CN108067289A - Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition - Google Patents

Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition Download PDF

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Publication number
CN108067289A
CN108067289A CN201611003643.7A CN201611003643A CN108067289A CN 108067289 A CN108067289 A CN 108067289A CN 201611003643 A CN201611003643 A CN 201611003643A CN 108067289 A CN108067289 A CN 108067289A
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catalyst
carrier
piperazine
ethylenediamine
monoethanolamine
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丁云杰
马雷
严丽
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/24—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • 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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    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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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
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—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
    • C07D295/08—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 bound oxygen or sulfur atoms
    • C07D295/084—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 bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—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 bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • 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
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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Abstract

A kind of monoethanolamine and ammonia under hydro condition are converted into the catalyst of ethylenediamine and piperazine, and catalyst, which includes main active component, auxiliary agent and carrier three parts composition, main active component, includes transition metal Ni, Cu or Co；Auxiliary agent is the one or more of the metals such as Fe, Cr, Re, Ru, B, Mg or oxide；Carrier is molecular sieve H ZSM 5, H β, H MOR or H Y etc..The preparation method of catalyst of the present invention is one kind or the combination of infusion process or the precipitation method.The catalyst of the present invention is in fixed bed reactors, at certain temperature and Hydrogen Vapor Pressure and a certain amount of catalysts conditions, monoethanolamine and liquefied ammonia can high conversion, highly selective be converted into target amine product ethylenediamine and piperazine.

Description

Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition
Technical field
The present invention relates to the catalyst that a kind of monoethanolamine and ammonia under hydro condition are converted into ethylenediamine and piperazine, in detail Ground is related to one kind and is converted into for monoethanolamine under hydro condition and ammonia based on ethylenediamine (EDA) and piperazine (PIP), co-production two The catalyst of ethylene triamine (DETA), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethyl ethylenediamine (AEEA) etc..
Background technology
Ethylenediamine product includes ethylenediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamine and cyclic amine such as piperazine Deng.Wherein, ethylenediamine and piperazine are the well sold and in short supply industrial chemicals in market, are had a wide range of applications in multiple fields.Ethylenediamine and piperazine Piperazine can be applied to the row such as high-molecular compound, medicine, dyestuff, pesticide as important industrial chemicals and fine-chemical intermediate In industry；It can also be used for the products such as production chelating agent, insect-proof agent, soil conditioner, lubricant, rubber accelerator；It can also be used for giving birth to It is very extensive to produce products, the purposes such as epoxy curing agent, emulsifier, antifreeze, organic solvent and chemical analysis reagent.
The method of industrial synthesis ethyleneamines is mainly dichloroethanes (EDC) method and ethanolamine (MEA) method at present.EDC methods There are serious corrosion of equipment, the shortcomings that energy consumption is big, therefore the technique is just gradually eliminated.It is low that there is MEA process process route to invest, The advantages that environmental pollution is small is divided into according to process route difference as two kinds of reductive amination method and condensation amination method：Reductive amination method It is reacted under the conditions of high-pressure hydro, product is based on chain amine, voluminous ethylenediamine；Condensation amination method need not face hydrogen, required anti- Answer temperature high, reaction product is based on cyclic amine, such as piperazine and its derivative.
The sixties in last century, BASF AG realize the industrialization of MEA process for the first time.The MEA process that BASF is developed is using drop Fluidized bed reactor using metals such as Ni, Co, Cu as catalyst, is reacted, product includes under high pressure (20.0~30.0MPa) Ethylenediamine, diethylenetriamine, hydroxyethyl ethylenediamine, piperazine, aminoethyl piperazine, hydroxyethyl piperazine etc., wherein ethylenediamine are main Product.At home, Shandong alliance chemical industry uses the MEA techniques of Dalian Inst of Chemicophysics, Chinese Academy of Sciences's exploitation, real for the first time The industrialization that Chinese MEA process prepares ethyleneamines is showed, which uses fixed bed reactors, with Al2O3Or SiO2The Ni of load or The metals such as Co are catalyst, and reaction temperature is 135~155 DEG C, and pressure is 6.5~8.0MPa, and product is based on ethylenediamine.
