CN114433096B - Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine - Google Patents

Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine Download PDF

Info

Publication number
CN114433096B
CN114433096B CN202011224375.8A CN202011224375A CN114433096B CN 114433096 B CN114433096 B CN 114433096B CN 202011224375 A CN202011224375 A CN 202011224375A CN 114433096 B CN114433096 B CN 114433096B
Authority
CN
China
Prior art keywords
carrier
ion
group
diethylenetriamine
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011224375.8A
Other languages
Chinese (zh)
Other versions
CN114433096A (en
Inventor
向良玉
田保亮
唐国旗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN202011224375.8A priority Critical patent/CN114433096B/en
Publication of CN114433096A publication Critical patent/CN114433096A/en
Application granted granted Critical
Publication of CN114433096B publication Critical patent/CN114433096B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8896—Rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of preparation of ethylenediamine and piperazine, and discloses a method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine. The method comprises the following steps: and contacting diethylenetriamine with ammonia in the presence of hydrogen and a catalyst to react, wherein the mol ratio of diethylenetriamine to ammonia is 1:4-30, the catalyst comprises a carrier, an active metal component and an optional auxiliary agent, wherein the active metal component comprises cobalt and/or nickel, and the auxiliary agent is selected from at least one of VIB group, VIIB group and IB group metals, and the active metal component is supported on the carrier. The method has higher selectivity and conversion rate when preparing ethylenediamine and co-producing piperazine, and has larger practical significance.

