CN112979474B - Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening - Google Patents

Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening Download PDF

Info

Publication number
CN112979474B
CN112979474B CN201911286310.3A CN201911286310A CN112979474B CN 112979474 B CN112979474 B CN 112979474B CN 201911286310 A CN201911286310 A CN 201911286310A CN 112979474 B CN112979474 B CN 112979474B
Authority
CN
China
Prior art keywords
catalyst
dicyanofuran
metal element
hexanediamine
hydrogen
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
CN201911286310.3A
Other languages
Chinese (zh)
Other versions
CN112979474A (en
Inventor
徐杰
高鸣霞
马继平
高进
范晓萌
苗虹
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.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
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 Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201911286310.3A priority Critical patent/CN112979474B/en
Publication of CN112979474A publication Critical patent/CN112979474A/en
Application granted granted Critical
Publication of CN112979474B publication Critical patent/CN112979474B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/36—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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with 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
    • 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
    • B01J23/745—Iron
    • 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
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8474—Niobium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/043—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
    • 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
    • B01J29/40—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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The application discloses a method for catalyzing ring opening synthesis of 1, 6-hexanediamine by hydrogenation of 2, 5-dicyanofuran. The method comprises the steps of contacting a material containing 2, 5-dicyanofuran with a catalyst in a hydrogen source environment, and reacting to obtain 1, 6-hexamethylene diamine; wherein the catalyst comprises an acidic carrier and a metal element; the metal element is supported on the acidic carrier. The method is a new hydrogenation ring-opening technology with high yield, low cost, easy catalyst separation and low pollution, and uses hydrogen as a hydrogen source to prepare 1, 6-hexamethylene diamine by ring-opening hydrogenation of 2, 5-dicyanofuran. The method has wide application prospect.

