temperature program: 80℃ (hold for 2 min) → 15℃ / min → 250℃ (hold for 10 min);
[0065] Detector: FID, temperature: 280℃, He: 40 mL / min, Air: 400 mL / min, Makeup (N2): 30 mL / min;
[0066] Sample pretreatment: dissolved and diluted to 5 mg / mL with anhydrous methanol, and passed through a 0.45 μm organic filter membrane.
[0067] The calculation formula of the conversion rate (X 乙醇胺 ) of ethanolamine:
[0068]
[0069] The calculation formula of the selectivity (S 乙醇二异丙醇胺 ) of monoethanol diisopropanolamine:
[0070]
[0071] C 乙醇胺 : gas chromatographic analysis of the amount of ethanolamine in the product, %;
[0072] C 乙醇二异丙醇胺: Ethanol monoiso-propanolamine content in product, %;
[0073] C 乙醇单丙醇胺 : Ethanol monoiso-propanolamine content in product, %;
[0074] 61: Relative molecular mass of ethanolamine, g / mol;
[0075] 163: Relative molecular mass of monoethanol di-iso-propanolamine, g / mol;
[0076] 116: Relative molecular mass of ethanol mono-iso-propanolamine, g / mol;
[0077] Yield of monoethanol di-iso-propanolamine (Y 乙醇二异丙醇胺 ) calculation formula:
[0078]
[0079] m 乙醇二异丙醇胺 : Mass of product monoethanol di-iso-propanolamine, g;
[0080] m 乙醇胺 : Mass of raw material ethanolamine, g.
[0081] Example 1
[0082] A bifunctional catalyst (i.e., catalyst S-1) was prepared by the following method, comprising: carrier pretreatment: Hβ molecular sieve (SiO2 / Al2O3molar ratio 26, specific surface area 580 m 2 / g) was immersed in dilute hydrochloric acid with a concentration of 1.0 mol / L at a solid-liquid ratio of 1:10 g / mL, stirred at 80°C for 4 hours; solid-liquid separation was performed, the solid was washed with deionized water until neutral, dried in an oven at 120°C for 10 hours, and then placed in a muffle furnace, heated from room temperature to 300°C at a heating rate of 4°C / min, and calcined at 300°C for 5 hours and then cooled; 2 g of ZnCl2was weighed and dissolved in 20 g of anhydrous ethanol to prepare a ZnCl2ethanol solution, and 20 g of the pretreated Hβ molecular sieve was immersed in the ZnCl2ethanol solution at room temperature for 12 h, and the ethanol was recovered by a rotary evaporator at 60°C and -0.08 MPa until the solid was semi-dry, dried in an oven at 120°C for 10 hours, transferred to a muffle furnace, and heated from room temperature to 350°C at a heating rate of 4°C / min under nitrogen protection, and calcined at 350°C for 5 hours to obtain catalyst S-1.
[0083] The high-pressure reactor was replaced 2-3 times with nitrogen. The molar ratio of ethanolamine: propylene oxide was controlled at 1:2.05, and 122 g of ethanolamine and 4.88 g of catalyst S-1 were added to the high-pressure reactor under nitrogen protection. The reactor was heated to 45°C under stirring (stirring speed 500 rpm), and the propylene oxide tank was pressurized with nitrogen. The dropping speed of PO was controlled at 1.5 mL / min by a flow meter, and 118.9 g of PO was added dropwise to the high-pressure reactor. After the addition was completed, the reaction temperature was controlled at 50°C, the reaction pressure was 0.5 MPa, and the reactor was kept at this temperature for 1.5 h. Then, 118.9 g of PO was added dropwise at a dropping speed of 0.5 mL / min. After the addition was completed, the temperature of the reactor was increased to 75°C, the reaction pressure was 0.5 MPa, and the reactor was kept at this temperature for 3 h. The temperature of the reactor was cooled to 60°C, and the unreacted PO was removed under vacuum at -0.085 MPa. The reactor was opened, and the catalyst S-1 was recovered by filtration. The crude product obtained by filtration was subjected to vacuum distillation at -0.09 MPa, and the fraction collected at 187°C was monoethanol diisopropanolamine. The chromatographic analysis X 乙醇胺 was 98.68%, S 乙醇二异丙醇胺 was 97.54%, and Y 乙醇二异丙醇胺 was 95.52% with a purity of 99.67%.
