WO2022099488A1 - 一种贵金属负载的蛋壳型催化剂及其制备方法与应用 - Google Patents

一种贵金属负载的蛋壳型催化剂及其制备方法与应用 Download PDF

Info

Publication number
WO2022099488A1
WO2022099488A1 PCT/CN2020/127943 CN2020127943W WO2022099488A1 WO 2022099488 A1 WO2022099488 A1 WO 2022099488A1 CN 2020127943 W CN2020127943 W CN 2020127943W WO 2022099488 A1 WO2022099488 A1 WO 2022099488A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
carrier
precious metal
catalyst
supported
Prior art date
Application number
PCT/CN2020/127943
Other languages
English (en)
French (fr)
Inventor
尹宏峰
励斌
严波
张洁
周生虎
Original Assignee
中国科学院宁波材料技术与工程研究所
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 中国科学院宁波材料技术与工程研究所 filed Critical 中国科学院宁波材料技术与工程研究所
Priority to US17/595,938 priority Critical patent/US20220347667A1/en
Priority to PCT/CN2020/127943 priority patent/WO2022099488A1/zh
Publication of WO2022099488A1 publication Critical patent/WO2022099488A1/zh

Links

Images

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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • 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
    • B01J23/58—Platinum group metals 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
    • B01J23/38—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
    • B01J23/63—Platinum group metals 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
    • B01J23/38—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
    • B01J23/6562—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
    • B01J23/89—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
    • 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
    • B01J23/892—Nickel 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
    • 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
    • B01J23/8926—Copper 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
    • 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
    • B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—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 also combined with metals, or metal 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
    • B01J23/89—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
    • B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—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 also combined with metals, or metal 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
    • 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
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof

Definitions

  • the application relates to an eggshell catalyst, in particular to a precious metal-supported eggshell catalyst used for the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol and a preparation method thereof, and the eggshell catalyst in the composition of 3 -
  • the application of hydroxypropionaldehyde hydrogenation to prepare 1,3-propanediol belongs to the technical field of catalyst preparation and application.
  • 1,3-Propanediol (referred to as 1,3-PDO) is a compound with a wide range of uses. In addition to being used in the production of polyurethane and cyclic compounds, it is also used in the production of polyethylene terephthalate fibers (referred to as 1,3-propylene terephthalate).
  • the main raw material of PTT The prepared PTT fiber not only has the properties of polyethylene terephthalate (PET), but also has the good resilience and pollution resistance of nylon. It is widely used in the fields of carpets, engineering plastics, clothing fabrics, etc. The hot spot in the development of synthetic fibers.
  • Preferred hydrogenation catalysts for the selective hydrogenation of 3-HPA to 1,3-PDO are generally classified into the following three types: (1) Raney nickel type catalysts or Raney nickel type catalysts modified by adding molybdenum, tungsten, etc.; ( 2 ) supported nickel catalysts (eg Ni/ Al2O3 ), and (3) supported platinum or palladium catalysts.
  • Patent US6,342,646 prepares a supported catalyst with precious metals such as Ru as active components, and the carrier is TiO 2 or SiO 2 .
  • the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol is carried out in a fixed bed reactor.
  • the hydrogen pressure of the reaction is 1 ⁇ 6MPa
  • the temperature of the reaction is 30 ⁇ 180 °C
  • the concentration of the 3-hydroxypropionaldehyde solution is 5 ⁇ 15wt%
  • the pH value of the 3-hydroxypropionaldehyde solution is 3.5 ⁇ 5.5
  • the volume space velocity ( LHSV) is 0.1 to 10h -1 .
  • the selectivity to 1,3-propanediol exceeded 98%.
  • the required precious metal content of the catalyst is relatively high, about 2-5 wt%, and the industrial cost is relatively high.
  • the main purpose of this application is to provide a precious metal-supported eggshell catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal and a preparation method thereof, so as to overcome the deficiencies of the prior art.
  • Another object of the present application is to provide the application of the precious metal-supported eggshell catalyst in the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol.
  • the embodiments of the present application provide a precious metal-supported eggshell catalyst, which includes a carrier, a precious metal and an auxiliary as active components supported on the carrier, and the precious metal and the auxiliary are uniformly distributed on the surface of the carrier , the auxiliary agent includes any one or a combination of two or more of noble metals, alkaline earth metals, transition metals lanthanide metals, and actinide metals and/or metal oxides thereof.
  • the chemical formula of the eggshell catalyst is M-X/A, wherein A is a carrier, M is a noble metal element, X is a noble metal element, an alkaline earth metal element, a transition metal lanthanide metal element, an actinide metal element Any one or a combination of two or more elements.
  • the noble metal includes any one or a combination of two or more of Pt, Pd, Ir, Ru, etc., but is not limited thereto.
  • the auxiliary agent includes any one or a combination of two or more of Na, Ca, Ni, Co, Mn, Cu, La, Rh, etc. and/or metal oxides thereof, but not limited to this.
  • Embodiments of the present application also provide a method for preparing the aforementioned precious metal-supported eggshell catalyst, comprising:
  • the carrier is fully immersed in the mixed solution of the metal salt precursor solution containing the precious metal element and the metal salt precursor solution containing the auxiliary metal element, taken out and dried, and then calcined to obtain the precious metal-supported eggshell type catalyst.
  • the immersion includes: firstly immersing the carrier in a mixed solution at a temperature of 40-70° C. for 1-4 hours, and then continuing to immerse the carrier for 6-16 hours at room temperature.
  • the temperature of the roasting treatment is 400-550° C., and the time is 2-10 h.
  • the examples of the present application also provide the use of the aforementioned precious metal-supported eggshell catalyst in the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol.
  • the embodiments of the present application also provide a method for preparing 1,3-propanediol, comprising:
  • 1,3-propanediol is prepared by hydrogenating the eggshell catalyst after reduction pretreatment with an aqueous solution containing 3-hydroxypropanal in a hydrogen atmosphere.
  • the precious metal-supported eggshell catalyst for the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol provided by this application is innovative in the structure of the catalyst, and the catalyst support is prepared into Raschig-shaped particles, thereby The catalyst structure is controlled to be an eggshell design. In this way, the main active components are evenly distributed on the surface of the carrier particles, which improves the utilization rate of precious metals. On the one hand, the activity and service life of the catalyst are enhanced; on the other hand, the preparation cost of the catalyst is reduced, which is more conducive to the industrialization process of the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol;
  • the precious metal-supported eggshell catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal introduces the second type of metal as an auxiliary agent, and on the surface of the catalyst carrier particles, the precious metal and the auxiliary metal are mixed. There is an obvious synergistic effect between them, thereby realizing (1) promoting the hydrogenation conversion of 3-hydroxypropionaldehyde; (2) improving the selectivity of the hydrogenation reaction of 3-hydroxypropionaldehyde and reducing the occurrence of side reactions; (3) the high selectivity of the product 1,3-propanediol is realized; (4) the usage amount of the precious metal is reduced, and the preparation cost of the catalyst is reduced;
  • the catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropionaldehyde provided in this application can be used in a continuous fixed bed hydrogenation process.
  • the continuous fixed-bed hydrogenation test of more than 300 hours can be successfully achieved; at the same time, after calcining the used catalyst, the catalyst can still be used.
  • the process for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal and has good activity.
  • FIG. 1 is a schematic diagram showing the results of a 300-hour fixed-bed continuous hydrogenation test of a precious metal-supported eggshell catalyst in a typical embodiment of the present application.
  • the metal concentration distribution of supported metal catalysts is a key factor affecting the activity, selectivity and service life of hydrogenation reactions.
  • the active metal is evenly distributed on the particle surface, which improves the utilization rate of the precious metal.
  • the introduction of the second type of metal as a promoter promotes the catalysis of the hydrogenation reaction through the synergistic effect between the noble metal and the second type of metal, thereby showing more excellent activity, selectivity and use in many hydrogenation reactions life.
  • the present application mainly provides a novel precious metal-supported eggshell catalyst and a preparation method and its application in preparing 1,3-propanediol from 3-hydroxypropanal.
  • the catalyst provided by the present application exhibits high conversion rate of reactant 3-hydroxypropionaldehyde, high selectivity of product 1,3-propanediol and long service life in fixed bed hydrogenation.
  • the catalyst provided by the present application has high utilization rate of precious metals, low preparation cost, and can be separated after separation. After calcination, it can be reused many times.
  • a precious metal-supported eggshell catalyst which includes a carrier, and a precious metal and an auxiliary as active components supported on the carrier, wherein the precious metal and the auxiliary are uniformly distributed in the catalyst.
  • the auxiliary agent includes any one or a combination of two or more of noble metals, alkaline earth metals, transition metals lanthanide metals, actinide metals, etc. and/or metal oxides thereof.
  • the chemical formula of the eggshell catalyst is M-X/A, wherein A is a carrier, M is a noble metal element, X is a noble metal element, an alkaline earth metal element, a transition metal lanthanide metal element, an actinide metal element Any one or a combination of two or more of the elements, etc.
  • the present application provides a catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal
  • the catalyst is a precious metal supported eggshell catalyst M-X/A
  • its carrier A is a metal Oxides or zeolites
  • the main active component M is a precious metal
  • the auxiliary metal X is a second type of metal other than the precious metal.
  • the eggshell structure means that the precious metal M and the auxiliary metal X are uniformly distributed on the surface area of the carrier at the same time.
  • the carrier is Raschig ring particles of metal oxide or zeolite.
  • the design mechanism of the present application is: the precious metal-supported eggshell catalyst introduces the second type of metal as an auxiliary, and on the surface of the catalyst carrier particles, an obvious synergistic effect occurs between the precious metal and the auxiliary metal, thereby realizing: ( 1) The hydrogenation conversion of 3-hydroxypropionaldehyde is promoted; (2) the selectivity of the hydrogenation reaction of 3-hydroxypropionaldehyde is improved, and the occurrence of side reactions is reduced; (3) the high 1,3-propanediol product is realized. Selectivity; (4) The usage amount of precious metals is reduced, and the preparation cost of the catalyst is reduced.
  • the main active component noble metal in the catalyst includes any one or a combination of two or more of Pt, Pd, Ir, Ru, etc., but is not limited thereto.
  • the auxiliary agent is a second type of metal other than noble metal, and it can also be noble metal.
  • the auxiliary agent can be any alkaline earth metal, transition metal lanthanide or actinide and the like.
  • auxiliary agent may exist in the form of metal or metal oxide.
  • it may specifically include any one or a combination of two or more of Na, Ca, Ni, Co, Mn, Cu, La, Rh, etc. and/or metal oxides thereof, but is not limited thereto.
  • the loading amount of the precious metal in the eggshell catalyst is about 0.1-10 wt%.
  • the loading amount of the auxiliary agent in the eggshell catalyst is 1-50 wt %, preferably 1-20 wt %.
  • the mass ratio of the auxiliary agent to the precious metal is between 2:1 and 500:1.
  • the carrier is a Raschig ring-shaped particle, and the material of the carrier includes oxides, molecular sieves, etc., but is not limited thereto.
  • the components of the carrier A of the catalyst can be oxides, such as any one or two or more of ⁇ -Al 2 O 3 , SiO 2 , MgO, TiO 2 , ZrO 2 , amorphous aluminum silicate, etc.
  • oxides such as any one or two or more of ⁇ -Al 2 O 3 , SiO 2 , MgO, TiO 2 , ZrO 2 , amorphous aluminum silicate, etc.
  • a combination of ⁇ -Al 2 O 3 , SiO 2 , TiO 2 , amorphous aluminum silicate, etc. preferably including any one or a combination of two or more, but not limited thereto.
  • the component of the carrier A of the catalyst can be molecular sieve, such as ZSM-5, H ⁇ molecular sieve, MCM-49, MCM-22, SAPO-11, SAPO-34, mordenite (MOR), beta zeolite, L zeolite , Y zeolite, ultra-stable Y zeolite (USY), etc. any one or a combination of two or more, preferably including any one or two of ZSM-5, H ⁇ molecular sieve, MCM-49, SAPO-11, ⁇ zeolite, etc. A combination of the above, but not limited to this.
  • molecular sieve such as ZSM-5, H ⁇ molecular sieve, MCM-49, MCM-22, SAPO-11, SAPO-34, mordenite (MOR), beta zeolite, L zeolite , Y zeolite, ultra-stable Y zeolite (USY), etc. any one or a combination of two or more, preferably including any one or two of
  • component of the carrier A of the catalyst can be a mixture of oxide and molecular sieve.
  • the particle size of the carrier is 1-8 mm, preferably 2-5 mm.
  • Another aspect of the embodiments of the present application also provides a method for preparing the aforementioned precious metal-supported eggshell catalyst, comprising:
  • the carrier is fully immersed in the mixed solution of the metal salt precursor solution containing the precious metal element and the metal salt precursor solution containing the auxiliary metal element, taken out and dried, and then calcined to obtain the precious metal-supported eggshell type catalyst.