Reductive amination method generates ethyleneamines to monoethanolamine in the presence of a catalyst, since product amine has compared with liquefied ammonia Higher reactivity, therefore react the polyalkylenepolyamines by-product that inevitably generation is complicated so that ethylenediamine and piperazine The yield of piperazine reduces, and increases separation costs.Common method can improve the selectivity of product ethylenediamine, but the selection of product piperazine Property is low, affects the production capacity of piperazine.Monoethanolamine is using condensation amination method production ethyleneamines, due to reaction mechanism and reduction amination Method is different, and monoethanolamine conversion ratio is higher, but product, based on piperazine and its derivative, the selectivity of ethylenediamine is low, and reacts Required temperature is high, and energy consumption is big.Therefore, it is necessary to the selectivity that a kind of catalyst can not only improve target product ethylenediamine and piperazine, And higher monoethanolamine conversion ratio can be kept.
United States Patent (USP) 4123462 uses different carrier to load metal Ni, and after adding auxiliary agent Re, it is anti-to not only increase amination The conversion ratio answered, and improve the selectivity of target product ethylenediamine.In addition, patent finds the species and specific surface area of carrier There is certain influence to the activity of catalyst.United States Patent (USP) 4209424 is with Al2O3Nickel based metal catalyst is prepared for carrier, finds to add After entering auxiliary agent Na and Rh, catalyst activity is significantly improved.United States Patent (USP) 5750790 reports the Ni- of different carriers load Re catalyst is found using transitional face Al2O3Carrier is conducive to improve the selectivity of catalyst activity and ethylenediamine, reduces simultaneously The selectivity of ring.United States Patent (USP) 6534441 uses SiO2-Al2O3The Ni-Re-B catalyst of load is given birth to for reduction amination Ethyleneamines is produced, auxiliary agent Re and B improve the stability of catalyst, and ethylenediamine is selectively improved to 70~80%.It is international special Profit 2013152548 is with the SiO of ammoniated treatment2Or Al2O3For carrier, active metal is Ni or Co, single after adding auxiliary agent Re and B Ethanolamine conversion ratio and ethylenediamine are selectively improved significantly.Chinese patent 101215239 uses condensation amination method in two steps Combine and prepare ethylenediamine and amine ethyl piperazidine：The first step, monoethanolamine and ammonia are in the mercerising boiling of condensation amination catalysis P Modification In the presence of stone, reaction generation ethylenediamine, piperazine and other amines, product separate to obtain product ethylenediamine；Second step, piperazine and not anti- The monoethanolamine continuation answered is reacted in the presence of the ZSM-5 of Si modification, after separating, purifying, obtains target product amine ethyl piperazine Piperazine.
Using the catalyst preparation ethyleneamines of the above-mentioned prior art, there are monoethanolamine conversion ratio is low, ethylenediamine or piperazine choosing Selecting property is low and the problem of the one or more aspects such as stability difference.
The content of the invention
It is an object of the invention to provide one kind be used under hydro condition monoethanolamine and ammonia can be converted into ethylenediamine and The catalyst of piperazine, the catalyst can realize it is following in it is one or more：(1) conversion of monoethanolamine and ammonia is improved The selectivity of target amine ethylenediamine and piperazine is improved in rate, (2), and (3) make monoethanolamine face hydrogen amination to prepare ethylenediamine and piperazine It is realized under relatively low reaction pressure, (4) reduce monoethanolamine and face the energy consumption that hydrogen amination prepares ethylenediamine and piperazine, (5) raising side The stability of method, (6) are realized easy to operate.