[0084] The catalyst S-1 was reused 10 times under the same reaction conditions, and the chromatographic analysis X 乙醇胺 was 97.23%, S 乙醇二异丙醇胺 was 97.59%.
[0085] Example 2
[0086] A bifunctional catalyst (i.e., catalyst S-2) was prepared by the following method, which included: carrier pretreatment: Hβ zeolite (SiO2 / Al2O3 molar ratio 27, specific surface area 550 m 2 / g) was soaked in 0.5 mol / L dilute sulfuric acid at 90°C for 8 hours under stirring. The solid-liquid separation was performed, the solid was washed with deionized water until neutral, and was dried in an oven at 120°C for 12 hours. The dried solid was transferred to a muffle furnace, and was heated from room temperature to 350°C at a heating rate of 5°C / min. The catalyst was calcined at 350°C for 10 hours. 1 g of ZnCl2 was weighed, and was dissolved in 20 g of anhydrous methanol to prepare a ZnCl2 methanol solution. 20 g of the pretreated Hβ zeolite was immersed in the ZnCl2 methanol solution at room temperature for 12 h. The methanol was recovered by a rotary evaporator at 60°C and -0.08 MPa until the solid was semi-dry. The solid was dried in an oven at 120°C for 9 hours. The dried solid was transferred to a tube furnace, and was heated from room temperature to 400°C at a heating rate of 4°C / min under nitrogen protection. The catalyst was calcined at 400°C for 8 hours to obtain catalyst S-2.
[0087] The high-pressure reactor was replaced 2-3 times with nitrogen. The molar ratio of ethanolamine to propylene oxide was controlled at 1:2.1, and 122 g of ethanolamine and 3.66 g of catalyst S-2 were added to the high-pressure reactor under nitrogen protection while stirring (stirring speed 500 rpm) and the temperature was increased to 45°C from room temperature. The propylene oxide tank was pressurized with nitrogen, and 121.8 g of PO was added to the high-pressure reactor at a dropwise addition rate of 1 mL / min controlled by a flow meter. After the dropwise addition was completed, the reaction temperature was controlled at 50°C, the reaction pressure was 0.5 MPa, and the reaction was kept for 2 h. Then, 121.8 g of PO was added at a dropwise addition rate of 0.5 mL / min, after which the temperature of the reactor was increased to 70°C, the reaction pressure was 0.5 MPa, and the reaction was kept for 3 h. The temperature of the reactor was cooled to 60°C, and the unreacted PO was removed under vacuum at -0.085 MPa. The reactor was opened, and the catalyst S-2 was recovered by filtration. The crude product obtained by filtration was subjected to vacuum distillation at -0.09 MPa, and the fraction collected at 187°C was monoethanol diisopropanolamine. The chromatographic analysis X 乙醇胺 was 96.68%, S 乙醇二异丙醇胺 was 98.69%, and Y 乙醇二异丙醇胺 was 95.14% with a purity of 99.71%.
[0088] The catalyst S-2 was reused 10 times under the same reaction conditions, and the X 乙醇胺 was 96.01%, S 乙醇二异丙醇胺 was 98.59%.
[0089] Example 3
[0090] A bifunctional catalyst (i.e., catalyst S-3) was prepared by the following method, which included: carrier pretreatment: catalyst S-3 preparation: Hβ zeolite (SiO2 / Al2O3 molar ratio 27, specific surface area 600 m 2 / g) was soaked in 1.5 mol / L dilute hydrochloric acid at 90°C for 6 hours, and then solid-liquid separation was performed. The solid was washed with deionized water until it was neutral, and then dried in an oven at 120°C for 12 hours. The dried solid was transferred to a muffle furnace, and then heated from room temperature to 350°C at a heating rate of 4°C / min. The temperature was kept at 350°C for 9 hours. Then, 2.4 g of ZnCl2 was weighed and dissolved in 20 g of anhydrous ethanol to prepare a ZnCl2 ethanol solution. The pretreated Hβ zeolite was soaked in the ZnCl2 ethanol solution at room temperature for 10 h. The ethanol solution was recovered by rotary evaporation at 60°C and -0.08 MPa until the solid was semi-dry. The semi-dry solid was dried in an oven at 120°C for 8 hours, and then transferred to a tube furnace. The temperature was increased from room temperature to 350°C at a heating rate of 4°C / min under nitrogen protection, and then kept at 350°C for 9 hours to obtain the catalyst S-3.
