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WO2023179110A1 - 一种催化合成多乙烯多胺的方法 - Google Patents

一种催化合成多乙烯多胺的方法 Download PDF

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WO2023179110A1
WO2023179110A1 PCT/CN2022/138260 CN2022138260W WO2023179110A1 WO 2023179110 A1 WO2023179110 A1 WO 2023179110A1 CN 2022138260 W CN2022138260 W CN 2022138260W WO 2023179110 A1 WO2023179110 A1 WO 2023179110A1
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catalyst
carrier
reaction
temperature
treatment
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English (en)
French (fr)
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马雷
严丽
丁云杰
于婷婷
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中国科学院大连化学物理研究所
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Publication of WO2023179110A1 publication Critical patent/WO2023179110A1/zh

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    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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    • 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
    • C07D295/04—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/08—Bridged systems
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a method for catalytically synthesizing polyethylene polyamines. More specifically, it relates to a modified carrier-loaded catalyst and an activation treatment method thereof, which are used to catalyze the raw materials monoethanolamine and ethylenediamine under a hydrogen atmosphere. The amination reaction converts into amine products based on linear polyethylene and polyamine.
  • Polyethylene polyamine is a type of ethylene amine, including linear homologs of ethylene diamine, branched chain or cyclic amines.
  • common linear polyethylene polyamines include diethylene triamine, triethylene tetraamine (linear), tetraethylene pentamine (linear), etc., which are widely used in papermaking, lubricating oil additives, chelating agents, curing agents and other fields.
  • my country's ethylenediamine market has gradually become saturated, but the production capacity of linear polyethylene polyamine is still low and high-quality products rely on imports, which limits the development of downstream industries.
  • the domestic chemical industry continues to mature and the industrial structure gradually optimizes, the market demand for high-purity linear polyethylene polyamine products is increasing.
  • the production processes of polyethylene polyamine mainly include dichloroethane method and monoethanolamine method.
  • dichloroethane method is gradually being eliminated due to serious equipment corrosion, high energy consumption, environmental pollution, and high investment costs.
  • the monoethanolamine method refers to a process in which the raw materials monoethanolamine and liquid ammonia are reacted under high pressure, hydrogen and a metal catalyst to generate ethyleneamine. It has the advantages of green and clean, low energy consumption, and good atom economy.
  • the product is based on ethylene. Mainly diamine, with a small amount of diethylene triamine as a by-product, and polyethylene polyamine products cannot be produced in large quantities.
  • the conversion rate of monoethanolamine in the gas phase reaction at 250-350°C can reach more than 40%, and the selectivity of acyclic polyethylene polyamine can reach more than 80%.
  • the product is mainly diethylenetriamine, but the active components are easily lost and cannot be operated for a long time.
  • U.S. Patent 5321160 uses a Ni-Y-Ir system supported catalyst for intermittent reaction in a reactor at 200°C.
  • the conversion rate of monoethanolamine can reach 27.8%, and the total selectivity of polyethylene polyamine is about 70.2%.
  • the catalytic system and process used to produce polyethylene polyamines still have one or more of the following shortcomings: 1. High energy consumption; 2. Easily corroded equipment; 3. Environmental pollution; 4. Linear polyethylene polyamines Low selectivity and few types; 5.
  • the catalyst is unstable; 6. There are many branched or cyclic amine by-products in the product; 7. Continuous production cannot be achieved; 8.
  • the catalyst activity is low.
  • the present invention provides a new method to overcome the above shortcomings.
  • the object of the present invention is to provide a method for catalytically synthesizing polyethylene polyamine, which method needs to be carried out in the presence of a supported metal catalyst and under hydrogen conditions.
  • This method is used in the reaction of monoethanolamine and ethylenediamine to produce polyethylene polyamine and has the characteristics of high linear polyethylene polyamine yield, rich species, few branched and cyclic by-products, high catalytic activity, adjustable product distribution, and good stability.
  • the reaction process is green and clean.
  • the invention provides a supported catalyst for synthesizing polyethylene polyamine products.
  • the catalyst consists of three parts: active metal, auxiliary elements and modified carrier.
  • the active metal and auxiliary elements are loaded on the modified carrier.
  • the catalyst is prepared by the following process: the precursors of active metals and auxiliary elements are impregnated or precipitated and loaded onto a modified carrier, and the catalyst is obtained after drying, roasting, and reduction activation treatment.
  • the modified carrier is an alkali metal modified carrier, wherein the alkali metal is selected from one or more of Na and K.
  • the carrier is one or a combination of two or more of Al 2 O 3 , activated carbon, SiO 2 , Al 2 O 3 -SiO 2 .
  • the carrier has a specific surface area of 50 to 1800 m 2 /g and a pore volume of 0.2 to 1.2 ml/g.
  • the specific surface area of the carrier is 70-700 m 2 /g, and the pore volume is 0.3-1.0 ml/g.
  • the preparation method of the modified carrier is as follows: loading the precursor of Na or K onto the carrier, and obtaining the modified carrier after roasting.
  • the precursor of Na or K is selected from carbonates, nitrates or hydrochlorides of Na or K.
  • the weight of Na or K accounts for 0.05 to 2% of the total mass of the modified carrier.
  • the weight of Na or K accounts for 0.1 to 1.2% of the total mass of the modified carrier.
  • the weight of Na or K accounts for 0.4-0.8% of the total mass of the modified carrier.
  • the roasting conditions in the modified carrier preparation method are: normal pressure, temperature 300-700°C, time 4-10 hours, atmosphere is one or a combination of two or more of air, oxygen, and nitrogen, and gas volume space velocity is 0- 2000h -1 .
  • the roasting process is carried out in a static (non-flowing) atmosphere.
  • roasting treatment of the modified carrier can be performed in the following equipment: muffle furnace, tube furnace, etc.
  • the roasting atmosphere of the modified carrier preparation method when the selected carrier is Al 2 O 3 , SiO 2 , Al 2 O 3 -SiO 2 , the roasting atmosphere is preferably air or oxygen; when the selected carrier is activated carbon, the roasting atmosphere Choose nitrogen.
  • the supported catalyst active metal is one or a combination of Ni and Co.
  • the weight of the active component accounts for 5 to 50% of the total weight of the catalyst.
  • the weight of the active component accounts for 10 to 30% of the total weight of the catalyst.
  • the additive is one or a combination of elements Fe, Ir, Re, Ru, Cu, Mn, B, and W.
  • the weight of the additive accounts for 0.05 to 10% of the total weight of the catalyst.
  • the weight of the auxiliary agent accounts for 0.5 to 6% of the total weight of the catalyst.
  • the preparation method of the supported catalyst is as follows: using at least one of the impregnation method and the precipitation method to load the active metal and auxiliary agent onto the modified carrier.
  • the process is as follows: the modified carrier is immersed in a solution containing an active metal element source and an auxiliary element source, and the catalyst is obtained after drying and roasting.
  • the process is as follows: a solution containing an active metal element source and an auxiliary element source is added to the suspension of the modified carrier together with the precipitant, precipitated, aged, washed, and dried. Calcined to obtain the catalyst.
  • the calcination temperature is 200-600°C
  • the calcination time is 0.5-15 hours
  • the calcination atmosphere is one or a combination of two or more of air, oxygen, and nitrogen.
  • the active component precursor includes a soluble salt of Ni and a soluble salt of Co.
  • the auxiliary precursor includes a soluble precursor of the auxiliary element.
  • the soluble salt of Ni used may be nickel nitrate, nickel acetate, nickel chloride, nickel sulfate or nickel citrate, preferably nickel nitrate or nickel acetate.
  • the soluble salt of Co used can be cobalt nitrate, cobalt acetate, cobalt chloride, cobalt sulfate or cobalt citrate, with cobalt nitrate and cobalt acetate being preferred.
  • the soluble salts of metal additives used are nitrates, hydrochlorides or ammonium salts.
  • the non-metallic additive B used is boric acid.
  • the preparation method of the catalyst can use one or a combination of impregnation and precipitation methods to load the active components and auxiliaries on the modified carrier (the loading amount is the mass content).
  • the active components and auxiliaries can be loaded on the modified carrier by impregnation.
  • a co-impregnation or step-by-step impregnation method can be used to load the active components and auxiliaries on the modified carrier.
  • the step of the above-mentioned impregnation method can be: preparing an aqueous solution containing an active component and an auxiliary precursor, wherein the weight of the active component accounts for 5 to 50% of the weight of the catalyst, and the weight of the auxiliary accounts for 0.05% of the weight of the catalyst. ⁇ 10%, the modified carrier is impregnated with an aqueous solution containing active components and additives, dried naturally, and then roasted.
  • the impregnation method can be one-time impregnation or multi-step impregnation.
  • the calcination temperature is usually 200-600°C and the calcination time is 0.5-15 hours.
  • the catalyst precursor can also be loaded on the modified carrier through precipitation.
  • the steps for preparing the catalyst by the above precipitation method may be: suspending the modified carrier in water, adding soluble precursors of active components and auxiliaries, such as metal salts, and then adding a precipitant to separate the active components and auxiliaries.
  • the agent is precipitated on the suspended modified carrier.
  • the weight of active components accounts for 5 to 50% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.05 to 10% of the weight of the catalyst.
  • the precipitated samples were aged, washed, filtered, dried and roasted.
  • the precipitating agent used is preferably an inorganic base, preferably sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate.
  • the precipitating agent used may also be an ammonium salt, which may be ammonium carbonate, ammonium hydroxide or ammonium halide.
  • the precipitation temperature may be 20-100°C, preferably 40-60°C.
  • the calcination temperature is usually 200-600°C and the calcination time is 0.5-15 hours.
  • the calcined catalyst needs to be subjected to reduction activation treatment.
  • the operation process of the reducing activity is as follows: the catalyst is treated at high temperature in a reducing atmosphere.
  • the reduction activation treatment process is carried out in a hydrogen atmosphere.
  • the conditions of the reduction treatment are: temperature 200-600°C, pressure 0.1MPa, time 0.5-10h, and hydrogen space velocity 20-3000h -1 .
  • the reducing atmosphere includes a mixture of hydrogen and an inert gas, where the inert gas may be nitrogen, helium, or argon.
  • the reducing atmosphere is hydrogen.
  • the present invention provides a method for treating a catalyst in a high-temperature ammonia atmosphere.
  • the supported catalyst needs to be treated in a high-temperature ammonia atmosphere before being used to catalytically synthesize polyethylene polyamine.
  • the operation process of the high-temperature ammonia atmosphere treatment is as follows: the catalyst is treated at high temperature in an ammonia atmosphere before being used to catalyze the synthesis of polyethylene polyamine.
  • the conditions for the high-temperature ammonia atmosphere treatment are: temperature 300-600°C, pressure 0.1-5MPa, and time 1-20 hours.
  • the conditions for the high-temperature ammonia atmosphere treatment are: temperature 350-450°C, pressure 1-4MPa, and time 5-15 hours.
  • the conditions for the high-temperature ammonia atmosphere treatment are: temperature 350-450°C, pressure 1.5-3MPa, and time 8-12 hours.
  • the ammonia source for the high-temperature ammonia atmosphere treatment is liquid ammonia, and the liquid hourly space velocity is 1 to 2h -1 .
  • the catalyst treated in a high-temperature ammonia atmosphere can be directly used in the reaction of hydroamination of monoethanolamine and ethylenediamine to synthesize polyethylene polyamine.
  • the catalyst prepared by this method is used for the hydroamination reaction of monoethanolamine and ethylenediamine. It has the advantages of high polyethylene polyamine yield, good stability, high activity, etc., and has broad industrial prospects.
  • the high-temperature ammonia atmosphere treatment process can be performed in situ on the reactor before the hydroamination reaction of monoethanolamine and ethylenediamine to synthesize polyethylene polyamine.
  • a process route for synthesizing polyethylene polyamine using monoethanolamine and ethylenediamine as main raw materials through a hydrogen catalytic amination reaction is provided.
  • the method has the advantages of easy availability of raw materials, good economy, and high product quality.
  • the distribution is adjustable, there are many types of linear polyethylene polyamines with high yields, continuous production can be achieved, and the process route is simple and easy to operate, etc.
  • the amination reaction uses monoethanolamine, ethylenediamine and ammonia as raw materials, uses the catalyst provided by the present invention, and produces linear polyethylene polyamine as the main product through a catalytic amination reaction under a hydrogen atmosphere and under certain reaction conditions. Amine products.