To achieve the above object, catalyst provided by the invention includes main active component, auxiliary agent and carrier, main active component Weight account for the 1.0~60.0% of catalyst weight, preferably 10.0~25.0%, the weight of auxiliary agent accounts for the 0.1 of catalyst weight ~30.0%, preferably 1.0~10.0%：
Main active component is the one or two or more kinds in transition metal Ni, Cu or Co, preferably W metal；
Auxiliary agent is one kind or two kinds in one or two or more kinds of metals or oxide in Fe, Cr, Re, Ru, B, Mg More than, preferred promoter Re, B, Mg；
Carrier is H-ZSM-5, H- β, H-MOR or H-Y molecular sieves；
The specific surface area of H-ZSM-5 is 300~800m in carrier2/ g, silica alumina ratio are 10.0~200.0；Preferably H- The specific surface area of ZSM-5 is 450~600m2/ g, silica alumina ratio are 50.0~100.0；
The specific surface area of H- β is 200~800m in carrier2/ g, silica alumina ratio are 20.0~80.0；The ratio table of preferably H- β Area is 400~700m2/ g, silica alumina ratio are 40.0~65.0；
The specific surface area of H-MOR is 200~700m in carrier2/ g, silica alumina ratio are 5.0~30.0；The ratio of preferably H-MOR Surface area is 350~500m2/ g, silica alumina ratio are 10.0~20.0；
The specific surface area of H-Y is 300~1000m in carrier2/ g, silica alumina ratio are 1.5~3.0；The preferably specific surface of H-Y Product is 550~800m2/ g, silica alumina ratio are 2.0~3.0；
The combination of one or both of the precipitation method, infusion process can be used by activity in the preparation method of the catalyst of the present invention Component is supported on carrier.
Application of the catalyst of the present invention under hydro condition in monoethanolamine and the reaction of ammonia synthesis ethylenediamine and piperazine, instead The condition is answered to be：120~240 DEG C of reaction temperature, preferably reaction temperature are 150~200 DEG C, reaction Hydrogen Vapor Pressure for 6.0~ 12.0MPa, preferably Hydrogen Vapor Pressure are 7~10MPa, and monoethanolamine liquid air speed is 0.1~1.0h-1, preferably liquid air speed For 0.3~0.7h-1。
The catalyst of the present invention carries out reduction activation under hydrogen atmosphere before application：Pressure is 0.1~1.0MPa, preferably Ground pressure is 0.1~0.5MPa, and temperature is 200~700 DEG C, and preferably temperature is 350~600 DEG C, hydrogen gas space velocity for 500~ 5000h-1, preferably hydrogen gas space velocity is 1500~3000h-1。
Compared with prior art, catalyst of the invention can significantly reduce energy consumption of reaction, improve under hydro condition The conversion ratio of monoethanolamine, while improve the yield of target product ethylenediamine and piperazine.
Specific embodiment
Present disclosure is illustrated in detail below.
The catalyst of the present invention be under hydro condition monoethanolamine and ammonia be converted into the reaction of ethylenediamine and piperazine. Catalyst includes main active component, auxiliary agent and carrier three parts composition, and main active component is one in transition metal Ni, Cu or Co Kind or several, the one or more of the metals such as auxiliary agent Fe, Cr, Re, Ru, B, Mg or oxide, carrier select H-ZSM-5, H- β, H-MOR or H-Y molecular sieve etc..The catalyst of the present invention, reacts, reactant monoethanolamine and ammonia exist in fixed bed reactors Under hydro condition can high activity, be converted into amine product based on ethylenediamine and piperazine with high selectivity.Specifically, product is with second Based on diamines (EDA) and piperazine (PIP), co-production diethylenetriamine (DETA), aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethyl ethylenediamine (AEEA) etc..
In the reaction system of the present invention, the monoethanolamine and ammonia mixture of liquid are pumped into preheater to be mixed in advance with hydrogen Heat to after 150 DEG C into fixed bed reactors.Monoethanolamine and ammonia need not add in any solvent dissolved dilution.
