CN113578372A - Catalyst for synthesizing morpholine from diethylene glycol and preparation method thereof - Google Patents

Catalyst for synthesizing morpholine from diethylene glycol and preparation method thereof Download PDF

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CN113578372A
CN113578372A CN202111017582.0A CN202111017582A CN113578372A CN 113578372 A CN113578372 A CN 113578372A CN 202111017582 A CN202111017582 A CN 202111017582A CN 113578372 A CN113578372 A CN 113578372A
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CN113578372B (en
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杨帅成
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Anhui Haoyuan Chemical Industry Group Co ltd
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Binzhou Zhongke Catalysis Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a preparation method of a catalyst for synthesizing morpholine by diethylene glycol, which comprises the following steps of (1) preparing a carrier: TiO is loaded in the pore canal of the mesoporous material SBA-15 in a dispersed state by taking isopropyl titanate as a titanium source2To prepare TiO2/SBA‑15；TiO2The mixed solution of SBA-15, aluminum nitrate as an aluminum source, ethanol and water is pretreated, and Al is loaded through hydrothermal synthesis reaction2O3Finally, Al is prepared2O3/TiO2The preparation method comprises the following steps of (1) preparing an SBA-15 composite carrier, (2) preparing an impregnation liquid: preparing soluble salt precursors of active components Cu, Ni and Fe and auxiliary agents Mn and Mg into a mixed solution A, (3) preparing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A, drying and roasting to obtain the supported metal catalystAn oxidizing agent. The catalyst prepared by the method has stable performance, good selectivity of morpholine and the advantage of environmental protection.

Description

Catalyst for synthesizing morpholine from diethylene glycol and preparation method thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for synthesizing morpholine from diethylene glycol and a preparation method thereof.
Background
Morpholine is 1, 4-oxazacyclohexane, is a colorless oily liquid at normal temperature, is weakly alkaline, has hygroscopicity and ammonia odor, and has slight toxicity. Can be mutually dissolved with water to form an azeotrope, is easily soluble in aromatic hydrocarbon, alcohol, ether, benzene, acetone, sesame oil and the like, is slightly soluble in aliphatic hydrocarbon and mineral oil, and has a special oxygen-nitrogen heterocyclic structure, so that morpholine becomes an intermediate for synthesizing a plurality of fine chemical products, and is widely applied in the fields of rubber, medicines, coatings, dyes and the like. The main method for producing morpholine at present is diglycol catalytic ammonolysis cyclization, i.e. diglycol and liquid ammonia are subjected to ammonolysis cyclization in the presence of catalyst and hydrogen. However, the morpholine synthesis process has the problems of short catalyst life, poor performance, low morpholine yield and the like.
In the organic catalysis industry, catalysts for catalyzing alcohol compounds to synthesize amine mainly comprise solid acid catalysts and metal-supported catalysts. Among the three metals having the best catalytic effect are those which adsorb and activate ammonia and hydrogen, respectively, and which are capable of undergoing an amination reaction with hydroxyl groups adsorbed on the surface of the catalyst.
The patent application number CN200410010816.9 discloses a synthetic morpholine catalyst which is clover type gamma-Al2O3·3H2O or (gamma + theta) -Al2O3Is used as a carrier, at least two elements of Ni, Cu and Co are used as active components to be loaded on the carrier, and the needed catalyst is prepared by an impregnation method. The prepared catalyst is evaluated to have the diethylene glycol (DEG) conversion rate of 98.1-99.8 mol% and the morpholine selectivity of 90.71-94.44 mol%. The method has the advantages of low consumption of active components, simple processing and low cost, and the method has high conversion rate of the diglycol, but relatively low selectivity of the morpholine.