Description

Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine
Technical Field
The invention relates to the field of preparation of ethylenediamine and piperazine, in particular to a method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine.
Background
Ethylenediamine, named ethyleneimine, EDA for short, also called 1, 2-diaminoethane, diaminoethylene, ethylenediamine, and its molecular formula is C 2 H 8 N 2 The transparent and colorless viscous liquid has a melting point of 8.5 ℃ and a boiling point of 116.5 ℃, is easily dissolved in water, can be mixed with ethanol, has the characteristics of alkalinity and surface activity, is an important chemical raw material and fine chemical intermediate, is widely applied to the fields of epoxy resin curing agents, pesticides, medicines, low-molecular-weight polyamide resins, chelating agents and the like, and relates to a plurality of industries.
Piperazine, english name Piperazine, PIP for short, molecular formula C 4 H 10 N 2 Piperazine and its derivatives are very important fine chemical products, are widely used in medicine, pesticide and dye intermediates, are raw materials of various medical products, and along with the continuous expansion of medical demands, especially the continuous improvement of the demands of quinolone medicines, the continuous rising of the market demands of piperazine and its derivatives.
Piperazine and ethylenediamine are important products of ethyleneamines, and the current industrial methods for producing ethyleneamines are mainly the dichloroethane method (EDC) and the ethanolamine Method (MEA). Because of low price of dichloroethane raw material and wide source, EDC method is mainly adopted in early ethylenediamine device, EDC method is a continuous reaction, polyene polyamine is used as main byproduct, but the pollution is serious, the equipment corrosion is serious, and the investment cost is high. The MEA route has relatively less pollution and low investment cost, and becomes an important process route and research hot spot for preparing the ethylene amine product in recent years.
Beginning in the 60 s of the 19 th century, BASF has realized industrialized application of ethanolamine method ethylene amine, ethanolamine and ammonia, hydrogen are mixed, under the catalysis of Ni, co and Cu catalysts, ammoniation reaction is carried out in trickle bed reactor under reaction pressure of 20MPa, and the generated products mainly comprise ethylenediamine and piperazine, and meanwhile, by-products of Diethylenetriamine (DETA), hydroxyethyl piperazine (HEP), N-Aminoethylpiperazine (AEP), hydroxyethyl ethylenediamine (AEEA) and the like.
CN101875014a discloses a catalyst for converting monoethanolamine and ammonia into ethylenediamine under hydrogen condition, the catalyst comprises main active component, auxiliary agent and carrier, the main active auxiliary agent is at least one of Co or nickel, the auxiliary agent is Re, fe, cu, ru, B, and the carrier is Al 2 O 3 Or SiO 2 . The reaction conditions are as follows: the reaction temperature is 135-155 ℃, the hydrogen reaction pressure is 6.5-8MPa, and the volume space velocity of monoethanolamine liquid is 0.35-0.65h -1 . The DETA selectivity is 7.1-9.5%.
CN109908900a discloses a supported catalyst for preparing ethylene amine by ethanolamine method, the main active component of the catalyst is Ni, co or Cu, and the auxiliary agent is at least one of Fe, cr, re, ru, B, mg, ba metal or oxide; the carrier is alumina, silica, alumina-silica, H-ZSM-5 or H-beta molecular sieve, under the condition of hydrogen, the reaction temperature of ethanolamine and liquid ammonia is 110-240 ℃, the reaction pressure is 5-12MPa, and the volume space velocity of ethanolamine liquid is 0.1-1H -1 ，MEA、NH 3 And H 2 The molar ratio of (2) is 1: (5-25): under the condition of (0.05-2), mainly producing ethylenediamine and piperazine, and simultaneously producing by-products of Diethylenetriamine (DETA), hydroxyethylpiperazine (HEP), N-Aminoethylpiperazine (AEP), hydroxyethylethylenediamine (AEEA) and the like, wherein the selectivity of diethylenetriamine is 6.9-18.3%.
At present, domestic ethylenediamine and piperazine and other ethylenediamine products basically depend on import, and the existing ethanolamine method for preparing ethylenediamine and piperazine routes has a large amount of byproducts, including triethylenediamine, hydroxyethyl ethylenediamine, hydroxyethyl piperazine, N-aminoethyl piperazine and the like, and a large amount of energy consumption is required for separation, and the yields of ethylenediamine and piperazine are seriously affected.
It is therefore desirable to develop a new route to ethylenediamine and piperazine to increase the yields and selectivity of ethylenediamine and piperazine.
Disclosure of Invention
The invention aims to overcome the technical defects of high separation energy consumption caused by low yield and selectivity in the preparation of ethylenediamine and piperazine in the prior art, and provides a method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine.
Based on the above technical problems in the prior art, the inventors of the present invention have found through intensive studies that the preparation of ethylenediamine and piperazine using diethylenetriamine as a reaction substrate has high selectivity and conversion, and therefore, the present invention provides a method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine, comprising: and contacting diethylenetriamine with an ammonia source for reaction in the presence of hydrogen and a catalyst, wherein the molar ratio of diethylenetriamine to ammonia source is 1:4-30, the catalyst comprises a carrier, an active metal component and an optional auxiliary agent, wherein the active metal component comprises cobalt and/or nickel, and the auxiliary agent is selected from at least one of group VIB, group VIIB and group IB metals, and the active metal component is supported on the carrier.
Compared with the prior art, the method has higher selectivity and conversion rate when preparing the ethylenediamine and co-producing the piperazine, has larger practical significance, and provides a new route for preparing the ethylenediamine and the piperazine.
Further, the present inventors have found that the ammonia adsorption amount and CO of the catalyst are changed 2 The adsorption quantity is more beneficial to improving the selectivity and conversion rate of preparing the ethylenediamine and the piperazine by the disproportionation of the diethylenetriamine, thereby further improving the yield of the ethylenediamine and the piperazine in a mode of overcoming technical prejudices.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine, which is characterized by comprising the following steps: and contacting diethylenetriamine with an ammonia source for reaction in the presence of hydrogen and a catalyst, wherein the molar ratio of diethylenetriamine to ammonia source is 1:4-30, the catalyst comprises a carrier, an active metal component and an optional auxiliary agent, wherein the active metal component comprises cobalt and/or nickel, and the auxiliary agent is selected from at least one of group VIB, group VIIB and group IB metals, and the active metal component is supported on the carrier.
According to the present invention, the contacting conditions may include: the temperature is 120-250 ℃, preferably 130-220 ℃.
According to the present invention, the contacting conditions may further include: the pressure is 3-18MPa, preferably 4-17MPa.
According to the present invention, the contacting conditions may further include: the liquid phase volume space velocity of diethylenetriamine is 0.05-0.8m 3 /(m 3 H), preferably 0.06-0.6m 3 /(m 3 ·h)。
According to the present invention, the contacting conditions may further include: the molar ratio of hydrogen, ammonia source and diethylenetriamine is 1-5:4-30:1, preferably 1-4:4-25:1.
According to the present invention, the diethylenetriamine may be reacted in the form of pure substances or formulated into a solution for reaction, and in order to further improve the conversion, reduce the formation of heavy components, and improve the selectivity of ethylenediamine and piperazine, the diethylenetriamine is preferably reacted in the form of a solution. There is no particular limitation on the concentration of diethylenetriamine in the solution, and it may be 10 to 80% by weight. The solvent in the solution can be various solvents which can dissolve diethylenetriamine and do not react with other reaction raw materials, can be water or organic solvents, and is preferably selected from water and/or 1, 4-dioxane.