  • an equal volume impregnation method is used to prepare the precious metal-supported eggshell catalyst for the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol, which specifically includes the following steps:
  • the dried catalyst is calcined in a muffle furnace, and then cooled down.
  • the precursor salts contained in the metal salt precursor solution containing noble metal elements include nitrates, chlorides and the like containing noble metal elements.
  • the concentration of the precious metal element-containing metal salt precursor solution is 0.1-1.0 mol/L.
  • the precursor salt contained in the metal salt precursor solution containing a metal auxiliary element includes nitrates, chlorides and the like containing noble metal elements.
  • the concentration of the metal salt precursor solution containing the auxiliary metal element is 1.0-10.0 mol/L.
  • the immersion includes: firstly immersing the carrier in a mixed solution with a temperature of 40-70° C. for 1-4 hours, and then continuing to immerse the carrier for 6-16 hours at room temperature.
  • the immersion process is carried out under the condition of a water bath at 40-70° C. for 1-4 hours; then, as for the inside of the tray, the immersion is continued at room temperature for 10-14 hours.
  • step (5) the calcination treatment is performed in an air atmosphere, the calcination treatment temperature is 400 ⁇ 550° C., and the time is 2 ⁇ 10 h.
  • the preparation method includes: raising the temperature of the air atmosphere to 400-550° C. at a temperature-raising rate of 0.5-3° C./min.
  • the calcination adopts temperature-programming, and the heating rate is 0.5-3° C./min, and then calcination is carried out at a temperature of 400-550° C. in an air atmosphere for 3-6 hours.
  • the preparation method of the catalyst carrier A comprises:
  • the mixture is molded into a mold, cut to a selected size, dried, and then calcined to obtain the carrier.
  • the catalyst carrier A can be prepared by conventional methods, including the following steps:
  • step (a) the mixing speed of the mixer is 20-80 rpm, and the mixing time is 1-4 h.
  • the binding agent is any one or a combination of two or more in dilute nitric acid, citric acid and silica sol, etc., but is not limited to this.
  • the mass ratio of the binder to the carrier is 0.5-6:100, that is, the amount of the binder added is 0.5-6wt% of the mass of the carrier.
  • step (c) the size of the cut is 2-5 mm.
  • the roasting treatment is carried out in an air atmosphere, the temperature of the roasting treatment is 700-900° C., and the time is 2-10 h.
  • the preparation method includes: raising the temperature of the air atmosphere to 700-900°C by using a heating rate of 1-5°C/min.
  • step (d) the roasting adopts temperature-programming, and the heating rate is 1-5°C/min, and then roasting is carried out at a temperature of 700-900°C under an air atmosphere for 3-6 hours.
  • Another aspect of the embodiments of the present application also provides the use of the aforementioned noble metal-supported eggshell catalyst in the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol.
  • Another aspect of the embodiments of the present application also provides a method for preparing 1,3-propanediol, comprising:
  • 1,3-propanediol is prepared by hydrogenating the eggshell catalyst after reduction pretreatment with an aqueous solution containing 3-hydroxypropanal in a hydrogen atmosphere.
  • the process conditions of the reduction pretreatment include: a hydrogen pressure of 1.0-4.0 MPa, a hydrogen space velocity of 50-500 h-1, a reduction temperature of 350-500 °C, and a reduction time of 2-10 h.
  • the eggshell catalyst supported by the precious metal needs to be reduced in a hydrogen atmosphere before use, and the reduction conditions are a hydrogen pressure of 0.1-5.0 MPa, a hydrogen space velocity of 10-1000 h-1, and a reduction temperature of 200-500 ° C.
  • the reduction time is 1-20 hours, preferably the hydrogen pressure is 1.0-4.0 MPa, the hydrogen space velocity is 50-500 h-1, the reduction temperature is 350-500°C, and the reduction time is 2-10 hours.
  • the process conditions for the hydrogenation reaction include: the temperature of the hydrogenation reaction is 40-130° C., the hydrogenation reaction pressure is 3-10MPa, and the concentration of the aqueous solution containing 3-hydroxypropionaldehyde is 5-100 MPa. 15wt%, the space velocity of the aqueous solution containing 3-hydroxypropanal is 0.1-1.0 h -1 , and the molar ratio of hydrogen to 3-hydroxypropanal is 2:1-20:1.
  • the eggshell catalyst provided by the present application When the eggshell catalyst provided by the present application is used for the reaction of preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal aqueous solution, the conversion rate of the reactant 3-hydroxypropanal is high, and the obtained 1,3-propanediol has good selectivity , High utilization rate of precious metals, good catalyst stability and long service life.
  • the catalyst particles are large, easy to separate from the reactants, and can be reused for many times after being calcined.
  • Embodiment 1 ⁇ 32 adopts the equal volume impregnation method to prepare the eggshell catalyst used for the hydrogenation of 3-hydroxypropanal to prepare 1,3-propanediol:
  • step (a) the mixing speed of the mixer is 20-80 rpm, and the mixing is performed for 1-4 h.
  • the binder is selected from dilute nitric acid, citric acid and silica sol.
  • the added amount of the binder is 0.5-6 wt % of the mass of the dry powder of the carrier.
  • step (c) the size of the cut is 2-5mm.
  • the calcination adopts a temperature-programmed temperature increase rate of 1-5°C/min, and then calcinates at a temperature of 700-900°C under an air atmosphere for 2-10 hours, preferably 3-6 hours.
  • the eggshell catalyst was prepared by the equal volume impregnation method:
  • the dried catalyst is calcined in a muffle furnace and then cooled down.
  • the noble metal salt in step (b), can be selected from nitrates, chloride salts, etc., and the molar concentration of the noble metal precursor solution is 0.1-1.0 mol/L.
  • the precursor salt can be selected from nitrates, chlorides, etc., and the molar concentration of the precursor solution of the auxiliary metal is 1.0-10.0 mol/L.
  • step (d) the immersion process is carried out under the condition of a water bath at 40-70° C. for 1-4 hours; after that, in the tray, the immersion is continued at room temperature for 6-16 hours.
  • the calcination adopts temperature-programmed heating, and the heating rate is 0.5-3°C/min, and then calcinates at a temperature of 400-550°C under an air atmosphere for 2-10 hours.
  • Reduction pretreatment after roasting and cooling down, the catalyst is loaded into a fixed bed reactor, and the hydrogen pressure is 1.0 ⁇ 4.0MPa, the hydrogen space velocity is 50 ⁇ 500h -1 , the reduction temperature is 350 ⁇ 500°C, and the reduction time is 2 ⁇ 4.0MPa. 10 hours. After the reduction procedure is completed, adjust to the conditions required for the reaction.
  • the catalyst compositions obtained in Examples 1-32 are shown in Table 1; the preparation process conditions used in Examples 1-32 are shown in Table 2; for the different catalysts obtained in Table 2, the catalyst evaluation conditions and The results are shown in Table 3;
  • the newly prepared catalyst is loaded into the fixed bed reactor, the reaction temperature of the hydrogenation section is 40-130°C; the hydrogenation reaction pressure of the hydrogenation section is 3-10MPa; the concentration of the 3-hydroxypropionaldehyde aqueous solution of the reaction raw material is 5-15wt %; the space velocity of the aqueous solution of 3-hydroxypropanal is 0.1-1.0h -1 ; the molar ratio of hydrogen to 3-hydroxypropanal is 2: 1 ⁇ 20: 1; sampling and analysis at the outlet of the reactor, calculating the reaction conversion rate and selective.
  • Table 3 The reaction conditions and results of each embodiment are shown in Table 3.
  • the hydrogenation catalyst in the prepared Example 4 was loaded into the fixed-bed reactor, and the reaction temperature in the hydrogenation section was 85 ° C; the hydrogenation reaction pressure in the hydrogenation section was 4MPa; 12wt%; the space velocity of the aqueous solution of 3-hydroxypropanal is 0.6h -1 ; the molar ratio of hydrogen to 3-hydroxypropanal is 4:1. After 300 hours of continuous hydrogenation in a fixed bed, samples were taken at the outlet of the reactor for analysis to calculate the conversion rate and selectivity of the reaction. The conversion of 3-hydroxypropanal was 99.9% and the selectivity to 1,3-propanediol was 96% (see Figure 1). This example shows that the catalyst of the present application has better stability and longer service life.
  • the catalyst in the reacted Example 33 was regenerated by reduction in a fixed bed reactor, the hydrogen pressure was 4.0 MPa, the hydrogen space velocity was 300 h ⁇ 1 , the reduction temperature was 500° C., and the reduction time was 8 hours.
  • the catalyst after reduction and regeneration is adjusted to the desired reaction conditions.
  • the reaction temperature of the hydrogenation section is 85°C; the hydrogenation reaction pressure of the hydrogenation section is 4MPa; the concentration of the reaction raw material 3-hydroxypropionaldehyde aqueous solution is 12wt%; the space velocity of the aqueous solution of 3-hydroxypropionaldehyde is 0.6h-1;
  • the molar ratio of 3-hydroxypropanal was 4:1.
  • Non-eggshell catalysts are generally prepared by excess impregnation method, and the preparation method is as follows:
  • the carrier powder to the mixer and mix at 20-80 rpm for 1-4 hours.
  • the binder is added dropwise to the stirring carrier powder, and the mass fraction of the binder is preferably 1-6% of the mass of the carrier powder.
  • the uniformly mixed carrier into the extruder, select a columnar die for molding, and cut it into strips of 2-5mm. In an air atmosphere of 90-150°C, it is left to dry for 12-24 hours, and then calcined in a muffle furnace at 700-900°C for 5-15 hours.
  • a large number of precursor solutions of noble metal and auxiliary metal are prepared respectively.
  • the pH of the precursor mixed solution is adjusted to 1-6 with an aqueous HCl solution.
  • the obtained carrier is placed in the mixed solution, and adsorbed at a water bath temperature of 40-70° C. for 12-24 hours, so that the carrier can fully adsorb precious metals and auxiliary metals.
  • the metal solution on the support surface was washed with deionized water. Then, in an air atmosphere of 90-130° C., the impregnated particles are allowed to stand for 12-24 hours, and then calcined in a muffle furnace at 450-650° C. for 5-10 hours.
  • the catalyst compositions of Comparative Examples A-D are shown in Table 1, the preparation conditions are shown in Table 2, and the catalytic evaluation conditions and results are shown in Table 3.
  • the catalyst compositions of Comparative Examples E-G are shown in Table 1, the preparation conditions are shown in Table 2, and the catalytic evaluation conditions and results are shown in Table 3.
  • the catalyst evaluation results of Examples E-F it can be seen that the catalyst that only supports the precious metal Pd and does not contain the promoter metal Ni has no synergistic effect between the metal and the promoter metal, and the conversion of 3-hydroxypropionaldehyde
  • the yield and the selectivity of the product 1,3-propanediol decreased significantly, which further proved that the synergistic effect between the metal and the auxiliary metal promoted the reaction.
  • the catalyst composition of Comparative Example H-I is shown in Table 1, its preparation conditions are shown in Table 2, and its catalytic evaluation conditions and results are shown in Table 3.
  • the catalyst evaluation results of Example H-I it can be seen that the catalyst that only supports the promoter metal Ni and does not contain the precious metal Pd still has a certain conversion rate of 3-hydroxypropanal and the selectivity of the product 1,3-propanediol. .
  • the results have a certain gap compared with catalysts loaded with both noble metal Pd and promoter metal Ni.
  • Comparative Examples E-F it is shown that the precious metal Pd plays a major role in the hydrogenation reaction of 3-hydroxypropionaldehyde.
  • the catalyst for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal provided in this application can be used in a continuous fixed bed hydrogenation process.
  • the continuous fixed-bed hydrogenation test of more than 300 hours can be successfully achieved; at the same time, after calcining the used catalyst, the catalyst can still be used.
  • the process for preparing 1,3-propanediol by hydrogenation of 3-hydroxypropanal and has good activity.
  • compositions taught herein will also be substantially The above consists of or consists of the recited components, and the processes taught herein also consist essentially of, or consist of, the recited process steps.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