The patent application number CN200610037328.6 discloses a catalyst for synthesizing morpholine by ammonifying diethylene glycol and a preparation method thereof, which uses Al2O3·3H2O is a carrier and loads Cu, Ni and Zn active components. The preparation method comprises mixing Al2O3·3H2Roasting at high temperature to obtain a preactivated carrier; preparing a nitrate mixed solution according to a certain concentration of copper, nickel and zinc, and carrying out precipitation reaction on a sodium carbonate solution; filtering and washing reactants, adding a pre-activated carrier for loading, washing, filtering, drying and roasting to obtain the morpholine catalyst, wherein the morpholine catalyst is obtained by coprecipitationThe preparation method has low preparation cost, but because the influence factors are more in the preparation process, the stability difference of the catalyst among different batches is easily larger, and the conversion rate of the diglycol and the selectivity of the morpholine are finally influenced.
Disclosure of Invention
Aiming at the problems of unstable performance and low morpholine selectivity of the prior morpholine catalyst synthesized by diethylene glycol, the invention provides a composite catalyst which has stable catalytic performance, good catalyst activity and selectivity and convenient preparation.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for preparing a catalyst for synthesizing morpholine from diethylene glycol comprises the following steps: (1) preparing a carrier: TiO is loaded in the pore canal of the mesoporous material SBA-15 in a dispersed state by taking isopropyl titanate as a titanium source2To prepare TiO2SBA-15; pretreating TiO2/SBA-15 with a mixed solution of aluminum nitrate, ethanol and water serving as an aluminum source, and carrying Al through hydrothermal synthesis reaction2O3Finally, Al is prepared2O3/TiO2a/SBA-15 composite carrier; (2) preparation of the impregnation liquid: preparing soluble salt precursors of active components Cu, Ni and Fe and auxiliaries Mn and Mg into a mixed solution A; (3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A, filtering, drying and roasting to obtain the supported metal catalyst.
Further, the preparation of the carrier in the step (1) specifically comprises the following steps: uniformly mixing SBA-15 containing 1% -3% of boron, absolute ethyl alcohol and isopropyl titanate to obtain a suspension I, adjusting the pH value of the system to 3-4, stirring until the suspension I forms a stable and transparent gel II, and aging, drying and calcining to obtain TiO2SBA-15; adding TiO into the mixture2Soaking SBA-15 in mixed solution III of aluminum nitrate nonahydrate, ethanol and water, filtering, drying, soaking, performing hydrothermal reaction, filtering, washing and calcining to obtain composite carrier Al2O3/TiO2/SBA-15。
Further, the volume ratio of the absolute ethyl alcohol to the isopropyl titanate is 3: 1-5: 1, and the mass fraction of the aluminum nitrate nonahydrate in the mixed solution III is 55-70%. Further, the aging time is 12-48 hours.
Furthermore, the solution used for adjusting the pH value of the system is a 10% dilute nitric acid aqueous solution with the pH value of 3, the aging time of the gel II is 12-48 hours, and the soaking method is to treat the gel II in an ammonia aqueous solution with the concentration of 0.5M for 8-16 hours.
Further, the hydrothermal reaction is carried out in a stainless steel reaction kettle with a polytetrafluoroethylene lining, the temperature of the hydrothermal reaction is 90-110 ℃, and the reaction time is 12-18 h.
Furthermore, the soluble salt precursor of the active component and the auxiliary agent in the step (2) comprises one or two of nitrate, sulfate or chloride, the molar ratio of Cu, Ni and Fe of the active component is 1: 1.5-3: 0.5-2, and the molar ratio of Mn and Mg of the auxiliary agent is 1: 2-4.
Further, the preparation method of the mixed solution II in the step (2) is as follows: and adding the active component precursor and the auxiliary agent precursor into deionized water to dissolve the active component precursor and the auxiliary agent precursor.
Further, Al is added in the step (3)2O3/TiO2The experiment steps of soaking the/SBA-15 composite carrier in the mixed solution A, filtering and drying are repeated for 2 times.
Further, the roasting temperature in the step (3) is 600 ℃, the roasting time is 6 hours, and the roasting atmosphere is nitrogen atmosphere.
A catalyst for synthesizing morpholine by diethylene glycol obtained by the preparation method.