The catalyst of the present invention, the main preferable weight percentage of activity component metal are 1.0~60.0%, optimal content For 10.0~25.0%；The preferable weight percentage of auxiliary agent is 0.1~30.0%, and optimal content is 1.0~10.0%；Carrier The preferable specific surface area that H-ZSM-5 can be used is 300~800m2/ g, optimal specific surface area are 450~600m2/ g, preferable sial Than for 10.0~200.0, optimal silica alumina ratio is 50.0~100.0；Carrier can be used the preferable specific surface area of H- β for 200~ 800m2/ g, optimal specific surface area are 400~700m2/ g, preferable silica alumina ratio are 20.0~80.0, optimal silica alumina ratio for 40.0~ 65.0；The preferable specific surface area that H-MOR can be used in carrier is 200~700m2/ g, optimal specific surface area are 350~500m2/ g, compared with Good silica alumina ratio is 5.0~30.0, and optimal silica alumina ratio is 10.0~20.0；Carrier can be used the preferable specific surface area of H-Y for 300~ 1000m2/ g, optimal specific surface area are 550~800m2/ g, preferable silica alumina ratio are 1.5~3.0, and optimal silica alumina ratio is 2.0~3.0.
The reaction temperature of the present invention is 160 DEG C, and reaction Hydrogen Vapor Pressure is 8.0MPa, and monoethanolamine liquid volume air speed is 0.5h-1And NH3:MEA:H2=10:1:Reaction evaluating is carried out under conditions of 0.015 (molar ratio).Catalyst filling amount is 5ml.
The catalyst of the present invention can be activated before the use by the hydrogen treat under certain condition.It is urged with Hydrogen activation The preferable condition of agent is：GHSV=2400h-1, pressure is normal pressure, and temperature is 400 DEG C, recovery time 4h.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
Catalyst is 15%Ni-1.5%Re/H-ZSM-5.The H-ZSM-5 of 10 grams of 20-40 mesh is weighed, using preceding through 120 DEG C Dry 4 it is small when, configuration 14ml contain 4.672 grams of Ni (NO3)2, 0.216 gram of NH4ReO4Aqueous solution, with this aqueous solution dipping on State H-ZSM-5 carriers, naturally dry, when 120 DEG C of ovens 4 are small, when 500 DEG C of Muffle furnace roastings 5 are small.Using preceding at 390 DEG C (normal pressure, 2400h in hydrogen-1) reduction activation 4 it is small when.
Embodiment 2
Catalyst is 10%Ni-2%Re/H-ZSM-5.Except configuration 14ml contains 3.114 grams of Ni (NO3)2, 0.288 gram NH4ReO4Aqueous solution outside, other preparation processes are same as Example 1.
Embodiment 3
Catalyst is 15%Ni-1.5%Re/H-MOR.Except substituting H-ZSM-5 points using 20-40 mesh H-MOR molecular sieves Son sieve, other preparation processes are same as Example 1.
Embodiment 4
Catalyst is 15%Ni-1.5%Re/H-Y.Except substituting H-ZSM-5 molecular sieves using 20-40 mesh H-Y molecular sieves, Other preparation processes are same as Example 1.
Embodiment 5
Catalyst is 15%Ni-1.5%Re/H- β.Except substituting H-ZSM-5 molecular sieves using 20-40 mesh H- beta-molecular sieves, Other preparation processes are same as Example 1.
Embodiment 6
Catalyst is 15%Ni-2%Ru/H-ZSM-5.Except configuration 14ml contains 4.672 grams of Ni (NO3)2, 0.304 gram RuCl3Aqueous solution outside, other preparation processes are same as Example 1.
Embodiment 7
Catalyst is 20%Ni-1%Cr/H-MOR.Except substituting H-ZSM-5 molecules using 20-40 mesh H-MOR molecular sieves Sieve, configuration 14ml contain 6.229 grams of Ni (NO3)2, 0.458 gram of Cr (NO3)3Aqueous solution outside, other preparation processes and embodiment 1 It is identical.