本申请公开了一种贵金属负载的蛋壳型催化剂及其制备方法与应用。所述蛋壳型催化剂包括载体以及负载在所述载体上的作为活性组分的贵金属和助剂，所述贵金属和助剂均匀分布于所述载体表面，所述助剂包括贵金属、碱土金属、过渡金属镧系金属、锕系金属中的任意一种或两种以上的组合和/或其金属氧化物。将本申请提供的蛋壳型催化剂用于3-羟基丙醛水溶液加氢制备1，3-丙二醇反应时，反应物3-羟基丙醛的转化率高，得到的1，3-丙二醇选择性好，贵金属使用率高，催化剂稳定性好，使用寿命长，300小时以上的连续性固定床加氢试验可以成功实现；并且催化剂颗粒较大，易于从反应物中分离，在经过煅烧之后可多次重复使用，且具有良好的活性。

Description

一种贵金属负载的蛋壳型催化剂及其制备方法与应用 技术领域
本申请涉及一种蛋壳型催化剂，具体涉及一种用于3-羟基丙醛加氢制备1，3-丙二醇的贵金属负载的蛋壳型催化剂及其制备方法，以及该蛋壳型催化剂在由3-羟基丙醛加氢制备1，3-丙二醇中的应用，属于催化剂制备与应用技术领域。
背景技术
1，3-丙二醇(简称1，3-PDO)是一种用途广泛的化合物，除可用于生产聚氨酯和环状化合物之外，更是生产聚对苯二甲酸1，3-丙二醇酯纤维(简称PTT)的主要原料。所制备的PTT纤维，既具有聚对苯二甲酸乙二酯(PET)的性能，又具有尼龙良好的回弹性和抗污染性，在地毯、工程塑料、服装面料等领域应用广泛，成为目前国际上合成纤维开发的热点。由于近几年PTT纤维的市场需求逐步提升，据估计1，3-PDO的市场规模将由2019年的4.9亿美元扩张到2024年的，复合年增长率为12.2％，聚对苯二甲酸1，3-丙二醇酯纤维的开发应用再次受到广泛关注。
据了解，目前由两种非均相催化生产1，3-丙二醇的路线被广泛应用，分别是丙烯醛生产1，3-PDO(Degussa-DuPont)或环氧乙烷生产1，3-PDO(Shell)。两种途径均通过丙烯醛的水合或环氧乙烷的加氢甲酰化而产生中间体3-羟基丙醛(简称3-HPA)，然后将3-HPA氢化成1，3-PDO。因此，开发高性能固体氢化催化剂已经成为1，3-PDO生产中的重要课题。用于将3-HPA选择性氢化为1，3-PDO的优选的氢化催化剂通常分为以下三种类型：(1)Raney镍型催化剂或通过添加钼，钨等改性的Raney镍型催化剂；(2)负载型镍催化剂(例如Ni/Al 2O 3)，和(3)负载型铂或钯催化剂。
目前有许多技术专利(CN1,178,884，US6,342,646，US5,334,778)涉及在间歇式釜式反应器和连续固定床反应器中，使用贵金属负载的催化剂将3-HPA两步加氢成1，3-PDO。该类负载 型催化剂中包含活性组分(例如钌、铂、钯或它们的组合)和载体(例如TiO 2、Al 2O 3、沸石、MgO、TiO2或SiO 2)。然而，这些催化剂通常表现出较低的活性和较弱的使用寿命，导致为了实现较高的3-HPA转化率，需要使用更多的贵金属，从而带来了较高的催化剂成本。为了更经济地生产1，3-PDO，开发用于3-HPA加氢的高性能催化剂非常重要。
专利US6,342,646中制备了一种Ru等贵金属为活性组分的负载型催化剂，载体为TiO 2或SiO 2。3-羟基丙醛加氢制备1，3-丙二醇的反应在固定床反应器中进行。反应的氢气压力为1～6MPa，反应的温度为30～180℃，3-羟基丙醛溶液的浓度为5～15wt％，3-羟基丙醛溶液的pH值为3.5～5.5，体积空速(LHSV)为0.1～10h -1。反应之后，1，3-丙二醇的选择性超过了98％。但该催化剂所需要的贵金属含量较高，约为2～5wt％，在工业上的成本比较高。
发明内容
本申请的主要目的在于提供一种用于3-羟基丙醛加氢制备1，3-丙二醇的贵金属负载的蛋壳型催化剂及其制备方法，以克服现有技术的不足。
本申请的另一目的还在于提供所述贵金属负载的蛋壳型催化剂在3-羟基丙醛加氢制备1，3-丙二醇中的应用。
为实现前述发明目的，本申请采用的技术方案包括：
本申请实施例提供了一种贵金属负载的蛋壳型催化剂，其包括载体以及负载在所述载体上的作为活性组分的贵金属和助剂，所述贵金属和助剂均匀分布于所述载体表面，所述助剂包括贵金属、碱土金属、过渡金属镧系金属、锕系金属中的任意一种或两种以上的组合和/或其金属氧化物。
在一些优选实施例中，所述蛋壳型催化剂的化学式为M-X/A，其中，A为载体，M为贵金属元素，X为贵金属元素、碱土金属元素、过渡金属镧系金属元素、锕系金属元素中的任意一种或两种以上的组合。
在一些优选实施例中，所述贵金属包括Pt、Pd、Ir、Ru等中的任意一种或两种以上的组合，但不限于此。
在一些优选实施例中，所述助剂包括Na、Ca、Ni、Co、Mn、Cu、La、Rh等中的任意一 种或两种以上的组合和/或其金属氧化物，但不限于此。
本申请实施例还提供了前述贵金属负载的蛋壳型催化剂的制备方法，其包括：
提供包含贵金属元素的金属盐前驱体溶液和包含助剂金属元素的金属盐前驱体溶液；
使载体充分浸渍于所述含贵金属元素的金属盐前驱体溶液和包含助剂金属元素的金属盐前驱体溶液的混合液中，取出干燥，之后再进行焙烧处理，获得所述贵金属负载的蛋壳型催化剂。
在一些优选实施例中，所述浸渍包括：先使所述载体在温度为40～70℃的混合液中浸渍1～4h，之后于室温下继续浸渍6～16h。
在一些优选实施例中，所述焙烧处理的温度为400～550℃，时间为2～10h。
本申请实施例还提供了前述贵金属负载的蛋壳型催化剂于3-羟基丙醛加氢制备1，3-丙二醇中的用途。
相应的，本申请实施例还提供了一种制备1，3-丙二醇的方法，其包括：
对前述贵金属负载的蛋壳型催化剂进行还原预处理；
使还原预处理后的蛋壳型催化剂与包含3-羟基丙醛的水溶液在氢气气氛中进行加氢反应，制得1，3-丙二醇。
与现有技术相比，本申请的有益效果至少在于：
1)本申请提供的用于3-羟基丙醛加氢制备1，3-丙二醇的贵金属负载的蛋壳型催化剂在催化剂的结构上进行了创新，催化剂载体制备成拉西环状的颗粒，从而使催化剂结构控制为蛋壳型设计，通过这种方式，主要活性组分均匀分布于载体颗粒表面，使贵金属的利用率得到了提升。一方面，使得催化剂的活性和使用寿命得到了增强，另一方面，降低了催化剂的制备成本，更有利于3-羟基丙醛加氢制备1，3-丙二醇项目的工业化进程；
2)本申请提供的用于3-羟基丙醛加氢制备1，3-丙二醇的贵金属负载的蛋壳型催化剂引入了第二类金属作为助剂，在催化剂载体颗粒表面，贵金属与助剂金属之间发生了明显的协同效应，从而实现了(1)促进了3-羟基丙醛的加氢转化；(2)提高3-羟基丙醛加氢反应的选择性，降低了副反应的发生；(3)实现了产物1，3-丙二醇的高选择性；(4)降低了贵金属的使用量，降低了催化剂的制备成本；
3)本申请提供的用于3-羟基丙醛加氢制备1，3-丙二醇的催化剂可以用于连续固定床加氢 工艺。将该催化剂用于3-羟基丙醛加氢制备1，3-丙二醇的工艺时，300小时以上的连续性固定床加氢试验可以成功实现；同时将使用完的催化剂煅烧之后，该催化剂仍可以用于3-羟基丙醛加氢制备1，3-丙二醇的工艺，且具有良好的活性。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本申请一典型实施例中一种贵金属负载的蛋壳型催化剂300小时固定床连续加氢试验结果示意图。
具体实施方式
众所周知，负载金属催化剂的金属浓度分布是影响氢化反应的活性，选择性和使用寿命的关键因素。与通过等体积浸渍方法制备的均匀分布的贵金属催化剂相比，将催化剂结构控制为蛋壳型设计时，活性金属均匀分布于颗粒表面，使贵金属的利用率得到了提升。同时引入第二类金属作为助剂，通过贵金属与第二类金属之间的协同效应，推动了对加氢反应的催化作用，从而对许多氢化反应均显示出更优异的活性，选择性和使用寿命。
为了克服现有的加氢催化剂在由3-羟基丙醛制备1，3-丙二醇的固定床加氢工艺中活性差，催化剂成本高等缺陷，本案发明人经长期研究和大量实践，得以提出本申请的技术方案。本申请主要是提供一种新的贵金属负载的蛋壳型催化剂和制备方法及其在由3-羟基丙醛制备1，3-丙二醇中的应用。本申请提供的催化剂在固定床加氢中表现出反应物3-羟基丙醛的高转化率，产物1，3-丙二醇的高选择性，使用寿命长。同时本申请提供的催化剂贵金属利用率高，制备成本低，且在分离之后。经过煅烧可多次重复使用。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
本申请实施例的一个方面提供的一种贵金属负载的蛋壳型催化剂，其包括载体以及负载在 所述载体上的作为活性组分的贵金属和助剂，所述贵金属和助剂均匀分布于所述载体表面，所述助剂包括贵金属、碱土金属、过渡金属镧系金属、锕系金属等中的任意一种或两种以上的组合和/或其金属氧化物。
在一些优选实施例中，所述蛋壳型催化剂的化学式为M-X/A，其中，A为载体，M为贵金属元素，X为贵金属元素、碱土金属元素、过渡金属镧系金属元素、锕系金属元素等中的任意一种或两种以上的组合。
