CN109590013B - Biomass supported catalyst for ring-opening hydrogenation and preparation method thereof - Google Patents

Biomass supported catalyst for ring-opening hydrogenation and preparation method thereof Download PDF

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CN109590013B
CN109590013B CN201811574650.1A CN201811574650A CN109590013B CN 109590013 B CN109590013 B CN 109590013B CN 201811574650 A CN201811574650 A CN 201811574650A CN 109590013 B CN109590013 B CN 109590013B
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ring
supported catalyst
biomass
opening hydrogenation
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CN109590013A (en
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王铁军
匡碧锋
仇松柏
秦延林
马宇飞
张浅
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Guangdong University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/043—Noble metals
    • 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

Abstract

The invention belongs to the technical field of biomass conversion, and particularly relates to a biomass supported catalyst for ring-opening hydrogenation and a preparation method thereof. A biomass supported catalyst for ring-opening hydrogenation is A-WO3The component A is one of Pt element and Rh element. A preparation method of a biomass supported catalyst for ring-opening hydrogenation comprises the following steps: preparing ammonium metatungstate and citric acid into a solution, adding the solution into a carrier MCM-41 for equal volume impregnation, performing first drying and first roasting, then impregnating with a soluble salt solution of A, and performing second drying and second roasting to obtain the biomass supported catalyst for ring-opening hydrogenation. The invention provides a biomass supported catalyst for ring-opening hydrogenation and a preparation method thereof, which solve the technical problems of poor stability, high cost and environmental friendliness of the existing method for synthesizing 1, 5-pentanediol.

Description

Biomass supported catalyst for ring-opening hydrogenation and preparation method thereof
Technical Field
The invention belongs to the technical field of biomass conversion, and particularly relates to a biomass supported catalyst for ring-opening hydrogenation and a preparation method thereof.
Background
Due to the diminishing petrochemical resources and the obvious environmental problems, new renewable resources are urgently needed to be developed. Biomass refers to various organisms produced by photosynthesis using the atmosphere, water, land, and the like, and all living organic substances that can grow are generally called biomass. It includes plants, animals and microorganisms. The biomass mainly refers to lignocellulose such as straws, trees and the like except grains and fruits in the production process of agriculture and forestry. The method has the advantages of wide distribution, large reserve, environmental protection, zero emission of greenhouse gases and the like. And the renewable energy which can be only converted into gas, liquid and solid fuels at the same time is one of the most potential new energy sources which can replace fossil energy at present. The biomass derivative furfural is an important platform molecule, can be prepared from hemicellulose, and can be used for preparing 1, 5-pentanediol through selective hydrogenation ring opening. 1, 5-pentanediol is a linear diol containing odd number of carbon atoms and diprimary hydroxyl, is colorless and viscous liquid, has the bitter taste, the density of 0.994(20 ℃), the melting point of-16 ℃, the boiling point of 239 ℃ (101.3KPa) and the flash point of 130 ℃, and is widely used for manufacturing products such as polyurethane, polyester, plasticizer, ink-jet ink or ink, paint, perfume and the like. At present, the prior art has the following methods for synthesizing 1, 5-pentanediol: the cyclopentadiene is photooxidized at normal temperature and normal pressure to prepare the cyclopentene oxide, and then the 1, 5-pentanediol is prepared by hydrogenation under the conditions of 70-100 ℃ and 7 MPa. Due to the problems of the design of the photo-oxidation reactor, the stability of the product quality and the like, the development of industrial production is greatly limited.
Chinese patent application CN1565728A discloses a method for preparing 1, 5-pentanediol by using 1, 5-dimethyl glutarate as a raw material and adopting a copper-zinc-aluminum catalyst under the conditions of temperature of 150-350 ℃ and pressure of 3-5 MPa. The raw material used by the method is prepared by purifying and hydrogenating the esterified 1, 5-glutaric acid, the reaction process is long, and glutaric acid is derived from petroleum and is not environment-friendly.
Chinese patent application CN102942448A discloses a method for preparing 1, 5-pentanediol by using tetrahydrofurfuryl alcohol as a raw material and platinum-loaded zirconium composite oxide as a catalyst under the conditions of temperature of 100-150 ℃ and pressure of 1-5MPa, and 1, 5-pentanediol is not refined at all.
The Catalysis Today 245(2015) 93-99 document reports Ir-VOX/SiO2Is used as a catalyst, and the method for preparing the 1, 5-pentanediol is catalyzed under the conditions that the temperature is 60-120 ℃ and the pressure is 1-6 MPa. The method uses supercritical CO2Is a solvent, increases the cost, and completely does not purify the 1, 5-pentanediol.
Therefore, the existing method for synthesizing 1, 5-pentanediol has poor stability, high cost and environmental unfriendliness, which is a technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention provides a biomass supported catalyst for ring-opening hydrogenation and a preparation method thereof, and solves the technical problems of poor stability, high cost and environmental friendliness of the existing method for synthesizing 1, 5-pentanediol.
The invention provides a biomass supported catalyst for ring-opening hydrogenation, which is A-WO3The component A is one of Pt element and Rh element.
Preferably, the loading of element A is 0.5-10%, WO3The mass percentage of the components is 5-60%.
The invention also provides a preparation method of the biomass supported catalyst for ring-opening hydrogenation, which comprises the following steps:
preparing ammonium metatungstate and citric acid into a solution, adding the solution into a carrier MCM-41 for equal volume impregnation, performing first drying and first roasting, then impregnating the solution with a soluble salt solution A, and performing second drying and second roasting to obtain a biomass supported catalyst for ring-opening hydrogenation;
wherein the component A is one of Pt element and Rh element.
Preferably, the temperature of the primary drying is 60 to 120 ℃.
Preferably, the temperature of the first roasting is 300-600 ℃.
Preferably, the preparation of the solution from ammonium metatungstate and citric acid specifically comprises the following steps of mixing ammonium metatungstate and citric acid according to the molar ratio of W element to citric acid of 1: 1 preparing a solution.
Preferably, the temperature of the second drying is 60 to 120 ℃.
Preferably, the temperature of the second roasting is 300-600 ℃.
In the biomass supported catalyst for ring-opening hydrogenation provided by the invention, 5 percent of Pt-WO is contained3WO in MCM-413Shows the best activity when the loading is 30%, and when WO is used3Load amount is less thanOr above 20%, the conversion rate decreases to various degrees, thus indicating that when WO is used3At a loading of 20%, WO3The dispersion of (A) is the best. 5% Rh-20% WO3The reaction of MCM-41 at 170 deg.c for 12 hr results in 84.4% conversion rate and 90.8% selectivity.
Detailed Description
The embodiment of the invention provides a biomass supported catalyst for ring-opening hydrogenation and a preparation method thereof, and solves the technical problems of poor stability, high cost and unfriendly environment of the existing method for synthesizing 1, 5-pentanediol.
In order to make the objects, features and advantages of the present invention more obvious and understandable, the embodiments of the present invention will be described in detail and fully with reference to the accompanying drawings. 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.
To further illustrate the invention, the following examples are set forth without limiting the scope of the invention.
The invention adopts gas chromatography for quantitative analysis, the adopted analytical instrument is Agilent 7820A, the chromatographic column is DB-624, the sample injection amount is as follows: 0.5 uL; flow rate: 5 mL/min; column temperature: 150-300 ℃ and 10 ℃/min; carrier gas: n is a radical of2(ii) a Auxiliary gas: o is2,H2Room temperature: at 25 ℃. The raw materials used in the examples of the present invention are all commercially available products.
Example 1
Firstly, carrying out pretreatment on commercial MCM-41, roasting for 4 hours at 550 ℃ to remove a template agent and water, weighing 1g for impregnation, respectively weighing 0.0531g and 0.0456g of ammonium metatungstate and citric acid to prepare solutions, impregnating in a carrier, standing for 4 hours, stirring at 60 ℃ to dry water, drying, roasting in a tubular furnace at 400 ℃ for 2 hours under nitrogen atmosphere, cooling to room temperature, roasting in a muffle furnace at 550 ℃ for 4 hours to obtain 20% WO3/MCM-41. Weighing chloroplatinic acid solution according to a certain metering ratioImpregnating in prepared 20% WO3MCM-41, standing for 4 hours, stirring at 60 ℃ to dry water, drying, and roasting in a muffle furnace at 400 ℃ for 2 hours to obtain 5% Pt-5% WO3/MCM-41。
Example 2
0.1062g and 0.0921g of ammonium metatungstate and citric acid were weighed and impregnated in MCM-41, and 5% Pt-10% WO was prepared under the same conditions as in example 13/MCM-41。
Example 3
0.2125g and 0.1824g of ammonium metatungstate and citric acid were respectively weighed and impregnated in MCM-41 under the same conditions as in example 1 to prepare 5% Pt-20% WO3/MCM-41。
Example 4
Separately weighing 0.3186g and 0.2736g of ammonium metatungstate and citric acid, soaking in MCM-41 under the same conditions as in example 1 to prepare 5% Pt-30% WO3/MCM-41。
Example 5
0.425g and 0.3648g of ammonium metatungstate and citric acid were weighed and impregnated in MCM-41, and 5% Pt-40% WO was prepared under the same conditions as in example 13/MCM-41。
Example 6
0.6375g and 0.5472g of ammonium metatungstate and citric acid were weighed and impregnated in MCM-41, and 5% Pt-60% WO was prepared under the same conditions as in example 13/MCM-41。
Example 7
Weighing rhodium trichloride solution according to a certain metering ratio, and soaking the rhodium trichloride solution in the prepared 20% WO3MCM-41, other conditions the same as in example 1, preparation of 5% Rh-20% WO3/MCM-41。
Example 8
The evaluation of the catalyst of the invention is carried out in a batch reactor, and the experimental process is as follows: 0.25g of catalyst was first reduced at 350 ℃ for 2h under a hydrogen flow of 50 mL/min. Then, 20g of a 5% tetrahydrofurfuryl alcohol aqueous solution was reacted at 200 ℃ for 12 hours, and a liquid sample was taken out, and the obtained reaction solution was quantitatively analyzed by gas chromatography, and the results were as follows:
Figure GDA0001982702450000041
from the above results, it can be concluded that: 5% Pt-WO3WO in MCM-413Shows the best activity when the loading is 30%, and when WO is used3At loadings below or above 20%, the conversion decreases to varying degrees, thus indicating that when WO is used3At a loading of 20%, WO3The dispersion of (A) is the best. 5% Rh-20% WO3The reaction of MCM-41 at 170 deg.c for 12 hr results in 84.4% conversion rate and 90.8% selectivity.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (6)

1. The application of biomass supported catalyst for ring-opening hydrogenation is characterized in that the catalyst is A-WO3The MCM-41 supported catalyst comprises a component A, a component B and a component B, wherein the component A is one of a Pt element and an Rh element, the supported amount of the element A is 5 percent, and WO3The mass percentage content of (A) is 20%;
the catalyst is applied to catalyzing the ring opening hydrogenation of the tetrahydrofurfuryl alcohol aqueous solution to selectively prepare 1, 5-pentanediol;
the preparation method of the catalyst comprises the following steps: preparing ammonium metatungstate and citric acid into a solution, adding the solution into a carrier MCM-41 for equal volume impregnation, performing first drying and first roasting, then impregnating with a soluble salt solution of A, and performing second drying and second roasting to obtain the biomass supported catalyst for ring-opening hydrogenation.
2. The use of a biomass-supported catalyst for ring-opening hydrogenation according to claim 1, wherein the temperature of the first drying is 60-120 ℃.
3. The application of the biomass-supported catalyst for ring-opening hydrogenation as claimed in claim 1, wherein the temperature of the first calcination is 300-600 ℃.
4. The use of the biomass-supported catalyst of claim 1 for ring-opening hydrogenation, wherein the step of preparing a solution of ammonium metatungstate and citric acid specifically comprises preparing a solution of ammonium metatungstate and citric acid in a molar ratio of 1: 1W element to citric acid.
5. The use of a biomass-supported catalyst for ring-opening hydrogenation according to claim 1, wherein the temperature of the second drying is 60-120 ℃.
6. The application of the biomass-supported catalyst for ring-opening hydrogenation as claimed in claim 1, wherein the temperature of the second calcination is 300-600 ℃.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008143798A (en) * 2006-12-06 2008-06-26 National Institute Of Advanced Industrial & Technology Method for preparing propanediol
CN102911011A (en) * 2011-08-03 2013-02-06 中国科学院大连化学物理研究所 Method for preparing 1,5-pentadiol by means of selective hydrogenolysis of tetrahydrofurfuryl alcohol
CN102942448A (en) * 2012-12-10 2013-02-27 南京工业大学 Method for continuously preparing 1, 5-pentanediol from tetrahydrofurfuryl alcohol
CN108187674A (en) * 2016-12-08 2018-06-22 中国科学院大连化学物理研究所 Tantalum base catalyst and its application in the reaction of tetrahydrofurfuryl alcohol 1,5- pentanediols

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US9018423B2 (en) * 2012-04-27 2015-04-28 E I Du Pont De Nemours And Company Production of alpha, omega-diols

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Publication number Priority date Publication date Assignee Title
JP2008143798A (en) * 2006-12-06 2008-06-26 National Institute Of Advanced Industrial & Technology Method for preparing propanediol
CN102911011A (en) * 2011-08-03 2013-02-06 中国科学院大连化学物理研究所 Method for preparing 1,5-pentadiol by means of selective hydrogenolysis of tetrahydrofurfuryl alcohol
CN102942448A (en) * 2012-12-10 2013-02-27 南京工业大学 Method for continuously preparing 1, 5-pentanediol from tetrahydrofurfuryl alcohol
CN108187674A (en) * 2016-12-08 2018-06-22 中国科学院大连化学物理研究所 Tantalum base catalyst and its application in the reaction of tetrahydrofurfuryl alcohol 1,5- pentanediols

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