  • the polyethylene polyamine products include linear polyethylene polyamine, branched polyethylene polyamine and cyclic polyethylene polyamine.
  • the linear polyethylene polyamine refers to a compound with the following structure. Among them, n ⁇ 1. Usually, 1 ⁇ n ⁇ 6.
  • the branched polyethylene polyamine refers to the non-cyclic isomer of linear polyethylene polyamine. Including but not limited to compounds with the following structures.
  • the cyclic polyethylene polyamine refers to a polyethylene polyamine with a cyclic structure, and the cyclic structure includes but is not limited to piperazine ring, pyrazine ring, morpholine ring, etc. Including but not limited to compounds with the following structures.
  • the molar ratio of monoethanolamine:ethylenediamine in the raw materials is 0 to 10:1.
  • the molar ratio of monoethanolamine:ethylenediamine in the raw material is 0 to 5:1.
  • the molar ratio of the liquid ammonia to the reaction raw materials is 0 to 90%.
  • the raw material may be diluted by adding a solvent, or no other solvent may be added.
  • reaction raw material ammonia is selected from ammonia gas, liquid ammonia and ammonia water.
  • the raw ammonia is selected from liquid ammonia.
  • the amination reaction is carried out under a hydrogen atmosphere
  • the hydrogen atmosphere refers to the conditions under which hydrogen gas is introduced.
  • the amination reaction process is carried out under hydrogen conditions, wherein the molar concentration of hydrogen in the total feed materials is 0.5 to 80%.
  • the molar concentration of hydrogen in the total feed material is 1 to 40%.
  • the raw materials are pumped into a preheater, preheated at 50-120°C and then entered into the reactor for reaction.
  • the amination reaction is carried out in a continuous or batch reactor.
  • the continuous or batch reactor is selected from one of a fixed bed, a high-pressure reactor, a slurry bed, and a fluidized bed.
  • the reactor is selected from fixed beds.
  • reaction conditions of the hydrogen catalytic amination are: reaction temperature 130-220°C, preferably 150-200°C; reaction pressure 1-30MPa, preferably 6-26MPa; the total liquid hourly space velocity of monoethanolamine and ethylenediamine is 0.02 ⁇ 15h -1 , preferably 0.1 ⁇ 10h -1 .
  • the catalytic system, its special treatment method and its application conditions described in this application are also suitable for use in the ammoniation reaction of other mono-alcohols or polyols or polyamines to prepare organic amines.
  • the monoalcohol substrate includes but is not limited to 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 6-amino-1-hexanol, etc.
  • the diol or polyol substrate includes, but is not limited to, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,2- Pentylene glycol, 1,6-hexanediol, diethylene glycol, polyether polyol PPG-230, polyether polyol PPG-440, 1,2,6-hexanetriol, etc.
  • the polyamines include but are not limited to aliphatic diamines or aromatic diamines, such as 1,2-propanediamine, 1,3-propanediamine, and 1,4-butanediamine. , 1,5-pentanediamine, 1,2-pentanediamine, 1,6-hexanediamine, furandimethylamine (2,5-diaminomethylfuran), octanediamine, decanediamine, etc.
  • the present invention uses active components Ni, Co, and auxiliary elements Fe, Ir, Re, Ru, Cu, Mn, B, W, and carriers Al 2 O 3 , activated carbon, SiO 2 and Al 2 O 3 -SiO
  • the combination of 2 produces a synergistic catalyst effect, thereby improving the catalytic activity of the catalyst in the hydroamination reaction of monoethanolamine and ethylenediamine.
  • the present invention affects the adsorption and activation ability of ammonia by active metals by subjecting the carrier to alkali metal modification treatment and subjecting the reduced catalyst to high-temperature treatment in an ammonia atmosphere, thereby regulating the ratio between active metals and active metal nitrides. , which has the effect of increasing the yield of linear polyethylene polyamine in the product.
  • the catalyst of the present invention When the catalyst of the present invention is used in the hydroamination reaction of monoethanolamine and ethylenediamine, it has the effect of increasing the yield of linear polyethylene polyamine and reducing the selectivity of branched or cyclic amine by-products. In particular, the yield of long-chain linear polyethylenepolyamines in the product can be increased.
  • the long-chain linear polyethylene polyamines include linear triethylenetetramine and higher linear ethylenediamine polymer homologues.
  • the catalyst has high activity and good stability, which can achieve long-term stable production.
  • the catalyst substrate of the present invention has good adaptability and shows excellent catalytic effect on raw materials with different proportions of monoethanolamine, ethylenediamine and ammonia.
  • the preparation method of Catalyst 1 is as follows. First, carry out carrier modification treatment: take 7.794 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of aqueous solution containing 0.014 grams of sodium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 to obtain a modified carrier of 0.08Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and soak it in the above 0.08Na-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • the obtained catalyst 1 is Ni10Co10Ru2/0.08Na-SiO 2 .
  • Catalyst 1 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 2MPa, the hourly space velocity of liquid ammonia is 1.5h -1 , and the treatment time is 10h.
  • the treated catalyst 1 is used for reaction evaluation.
  • the reaction temperature is 170°C
  • the pressure is 12MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 0.3: 1:1, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 1h -1 , and the molar concentration of hydrogen is 10%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the preparation method of Catalyst 2 is as follows. First, carry out carrier modification treatment: take 7.78 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of an aqueous solution containing 0.045 grams of sodium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 to obtain a modified carrier of 0.25Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divided equally into two equal parts, and repeated the following process twice: Dip a portion of the aqueous solution into the above 0.25Na-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • the obtained catalyst 2 is Ni10Co10Ru2/0.25Na-SiO 2 .
  • the treated catalyst 2 was used for reaction evaluation, and the reaction conditions were the same as in Example 1. The results are shown in Table 1.
  • the preparation method of Catalyst 3 is as follows. First, carry out carrier modification treatment: take 7.753 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of aqueous solution containing 0.108 grams of sodium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 to obtain a modified carrier of 0.6Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and soak it in the above 0.6Na-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • Catalyst 3 was obtained as Ni10Co10Ru2/0.6Na-SiO 2 .
  • the high-temperature ammonia atmosphere treatment process before catalyst 3 is used for the reaction is the same as that in Example 1.
  • the treated catalyst 3 was used for reaction evaluation, and the reaction conditions were the same as in Example 1. The results are shown in Table 1.
  • the preparation method of Catalyst 4 is as follows. First, carry out carrier modification treatment: take 7.722 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of aqueous solution containing 0.18 grams of sodium carbonate, impregnate the above carrier with this aqueous solution, dry naturally, and bake in an air atmosphere at 400°C for 6 hours with a gas volume space velocity of 0h -1 to obtain a modified carrier of 1Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and soak it in the above 1Na-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • Catalyst 4 was obtained as Ni10Co10Ru2/1Na-SiO 2 .
  • the treated catalyst 4 was used for reaction evaluation, and the reaction conditions were the same as in Example 1. The results are shown in Table 1.
  • the preparation method of Catalyst 5 is as follows. First, carry out carrier modification treatment: take 7.66 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of aqueous solution containing 0.3236 grams of sodium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 to obtain a modified carrier of 1.8Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and soak it in the above 1.8Na-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • the obtained catalyst 5 is Ni10Co10Ru2/1.8Na-SiO 2 .
  • the treated catalyst 5 was used for reaction evaluation, and the reaction conditions were the same as in Example 1. The results are shown in Table 1.
  • the preparation method of Catalyst 6 is as follows. First, carry out carrier modification treatment: take 7.777 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of an aqueous solution containing 0.054 grams of sodium carbonate and 0.041 grams of potassium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 .
  • the modified carrier is obtained: 0.3Na0.3K-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide into two equal parts, and repeat the following process twice: take one part of the aqueous solution and soak it in the above 0.3Na0.3K-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • the obtained catalyst 6 is Ni10Co10Ru2/0.3Na0.3K-SiO 2 .
  • the treated catalyst 6 was used for reaction evaluation, and the reaction conditions were the same as in Example 1. The results are shown in Table 1.
  • the preparation method of Catalyst 7 is as follows. First, carry out carrier modification treatment: take 7.654 grams of alumina carrier, dry it at 120°C and set it aside. Prepare 6 ml of aqueous solution containing 0.119 grams of potassium nitrate, impregnate the above carrier with this aqueous solution, dry naturally, and bake in an air atmosphere at 600°C for 5 hours with a gas volume space velocity of 200h -1 to obtain a modified carrier of 0.6K-Al 2 O 3 .
  • the second step is to load active metals and additives: configure 12ml containing 7.432 grams Ni(NO 3 ) 2 ⁇ 6H 2 O, 2.469 grams Co(NO 3 ) 2 ⁇ 6H 2 O, 1.14 grams Cu(NO 3 ) 2 ⁇ 3H Divide the aqueous solution of 2 O into two equal parts, and repeat the following process twice: Dip one part of the aqueous solution into the above 0.6K-Al 2 O 3 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 400°C for 10h. Carry out reduction treatment: the reduction conditions are a temperature of 450°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 500h -1 , and a reduction time of 8h. Catalyst 7 was obtained as Ni15Co5Cu3/0.6K-Al 2 O 3 .
  • Catalyst 7 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 320°C, the pressure is 2MPa, the hourly space velocity of liquid ammonia is 1.8h -1 , and the treatment time is 10h.
  • the treated catalyst 7 is used for reaction evaluation.
  • the reaction temperature is 180°C
  • the pressure is 14MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 0.2: 1:1, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 2h -1 , and the molar concentration of hydrogen is 15%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • Catalyst 7 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 2MPa, the hourly space velocity of liquid ammonia is 1.8h -1 , and the treatment time is 10h.
  • the treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as those in Example 7.
  • Catalyst 7 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 580°C, the pressure is 2MPa, the hourly space velocity of liquid ammonia is 1.8h -1 , and the treatment time is 10h.
  • the treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as those in Example 7.
  • the preparation method of Catalyst 8 is as follows. First, carry out carrier modification treatment: take 7.547 grams of alumina-silica carrier, dry it at 120°C and set it aside. Prepare 7 ml of aqueous solution containing 0.094 grams of potassium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 550°C for 6 hours. The gas volume space velocity is 1000h -1 to obtain a modified carrier of 0.7K-Al 2 O. 3 SiO 2 .
  • the second step is to load active metals and additives: prepare 14 ml of aqueous solution containing 9.909 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 0.988 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.288 grams of NH 4 ReO 4 , all Divide it into two equal parts and repeat the following process twice: take one part of the aqueous solution and impregnate it with the above 0.7K-Al 2 O 3 -SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 350°C for 12h.
  • the reduction conditions are a temperature of 460°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 200h -1 , and a reduction time of 10h.
  • Catalyst 8 was obtained as Ni20Co2Re2/0.7K-Al 2 O 3 -SiO 2 .
  • Catalyst 8 is used for high-temperature ammonia atmosphere treatment before the reaction: the ammonia treatment temperature is 380°C, the pressure is 0.2MPa, the hourly space velocity of liquid ammonia is 2h -1 , and the treatment time is 10h.
  • the treated catalyst 8 is used for reaction evaluation.
  • the reaction temperature is 190°C
  • the pressure is 25MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 1: 1:5, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 4h -1 , and the molar concentration of hydrogen is 5%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • Catalyst 8 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 1.1MPa, the hourly space velocity of liquid ammonia is 2h -1 , and the treatment time is 10h.
  • the treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as those in Example 10.
  • Catalyst 8 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 2MPa, the hourly space velocity of liquid ammonia is 2h -1 , and the treatment time is 10h.
  • the treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as those in Example 10.
  • the stability of the catalyst was evaluated, and samples were taken for analysis after continuous evaluation for 50h and 2000h in the fixed-bed reactor. The results are shown in Table 1, in which the upper and lower rows of Example 12 correspond to the reaction evaluation results of 50h and 2000h respectively.
  • Catalyst 8 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 3.8MPa, the hourly space velocity of liquid ammonia is 2h -1 , and the treatment time is 10h.
  • the treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as those in Example 10.
  • Catalyst 8 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 4.9MPa, the hourly space velocity of liquid ammonia is 2h -1 , and the treatment time is 10h.
  • the treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as those in Example 10.
  • the activated catalyst 8 was used for reaction evaluation.
  • the reaction temperature was 190°C
  • the pressure was 25MPa
  • the liquid phase feed was ethylenediamine
  • the liquid hourly space velocity of ethylenediamine was 4h -1
  • the hydrogen molar concentration was 5%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the treated catalyst 8 is used for reaction evaluation.