在一些更为优选实施例中，本申请提供了一种3-羟基丙醛加氢制备1，3-丙二醇的催化剂，该催化剂为贵金属负载的蛋壳型催化剂M-X/A，其载体A是金属氧化物或沸石，其主要活性成分M为贵金属，助剂金属X为除贵金属外的第二类金属。所述蛋壳型结构是指贵金属M和助剂金属X同时均匀分布在载体表面区域。其中，所述的载体为金属氧化物或沸石成分的拉西环状颗粒。
本申请的设计机理在于：该贵金属负载的蛋壳型催化剂引入了第二类金属作为助剂，在催化剂载体颗粒表面，贵金属与助剂金属之间发生了明显的协同效应，从而实现了：(1)促进了3-羟基丙醛的加氢转化；(2)提高3-羟基丙醛加氢反应的选择性，降低了副反应的发生；(3)实现了产物1，3-丙二醇的高选择性；(4)降低了贵金属的使用量，降低了催化剂的制备成本。
在一些优选实施例中，所述催化剂中的主要活性组分贵金属包括Pt、Pd、Ir、Ru等中的任意一种或两种以上的组合但不限于此。
在一些优选实施例中，所述助剂为除贵金属外的第二类金属，也可以是贵金属。其中，所述助剂可以是任何碱土金属、过渡金属镧系元素或锕系元素等。
进一步地，所述助剂可以以金属或者金属氧化物的形式存在。例如，具体可以包括Na、Ca、Ni、Co、Mn、Cu、La、Rh等中的任意一种或两种以上的组合和/或其金属氧化物，但不限于此。
在一些优选实施例中，所述蛋壳型催化剂中贵金属的负载量约为0.1～10wt％。
在一些优选实施例中，所述蛋壳型催化剂中助剂的负载量为1～50wt％，优选为1～20wt％。
在一些优选实施例中，在所述蛋壳型催化剂中，以所述催化剂的总量为基准，以金属元素计，所述助剂与贵金属的质量比在2：1～500：1之间。
在一些优选实施例中，所述载体为拉西环形状的颗粒，所述载体的材质包括氧化物、分子 筛等，但不限于此。
进一步地，所述催化剂的载体A的成分可以是氧化物，例如γ-Al 2O 3、SiO 2、MgO、TiO 2、ZrO 2、无定形硅酸铝等中的任意一种或两种以上的组合，优选包括γ-Al 2O 3、SiO 2、TiO 2、无定形硅酸铝等中的任意一种或两种以上的组合，但不限于此。
进一步地，所述催化剂的载体A的成分可以是分子筛，例如ZSM-5、Hβ分子筛、MCM-49、MCM-22、SAPO-11、SAPO-34、丝光沸石(MOR)、β沸石、L沸石、Y沸石、超稳Y沸石(USY)等的任意一种或两种以上的组合，优选包括ZSM-5、Hβ分子筛、MCM-49、SAPO-11、β沸石等的任意一种或两种以上的组合，但不限于此。
进一步地，所述催化剂的载体A的成分可以是氧化物和分子筛的混合体。
在一些优选实施例中，所述载体的粒径为1～8mm，优选为2～5mm。
本申请实施例的另一个方面还提供了前述贵金属负载的蛋壳型催化剂的制备方法，其包括：
提供包含贵金属元素的金属盐前驱体溶液和包含助剂金属元素的金属盐前驱体溶液；
使载体充分浸渍于所述含贵金属元素的金属盐前驱体溶液和包含助剂金属元素的金属盐前驱体溶液的混合液中，取出干燥，之后再进行焙烧处理，获得所述贵金属负载的蛋壳型催化剂。
在一些优选实施例中，采用等体积浸渍法制备所述用于3-羟基丙醛加氢制备1，3-丙二醇的贵金属负载的蛋壳型催化剂，具体包括以下步骤：
(1)测定载体的吸水量，以每100g载体H 2O的克数为单位计量；
(2)按计量称取Pt、Pd、Ir、Ru等贵金属的金属盐配置包含贵金属元素的金属盐前驱体溶液；
(3)按计量称取Na、Ca、Ni、Co、Mn、Cu、La、Rh等助剂金属的金属盐配置包含助剂金属元素的金属盐前驱体溶液；
(4)将两种盐前驱体溶液混合均匀，并加入载体中，搅拌均匀，充分浸渍；
(5)干燥后的催化剂，在马弗炉中焙烧，然后降温即得。
在一些优选实施例中，步骤(2)中，所述包含贵金属元素的金属盐前驱体溶液所含前驱体盐包括包含贵金属元素的硝酸盐、氯化盐等。
进一步地，所述含贵金属元素的金属盐前驱体溶液的浓度为0.1～1.0mol/L。
在一些优选实施例中，步骤(3)中，所述包含助剂金属元素的金属盐前驱体溶液所含前驱体盐包括包含贵助剂金属元素的硝酸盐、氯化盐等。
进一步地，所述包含助剂金属元素的金属盐前驱体溶液的浓度为1.0～10.0mol/L。
在一些优选实施例中，步骤(4)中，所述浸渍包括：先使所述载体在温度为40～70℃的混合液中浸渍1～4h，之后于室温下继续浸渍6～16h。
进一步地，所述浸渍过程在40～70℃的水浴条件下进行，浸渍1～4h；之后至于托盘内，在室温下继续浸渍10～14h。
在一些优选实施例中，步骤(5)中，所述焙烧处理在空气气氛中进行，所述焙烧处理的温度为400～550℃，时间为2～10h。
进一步地，所述制备方法包括：采用0.5～3℃/min的升温速率将空气气氛的温度升温至400～550℃。
进一步地，所述的焙烧采用程序升温，升温速率为0.5～3℃/min，然后在温度400～550℃下，空气气氛下焙烧3～6小时。
在一些优选实施例中，所述催化剂载体A的制备方法包括：
将包含载体各组分的颗粒与粘结剂混合均匀，获得混合物；
使所述混合物进行模具成型，再剪切至选定尺寸，并烘干，再进行焙烧处理，获得所述载体。
在一些更为优选的具体案例之中，所述催化剂载体A可通过常规方法制备，具体包括以下步骤：
(a)所述载体中的任何一种或它们的混合物加入混料机搅拌；
(b)配置适量的粘结剂，以滴加的方式加入载体；
(c)混合均匀的载体加入挤料机，先通过模具成型，再剪切至合适的尺寸，最后置于室温下烘干；
(d)在马弗炉中焙烧，然后降温即得。
进一步地，步骤(a)中，所述混料机的混合搅拌速率为20～80rpm，混合搅拌时间为1～4h。
进一步地，步骤(b)中，所述粘结剂为稀硝酸、柠檬酸和硅溶胶等中的任意一种或两种以 上的组合，但不限于此。
进一步地，步骤(b)中，所述粘结剂与所述载体的质量比为0.5～6：100，亦即，所述的粘结剂加入量为载体质量的0.5～6wt％。
进一步地，步骤(c)中，所述剪切的尺寸为2～5mm。
进一步地，所述焙烧处理在空气气氛中进行，所述焙烧处理的温度为700～900℃，时间为2～10h。
进一步地，所述制备方法包括：采用1～5℃/min的升温速率将空气气氛的温度升温至700～900℃。
进一步地，步骤(d)中，所述的焙烧采用程序升温，升温速率为1～5℃/min，然后在温度700～900℃下，空气气氛下焙烧3～6小时。
本申请实施例的另一个方面还提供了前述贵金属负载的蛋壳型催化剂于3-羟基丙醛加氢制备1，3-丙二醇中的用途。
相应的，本申请实施例的另一个方面还提供了一种制备1，3-丙二醇的方法，其包括：
对前述贵金属负载的蛋壳型催化剂进行还原预处理；
使还原预处理后的蛋壳型催化剂与包含3-羟基丙醛的水溶液在氢气气氛中进行加氢反应，制得1，3-丙二醇。
在一些优选实施例中，所述还原预处理的工艺条件包括：氢气压力为1.0～4.0MPa，氢气空速为50～500h-1，还原温度为350～500℃，还原时间为2～10h。
进一步地，所述贵金属负载的蛋壳型催化剂在使用前需要在氢气气氛下进行还原，还原条件为氢气压力0.1～5.0MPa、氢气空速为10～1000h-1、还原温度为200～500℃、还原时间为1～20小时，优选为氢气压力1.0～4.0MPa、氢气空速为50～500h-1、还原温度为350～500℃、还原时间为2～10小时。
在一些优选实施例中，所述加氢反应的工艺条件包括：加氢反应的温度为40～130℃，加氢反应压力为3～10MPa，包含3-羟基丙醛的水溶液的浓度为5～15wt％，包含3-羟基丙醛的水溶液的空速为0.1～1.0h -1，氢气与3-羟基丙醛的摩尔比为2∶1～20∶1。
将本申请提供的蛋壳型催化剂用于3-羟基丙醛水溶液加氢制备1，3-丙二醇反应时，反应 物3-羟基丙醛的转化率高，得到的1，3-丙二醇选择性好，贵金属使用率高，催化剂稳定性好，使用寿命长。且催化剂颗粒较大，易于从反应物中分离，在经过煅烧之后可多次重复使用。
以下通过具体的实施例及附图说明本申请的技术方案。应理解，本申请提到的一个或多个方法步骤并不排斥在所属组合步骤前后还存在其他方法步骤或在这些明确提到的步骤之前还可以插入其他方法步骤；还应理解，这些事例仅用于说明本申请而不用于限制本申请的范围。而且，除非另有说明，各方法步骤的编号仅为鉴别个方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本申请可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本申请可实施的范畴。
实施例1～32采用等体积浸渍法制备用于3-羟基丙醛加氢制备1，3-丙二醇的蛋壳型催化剂：
催化剂载体的制备：
(a)选取2000克分子筛ZSM-5、Hβ、MCM-49、SAPO-11、β沸石或氧化物γ-Al 2O 3、SiO 2、TiO 2或无定形硅酸铝中的任何一种或它们的混合物，将其置于混料机中搅拌；
(b)选取适量的粘合剂，以滴加的方式加入载体；
(c)充分搅拌均匀后，加入挤料机，通过拉西环模具成型，并剪切至合适的尺寸，最终制成蛋壳型载体；
(d)载体在室温下烘干后，在马弗炉中充分焙烧。煅烧完毕后，等其降至室温，置于一边备用。