According to the present invention, the ammonia source is a reactant capable of providing an amino group and/or an amine group, and may be selected from at least one of ammonia, primary amines of C1-12, and secondary amines of C2-12, preferably at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine, and diethylamine. "C1-12" refers to primary or secondary amines having 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 carbon atoms.
According to the invention, the method may further comprise the step of separating and purifying the product of the ammonification reaction to obtain piperazine and ethylenediamine, respectively. The separation and purification mode can be rectification.
According to the present invention, the ammonification reaction may be continuous or batch, and one of the reaction apparatuses such as a fixed bed tubular reactor, a high pressure stirred tank, a bubbling bed reactor, a fluidized bed reactor, a microchannel reactor, etc. may be selected.
According to a preferred embodiment of the present invention, the catalyst used is one in which the support is at least one selected from the group consisting of doped alumina, doped silica, doped molecular sieves and doped aluminum silicate; the ammonia adsorption capacity of the carrier is 0.2-0.6mmol/g, and the carbon dioxide adsorption capacity of the carrier is 0.05-0.3mmol/g.
According to the present invention, the ammonia adsorption amount of the carrier is preferably 0.3 to 0.5mmol/g, more preferably 0.3 to 0.42mmol/g.
According to the present invention, the carbon dioxide adsorption amount of the carrier is preferably 0.06 to 0.2mmol/g, more preferably 0.06 to 0.17mmol/g.
According to a preferred embodiment of the present invention, the content of the doping element (doping element) incorporated in the carrier is 0.03 to 2 wt%, more preferably 0.08 to 1 wt% based on the total weight of the non-doping element component in the carrier. "non-impurity element component" refers to the generic term for components other than the impurity element (alumina, silica, molecular sieve, aluminum silicate, etc.) in the carrier.
According to a preferred embodiment of the present invention, the doping element in the carrier includes a metal element and a non-metal element. The weight ratio of the metallic element to the nonmetallic element may be 1:0.05-50, preferably 1:0.2-8.
More preferably, the metal element is selected from at least one of group IA metal element, group IIA metal element, group VA metal element and lanthanide series metal element, and further preferably at least one of calcium, magnesium, potassium, bismuth, strontium, barium and lanthanum.
More preferably, the nonmetallic element is selected from at least one of group IIIA nonmetallic element, group VA nonmetallic element, group VIA nonmetallic element, and group VIIA nonmetallic element, further preferably at least one of boron, fluorine, phosphorus, sulfur, and selenium.
According to a preferred embodiment of the invention, the doping elements in the support are derived from metal cations and acid ions and do not include sodium ions and chloride ions. Since the incorporated hetero elements are introduced during the preparation of the carrier, the incorporated hetero elements are mainly present in the bulk phase of the carrier.
According to a more preferred embodiment of the present invention, the metal cation may be selected from at least one of group IA metal cations, group IIA metal ions, group VA metal ions, and lanthanide metal ions, and more preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions, and lanthanum ions.
According to a more preferred embodiment of the present invention, the acid ion may be selected from at least one of nonmetallic acid ions, and more preferably at least one of borate ion, fluoride ion, phosphate ion, sulfate ion, and selenate ion.
According to a preferred embodiment of the invention, the specific surface area of the support is 120-240m 2 /g。
According to a preferred embodiment of the invention, the pore volume of the support is 0.5-1ml/g.
In the invention, the specific surface area and pore volume of the carrier are measured by a nitrogen adsorption-desorption method, and the specific surface area and pore volume of the carrier are specifically measured by GB/T6609.35-2009.
According to the invention, the active ingredient may be present in an amount of 5 to 42g, preferably 10 to 35g, more preferably 10 to 30g, per 100g of carrier by weight of non-hetero element ingredients.
According to the invention, the catalyst may further comprise an auxiliary agent in order to better exert the performance of the catalyst of the invention, to adjust the reaction product ratio, and to reduce unwanted side reactions. The promoter may be selected from at least one of group VIB, VIIB and IB metals, preferably at least one of Mo, W, mn, re, cu and Ag.
According to the invention, the content of the auxiliary agent may be from 0 to 10g, preferably from 0.5 to 6g, per 100g of carrier by weight of non-hetero element ingredients.
According to the present invention, the carrier can be prepared by an existing method capable of obtaining ammonia adsorption amount and carbon dioxide adsorption amount satisfying the above ranges, and obtaining a carrier having ammonia adsorption amount and carbon dioxide adsorption amount satisfying the above ranges can be performed by a person skilled in the art. According to a preferred embodiment of the invention, however, the carrier is prepared by a process comprising the steps of: and sequentially forming, drying and roasting the mixture containing the doping element and a carrier source, wherein the carrier source is selected from at least one of pseudo-boehmite, a silicon oxide precursor (such as silica sol), a molecular sieve precursor (such as ZSM-5) and an aluminum silicate precursor. The molding method may use kneading, rolling or sheeting, etc.
In the above preparation method of the carrier, those skilled in the art will understand that: if the raw material for providing the carrier source already contains the desired amount of the doping element, the raw material is used only for molding, and if the raw material for providing the carrier source does not contain the doping element or the content of the doping element is low (insufficient), the doping element can be additionally introduced.
In the above method for producing a support, the doping element is preferably used in such an amount that the content of the doping element incorporated in the support is 0.03 to 2 wt%, more preferably 0.08 to 1 wt% (for example, may be 0.08 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1 wt%, or any value between any two of the above values) based on the total weight of the non-hetero element components in the support. The person skilled in the art will be able to determine the amount of a component material (e.g. carrier modifier) based on the amount of the component in the final carrier, and thus, some of the material amounts are not shown herein.
Wherein the doping element is provided by a carrier modifier, which is preferably at least one of a compound that can provide a cation and an anion (the cation of the compound does not include sodium ions, and the anion of the compound does not include chloride ions).
In the above preparation method of the carrier, the cation of the compound may be selected from at least one of group IA cations, group IIA metal ions, group VA metal ions and lanthanide metal ions, preferably at least one of calcium ions, magnesium ions, potassium ions, bismuth ions, strontium ions, barium ions and lanthanum ions.
In the above method for preparing the carrier, the anion of the compound may be selected from at least one of nonmetallic acid ions, preferably at least one of borate ion, fluoride ion, phosphate ion, sulfate ion and selenate ion.
In the preparation method of the carrier, the carrier modifier is at least one selected from boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, potassium phosphate, monopotassium phosphate, potassium hydrogen phosphate, magnesium phosphate, calcium phosphate, sulfuric acid, cobalt sulfate, nickel sulfate, aluminum sulfate, calcium sulfate, bismuth nitrate, potassium sulfate, potassium carbonate, magnesium nitrate, magnesium sulfate, basic magnesium carbonate, calcium nitrate, basic calcium carbonate, strontium nitrate, strontium phosphate, strontium sulfate, barium nitrate, lanthanum nitrate and selenate.
In the above method of preparing a carrier, the carrier source is preferably pseudo-boehmite. The pseudo-boehmite can be prepared by at least one of carbonization, organoaluminum hydrolysis, aluminum sulfate and nitric acid. The specific surface area of the pseudo-boehmite is preferably 250-330m 2 And/g. The pore volume of the pseudo-boehmite is preferably 0.8-1.3ml/g. Pseudo-boehmite with specific pore structure can be obtainedA catalyst with better performance.