Description

Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening
Technical Field
The application relates to a method for catalyzing 2, 5-dicyanofuran to be subjected to ring-opening hydrogenation to synthesize 1, 6-hexanediamine, and belongs to the technical field of chemical synthesis.
Background
The renewable biomass resources are catalytically converted to prepare chemicals and liquid fuels with high added values, and the chemicals and the liquid fuels are used as the supplement of the traditional fossil resource synthesis route and are widely concerned. 2, 5-Diformylfuran is an important intermediate for the synthesis of various fine chemicals and furan-based polymers, and can be synthesized by Cu (NO) 3 ) 2 /VOSO 4 Catalytic selective oxidation of 5-hydroxymethylfurfural (appl.Catal.A-Gen.2014,482, 231-236). 2, 5-dicyanofuran (ACS Sustain. chem. Eng.2018,6, 2888-. 2, 5-dicyanofuran is an important homobifunctional molecule in chemistry and biology, has very wide application, and is applied to synthesis of drugs, dyes, polyurethane, polyamide materials and the like (Angew. chem. -int. Edit.2012,51, 11948-11959).
1, 6-hexanediamine is a polymer monomer used in the production of nylon-66 and nylon-610. In addition, the 1, 6-hexamethylene diamine is also an important chemical intermediate, has wide application range, has huge application potential in chemical fiber industry, clothing and textile industry, electronic industry, high polymer material industry and other industries, and has high market value. Through literature research, no report on the synthesis of 1, 6-hexanediamine by catalyzing the ring opening of 2, 5-dicyanofuran through hydrogenation is found at present.
Disclosure of Invention
According to one aspect of the application, the method for synthesizing the 1, 6-hexanediamine by catalyzing the hydrogenation ring-opening of the 2, 5-dicyanofuran is provided, and the method is a new hydrogenation ring-opening technology which has high yield, low cost, easy separation of a catalyst and low pollution, and uses hydrogen as a hydrogen source to prepare the 1, 6-hexanediamine by ring-opening hydrogenation of the 2, 5-dicyanofuran. The method has wide application prospect.
A method for catalyzing 2, 5-dicyanofuran to be hydrogenated and ring-opened to synthesize 1, 6-hexanediamine comprises the steps of contacting a material containing 2, 5-dicyanofuran with a catalyst in a hydrogen source environment, and reacting to obtain 1, 6-hexanediamine;
wherein the catalyst comprises an acidic carrier and a metal element;
the metal element is supported on the acidic carrier.
The invention provides a method for synthesizing 1, 6-hexamethylene diamine by catalyzing 2, 5-dicyanofuran hydrogenation ring-opening, which takes metal loaded by an acidic carrier as a catalyst to convert 2, 5-dicyanofuran hydrogenation ring-opening into 1, 6-hexamethylene diamine, and has the advantages of mild reaction conditions, less catalyst consumption, easy separation, high product yield, simple and convenient operation, environmental protection and economy.
The method of the invention is shown as formula 1:
Figure BDA0002318066360000021
the technical scheme adopted by the invention is to take hydrogen as a hydrogen source, the partial pressure of the hydrogen is 0.1-6.0MPa, the reaction is carried out for 0.5-72h at 30-250 ℃ under the action of a catalyst, and a product is separated to obtain the 1, 6-hexamethylene diamine.
According to the route provided by the invention, furan ring and cyano hydrogenation is realized by 2, 5-dicyanofuran under the catalytic action, and the hydrogenation product is further subjected to ring opening and dehydroxylation to generate 1, 6-hexanediamine.
Analyzing the process of preparing 1, 6-hexanediamine by hydrogenating and ring-opening 2, 5-dicyanofuran, the 2, 5-dicyanofuran and hydrogen are subjected to hydrogenation reaction under the action of a catalyst to generate 2, 5-dimethylamino tetrahydrofuran, and then the ring-opening dehydroxylation of the 2, 5-dimethylamino tetrahydrofuran is carried out under the action of the catalyst to obtain the 1, 6-hexanediamine. The key step in this process is the 2, 5-dicyanofuran hydrocyclo-opening. Thus, the present invention provides a catalyst system which is a metal catalyst supported on an acidic support having the ability to impose hydrogen ring opening.
The catalytic system of the invention refers to a metal catalyst loaded by an acidic carrier, which comprises an active metal element (M) and the acidic carrier, wherein the acidic carrier comprises any one of metal oxide, ion exchange resin and molecular sieve.
Optionally, the metal element includes at least one of Pd, Pt, Ni, Rh, Ru, Re, Ir, Co, Cu, Fe, Au.
Optionally, in the catalyst, the acidic support is selected from any one of carbon materials, metal oxides, ion exchange resins, hydrogen form molecular sieves.
Optionally, the metal oxide comprises Re 2 O 7 、Y 2 O 3 、CeO 2 、ZrO 2 、WO 3 、Al 2 O 3 、TiO 2 、Nb 2 O 5 、V 2 O 5 、MnO 2 、Fe 2 O 3 、Cr 2 O 4 、MoO 3 Any one of (a) to (b);
the ion exchange resin is selected from
Figure BDA0002318066360000031
Any one of IR-120H, Amberlyst-15;
the hydrogen-type molecule is selected from at least one of HMCM-41 and HZSM-5.
Optionally, the mass percentage of the metal element in the catalyst is 0.1-40 wt%;
wherein the mass of the metal element is calculated by the weight of the catalyst;
the mass of the catalyst is based on the mass of the catalyst itself.
Specifically, the upper limit of the mass percent content of the metal element in the catalyst is independently selected from 5 wt%, 8 wt%, 10 wt%, 12 wt%, 13 wt%, 15 wt%, 18 wt%, 20 wt%, 23 wt%, 25 wt%, 26 wt%, 30 wt%, 32 wt%, 38 wt%, 40 wt%; the lower limit of the mass percent content of the metal element in the catalyst is independently selected from 0.1 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 13 wt%, 15 wt%, 18 wt%, 20 wt%, 23 wt%, 25 wt%, 26 wt%, 30 wt%, 32 wt%, 38 wt%.
Optionally, the amount of the catalyst is 0.1-30 mol% of the mass of the 2, 5-dicyanofuran;