  • the reaction temperature is 190°C
  • the pressure is 25MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 7: 1:15, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 4h -1 , and the hydrogen molar concentration is 5%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the preparation method of Catalyst 9 is as follows. First, carry out carrier modification treatment: take 7.214 grams of alumina carrier, dry it at 120°C and set it aside. Prepare 6.8 ml of an aqueous solution containing 0.134 grams of sodium nitrate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 350°C for 8 hours. The gas volume space velocity is 1500h -1 to obtain a modified carrier of 0.5Na-Al 2 O 3 . The second step is to load active metals and additives: disperse 0.5Na-Al 2 O 3 in water to form a suspension, and stir at a medium speed at a constant temperature of 50°C.
  • a precursor liquid containing 7.408 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, and 0.459 grams of IrCl 3 ⁇ 3H 2 O was prepared.
  • the precipitating agent used was 2 mol/L NaOH solution. Add the precursor liquid and precipitant dropwise to the above suspension at a rate of 1 ml/min at the same time. Keep the pH value at 9 until the precipitation is complete. The precipitate is washed with deionized water until neutral, filtered, dried, and dried at 120°C for 10 hours. , roasted at 550°C for 4 hours in air.
  • the reduction conditions are a temperature of 450°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 2000h -1 , and a reduction time of 4h.
  • Catalyst 9 was obtained as Co15Ni10Ir2.5/0.5Na-Al 2 O 3 .
  • Catalyst 9 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 2h.
  • the treated catalyst 9 is used for reaction evaluation.
  • the reaction temperature is 160°C
  • the pressure is 20MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 0.5: 1:0.1, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 0.6h -1 , and the hydrogen molar concentration is 20%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • Catalyst 9 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 6h.
  • the treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in Example 17.
  • Catalyst 9 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 10h.
  • the treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in Example 17.
  • Catalyst 9 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 14h.
  • the treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in Example 17.
  • Catalyst 9 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 20h.
  • the treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in Example 17.
  • Catalyst 10 is prepared as follows. First, carry out carrier modification treatment: 8.201 grams of activated carbon carrier, dry at 120°C and set aside. Prepare 10 ml of an aqueous solution containing 0.126 grams of sodium chloride, impregnate the above carrier with this aqueous solution, dry it naturally, and bake it in a nitrogen atmosphere at 400°C for 10 hours with a gas volume space velocity of 100h -1 to obtain a modified carrier of 0.6Na-C.
  • the second step is to load active metals and additives: prepare 20 ml of aqueous solution containing 7.408 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, 0.866 grams of Fe(NO 3 ) 3 , and 0.129 grams of RuCl 3 ⁇ 3H 2 O, divided equally into Repeat the following process twice for two equal parts: Dip one part of the aqueous solution into the above 0.6Na-C carrier, dry it naturally, dry it at 120°C for 10h, and bake it in nitrogen at 400°C for 4h. Carry out reduction treatment: the reduction conditions are a temperature of 400°C, an atmosphere of hydrogen at normal pressure, a volume space velocity of 800h -1 , and a reduction time of 5h.
  • the obtained catalyst 10 is Co15Fe2Ru0.5/0.6Na-C.
  • Catalyst 10 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1.1h -1 , and the treatment time is 10h.
  • the treated catalyst 10 is used for reaction evaluation.
  • the reaction temperature is 200°C
  • the pressure is 18MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 1.5: 1:10, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 7h -1 , and the hydrogen molar concentration is 30%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the preparation method of Catalyst 11 is as follows. First, the carrier modification treatment is carried out: 7.661 grams of silica carrier is dried at 120°C and set aside. Prepare 7 ml of an aqueous solution containing 0.099 grams of potassium nitrate, impregnate the above carrier with this aqueous solution, dry naturally, and bake in an air atmosphere at 400°C for 10 hours with a gas volume space velocity of 0h -1 to obtain a modified carrier of 0.5K-SiO 2 .
  • the second step is to load active metals and additives: prepare 14 ml of aqueous solution containing 9.909 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 1.145 grams of H 3 BO 3 , and 0.326 grams of Mn(NO 3 ) 2 , and divide them into two equal parts. parts, repeat the following process twice: Take one part of the aqueous solution and soak it in the above 0.5K-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 400°C for 6h. Carry out reduction treatment: the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 500h -1 , and a reduction time of 5h.
  • the obtained catalyst 11 is Ni20B2Mn1/0.5K-SiO 2 .
  • Catalyst 11 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1.2h -1 , and the treatment time is 10h.
  • the treated catalyst 11 is used for reaction evaluation.
  • the reaction temperature is 185°C
  • the pressure is 15MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 1.5: 1:10, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 3.5h -1 , and the hydrogen molar concentration is 3%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the preparation method of catalyst 12 is as follows. First, the carrier modification treatment is carried out: 7.761 grams of alumina carrier is dried at 120°C before use. Prepare 6.8ml of an aqueous solution containing 0.101g of potassium nitrate, impregnate the above carrier with this aqueous solution, dry it naturally, and bake it in an air atmosphere at 400°C for 10h with a gas volume space velocity of 50h -1 to obtain a modified carrier of 0.5K-Al 2 O 3 .
  • the second step is to load active metals and additives: configure 13.6ml containing 4.955g Ni(NO 3 ) 2 ⁇ 6H 2 O, 2.469g Co(NO 3 ) 2 ⁇ 6H 2 O, 0.572g H 3 BO 3 , 0.154g Divide the aqueous solution of (NH 4 ) 2 WO 4 into two equal parts and repeat the following process twice: take one part of the aqueous solution and impregnate it with the above 0.5K-Al 2 O 3 carrier, dry it naturally, dry it at 120°C for 10h, and expose it to 400°C in the air. Roast at °C for 6h.
  • the reduction conditions are a temperature of 450°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 500h -1 , and a reduction time of 5h.
  • Catalyst 12 was obtained as Ni10Co5B1W1/0.5K-Al 2 O 3 .
  • Catalyst 12 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1.2h -1 , and the treatment time is 10h.
  • the treated catalyst 12 is used for reaction evaluation.
  • the reaction temperature is 155°C
  • the pressure is 15MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 1.5: 1:10, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 0.4h -1 , and the hydrogen molar concentration is 8%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the preparation method of Catalyst 13 is as follows. First, the carrier modification treatment is carried out: 9.244 grams of silica carrier is dried at 120°C before use. Prepare 9 ml of aqueous solution containing 0.206 grams of sodium nitrate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 10 hours with a gas volume space velocity of 50h -1 to obtain a modified carrier of 0.6Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 18 ml of aqueous solution containing 2.477 grams Ni(NO 3 ) 2 ⁇ 6H 2 O, 0.494 grams Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.144 grams NH 4 ReO 4 , all Divide into two equal parts and repeat the following process twice: take one part of the aqueous solution and impregnate the above 0.6Na-SiO 2 carrier, dry naturally, dry at 120°C for 10h, and roast at 400°C in the air for 6h. Carry out reduction treatment: the reduction conditions are a temperature of 450°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 500h -1 , and a reduction time of 5h. Catalyst 13 was obtained as Ni5Co1Re1/0.6Na-SiO 2 .
  • Catalyst 13 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1.2h -1 , and the treatment time is 10h.
  • the treated catalyst 13 is used for reaction evaluation.
  • the reaction temperature is 185°C
  • the pressure is 15MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 1.5: 1:10, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 3h -1 , and the molar concentration of hydrogen is 10%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • Catalyst 14 is prepared as follows. First, the carrier modification treatment is carried out: 5.268 grams of alumina carrier is dried at 120°C before use. Prepare 5 ml of an aqueous solution containing 0.117 grams of sodium nitrate, impregnate the above carrier with this aqueous solution, dry naturally, and bake in an air atmosphere at 500°C for 10 hours with a gas volume space velocity of 200h -1 to obtain a modified carrier of 0.6Na-Al 2 O 3 . The second step is to load active metals and additives: disperse 0.6Na-Al 2 O 3 in water to form a suspension, and stir at a medium speed at a constant temperature of 50°C.
  • a precursor liquid containing 19.819 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 2.862 grams of H 3 BO 3 and 0.367 grams of IrCl 3 ⁇ 3H 2 O was prepared.
  • the precipitating agent used was 3mol/L NaOH solution. Add the precursor liquid and precipitant dropwise to the above suspension at a rate of 1 ml/min at the same time. Keep the pH value at 9 until the precipitation is complete. The precipitate is washed with deionized water until neutral, filtered, dried, and dried at 120°C for 10 hours. , roasted at 400°C for 6 hours in air.
  • the reduction conditions are a temperature of 450°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 100h -1 , and a reduction time of 10h.
  • Catalyst 14 was obtained as Ni40B5Ir2/0.6Na-Al 2 O 3 .
  • Catalyst 14 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1.2h -1 , and the treatment time is 10h.
  • the treated catalyst 14 is used for reaction evaluation.
  • the reaction temperature is 185°C
  • the pressure is 15MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 1.5: 1:10, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 3h -1 , and the molar concentration of hydrogen is 10%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the catalyst is 30% Ni-2% Re-1.2% B/Al 2 O 3 and is prepared according to the method described in Example 8 of patent WO 2013/152548.
  • the catalyst 30% Ni-2% Re-1.2% B/Al 2 O 3 reduction process is as described in the examples of patent WO 2013/152548.
  • the reduced catalyst was used for reaction evaluation, and the reaction conditions were the same as in Example 1.
  • the catalyst was 34% H 3 PO 4 supported on silica, prepared according to the method described in Example 1 of patent US 4503253. According to patent US 4503253, the catalyst does not require activation treatment before use.
  • the catalyst is acidic lanthanum phosphate, prepared according to the method described in Catalyst-B acidic lanthanum phosphate in patent US 4617418. According to patent US 4617418, the catalyst does not require activation treatment before use.
  • the catalyst is Ni-Y-Ir/Al 2 O 3 and is prepared according to the method described in Catalyst-19 in patent US 5321160.
  • the catalyst Ni-Y-Ir/Al 2 O 3 reduction process is as described in the example of patent US 5321160.
  • the catalyst is a Lewis acid halide, tin chloride as described in Example 7 of patent US 4399308.
  • Catalyst tin chloride was used for reaction evaluation, and the reaction conditions were the same as in Example 1. No reaction product was detected in the product, which is indicated by "-" in Table 1 - Comparative Example 5.
  • the preparation process of catalyst 15 is as follows.
  • the support is not modified with alkali metals. Take 7.8 grams of silica carrier and dry it at 120°C for later use. Prepare 15ml of aqueous solution containing 4.955g Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939g Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517g RuCl 3 ⁇ 3H 2 O. Divide it into two equal parts and repeat the following process. 2 times: Dip a portion of the aqueous solution into the above-mentioned SiO2 carrier, dry naturally, dry at 120°C for 10h, and bake at 500°C in the air for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • Catalyst 15 was obtained as Ni10Co10Ru2/SiO 2 .
  • the high-temperature ammonia atmosphere treatment process before the catalyst 15 is used for the reaction is the same as that in Example 1.
  • the treated catalyst 15 was used for reaction evaluation, and the reaction conditions were the same as in Example 1.
  • the preparation process of catalyst 16 is as follows. First, carry out carrier modification treatment: take 7.753 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of an aqueous solution containing 0.276 grams of Ca(NO 3 ) 2 ⁇ 4H 2 O. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 to obtain the modified carrier. The sexual carrier is 0.6Ca-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and soak it in the above 0.6Ca-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • Catalyst 16 was obtained as Ni10Co10Ru2/0.6Ca-SiO 2 .
  • the treated catalyst 16 was used for reaction evaluation, and the reaction conditions were the same as in Example 1.
  • the preparation process of catalyst 17 is as follows. First, carry out carrier modification treatment: take 7.753 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of an aqueous solution containing 0.285 grams of Mg(NO 3 ) 2. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 to obtain a modified carrier of 0.6 Mg-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and soak it in the above 0.6Mg-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • Catalyst 17 was obtained as Ni10Co10Ru2/0.6Mg-SiO 2 .
  • the treated catalyst 17 was used for reaction evaluation, and the reaction conditions were the same as in Example 1.
  • the preparation process of catalyst 18 is as follows. First, carry out carrier modification treatment: take 7.799 grams of silica carrier, dry it at 120°C and set it aside. Prepare 7.5 ml of aqueous solution containing 0.002 grams of sodium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours. The gas volume space velocity is 0h -1 to obtain a modified carrier of 0.01Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divided equally into two equal parts, and repeated the following process twice: Dip a portion of the aqueous solution into the above 0.01Na-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • Catalyst 18 was obtained as Ni10Co10Ru2/0.01Na-SiO 2 .