In the above method for preparing a carrier, the drying conditions may include: the temperature is 80-150deg.C (for example, 80deg.C, 85deg.C, 90deg.C, 95deg.C, 100deg.C, 105deg.C, 110deg.C, 120deg.C, 130deg.C, 150deg.C, or any value between any two of the above) and the time is 6-20h (for example, 6h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 10h, 11h, 11.5h, 12h, 12.5h, 13h, 14h, 14.5h, 15h, 15.5h, 16h, 17h, 18h, 19h, 20h, or any value between any two of the above).
In the above method for preparing a carrier, the conditions for firing may include: the temperature is 600-1100 ℃ (for example, 600 ℃, 650 ℃, 680 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 990 ℃, 1000 ℃, 1050 ℃, 1100 ℃, or any value between any two of the above values) and the time is 2-20 hours (for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 12 hours, 15 hours, 18 hours, 20 hours, or any value between any two of the above values).
According to the invention, the catalyst may be used after reduction. The reduction may be carried out with a gas containing hydrogen at 350-500 c, preferably 350-450 c, more preferably 400-450 c. The hydrogen may be pure hydrogen or inert gas diluted hydrogen, such as a mixture of nitrogen and hydrogen. The reduction temperature is gradually increased during the reduction, and the temperature is not preferably increased too rapidly, for example not more than 20 ℃/h. By monitoring H in the reduction system 2 O generation determines the time of reduction, i.e. when the reduction system no longer generates new H 2 At O, the reduction is ended, and the person skilled in the art can choose the time for the reduction accordingly, which will not be described in detail, for example, the reduction time may be 2-5h at the highest temperature. The reduction may be carried out directly in the reactor, followed by a catalytic reaction. The reduction may also be carried out in a separate reactor, also referred to as off-reactor reduction, and the reduction may be followed by passivation with a mixture of oxygen, for example at a temperature of 10 to 60℃and in particular 20 to 40℃before discharge from the reactor.The reduced and passivated catalyst is charged to the reactor before use and may be activated with hydrogen or a mixture of hydrogen and nitrogen, for example at a temperature of 150-250 c, preferably 170-240 c. By monitoring H in the activation system 2 O generation determines the activation time, i.e. when the activation system no longer generates new H 2 The activation is terminated at O, and the person skilled in the art will be able to choose the activation time accordingly, which will not be described in detail, for example, the activation time is, for example, from 1 to 5 hours, preferably from 2 to 3 hours, at the highest temperature, or it may be used without activation, depending on the extent to which the active components and auxiliaries in the catalyst are oxidized.
The present invention also provides a process for preparing a catalyst as described above, which process comprises: the active ingredient and optional adjuvants are supported on a carrier.
It will be appreciated that the method of preparing the catalyst may further comprise: a step of preparing the carrier according to the aforementioned method.
In the present invention, the method of supporting the active ingredient and the optional auxiliary agent on the carrier may be an impregnation method, that is, impregnating the carrier with a solution containing the active ingredient precursor and the optional auxiliary agent precursor, followed by drying and calcination. The impregnation method is to soak the carrier in a proper solution containing the active component and the precursor of the auxiliary agent, and the precursor is adsorbed and loaded on the carrier. The impregnation method is subdivided into a dry impregnation method, an wet impregnation method, a multiple impregnation method, a mixed impregnation method, a spray impregnation method and the like. Dry and wet impregnation refers to the state of the support prior to impregnation with the active component precursor, whether dry or pre-wet with water. Multiple impregnation refers to multiple impregnations of a precursor mixture of one or more components, or multiple impregnations of different precursor groups in batches, each of which requires drying and baking after each impregnation to "anchor" the impregnated component. The mixed impregnation method is to impregnate the active component and the precursor used as the auxiliary agent together when no precipitation reaction occurs between the active component and the precursor. The spray dipping method is to spray dipping solution onto a continuously rotating carrier by a spray gun, so that the dipping solution just fills and saturates the pore volume of the carrier. The catalyst of the present invention may be suitably selected in terms of the impregnation method according to the condition of the processing plant.
The metal (cobalt and/or nickel) impregnating the support is preferably used in the form of a solution of a metal salt, such as nitrate, formate, oxalate, lactate, or the like. The solvent is preferably water, and some organic solvents may be used, such as ethanol. The impregnation of the support with the metal salt solution may be carried out in any desired order, or may be carried out continuously with a plurality of solutions containing one or more metal salts. All or a single impregnation step may be performed in several times, and the impregnation sequence may also be changed. The concentration of the solution is selected so that the desired amount of metal is supported on the carrier. The impregnated support is preferably dried at 80-150 c, more preferably at 80-120 c. The drying time is reasonably selected according to the drying temperature, the quantity of the dried materials, the drying equipment and the like, for example, 8 hours, and the water content after drying is taken as a criterion that the subsequent roasting is not influenced. Drying and then roasting at 150-500 ℃ to remove the crystal water in the salt or decompose the salt into oxide, preferably roasting at 300-500 ℃ for 1-6h. In the case of multiple impregnations, it is preferable to carry out drying and calcination after each impregnation.
In the present invention, the operation of loading the active component has little influence on the microstructure of the catalyst, and thus the resulting catalyst has a similar pore structure to the carrier.
According to the invention, the method comprises the steps of screening the catalyst, screening the catalyst with the composition or structure parameters meeting the requirements, and carrying out ammonification according to the mode.
The present invention will be described in detail by examples. In the following examples, the dry basis (Al 2 O 3 ) The content was 72% by weight.
Preparation example 1
Pseudo-boehmite powder (specific surface 298 m) 2 Adding dilute acid aqueous solution of calcium nitrate tetrahydrate (analytically pure), nitric acid and phosphoric acid into the mixture in the kneading process, extruding the mixture into strips with the diameter of 5mm, cutting the strips into strips with the length of 4mm, drying the strips at 100 ℃ for 12 hours, and roasting the strips at 720 ℃ for 8 hours to prepare the required carrier, wherein the strips are prepared by using Al for every 100g 2 O 3 The calculated pseudo-boehmite powder, the calcium nitrate tetrahydrate (analytically pure) dosage is 2.95g, the nitric acid dosage is 6.5g, and the phosphoric acid dosage is 0.63g.
176.4g of cobalt nitrate hexahydrate (technical grade, purity 98%) was dissolved in water to 182mL of a solution, the solution was loaded on 100g of the obtained carrier by spray dipping twice, dried at 120 ℃ for 8 hours after each spray dipping, then calcined at 400 ℃ for 4 hours, then gradually reduced with hydrogen at a temperature rising reduction rate of 20 ℃/hour, and finally reduced at 430 ℃ for 3 hours to obtain catalyst a-1.
Preparation example 2
Pseudo-boehmite powder (specific surface area 286 m) 2 Per gram, pore volume 0.88 ml/g) of potassium nitrate (analytically pure) aqueous solution, dilute acid aqueous solution of nitric acid and boric acid were added successively during kneading, kneaded and extruded into a 3mm thick clover shape, dried at 120℃for 8 hours, and then calcined at 690℃for 10 hours to prepare the desired carrier, wherein, per 100g of the carrier, the aqueous solution was prepared as an Al phase 2 O 3 The calculated pseudo-boehmite powder has the dosage of 0.26g of potassium nitrate (analytically pure), 5.2g of nitric acid and 4.57g of boric acid.