The invention has the following beneficial effects:
1. compared with the existing catalyst for synthesizing morpholine by diethylene glycol, the catalyst carrier prepared by the invention is Al2O3/TiO2the/SBA-15 composite carrier uses the mesoporous silicon molecular sieve SBA-15, and a small amount of boron is added into the carrier, so that the mesoporous material has the advantages of more stable hollow structure, larger pore diameter, good hydrothermal stability, high catalytic activity, easiness in product separation and environmental friendliness.
2. The active components of the catalyst comprise Cu, Ni, Fe and auxiliary agents Mn and Mg, and the catalyst has good morpholine selectivity.
3. The preparation raw materials adopted by the invention have wide sources and low price, and the preparation cost of the catalyst is lower.
Drawings
FIG. 1 is a chromatogram of the results of gas phase detection after the reaction in example 4.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments.
Example 1
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 8 hours, filtering, placing a filter cake in an oven for drying at 40 ℃ to remove water, soaking in 0.5M ammonia water solution for 10 hours, taking out, placing in a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) will be Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake in a 60 ℃ oven for 5 hours after filtering, and roasting in a muffle furnace in the atmosphere containing hydrogen at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 99.8 mol%, and the selectivity of morpholine was 99.96 mol%.
Example 2
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II at room temperature for 12h, drying at 85 ℃ for 4h, and finally calcining at 550 ℃ for 2h to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying in an oven at 40 ℃ to remove water, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with a collected ammonia material and a polytetrafluoroethylene lining, performing hydrothermal reaction at 110 ℃ for 24 hours, filtering, washingThen calcining the mixture for 2 hours at 550 ℃ to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 99.6 mol%, and the selectivity of morpholine was 98.72 mol%.
Example 3
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 4 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 48h at room temperature, drying at 85 ℃ for 4h, and finally, constantly keeping the temperature at 550 ℃ for 4hCalcining for 2h to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)20.376g、Ni(NO3)21.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 98.7 mol%, and the selectivity of morpholine was 98.35 mol%.
Example 4
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1)preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 90 ℃ for 18 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 400 ℃ for 7 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction is carried out for synthesizing morpholine by a diethylene glycol gas phase method under the reaction conditionsComprises the following steps: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 97.6 mol%, and the selectivity of morpholine was 98.25 mol%.
Example 5
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 12 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake in a 60 ℃ oven for 5 hours after filtering, and roasting in a muffle furnace containing nitrogen atmosphere at 700 ℃ for 4 hours to obtain the supported metal catalyst。
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 98.3 mol%, and the selectivity of morpholine was 97.66 mol%.
Example 6
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 8 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 99.0 mol%, and the selectivity of morpholine was 99.1 mol%.
Example 7
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2SBA-15 is soaked in the mixed solution III for 1 hour in an oven at 40 DEG CDrying to remove water, soaking in 0.5M ammonia water solution for 16h, taking out, placing into stainless steel reaction kettle equipped with polytetrafluoroethylene lining and containing collected ammonia material, performing hydrothermal reaction at 110 deg.C for 24h, filtering, washing, and calcining at 550 deg.C for 2h to obtain composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 99.3 mol%, and the selectivity of morpholine was 99.21 mol%.
Example 8
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, and then using the pH value of 3 to obtain a mixed solutionAdjusting the pH value of the mixed solution to 3 with 10% dilute nitric acid aqueous solution, continuously stirring until the mixed solution forms stable and transparent gel II, aging the gel II at room temperature for 24h, drying at 85 ℃ for 4h, and finally calcining at 550 ℃ for 2h to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 0.873g、Fe(NO3)30.242g and Co-precursor Mn (NO)3)20.151g and Mg (NO)3)20.249g of deionized water (10 mL) is added to prepare a mixed solution A;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 98.2 mol%, and the selectivity of morpholine was 99.15 mol%.