  • the catalyst 18 is used in the same high-temperature ammonia atmosphere treatment process as in Example 1 before the reaction.
  • the treated catalyst 18 was used for reaction evaluation, and the reaction conditions were the same as in Example 1.
  • the preparation process of catalyst 19 is as follows. First, carry out carrier modification treatment: take 7.41 grams of silica carrier, dry it at 120°C and set aside. Prepare 7.5 ml of an aqueous solution containing 0.899 grams of sodium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 400°C for 6 hours with a gas volume space velocity of 0h -1 to obtain a modified carrier of 5Na-SiO 2 .
  • the second step is to load active metals and additives: prepare 15 ml of aqueous solution containing 4.955 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RuCl 3 ⁇ 3H 2 O , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and impregnate it with the above 5Na-SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • Catalyst 19 was obtained as Ni10Co10Ru2/5Na-SiO 2 .
  • the treated catalyst 19 was used for reaction evaluation, and the reaction conditions were the same as in Example 1.
  • the preparation process of catalyst 20 is as follows. First, carry out carrier modification treatment: take 7.753 grams of silica carrier, dry it at 120°C and set it aside. Prepare 15ml of aqueous solution containing 0.108g Na 2 CO 3 , 4.955g Ni(NO 3 ) 2 ⁇ 6H 2 O, 4.939g Co(NO 3 ) 2 ⁇ 6H 2 O, 0.517g RuCl 3 ⁇ 3H 2 O, and divide it equally into Repeat the following process twice in two equal parts: take one part of the aqueous solution and impregnate the above-mentioned SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 500°C for 5h.
  • the reduction conditions are a temperature of 400°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 1000h -1 , and a reduction time of 6h.
  • the obtained catalyst 20 is Ni10Co10Ru2Na0.6/SiO 2 .
  • the high-temperature ammonia atmosphere treatment process before the catalyst 20 is used for the reaction is the same as that in Example 1.
  • the treated catalyst 20 was used for reaction evaluation, and the reaction conditions were the same as in Example 1.
  • Catalyst 7 is not subjected to high-temperature ammonia atmosphere treatment before reaction.
  • Catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as Example 7.
  • Catalyst 7 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 240°C, the pressure is 2MPa, the hourly space velocity of liquid ammonia is 1.8h -1 , and the treatment time is 10h.
  • the treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as those in Example 7.
  • Catalyst 7 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 750°C, the pressure is 2MPa, the hourly space velocity of liquid ammonia is 1.8h -1 , and the treatment time is 10h.
  • the treated catalyst 7 was used for reaction evaluation, and the reaction conditions were the same as those in Example 7.
  • Catalyst 8 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 380°C, the pressure is 8MPa, the hourly space velocity of liquid ammonia is 2h -1 , and the treatment time is 10h.
  • the treated catalyst 8 was used for reaction evaluation, and the reaction conditions were the same as those in Example 10.
  • Catalyst 9 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 0.2h.
  • the treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in Example 17.
  • Catalyst 9 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 100h.
  • the treated catalyst 9 was used for reaction evaluation, and the reaction conditions were the same as in Example 17.
  • the preparation method of catalyst 21 is as follows. First, carry out carrier modification treatment: take 7.711 grams of alumina carrier, dry it at 120°C and set it aside. Prepare 6.8 ml of an aqueous solution containing 0.143 grams of sodium nitrate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 350°C for 8 hours. The gas volume space velocity is 1500h -1 to obtain a modified carrier of 0.5Na-Al 2 O 3 . The second step is to load active metals and additives: disperse 0.5Na-Al 2 O 3 in water to form a suspension, and stir at a medium speed at a constant temperature of 50°C.
  • a precursor liquid containing 8.663 grams of Fe(NO 3 ) 3 and 0.459 grams of IrCl 3 ⁇ 3H 2 O was prepared.
  • the precipitating agent used was 2 mol/L NaOH solution.
  • the precipitate is washed with deionized water until neutral, filtered, dried, and dried at 120°C for 10 hours. , roasted at 550°C for 4 hours in air.
  • Catalyst 21 was obtained as Fe20Ir2.5/0.5Na-Al 2 O 3 .
  • Catalyst 21 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 10h.
  • the treated catalyst 21 was used for reaction evaluation, and the reaction conditions were the same as those in Example 17.
  • Catalyst 22 is prepared as follows. First, carry out carrier modification treatment: take 7.711 grams of alumina carrier, dry it at 120°C and set it aside. Prepare 6.8 ml of an aqueous solution containing 0.143 grams of sodium nitrate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 350°C for 8 hours. The gas volume space velocity is 1500h -1 to obtain a modified carrier of 0.5Na-Al 2 O 3 . The second step is to load active metals and additives: disperse 0.5Na-Al 2 O 3 in water to form a suspension, and stir at a medium speed at a constant temperature of 50°C.
  • a precursor liquid containing 7.602 grams of Cu(NO 3 ) 2 ⁇ 3H 2 O and 0.459 grams of IrCl 3 ⁇ 3H 2 O was prepared.
  • the precipitating agent used was 2 mol/L NaOH solution.
  • the precipitate is washed with deionized water until neutral, filtered, dried, and dried at 120°C for 10 hours. , roasted at 550°C for 4 hours in air.
  • the obtained catalyst 22 is Cu20Ir2.5/0.5Na-Al 2 O 3 .
  • the catalyst 22 was used in the same high-temperature ammonia atmosphere treatment process before the reaction as in Comparative Example 18.
  • the treated catalyst 22 was used for reaction evaluation, and the reaction conditions were the same as those in Example 17.
  • the preparation method of catalyst 23 is as follows. First, carry out carrier modification treatment: take 7.711 grams of alumina carrier, dry it at 120°C and set it aside. Prepare 6.8 ml of an aqueous solution containing 0.143 grams of sodium nitrate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 350°C for 8 hours. The gas volume space velocity is 1500h -1 to obtain a modified carrier of 0.5Na-Al 2 O 3 . The second step is to load active metals and additives: disperse 0.5Na-Al 2 O 3 in water to form a suspension, and stir at a medium speed at a constant temperature of 50°C.
  • a precursor liquid containing 5.309 grams of H 2 PtCl 6 ⁇ 6H 2 O and 0.459 grams of IrCl 3 ⁇ 3H 2 O was prepared.
  • the precipitating agent used was 2 mol/L NaOH solution.
  • the precipitate is washed with deionized water until neutral, filtered, dried, and dried at 120°C for 10 hours. , roasted at 550°C for 4 hours in air.
  • Catalyst 23 was obtained as Pt20Ir2.5/0.5Na-Al 2 O 3 .
  • Catalyst 23 is used for high-temperature ammonia atmosphere treatment before reaction: the ammonia treatment temperature is 400°C, the pressure is 1.8MPa, the hourly space velocity of liquid ammonia is 1h -1 , and the treatment time is 10h.
  • the treated catalyst 23 was used for reaction evaluation, and the reaction conditions were the same as those in Example 17.
  • Catalyst 24 is prepared as follows. First, carry out carrier modification treatment: take 7.547 grams of alumina-silica carrier, dry it at 120°C and set it aside. Prepare 7 ml of aqueous solution containing 0.094 grams of potassium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 550°C for 6 hours. The gas volume space velocity is 1000h -1 to obtain a modified carrier of 0.7K-Al 2 O. 3 -SiO 2 .
  • the second step is to load active metals and additives: prepare 14 ml of an aqueous solution containing 9.909 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O, 0.988 grams of Co(NO 3 ) 2 ⁇ 6H 2 O, and 0.517 grams of RhCl 3 ⁇ 3H 2 O. , divide it into two equal parts, and repeat the following process twice: take one part of the aqueous solution and impregnate it with the above 0.7K-Al 2 O 3 -SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 350°C for 12h.
  • the reduction conditions are a temperature of 460°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 200h -1 , and a reduction time of 10h.
  • the obtained catalyst 24 is Ni20Co2Rh2/0.7K-Al 2 O 3 -SiO 2 .
  • the treated catalyst 24 was used for reaction evaluation, and the reaction conditions were the same as those in Example 12.
  • Catalyst 25 is prepared as follows. First, carry out carrier modification treatment: take 7.547 grams of alumina-silica carrier, dry it at 120°C and set it aside. Prepare 7 ml of aqueous solution containing 0.094 grams of potassium carbonate. Use this aqueous solution to impregnate the above carrier, dry it naturally, and bake it in an air atmosphere at 550°C for 6 hours. The gas volume space velocity is 1000h -1 to obtain a modified carrier of 0.7K-Al 2 O. 3 -SiO 2 .
  • the second step is to load active metals and additives: configure 14ml containing 9.909 grams Ni(NO 3 ) 2 ⁇ 6H 2 O, 0.988 grams Co(NO 3 ) 2 ⁇ 6H 2 O, 1.539 grams Cr(NO 3 ) 3 ⁇ 9H 2 O aqueous solution, divide it into two equal parts, repeat the following process twice: take one part of the aqueous solution and soak it in the above 0.7K-Al 2 O 3 -SiO 2 carrier, dry it naturally, dry it at 120°C for 10h, and bake it in the air at 350°C 12h.
  • the reduction conditions are a temperature of 460°C, an atmosphere of normal pressure hydrogen, a volume space velocity of 200h -1 , and a reduction time of 10h.
  • the obtained catalyst 25 is Ni20Co2Cr2/0.7K-Al 2 O 3 -SiO 2 .
  • the treated catalyst 25 was used for reaction evaluation, and the reaction conditions were the same as those in Example 12.
  • the treated catalyst 8 is used for reaction evaluation.
  • the reaction temperature is 190°C
  • the pressure is 25MPa
  • the liquid phase feed is monoethanolamine, ethylenediamine and liquid ammonia.
  • the molar ratio of monoethanolamine:ethylenediamine:liquid ammonia is 15: 1:5, in which the liquid hourly space velocity of monoethanolamine and ethylenediamine is 4h -1 , and the molar concentration of hydrogen is 5%.
  • Samples were taken for analysis after continuous reaction in the fixed-bed reactor for 50 h. The results are shown in Table 1.
  • the beneficial effects of this patent are to improve the substrate conversion rate and the selectivity of linear polyethylene polyamines.
  • it can improve the selectivity of long-chain linear polyethylene polyamines in the product.
  • long-chain linear polyethylene polyamines include linear triethylenetetramine, linear tetraethylenepentamine and linear pentaethylenehexamine.
  • the catalyst in Table 1 it can be seen from Examples 1-6, Comparative Examples 6, and Comparative Examples 9-10 that when the loading amount of the alkali metal Na and K pretreated on the carrier is less than 0.05% or not modified, Although the catalyst shows high activity, its linear polyethylene polyamine selectivity is low and there are more cyclic amine by-products.
  • the catalyst activity shows a trend of first gentle and then rapid decline, and at the same time, the product contains The selectivity of linear polyethylene polyamine first increases and then decreases; compared with the effect of the optional range of 0.05-2% loading, when it is in the preferred range of 0.1-1.2%, it has higher selectivity of linear polyethylene polyamine; with Compared with the effect of the loading amount in the preferred range of 0.1 to 1.2%, the more preferred range of 0.4 to 0.8% has the highest long-chain linear polyethylene polyamine selectivity and a higher monoethanolamine conversion rate.
  • the selectivity of polyamines is poor; as the ammonia treatment temperature increases, the conversion rate shows a trend of first gentle and then rapid decline, and the selectivity of linear polyethylene polyamine shows a trend of first increase and then decrease; with the optional ammonia treatment temperature of 300 ⁇ Compared with 600°C, the preferred ammonia treatment temperature is 350-450°C, which has the highest long-chain linear polyethylene polyamine selectivity while maintaining a higher conversion rate and linear polyethylene polyamine selectivity; ammonia atmosphere activation temperature Too high may cause the catalyst to sinter, resulting in a significant decrease in activity.
  • Example 12 From the evaluation results at 50h and 2000h in Example 12, it can be seen that as the reaction time is extended to 2000h, the conversion rate and selectivity data do not change much, proving that the stability of the catalyst of the present invention is excellent. It can be seen from Examples 10-14 and Comparative Example 15 that with the increase of ammonia atmosphere treatment pressure, the conversion rate shows a trend of first gentle and then rapid decline, and the selectivity of linear polyethylene polyamine first increases and then decreases; with the optional ammonia atmosphere Compared with the treatment pressure of 0.1 to 5MPa, the preferred pressure is 1 to 4MPa, which has higher conversion rate or long-chain linear polyethylene polyamine selectivity; compared with the preferred ammonia atmosphere treatment pressure of 1 to 4MPa, the preferred pressure is 1.5 to 3MPa.