151.7g of nickel nitrate hexahydrate (technical grade, purity 98%) was dissolved in water to 168mL of a solution, the solution was supported on 100g of the obtained carrier by spray dipping twice, dried at 120℃for 4 hours after each spray dipping, then calcined at 390℃for 4 hours, then gradually reduced with hydrogen at a rate of 20℃per hour, and finally reduced at 440℃for 3 hours to obtain catalyst A-2.
Preparation example 3
Pseudo-boehmite powder (specific surface area 310 m) 2 Per g, pore volume 0.92 ml/g) of magnesium nitrate hexahydrate (analytically pure) aqueous solution, dilute acid aqueous solution of nitric acid and sulfuric acid were added successively during kneading, kneaded and extruded into toothed spheres having a diameter of 4mm, dried at 100℃for 15 hours, and then calcined at 780℃for 10 hours to give the desired support, wherein Al was added per 100g 2 O 3 The calculated pseudo-boehmite powder, the magnesium nitrate hexahydrate (analytically pure) dosage is 0.84g, the nitric acid dosage is 6.1g, and the sulfuric acid dosage is 1.22g.
50.4g of cobalt nitrate hexahydrate (technical grade, purity 98%) and 32.6g of 50wt% manganese nitrate aqueous solution were dissolved with water to 156mL of a solution, the solution was supported on the obtained 100g of carrier by spray dipping twice, dried at 120℃for 4 hours after each spray dipping, then calcined at 400℃for 4 hours, then gradually reduced with hydrogen at a temperature-raising reduction rate of 20℃per hour, and finally reduced at 430℃for 3 hours, to obtain catalyst A-3.
Preparation example 4
Pseudo-boehmite powder (specific surface area 321 m) 2 Per gram, pore volume 0.93 ml/g) of bismuth nitrate pentahydrate (analytically pure) aqueous solution, dilute acid aqueous solution of nitric acid and phosphoric acid are added successively in the kneading process, kneaded, extruded into strips with a diameter of 5mm, cut into strips with a length of 4mm, dried at 80 ℃ for 20 hours, and then calcined at 660 ℃ for 15 hours to prepare the desired carrier, wherein, per 100g of the carrier, the aqueous solution of bismuth nitrate pentahydrate, nitric acid and phosphoric acid are prepared in the form of Al 2 O 3 The calculated pseudo-boehmite powder has the dosage of bismuth nitrate pentahydrate (analytically pure) of 1.86g, nitric acid of 6.5g and phosphoric acid of 1.9g.
75.6g of cobalt nitrate hexahydrate (technical grade, purity 98%) and 50.6g of nickel nitrate hexahydrate (technical grade, purity 98%) were dissolved in water to 166mL of a solution, the solution was supported on 100g of the obtained carrier by spray dipping twice, dried at 120℃for 4 hours after each spray dipping, then calcined at 400℃for 4 hours, then gradually reduced with hydrogen at a temperature increase reduction rate of 20℃per hour, and finally reduced at 430℃for 3 hours, to obtain catalyst A-4.
Preparation example 5
Pseudo-boehmite powder (specific surface 275 m) 2 Per gram, pore volume 0.85 ml/g) of barium nitrate (analytically pure) aqueous solution, dilute acid aqueous solution of nitric acid and boric acid were added successively during kneading, kneaded and extruded into a 3mm thick clover shape, dried at 150℃for 6 hours, and then calcined at 810℃for 5 hours to prepare the desired support, wherein the ratio of Al per 100g 2 O 3 The calculated pseudo-boehmite powder has the dosage of 0.19g of barium nitrate (analytically pure), 6.5g of nitric acid and 2.29g of boric acid.
126.4g of nickel nitrate hexahydrate (technical grade, purity 98%) and 2.9g of ammonium perrhenate (purity 99%) were dissolved in water to 160mL of a solution, and the solution was supported on 100g of the obtained carrier by spray dipping twice, dried at 120℃for 4 hours after each spray dipping, then calcined at 390℃for 4 hours, then gradually reduced with hydrogen at a temperature-increasing reduction rate of 20℃per hour, and finally reduced at 440℃for 3 hours, to obtain catalyst A-5.
Preparation example 6
Pseudo-boehmite powder (specific surface 269 m) 2 Per gram, pore volume 0.86 ml/g) of cesium nitrate (analytically pure) aqueous solution, dilute acid aqueous solution of nitric acid and sulfuric acid, kneading, extruding into toothed spheres with diameter of 4mm, drying at 120℃for 8 hours, and calcining at 830℃for 4 hours to obtain the desired carrier, wherein the aqueous solution of cesium nitrate (analytically pure) and the dilute acid aqueous solution of sulfuric acid are added in succession per 100g of the carrier, wherein the aqueous solution of cesium nitrate (analytically pure) and the dilute acid aqueous solution of sulfuric acid are added in the form of Al 2 O 3 The calculated pseudo-boehmite powder comprises 0.03g of cesium nitrate, 6.2g of nitric acid and 0.09g of sulfuric acid.
201.6g of cobalt nitrate hexahydrate (technical grade, purity 98%) was dissolved in water as 156mL solution; 7.4g of ammonium molybdate tetrahydrate (analytically pure) were dissolved in water to 78ml of solution; carrying cobalt nitrate solution on 100g of obtained carrier by spray leaching method twice; and then loading the ammonium molybdate solution on a carrier by using a spray dipping method, drying for 4 hours at 120 ℃ after spray dipping, roasting for 4 hours at 400 ℃, gradually heating and reducing by using hydrogen, heating and reducing at a speed of 20 ℃/hour, and finally reducing for 3 hours at 430 ℃ to obtain the catalyst A-6.
Preparation example 7
Pseudo-boehmite powder (specific surface area 259 m) 2 Adding lanthanum nitrate hexahydrate (analytically pure) aqueous solution, nitric acid and sulfuric acid in sequence during kneading, extruding into toothed spheres with diameter of 4mm, drying at 100deg.C for 10 hr, and calcining at 980 deg.C for 5 hr to obtain the desired carrier, wherein per 100g of the carrier is Al 2 O 3 The calculated pseudo-boehmite powder, the lanthanum nitrate hexahydrate (analytically pure) dosage is 0.47g, the nitric acid dosage is 5g, and the sulfuric acid dosage is 0.61g.
100.8g of cobalt nitrate hexahydrate (technical grade, purity 98) and 14.1g of copper nitrate trihydrate (analytically pure) were dissolved in water to 176mL of a solution, and the solution was supported on 100g of the obtained carrier by spray dipping twice, dried at 120℃for 4 hours after each spray dipping, then calcined at 400℃for 4 hours, then gradually reduced with hydrogen at a temperature-raising reduction rate of 20℃per hour, and finally reduced at 430℃for 3 hours, to obtain catalyst A-7.
Preparation example 8
Pseudo-boehmite powder (specific surface area 291 m) 2 Adding lanthanum nitrate hexahydrate (analytically pure) aqueous solution, nitric acid and hydrofluoric acid diluted acid water into the mixture in kneading process, kneading, extruding into toothed spheres with diameter of 4mm, drying at 90deg.C for 12 hr, and calcining at 900deg.C for 3 hr to obtain the desired carrier, wherein the ratio of Al to Al per 100g 2 O 3 The calculated pseudo-boehmite powder, lanthanum nitrate hexahydrate (analytically pure) with the dosage of 0.62g, nitric acid with the dosage of 5.5g and hydrofluoric acid with the dosage of 0.05g.
126g of cobalt nitrate hexahydrate (technical grade, purity 98%) and 25.3g of nickel nitrate hexahydrate (technical grade, purity 98%) were dissolved in water to 177mL of a solution, the solution was supported on 100g of the obtained carrier by spray dipping 3 times, dried at 120℃for 4 hours after each spray dipping, then calcined at 400℃for 4 hours, then gradually reduced with hydrogen at a temperature increase reduction rate of 20℃per hour, and finally reduced at 430℃for 3 hours, to obtain catalyst A-8.
Preparation example 9
Pseudo-boehmite powder (specific surface area 312 m) 2 Adding calcium nitrate tetrahydrate (analytically pure) aqueous solution, nitric acid and hydrofluoric acid dilute acid into the mixture in the kneading process, kneading, extruding into coarse clover with the thickness of 4mm, drying at 100 deg.C for 8 hr, and roasting at 930 deg.C for 3 hr to obtain the required carrier, wherein the ratio of Al to Al per 100g 2 O 3 The calculated pseudo-boehmite powder has the dosage of calcium nitrate tetrahydrate (analytically pure) of 3.54g, the dosage of nitric acid of 6.5g and the dosage of hydrofluoric acid of 0.13g.
176.4g of cobalt nitrate hexahydrate (technical grade, purity 98%) and 1.3g of silver nitrate (analytically pure) were dissolved in water to 188mL of a solution, and the solution was supported on 100g of the obtained carrier by spray dipping 3 times, dried at 120 ℃ for 4 hours after each spray dipping, then calcined at 390 ℃ for 4 hours, then gradually reduced with hydrogen at a temperature-raising reduction rate of 20 ℃/hour, and finally reduced at 440 ℃ for 3 hours, to obtain catalyst a-9.
Preparation example 10