其中，步骤(a)中，所述混料机的混合速率为20-80rpm，混合搅拌1-4h。步骤(b)中，所述的粘结剂选自稀硝酸、柠檬酸和硅溶胶。步骤(b)中，所述的粘结剂加入量为载体干粉质量的0.5-6wt％。步骤(c)中，剪切的尺寸为2-5mm。步骤(d)中，所述的焙烧采用程序升温，升温速率1-5℃/min，然后在温度700～900℃下，空气气氛下焙烧2～10小时，优选3～6小时。
采用等体积浸渍法制备蛋壳型催化剂：
(a)测定载体的吸水量，以每100g载体H 2O的克数为单位计量；
(b)按计量称取Pt、Pd、Ir或Ru等贵金属盐配置前驱体溶液；
(c)按计量称取Na、Ca、Ni、Co、Mn、Cu、La、Rh等助剂金属的金属盐配置前驱体溶液；
(d)按照一定的计量比，加入催化剂载体中均匀搅拌，充分浸渍；
(e)干燥后的催化剂，在马弗炉中焙烧，然后降温即得。
其中，步骤(b)中，所述的贵金属盐可选自硝酸盐、氯化盐等，所述的贵金属的前驱体溶液的摩尔浓度为0.1～1.0mol/L。
步骤(c)中，所述的前驱体盐可选自硝酸盐、氯化盐等，所述的助剂金属的前驱体溶液的摩尔浓度为1.0～10.0mol/L。
步骤(d)中，所述浸渍过程在40～70℃的水浴条件下进行，浸渍1～4h；之后至于托盘内，在室温下继续浸渍6～16h。
步骤(e)中，所述的焙烧采用程序升温，升温速率0.5-3℃/min，然后在温度400～550℃下，空气气氛下焙烧2～10小时。
还原预处理：焙烧降温后，将催化剂装入固定床反应器中，在氢气压力为1.0～4.0MPa、氢气空速为50～500h -1、还原温度为350～500℃、还原时间为2～10小时。还原程序结束后，调整至反应所需条件。
实施例1-32中获得的催化剂组成，如表1所示；实施例1-32中采用的制备工艺条件，如表2所示；针对表2中所得到的不同催化剂，其催化剂评价条件和结果，如表3所示；
表1 实施例1-32中的催化剂组成
Figure PCTCN2020127943-appb-000001
Figure PCTCN2020127943-appb-000002
Figure PCTCN2020127943-appb-000003
表2 实施例1-32中的制备工艺条件
Figure PCTCN2020127943-appb-000004
Figure PCTCN2020127943-appb-000005
Figure PCTCN2020127943-appb-000006
催化剂活性评价：
将新制备的催化剂装入固定床反应器中，加氢工段反应温度为40～130℃；加氢工段的加氢反应压力为3-10MPa；反应原料3-羟基丙醛水溶液浓度为5-15wt％；3-羟基丙醛的水溶液空速为0.1-1.0h -1；氢气与3-羟基丙醛的摩尔比为2∶1～20∶1；在反应器出口段取样分析，计算反应转化率和选择性。各实施例的反应条件及结果如表3。
Figure PCTCN2020127943-appb-000007
Figure PCTCN2020127943-appb-000008
表3 实施例1-32中的催化剂评价条件及结果
Figure PCTCN2020127943-appb-000009
Figure PCTCN2020127943-appb-000010
Figure PCTCN2020127943-appb-000011
实施例33
将制备好的实施例4中的加氢催化剂装入固定床反应器中，加氢工段反应温度为85℃；加氢工段的加氢反应压力为4MPa；反应原料3-羟基丙醛水溶液浓度为12wt％；3-羟基丙醛的水溶液空速为0.6h -1；氢气与3-羟基丙醛的摩尔比为4∶1。经过300小时固定床连续加氢反应，在反应器出口段取样分析，计算反应转化率和选择性。3-羟基丙醛的转化率99.9％，1，3-丙二醇的选择性为96％(请参阅图1所示)。该实施例说明本申请催化剂具有较好的稳定性和较长的使用寿命。
实施例34
将反应后的实施例33中的催化剂在固定床反应器中进行还原再生，氢气压力4.0MPa、氢 气空速为300h -1、还原温度为500℃、还原时间为8小时。还原再生后的催化剂调整成所需的反应条件。加氢工段反应温度为85℃；加氢工段的加氢反应压力为4MPa；反应原料3-羟基丙醛水溶液浓度为12wt％；3-羟基丙醛的水溶液空速为0.6h-1；氢气与3-羟基丙醛的摩尔比为4∶1。在反应器出口段取样分析，计算反应转化率和选择性。3-羟基丙醛的转化率98.9％，1，3-丙二醇的选择性为91％。该实施例说明本申请催化剂还原再生仍可继续使用。
对比例A～D
非蛋壳型催化剂一般使用过量浸渍法制备，制备方法如下：
将载体粉末加入混料机中，并以20-80rpm的速度搅拌1-4小时。将粘合剂以滴加的形式加入搅拌中的载体粉末，同时粘合剂的质量分数优选为载体粉末质量的1～6％。然后将混合搅拌均匀的载体加入挤料机，选择柱状模具进行成型，并剪切为2-5mm的条状。在90～150℃的空气气氛下，静置干燥12～24小时，然后在马弗炉中于700-900℃煅烧5～15小时。
接下来分别制备大量的贵金属和助剂金属的前驱体溶液。将两种前驱体溶液混合均匀后，用HCl水溶液将前驱体混合溶液的pH调节至1-6。将得到的载体置于混合溶液中，以40-70℃的水浴温度下吸附12-24小时，使载体充分吸附贵金属和助剂金属。吸附过程完成后，用去离子水洗去载体表面金属溶液。之后在90～130℃的空气气氛下，浸渍完的颗粒静置12～24小时，之后在马弗炉中于450-650摄氏度下煅烧5-10小时。
对比实施例A-D的催化剂组成如表1所示，其制备条件如表2所示，其催化评价条件和结果如表3所示。通过比对实施例A-D的催化剂评价结果，可以说明要得到3-羟基丙醛的高转化率以及产物1，3-丙二醇的高选择性，相较于非蛋壳型催化剂，蛋壳型催化剂所需的贵金属以及助剂金属量更少，金属利用率更高，制备成本更低。
对比例E～G
对比实施例E-G的催化剂组成如表1所示，其制备条件如表2所示，其催化评价条件和结果如表3所示。通过对比实施例E-F的催化剂评价结果，可以看出，仅负载贵金属Pd，不含助剂金属Ni的催化剂，由于没有金属与助剂金属之间无法发生协同效应，其3-羟基丙醛的转化率以及产物1，3-丙二醇的选择性均有明显的下降，进一步证明了金属与助剂金属之间所产生的协同作用对该反应的促进作用。同时通过比较对比实施例G与实施例4的催化剂评价结果，可 以看出，在缺乏贵金属Pd与助剂金属Ni的协同作用的条件下，要达到与实施例4同等的催化剂评价结果，需要更多的贵金属负载量，说明金属间协同作用促进了贵金属的活性，大大提高了贵金属的使用率，从而降低了催化剂制备成本。
对比例H～I
对比实施例H-I的催化剂组成如表1所示，其制备条件如表2所示，其催化评价条件和结果如表3所示。通过对比实施例H-I的催化剂评价结果，可以看出，仅负载助剂金属Ni，不含贵金属Pd的催化剂，仍然具有一定的3-羟基丙醛的转化率以及产物1，3-丙二醇的选择性。但由于不存在贵金属与助剂金属之间的协同效应，其结果较负载同时贵金属Pd和助剂金属Ni的催化剂有一定的差距。同时较对比实施例E-F的结果，体现了贵金属Pd在3-羟基丙醛加氢反应中起到了主要作用。
对比例J～K
对比实施例J-K的催化剂组成如表1所示，其制备条件如表2所示，其催化评价条件和结果如表3所示。通过比较对比实施例J-K和实施例4的催化剂评价结果，可以看出，催化剂的最佳制备工艺条件，即如实施例4的制备工艺条件所示。
综上所述，本申请提供的用于3-羟基丙醛加氢制备1，3-丙二醇的催化剂可以用于连续固定床加氢工艺。将该催化剂用于3-羟基丙醛加氢制备1，3-丙二醇的工艺时，300小时以上的连续性固定床加氢试验可以成功实现；同时将使用完的催化剂煅烧之后，该催化剂仍可以用于3-羟基丙醛加氢制备1，3-丙二醇的工艺，且具有良好的活性。
本申请的各方面、实施例、特征及实例应视为在所有方面为说明性的且不打算限制本申请，本申请的范围仅由权利要求书界定。在不背离所主张的本申请的精神及范围的情况下，所属领域的技术人员将明了其它实施例、修改及使用。
在本申请案中标题及章节的使用不意味着限制本申请；每一章节可应用于本申请的任何方面、实施例或特征。
在本申请案通篇中，在将组合物描述为具有、包含或包括特定组份之处或者在将过程描述为具有、包含或包括特定过程步骤之处，预期本申请教示的组合物也基本上由所叙述组份组成或由所叙述组份组成，且本申请教示的过程也基本上由所叙述过程步骤组成或由所叙述过程步 骤组组成。
应理解，各步骤的次序或执行特定动作的次序并非十分重要，只要本申请教示保持可操作即可。此外，可同时进行两个或两个以上步骤或动作。
此外，本案发明人还参照前述实施例，以本说明书述及的其它原料、工艺操作、工艺条件进行了试验，并均获得了较为理想的结果。
尽管已参考说明性实施例描述了本申请，但所属领域的技术人员将理解，在不背离本申请的精神及范围的情况下可做出各种其它改变、省略及/或添加且可用实质等效物替代所述实施例的元件。另外，可在不背离本申请的范围的情况下做出许多修改以使特定情形或材料适应本申请的教示。因此，本文并不打算将本申请限制于用于执行本申请的所揭示特定实施例，而是打算使本申请将包含归属于所附权利要求书的范围内的所有实施例。