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Abstract

一种催化合成多乙烯多胺的方法，以单乙醇胺和乙二胺为主原料，在催化剂的作用下经临氢胺化反应合成多乙烯多胺产品。所述催化剂由活性金属、助剂、载体三部分组成：活性金属为Ni、Co中的一种或组合，助剂为元素Fe、Ir、Re、Ru、Cu、Mn、B、W中的一种或组合，载体选自Al 2O 3、活性炭、SiO 2、Al 2O 3-SiO 2的一种或组合。载体在使用前经碱金属或碱土金属改性，所述碱金属为Na、K中的一种或组合。还原活化后的催化剂经氨气氛高温处理。该方法制得的催化剂用于单乙醇胺和乙二胺的临氢胺化反应，具有多乙烯多胺产率高、稳定性好、活性高等优点，工业前景广阔。

Description

一种催化合成多乙烯多胺的方法 技术领域
本发明涉及到一种催化合成多乙烯多胺的方法，更详细地，涉及一种改性载体负载的催化剂及其活化处理方法，用于临氢气氛下将原料单乙醇胺和乙二胺经催化胺化反应转化为线性多乙烯多胺为主的胺类产品。
背景技术
多乙烯多胺是乙撑胺的一种，包括乙二胺的线性同系物、支链或环状胺类。其中，常见的线性多乙烯多胺有二乙烯三胺、三乙烯四胺(直链)、四乙烯五胺(直链)等，在造纸、润滑油添加剂、螯合剂、固化剂等领域应用广泛。近年来，我国乙二胺市场逐渐趋于饱和，但线性多乙烯多胺的产能仍较低、高品质产品依赖进口，限制了下游行业的发展。随着国内化工领域的不断成熟和产业结构的逐渐优化，对高纯度的线性多乙烯多胺产品的市场需求日益增加。
目前多乙烯多胺的生产工艺主要包括二氯乙烷法、单乙醇胺法。其中二氯乙烷法由于设备腐蚀严重、能耗高、污染环境、投资成本高等问题逐渐被淘汰。单乙醇胺法是指原料单乙醇胺和液氨在高压、临氢及金属催化剂的存在下经反应生成乙撑胺的工艺，具有绿色清洁、能耗低、原子经济性好等优点，然而产品以乙二胺为主，副产少量的二乙烯三胺，无法大量生成多乙烯多胺产品。因此，目前工业上仍采用技术落后的二氯乙烷法生产多乙烯多胺，为寻找高效、环境友好的多乙烯多胺生产工艺，研究者们提出了以单乙醇胺、乙二胺及氨为原料生产多乙烯多胺的工艺路线。美国专利4399308采用路易斯酸卤化物为催化剂，当采用氯化锡为催化剂、300℃下反应时，非环状多乙烯多胺选择性达71.4％，产品以三乙烯四胺和三氨乙基胺为主。美国专利4503253和4617418采用负载型磷酸或稀土改性的磷酸催化剂，在250-350℃下气相反应单乙醇胺转化率可达40％以上、非环状多乙烯多胺选择性可达80％以上，产品以二乙烯三胺为主，然而活性组分易流失，无法实现长期运行。美国专利5321160采用Ni-Y-Ir体系的负载型催化剂，在反应釜、200℃下间歇反应，单乙醇胺转化率可达27.8％，多乙烯多胺总选择性约70.2％。
综上分析，先用生产多乙烯多胺的催化体系及工艺仍存在以下一种或几种缺点：1.能耗高；2.易腐蚀设备；3.环境污染；4.线性多乙烯多胺选择性低、种类少；5.催化剂不稳定；6.产品中支链或环状胺类副产物较多；7.不能实现连续生产；8.催化剂活性低。本发明为克服以上缺点提供了新的方法。
发明内容
本发明的目的是提供一种催化合成多乙烯多胺的方法，所述方法需要在负载型金属催化剂的存在及临氢条件下进行。该方法用于单乙醇胺和乙二胺生产多乙烯多胺反应具有线性多乙烯多胺产率高、种类丰富、支链及环状副产品少、催化活性高、产物分布可调节、稳定性好、反应过程绿色清洁等特点。
根据本发明的一个方面，本发明提供一种用于合成多乙烯多胺产品的负载型催化剂。
所述催化剂由活性金属、助剂元素和改性载体三部分组成，活性金属、助剂元素负载于改性载体上。
所述催化剂由如下过程制得：将活性金属和助剂元素的前驱体经浸渍或沉淀负载到改性载体上，经干燥、焙烧、还原活化处理后得到所述催化剂。
所述改性载体为碱金属改性的载体，其中，所述碱金属选自Na、K中的一种或两种以上。
所述载体为Al 2O 3、活性炭、SiO 2、Al 2O 3-SiO 2的一种或两种以上组合。
所述载体的比表面积为50～1800m 2/g，孔容0.2～1.2ml/g。
一个优选方案中，所述载体的比表面积为70～700m 2/g，孔容0.3～1.0ml/g。
所述改性载体制备方法为：将Na或K的前体物负载到载体上，经焙烧处理后得到改性载体。
其中，所述Na或K的前体物选自Na或K的碳酸盐类、硝酸盐类或盐酸盐。
所述Na或K的重量占改性载体总质量的0.05～2％。
一个优选方案中，所述Na或K的重量占改性载体总质量的0.1～1.2％。
一个更优选方案中，所述Na或K的重量占改性载体总质量的0.4～0.8％。
所述改性载体制备方法中焙烧条件为：常压，温度300～700℃，时间4～10h，气氛为空气、氧气、氮气中的一种或两种以上组合，气体体积空速为0～2000h -1。
可选地，当所述改性载体的焙烧气体体积空速为0h -1时，即焙烧过程在静止(非流动)的气氛中进行。
可选地，所述改性载体的焙烧处理可在以下设备中进行：马弗炉、管式炉等。
所述改性载体制备方法的焙烧气氛：当所选载体为Al 2O 3、SiO 2、Al 2O 3-SiO 2时，焙烧气氛优选空气或氧气；当所选载体为活性炭时，焙烧气氛选择氮气。
所述负载型催化剂活性金属为Ni、Co中的一种或组合。
所述活性组分的重量占催化剂总重量的5～50％。
一个优选方案中，所述活性组分的重量占催化剂总重量的10～30％。
所述助剂为元素Fe、Ir、Re、Ru、Cu、Mn、B、W中的一种或组合。
所述助剂的重量占催化剂总重量的0.05～10％。
一个优选方案中，所述助剂的重量占催化剂总重量的0.5～6％。
所述负载型催化剂的制备方法如下：采用浸渍法、沉淀法中的至少一种将活性金属和助剂负载到改性载体上。
更具体而言，当采用浸渍法时，过程如下：将改性载体浸渍于含有活性金属元素源和助剂元素源的溶液中，经干燥，焙烧后得到所述催化剂。
更具体而言，当采用沉淀法时，过程如下：将含有活性金属元素源和助剂元素源的溶液与沉淀剂一起加入到改性载体的悬浮液中，沉淀，陈化，洗涤，干燥，焙烧，得到所述催化剂。
可选地，焙烧温度200～600℃，焙烧时间0.5～15h，焙烧气氛为空气、氧气、氮气中的一种或两种以上组合。
可选地，所述活性组分前驱体包括Ni的可溶性盐、Co的可溶性盐。
可选地，所述助剂前驱体包括助剂元素的可溶性前驱体。
具体地，所用的Ni的可溶性盐可以为硝酸镍、醋酸镍、氯化镍、硫酸镍或柠檬酸镍，优选硝酸镍、醋酸镍。
所用的Co的可溶性盐可以为硝酸钴、醋酸钴、氯化钴、硫酸钴或柠檬酸钴，优 选硝酸钴、醋酸钴。
所用的金属助剂的可溶性盐为硝酸盐、盐酸盐或铵盐。
所用的非金属助剂B为硼酸。
可选地，所述的催化剂的制备方法可采用浸渍法、沉淀法中的一种或两种的结合将活性组分和助剂负载在改性载体上(负载量是质量含量)。
优选方案中，可通过浸渍法将活性组分和助剂负载于改性载体上。
可选地，浸渍法实施方案中，可采用共浸渍或分步浸渍的方法将活性组分和助剂负载于改性载体上。
可选地，上述浸渍法的步骤可以为：配置含有活性组分和助剂前体物的水溶液，其中活性组分的重量占催化剂重量的5～50％，助剂的重量占催化剂重量的0.05～10％，将含有活性组分和助剂的水溶液浸渍改性载体，自然晾干，焙烧处理。
可选地，所述浸渍法可以为一次浸渍或多步浸渍。
可选地，所述焙烧温度常为200～600℃，时间0.5～15h。
可选地，催化剂前体物还可通过沉淀法负载于改性载体上。
可选地，上述沉淀法制备催化剂的步骤可以为：将改性载体悬浮于水中，加入活性组分和助剂的可溶性前体物，如金属盐类，随后加入沉淀剂将活性组分和助剂沉淀于悬浮的改性载体上。其中活性组分的重量占催化剂重量的5～50％，助剂的重量占催化剂重量的0.05～10％。将沉淀后的样品陈化，洗涤，过滤，干燥，焙烧处理。
可选地，所用沉淀剂优选为无机碱类，优选为氢氧化钠、碳酸钠、氢氧化钾或碳酸钾。
可选地，所用沉淀剂还可为铵盐类，可以为碳酸铵、氢氧化铵或卤化铵。
可选地，所述沉淀温度可以为20～100℃，优选为40～60℃。
可选地，所述焙烧温度常为200～600℃，时间0.5～15h。
所述焙烧后的催化剂需要进行还原活性化处理。
所述还原活性的操作过程为：催化剂在还原气氛下高温处理。
所述还原活化处理的过程在氢气气氛下进行。
所述还原处理的条件为：温度200～600℃，压力0.1MPa，时间0.5～10h，氢气空速20～3000h -1。
可选地，所述还原气氛包括氢气和惰性气体混合物，其中，惰性气体可为氮气、氦气、氩气。
优选地，还原气氛为氢气。
根据本发明的另一个方面，本发明提供了一种高温氨气氛处理催化剂的方法。
所述负载型催化剂用于催化合成多乙烯多胺前需要进行高温氨气氛处理。
所述高温氨气氛处理的操作过程为：催化剂用于催化合成多乙烯多胺反应前在氨气氛下高温处理。
所述高温氨气氛处理的条件为：温度300～600℃，压力0.1～5MPa，时间1～20h。
一个优选方案中，所述高温氨气氛处理的条件为：温度350～450℃，压力1～4MPa，时间5～15h。
一个更优选方案中，所述高温氨气氛处理的条件为：温度350～450℃，压力1.5～3MPa，时间8～12h。
所述高温氨气氛处理的氨源为液氨，液时空速为1～2h -1。
所述经高温氨气氛处理后的催化剂可直接用于单乙醇胺和乙二胺临氢胺化合成多乙烯多胺的反应。
该方法制得的催化剂用于单乙醇胺和乙二胺的临氢胺化反应，具有多乙烯多胺产率高、稳定性好、活性高等优点，工业前景广阔。
一种可选地方案中，所述高温氨气氛处理过程可在用于单乙醇胺和乙二胺临氢胺化合成多乙烯多胺反应前在反应器上原位进行。
根据本发明的又一方面，提供了一种以单乙醇胺和乙二胺为主原料经临氢催化胺化反应合成多乙烯多胺的工艺路线，该方法具有原料易得、经济性好、产物分布可调节、线性多乙烯多胺种类多且产率高、可实现连续生产、工艺路线简单易操作等一个或多个优点。
所述胺化反应以单乙醇胺、乙二胺和氨为原料，采用本发明所提供的催化剂，在氢气气氛下，一定反应条件下经催化胺化反应生成以线性多乙烯多胺为主产物的胺类产品。
所述多乙烯多胺产品包括线性多乙烯多胺、支链型多乙烯多胺及环状多乙烯多胺。
所述线性多乙烯多胺是指具有如下结构的化合物。其中，n≥1。通常，1≤n≤6。
Figure PCTCN2022138260-appb-000001
所述支链型多乙烯多胺是指线性多乙烯多胺的非环状同分异构体。包括但不限于以下结构的化合物。
Figure PCTCN2022138260-appb-000002
所述环状多乙烯多胺是指具有具有环状结构的多乙烯多胺，环状结构包括但不限于哌嗪环、吡嗪环、吗啉环等。包括但不限于以下结构的化合物。
Figure PCTCN2022138260-appb-000003
Figure PCTCN2022138260-appb-000004
所述原料中单乙醇胺:乙二胺的摩尔比例为0～10:1。
优选地，所述原料中单乙醇胺:乙二胺的摩尔比例为0～5:1。
所述液氨占反应原料的摩尔比例为0～90％。
可选地，当液氨占反应原料的摩尔比例为0％时，即原料中不加入液氨。
可选地，所述原料可添加溶剂稀释，也可不添加其他溶剂。
优选地，所述原料中不需要加入其他溶剂。
可选地，所述反应原料氨选自氨气、液氨和氨水。
优选地，所述原料氨选自液氨。
本发明中，胺化反应在氢气气氛下进行，所述氢气气氛是指在通入氢气的条件下。
所述胺化反应过程在临氢条件下进行，其中氢气占总进料物质的摩尔浓度为0.5～80％。
优选地，氢气占总进料物质的摩尔浓度为1～40％。
可选地，所述原料泵入预热器，经50～120℃预热后进入反应器中进行反应。
所述胺化反应在连续式或间歇式反应器中进行。
可选地，所述连续式或间歇式反应器选自固定床、高压反应釜、浆态床、流化床中的一种。
优选地，所述反应器选自固定床。
所述临氢催化胺化的反应条件为：反应温度130～220℃，优选150～200℃；反应压力为1～30MPa，优选6～26MPa；单乙醇胺和乙二胺的总液时空速为0.02～15h -1，优选0.1～10h -1。
本申请所述催化体系及其特殊处理方法及其应用条件，同样适合应用于其他单元醇或多元醇类或多元胺类氨化制备有机胺类的反应。
可选地，所述单元醇底物包括但不限于3-氨基-1-丙醇、2-氨基-1-丙醇、1-氨基-2-丙醇、4-氨基-1-丁醇、5-氨基-1-戊醇、2-氨基-1-戊醇、6-氨基-1-己醇等。
可选地，所述二元醇或多元醇底物包括但不限于1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,5-戊二醇、1,2-戊二醇、1,6-己二醇、二甘醇、聚醚多元醇PPG-230、聚醚多元醇PPG-440、1,2,6-己三醇等。
可选地，所述多元胺类包括但不限于脂肪族二元胺或芳族二元胺等，如1,2-丙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,2-戊二胺、1,6-己二胺、呋喃二甲胺(2,5-二氨甲基呋喃)、辛二胺、癸二胺等。
本发明的有益效果在于：
1)本发明通过活性组分Ni、Co，及助剂元素Fe、Ir、Re、Ru、Cu、Mn、B、W，及载体Al 2O 3、活性炭、SiO 2和Al 2O 3-SiO 2之间的组合，产生协同催化剂效应，从而提高催化剂在单乙醇胺和乙二胺临氢胺化反应中的催化活性。
2)本发明通过对载体进行碱金属改性处理以及对还原后的催化剂进行氨气氛高温处理的方法，影响活性金属对氨的吸附活化能力，从而调控活性金属和活性金属氮化物之间的比例，起到提高产物中线性多乙烯多胺产率的效果。
3)本发明的催化剂用于单乙醇胺和乙二胺临氢胺化反应时，具有提高线性多乙烯多胺产率，降低支链或环状胺类副产品选择性的效果。特别地，可提高产物中长链线性多乙烯多胺的产率。所述长链线性多乙烯多胺包括线性三乙烯四胺及更高线性乙二胺多聚同系物。同时催化剂活性高、稳定性好，可实现长周期稳定生产。
4)本发明的催化剂底物适应性好，对不同单乙醇胺、乙二胺和氨比例的原料均表现出优异的催化效果。
具体实施方式
实施例1
催化剂1的制备方法如下。首先进行载体改性处理：取7.794克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.014克碳酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为0.08Na-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.08Na-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂1为Ni10Co10Ru2/0.08Na-SiO 2。