the mass of the catalyst is based on the weight of the catalyst itself.
Specifically, the amount of the catalyst is such that the upper limit of the mass of the 2, 5-dicyanofuran is independently selected from 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.2 mol%, 2.7 mol%, 5 mol%, 6 mol%, 8 mol%, 9 mol%, 10 mol%, 12 mol%, 14 mol%, 15 mol%, 18 mol%, 20 mol%, 22 mol%, 25 mol%, 30 mol%; the amount of the catalyst used is such that the lower limit of the mass of the 2, 5-dicyanofuran is independently selected from 0.1 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.2 mol%, 2.7 mol%, 5 mol%, 6 mol%, 8 mol%, 9 mol%, 10 mol%, 12 mol%, 14 mol%, 15 mol%, 18 mol%, 20 mol%, 22 mol%, 25 mol%.
In the present application, the preparation method of the catalyst is a means commonly used in the prior art, and the present application is not particularly limited. The preferred catalyst preparation method is described below:
the catalyst is prepared by adopting an impregnation loading method, the aqueous solution of the active metal component precursor and the acidic carrier are uniformly mixed and fully impregnated according to the required proportion, and after drying at 70-150 ℃, hydrogen with the concentration of 5-60mL/min is reduced for 1-6h at the temperature of 100-600 ℃. The active metal component precursor is one or more of hydrochloride, sulfate, nitrate and acetate of corresponding metal.
For example: the precursor of the active metal component is as follows: palladium nitrate, ferric sulfate, copper acetate, cobalt chloride, rhodium trichloride, ruthenium trichloride, nickel nitrate, chloroauric acid, platinum acetylacetonate, ammonium perrhenate and ammonium hexachloroiridate.
Optionally, the hydrogen source comprises any one of hydrogen gas, formic acid, isopropanol.
Optionally, the reaction conditions are:
the partial pressure of hydrogen source is 0.1-6.0 MPa;
the reaction temperature is 30-250 ℃;
the reaction time is 0.5-72 h.
Specifically, the upper limit of the hydrogen source partial pressure is independently selected from 0.5MPa, 1.0MPa, 1.3MPa, 1.5MPa, 2.0MPa, 2.2MPa, 2.5MPa, 2.8MPa, 3.0MPa, 3.5MPa, 3.8MPa, 4.0MPa, 4.5MPa, 4.6MPa, 5.2MPa, 5.5MPa, 6.0 MPa; the lower limit of the partial pressure of the hydrogen source is independently selected from the group consisting of 0.1MPa, 0.5MPa, 1.0MPa, 1.3MPa, 1.5MPa, 2.0MPa, 2.2MPa, 2.5MPa, 2.8MPa, 3.0MPa, 3.5MPa, 3.8MPa, 4.0MPa, 4.5MPa, 4.6MPa, 5.2MPa, 5.5 MPa.
The upper limit of the reaction temperature is independently selected from the group consisting of 50 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 220 ℃, 230 ℃ and 250 ℃; the lower limit of the reaction temperature is independently selected from the group consisting of 30 ℃, 50 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 220 ℃ and 230 ℃.
The upper limit of the reaction time is independently selected from 1h, 2h, 4h, 8h, 10h, 18h, 20h, 24h, 26h, 32h, 36h, 45h, 48h, 60h, 66h, 72 h; the lower limit of the reaction time is independently selected from 0.5h, 1h, 2h, 4h, 8h, 10h, 18h, 20h, 24h, 26h, 32h, 36h, 45h, 48h, 60h and 66 h.
Preferably, the reaction conditions are:
the partial pressure of hydrogen source is 1-4.0 MPa;
the reaction temperature is 50-200 ℃;
the reaction time is 1-48 h.
It is still further preferred that the first and second liquid,
the partial pressure of hydrogen source is 2-3 MPa;
the reaction temperature is 80-100 ℃;
the reaction time is 18-24 h.
Optionally, the material also contains a solvent; the solvent comprises any one of acetonitrile, methanol, ethanol, isopropanol, tetrahydrofuran, dichloromethane, N-dimethylformamide, toluene, o-xylene and p-xylene.
Optionally, adding 2, 5-dicyanofuran, a catalyst and a solvent into a reaction kettle, mixing, heating to 30-250 ℃, controlling the hydrogen partial pressure to be 0.1-6.0MPa and the reaction time to be 0.5-72h, and carrying out ring opening hydrogenation on the 2, 5-dicyanofuran to obtain the 1, 6-hexanediamine.
Optionally, after the obtaining of the 1, 6-hexamethylenediamine, isolating the 1, 6-hexamethylenediamine is further included; said isolating said 1, 6-hexanediamine comprises the steps of: and after the reaction is finished, centrifuging to remove the catalyst, performing rotary evaporation to remove the solvent, washing the solid, and drying to obtain a white solid, namely the 1, 6-hexanediamine.
Specifically, according to the method provided by the invention, the separation method of the hydrogenation ring-opening product comprises the steps of naturally cooling a mixture after the reaction is finished, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, fully washing the solid with saturated salt water, performing suction filtration, and performing vacuum drying to obtain a white solid.
The beneficial effect that this application can produce includes:
1) the invention realizes the ring-opening synthesis of 1, 6-hexanediamine by catalytic hydrogenation of 2, 5-dicyanofuran for the first time.
2) The catalyst system has high activity, good product selectivity, low consumption, low cost, easy obtaining, environmental protection and economy.
3) The separated and purified product has high quality, and the purity of the separated product reaches over 99 percent through test analysis of gas chromatography-mass spectrometry, nuclear magnetic resonance spectrometer and the like and comparison with the retention time of a standard sample.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
A method for catalyzing 2, 5-dicyanofuran to be subjected to ring-opening hydrogenation to synthesize 1, 6-hexanediamine comprises the steps of taking metal loaded on an acidic carrier as a catalyst and hydrogen as a hydrogen source, carrying out ring-opening hydrogenation conversion on 2, 5-dicyanofuran, and separating a product to obtain the 1, 6-hexanediamine.
Preferably, the active metal component is one or more of Pd, Pt, Ni, Rh, Ru, Re, Ir, Co, Cu, Fe and Au, and the content of the active metal component is 0.1-40 wt% of the mass of the catalyst calculated by metal (M).