Silica gel powder (specific surface 385 m) 2 Per gram, pore volume of 0.95 ml/g), processing into 4mm toothed spheres using dilute acid water spheres containing magnesium nitrate, nitric acid and sulfuric acid, drying at 80deg.C for 15h, and then calcining at 750deg.C for 8h to obtain the desired carrier, wherein per 100g of the carrier is prepared by SiO 2 The amount of the silica gel powder, magnesium nitrate hexahydrate (analytically pure) is 8.44g, the amount of nitric acid is 6.1g, and the amount of sulfuric acid is 4.28g.
The rest of the procedure was the same as in preparation example 3 to obtain catalyst A-10.
PREPARATION EXAMPLE 11
Pseudo-boehmite powder (specific surface 261 m) 2 Per gram, pore volume 0.83 ml/g) in the kneading process, adding aqueous potassium nitrate (analytically pure) solution, dilute acid solution of nitric acid and phosphoric acid successively, kneading, extruding into 4mm toothed spheres, drying at 100℃for 10 hours, and then calcining at 1030℃for 5 hours to prepare the desired carrier, wherein, per 100g of the carrier, the catalyst is prepared in the form of Al 2 O 3 The calculated pseudo-boehmite powder has the dosage of 1.29g of potassium nitrate (analytically pure), 6.3g of nitric acid and 4.9g of phosphoric acid.
The rest of the procedure was the same as in preparation example 3 to obtain catalyst A-11.
Comparative preparation example 1
A catalyst was prepared according to the method of preparation example 5, except that for every 100g of the catalyst was prepared as Al 2 O 3 The calculated pseudo-boehmite powder comprises 3.43g of boric acid, 4.76g of barium nitrate (analytically pure) and 6.5g of nitric acid. The catalyst prepared was designated as D-1.
Comparative preparation example 2
A catalyst was prepared in the same manner as in preparation example 3 except that only dilute acid water of nitric acid was added during kneading, wherein, per 100g of the catalyst was kneaded with Al 2 O 3 The amount of nitric acid is 6.1g. The catalyst prepared was designated D-2.
Comparative preparation example 3
A catalyst was prepared in the same manner as in preparation example 3 except that the dilute acid water of nitric acid and phosphoric acid was added during kneading, wherein, per 100g of the catalyst, the catalyst was kneaded with Al 2 O 3 The amount of phosphoric acid is 15.82g and the amount of nitric acid is 6.2g. The catalyst prepared was designated as D-3.
Test example 1
Analysis of elemental composition of the support and catalyst by plasma emission spectrometer, the elemental (ion) content of the other than the support was calculated as relative 100g based on the non-hetero element component (e.g., al when pseudo-boehmite was the support source 2 O 3 Meter) carrier content; by NH 3 -TPD、CO 2 The carrier prepared above was characterized by TPD, BET nitrogen adsorption and desorption methods, and the specific procedure was as follows, and the results are shown in table 1.
NH 3 TPD test
Test instrument: full-automatic chemical adsorption instrument (Automated Catalyst Characterization System) instrument model: autochem 2920, MICROMERITICS, inc. of America
Test conditions: accurately weighing about 0.1g of sample, placing into a sample tube, heating to 600deg.C at 10deg.C/min under He gas purging, standing for 1 hr, cooling to 120deg.C, and changing gas to 10% NH 3 And (3) absorbing the He mixed gas for 60min, then changing the He mixed gas into the He gas for purging for 1h, starting counting after the baseline is stable, rising to 600 ℃ at 10 ℃/min, keeping for 30min, stopping recording, and completing the experiment. Integrating and calculating the peak area to obtain NH 3 Desorption amount.
CO 2 TPD test
Test instrument: full-automatic chemical adsorption instrument (Automated Catalyst Characterization System) instrument model: autochem 2920, MICROMERITICS, inc. of America
Test conditions: accurately weighing about 0.1g of sample, placing into a sample tube, heating to 600deg.C at 10deg.C/min under He gas purging, standing for 1 hr, cooling to 120deg.C, and changing gas to 10% CO 2 The mixture of He and the catalyst is adsorbed for 60min, then the mixture is changed into the mixture of He and the mixture is purged for 1h, the mixture starts to count after the baseline is stabilized, the mixture is heated to 600 ℃ at 10 ℃/min, and the mixture is kept for 30miAnd n, stopping recording and completing the experiment. Integrating and calculating the peak area to obtain CO 2 Desorption amount.
BET test
Instrument name: a fully automatic physico-chemical adsorption analyzer (Automatic Micropore & Chemisorption Analyzer); instrument model: ASAP2420, MICromeritcs (Mich instruments Co., USA)
Test conditions: experimental gas: n (N) 2 (purity 99.999%); degassing conditions: raising the temperature to 350 ℃ at 10 ℃/min, and vacuumizing for 4 hours; analysis conditions: and (5) performing full analysis on the mesoporous isotherm. The specific surface area and pore volume are obtained.
TABLE 1
Example 1
100 milliliters of catalysts A-1 to D-3 prepared in the preparation example are respectively measured and filled in a fixed bed reactor, hydrogen is used for activating for 2.5 hours at 230 ℃, then the temperature is reduced to 175 ℃, the pressure of the system is increased to 10.5MPa by the hydrogen, then ammonia is metered by a metering pump and then is fed into a reaction system, the ammonia is preheated to 160 ℃ and enters the upper end of the reactor, diethylenetriamine is fed into the upper end of the reactor by the metering pump, the hydrogen is stably fed in through a gas mass flowmeter, the molar ratio of the hydrogen to the diethylenetriamine is 3:18:1, and the liquid phase volume space velocity of the diethylenetriamine is 0.3h -1 The catalytic reaction was carried out in the reactor, and after the reaction was stabilized (i.e., at 20 hours of reaction), the reaction solution was sampled and analyzed, and the analysis results are shown in Table 2.
The sampling analysis method is gas chromatography analysis, and calibration is carried out by preparing a correction factor of a standard sample;
conversion and selectivity were calculated as the molar content of each component in the reaction solution.
n x Represents the number of moles of diethylenetriamine required for conversion to one mole of product x;
the product x comprises ethylenediamine, piperazine, triethylenediamine, N-aminoethylpiperazine, monoethylamine, micro dimerization and trimerization products
n x Represents the number of moles of diethylenetriamine required for conversion to one mole of product x;
n ethylenediamine Represents the number of moles of diethylenetriamine required for conversion to one mole of ethylenediamine
The product x comprises ethylenediamine, piperazine, triethylenediamine, N-aminoethylpiperazine, monoethylamine, micro dimerization and trimerization products
The selectivity of other products only needs to be that of the molecules n in the formula Ethylenediamine And the corresponding molar content is replaced by the corresponding value.
TABLE 2
Example 2
100 ml of catalyst A-7 was measured and placed in a fixed bed reactor, and the catalyst was activated with hydrogen at 230℃for 2 hours, and the other experimental methods were the same as in example 1, except that experimental conditions, such as temperature, pressure, molar ratio of hydrogen to ammonia to diethylenetriamine, liquid-phase volume space velocity of diethylenetriamine, etc., were changed, and the reaction results under different reaction conditions were sampled and analyzed (analysis conditions and conversion, selectivity calculation method were the same as in example 1), and the results are shown in Table 3.
TABLE 3 Table 3
Example 3
Measuring 100 ml of catalyst A-7, placing the catalyst A-7 in a fixed bed reactor, activating the catalyst in the fixed bed reactor for 2 hours at 220 ℃, then cooling the catalyst to 175 ℃, increasing the pressure of the system to 10MPa by using hydrogen, metering ammonia by using a metering pump, feeding the ammonia into a reaction system, preheating the ammonia to 160 ℃, feeding a mixed solution of 30wt% of diethylenetriamine and 70wt% of 1, 4-dioxane into the upper end of the reactor by using the metering pump, feeding the hydrogen stably by using a gas mass flowmeter, wherein the molar ratio of the hydrogen to the diethylenetriamine is 3:18:1, and the liquid phase volume space velocity of the diethylenetriamine is 0.3 hour -1 After the reaction was carried out in the reactor and the reaction was stabilized, the reaction solution was sampled and analyzed (analysis conditions and conversion, selectivity calculation method were the same as in example 1), and the analysis results are shown in Table 4.
TABLE 4 Table 4
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (16)