Embodiment 8
Catalyst is 15%Ni-3.5%Mg/H-MOR.Except substituting H-ZSM-5 points using 20-40 mesh H-MOR molecular sieves Son sieve, configuration 14ml contain 4.672 grams of Ni (NO3)2, 2.132 grams of Mg (NO3)2Aqueous solution outside, other preparation processes with implement Example 1 is identical.
Embodiment 9
Catalyst is 10%Ni-10%Cu-1%B/H-ZSM-5.Except configuration 14ml contains 3.114 grams of Ni (NO3)2, 2.951 grams of Cu (NO3)2, 0.572 gram of H3BO3Aqueous solution outside, other preparation processes are same as Example 1.
Embodiment 10
Catalyst is 25%Co-5%Re/H-MOR.Except substituting H-ZSM-5 molecules using 20-40 mesh H-MOR molecular sieves Sieve, configuration 14ml contain 7.766 grams of Co (NO3)2, 0.720 gram of NH4ReO4Aqueous solution outside, other preparation processes and embodiment 1 It is identical.
Embodiment 11
Catalyst is 5%Ni-2%Re/H-ZSM-5.Except configuration 14ml contains 1.557 grams of Ni (NO3)2, 0.288 gram NH4ReO4Aqueous solution outside, other preparation processes are same as Example 1.
Embodiment 12
Catalyst is 40%Ni-2%Re/H-ZSM-5.Except configuration 14ml contains 12.457 grams of Ni (NO3)2, 0.288 gram NH4ReO4Aqueous solution outside, other preparation processes are same as Example 1.
Embodiment 13
Catalyst is 15%Ni-0.1%Re/H-MOR.Except substituting H-ZSM-5 points using 20-40 mesh H-MOR molecular sieves Son sieve, configuration 14ml contain 4.672 grams of Ni (NO3)2, 0.014 gram of NH4ReO4Aqueous solution outside, other preparation processes with implement Example 1 is identical.
Embodiment 14
Catalyst is 15%Ni-18%Re/H-Y.Except substituting H-ZSM-5 molecular sieves using 20-40 mesh H-Y molecular sieves, Configuration 14ml contains 4.672 grams of Ni (NO3)2, 2.593 grams of NH4ReO4Aqueous solution outside, other preparation processes and 1 phase of embodiment Together.
Embodiment 15
Catalyst is 20%Cu-5%Mg/H-Y.Except substituting H-ZSM-5 molecular sieves using 20-40 mesh H-Y molecular sieves, match somebody with somebody It puts 14ml and contains 5.903 grams of Cu (NO3)2, 3.045 grams of Mg (NO3)2Aqueous solution outside, other preparation processes and 1 phase of embodiment Together.
Embodiment 16
Catalyst is 20%Co-3%Fe/H-MOR.Except substituting H-ZSM-5 molecules using 20-40 mesh H-MOR molecular sieves Sieve, configuration 14ml contain 6.212 grams of Co (NO3)2, 1.299 grams of Fe (NO3)3Aqueous solution outside, other preparation processes and embodiment 1 It is identical.
Catalyst prepared by the above method carries out reaction evaluating using fixed bed reactors, and reaction temperature is 160 DEG C, hydrogen Pressure 8.0MPa, monoethanolamine liquid volume air speed are 0.5h-1, NH3:MEA:H2=10:1:0.015 (molar ratio), during reaction Between for 50 it is small when.Sampling analysis is analyzed using 7890 gas chromatographs of Agilent, and chromatographic column is DB-35 capillary colors Column is composed, detector is hydrogen flame detector.Quantitative analysis is carried out as internal standard using N,N-dimethylformamide (DMFA).Reaction As a result it is summarised in table 1.