Preferably, the catalyst acidic carrier is a metal oxide or an ion exchange resin or a molecular sieve, in particular Re 2 O 7 、Y 2 O 3 、CeO 2 、ZrO 2 、WO 3 、Al 2 O 3 、TiO 2 、Nb 2 O 5 、V 2 O 5 、MnO 2 、Fe 2 O 3 、Cr 2 O 4 、MoO 3 、C、
Figure BDA0002318066360000062
One or more of IR-120H, Amberlyst-15, HMCM-41 and HZSM-5.
Preferably, the metal catalyst supported on an acidic carrier is added in an amount of 0.1 to 30mol% based on the metal (M) of the amount of 2, 5-dicyanofuran as a substrate.
Preferably, the hydrogen source is hydrogen, the partial pressure of the hydrogen is 0.1-6.0MPa, the reaction temperature is 30-250 ℃, and the reaction time is 0.5-72 h.
Preferably, the separation method of the hydrogenation ring-opening product comprises the steps of naturally cooling the mixture after the reaction is finished, centrifuging to remove the catalyst, removing the solvent by rotary evaporation, fully washing the solid with saturated salt water, performing suction filtration, and performing vacuum drying to obtain a white solid.
Preferably, in the specific operation, the active metal component catalyst loaded by the acidic carrier and the 2, 5-dicyanofuran are put into a reaction kettle, an organic solvent is added, the temperature is raised to 30-250 ℃, the hydrogen partial pressure is 0.1-6.0MPa, the reaction time is 0.5-72h, and the 2, 5-dicyanofuran is subjected to hydrogenation ring-opening to form the 1, 6-hexanediamine.
Preferably, the hydrogen partial pressure is preferably in the range of 1.0 to 4.0MPa, most preferably in the range of 2 to 3MPa, the reaction temperature is preferably in the range of 50 to 200 deg.C, most preferably in the range of 80 to 100 deg.C, and the reaction time is preferably in the range of 1 to 48 hours, most preferably in the range of 18 to 24 hours.
Preferably, the organic solvent is one or more of acetonitrile, methanol, ethanol, isopropanol, tetrahydrofuran, dichloromethane, N-dimethylformamide, toluene, o-xylene, and p-xylene.
The invention provides a method for synthesizing 1, 6-hexamethylene diamine by catalyzing 2, 5-dicyanofuran to be subjected to hydrogenation ring-opening, which takes hydrogen as a hydrogen source and takes metal loaded by an acidic carrier as a catalyst to convert 2, 5-dicyanofuran into 1, 6-hexamethylene diamine by hydrogenation ring-opening. The 1, 6-hexamethylene diamine product prepared by the method has high purity, the used heterogeneous catalyst has simple preparation method and high hydrogenation ring-opening efficiency, is easy to separate from a reaction system, and can still maintain higher catalytic activity after being recycled for multiple times.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The conversion, selectivity, separation in the examples of the application were calculated as follows:
Figure BDA0002318066360000061
Figure BDA0002318066360000071
Figure BDA0002318066360000072
example 1:
Pt/TiO 2 the catalyst is prepared by adopting an impregnation loading method, and the aqueous solution of acetylacetone platinum (the Pt concentration in the solution is 5 wt%) and TiO are mixed according to the required mass ratio (specifically 1: 1) 2 Mixing, soaking, oven drying at 80 deg.C, reducing with 45mL/min hydrogen at 200 deg.C for 4 hr to obtain 5 wt% Pt/TiO 2 A catalyst.
1mmol of 2, 5-dicyanofuran, 0.005mmol of 5 wt% Pt/TiO 2 Adding a catalyst and 5mL of ethanol into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 1.0MPa of hydrogen, heating to 100 ℃, and reacting for 4 hours at the temperature. After the reaction, the reaction mixture was naturally cooled to room temperature, and the catalyst was removed by centrifugation. 1mL of internal standard mesitylene was added, and samples were taken and analyzed by gas chromatography. Removing solvent by rotary evaporation, and adding saturated salt solutionWashing the solid, filtering, drying in vacuum to obtain white solid with Gas Chromatography (GC) purity over 99%.
The conversion of 2, 5-dicyanofuran, the GC yield of 1, 6-hexamethylenediamine and the isolation yield of 1, 6-hexamethylenediamine were calculated, respectively. The conversion of 2, 5-dicyanofuran was 99%, the GC yield of 1, 6-hexamethylenediamine was 98%, and the isolation yield of 1, 6-hexamethylenediamine was 95%.
In this example, "5 wt% Pt/TiO 2 Catalyst "means that the mass content of the metal element in the catalyst is 5 wt%. In the catalyst, similar expressions in other examples are similar to the explanation.
Example 2
The difference from the catalyst preparation method in example 1 is that: platinum acetylacetonate was replaced by rhodium trichloride (Rh concentration in solution: 20 wt%), and TiO was added 2 Replacement by Re 2 O 7 After being dried at 120 ℃ after being dipped, 60mL/min hydrogen is reduced for 3h at 300 ℃.
1mmol of 2, 5-diformylfuran, 0.05mmol of 20 wt% Rh/Re 2 O 7 Adding a catalyst and 5mL of toluene into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 3.0MPa of hydrogen, heating to 70 ℃, and reacting for 48 hours at the temperature. After the reaction was completed, according to the method described in example 1, cooling and sampling analysis, the conversion of 2, 5-dicyanofuran was 98%, the GC yield of 1, 6-hexamethylenediamine was 97%, and the isolation yield was 96%.
Example 3
The difference from the catalyst preparation method in example 1 is that: platinum acetylacetonate was replaced with nickel nitrate (Ni concentration in solution 0.1 wt%), and TiO was added 2 Substitution to Y 2 O 3 After being dried at 90 ℃ after dipping, 30mL/min of hydrogen is reduced for 5h at 500 ℃.
1mmol of 2, 5-diformylfuran, 0.08mmol of 0.1 wt% Ni/Y 2 O 3 Adding a catalyst and 5mL of acetonitrile into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 0.5MPa of hydrogen, heating to 180 ℃, and reacting for 2 hours at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the 2, 5-dicyanofuran was transferredThe conversion rate was 97%, the GC yield of 1, 6-hexanediamine was 96%, and the isolation yield was 94%.
Example 4
The difference from the catalyst preparation method in example 1 is that: the acetylacetone platinum was replaced with cobalt chloride (Co concentration in solution: 10 wt%), and TiO was added 2 Replacement is MoO 3 After being dried at 150 ℃ after being dipped, 5mL/min of hydrogen is reduced for 6h at 600 ℃.