Example 9
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.746g、Fe(NO3)30.968g and Mn (NO) as a precursor of auxiliary3)20.151g and Mg (NO)3)20.498g of the mixed solution A is added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
in a stainless steel fixed bed with an inner diameter of 10mmTaking 5mL of catalyst, placing the catalyst in a constant temperature area of a reaction tube, reducing and activating the catalyst by using mixed gas of 20% of hydrogen and 80% of nitrogen, and then carrying out a diethylene glycol gas phase method to synthesize morpholine, wherein the reaction conditions are as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 99.6 mol%, and the selectivity of morpholine was 99.56 mol%.
Example 10
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.3g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 4.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 30g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.746g、Fe(NO3)30.968g and Mn (NO) as a precursor of auxiliary3)20.151g and Mg (NO)3)20.498g of the mixed solution A is added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, filtering, drying in a 60 ℃ oven for 5 hours, repeatedly soaking a dried sample in the mixed solution A for 12 hours after drying, drying a filter cake in the 60 ℃ oven for 5 hours after filtering, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 99.4 mol%, and the selectivity of morpholine was 99.76 mol%.
Example 11
Gas chromatography detection of morpholine and diethylene glycol:
the detection method is a gas phase method, a gas phase instrument is Agilent 7890, a chromatographic column is HP-5, N2As carrier gas, column temperature: 210 ℃, detector temperature: 265 ℃, injector temperature: 250 ℃, injection volume: 1uL, detection time 16min, morpholine retention time: 12.918, diethylene glycol retention time: 14.831.
comparative example 1
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until stable and transparent gel II is formed, aging the gel II at room temperature for 50h,drying at 85 deg.C for 4h, and calcining at 550 deg.C for 2h to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 90.5 mol%, and the selectivity of morpholine was 98.89 mol%.
Comparative example 2
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II at room temperature for 8h, drying at 85 ℃ for 4h, and finally calcining at 550 ℃ for 2h to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
in a stainless steel fixed bed reactor with an inner diameter of 10mm, 5mL of the catalyst is placed in a constant temperature area of a reaction tube, and diethylene glycol is carried out after the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogenSynthesizing morpholine by a gas phase method, wherein the reaction conditions are as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 91.3 mol%, and the selectivity of morpholine was 98.44 mol%.
Comparative example 3
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 80 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtration in a 60 ℃ oven for 5 hours, and baking in a muffle furnace containing nitrogen atmosphere at 350 DEG CAnd obtaining the supported metal catalyst after 7 hours of burning.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 91.8 mol%, and the selectivity of morpholine was 90.6 mol%.
Comparative example 4
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 10 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 1.164g、Fe(NO3)30.484g and the promoter precursor Mn (NO)3)20.151g and Mg (NO)3)20.373g of the mixed solution A was added with 10mL of deionized water;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 800 ℃ for 4 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 93.4 mol%, and the selectivity of morpholine was 89.5 mol%.
Comparative example 5
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2SBA-15 in the above mixtureSoaking the mixed solution III in water for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle which is filled with collected ammonia material and is provided with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 3.492g、Fe(NO3)31.452g and Co precursor Mn (NO)3)20.151g and Mg (NO)3)20.746g is added with 10mL of deionized water to prepare a mixed solution A;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion of diethylene glycol was 94.4 mol%, and the selectivity for morpholine was 96.2 mol%.
Comparative example 6
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of absolute ethyl alcohol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, and then continuously adding 5mL of absolute ethyl alcohol and 2mL of deionized water into the suspension I to obtain the productAdding into mixed solution, adjusting pH to 3 with 10% dilute nitric acid water solution with pH of 3, stirring to form stable transparent gel II, aging at room temperature for 24 hr, drying at 85 deg.C for 4 hr, and calcining at 550 deg.C for 2 hr to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 10 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 0.291g、Fe(NO3)30.048g and the Co-precursor Mn (NO)3)20.151g and Mg (NO)3)20.127g of the mixed solution is added with 10mL of deionized water to prepare a mixed solution; (3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 93.5 mol%, and the selectivity of morpholine was 96.5 mol%.