[0091] The high-pressure reactor was replaced 2-3 times with nitrogen. The molar ratio of ethanolamine: propylene oxide was controlled at 1:2.2, and 122 g of ethanolamine and 4.88 g of catalyst S-3 were added to the high-pressure reactor under nitrogen protection while stirring (stirring speed 400 rpm) and the temperature was increased to 50°C. The propylene oxide tank was pressurized with nitrogen, and 127.6 g of PO was added to the high-pressure reactor at a flow rate of 2 mL / min controlled by a flow meter. After the addition was completed, the reaction temperature was controlled at 50°C, the reaction pressure was 0.5 MPa, and the reaction was maintained for 2 h. Then 127.6 g of PO was added at a flow rate of 1 mL / min, after the addition was completed, the temperature of the reactor was increased to 75°C, the reaction pressure was 0.5 MPa, and the reaction was maintained for 3 h. The temperature of the reactor was cooled to 60°C, and the unreacted PO was removed under vacuum at -0.085 MPa. The reactor was opened, and the catalyst S-3 was recovered by filtration. The crude product obtained by filtration was subjected to vacuum distillation at -0.09 MPa, and the fraction collected at 187°C was monoethanol diisopropanolamine. The purity of the product was determined by chromatographic analysis X 乙醇胺 was 97.43%, and the purity of the product after purification was Y 乙醇二异丙醇胺 was 97.43%, and the purity of the product after purification was Y 乙醇二异丙醇胺 was 95.48%, and the purity of the product was 99.61%.
[0092] The catalyst S-3 was reused 10 times under the same reaction conditions, and the purity of the product was X 乙醇胺 was 97.43%, and the purity of the product after purification was Y 乙醇二异丙醇胺 was 97.43%, and the purity of the product after purification was Y
[0093] Example 4
[0094] A bifunctional catalyst (i.e., catalyst S-4) was prepared by the following method, which included: carrier pretreatment: catalyst S-4 preparation: Hβ zeolite (SiO2 / Al2O3 molar ratio 25, specific surface area 500 m 2 / g) was soaked in 1.0 mol / L dilute hydrochloric acid at 90°C for 8 hours, and then solid-liquid separation was performed. The solid was washed with deionized water until it was neutral, and then dried in an oven at 120°C for 12 hours. The dried solid was transferred to a muffle furnace, and then heated from room temperature to 350°C at a rate of 4°C / min, and calcined at 350°C for 9 hours. Then 0.8 g of ZnCl2 was weighed, and dissolved in 20 g of anhydrous isopropanol to prepare a ZnCl2 isopropanol solution. 20 g of the pretreated Hβ zeolite was soaked in the ZnCl2 isopropanol solution at room temperature for 10 hours. The isopropanol was recovered by rotary evaporation at 60°C and -0.08 MPa until the solid was semi-dry. The soaked material was dried in an oven at 120°C for 8 hours, and then transferred to a tube furnace. The temperature was increased from room temperature to 380°C at a rate of 5°C / min under nitrogen protection, and then calcined at 380°C for 9 hours to obtain the catalyst S-4.
[0095] The high-pressure reactor was replaced 2-3 times with nitrogen. The molar ratio of ethanolamine: propylene oxide was controlled at 1:2.0, and 122 g of ethanolamine and 6.1 g of catalyst S-4 were added to the high-pressure reactor under nitrogen protection while stirring (stirring speed 400 rpm) and the temperature was increased from room temperature to 50°C. The propylene oxide tank was pressurized with nitrogen, and 127.6 g of PO was added dropwise to the high-pressure reactor at a flow rate of 2 mL / min controlled by a flow meter. After the dropwise addition was completed, the reaction temperature was controlled at 50°C, the reaction pressure was 0.5 MPa, and the reaction was maintained for 2 h. Then 127.6 g of PO was added dropwise at a flow rate of 1 mL / min, after the dropwise addition was completed, the temperature of the reactor was increased to 75°C, the reaction pressure was 0.5 MPa, and the reaction was maintained for 3 h. The temperature of the reactor was cooled to 60°C, and the unreacted PO was removed under vacuum at -0.085 MPa. The reactor was opened, and the catalyst S-4 was recovered by filtration. The crude product obtained by filtration was distilled under reduced pressure at -0.09 MPa, and the fraction collected at 187°C was monoethanol diisopropanolamine. The chromatographic analysis X 乙醇胺 was 96.21%, S 乙醇二异丙醇胺 was 98.58%, and Y 乙醇二异丙醇胺 was 93.67% with a purity of 99.78%.