Claims (10)

  1. 一种贵金属负载的蛋壳型催化剂，其特征在于，所述蛋壳型催化剂包括载体以及负载在所述载体上的作为活性组分的贵金属和助剂，所述贵金属和助剂均匀分布于所述载体表面，所述助剂包括贵金属、碱土金属、过渡金属镧系金属、锕系金属中的任意一种或两种以上的组合和/或其金属氧化物。
  2. 根据权利要求1所述的所述贵金属负载的蛋壳型催化剂，其特征在于：所述蛋壳型催化剂的化学式为M-X/A，其中，A为载体，M为贵金属元素，X为贵金属元素、碱土金属元素、过渡金属镧系金属元素、锕系金属元素中的任意一种或两种以上的组合。
  3. 根据权利要求1所述的所述贵金属负载的蛋壳型催化剂，其特征在于：所述贵金属包括Pt、Pd、Ir、Ru中的任意一种或两种以上的组合；和/或，所述助剂包括Na、Ca、Ni、Co、Mn、Cu、La、Rh中的任意一种或两种以上的组合和/或其金属氧化物。
  4. 根据权利要求1所述的所述贵金属负载的蛋壳型催化剂，其特征在于：所述蛋壳型催化剂中贵金属的负载量为0.1～10wt％；和/或，所述蛋壳型催化剂中助剂的负载量为1～50wt％，优选为1～20wt％；和/或，在所述蛋壳型催化剂中，以金属元素计，所述助剂与贵金属的质量比为2∶1～500∶1。
  5. 根据权利要求1所述的所述贵金属负载的蛋壳型催化剂，其特征在于：所述载体为拉西环形状的颗粒，所述载体的材质包括氧化物和/或分子筛；优选的，所述氧化物包括γ-Al 2O 3、SiO 2、MgO、TiO 2、ZrO 2、无定形硅酸铝中的任意一种或两种以上的组合，尤其优选包括γ-Al 2O 3、SiO 2、TiO 2、无定形硅酸铝中的任意一种或两种以上的组合；优选的，所述分子筛包括ZSM-5、Hβ分子筛、MCM-49、MCM-22、SAPO-11、SAPO-34、丝光沸石、β沸石、L沸石、Y沸石、超稳Y沸石中的任意一种或两种以上的组合，尤其优选包括ZSM-5、Hβ分子筛、MCM-49、SAPO-11、β沸石中的任意一种或两种以上的组合；
    和/或，所述载体的粒径为1～8mm，优选为2～5mm。
  6. 如权利要求1-5中任一项所述贵金属负载的蛋壳型催化剂的制备方法，其特征在于包括：
    提供包含贵金属元素的金属盐前驱体溶液和包含助剂金属元素的金属盐前驱体溶液；
    使载体充分浸渍于所述含贵金属元素的金属盐前驱体溶液和包含助剂金属元素的金属盐前驱体溶液的混合液中，取出干燥，之后再进行焙烧处理，获得所述贵金属负载的蛋壳型催化剂。
  7. 根据权利要求6所述的制备方法，其特征在于：所述包含贵金属元素的金属盐前驱体溶液所含前驱体盐包括包含贵金属元素的硝酸盐和/或氯化盐；和/或，所述含贵金属元素的金属盐前驱体溶液的浓度为0.1～1.0mol/L；
    和/或，所述包含助剂金属元素的金属盐前驱体溶液所含前驱体盐包括包含贵助剂金属元素的硝酸盐和/或氯化盐；和/或，所述包含助剂金属元素的金属盐前驱体溶液的浓度为1.0～10.0mol/L。
  8. 根据权利要求6所述的制备方法，其特征在于，所述浸渍包括：先使所述载体在温度为40～70℃的混合液中浸渍1～4h，之后于室温下继续浸渍6～16h，优选为10～14h；
    和/或，所述焙烧处理在空气气氛中进行，所述焙烧处理的温度为400～550℃，时间为2～10h，优选为3～6h；优选的，所述制备方法包括：采用0.5～3℃/min的升温速率将空气气氛的温度升温至400～550℃；
    和/或，所述载体的制备方法包括：
    将包含载体各组分的颗粒与粘结剂混合均匀，获得混合物；
    使所述混合物进行模具成型，再剪切至选定尺寸，并烘干，再进行焙烧处理，获得所述载体；
    优选的，所述混合的搅拌速率为20～80rpm，搅拌时间为1～4h；
    优选的，所述粘结剂包括稀硝酸、柠檬酸和硅溶胶中的任意一种或两种以上的组合；
    优选的，所述粘结剂与所述载体的质量比为0.5～6∶100；
    优选的，所述选定尺寸为2～5mm；
    优选的，所述焙烧处理在空气气氛中进行，所述焙烧处理的温度为700～900℃，时间为2～10h，优选为3～6h；优选的，所述制备方法包括：采用1～5℃/min的升温速率将空气气氛的温度升温至700～900℃。
  9. 权利要求1-5中任一项所述贵金属负载的蛋壳型催化剂于3-羟基丙醛加氢制备1，3-丙二醇中的用途。
  10. 一种制备1，3-丙二醇的方法，其特征在于包括：
    对权利要求1-5中任一项所述贵金属负载的蛋壳型催化剂进行还原预处理；
    使还原预处理后的蛋壳型催化剂与包含3-羟基丙醛的水溶液在氢气气氛中进行加氢反应，制得1，3-丙二醇；
    优选的，所述还原预处理的工艺条件包括：氢气压力为0.1～5.0MPa，优选为1.0～4.0MPa，氢气空速为10～1000h -1，优选为50～500h -1，还原温度为200～500℃，优选为350～500℃，还原时间为1～20h，优选为2～10h；
    优选的，所述加氢反应的工艺条件包括：加氢反应的温度为40～130℃，加氢反应压力为3～10MPa，包含3-羟基丙醛的水溶液的浓度为5～15wt％，包含3-羟基丙醛的水溶液的空速为0.1～1.0h -1，氢气与3-羟基丙醛的摩尔比为2∶1～20∶1。
PCT/CN2020/127943 2020-11-11 2020-11-11 一种贵金属负载的蛋壳型催化剂及其制备方法与应用 WO2022099488A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US17/595,938 US20220347667A1 (en) 2020-11-11 2020-11-11 Precious metal-supported eggshell catalyst as well as preparation method and use thereof
PCT/CN2020/127943 WO2022099488A1 (zh) 2020-11-11 2020-11-11 一种贵金属负载的蛋壳型催化剂及其制备方法与应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2020/127943 WO2022099488A1 (zh) 2020-11-11 2020-11-11 一种贵金属负载的蛋壳型催化剂及其制备方法与应用