Comparative example 7
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 0.1g of boron, 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II for 24 hours at room temperature, drying for 4 hours at 85 ℃, and finally calcining for 2 hours at the constant temperature of 550 ℃ to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 24 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 0.291g、Fe(NO3)30.048g and the Co-precursor Mn (NO)3)20.151g and Mg (NO)3)20.127g of the mixed solution is added with 10mL of deionized water to prepare a mixed solution A;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A for 12 hours, drying a filter cake after filtering in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
in a stainless steel fixed bed with an inner diameter of 10mmTaking 5mL of catalyst in a reactor, placing the catalyst in a constant temperature area of a reaction tube, reducing and activating the catalyst by using mixed gas of 20% of hydrogen and 80% of nitrogen, and then carrying out a diethylene glycol gas phase method to synthesize morpholine, wherein the reaction conditions are as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 92.6 mol%, and the selectivity of morpholine was 91.56 mol%.
Comparative example 8
The preparation method of the morpholine catalyst synthesized from diethylene glycol comprises the following steps:
(1) preparing a carrier: respectively putting 1.0g of SBA-15, 15mL of anhydrous ethanol and 5.0g of isopropyl titanate which are weighed into a 50mL beaker, fully and uniformly mixing to form a suspension I, then continuously adding 5mL of anhydrous ethanol and 2mL of deionized water into the suspension I to obtain a mixed solution, then adjusting the pH value of the mixed solution to 3 by using 10% dilute nitric acid aqueous solution with the pH value of 3, continuously stirring until a stable and transparent gel II is formed, aging the gel II at room temperature for 24 hours, drying at 85 ℃ for 4 hours, and finally calcining at 550 ℃ for 2 hours at constant temperature to obtain white powder TiO2/SBA-15；
Weighing 26g of aluminum nitrate nonahydrate, 50mL of ethanol and 5mL of deionized water to prepare a mixed solution III, and mixing the white powder TiO2Soaking SBA-15 in the mixed solution III for 1 hour, drying and dewatering in an oven at 40 ℃, soaking in 0.5M ammonia water solution for 24 hours, taking out, putting into a stainless steel reaction kettle provided with collected ammonia material and a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24 hours, filtering, washing, and calcining at 550 ℃ for 2 hours to obtain the composite carrier Al2O3/TiO2/SBA-15；
(2) Preparation of the impregnation liquid: separately weighing the active component precursor Cu (NO)3)2 0.376g、Ni(NO3)2 0.291g、Fe(NO3)30.048g and the Co-precursor Mn (NO)3)20.151g and Mg (NO)3)20.127g of the mixed solution is added with 10mL of deionized water to prepare a mixed solution A;
(3) mixing Al2O3/TiO2/SBA-15 soaking the composite carrier in the mixed solution A for 12 hours, filtering, drying a filter cake in a 60 ℃ oven for 5 hours, and roasting in a muffle furnace containing nitrogen atmosphere at 600 ℃ for 6 hours to obtain the supported metal catalyst.
The mass ratios of the carrier, the active component and the auxiliary agent of the catalyst obtained above are specifically shown in table 1.
Evaluation of catalyst Activity:
the method is carried out in a stainless steel fixed bed reactor with the inner diameter of 10mm, 5mL of catalyst is placed in a constant temperature area of a reaction tube, the catalyst is reduced and activated by mixed gas of 20 percent of hydrogen and 80 percent of nitrogen, and then the reaction condition is as follows: the reaction temperature is 220 ℃, the reaction pressure is 2.0MPa, and the airspeed of the diglycol liquid is 0.2h-1The mol ratio of ammonia to alcohol is 5: 1. The product obtained was analyzed by gas chromatography.
The experimental results are as follows: after the reaction, the conversion rate of diethylene glycol was 93.6 mol%, and the selectivity of morpholine was 94.56 mol%.
In order to more intuitively illustrate the parameters corresponding to the components of the catalysts in each example and comparative example, the catalyst conditions of the specific examples and comparative examples are summarized as shown in the following table 1:
TABLE 1
Figure BDA0003238500770000181
The molar ratios of the catalyst support preparation process parameters, active component and auxiliary loading parameters in table 1 have been scaled according to the mass in the examples.