[0096] The catalyst S-4 was reused 10 times under the same reaction conditions, and the X 乙醇胺 was 96.66%, S 乙醇二异丙醇胺 was 98.52%.
[0097] Example 5
[0098] A bifunctional catalyst (i.e., catalyst S-5) was prepared by the following method, which included: carrier pretreatment: catalyst S-5 preparation: Hβ molecular sieve (SiO2 / Al2O3 molar ratio 26, specific surface area 600 m 2 / g) carrier was soaked in 1.0 mol / L dilute sulfuric acid at 100°C for 5 hours; solid-liquid separation was performed, the solid was washed with deionized water until neutral, and was dried in an oven at 110°C for 10 hours, was transferred to a muffle furnace, and was heated from room temperature to 250°C at a heating rate of 3.5°C / min, and was calcined at 250°C for 5 hours; 1.6 g of ZnCl2 was weighed, and was prepared into a ZnCl2 isopropanol solution using 20 g of anhydrous isopropanol; 20 g of the pretreated Hβ molecular sieve was immersed in the above ZnCl2 isopropanol solution at room temperature for 24 h; a rotary evaporator was used to recover the isopropanol under the conditions of 60°C and -0.08 MPa; the immersed material was dried in an oven at 120°C for 15 hours; was transferred to a tube furnace, and was heated from room temperature to 400°C at a heating rate of 4°C / min under nitrogen protection, and was calcined at 400°C for 10 hours to obtain the catalyst S-5.
[0099] The high-pressure reactor was replaced 2-3 times with nitrogen. The molar ratio of ethanolamine: propylene oxide was controlled at 1:2.05, and 122 g of ethanolamine and 2.44 g of catalyst S-5 were added to the high-pressure reactor under nitrogen protection while stirring (stirring speed 450 rpm) and heating from room temperature to 50°C. The propylene oxide tank was pressurized with nitrogen, and 118.9 g of PO was added to the high-pressure reactor at a flow rate of 1.5 mL / min controlled by a flow meter. After the addition was completed, the reaction temperature was controlled at 50°C, the reaction pressure was 0.45 MPa, and the reaction was maintained for 1.5 h. Then, the remaining 118.9 g of PO was added at a flow rate of 0.8 mL / min, after which the temperature of the reactor was increased to 75°C, the reaction pressure was 0.5 MPa, and the reaction was maintained for 3.5 h. The temperature of the reactor was cooled to 60°C, and the unreacted PO was removed under vacuum at -0.085 MPa. The catalyst S-5 was recovered by opening the reactor. The crude product obtained by filtration was subjected to vacuum distillation at -0.09 MPa to collect the fraction at 187°C, which was ethanol diisopropanolamine. The chromatographic analysis X 乙醇胺 was 97.28%, S 乙醇二异丙醇胺 was 97.88%, and Y 乙醇二异丙醇胺 was 93.24% with a purity of 99.89%.
[0100] The catalyst S-5 was reused 10 times under the same reaction conditions, and the X 乙醇胺 was 96.04%, S 乙醇二异丙醇胺 was 97.34%.
[0101] Example 6
[0102] A bifunctional catalyst (i.e., catalyst S-6) was prepared by the following method, which included: carrier pretreatment: catalyst S-6 preparation: Hβ zeolite (SiO2 / Al2O3 molar ratio 25, specific surface area 580 m 2 / g) was soaked in 0.5 mol / L dilute nitric acid at 100°C for 4 hours with stirring. The solid-liquid separation was performed, the solid was washed with deionized water until it was neutral, and was dried in an oven at 100°C for 14 hours. It was then transferred to a muffle furnace and heated from room temperature to 300°C at a rate of 2°C / min, and calcined at 300°C for 8.5 hours. 2 g of ZnCl2 was weighed and dissolved in 20 g of anhydrous ethanol to prepare an ethanol solution. 20 g of the pretreated Hβ zeolite was immersed in the ZnCl2 ethanol solution at room temperature for 20 h. An rotary evaporator was used to recover the ethanol under the conditions of 60°C and -0.08 MPa until the solid was semi-dry. The immersed material was dried in an oven at 110°C for 10 hours, and then transferred to a tube furnace and heated from room temperature to 450°C at a rate of 4°C / min under nitrogen protection, and calcined at 450°C for 8 hours to obtain the catalyst S-6.
[0103] The high-pressure reactor was replaced 2-3 times with nitrogen. The molar ratio of ethanolamine: propylene oxide was controlled to be 1:2.05, and 122 g of ethanolamine and 4.88 g of catalyst S-6 were added to the high-pressure reactor under nitrogen protection while stirring (stirring speed 400 rpm) and heating from room temperature to 50°C. The propylene oxide tank was pressurized with nitrogen, and 118.9 g of PO was added dropwise to the high-pressure reactor at a flow rate of 1.5 mL / min controlled by a flow meter. After the dropwise addition was completed, the reaction temperature was controlled at 50°C, the reaction pressure was 0.45 MPa, and the reaction was maintained for 1.5 h. Then, 118.9 g of PO was added dropwise at a flow rate of 0.8 mL / min, and after the dropwise addition was completed, the temperature of the reactor was increased to 75°C and the reaction pressure was 0.5 MPa. The reaction was maintained for 3.5 h. The temperature of the reactor was cooled to 60°C, and the unreacted PO was removed under vacuum at -0.085 MPa. The reactor was opened, and the catalyst S-6 was recovered by filtration. The crude product obtained by filtration was subjected to vacuum distillation at -0.09 MPa, and the fraction collected at 187°C was monoethanol diisopropanolamine. The chromatographic analysis X 乙醇胺 was 98.16%, S 乙醇二异丙醇胺 was 98.38%, and Y 乙醇二异丙醇胺 was 95.89% with a purity of 99.69%.
[0104] The catalyst S-6 was reused 10 times under the same reaction conditions, and the chromatographic analysis X 乙醇胺 was 97.89%, S 乙醇二异丙醇胺 was 97.02%.
[0105] Comparative Example 1
[0106] Hβ zeolite with a specific surface area of 450 m 2 / g was used instead of the Hβ zeolite in Example 1, and the other preparation conditions of the catalyst and the preparation conditions of monoethanol diisopropanolamine were consistent with those of Example 1, and the chromatographic analysis X 乙醇胺 was 92.18%, S 乙醇二异丙醇胺 was 97.27%, and Y 乙醇二异丙醇胺 was 88.42% with a purity of 99.01%.
[0107] The catalyst was reused 10 times under the same reaction conditions, and the chromatographic analysis X 乙醇胺 was 90.15%, S 乙醇二异丙醇胺 was 97.68%.
[0108] Comparative Example 2
[0109] 2.4 g of ZnCl2 was weighed and dissolved in 20 g of water to prepare a ZnCl2 aqueous solution. The ZnCl2 ethanol solution in Example 3 was replaced with the ZnCl2 aqueous solution, and the other preparation conditions of the catalyst and the preparation conditions of monoethanol diisopropanolamine were consistent with those of Example 3.乙醇胺 89.24%, S 乙醇二异丙醇胺 97.11%, Y 乙醇二异丙醇胺 86.13%, 99.21% purity.
[0110] 10 times, X 乙醇胺 86.27%, S 乙醇二异丙醇胺 97.22%.
[0111] Comparative Example 3
[0112] The catalyst S-4 was used, except that 255.2 g of propylene oxide was added dropwise at a rate of 1 mL / min in one portion. The other preparation conditions of the catalyst and the preparation conditions of the monoethanol diisopropanolamine were the same as in Example 4. X 乙醇胺 95.98%, S 乙醇二异丙醇胺 88.45%, Y 乙醇二异丙醇胺 83.18%, 98.27% purity.
[0113] Comparative Example 4
[0114] The catalyst Y was used instead of the Hβ molecular sieve in Example 4. The other preparation conditions of the catalyst and the preparation conditions of the monoethanol diisopropanolamine were the same as in Example 4. X 乙醇胺 89.14%, S 乙醇二异丙醇胺 93.33%, Y 乙醇二异丙醇胺 81.68%, 98.31% purity.
[0115] Comparative Example 5
[0116] The high-pressure reactor was replaced with nitrogen for 2-3 times. The molar ratio of ethanolamine to propylene oxide was controlled to be 1:2.05. 122 g of ethanolamine and 1.22 g of solid NaOH (catalyst) were added into the high-pressure reactor under nitrogen protection. The stirring speed was 400 rpm and the temperature was raised to 50°C. The propylene oxide tank was pressurized with nitrogen. The dropwise addition of PO was controlled by a flowmeter at a rate of 1.5 mL / min. 118.9 g of PO was added dropwise into the high-pressure reactor. After the dropwise addition was completed, the reaction temperature was controlled at 50°C and the reaction pressure was controlled at 0.45 MPa. The reaction was maintained for 1.5 h. Then, 118.9 g of PO was added dropwise at a rate of 0.8 mL / min. After the dropwise addition was completed, the temperature of the reactor was raised to 75°C and the reaction pressure was controlled at 0.5 MPa. The reaction was maintained for 3.5 h. The temperature of the reactor was cooled to 60°C and vacuum was opened to remove the unreacted PO at -0.085 MPa. The product was neutralized with phosphoric acid and washed with water. Filtration, dehydration by vacuum distillation, and vacuum distillation at -0.09 MPa to collect the fraction at 187°C gave the monoethanol diisopropanolamine. X 乙醇胺 98.96%, S 乙醇二异丙醇胺89.24%, Y 乙醇二异丙醇胺 86.09%, 97.43% purity.
[0117] Comparative Example 6
[0118] Preparation of catalyst S-7: Hβ zeolite (SiO2 / Al2O3 molar ratio 26, specific surface area 600 m 2 / g) was dried in an oven at 110°C for 10 hours; 1.6 g of ZnCl2was weighed and dissolved in 20 g of anhydrous isopropanol to obtain an isopropanol solution; 20 g of Hβ zeolite was immersed in the isopropanol solution of ZnCl2at room temperature for 24 h; a rotary evaporator was used to recover the isopropanol at 60°C and -0.08 MPa until the solid was in a semi-dry state; the immersed material was dried in an oven at 120°C for 15 hours, and then transferred to a muffle furnace, which was heated at a rate of 4°C / min from room temperature to 400°C under nitrogen protection, and calcined at 400°C for 10 hours to obtain catalyst S-7.
[0119] The high-pressure reactor was replaced 2-3 times with nitrogen. The molar ratio of ethanolamine to propylene oxide was controlled to be 1:2.05, and 122 g of ethanolamine and 2.44 g of catalyst S-7 were added to the high-pressure reactor under nitrogen protection, and stirring was started at a speed of 450 rpm, and the temperature was raised to 50°C; the propylene oxide tank was pressurized with nitrogen, and the dropwise addition rate of PO was controlled to be 1.5 mL / min by using a flowmeter, and 118.9 g of PO was added dropwise to the high-pressure reactor, and after the dropwise addition was completed, the reaction temperature was controlled at 50°C, and the reaction pressure was 0.45 MPa, and the reaction was kept for 1.5 h; then 118.9 g of PO was added dropwise at a dropwise addition rate of 0.8 mL / min, and after the dropwise addition was completed, the temperature of the reactor was raised to 75°C, and the reaction pressure was 0.5 MPa, and the reaction was kept for 3.5 h; the temperature of the reactor was cooled to 60°C, and vacuum was opened at -0.085 MPa to remove unreacted PO; the reactor was opened, and the catalyst S-7 was recovered by filtration; the crude product obtained by filtration was subjected to vacuum distillation at -0.09 MPa, and the fraction collected at 187°C was monoethanol diisopropanolamine. The content of X 乙醇胺 90.11%, S 乙醇二异丙醇胺 94.45%, Y 乙醇二异丙醇胺 84.26%, 99.89% purity.
[0120] It can be seen from Examples 1-6 and Comparative Examples 1-6 that the supported catalyst of the present application can replace traditional acid-base neutralization, reduce salt-containing wastewater discharge, and the catalyst can be recycled for more than 10 times. The supported catalyst of the present application is used to catalyze the preparation of monoethanol diisopropanolamine from ethanolamine and propylene oxide, the reaction time is short, the reaction steps are simple, the product yield and purity are high, the ethanolamine conversion rate is ≥96%, the monoethanol diisopropanolamine selectivity is ≥97%, the monoethanol diisopropanolamine yield after purification is ≥93%, and the purity is ≥99%.
[0121] As described above, although the present application has been indicated and expressed with reference to specific preferred embodiments, it must not be interpreted as a limitation of the present application itself. Various changes can be made in form and details without departing from the spirit and scope of the present application defined by the appended claims.
Claims
1. A bifunctional supported catalyst characterized by: It is a kind of bifunctional catalyst, which is prepared by impregnation method using pretreated Hβ zeolite as carrier and ZnCl2 as active component.
2. The dual duty cycle energy catalyst of claim 1, wherein: The Hbeta molecular sieve has a molar ratio of SiO2 / Al2O3 of 25-30, a specific surface area of ≥500 m 2 / g.
3. The bifunctional supported catalyst of claim 1, wherein: The pretreatment of Hβ zeolite includes dilute acid soaking and calcination.
4. The bifunctional supported catalyst of claim 1, wherein: The dilute acid is one or more of dilute hydrochloric acid, dilute sulfuric acid and dilute nitric acid, and the concentration of dilute acid is 0.5-1.5 mol / L; the solid-liquid ratio of Hβ zeolite to dilute acid is 1:5-1:15 g / mL; the temperature of dilute acid soaking is 60-100 ℃, and the time of dilute acid soaking is 4-8 hours.
5. The bifunctional supported catalyst of claim 1, wherein: The temperature of calcination is 200-350 ℃, and the time of calcination is 3-10 hours.
6. A process for the preparation of the bifunctional supported catalyst of claim 1, characterized by: The loading amount of ZnCl2 in the bifunctional catalyst is 3.5-15% wt. It comprises the following steps: Step (1), carrier pretreatment: Hβ zeolite carrier is soaked in dilute acid at 60-100 ℃ for 4-8 hours, then solid-liquid separation is performed, and the carrier is washed with deionized water until neutral, dried at 100-130 ℃ for 8-14 hours, and calcined at 200-350 ℃ for 3-10 hours, and then cooled; Step (2), active component impregnation: the pretreated Hβ zeolite is impregnated in ZnCl2 alcohol solution at room temperature for 10-24 hours, and the alcohol solution is recovered under reduced pressure; 7. The method for preparing a bifunctional supported catalyst according to claim 6, characterized in that: Step (3), drying and calcination: the impregnated material is dried at 100-120 ℃ for 6-15 hours, and then calcined at 300-450 ℃ for 4-10 hours under nitrogen protection in a tube furnace to obtain a bifunctional supported catalyst. In step (2), the ZnCl2 alcohol solution is prepared by using anhydrous alcohol solvent, and the anhydrous alcohol solvent is one or more of anhydrous methanol, anhydrous ethanol or anhydrous isopropyl alcohol; the concentration of ZnCl2 alcohol solution is 3.5%-15%; 8. A process for the efficient green synthesis of alcohol amines characterized in that: The recovery of alcohol solution under reduced pressure is carried out at 60 ℃ and -0.08 MPa. It comprises the following steps: Step (1), under nitrogen protection, ethanolamine and the bifunctional supported catalyst of claim 1 are added into a reaction device, and the temperature is increased to 40-50 ℃ under stirring; propylene oxide is pressurized into the reaction device by using nitrogen gas by positive pressure method, and 45-55% of the total amount of propylene oxide is added dropwise; after the dropwise addition is completed, the reaction temperature is controlled at 45-55 ℃, the reaction pressure is controlled at 0.4-0.55 MPa, and the reaction is carried out for 1-2 hours; then the remaining propylene oxide is slowly added dropwise, the reaction temperature is increased to 70-75 ℃, the reaction pressure is 0.4-0.55 MPa, and the reaction is carried out for 2-4 hours; 9. The process for the high efficient green synthesis of alcohol amine as claimed in claim 8, wherein: Step (2), after the reaction is completed, the temperature is cooled to 60 ℃, and unreacted propylene oxide is removed under vacuum; the catalyst is recovered by filtration; the crude product is subjected to vacuum distillation at -0.09 MPa, and the fraction collected at 180-190 ℃ is monoethanol diisopropanolamine.
10. The process for the high efficient green synthesis of alcohol amine as claimed in claim 8, wherein: The molar ratio of ethanolamine to propylene oxide is 1:2-1:2.2; the first dropwise addition speed of propylene oxide is 1-2 mL / min, and the second dropwise addition speed of propylene oxide is 0.5-1.0 mL / min. The addition amount of the bifunctional supported catalyst is 1-5% wt. of the total amount of ethanolamine.