1mmol of 2, 5-diformylfuran, 0.3mmol of 10 wt% Co/MoO 3 Adding a catalyst and 5mL o-xylene into a 15mL reaction kettle, closing the kettle, replacing the air in the kettle with hydrogen for 10 times, filling 6.0MPa hydrogen, heating to 150 ℃, and reacting for 0.5h at the temperature. After the reaction was completed, according to the method described in example 1, cooling and sampling analysis, the conversion of 2, 5-dicyanofuran was 99%, the GC yield of 1, 6-hexamethylenediamine was 96%, and the isolation yield was 95%.
Example 5
The difference from the catalyst preparation method in example 1 is that: the acetylacetone platinum was replaced with ruthenium trichloride (Ru concentration in solution: 30 wt%), and TiO was added 2 Alternative is WO 3 After being dried at 70 ℃ after dipping, 30mL/min of hydrogen is reduced for 2h at 400 ℃.
1mmol of 2, 5-diformylfuran, 0.1mmol of 30 wt% Ru/WO 3 Adding a catalyst and 5mL of dichloromethane into a 15mL reaction kettle, closing the kettle, replacing the air in the kettle by hydrogen for 10 times, filling 4.0MPa hydrogen, heating to 250 ℃, and reacting for 36 hours at the temperature. After the reaction was completed, according to the method described in example 1, cooling and sampling analysis, the conversion of 2, 5-dicyanofuran was 98%, the GC yield of 1, 6-hexamethylenediamine was 96%, and the isolation yield was 93%.
Example 6
The difference from the catalyst preparation method in example 1 is that: the acetylacetone platinum was replaced with ferric sulfate (Fe concentration in solution 15 wt%), and TiO was added 2 Substituted by ZrO 2 After the impregnation, the mixture is dried at 130 ℃ and reduced for 1h at 100 ℃ by 50mL/min of hydrogen.
1mmol of 2, 5-diformylfuran, 0.15mmol of 15 wt% Fe/ZrO 2 Catalyst, 5mL isopropanol was added to a 15mL autoclave, which was closedReplacing the air in the kettle with hydrogen for 10 times, charging 2.0MPa hydrogen, heating to 50 ℃, and reacting for 72h at the temperature. After the reaction was completed, according to the method described in example 1, the conversion of 2, 5-dicyanofuran was 99%, the GC yield of 1, 6-hexamethylenediamine was 97%, and the isolation yield was 95% by cooling and sampling.
Example 7
The difference from the catalyst preparation method in example 1 is that: platinum acetylacetonate was replaced by chloroauric acid (Au concentration in solution 25 wt%), and TiO was added 2 Replacement to MnO 2 After being dried at 110 ℃ after being dipped, 20mL/min of hydrogen is reduced for 2h at 200 ℃.
1mmol of 2, 5-diformylfuran, 0.06mmol of 25 wt% Au/MnO 2 Adding a catalyst and 5mL of methanol into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 4.5MPa of hydrogen, heating to 160 ℃, and reacting for 18 hours at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 97%, the GC yield of 1, 6-hexamethylenediamine was 96% and the isolation yield was 94%.
Example 8
The difference from the catalyst preparation method in example 1 is that: the Pt concentration in the acetylacetone platinum aqueous solution is 18wt percent, and TiO is added 2 Replacement by Cr 2 O 4 After being dried at 100 ℃ after being dipped, 35mL/min of hydrogen is reduced for 3h at 350 ℃.
1mmol of 2, 5-diformylfuran, 0.008mmol of 18 wt% Pt/Cr 2 O 4 Adding a catalyst and 5mL of acetonitrile into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 5.5MPa of hydrogen, heating to 220 ℃, and reacting for 1h at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 98%, the GC yield of 1, 6-hexamethylenediamine was 96% and the isolation yield was 93%.
Example 9
The difference from the catalyst preparation method in example 1 is that: the acetylacetonatoplatinum was replaced with palladium nitrate (Pd concentration in the solution: 32 wt%), and TiO was added 2 Replacing with HMCM-41, soaking, oven drying at 140 deg.C, and collecting the solution in 45 mL/containermin hydrogen reduction at 450 ℃ for 4 h.
Adding 1mmol of 2, 5-diformylfuran, 0.012mmol of 32 wt% Pd/HMCM-41 catalyst and 5mL of toluene into a 15mL reaction kettle, closing the kettle, replacing the air in the kettle with hydrogen for 10 times, filling 1.5MPa hydrogen, heating to 80 ℃, and reacting for 10 hours at the temperature. After the reaction was completed, according to the method described in example 1, cooling and sampling analysis, the conversion of 2, 5-dicyanofuran was 99%, the GC yield of 1, 6-hexamethylenediamine was 96%, and the isolation yield was 95%.
Example 10
The difference from the catalyst preparation method in example 1 is that: replacing acetylacetone platinum with rhodium chloride (Rh concentration of 26 wt%) and adding TiO 2 Instead of using
Figure BDA0002318066360000101
IR-120H, soaking, drying at 110 ℃, and reducing by 15mL/min hydrogen at 350 ℃ for 3H.
1mmol of 2, 5-diformylfuran, 0.25mmol of 26 wt.% Rh-
Figure BDA0002318066360000102
Adding an IR-120H catalyst and 5mL of ethanol into a 15mL reaction kettle, closing the kettle, replacing the air in the kettle by hydrogen for 10 times, filling hydrogen with 2.5MPa, heating to 90 ℃, and reacting for 24 hours at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 97%, the GC yield of 1, 6-hexamethylenediamine was 96% and the isolation yield was 93%.
Example 11
The difference from the catalyst preparation method in example 1 is that: replacement of platinum acetylacetonate with ammonium perrhenate (Re concentration in solution 13 wt%), and TiO 2 2 Replacement by CeO 2 After being dried at 120 ℃ after being dipped, 25mL/min hydrogen is reduced for 2h at 250 ℃.
1mmol of 2, 5-diformylfuran, 0.007mmol of 13 wt% Re/CeO 2 Adding a catalyst and 5mL of isopropanol into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 3.5MPa of hydrogen, heating to 140 ℃, and reacting for 20 hours at the temperature. The reaction is finishedThereafter, according to the method described in example 1, cooling and sampling analysis, the conversion of 2, 5-dicyanofuran was 98%, the GC yield of 1, 6-hexamethylenediamine was 97%, and the isolation yield was 93%.