Compared with example 1, when the carrier is prepared, the aging time is changed, and the activity and selectivity of the prepared catalyst for catalyzing diethylene glycol to synthesize morpholine are detected, and the specific results are shown in the following table 2.
TABLE 2
Figure BDA0003238500770000191
The final catalytic activity of the catalysts obtained from the carriers prepared by different aging times in table 2 shows that the aging time is not as long as possible, the aging time is 12-48 hours, and the corresponding catalysts have better catalytic activity and selectivity for synthesizing morpholine from diethylene glycol.
Compared with the example 1, when the carrier is prepared, the single-factor variable soaking time is changed, the activity and the selectivity of the prepared catalyst for catalyzing diglycol to synthesize morpholine are detected, and the specific results are shown in the following table 3.
TABLE 3
Figure BDA0003238500770000201
The final catalytic activity of the catalyst obtained by preparing the carrier through different soaking times in the above table 3 shows that the soaking time exceeds 16 hours, the catalytic activity of the catalyst is obviously reduced, and the corresponding morpholine selectivity is also poor, so that the ball milling time needs to be controlled between 8 and 16 hours when the carrier is prepared.
Compared with example 1, the activity of the prepared catalyst for synthesizing morpholine from diethylene glycol is detected by changing the temperature and time of the hydrothermal reaction in the process of preparing the carrier, and the specific results are shown in the following table 4.
TABLE 4
Figure BDA0003238500770000202
From the final catalytic activity of the catalyst prepared at different hydrothermal temperatures and times in table 4 above, it can be seen that the activity of the final catalyst is affected by over-high or under-low hydrothermal temperature and the calcination time, and the optimal hydrothermal temperature range is 90-110 ℃, and the corresponding optimal hydrothermal reaction time is 12-18 hours.
Compared with example 1, in the experimental operation of loading metal on the carrier, the molar ratio of the active component to the auxiliary agent is changed, and the activity and selectivity of the prepared catalyst for synthesizing morpholine from diethylene glycol are detected, and the specific results are shown in table 5 below.
TABLE 5
Figure BDA0003238500770000211
In Table 5, the molar ratio of the active component to the auxiliary is changed, and compared with the activity of diethylene glycol and the selectivity of morpholine, the molar ratio of Cu (NO3)2 to Ni (NO3)2 to Fe (NO3)3 is preferably 1 to (1.5-3) to (0.5-2), and the molar ratio of the auxiliary precursor Mn (NO3)2 to Mg (NO3)2 is 1 to (2-4), and it is clear from the results of the catalytic activity and selectivity of comparative examples 5 and 6 that the activity and selectivity of the catalyst are remarkably reduced beyond the above ranges.

Claims (10)

1. A preparation method of a catalyst for synthesizing morpholine from diethylene glycol is characterized by comprising the following steps:
(1) preparing a carrier: TiO is loaded in the pore canal of the mesoporous material SBA-15 in a dispersed state by taking isopropyl titanate as a titanium source2To prepare TiO2/SBA-15；TiO2The mixed solution of SBA-15, aluminum nitrate as an aluminum source, ethanol and water is pretreated, and Al is loaded through hydrothermal synthesis reaction2O3Finally, Al is prepared2O3/TiO2a/SBA-15 composite carrier;
(2) preparing an impregnation solution, namely preparing soluble salt precursors of active components Cu, Ni and Fe and auxiliaries Mn and Mg into a mixed solution A;
(3) mixing Al2O3/TiO2Soaking the/SBA-15 composite carrier in the mixed solution A, filtering, drying and roasting to obtain the supported metal catalyst.