The conversion ratio of term monoethanolamine (MEA), ethylenediamine (EDA), piperazine (PIP), diethylenetriamine in table 1 (DETA), the selectivity of aminoethyl piperazine (AEP), hydroxyethyl piperazine (HEP) and hydroxyethyl ethylenediamine (AEEA) is defined as follows：
Table 1：Monoethanolamine and ammonia are converted into the evaluating catalyst result of ethylenediamine and piperazine under hydro condition.
Evaluation result shows：When main active component weight content is in the range of 10.0~25.0%, the conversion of monoethanolamine Rate is higher；When auxiliary agent weight content is in the range of 1.0~10.0%, the conversion ratio of monoethanolamine is higher；W metal is as main work Property component or main active component in it is a kind of when, catalyst have greater activity；Re, B, Mg are as one kind in auxiliary agent or auxiliary agent When, catalyst has greater activity；When H-ZSM-5 or H-Y molecular sieves are as carrier, there is higher choosing to ethylenediamine and piperazine Selecting property；When H-MOR molecular sieves are as carrier, there is higher selectivity to ethylenediamine；When H-Y molecular sieves are as carrier, to piperazine Piperazine has higher selectivity.

Claims (7)

1. a kind of catalyst, wherein：
The catalyst includes main active component, auxiliary agent and carrier, the weight of main active component account for catalyst weight 1.0~ 60.0%, preferably 10.0~25.0%；The weight of auxiliary agent accounts for the 0.1~30.0% of catalyst weight, preferably 1.0~10.0%：
Main active component is the one or two or more kinds in transition metal Ni, Cu or Co, preferably W metal；
Auxiliary agent is the one or two or more kinds in one or two or more kinds of metals or oxide in Fe, Cr, Re, Ru, B, Mg, Preferred promoter Re, B, Mg；
Carrier is H- type molecular sieves.
2. catalyst according to claim 1, wherein, H- types molecular sieve is included in H-ZSM-5, H- β, H-MOR or H-Y It is one or two or more kinds of.
3. catalyst according to claim 1 or 2, wherein, the specific surface area of carrier H-ZSM-5 is 300~800m2/ g, silicon Aluminium ratio is 10.0~200.0；
The specific surface area of carrier H- β is 200~800m2/ g, silica alumina ratio are 20.0~80.0；
The specific surface area of carrier H-MOR is 200~700m2/ g, silica alumina ratio are 5.0~30.0；
The specific surface area of carrier H-Y is 300~1000m2/ g, silica alumina ratio are 1.5~3.0.
4. a kind of any method for preparing catalyst of claim 1-3, using one or both of the precipitation method, infusion process Combination active component and auxiliary agent are supported on carrier.
5. a kind of claim 1-3 any catalyst monoethanolamine and liquefied ammonia synthesis of ethylenediamine and piperazine under hydro condition Application in piperazine reaction.
6. application according to claim 5, it is characterised in that：120~240 DEG C of reaction temperature, hydrogen reaction pressure are 6.0 ~12.0MPa, monoethanolamine liquid volume air speed are 0.1~1.0h-1。
7. application according to claim 5 or 6, wherein, reactor is fixed bed reactors, and catalyst is before application in hydrogen Reduction activation is carried out under gas atmosphere：Pressure is 0.1~1.0MPa, and temperature is 200~700 DEG C, and hydrogen gas space velocity is 500~5000h-1。
CN201611003643.7A 2016-11-15 2016-11-15 Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition Pending CN108067289A (en)

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CN112495424A (en) * 2020-11-16 2021-03-16 华南理工大学 Modified molecular sieve supported ruthenium catalyst, preparation thereof and application thereof in preparation of hydrocarbon substances from lignin
CN114605268A (en) * 2022-03-22 2022-06-10 中国科学院大连化学物理研究所 Method for catalytically synthesizing polyethylene polyamine
CN114605268B (en) * 2022-03-22 2023-02-28 中国科学院大连化学物理研究所 Method for catalytically synthesizing polyethylene polyamine

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