1. A process for preparing ethylenediamine and piperazine from the disproportionation of diethylenetriamine, the process comprising: contacting diethylenetriamine with an ammonia source in the presence of hydrogen and a catalyst to react, wherein the molar ratio of diethylenetriamine to ammonia source is 1:4-30, the catalyst comprises a carrier, an active metal component and an optional auxiliary agent, wherein the active metal component comprises cobalt and/or nickel, and the auxiliary agent is selected from at least one of group VIB, group VIIB and group IB metals, and the active metal component is supported on the carrier; the ammonia adsorption capacity of the carrier is 0.2-0.6mmol/g, and the carbon dioxide adsorption capacity of the carrier is 0.05-0.3mmol/g.
2. The method of claim 1, wherein the contacting conditions comprise: the temperature is 120-250 ℃, the pressure is 3-18MPa, and the liquid phase volume space velocity of diethylenetriamine is 0.05-0.8m 3 /(m 3 H), the molar ratio of the hydrogen, the ammonia source and the diethylenetriamine is 1-5:4-30:1.
3. The method of claim 1, wherein the contacting conditions comprise: the temperature is 130-220 ℃, the pressure is 4-17MPa, and the liquid phase volume space velocity of diethylenetriamine is 0.06-0.6m 3 /(m 3 H), the molar ratio of the hydrogen, the ammonia source and the diethylenetriamine is 1-4:4-25:1.
4. The process according to claim 1, wherein the diethylenetriamine is reacted in a solution having a concentration of diethylenetriamine of 10-80 wt%, the solvent in the solution being selected from water and/or 1, 4-dioxane;
and/or the ammonia source is selected from at least one of ammonia, primary amines of C1-12, and secondary amines of C2-12.
5. The method of claim 1 or 4, wherein the ammonia source is at least one of ammonia, monomethylamine, dimethylamine, methylethylamine, monoethylamine, and diethylamine.
6. The method of claim 1, wherein the support is selected from at least one of doped alumina, doped silica, doped molecular sieves, and doped aluminum silicate.
7. The method according to claim 1 or 6, wherein the ammonia adsorption amount of the carrier is 0.3-0.5mmol/g;
and/or the carbon dioxide adsorption amount of the carrier is 0.06-0.2mmol/g;
and/or the content of the mixed elements doped in the carrier accounts for 0.03-2 wt% of the total weight of the non-mixed element components in the carrier;
and/or the mixed elements doped in the carrier comprise metal elements and nonmetal elements, wherein the metal elements are selected from at least one of group IA metal elements, group IIA metal elements, group VA metal elements and lanthanide series metal elements; the nonmetallic element is selected from at least one of a group IIIA nonmetallic element, a group VA nonmetallic element, a group VIA nonmetallic element and a group VIIA nonmetallic element;
and/or the specific surface area of the carrier is 120-240m 2 /g；
And/or the pore volume of the carrier is 0.5-1ml/g;
and/or the content of the active ingredient is 5 to 42g per 100g of carrier by weight of non-hetero element ingredients;
and/or, the content of the auxiliary agent is 0-10g for every 100g of carrier based on the weight of non-hetero element component;
and/or the auxiliary agent is selected from at least one of Mo, W, mn, re, cu and Ag.
8. The method of claim 7, wherein the amount of the impurity element incorporated in the carrier is 0.08 to 1 wt% based on the total weight of the non-impurity element component in the carrier;
and/or the metal element is at least one of calcium, magnesium, potassium, bismuth, strontium, barium and lanthanum;
and/or the nonmetallic element is at least one of boron, fluorine, phosphorus, sulfur and selenium;
and/or the content of the active ingredient is 10 to 35g per 100g of carrier by weight of non-hetero element ingredients;
and/or the content of the auxiliary agent is 0.5-6g per 100g of the carrier based on the weight of the non-hetero element component.
9. The method of claim 1 or 6, wherein the doping of the support is from metal cations and acid ions and does not include sodium ions and chloride ions; the metal cation is selected from at least one of group IA metal cations, group IIA metal ions, group VA metal ions and lanthanide metal ions; the acid radical ion is at least one selected from nonmetallic acid radical ions.
10. The method of claim 9, wherein the metal cation is at least one of calcium ion, magnesium ion, potassium ion, bismuth ion, strontium ion, barium ion, and lanthanum ion;
and/or the acid radical ion is at least one of boric acid radical ion, fluoride ion, phosphate radical ion, sulfate radical ion and selenate radical ion.
11. The method according to claim 1 or 6, wherein the carrier is prepared by a method comprising the steps of: the mixture containing the doping element and the carrier source is sequentially molded, dried and roasted, wherein the carrier source is at least one of pseudo-boehmite, silicon oxide, molecular sieve and aluminum silicate.
12. The method of claim 11, wherein the doping element is provided by a carrier modifier that is at least one of a compound capable of providing a cation and an anion, wherein the cation is selected from at least one of a group IA cation, a group IIA metal ion, a group VA metal ion, and a lanthanide metal ion; the anion is selected from at least one of nonmetallic acid radical ions.
13. The method of claim 12, wherein the cation is at least one of calcium ion, magnesium ion, potassium ion, bismuth ion, strontium ion, barium ion, and lanthanum ion;
and/or the anion is at least one of borate ion, fluoride ion, phosphate ion, sulfate ion and selenate ion.
14. The method of claim 12, wherein the carrier modifier is selected from at least one of boric acid, nickel borate, cobalt borate, potassium borate, hydrofluoric acid, potassium fluoride, cobalt fluoride, nickel fluoride, phosphoric acid, aluminum phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, magnesium phosphate, calcium phosphate, sulfuric acid, cobalt sulfate, nickel sulfate, aluminum sulfate, calcium sulfate, bismuth nitrate, potassium sulfate, potassium carbonate, magnesium nitrate, magnesium sulfate, basic magnesium carbonate, calcium nitrate, basic calcium carbonate, strontium nitrate, strontium phosphate, strontium sulfate, barium nitrate, lanthanum nitrate, and selenate.
15. The method according to claim 11, wherein the specific surface area of the pseudo-boehmite is 250-330m 2 Per g, pore volume is 0.8-1.3ml/g.
16. The method of claim 11, wherein the drying conditions comprise: the temperature is 80-150 ℃ and the time is 6-20h;
and/or, the roasting conditions include: the temperature is 600-1100 ℃ and the time is 2-20h.
CN202011224375.8A 2020-11-05 2020-11-05 Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine Active CN114433096B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011224375.8A CN114433096B (en) 2020-11-05 2020-11-05 Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011224375.8A CN114433096B (en) 2020-11-05 2020-11-05 Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine

Publications (2)

Publication Number Publication Date
CN114433096A CN114433096A (en) 2022-05-06
CN114433096B true CN114433096B (en) 2023-12-08

Family

ID=81360717

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011224375.8A Active CN114433096B (en) 2020-11-05 2020-11-05 Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine

Country Status (1)

Country Link
CN (1) CN114433096B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101704753A (en) * 2009-11-17 2010-05-12 中国科学院大连化学物理研究所 Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition
CN106607060A (en) * 2015-10-26 2017-05-03 中国石油化工股份有限公司 Catalyst and its preparation method and application, and method for preparing ethanediamine through ethylene glycol hydrogenation amination
CN108067289A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition
CN109908900A (en) * 2017-12-12 2019-06-21 中国科学院大连化学物理研究所 A kind of loaded catalyst and the preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101704753A (en) * 2009-11-17 2010-05-12 中国科学院大连化学物理研究所 Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition
CN106607060A (en) * 2015-10-26 2017-05-03 中国石油化工股份有限公司 Catalyst and its preparation method and application, and method for preparing ethanediamine through ethylene glycol hydrogenation amination
CN108067289A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 Catalyst and preparation and the application that ethylenediamine and piperazine are produced under hydro condition
CN109908900A (en) * 2017-12-12 2019-06-21 中国科学院大连化学物理研究所 A kind of loaded catalyst and the preparation method and application thereof

Also Published As

Publication number Publication date
CN114433096A (en) 2022-05-06

Similar Documents

Publication Publication Date Title
CN114433113B (en) Catalyst and carrier with alcohol ammonification catalysis function, and preparation method and application thereof
CN114433089B (en) Titanium-containing catalyst with ammoniation function and preparation method and application thereof
US9920008B2 (en) Catalyst for synthesizing ethylenimine as well as preparation method and application thereof
CN114433096B (en) Method for preparing ethylenediamine and piperazine by disproportionation of diethylenetriamine
CN114433088B (en) Catalyst and carrier with function of catalyzing hydro-ammonification of alcohol to generate organic amine, and preparation method and application thereof
KR101336975B1 (en) Catalyst for manufacturing alkylamine from reductive amination
CN114433087A (en) Catalyst and carrier with function of preparing amine by alcohol hydroamination, and preparation method and application thereof
CN114436993B (en) Process for the preparation of piperazine
CN114433064B (en) Method for preparing piperazine and ethylenediamine from hydroxyethyl ethylenediamine
CN110721732B (en) Method for producing p-tert-butylphenol
CN114436849B (en) Process for preparing ethylenediamine and piperazine
CN114433090B (en) Catalyst and carrier with function of catalyzing and synthesizing amine by taking alcohol as raw material, and preparation method and application thereof
US8529869B2 (en) Catalysts and method for the hydroamination of olefins
CN114433086A (en) Catalyst and carrier with function of catalyzing alcohol hydroamination to synthesize organic amine, and preparation method and application thereof
CN114433122B (en) Catalyst and carrier with function of catalyzing hydro-ammonification of alcohol, and preparation method and application thereof
JP2012524651A5 (en)
CN114433121B (en) Catalyst and carrier with amine preparation function by catalytic ammonification, and preparation method and application thereof
CN114433106B (en) Catalyst and carrier with catalytic function for preparing amine from alcohol, and preparation method and application thereof
CN115672394B (en) Preparation method of Cs/Eu-AFN molecular sieve catalyst and preparation method of 1, 2-di-n-propoxybenzene
CN100413579C (en) Catalyst used for hydrating epoxy ethane to prepare ethandiol
WO2023063244A1 (en) Solid catalyst, method for producing solid catalyst and method for producing monomethyl amine
CN117003648A (en) Method for preparing hexamethylenediamine from caprolactam
CN117986124A (en) Method for catalyzing bis (hexamethylenetriamine) to carry out ammonolysis
JP2022533750A (en) Heterogeneous catalytic process for the production of 2,2,6,6-tetramethyl-4-piperidone
JP6378680B2 (en) Method for producing 1-alkylimidazole compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant