CN115041193A - Catalyst and preparation method and application thereof - Google Patents

Catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN115041193A
CN115041193A CN202210898330.1A CN202210898330A CN115041193A CN 115041193 A CN115041193 A CN 115041193A CN 202210898330 A CN202210898330 A CN 202210898330A CN 115041193 A CN115041193 A CN 115041193A
Authority
CN
China
Prior art keywords
catalyst
component
composite oxide
auxiliary agent
ethylenediamine
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.)
Pending
Application number
CN202210898330.1A
Other languages
Chinese (zh)
Inventor
李爽
侯珂珂
王东超
史会兵
陈琛
赵德明
张凤岐
王耀伟
栾波
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.)
Shandong Chambroad Petrochemicals Co Ltd
Original Assignee
Shandong Chambroad Petrochemicals Co Ltd
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 Shandong Chambroad Petrochemicals Co Ltd filed Critical Shandong Chambroad Petrochemicals Co Ltd
Priority to CN202210898330.1A priority Critical patent/CN115041193A/en
Publication of CN115041193A publication Critical patent/CN115041193A/en
Pending legal-status Critical Current

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
    • 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
    • B01J23/8993—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 chromium, molybdenum or 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • 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
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Landscapes

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

Abstract

The invention provides a catalyst for preparing 1, 3-propylene glycol by efficiently hydrogenating glycerol, which is composed of a composite oxide carrier prepared by a sol-gel method, an acid component WOx, a hydrogenation active component Pt and an auxiliary agent. The catalyst provided by the invention has higher yield of 1, 3-propylene glycol and high reaction stability in the reaction of preparing the 1, 3-propylene glycol by hydrogenating glycerol. The invention also provides a preparation method and application of the catalyst for preparing 1, 3-propylene glycol by efficient glycerol hydrogenation.

Description

Catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a catalyst, a preparation method and application thereof, in particular to a preparation method of a catalyst for preparing 1, 3-propylene glycol by high-efficiency glycerol hydrogenation.
Background
Glycerol, as a by-product of biodiesel production, has the advantages of availability and low cost, and is considered an ideal renewable feedstock for the production of high value important chemicals. Among the various potential applications of glycerol, 1, 3-propanediol (1,3-PDO) is the most important one, which has been widely used to produce polytrimethylene terephthalate (PTT), a high performance polyester. The PTT fiber has the performance of PET, the good rebound resilience and pollution resistance of nylon, has good application prospect in the fields of carpets, engineering plastics, clothing fabrics and the like, and is a hot spot for the international development of synthetic fibers at present. Under the promotion of great demand for PTT in the industrial field, 1, 3-propanediol is certainly developed as a raw material for synthesizing PTT. The production process for preparing 1, 3-propanediol by directly hydrogenizing glycerol is not applied to industrial production, mainly because the requirements on energy consumption and equipment for the hydrogenolysis reaction of glycerol are relatively high, and the selectivity of 1,3-PDO is relatively low; the catalyst has poor stability, short service life and relatively poor activity in the reaction process, so that the research on the catalyst for preparing the 1,3-PDO with high selectivity has important significance.
The catalyst provided by the prior art has the defects of low glycerol concentration, low glycerol conversion rate, low 1, 3-propylene glycol yield, harsh reaction conditions and poor stability, and the reaction product has high water content and low 1, 3-propylene glycol concentration, and has high energy consumption in the subsequent separation process, so that the whole production cost is high and the competitiveness is poor. Therefore, it is necessary to provide a method for increasing the yield of 1, 3-propanediol by increasing the conversion of glycerol and the selectivity of 1, 3-propanediol.
Disclosure of Invention
In view of this, an object of the embodiments of the present invention is to provide a catalyst, a preparation method and an application thereof, where the catalyst provided by the present invention has a good effect when used for preparing 1, 3-propanediol.
The present invention provides a catalyst comprising:
a composite oxide support;
an acidic component;
a hydrogenation active component;
an inorganic auxiliary component;
an organic auxiliary agent.
Preferably, the catalyst comprises the following components:
50-90 wt% of a composite oxide carrier;
5 to 25 wt% of an acidic component;
3-6 wt% of a hydrogenation active component;
5-10 wt% of an inorganic auxiliary component;
the balance of organic auxiliary agent.
Preferably, the composite oxide support is selected from Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、P 2 O 5 、B 2 O 3 、MgO、MnO X 、La 2 O 3 、Ce 2 O 3 And two or more kinds of ZnO.
Preferably, the acidic component is WOx, x is 3;
the hydrogenation active component is Pt.
Preferably, the inorganic auxiliary agent component is one or more selected from Cu, Ni, Co, Ag, Au, Re and Ir.
Preferably, the organic auxiliary agent is one or more selected from ethylamine, n-propylamine, n-butylamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine and hexylenediamine.
The invention provides a preparation method of the catalyst in the technical scheme, which comprises the following steps:
loading an acidic component on a composite oxide carrier to obtain a first intermediate product;
loading a hydrogenation active component, an inorganic auxiliary agent and an organic auxiliary agent on the first intermediate product to obtain a second intermediate product;
and heating the second intermediate product to obtain the catalyst.
Preferably, the temperature of the heating treatment is 300-600 ℃; the time is 5-12 h; the atmosphere is a hydrogen-containing atmosphere.
The invention provides a preparation method of 1, 3-propylene glycol, which comprises the following steps:
reacting glycerol with hydrogen under the action of a catalyst to obtain 1, 3-propylene glycol;
the catalyst is the catalyst in the technical scheme.
Preferably, the reaction temperature is 120-170 ℃, and the pressure is 1.0-5.0 MPa.
The invention provides a preparation method of a high-efficiency catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenolysis, wherein an acidic component and a metal component in the adopted catalyst are uniformly dispersed on a carrier, meanwhile, an organic auxiliary agent component is added, so that a high-content active component can be dispersed on the carrier in a highly dispersed state, and the catalyst is directly used without roasting after being formed, thereby avoiding the agglomeration of hydrogenation active components due to multiple roasting, reducing the reaction severity, and improving the stability, the activity and the target product selectivity of the catalyst in the reaction process of high-concentration raw materials.
Drawings
FIG. 1 is a gas chromatogram of 1, 3-propanediol prepared with the catalyst prepared in example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention provides a catalyst comprising:
a composite oxide support;
an acidic component;
a hydrogenation active component;
an inorganic adjuvant component;
an organic auxiliary agent.
In the present invention, the components of the catalyst are preferably:
50-90 wt% of a composite oxide carrier;
5 to 25 wt% of an acidic component;
3-6 wt% of a hydrogenation active component;
5-10 wt% of an inorganic auxiliary component;
the balance of organic auxiliary agent.
In the invention, the catalyst is composed of a composite oxide carrier prepared by a sol-gel method, an acidic component WOx, a hydrogenation active component composed of Pt and an auxiliary agent component, the total mass fraction of the composite oxide carrier is 50-90%, the mass fraction of WOx is 5-25%, the mass fraction of Pt is 3-6%, the mass fraction of an inorganic auxiliary agent oxide is 5-10%, and the balance is a substance generated after the decomposition of an organic auxiliary agent.
In the present invention, the mass content of the composite oxide support is preferably 60 to 90%, more preferably 70 to 80%, and most preferably 75%.
In the present invention, the composite oxide support is preferably selected from Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、P 2 O 5 、B 2 O 3 、MgO、MnO X 、La 2 O 3 、Ce 2 O 3 And ZnO, more preferably Al 2 O 3 、SiO 2 、TiO 2 、P 2 O 5 、MnO x 、Ce 2 O 3 Or a combination of two or more of them.
In the present invention, the composite oxide support is preferably prepared by a sol-gel method.
In the present invention, the method for producing the composite oxide support preferably includes:
dissolving the precursor of the composite oxide carrier, mixing, adjusting the pH value, aging, carrying out hydrothermal treatment, washing, drying and roasting to obtain the composite oxide carrier.
In the present invention, the precursor of the composite oxide support is preferably Al 2 O 3 When the composite oxide carrier precursor is used, the composite oxide carrier precursor is preferably selected from one or more of aluminum hydroxide dry glue, pseudo-boehmite, aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum sulfate and acidic aluminum sol; more preferably one or more selected from aluminum hydroxide dry glue, pseudo-boehmite and aluminum sulfate.
In the invention, the composite oxide carrier is SiO 2 In this case, the composite oxide carrier precursor is preferably selected from the group consisting of white carbon black and SiO 2 One or more of aerogel, sodium silicate, water glass, alkaline silica sol and neutral silica sol; more preferably selected from the group consisting of silica and SiO 2 One or more of aerogel, alkaline silica sol and neutral silica sol.
In the invention, the composite oxide carrier is TiO 2 When the composite oxide carrier precursor is used, the composite oxide carrier precursor is preferably selected from one or more of tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, titanium sulfate and titanium tetrachloride; more preferably one or more selected from tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate.
In the present invention, the composite oxide support is P 2 O 5 In the case, the composite oxide support precursor is preferably selected from one or more of phosphoric acid, dimeric phosphoric acid, polyphosphoric acid, pyrophosphoric acid and corresponding soluble salts thereof, and soluble phosphate esters such as trimethyl phosphate and triethyl phosphate; more preferably one or more selected from phosphoric acid, ammonium dihydrogen phosphate, trimethyl phosphate and triethyl phosphate.
In the invention, the composite oxide carrier is B 2 O 3 In the case, the composite oxide support precursor is preferably selected from one or more of soluble boron compounds such as boric acid and borax; more preferably boric acid.
In the present invention, the composite oxide support is ZrO 2 、MgO、MnO X 、La 2 O 3 、Ce 2 O 3 When ZnO is used, the precursor of the composite oxide carrier can be selectedThe soluble salt corresponding to the metal element is preferably nitrate.
In the present invention, the dissolution may be peptization; preferably, acid, alkali or water is adopted to dissolve at 25-80 ℃, more preferably 30-70 ℃, more preferably 40-60 ℃ and most preferably 50 ℃; the mixing is preferably stirring mixing, and the mixing temperature is preferably 25-80 ℃, more preferably 30-70 ℃, more preferably 40-60 ℃, and most preferably 50-80 ℃; the mixing is preferably performed by mixing two or more composite oxide precursors; the pH value is preferably adjusted by adopting an acid or alkali adjusting system, and the pH value is preferably adjusted to 6-8, more preferably 7; the temperature of the aging treatment is preferably 50-80 ℃, more preferably 60-70 ℃, and most preferably 65 ℃; the time of the aging treatment is preferably 0.5-6 h, more preferably 1-6 h, more preferably 2-5 h, and most preferably 3-4 h; the hydrothermal treatment is preferably carried out in an autoclave with a polytetrafluoroethylene lining; the temperature of the hydrothermal treatment is preferably 120-170 ℃, more preferably 130-160 ℃, and most preferably 140-150 ℃; the time of the hydrothermal treatment is preferably 4-24 h, more preferably 8-20 h, more preferably 8-16 h, and most preferably 15 h; the washing is preferably carried out after filtration; the washing is preferably deionized water washing to neutrality; the drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; the drying time is preferably 5-24 h, more preferably 10-20 h, and most preferably 15 h; the roasting temperature is preferably 500-1000 ℃, more preferably 550-850 ℃, and most preferably 700-800 ℃; the roasting time is preferably 2-10 h, more preferably 3-9 h, more preferably 4-8 h, more preferably 5-7 h, and most preferably 6 h.
In the present invention, the method for producing the composite oxide support preferably includes:
the precursor corresponding to the carrier is subjected to gelation or dissolution by adopting acid, alkali or water at the temperature of 25-80 ℃; stirring and mixing two or more precursor solutions at the temperature of 25-80 ℃, adjusting the pH value of the system to 6-8 by adopting acid or alkali, aging at the temperature of 50-80 ℃ for 0.5-6 h, and transferring the system to an autoclave with a polytetrafluoroethylene lining for hydrothermal treatment for 4-24 h; filtering, washing with deionized water to neutrality, drying at 80-120 ℃ for 5-24 h, and roasting at 500-1000 ℃ for 2-10 h to obtain the composite oxide carrier.
In the present invention, the mass content of the acidic component is preferably 10 to 20%, and more preferably 15%.
In the present invention, the acidic component is preferably WOx, and x is preferably 3.
In the invention, the mass content of the hydrogenation active component is preferably 4-5%, and more preferably 4.5%.
In the present invention, the hydrogenation active component is preferably Pt.
In the invention, the mass content of the inorganic auxiliary agent component is preferably 6-9%, and more preferably 7-8%.
In the invention, the inorganic auxiliary agent component is preferably selected from one or more of Cu, Ni, Co, Ag, Au, Re and Ir.
In the invention, the organic auxiliary agent is preferably selected from one or more of ethylamine, n-propylamine, n-butylamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine and hexylenediamine, or substances generated after decomposition of the organic auxiliary agent; more preferably one or more selected from ethylenediamine, propylenediamine and hexamethylenediamine.
The invention provides a preparation method of the catalyst in the technical scheme, which comprises the following steps:
loading an acidic component on a composite oxide carrier to obtain a first intermediate product;
loading a hydrogenation active component, an inorganic auxiliary agent and an organic auxiliary agent on the first intermediate product to obtain a second intermediate product;
and heating the second intermediate product to obtain the catalyst.
In the present invention, the method for preparing the first intermediate product preferably comprises:
dissolving a precursor of the acidic component in a solvent, loading the precursor on a composite oxide carrier, drying and roasting to obtain a first intermediate product.
In the present invention, the precursor of the acidic component is preferably selected from one or more soluble tungstate salts, such as ammonium tungstate, ammonium metatungstate, and ammonium paratungstate.
In the present invention, the method of supporting on the composite oxide support is preferably an equivalent-volume impregnation method.
In the invention, the drying temperature is preferably 110-130 ℃, more preferably 115-125 ℃, and most preferably 120 ℃; the drying time is preferably 20-30 h, more preferably 22-28 h, and most preferably 24-26 h.
In the invention, the roasting temperature is preferably 500-1000 ℃, more preferably 650-900 ℃, and most preferably 700-800 ℃; the roasting time is preferably 5-12 hours, more preferably 6-10 hours, and most preferably 7-8 hours.
In the present invention, the method for preparing the second intermediate product preferably comprises:
and mixing a precursor of the hydrogenation active component, a precursor of the inorganic auxiliary agent and the organic auxiliary agent, loading the mixture on the first intermediate product, drying, tabletting and molding to obtain a second intermediate product.
In the invention, the precursor of the hydrogenation active component is preferably selected from one or more of platinum chloride, chloroplatinic acid and platinum nitrate.
In the invention, the precursor of the inorganic auxiliary agent is preferably selected from one or more of soluble chloride, nitrate, acetate and oxalate corresponding to the inorganic auxiliary agent.
In the present invention, the method of mixing preferably comprises:
respectively carrying out first mixing on a precursor of the hydrogenation active component and a precursor of the inorganic auxiliary agent and the organic auxiliary agent, and then carrying out second mixing on the two obtained mixtures, and uniformly mixing.
In the present invention, the molar ratio of the precursor of the hydrogenation active component to the organic auxiliary agent is preferably 1: (1-3), more preferably 1: (1.5-2.5), most preferably 1: 2; the molar ratio of the precursor of the inorganic auxiliary agent to the organic auxiliary agent is preferably 1: (2-5), more preferably 1: (2.5 to 4.0), most preferably 1: (3.0-3.5).
In the present invention, the first mixing is preferably performed under stirring; the stirring time is preferably 5-24 h, more preferably 10-20 h, and most preferably 15 h; the first mixing is preferably carried out at room temperature.
In the present invention, the method of supporting the first intermediate product is preferably an isometric impregnation method.
In the present invention, the drying is preferably vacuum drying; the drying temperature is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 80 ℃; the drying time is preferably 20-30 h, more preferably 22-28 h, and most preferably 24-26 h.
In the present invention, the tableting is preferably performed by using a tableting machine.
In the present invention, the heat treatment is preferably carried out in a fixed bed reactor; the heat treatment is preferably performed in an atmosphere containing hydrogen gas; the hydrogen-containing atmosphere may be a 100% hydrogen atmosphere or a mixed gas of hydrogen and nitrogen; the hydrogen gas is preferably present in the gas mixture in a percentage by volume of > 30%.
In the invention, the temperature of the heating treatment is preferably 200-600 ℃, more preferably 300-500 ℃, and most preferably 450 ℃; the time of the heating treatment is preferably 5-15 h, more preferably 6-10 h, and most preferably 8-9 h; the heat treatment is preferably carried out in a reactor, and is preferably fed after the temperature is lowered to the heating temperature (reaction temperature).
The invention provides a preparation method of 1, 3-propylene glycol, which comprises the following steps:
reacting glycerol with hydrogen under the action of a catalyst to obtain 1, 3-propylene glycol;
the catalyst is the catalyst in the technical scheme or the catalyst prepared by the method in the technical scheme.
In the present invention, the glycerin is preferably a glycerin solution, more preferably a glycerin aqueous solution; the mass fraction of the glycerin solution is preferably 30% or more, more preferably 50% or more, and most preferably 50 to 80%.
In the invention, the reaction temperature is preferably 120-170 ℃, more preferably 130-160 ℃, and most preferably 140-150 ℃; the pressure of the reaction is preferably 1.0-5.0 MPa, more preferably 1.5-3.5 MPa, and most preferably 3.0 MPa; the volume ratio of the glycerol solution to the hydrogen gas entering the reactor in the reaction process is preferably 1: (100 to 800), more preferably 1: (150 to 650), more preferably 1: (300-600), most preferably 1: (400-500); the mass space velocity of the glycerol solution in the reaction process is preferably 1.0-5.0 h -1 More preferably 1.0 to 3.0 hours -1 Most preferably 2.0h -1 。
The invention provides a preparation method of a high-efficiency catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenolysis, wherein an acidic component and a metal component in the adopted catalyst are uniformly dispersed on a carrier, meanwhile, an organic auxiliary agent component is added, so that a high-content active component can be dispersed on the carrier in a highly dispersed state, and the catalyst is directly used without roasting after being formed, thereby avoiding the agglomeration of hydrogenation active components due to multiple roasting, reducing the reaction severity, and improving the stability, the activity and the target product selectivity of the catalyst in the reaction process of high-concentration raw materials.
Example 1
According to Al in the carrier 2 O 3 With SiO 2 The mass ratio is 90: 10, collocating 5.92g of aluminum hydroxide dry glue (dry basis is 70%) with 30% hydrochloric acid solution at 50 ℃ to form transparent glue; 0.96g of white carbon black (SiO) 2 Content 90%) was dissolved in 1mol/L sodium hydroxide at 50 ℃ to give a transparent colloid. Mixing the two colloids at 70 ℃ under the condition of stirring, and adjusting the pH value to 6-8 by using 0.1mol/L NaOH solution; keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting for 6h at 600 ℃ to obtain the material a.
2.15g of ammonium metatungstate was dissolved in 5.43g of water, and the above-mentioned material a was added; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
Take 6.82g of PtCl 2 According to the molar ratio of Pt to ethylenediamine of 1: 2.1.92 g of ethylenediamine were dissolved in water and PtCl was added 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; 3.45g of CuCl are weighed out 2 According to the molar ratio of Cu to ethylenediamine of 1: 3 weighing 0.8g of ethylenediamine in water, and adding CuCl 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; mixing the two, and adding the material b; drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Example 2
According to Al in the carrier 2 O 3 With TiO 2 The mass ratio is 90: 10, collocating 5.92g of aluminum hydroxide dry glue (dry basis is 70%) with 30% hydrochloric acid solution at 50 ℃ to form transparent glue; dissolving 4.12g of tetrabutyl titanate in isopropanol, adding the tetrabutyl titanate into the aluminum colloidal sol under the condition of stirring at 70 ℃, and adjusting the pH to 6-8 by using 0.1mol/L sodium hydroxide solution; keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting at 600 ℃ for 6 h; the material a is obtained.
2.15g of ammonium metatungstate was dissolved in 5.43g of water, and the above-mentioned material a was added; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
6.82g of PtCl was taken 2 According to the molar ratio of Pt to ethylenediamine of 1: 2.1.92 g of ethylenediamine were dissolved in water and PtCl was added 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; 3.45g of CuCl are weighed out 2 According to the molar ratio of Cu to ethylenediamine of 1: 3 weighing 0.8g of ethylenediamine in water, and adding CuCl 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; mixing the two, and adding the material b; drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Example 3
According to Al in the carrier 2 O 3 ，SiO 2 And ZrO 2 The mass ratio is 70: 10: 20, 5.27g of aluminum hydroxide dry glue (dry basis 70%) was usedThe colloidal volume of 30% hydrochloric acid solution is at 50 ℃ to make it transparent colloid; 0.83g of white carbon black (SiO) 2 Content 90%) is dissolved in 1mol/L sodium hydroxide at 50 ℃ to form transparent colloid; 5.18g of zirconium nitrate was dissolved in 7.40g of water; at 70 ℃, under the condition of stirring, firstly uniformly mixing the zirconium nitrate solution and the acidified aluminum colloid solution, and then slowly adding SiO 2 A colloidal solution; after the mixture is uniformly mixed, adjusting the pH of the slurry to 6-8 by using 0.1mol/L NaOH solution; keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting for 6h at 600 ℃ to obtain the material a.
2.15g of ammonium metatungstate was dissolved in 5.43g of water, and the above-mentioned material a was added; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
6.82g of PtCl was taken 2 According to the molar ratio of Pt to ethylenediamine of 1: 2.1.92 g of ethylenediamine were dissolved in water and PtCl was added 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; 3.45g of CuCl are weighed out 2 According to the molar ratio of Cu to ethylenediamine of 1: 3 weighing 0.8g of ethylenediamine in water, and adding CuCl 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; the two were mixed and the material b described above was added. Drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Example 4
According to Al in the carrier 2 O 3 ，SiO 2 And P 2 O 5 The mass ratio is 70: 20: 10, collocating 5.27g of aluminum hydroxide dry glue (dry basis is 70%) with 30% hydrochloric acid solution at 50 ℃ to form transparent glue; 1.67g of white carbon black (SiO) 2 Content 90%) is dissolved in 1mol/L sodium hydroxide at 50 ℃ to form transparent colloid; 7.71g of trimethyl phosphate are dissolved in 11.01g of water; at 70 ℃, under the condition of stirring, firstly uniformly mixing trimethyl phosphate solution and acidified aluminum colloid solution, and then slowly adding SiO 2 A colloidal solution. After the slurry is uniformly mixed, adjusting the pH of the slurry to 6-8 by using 0.1mol/L NaOH solution;keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting for 6h at 600 ℃ to obtain the material a.
2.15g of ammonium metatungstate was dissolved in 5.43g of water, and the above-mentioned material a was added; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
6.82g of PtCl was taken 2 According to the molar ratio of Pt to ethylenediamine of 1: 2.1 g of ethylenediamine in water, PtCl 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; 3.45g of CuCl are weighed out 2 According to the molar ratio of Cu to ethylenediamine of 1: 3 weighing 0.8g of ethylenediamine in water, and adding CuCl 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; mixing the two, and adding the material b; drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Example 5
According to Al in the carrier 2 O 3 ，SiO 2 And MnO x The mass ratio is 70: 10: 20, collocating 5.27g of aluminum hydroxide dry glue (dry basis is 70%) with 30% hydrochloric acid solution at 50 ℃ to form transparent colloid; 0.83g of white carbon black (SiO) 2 Content 90%) is dissolved in 1mol/L sodium hydroxide at 50 ℃ to form transparent colloid; 4.22g of manganese chloride tetrahydrate are dissolved in 6.03g of water; at 70 ℃, under the condition of stirring, firstly uniformly mixing the zirconium nitrate solution and the acidified aluminum colloid solution, and then slowly adding SiO 2 A colloidal solution; after the mixture is uniformly mixed, adjusting the pH of the slurry to 6-8 by using 0.1mol/L NaOH solution; keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting for 6h at 600 ℃ to obtain the material a.
2.15g of ammonium metatungstate was dissolved in 5.43g of water, and the above-mentioned material a was added; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
6.82g of PtCl was taken 2 According toThe molar ratio of Pt to ethylenediamine is 1: 2.1.92 g of ethylenediamine were dissolved in water and PtCl was added 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; 3.45g of CuCl are weighed out 2 According to the molar ratio of Cu to ethylenediamine of 1: 3 weighing 0.8g of ethylenediamine in water, and adding CuCl 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; the two were mixed and the material b described above was added. Drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Example 6
According to Al in the carrier 2 O 3 With SiO 2 The mass ratio is 90: 10, collocating 5.92g of aluminum hydroxide dry glue (dry basis is 70%) with 30% hydrochloric acid solution at 50 ℃ to form transparent glue; 0.96g of white carbon black (SiO) 2 Content 90%) is dissolved in 1mol/L sodium hydroxide at 50 ℃ to form transparent colloid; mixing the two colloids at 70 ℃ under the condition of stirring, and adjusting the pH value to 6-8 by using 0.1mol/L NaOH solution; keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting for 6h at 600 ℃ to obtain the material a.
2.15g of ammonium metatungstate was dissolved in 5.43g of water, and the above-mentioned material a was added; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
6.82g of PtCl was taken 2 According to the molar ratio of Pt to ethylenediamine of 1: 2.1.92 g of ethylenediamine were dissolved in water and PtCl was added 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; 2.43g of NiCl were weighed 2 According to the molar ratio of Ni to ethylenediamine of 1: 3 weighing 0.8g of ethylenediamine in water, and mixing NiCl 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; mixing the two, and adding the material b; drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Example 7
According to Al in the carrier 2 O 3 With SiO 2 The mass ratio is 90: 10, mixing 5.92g of aluminum hydroxide dry glue(dry basis 70%) is colloidally dissolved with 30% hydrochloric acid solution at 50 ℃ to form transparent colloid; 0.96g of white carbon black (SiO) 2 Content 90%) is dissolved in 1mol/L sodium hydroxide at 50 ℃ to form transparent colloid; mixing the two colloids at 70 ℃ under the condition of stirring, and adjusting the pH value to 6-8 by using 0.1mol/L NaOH solution; keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting for 6h at 600 ℃ to obtain the material a.
Weighing 2.15g of ammonium metatungstate, dissolving the ammonium metatungstate in 5.43g of water, and adding the material a; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
Take 6.82g of PtCl 2 According to the molar ratio of Pt to ethylenediamine of 1: 2.1.92 g of ethylenediamine were dissolved in water and PtCl was added 2 Dissolving in the water solution of ethylenediamine to form a uniform solution; 2.96g of AuCl are weighed out 4 H, according to the molar ratio of Au to ethylenediamine of 1: 3 weighing 0.8g of ethylenediamine dissolved in water, and adding AuCl 4 Dissolving H in the aqueous solution of ethylenediamine to form a uniform solution; mixing the two, and adding the material b; drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Example 8
According to Al in the carrier 2 O 3 With SiO 2 The mass ratio is 90: 10, collocating 5.92g of aluminum hydroxide dry glue (dry basis is 70%) with 30% hydrochloric acid solution at 50 ℃ to form transparent glue; 0.96g of white carbon black (SiO) 2 Content 90%) is dissolved in 1mol/L sodium hydroxide at 50 ℃ to form transparent colloid; mixing the two colloids at 70 ℃ under the condition of stirring, and adjusting the pH value to 6-8 by using 0.1mol/L NaOH solution; keeping the mixed slurry at 70 ℃ for 2h under the stirring condition, and putting the slurry into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining and keeping the slurry at 130 ℃ for 12 h; filtering and washing until the sodium content in the product is less than 0.1%, and roasting for 6h at 600 ℃ to obtain the material a.
2.15g of ammonium metatungstate was dissolved in 5.43g of water, and the above-mentioned material a was added; drying at 120 ℃ for 24h, and roasting at 700 ℃ for 6h to obtain a material b.
6.82g of PtCl was taken 2 According to a Pt/hexamethylenediamine molar ratio of 1: 2.7 g of hexamethylenediamine are weighed out in water and PtCl is dissolved 2 Dissolving in a hexanediamine aqueous solution to form a uniform solution; 3.45g of CuCl are weighed out 2 According to the molar ratio of Cu to hexamethylene diamine of 1: 3.89 g of hexamethylenediamine are dissolved in water and the CuCl is added 2 Dissolving in a hexanediamine aqueous solution to form a uniform solution; mixing the two, and adding the material b; drying for 24h at the temperature of 80 ℃ in vacuum, and tabletting and forming by a tabletting machine to obtain the formed catalyst.
Comparative example 1
A shaped catalyst was prepared as in example 1, except that PtCl was adjusted 2 The amount of (b) was such that the mass content of Pt in the shaped catalyst was 2%.
Comparative example 2
A shaped catalyst was prepared as in example 1, except that in the impregnation of Pt and Cu, ethylenediamine, which is an organic auxiliary, was not added.
Comparative example 3
A shaped catalyst was prepared by following the procedure of example 1, except that the inorganic metal additive Cu was not added and the organic additive ethylenediamine was not added, as in example 1.
Performance detection
The shaped catalysts prepared in examples and comparative examples were treated at 300 ℃ under normal pressure in a mixed atmosphere of 50% hydrogen and nitrogen for 8 hours before being fed; when the temperature is reduced to 150 ℃, starting the feeding reaction; the reaction raw materials are a glycerol aqueous solution with the mass fraction of 40% and hydrogen, and the feeding volume ratio of the glycerol aqueous solution to the hydrogen is 1: 100-800 parts; the reaction temperature is 150 ℃, the reaction pressure is 5MPa, and the feeding airspeed is 2h -1 To obtain the 1, 3-propylene glycol.
The gas chromatogram of 1, 3-propanediol prepared from the shaped catalyst prepared in example 3 is shown in fig. 1, and it is understood that the catalyst provided by the present invention can prepare the desired product.
The performance of the catalyst was measured by the method of conversion (%) -mole of glycerin before reaction-mole of glycerin after reaction/mole of glycerin before reaction × 100%; the selectivity of 1, 3-propanediol was determined as the selectivity (%) ═ moles of carbon of product/moles of carbon converted to glycerol × 100%; the yield of 1, 3-propanediol was determined by the method of yield (%) ═ conversion × selectivity × 100%; the moles of glycerol and the moles of carbon in the product can be determined by gas chromatography.
The detection results are as follows:
examples Conversion (%) 1, 3-propanediol selectivity (%) Yield (%) of 1, 3-propanediol
Example 1 72.8 51.8 37.7
Example 2 76.6 44.3 33.9
Example 3 80.3 50.4 40.5
Example 4 78.6 46.5 36.5
Example 5 85.3 45.9 39.2
Example 6 82.1 46.2 37.9
Example 7 83.7 51.5 43.1
Example 8 79.7 50.8 40.5
Comparative example 1 65.5 37.1 24.3
Comparative example 2 67.3 40.3 26.5
Comparative example 3 60.1 35.3 21.2
As can be seen from the above examples and comparative example data, the addition of both the adjuvant and the high level of precious metal increased both the conversion of glycerol and the yield of 1, 3-propanediol.
The invention provides a preparation method of a high-efficiency 1, 3-propanediol catalyst by glycerol hydrogenolysis, wherein an acidic component and a metal component in the adopted catalyst are uniformly dispersed on a carrier, meanwhile, an organic auxiliary agent component is added, so that a high-content active component can be dispersed on the carrier in a highly dispersed state, and the catalyst is directly used without roasting after being formed, thereby avoiding the agglomeration of hydrogenation active components caused by multiple roasting, reducing the reaction severity, and improving the stability, the activity and the target product selectivity of the catalyst in the reaction process of high-concentration raw materials.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A catalyst, comprising:
a composite oxide support;
an acidic component;
a hydrogenation active component;
an inorganic adjuvant component;
an organic auxiliary agent.
2. The catalyst of claim 1, wherein the catalyst comprises the following composition:
50-90 wt% of a composite oxide carrier;
5 to 25 wt% of an acidic component;
3-6 wt% of a hydrogenation active component;
5-10 wt% of an inorganic auxiliary component;
the balance of organic auxiliary agent.
3. The catalyst according to claim 1, wherein the composite oxide support is selected from Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、P 2 O 5 、B 2 O 3 、MgO、MnO X 、La 2 O 3 、Ce 2 O 3 And two or more kinds of ZnO.
4. The catalyst according to claim 1, wherein the acidic component is WOx, the WOx is 5-25% by mass, and x is 2.9-3;
the hydrogenation active component is Pt.
5. The catalyst according to claim 1, wherein the inorganic auxiliary component is one or more selected from the group consisting of Cu, Ni, Co, Ag, Au, Re, and Ir.
6. The catalyst according to claim 1, wherein the organic auxiliary agent is one or more selected from ethylamine, n-propylamine, n-butylamine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, and hexylenediamine.
7. A method of preparing the catalyst of claim 1, comprising:
loading an acidic component on a composite oxide carrier to obtain a first intermediate product;
loading a hydrogenation active component, an inorganic auxiliary agent and an organic auxiliary agent on the first intermediate product to obtain a second intermediate product;
and heating the second intermediate product to obtain the catalyst.
8. The method according to claim 7, wherein the temperature of the heat treatment is 300 to 600 ℃; the time is 5-12 h; the atmosphere is a hydrogen-containing atmosphere.
9. A method for preparing 1, 3-propanediol comprising:
reacting glycerol with hydrogen under the action of a catalyst to obtain 1, 3-propylene glycol;
the catalyst is the catalyst of claim 1.
10. The method of claim 9, wherein the reaction temperature is 120 to 170 ℃ and the pressure is 1.0 to 5.0 MPa.
CN202210898330.1A 2022-07-28 2022-07-28 Catalyst and preparation method and application thereof Pending CN115041193A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210898330.1A CN115041193A (en) 2022-07-28 2022-07-28 Catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210898330.1A CN115041193A (en) 2022-07-28 2022-07-28 Catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115041193A true CN115041193A (en) 2022-09-13

Family

ID=83167615

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210898330.1A Pending CN115041193A (en) 2022-07-28 2022-07-28 Catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115041193A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101723801A (en) * 2008-10-24 2010-06-09 中国科学院大连化学物理研究所 Method for preparing 1,3-propylene glycol by directly hydrogenizing glycerol
CN102145284A (en) * 2011-01-21 2011-08-10 中国科学院大连化学物理研究所 Catalyst for preparing 1,3-propylene glycol by directly carrying out hydrotreating on glycerin and preparation method of catalyst
CN106215961A (en) * 2016-07-30 2016-12-14 青岛科技大学 Hydrobon catalyst and preparation method thereof
CN106883098A (en) * 2015-12-15 2017-06-23 中国科学院大连化学物理研究所 Application of the multiple active components catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols
CN106944050A (en) * 2017-04-14 2017-07-14 太原理工大学 A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application
CN107199036A (en) * 2017-06-05 2017-09-26 扬州大学 Supporting Pt and WOx a kind of catalyst and preparation method thereof
CN110026191A (en) * 2019-04-08 2019-07-19 珠海凯美科技有限公司 A kind of method that catalyst and hydrogenolysis of glycerin prepare 1,3- propylene glycol
CN110935447A (en) * 2018-09-25 2020-03-31 中国科学院大连化学物理研究所 Catalyst for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol aqueous solution and preparation method thereof
CN111389397A (en) * 2020-03-03 2020-07-10 浙江镇洋发展股份有限公司 Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and preparation method thereof
CN112898558A (en) * 2019-12-03 2021-06-04 中国科学院大连化学物理研究所 Method for preparing polyether amine by hydroamination of polyether polyol

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101723801A (en) * 2008-10-24 2010-06-09 中国科学院大连化学物理研究所 Method for preparing 1,3-propylene glycol by directly hydrogenizing glycerol
CN102145284A (en) * 2011-01-21 2011-08-10 中国科学院大连化学物理研究所 Catalyst for preparing 1,3-propylene glycol by directly carrying out hydrotreating on glycerin and preparation method of catalyst
CN106883098A (en) * 2015-12-15 2017-06-23 中国科学院大连化学物理研究所 Application of the multiple active components catalyst in hydrogenolysis of glycerin prepares 1,3- propane diols
CN106215961A (en) * 2016-07-30 2016-12-14 青岛科技大学 Hydrobon catalyst and preparation method thereof
CN106944050A (en) * 2017-04-14 2017-07-14 太原理工大学 A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application
CN107199036A (en) * 2017-06-05 2017-09-26 扬州大学 Supporting Pt and WOx a kind of catalyst and preparation method thereof
CN110935447A (en) * 2018-09-25 2020-03-31 中国科学院大连化学物理研究所 Catalyst for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol aqueous solution and preparation method thereof
CN110026191A (en) * 2019-04-08 2019-07-19 珠海凯美科技有限公司 A kind of method that catalyst and hydrogenolysis of glycerin prepare 1,3- propylene glycol
CN112898558A (en) * 2019-12-03 2021-06-04 中国科学院大连化学物理研究所 Method for preparing polyether amine by hydroamination of polyether polyol
CN111389397A (en) * 2020-03-03 2020-07-10 浙江镇洋发展股份有限公司 Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and preparation method thereof

Similar Documents

Publication Publication Date Title
CN105478107B (en) Application of the platinum catalyst in propane prepares propylene
CN1775361A (en) Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use
CN110947382B (en) Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof
CN103785418A (en) Cobalt tin catalyst for preparing alcohol by carboxylic acid hydrogenation
CN111992213A (en) Preparation method of core-shell catalyst for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN114029070A (en) In-situ hydrogenolysis aryl ether bond catalyst and preparation method and application thereof
CN101612559A (en) The preparation technology of a kind of solid alkali and super basic catalyst
CN113976131B (en) Heterogeneous catalyst and method for preparing 2, 5-furandimethylamine from 5-hydroxymethylfurfural
CN115041193A (en) Catalyst and preparation method and application thereof
CN110170333B (en) Catalyst for preparing ethylene from ethane in carbon dioxide atmosphere and preparation method thereof
CN111229302A (en) Cobalt-based catalyst and application thereof
CN102294251B (en) Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof
KR20130048716A (en) Catalysts and processes for the hydrogenolysis of glycerol and other organic compounds for producing polyols and propylene glycol
CN116273006A (en) Halogen modified nickel-aluminum hydrotalcite, preparation method thereof and application thereof in lignin catalytic hydrogenation
CN114618501A (en) Copper-based catalyst for preparing neopentyl glycol by hydrogenation method and preparation method thereof
CN114130416A (en) Preparation method of carbon-supported multi-metal catalyst and application of carbon-supported multi-metal catalyst in N-alkylation reaction
KR102544718B1 (en) Catalyst for Decomposing Ammonia, Method of Preparing the Same and Method for Generating Hydrogen Using the Same
CN111468112B (en) Catalyst for preparing 1, 4-cyclohexane dimethyl phthalate by selective hydrogenation of dimethyl terephthalate and preparation method thereof
CN115155627A (en) Multi-component composite catalyst for preparing 1, 3-propylene glycol by hydrogenating methyl 3-hydroxypropionate and preparation method thereof
CN1363544A (en) Impregnation method for preparing 3-hydroxypropanal as hydrocatalyst
CN107737592B (en) Preparation method and application of ordered mesoporous carbon catalyst inlaid with nickel particles
CN113289637A (en) Hydrotalcite-like catalyst, preparation method and application thereof
CN112973689B (en) Acetate hydrogenation catalyst, and preparation method and application thereof
CN115779925B (en) Catalyst composition for preparing ethylene glycol from biomass raw material, and preparation method and application thereof
CN111036250B (en) Phosphorus-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method

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
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Zhang Fengqi

Inventor after: Li Shuang

Inventor after: Hou Keke

Inventor after: Wang Dongchao

Inventor after: Shi Huibing

Inventor after: Chen Chen

Inventor after: Zhao Deming

Inventor after: Wang Yaowei

Inventor after: Luan Bo

Inventor before: Li Shuang

Inventor before: Hou Keke

Inventor before: Wang Dongchao

Inventor before: Shi Huibing

Inventor before: Chen Chen

Inventor before: Zhao Deming

Inventor before: Zhang Fengqi

Inventor before: Wang Yaowei

Inventor before: Luan Bo