2. The preparation method according to claim 1, wherein the preparation of the carrier in the step (1) is specifically: uniformly mixing SBA-15 containing 1% -3% of boron, absolute ethyl alcohol and isopropyl titanate to obtain a suspension I, adjusting the pH value of the system to 3-4, stirring until the suspension I forms a stable and transparent gel II, and aging, drying and calcining to obtain TiO2SBA-15; adding TiO into the mixture2Soaking SBA-15 in mixed solution III of aluminum nitrate nonahydrate, ethanol and water, filtering, drying, soaking, performing hydrothermal reaction,filtering, washing and calcining to obtain the composite carrier Al2O3/TiO2/SBA-15。
3. The preparation method according to claim 2, wherein the volume ratio of the absolute ethyl alcohol to the isopropyl titanate is 3: 1-5: 1, the mass fraction of the aluminum nitrate nonahydrate in the mixed solution III is 55-70%.
4. The process according to claim 2, wherein the solution used for adjusting the pH value of the system is a 10% dilute aqueous solution of nitric acid having a pH of 3, the gel II is aged for 12 to 48 hours, and the impregnation process is carried out in a 0.5M aqueous ammonia solution for 8 to 16 hours.
5. The preparation method according to claim 2, wherein the hydrothermal reaction is carried out in a stainless steel reaction kettle with a polytetrafluoroethylene lining, the hydrothermal reaction temperature is 90-110 ℃, and the reaction time is 12-18 h.
6. The preparation method according to claim 1, wherein the soluble salt precursor of the active component and the auxiliary agent in the step (2) comprises one or two of nitrate, sulfate or chloride,
the mol ratio of the active components Cu, Ni and Fe is 1: (1.5-3): (0.5-2), and the molar ratio of the auxiliary agent Mn to the auxiliary agent Mg is 1: (2-4).
7. The method according to claim 1, wherein the mixed solution II in the step (2) is prepared by: and adding the active component precursor and the auxiliary agent precursor into deionized water to dissolve the active component precursor and the auxiliary agent precursor.
8. The production method according to claim 1, wherein Al is added in the step (3)2O3/TiO2The experiment steps of soaking the/SBA-15 composite carrier in the mixed solution A, filtering and drying are repeated for 2 times.
9. The method for preparing a catalyst according to claim 1, wherein the calcination temperature in the step (3) is 600 ℃, the calcination time is 6 hours, and the calcination atmosphere is a nitrogen atmosphere.
10. Catalyst for synthesizing morpholine from diethylene glycol, characterized in that it is obtained by the preparation method according to claims 1-9.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58225078A (en) * 1982-06-25 1983-12-27 Nippon Shokubai Kagaku Kogyo Co Ltd Catalyst for preparation of morpholine
US20090203933A1 (en) * 2008-02-11 2009-08-13 Catalytic Distillation Technologies Process for continuous production of organic carbonates or organic carbamates and solid catalysts therefore
CN103962144A (en) * 2014-05-06 2014-08-06 广西大学 Catalyst for synthesizing morpholine by gas-solid phase catalysis and preparation method thereof
CN110586110A (en) * 2019-10-09 2019-12-20 四川鸿鹏新材料有限公司 Supported catalyst for preparing morpholine from diethylene glycol and preparation method thereof
CN112920139A (en) * 2021-01-25 2021-06-08 美思德(吉林)新材料有限公司 Dimorpholinyl diethyl ether and preparation process thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58225078A (en) * 1982-06-25 1983-12-27 Nippon Shokubai Kagaku Kogyo Co Ltd Catalyst for preparation of morpholine
US20090203933A1 (en) * 2008-02-11 2009-08-13 Catalytic Distillation Technologies Process for continuous production of organic carbonates or organic carbamates and solid catalysts therefore
CN103962144A (en) * 2014-05-06 2014-08-06 广西大学 Catalyst for synthesizing morpholine by gas-solid phase catalysis and preparation method thereof
CN110586110A (en) * 2019-10-09 2019-12-20 四川鸿鹏新材料有限公司 Supported catalyst for preparing morpholine from diethylene glycol and preparation method thereof
CN112920139A (en) * 2021-01-25 2021-06-08 美思德(吉林)新材料有限公司 Dimorpholinyl diethyl ether and preparation process thereof

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