催化剂1用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为2MPa，液氨液时空速为1.5h -1，处理时间为10h。
处理后的催化剂1用于反应评价，反应温度为170℃，压力为12MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为0.3:1:1，其中单乙醇胺和乙二胺的液时空速为1h -1,氢气摩尔浓度为10％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例2
催化剂2的制备方法如下。首先进行载体改性处理：取7.78克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.045克碳酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为0.25Na-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.25Na-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂2为Ni10Co10Ru2/0.25Na-SiO 2。
催化剂2用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂2用于反应评价，反应条件与实施例1相同。结果见表1。
实施例3
催化剂3的制备方法如下。首先进行载体改性处理：取7.753克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.108克碳酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为0.6Na-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.6Na-SiO 2载体，自然晾干，120℃干燥10h，空 气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂3为Ni10Co10Ru2/0.6Na-SiO 2。
催化剂3用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂3用于反应评价，反应条件与实施例1相同。结果见表1。
实施例4
催化剂4的制备方法如下。首先进行载体改性处理：取7.722克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.18克碳酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为1Na-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述1Na-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂4为Ni10Co10Ru2/1Na-SiO 2。
催化剂4用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂4用于反应评价，反应条件与实施例1相同。结果见表1。
实施例5
催化剂5的制备方法如下。首先进行载体改性处理：取7.66克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.3236克碳酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为1.8Na-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述1.8Na-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂5为Ni10Co10Ru2/1.8Na-SiO 2。
催化剂5用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂5用于反应评价，反应条件与实施例1相同。结果见表1。
实施例6
催化剂6的制备方法如下。首先进行载体改性处理：取7.777克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.054克碳酸钠和0.041克碳酸钾的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为0.3Na0.3K-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.3Na0.3K-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂6为Ni10Co10Ru2/0.3Na0.3K-SiO 2。
催化剂6用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂6用于反应评价，反应条件与实施例1相同。结果见表1。
实施例7
催化剂7的制备方法如下。首先进行载体改性处理：取7.654克氧化铝载体，120℃ 烘干后备用。配置6ml含有0.119克硝酸钾的水溶液，用此水溶液浸渍上述载体，自然晾干，600℃在空气气氛中焙烧5h，气体体积空速为200h -1，得到改性载体为0.6K-Al 2O 3。第二步进行活性金属和助剂负载：配置12ml含有7.432克Ni(NO 3) 2·6H 2O，2.469克Co(NO 3) 2·6H 2O，1.14克Cu(NO 3) 2·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.6K-Al 2O 3载体，自然晾干，120℃干燥10h，空气中400℃焙烧10h。进行还原处理：还原条件为温度450℃，气氛为常压氢气，体积空速为500h -1，还原时间8h。得到催化剂7为Ni15Co5Cu3/0.6K-Al 2O 3。
催化剂7用于反应前的高温氨气氛处理：氨处理温度为320℃，压力为2MPa，液氨液时空速为1.8h -1，处理时间为10h。
处理后的催化剂7用于反应评价，反应温度为180℃，压力为14MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为0.2:1:1，其中单乙醇胺和乙二胺的液时空速为2h -1,氢气摩尔浓度为15％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例8
催化剂7用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为2MPa，液氨液时空速为1.8h -1，处理时间为10h。
处理后的催化剂7用于反应评价，反应条件与实施例7相同。
实施例9
催化剂7用于反应前的高温氨气氛处理：氨处理温度为580℃，压力为2MPa，液氨液时空速为1.8h -1，处理时间为10h。
处理后的催化剂7用于反应评价，反应条件与实施例7相同。
实施例10
催化剂8的制备方法如下。首先进行载体改性处理：取7.547克氧化铝-氧化硅载体，120℃烘干后备用。配置7ml含有0.094克碳酸钾的水溶液，用此水溶液浸渍上述载体，自然晾干，550℃在空气气氛中焙烧6h，气体体积空速为1000h -1，得到改性载体为0.7K-Al 2O 3SiO 2。第二步进行活性金属和助剂负载：配置14ml含有9.909克Ni(NO 3) 2·6H 2O，0.988克Co(NO 3) 2·6H 2O，0.288克NH 4ReO 4的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.7K-Al 2O 3-SiO 2载体，自然晾干，120℃干燥10h，空气中350℃焙烧12h。进行还原处理：还原条件为温度460℃，气氛为常压氢气，体积空速为200h -1，还原时间10h。得到催化剂8为Ni20Co2Re2/0.7K-Al 2O 3-SiO 2。
催化剂8用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为0.2MPa，液氨液时空速为2h -1，处理时间为10h。
处理后的催化剂8用于反应评价，反应温度为190℃，压力为25MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为1:1:5，其中单乙醇胺和乙二胺的液时空速为4h -1,氢气摩尔浓度为5％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例11
催化剂8用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为1.1MPa，液氨液时空速为2h -1，处理时间为10h。
处理后的催化剂8用于反应评价，反应条件与实施例10相同。
实施例12
催化剂8用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为2MPa，液氨液时空速为2h -1，处理时间为10h。
处理后的催化剂8用于反应评价，反应条件与实施例10相同。对催化剂进行稳定性评价，在固定床反应器连续评价50h和2000h后分别取样分析。结果见表1，其中实施例12的上下两行分别对应50h和2000h的反应评价结果。
实施例13
催化剂8用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为3.8MPa，液氨液时空速为2h -1，处理时间为10h。
处理后的催化剂8用于反应评价，反应条件与实施例10相同。
实施例14
催化剂8用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为4.9MPa，液氨液时空速为2h -1，处理时间为10h。
处理后的催化剂8用于反应评价，反应条件与实施例10相同。
实施例15
催化剂8用于反应前的高温氨气氛处理过程与实施例12相同。
活化处理后的催化剂8用于反应评价，反应温度为190℃，压力为25MPa，液相进料为乙二胺，乙二胺的液时空速为4h -1,氢气摩尔浓度为5％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例16
催化剂8用于反应前的高温氨气氛处理过程与实施例12相同。
处理后的催化剂8用于反应评价，反应温度为190℃，压力为25MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为7:1:15，其中单乙醇胺和乙二胺的液时空速为4h -1,氢气摩尔浓度为5％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例17
催化剂9的制备方法如下。首先进行载体改性处理：取7.214克氧化铝载体，120℃烘干后备用。配置6.8ml含有0.134克硝酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，350℃在空气气氛中焙烧8h，气体体积空速为1500h -1，得到改性载体为0.5Na-Al 2O 3。第二步进行活性金属和助剂负载：将0.5Na-Al 2O 3分散于水中形成悬浮液，在50℃恒温下中速搅拌。配置含有7.408克Co(NO 3) 2·6H 2O，4.955克Ni(NO 3) 2·6H 2O，0.459克IrCl 3·3H 2O的前体液。所用沉淀剂为2mol/L的NaOH溶液。将前体液和沉淀剂同时以1ml/min的速率滴加到上述悬浮液中，保持pH值为9，直到沉淀完全，沉淀物用去离子水洗至中性，过滤，晾干，120℃干燥10h，空气中550℃焙烧4h。进行还原处理：还原条件为温度450℃，气氛为常压氢气，体积空速为2000h -1，还原时间4h。得到催化剂9为Co15Ni10Ir2.5/0.5Na-Al 2O 3。
催化剂9用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为2h。
处理后的催化剂9用于反应评价，反应温度为160℃，压力为20MPa，液相进料为单 乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为0.5:1:0.1，其中单乙醇胺和乙二胺的液时空速为0.6h -1,氢气摩尔浓度为20％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例18
催化剂9用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为6h。
处理后的催化剂9用于反应评价，反应条件与实施例17相同。
实施例19
催化剂9用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为10h。
处理后的催化剂9用于反应评价，反应条件与实施例17相同。
实施例20
催化剂9用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为14h。
处理后的催化剂9用于反应评价，反应条件与实施例17相同。
实施例21
催化剂9用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为20h。
处理后的催化剂9用于反应评价，反应条件与实施例17相同。
实施例22
催化剂10的制备方法如下。首先进行载体改性处理：8.201克活性炭载体，120℃烘干后备用。配置10ml含有0.126克氯化钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在氮气气氛中焙烧10h，气体体积空速为100h -1，得到改性载体为0.6Na-C。第二步进行活性金属和助剂负载：配置20ml含有7.408克Co(NO 3) 2·6H 2O，0.866克Fe(NO 3) 3，0.129克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.6Na-C载体，自然晾干，120℃干燥10h，氮气中400℃焙烧4h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为800h -1，还原时间5h。得到催化剂10为Co15Fe2Ru0.5/0.6Na-C。