Example 12
The difference from the catalyst preparation method in example 1 is that: replacing platinum acetylacetonate with ammonium hexachloroiridate (Ir concentration in solution: 38 wt%), and adding TiO 2 Is replaced by V 2 O 5 After being dried at 110 ℃ after being impregnated, 35mL/min of hydrogen is reduced for 4 hours at 150 ℃.
1mmol of 2, 5-diformylfuran, 0.18mmol of 38 wt% Ir/V 2 O 5 Adding 5mL of p-xylene serving as a catalyst into a 15mL reaction kettle, closing the kettle, replacing air in the kettle by hydrogen for 10 times, filling 4.6MPa of hydrogen, heating to 230 ℃, and reacting for 66 hours at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 96%, the GC yield of 1, 6-hexamethylenediamine was 95% and the isolation yield was 92%.
Example 13
The difference from the catalyst preparation method in example 1 is that: the Pt concentration in the acetylacetone platinum aqueous solution is 23wt percent, and TiO is added 2 Substitution with Al 2 O 3 After being dried at 130 ℃ after dipping, 45mL/min of hydrogen is reduced for 2h at 450 ℃.
1mmol of 2, 5-diformylfuran, 0.22mmol of 23 wt% Pt/Al 2 O 3 Adding a catalyst and 5mL of tetrahydrofuran into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 3.8MPa hydrogen, heating to 130 ℃, and reacting for 8 hours at the temperature. After the reaction was completed, according to the method described in example 1, cooling and sampling analysis, the conversion of 2, 5-dicyanofuran was 99%, the GC yield of 1, 6-hexamethylenediamine was 96%, and the isolation yield was 94%.
Example 14
The difference from the catalyst preparation method in example 1 is that: the acetylacetone platinum was replaced with ruthenium trichloride (Ru concentration in solution: 13 wt%), and TiO was added 2 The solution was replaced with Amberlyst-15, and after immersion and drying at 110 deg.C, 35mL/min hydrogen was reduced at 250 deg.C for 3 h. Amberlyst-15 (dry) is from Shanghai alatinLimited company.
1mmol of 2, 5-diformylfuran, 0.2mmol of 13 wt% Ru/Amberlyst-15 catalyst and 5mL of isopropanol are added into a 15mL reaction kettle, the kettle is closed, the air in the kettle is replaced by hydrogen for 10 times, 3.5MPa hydrogen is charged, the temperature is raised to 160 ℃, and the reaction is carried out for 32h at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 97%, the GC yield of 1, 6-hexamethylenediamine was 95% and the isolation yield was 93%.
Example 15
The difference from the catalyst preparation method in example 1 is that: the acetylacetone platinum was replaced by cobalt chloride (Co concentration in solution: 15 wt%), and TiO was added 2 Replacing with HZSM-5, impregnating, drying at 120 ℃, and reducing with 45mL/min hydrogen at 450 ℃ for 3 h. HZSM-5 having a Si/Al ratio of 20 and available from Nanjing university catalyst factory
Adding 1mmol of 2, 5-diformylfuran, 0.14mmol of 15 wt% Co/HZSM-5 catalyst and 5mL of o-xylene into a 15mL reaction kettle, closing the kettle, replacing the air in the kettle with hydrogen for 10 times, filling 2.2MPa hydrogen, heating to 150 ℃, and reacting for 20 hours at the temperature. After the reaction was completed, according to the method described in example 1, cooling and sampling analysis, the conversion of 2, 5-dicyanofuran was 98%, the GC yield of 1, 6-hexamethylenediamine was 96%, and the isolation yield was 95%.
Example 16
The difference from the catalyst preparation method in example 1 is that: the acetylacetone platinum was replaced with copper acetate (Cu concentration in solution: 8 wt%), and TiO was added 2 Substituted by Nb 2 O 5 After being dried at 140 ℃ after being dipped, 35mL/min of hydrogen is reduced for 4h at 300 ℃.
1mmol of 2, 5-diformylfuran, 0.09mmol of 8 wt% Cu/Nb 2 O 5 Adding a catalyst and 5mL of methanol into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 5.2MPa hydrogen, heating to 90 ℃, and reacting for 60 hours at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 98%, the GC yield of 1, 6-hexamethylenediamine was 97%, and the isolation yield was 94%.
Example 17
The difference from the catalyst preparation method in example 1 is that: the acetylacetone platinum was replaced with nickel nitrate (Ni concentration in solution: 32 wt%), and TiO was added 2 Replacement by Fe 2 O 3 After being dried at 110 ℃ after being dipped, 55mL/min of hydrogen is reduced for 2h at 500 ℃.
1mmol of 2, 5-diformylfuran, 0.027mmol of 32 wt% Ni/Fe 2 O 3 Adding a catalyst and 5mL of methanol into a 15mL reaction kettle, closing the kettle, replacing air in the kettle with hydrogen for 10 times, filling 2.8MPa hydrogen, heating to 80 ℃, and reacting for 26 hours at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 97%, the GC yield of 1, 6-hexamethylenediamine was 95% and the isolation yield was 92%.
Example 18
The difference from the catalyst preparation method in example 1 is that: the acetylacetonatoplatinum was replaced with palladium nitrate (Pd concentration in the solution: 12 wt%), and TiO was added 2 Replacing the solution with C, drying at 120 ℃ after dipping, and reducing by 45mL/min hydrogen at 200 ℃ for 3 h.
1mmol of 2, 5-diformylfuran, 0.12mmol of 12 wt% Pd/C catalyst and 5mL of N, N-dimethylformamide are added into a 15mL reaction kettle, the kettle is closed, air in the kettle is replaced by hydrogen for 10 times, 1.3MPa hydrogen is filled, the temperature is raised to 170 ℃, and the reaction is carried out for 45 hours at the temperature. After the reaction was complete, the reaction mixture was cooled and sampled for analysis as described in example 1, and the conversion of 2, 5-dicyanofuran was 98%, the GC yield of 1, 6-hexamethylenediamine was 96% and the isolation yield was 95%.
The invention has mild reaction condition, simple preparation process of the used heterogeneous catalyst, less dosage, easy separation from a reaction system and high activity after repeated recycling. The prepared 1, 6-hexamethylene diamine product has high purity which reaches more than 99 percent, and has wide application prospect.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (8)