Publications (1)

Publication Number Publication Date
WO2022099488A1 true WO2022099488A1 (zh) 2022-05-19

Family

ID=81601856

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/127943 WO2022099488A1 (zh) 2020-11-11 2020-11-11 一种贵金属负载的蛋壳型催化剂及其制备方法与应用

Country Status (2)

Country Link
US (1) US20220347667A1 (zh)
WO (1) WO2022099488A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115672322A (zh) * 2022-10-12 2023-02-03 中国石油大学(华东) 一种Cu系蛋壳型催化剂、制备方法及草酸二酯加氢的方法
CN115672333A (zh) * 2022-10-12 2023-02-03 中国石油大学(华东) 一种Ni系蛋壳型催化剂、制备方法及重整生成油选择性加氢脱烯烃的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5334778A (en) * 1992-06-03 1994-08-02 Degussa Aktiengesellschaft Process for the production of 1,3-propanediol
CN1475472A (zh) * 2003-06-30 2004-02-18 华东理工大学 1，3－丙二醇的制备方法
CN1736604A (zh) * 2005-07-27 2006-02-22 北京化工大学 一种蛋壳型金属催化剂及其制备方法和应用
CN103769094A (zh) * 2014-01-20 2014-05-07 中国科学院宁波材料技术与工程研究所 一种用于选择性加氢反应的蛋壳型催化剂、制备方法及应用
CN105709778A (zh) * 2014-12-05 2016-06-29 上海华谊能源化工有限公司 一种3-羟基丙醛催化加氢制备1，3-丙二醇的催化剂及其制备方法与应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5334778A (en) * 1992-06-03 1994-08-02 Degussa Aktiengesellschaft Process for the production of 1,3-propanediol
CN1475472A (zh) * 2003-06-30 2004-02-18 华东理工大学 1，3－丙二醇的制备方法
CN1736604A (zh) * 2005-07-27 2006-02-22 北京化工大学 一种蛋壳型金属催化剂及其制备方法和应用
CN103769094A (zh) * 2014-01-20 2014-05-07 中国科学院宁波材料技术与工程研究所 一种用于选择性加氢反应的蛋壳型催化剂、制备方法及应用
CN105709778A (zh) * 2014-12-05 2016-06-29 上海华谊能源化工有限公司 一种3-羟基丙醛催化加氢制备1，3-丙二醇的催化剂及其制备方法与应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115672322A (zh) * 2022-10-12 2023-02-03 中国石油大学(华东) 一种Cu系蛋壳型催化剂、制备方法及草酸二酯加氢的方法
CN115672333A (zh) * 2022-10-12 2023-02-03 中国石油大学(华东) 一种Ni系蛋壳型催化剂、制备方法及重整生成油选择性加氢脱烯烃的方法

Also Published As

Publication number Publication date
US20220347667A1 (en) 2022-11-03

Similar Documents

Publication Publication Date Title
CN112264038B (zh) 一种贵金属负载的蛋壳型催化剂及其制备方法与应用
JP5357170B2 (ja) 選択的ニッケル系水素化触媒及びその製造
WO2022099488A1 (zh) 一种贵金属负载的蛋壳型催化剂及其制备方法与应用
CN103120955B (zh) 多环芳烃转化为单环芳烃的催化剂及其制备方法
CN105408018B (zh) 氧化锰稳定的氧化锆催化剂支撑体材料
CN105709778B (zh) 一种3-羟基丙醛催化加氢制备1，3-丙二醇的催化剂及其制备方法与应用
CN101269326A (zh) 用于苯加氢制环己烯的整体催化剂及其制备方法
CN103521234A (zh) 由丙烯醛氧化制备丙烯酸的催化剂及其制备方法
CN102836737A (zh) 一种萘加氢催化剂及其制备方法
CN102091648B (zh) 一种全白土型脱烯烃催化剂的制备方法
CN108579742B (zh) 脱氢催化剂及其制备方法
CN112206816B (zh) 一种用于丙烷脱氢制烯烃复合分子筛催化剂及其制备方法
CN112517059B (zh) 一种二甲基苄醇氢解催化剂及其制备方法
CN102233274A (zh) 降低芳烃中烯烃含量的催化剂及制备方法
CN112570016B (zh) 抗氮芳烃型加氢裂化催化剂及其制法和应用
CN102838438A (zh) 一种萘加氢生产四氢萘的方法
CN103230809A (zh) 一种全白土型重芳烃烷基转移催化剂的制备方法
CN114433220B (zh) 一种苯和合成气烷基化催化剂的制备方法
CN114433218B (zh) 一种苯和合成气烷基化催化剂及其制备方法和应用
CN114433217B (zh) 苯和合成气烷基化催化剂及其制备方法和应用
CN110694675A (zh) 一种低碳烃择形芳构化高效合成对二甲苯的催化剂
CN106582628B (zh) 选择性开环催化剂及其制备方法
CN112439401B (zh) 一种氢解催化剂和制备方法及其在α,α-二甲基苄醇氢解制异丙苯中的应用
CN112691677B (zh) 一种乙醇临氢氨化制备乙胺的催化剂及其制法和应用
CN118304928A (zh) 一种制苯催化剂

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20961047

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20961047

Country of ref document: EP

Kind code of ref document: A1