催化剂10用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1.1h -1，处理时间为10h。
处理后的催化剂10用于反应评价，反应温度为200℃，压力为18MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为1.5:1:10，其中单乙醇胺和乙二胺的液时空速为7h -1,氢气摩尔浓度为30％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例23
催化剂11的制备方法如下。首先进行载体改性处理：7.661克氧化硅载体，120℃烘干后备用。配置7ml含有0.099克硝酸钾的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧10h，气体体积空速为0h -1，得到改性载体为0.5K-SiO 2。第二步进行活性金属和助剂负载：配置14ml含有9.909克Ni(NO 3) 2·6H 2O，1.145克H 3BO 3，0.326克Mn(NO 3) 2的水溶液，均分为两等份，重复以下过程2次： 取一份水溶液浸渍上述0.5K-SiO 2载体，自然晾干，120℃干燥10h，空气中400℃焙烧6h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为500h -1，还原时间5h。得到催化剂11为Ni20B2Mn1/0.5K-SiO 2。
催化剂11用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为1.8MPa，液氨液时空速为1.2h -1，处理时间为10h。
处理后的催化剂11用于反应评价，反应温度为185℃，压力为15MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为1.5:1:10，其中单乙醇胺和乙二胺的液时空速为3.5h -1,氢气摩尔浓度为3％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例24
催化剂12的制备方法如下。首先进行载体改性处理：7.761克氧化铝载体，120℃烘干后备用。配置6.8ml含有0.101克硝酸钾的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧10h，气体体积空速为50h -1，得到改性载体为0.5K-Al 2O 3。第二步进行活性金属和助剂负载：配置13.6ml含有4.955克Ni(NO 3) 2·6H 2O，2.469克Co(NO 3) 2·6H 2O，0.572克H 3BO 3，0.154克(NH 4) 2WO 4的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.5K-Al 2O 3载体，自然晾干，120℃干燥10h，空气中400℃焙烧6h。进行还原处理：还原条件为温度450℃，气氛为常压氢气，体积空速为500h -1，还原时间5h。得到催化剂12为Ni10Co5B1W1/0.5K-Al 2O 3。
催化剂12用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为1.8MPa，液氨液时空速为1.2h -1，处理时间为10h。
处理后的催化剂12用于反应评价，反应温度为155℃，压力为15MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为1.5:1:10，其中单乙醇胺和乙二胺的液时空速为0.4h -1,氢气摩尔浓度为8％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例25
催化剂13的制备方法如下。首先进行载体改性处理：9.244克氧化硅载体，120℃烘干后备用。配置9ml含有0.206克硝酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧10h，气体体积空速为50h -1，得到改性载体为0.6Na-SiO 2。第二步进行活性金属和助剂负载：配置18ml含有2.477克Ni(NO 3) 2·6H 2O，0.494克Co(NO 3) 2·6H 2O，0.144克NH 4ReO 4的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.6Na-SiO 2载体，自然晾干，120℃干燥10h，空气中400℃焙烧6h。进行还原处理：还原条件为温度450℃，气氛为常压氢气，体积空速为500h -1，还原时间5h。得到催化剂13为Ni5Co1Re1/0.6Na-SiO 2。
催化剂13用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为1.8MPa，液氨液时空速为1.2h -1，处理时间为10h。
处理后的催化剂13用于反应评价，反应温度为185℃，压力为15MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为1.5:1:10，其中单乙醇胺和乙二胺的液时空速为3h -1,氢气摩尔浓度为10％。在固定床反应器连续反应50h后取样分析。结果见表1。
实施例26
催化剂14的制备方法如下。首先进行载体改性处理：5.268克氧化铝载体，120℃烘干后备用。配置5ml含有0.117克硝酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，500℃在空气气氛中焙烧10h，气体体积空速为200h -1，得到改性载体为0.6Na-Al 2O 3。第二步进行活性金属和助剂负载：将0.6Na-Al 2O 3分散于水中形成悬浮液，在50℃恒温下中速搅拌。配置含有19.819克Ni(NO 3) 2·6H 2O，2.862克H 3BO 3，0.367克IrCl 3·3H 2O的前体液。所用沉淀剂为3mol/L的NaOH溶液。将前体液和沉淀剂同时以1ml/min的速率滴加到上述悬浮液中，保持pH值为9，直到沉淀完全，沉淀物用去离子水洗至中性，过滤，晾干，120℃干燥10h，空气中400℃焙烧6h。进行还原处理：还原条件为温度450℃，气氛为常压氢气，体积空速为100h -1，还原时间10h。得到催化剂14为Ni40B5Ir2/0.6Na-Al 2O 3。
催化剂14用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为1.8MPa，液氨液时空速为1.2h -1，处理时间为10h。
处理后的催化剂14用于反应评价，反应温度为185℃，压力为15MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为1.5:1:10，其中单乙醇胺和乙二胺的液时空速为3h -1,氢气摩尔浓度为10％。在固定床反应器连续反应50h后取样分析。结果见表1。
对比例1
催化剂为30％Ni-2％Re-1.2％B/Al 2O 3，按照专利WO 2013/152548实施例8中所述的方法制备。
催化剂30％Ni-2％Re-1.2％B/Al 2O 3还原过程按照专利WO 2013/152548实施例所述。
还原后催化剂用于反应评价，反应条件与实施例1相同。
对比例2
催化剂为氧化硅负载的34％H 3PO 4，按照专利US 4503253中Example 1中所述的方法制备。按照专利US 4503253所述，催化剂在使用前不需要活化处理。
催化剂氧化硅负载的34％H 3PO 4用于反应评价，反应条件与实施例1相同。产品中未检测到反应产物，表1-对比例2中用“-”表示。
对比例3
催化剂为酸性磷酸镧，按照专利US 4617418中Catalyst-B酸性磷酸镧所述的方法制备。按照专利US 4617418所述，催化剂在使用前不需要活化处理。
催化剂酸性磷酸镧用于反应评价，反应条件与实施例1相同。产品中未检测到反应产物，表1-对比例3中用“-”表示。
对比例4
催化剂为Ni-Y-Ir/Al 2O 3，按照专利US 5321160中Catalyst-19所述的方法制备。
催化剂Ni-Y-Ir/Al 2O 3还原过程按照专利US 5321160实施例所述。
催化剂Ni-Y-Ir/Al 2O 3用于反应评价，反应条件与实施例1相同。
对比例5
催化剂为路易斯酸卤化物，按照专利US 4399308中Example 7所述的氯化锡。
催化剂氯化锡用于反应评价，反应条件与实施例1相同。产品中未检测到反应产 物，表1-对比例5中用“-”表示。
对比例6
催化剂15的制备过程如下。载体不进行碱金属改性。取7.8克二氧化硅载体，120℃烘干后备用。配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂15为Ni10Co10Ru2/SiO 2。
催化剂15用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂15用于反应评价，反应条件与实施例1相同。
对比例7
催化剂16的制备过程如下。首先进行载体改性处理：取7.753克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.276克Ca(NO 3) 2·4H 2O的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为0.6Ca-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.6Ca-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂16为Ni10Co10Ru2/0.6Ca-SiO 2。
催化剂16用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂16用于反应评价，反应条件与实施例1相同。
对比例8
催化剂17的制备过程如下。首先进行载体改性处理：取7.753克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.285克Mg(NO 3) 2的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为0.6Mg-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.6Mg-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂17为Ni10Co10Ru2/0.6Mg-SiO 2。
催化剂17用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂17用于反应评价，反应条件与实施例1相同。
对比例9
催化剂18的制备过程如下。首先进行载体改性处理：取7.799克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.002克碳酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为0.01Na-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.01Na-SiO 2载体，自然晾干，120℃ 干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂18为Ni10Co10Ru2/0.01Na-SiO 2。
催化剂18用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂18用于反应评价，反应条件与实施例1相同。
对比例10
催化剂19的制备过程如下。首先进行载体改性处理：取7.41克二氧化硅载体，120℃烘干后备用。配置7.5ml含有0.899克碳酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，400℃在空气气氛中焙烧6h，气体体积空速为0h -1，得到改性载体为5Na-SiO 2。第二步进行活性金属和助剂负载：配置15ml含有4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述5Na-SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂19为Ni10Co10Ru2/5Na-SiO 2。
催化剂19用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂19用于反应评价，反应条件与实施例1相同。
对比例11
催化剂20的制备过程如下。首先进行载体改性处理：取7.753克二氧化硅载体，120℃烘干后备用。配置15ml含有0.108克Na 2CO 3，4.955克Ni(NO 3) 2·6H 2O，4.939克Co(NO 3) 2·6H 2O，0.517克RuCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述SiO 2载体，自然晾干，120℃干燥10h，空气中500℃焙烧5h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为1000h -1，还原时间6h。得到催化剂20为Ni10Co10Ru2Na0.6/SiO 2。
催化剂20用于反应前的高温氨气氛处理过程与实施例1相同。
处理后的催化剂20用于反应评价，反应条件与实施例1相同。
对比例12
催化剂7用于反应前不进行高温氨气氛处理。
催化剂7用于反应评价，反应条件与实施例7相同。
对比例13
催化剂7用于反应前的高温氨气氛处理：氨处理温度为240℃，压力为2MPa，液氨液时空速为1.8h -1，处理时间为10h。
处理后的催化剂7用于反应评价，反应条件与实施例7相同。
对比例14
催化剂7用于反应前的高温氨气氛处理：氨处理温度为750℃，压力为2MPa，液氨液时空速为1.8h -1，处理时间为10h。
处理后的催化剂7用于反应评价，反应条件与实施例7相同。
对比例15
催化剂8用于反应前的高温氨气氛处理：氨处理温度为380℃，压力为8MPa，液氨液时空速为2h -1，处理时间为10h。
处理后的催化剂8用于反应评价，反应条件与实施例10相同。
对比例16
催化剂9用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为0.2h。