1. A method for catalyzing 2, 5-dicyanofuran to be hydrogenated and ring-opened to synthesize 1, 6-hexanediamine is characterized in that a material containing 2, 5-dicyanofuran is contacted with a catalyst in a hydrogen source environment and reacts to obtain 1, 6-hexanediamine;
wherein the catalyst comprises an acidic carrier and a metal element; the metal element is loaded on the acidic carrier;
the metal element comprises at least one of Pd, Pt, Ni, Rh, Ru, Re, Ir, Co, Cu, Fe and Au;
in the catalyst, the acidic carrier is selected from any one of carbon materials, metal oxides, ion exchange resins, and hydrogen-type molecular sieves;
the metal oxide comprises Re 2 O 7 、Y 2 O 3 、CeO 2 、ZrO 2 、WO 3 、Al 2 O 3 、TiO 2 、Nb 2 O 5 、V 2 O 5 、MnO 2 、Fe 2 O 3 、Cr 2 O 4 、MoO 3 Any one of (a) to (b); the ion exchange resin is selected from any one of Amberlite IR-120H, Amberlyst-15;
the hydrogen type molecular sieve is selected from at least one of HMCM-41 and HZSM-5;
when the metal element is Pt, the carrier is TiO 2 Or Cr 2 O 4 Or Al 2 O 3 ；
When the metal element is Rh, the carrier is Re 2 O 7 Or Amberlite IR-120H;
when the metal element is Ni, the carrier is Y 2 O 3 Or Fe 2 O 3 ；
When the metal element is Co, the carrier is MoO 3 Or HZSM-5;
when the metal element is RuThe carrier is WO 3 Or Amberlyst-15;
when the metal element is Fe, the carrier is ZrO 2 ；
When the metal element is Au, the carrier is MnO 2 ；
When the metal element is Pd, the carrier is HMCM-41 or C;
when the metal element is Re, the carrier is CeO 2 ；
When the metal element is Ir, the carrier is V 2 O 5 ；
When the metal element is Cu, the carrier is Nb 2 O 5 。
2. The method for catalyzing the ring-opening synthesis of 1, 6-hexanediamine by hydrogenating 2, 5-dicyanofuran according to claim 1, wherein the metal element accounts for 0.1-40 wt% of the catalyst;
wherein the mass of the metal element is based on the mass of the metal itself; the mass of the catalyst is based on the mass of the catalyst itself.
3. The method for catalyzing the ring-opening synthesis of 1, 6-hexanediamine by the hydrogenation of 2, 5-dicyanofuran according to claim 1, wherein the amount of the catalyst is 0.1-30 mol% of the mass of 2, 5-dicyanofuran;
the mass of the catalyst is based on the weight of the catalyst itself.
4. The method for catalyzing the ring-opening hydrogenation of 2, 5-dicyanofuran to synthesize 1, 6-hexamethylenediamine according to claim 1, wherein the hydrogen source is any one of hydrogen, formic acid and isopropanol.
5. The method for catalyzing the ring-opening synthesis of 1, 6-hexanediamine by the hydrogenation of 2, 5-dicyanofuran according to claim 1, wherein the reaction conditions are as follows:
the partial pressure of hydrogen source is 0.1-6.0 MPa;
the reaction temperature is 30-250% o C；
The reaction time is 0.5-72 h.
6. The method for catalyzing the ring-opening synthesis of 1, 6-hexanediamine by hydrogenating 2, 5-dicyanofuran according to claim 1, wherein the reaction conditions are as follows:
the reaction conditions are as follows:
the partial pressure of hydrogen source is 1-4.0 MPa;
the reaction temperature is 50-200% o C；
The reaction time is 1-48 h.
7. The method for catalyzing the ring-opening synthesis of 1, 6-hexanediamine by the hydrogenation of 2, 5-dicyanofuran according to claim 1, wherein the material further comprises a solvent;
the solvent comprises any one of acetonitrile, methanol, ethanol, isopropanol, tetrahydrofuran, dichloromethane, N-dimethylformamide, toluene, o-xylene and p-xylene.
8. The method for catalyzing the ring-opening hydrogenation of 2, 5-dicyanofuran to synthesize 1, 6-hexanediamine according to claim 1, wherein after the 1, 6-hexanediamine is obtained, the method further comprises separating the 1, 6-hexanediamine;
the isolation of the 1, 6-hexanediamine comprises the steps of: and after the reaction is finished, centrifuging to remove the catalyst, performing rotary evaporation to remove the solvent, washing the solid, and drying to obtain a white solid, namely the 1, 6-hexanediamine.
CN201911286310.3A 2019-12-13 2019-12-13 Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening Active CN112979474B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911286310.3A CN112979474B (en) 2019-12-13 2019-12-13 Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911286310.3A CN112979474B (en) 2019-12-13 2019-12-13 Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening

Publications (2)

Publication Number Publication Date
CN112979474A CN112979474A (en) 2021-06-18
CN112979474B true CN112979474B (en) 2022-09-06

Family

ID=76342575

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911286310.3A Active CN112979474B (en) 2019-12-13 2019-12-13 Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening

Country Status (1)

Country Link
CN (1) CN112979474B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112898164B (en) * 2019-12-03 2022-03-04 中国科学院大连化学物理研究所 Method for preparing 1, 6-hexamethylene diamine from 5-hydroxymethylfurfural

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008143832A (en) * 2006-12-08 2008-06-26 New Japan Chem Co Ltd Method for producing alicyclic amine or saturated heterocyclic amine
CN102068986A (en) * 2011-01-06 2011-05-25 华东理工大学 Catalyst used in ring-opening hydrogenation reaction of furan derivative
CN102803196A (en) * 2009-06-13 2012-11-28 莱诺维亚公司 Production of adipic acid and derivatives from carbohydrate-containing materials
CN106660935A (en) * 2014-05-12 2017-05-10 微麦德斯公司 Methods of producing compounds from 5-(halomethyl)furfural
CN107011154A (en) * 2016-01-28 2017-08-04 北京大学 A kind of method that adipic acid is prepared by furans -2,5- dicarboxylic acids
CN107805203A (en) * 2017-11-15 2018-03-16 上海应用技术大学 A kind of preparation method of hexamethylene diamine
CN108129426A (en) * 2016-12-01 2018-06-08 中国科学院大连化学物理研究所 A kind of method of 2,5- dicyanos furans catalytic hydrogenation synthesis 2,5- dimethylamino furans

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2935201A4 (en) * 2012-12-21 2016-08-03 Rhodia Operations Process for forming a primary, a secondary or a tertiary amine via a direct amination reaction
WO2016022943A2 (en) * 2014-08-08 2016-02-11 Ndsu Research Foundation Novel monomers from biomass

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008143832A (en) * 2006-12-08 2008-06-26 New Japan Chem Co Ltd Method for producing alicyclic amine or saturated heterocyclic amine
CN102803196A (en) * 2009-06-13 2012-11-28 莱诺维亚公司 Production of adipic acid and derivatives from carbohydrate-containing materials
CN102068986A (en) * 2011-01-06 2011-05-25 华东理工大学 Catalyst used in ring-opening hydrogenation reaction of furan derivative
CN106660935A (en) * 2014-05-12 2017-05-10 微麦德斯公司 Methods of producing compounds from 5-(halomethyl)furfural
CN107011154A (en) * 2016-01-28 2017-08-04 北京大学 A kind of method that adipic acid is prepared by furans -2,5- dicarboxylic acids
CN108129426A (en) * 2016-12-01 2018-06-08 中国科学院大连化学物理研究所 A kind of method of 2,5- dicyanos furans catalytic hydrogenation synthesis 2,5- dimethylamino furans
CN107805203A (en) * 2017-11-15 2018-03-16 上海应用技术大学 A kind of preparation method of hexamethylene diamine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Selective synthesis of 2,5-bis(aminomethyl)furan via enhancing catalytic dehydration-hydrogenation of 2,5-diformylfuran dioxime;Yongming Xu 等;《GREEN CHEMISTRY》;20180425 *

Also Published As

Publication number Publication date
CN112979474A (en) 2021-06-18

Similar Documents

Publication Publication Date Title
US11584729B2 (en) Hydrophobic palladium/metal organic framework material, preparation method thereof, and application therefor for use in synthesizing 2,5-dimethylfuran
CN107935816B (en) Method for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN108393092A (en) Preparation method of catalyst for nitrile compounds Hydrogenation secondary amine and products thereof and application
CN110961110B (en) Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination
CN108620122A (en) A kind of biomass prepares the catalyst of pentanediol, and its preparation method and application
CN109824630B (en) Method for preparing furfuryl alcohol by one-pot xylose method under hydrogen supply of formic acid
CN106215953A (en) The synthesis of controlled number of plies molybdenum sulfide and the application in fragrance phenol and ethers reaction thereof
CN112341312B (en) Method for preparing cyclohexanol and derivative thereof by selective hydrogenolysis of lignin
CN109232188B (en) Preparation method of hydrogenated bisphenol A
CN112871198A (en) Catalyst for synthesizing formic acid by carbon dioxide hydrogenation, preparation method and application thereof
CN110711588A (en) Application of hydrotalcite-based catalyst in conversion of high-concentration sugar to 1, 2-propylene glycol
CN111875566A (en) Method for preparing 2, 5-dimethylfuran
CN108048125A (en) A kind of method of high selection catalytic transfer hydrogenation lignin derivative aromatic hydrocarbons
CN113908840A (en) Fe-based multifunctional catalyst and preparation method and application thereof
CN112979474B (en) Method for synthesizing 1, 6-hexanediamine by catalyzing 2, 5-dicyanofuran hydrogenation ring opening
CN106279075A (en) The method that a kind of catalysis 5 Hydroxymethylfurfural prepare 2,5 dimethyl furans
CN113731441A (en) Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof
CN111135828B (en) Catalyst and application, preparation and performance test method of catalyst
CN109701574B (en) Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of pyridine ring compounds
CN114410336B (en) Method for directly preparing long-chain alkane based on biomass levulinic acid
CN114570429B (en) Single-atom-loaded covalent organic framework material, preparation thereof and application thereof in hydrogen production by photolysis of water
CN111217750B (en) Preparation method of caprolactam
CN109999799B (en) Preparation method, performance test method and application of zirconium-containing supported nano ruthenium catalyst
CN113244944A (en) Co-based catalyst for preparing cyclohexanol by phenol hydrogenation and application method thereof
CN113372303A (en) Method for preparing tetrahydrofuran dimethanol dialkyl ether

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