处理后的催化剂9用于反应评价，反应条件与实施例17相同。
对比例17
催化剂9用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为100h。
处理后的催化剂9用于反应评价，反应条件与实施例17相同。
对比例18
催化剂21的制备方法如下。首先进行载体改性处理：取7.711克氧化铝载体，120℃烘干后备用。配置6.8ml含有0.143克硝酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，350℃在空气气氛中焙烧8h，气体体积空速为1500h -1，得到改性载体为0.5Na-Al 2O 3。第二步进行活性金属和助剂负载：将0.5Na-Al 2O 3分散于水中形成悬浮液，在50℃恒温下中速搅拌。配置含有8.663克Fe(NO 3) 3，0.459克IrCl 3·3H 2O的前体液。所用沉淀剂为2mol/L的NaOH溶液。将前体液和沉淀剂同时以1ml/min的速率滴加到上述悬浮液中，保持pH值为9，直到沉淀完全，沉淀物用去离子水洗至中性，过滤，晾干，120℃干燥10h，空气中550℃焙烧4h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为2000h -1，还原时间4h。得到催化剂21为Fe20Ir2.5/0.5Na-Al 2O 3。
催化剂21用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为10h。
处理后的催化剂21用于反应评价，反应条件与实施例17相同。
对比例19
催化剂22的制备方法如下。首先进行载体改性处理：取7.711克氧化铝载体，120℃烘干后备用。配置6.8ml含有0.143克硝酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，350℃在空气气氛中焙烧8h，气体体积空速为1500h -1，得到改性载体为0.5Na-Al 2O 3。第二步进行活性金属和助剂负载：将0.5Na-Al 2O 3分散于水中形成悬浮液，在50℃恒温下中速搅拌。配置含有7.602克Cu(NO 3) 2·3H 2O，0.459克IrCl 3·3H 2O的前体液。所用沉淀剂为2mol/L的NaOH溶液。将前体液和沉淀剂同时以1ml/min的速率滴加到上述悬浮液中，保持pH值为9，直到沉淀完全，沉淀物用去离子水洗至中性，过滤，晾干，120℃干燥10h，空气中550℃焙烧4h。进行还原处理：还原条件为温度400℃，气氛为常压氢气，体积空速为2000h -1，还原时间4h。得到催化剂22为Cu20Ir2.5/0.5Na-Al 2O 3。
催化剂22用于反应前的高温氨气氛处理过程与对比例18相同。
处理后的催化剂22用于反应评价，反应条件与实施例17相同。
对比例20
催化剂23的制备方法如下。首先进行载体改性处理：取7.711克氧化铝载体，120℃烘干后备用。配置6.8ml含有0.143克硝酸钠的水溶液，用此水溶液浸渍上述载体，自然晾干，350℃在空气气氛中焙烧8h，气体体积空速为1500h -1，得到改性载体为0.5Na-Al 2O 3。第二步进行活性金属和助剂负载：将0.5Na-Al 2O 3分散于水中形成 悬浮液，在50℃恒温下中速搅拌。配置含有5.309克H 2PtCl 6·6H 2O，0.459克IrCl 3·3H 2O的前体液。所用沉淀剂为2mol/L的NaOH溶液。将前体液和沉淀剂同时以1ml/min的速率滴加到上述悬浮液中，保持pH值为9，直到沉淀完全，沉淀物用去离子水洗至中性，过滤，晾干，120℃干燥10h，空气中550℃焙烧4h。进行还原处理：还原条件为温度300℃，气氛为常压氢气，体积空速为2000h -1，还原时间4h。得到催化剂23为Pt20Ir2.5/0.5Na-Al 2O 3。
催化剂23用于反应前的高温氨气氛处理：氨处理温度为400℃，压力为1.8MPa，液氨液时空速为1h -1，处理时间为10h。
处理后的催化剂23用于反应评价，反应条件与实施例17相同。
对比例21
催化剂24的制备方法如下。首先进行载体改性处理：取7.547克氧化铝-氧化硅载体，120℃烘干后备用。配置7ml含有0.094克碳酸钾的水溶液，用此水溶液浸渍上述载体，自然晾干，550℃在空气气氛中焙烧6h，气体体积空速为1000h -1，得到改性载体为0.7K-Al 2O 3-SiO 2。第二步进行活性金属和助剂负载：配置14ml含有9.909克Ni(NO 3) 2·6H 2O，0.988克Co(NO 3) 2·6H 2O，0.517克RhCl 3·3H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.7K-Al 2O 3-SiO 2载体，自然晾干，120℃干燥10h，空气中350℃焙烧12h。进行还原处理：还原条件为温度460℃，气氛为常压氢气，体积空速为200h -1，还原时间10h。得到催化剂24为Ni20Co2Rh2/0.7K-Al 2O 3-SiO 2。
催化剂24用于反应前的高温氨气氛处理过程与实施例12相同。
处理后的催化剂24用于反应评价，反应条件与实施例12相同。
对比例22
催化剂25的制备方法如下。首先进行载体改性处理：取7.547克氧化铝-氧化硅载体，120℃烘干后备用。配置7ml含有0.094克碳酸钾的水溶液，用此水溶液浸渍上述载体，自然晾干，550℃在空气气氛中焙烧6h，气体体积空速为1000h -1，得到改性载体为0.7K-Al 2O 3-SiO 2。第二步进行活性金属和助剂负载：配置14ml含有9.909克Ni(NO 3) 2·6H 2O，0.988克Co(NO 3) 2·6H 2O，1.539克Cr(NO 3) 3·9H 2O的水溶液，均分为两等份，重复以下过程2次：取一份水溶液浸渍上述0.7K-Al 2O 3-SiO 2载体，自然晾干，120℃干燥10h，空气中350℃焙烧12h。进行还原处理：还原条件为温度460℃，气氛为常压氢气，体积空速为200h -1，还原时间10h。得到催化剂25为Ni20Co2Cr2/0.7K-Al 2O 3-SiO 2。
催化剂25用于反应前的高温氨气氛处理过程与实施例12相同。
处理后的催化剂25用于反应评价，反应条件与实施例12相同。
对比例23
催化剂8用于反应前的高温氨气氛处理过程与实施例12相同。
处理后的催化剂8用于反应评价，反应温度为190℃，压力为25MPa，液相进料为单乙醇胺、乙二胺和液氨，单乙醇胺:乙二胺:液氨的摩尔比为15:1:5，其中单乙醇胺和乙二胺的液时空速为4h -1,氢气摩尔浓度为5％。在固定床反应器连续反应50h后取样分析。结果见表1。
表1临氢氨化制备多乙烯多胺催化剂评价结果
Figure PCTCN2022138260-appb-000005
续-表1临氢氨化制备多乙烯多胺催化剂评价结果
Figure PCTCN2022138260-appb-000006
本专利的有益效果是提高底物转化率、线性多乙烯多胺选择性的，特别地，可提高产物中长链线性多乙烯多胺的选择性。其中，长链线性多乙烯多胺包括线性三乙烯四胺、线性四乙烯五胺和线性五乙烯六胺。根据表1催化剂的反应评价结果，由实施例1-6、对比例6、对比例9-10可知，当载体预处理的碱金属Na、K的负载量小于0.05％或不进行改性时，催化剂虽然表现出较高活性，但线性多乙烯多胺选择性低，环状胺副产物较多；随着Na、K的负载量增加，催化剂活性呈先平缓再迅速下降的趋势，同时产物中线性多乙烯多胺的选择性先增加后减少；与可选范围0.05～2％负载量的效果相比，处于优选范围0.1～1.2％时，具有更高的线性多乙烯多胺选择性；与优选范围0.1～1.2％负载量的效果相比，处于更优选范围0.4～0.8％时，具有最高的长链线性多乙烯多胺选择性，同时具有较高的单乙醇胺转化率。由对比例7-8可知，选用Ca、Mg进行载体预处理无法起到Na、K的效果，存在活性低或线性多乙烯多胺选择性差的问题。由对比例11可知，当碱金属Na、K与活性金属、助剂同时负载时，存在活性低或线性多乙烯多胺选择性差的问题。由实施例7-9和对比例12-14可知，氨气氛活化处理温度对催化性能影响显著，不进行氨气氛活化处理或处理温度低于可选范围300～600℃时，易导致线性多乙烯多胺选择性差；随着氨化处理温度升高，转化率呈先平缓再快速下降的趋势，线性多乙烯多胺选择性呈先升高再下降的趋势；与可选氨化处理温度300～600℃相比，优选氨化处理温度350～450℃时，在保持较高转化率和线性多乙烯多胺选择性的同时，具有最高的长链线性多乙烯多胺选择性；氨气氛活化温度过高可能会导致催化剂烧结，从而使活性显著下降。由实施例12中50h 和2000h的评价结果可知，随着反应时间延长到2000h，转化率和选择性数据变化不大，证明本发明催化剂的稳定性优异。由实施例10-14和对比例15可知，随氨气氛处理压力的增加，转化率呈先平缓再快速下降的趋势，线性多乙烯多胺的选择性先升高后降低；与可选氨气氛处理压力0.1～5MPa相比，优选压力1～4MPa时具有更高的转化率或长链线性多乙烯多胺选择性；与优选氨气氛处理压力1～4MPa相比，更优选压力1.5～3MPa时具有最高的长链线性多乙烯多胺选择性，同时具有较高的转化率；当压力过高时，会导致催化剂活性金属失活，从而转化率显著下降。由实施例15-16和对比例23可知，随着原料中单乙醇胺的比例增加，产物中AEEA和环状副产物的比例逐渐增大。由实施例17-21和对比例16-17的结果可知，随氨气氛处理时间增加，转化率呈先平缓再快速下降的趋势，线性多乙烯多胺的选择性先升高后降低；与对比例16相比，当氨气氛处理时间在可选范围1～20h时，具有较高的线性多乙烯多胺选择性；与可选处理时间范围1～20h相比，当优选处理时间5～15h时，具有更高的转化率或线性多乙烯多胺选择性；与优选处理时间5～15h相比，当更优选处理时间8～12h时，具有最高的长链线性多乙烯多胺选择性；当处理时间过长时，转化率下降显著。由实施例22-26和对比例18-22可知，采用本发明限定外的活性组分、助剂元素时，可能存在催化活性低、线性多乙烯多胺选择性差等问题。通过以上分析可知，采用所述方法的催化剂用于临氢胺化制备多乙烯多胺可实现以下中的一项或多项：(1)催化剂制备过程简单易操作；(2)线性多乙烯多胺选择性高，且长链线性多乙烯多胺种类多、选择性高；(3)生成环状副产物选择性低；(4)催化剂活性高；(5)过程经济性好；(6)催化剂稳定性好；(7)反应条件温和；(8)可实现连续生产；(9)反应过程绿色清洁。

Claims (6)

  1. 一种催化合成多乙烯多胺的方法，其特征在于所述方法在催化剂的存在下进行；
    所述催化剂由活性金属、助剂元素和改性载体三部分组成，活性金属和助剂元素负载于改性载体上；
    所述改性载体为碱金属改性的载体；所述碱金属选自Na、K中的一种或两种；所述载体为Al 2O 3、活性炭、SiO 2和Al 2O 3-SiO 2的一种或两种以上；
    所述活性金属为Ni、Co中的一种或两种组合；所述助剂为元素Fe、Ir、Re、Ru、Cu、Mn、B、W中的一种或两种以上组合；
    所述催化剂由如下过程制得：将活性金属和助剂元素的前驱体经浸渍或沉淀负载到改性载体上，经干燥、焙烧、还原活化处理后得到所述催化剂；
    还原活化处理的条件为：温度200～600℃，压力0.1MPa，时间0.5～10h，氢气空速20～3000h -1；
    所述催化剂用于催化合成多乙烯多胺反应前，需要进行高温氨气氛处理；所述高温氨气氛处理条件为：温度300～600℃，优选350～450℃；压力0.1～5MPa，优选1～4MPa，更优选1.5～3MPa；
    时间1～20h，优选5～15h，更优选8～12h；氨源为液氨，液时空速为1～2h -1。
  2. 根据权利要求1所述的催化剂，其特征在于：
    所述活性组分的重量占催化剂总重量的5～50％，优选10～30％；
    所述助剂的重量占催化剂总重量的0.05～10％，优选0.5～6％；
    所述载体的比表面积为50～1800m 2/g，优选70～700m 2/g；孔容0.2～1.2ml/g，优选0.3～1.0ml/g。
  3. 根据权利要求1或2所述的催化剂，其特征在于，
    所述碱金属改性的载体的碱金属为Na和/或K，载体改性方法为：将Na和/或K的前驱体采用浸渍法负载到载体上，经焙烧处理后得到改性载体；
    所述Na和/或K的前体物选自Na和/或K的碳酸盐类、硝酸盐类或盐酸盐中的一种或两种以上；
    所述Na和/或K的重量占改性载体总质量的0.05～2％，优选0.1～1.2％，更优选0.4～0.8％；
    所述焙烧条件为：常压，温度300～700℃，时间4～10h，气氛为空气、氧气、氮气中的一种或两种以上组合，其于静止或流动的气氛进行，气体体积空速为0～2000h -1。
  4. 根据权利要求1-3所述的催化剂，其特征在于，采用浸渍法、沉淀法中的至少一种或二种将活性金属和助剂负载到改性载体上：具体为，
    将改性载体浸渍于含有活性金属元素源和助剂元素源的溶液中，经干燥，焙烧后得到所述催化剂；
    或将含有活性金属元素源和助剂元素源的溶液与沉淀剂一起加入到改性载体的悬浮液中，沉淀，陈化，洗涤，干燥，焙烧，得到所述催化剂；
    所述焙烧的条件为：温度200～600℃，时间0.5～15h，气氛为空气、氧气、氮气中的一种或两种以上组合。
  5. 根据权利要求1所述的催化合成多乙烯多胺的方法，其特征在于：
    所述催化合成多乙烯多胺的反应原料包括乙二胺，或乙二胺与单乙醇胺或液氨中的一种或两种组合；
    所述反应原料中单乙醇胺:乙二胺的摩尔比例为0～10:1，优选0～5:1；所述液氨占反应原料的摩尔比例为0～90％；
    所述催化反应过程在临氢条件下进行，其中氢气占总进料物质(包括氢气和反应原料)的摩尔比例为0.5～80％，优选1～40％；
    所述反应条件为：温度130～220℃，优选150～200℃；压力1～30MPa，优选6～26MPa；
    单乙醇胺和乙二胺的总液时空速为0.02～15h -1，优选0.1～10h -1。
  6. 根据权利要求1或5所述，其特征在于，催化合成多乙烯多胺的反应在反应器中进行，所述反应器包括连续式、间歇式反应器中的一种或两种；其中，所述连续式反应器选自固定床反应器、连续搅拌釜反应器、浆态床反应器、流化床反应器中的一种或两种以上；所述间歇式反应器选自高压釜反应器；优选固定床反应器、高压釜反应器中的一种或两种。
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