CN109590013A - A kind of biomass loaded catalyst and preparation method thereof adding hydrogen for open loop - Google Patents

A kind of biomass loaded catalyst and preparation method thereof adding hydrogen for open loop Download PDF

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Publication number
CN109590013A
CN109590013A CN201811574650.1A CN201811574650A CN109590013A CN 109590013 A CN109590013 A CN 109590013A CN 201811574650 A CN201811574650 A CN 201811574650A CN 109590013 A CN109590013 A CN 109590013A
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open loop
loaded catalyst
biomass
adding hydrogen
preparation
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CN109590013B (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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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 biomass transformation technology field more particularly to a kind of biomass loaded catalysts and preparation method thereof for adding hydrogen for open loop.A kind of biomass loaded catalyst adding hydrogen for open loop, is A-WO3/ MCM-41 loaded catalyst, wherein component A is one of Pt element and Rh element.A kind of preparation method for the biomass loaded catalyst adding hydrogen for open loop, it include: that ammonium metatungstate and citric acid wiring solution-forming are added to the medium volume impregnation of carrier MCM-41, it is impregnated again with the soluble salt solutions of A after first is dry, first roasts, the biomass loaded catalyst for obtaining adding for open loop hydrogen is roasted through the second drying and second.A kind of biomass loaded catalyst and preparation method thereof adding hydrogen for open loop provided by the invention, the method stability for solving existing synthesis 1,5-PD is poor, higher cost and the disagreeableness technical problem of environment.

Description

A kind of biomass loaded catalyst and preparation method thereof adding hydrogen for open loop
Technical field
The invention belongs to biomass transformation technology field more particularly to a kind of biomass support types for adding hydrogen for open loop Catalyst and preparation method thereof.
Background technique
The increasingly reduction of fossil resources and environmental problem are prominent, are badly in need of developing new renewable resource.Biomass refers to benefit The various organisms generated with big gas and water, soil etc. by photosynthesis, i.e., all it is lived can grow it is organic Substance is commonly referred to as biomass.It includes plant, animal and microorganism.And biomass master refers in agriculture and forestry production process except grain The lignocellulosics such as stalk, trees other than food, fruit.It is wide with distribution, reserves are big, environmental-friendly, especially greenhouse gas The advantages that body zero-emission.And it can uniquely be converted into the renewable energy of gas, liquid and solid fuel simultaneously, it is at present most Has one of the new energy that can replace fossil energy of potentiality.Biomass derivatives furfural is important plateform molecules, can lead to It crosses hemicellulose to be made, 1,5-PD can be prepared by selective hydrogenation open loop.1,5-PD is that a kind of carbon containing odd number is former The linear diols of son and diprimary, colorless viscous shape liquid have bitter taste, and density is 0.994 (20 DEG C), and fusing point is -16 DEG C, boiling point be 239 DEG C (101.3KPa), 130 DEG C of flash-point, be widely used in manufacture polyurethane, polyester, plasticizer, jetted ink or The products such as ink, coating and fragrance.Currently, having in the prior art about the synthetic method of 1,5-PD: cyclopentadiene room temperature Epoxypentenal is made in photooxidation under normal pressure, then adds hydrogen that 1,5-PD is made under conditions of 70-100 DEG C, 7MPa.By In the design and stable product quality of photooxidation reaction device the problems such as, exploitation industrialized production receives considerable restraint.
Chinese patent application CN1565728A discloses one kind with 1,5- dimethyl glutarate for raw material, using copper zinc-aluminium Catalyst is 150-350 DEG C in temperature, the method that catalysis prepares 1,5-PD under conditions of pressure is 3-5MPa.This method Purifying plus hydrogen are made after the raw material used is esterified by 1,5- glutaric acid, and reaction process is long and glutaric acid derives from petroleum, and environment is not It is friendly.
Chinese patent application CN102942448A discloses one kind using tetrahydrofurfuryl alcohol as raw material, using the Chinese parasol tree zirconium of Supported Pt Nanoparticles Composite oxides are catalyst, are 100-150 DEG C in temperature, pressure prepares the side of 1,5-PD under conditions of being 1-5MPa Method, and absolutely not refine 1,5-PD.
Document Catalysis Today 245 (2015) 93-99 is reported with Ir-VOX/SiO2For catalyst, in temperature It is 60-120 DEG C, the method that catalysis prepares 1,5-PD under conditions of the 1-6MPa of pressure position.This method uses supercritical CO2 For solvent, cost is improved, and absolutely not refines 1,5-PD.
Therefore, the method stability of existing synthesis 1,5-PD is poor, higher cost and environment is unfriendly becomes Those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
The present invention provides a kind of biomass loaded catalysts and preparation method thereof for adding hydrogen for open loop, solve The method stability of existing synthesis 1,5-PD is poor, higher cost and the disagreeableness technical problem of environment.
The present invention provides a kind of biomass loaded catalysts for adding hydrogen for open loop, are A-WO3/ MCM-41 is negative Supported catalyst, wherein component A is one of Pt element and Rh element.
Preferably, the load capacity of elements A is 0.5-10%, WO3Mass percentage be 5-60%.
The present invention also provides a kind of preparation methods of biomass loaded catalyst for adding hydrogen for open loop, comprising:
Ammonium metatungstate and citric acid wiring solution-forming are added to the medium volume impregnation of carrier MCM-41, through it is first dry, the It is impregnated again with the soluble salt solutions of A after one roasting, obtains the biomass for adding hydrogen for open loop through the second drying and the second roasting Loaded catalyst；
Wherein component A is one of Pt element and Rh element.
Preferably, the described first dry temperature is 60-120 DEG C.
Preferably, the temperature of first roasting is 300-600 DEG C.
Preferably, by ammonium metatungstate and citric acid wiring solution-forming specifically include by ammonium metatungstate and citric acid by W element With citric acid molar ratio 1:1 wiring solution-forming.
Preferably, the described second dry temperature is 60-120 DEG C.
Preferably, the temperature of second roasting is 300-600 DEG C.
Open loop provided by the invention adds in the biomass loaded catalyst of hydrogen, wherein 5%Pt-WO3In/MCM-41 when WO3Load capacity be 30% when show best activity, work as WO3When load capacity is below or above 20%, conversion ratio is different The decline of degree, therefore explanation works as WO3Load capacity be 20% when, WO3Dispersion degree be best.5%Rh-20%WO3/ MCM-41 reaches 84.4% and 90.8% in 170 DEG C of reaction 12h, conversion ratio and selectivity.
Specific embodiment
The embodiment of the invention provides a kind of biomass loaded catalyst and preparation method thereof for adding hydrogen for open loop, The method stability for solving existing synthesis 1,5-PD is poor, higher cost and the disagreeableness technical problem of environment.
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with this hair Bright embodiment, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that implementation disclosed below Example is only a part of the embodiment of the present invention, and not all embodiment.Based on the embodiments of the present invention, this field is common Technical staff's all other embodiment obtained without making creative work belongs to what the present invention protected Range.
In order to further illustrate the present invention, following embodiment is enumerated, but is not intended to limit the scope of the invention.
The present invention uses quantitative analysis by gas chromatography, and the analysis instrument used is Agilent 7820A, chromatographic column DB- 624, sample volume: 0.5uL；Flow velocity: 5mL/min；Column temperature: 150 DEG C~300 DEG C, 10 DEG C/min；Carrier gas: N2；Assist gas: O2,H2 Room temperature: 25 DEG C.The raw materials used embodiment of the present invention is commercial goods.
Embodiment 1
First business MCM-41 is pre-processed, 4h is roasted at 550 DEG C and removes template and water, then 1g is claimed to be used for Dipping weighs ammonium metatungstate and citric acid 0.0531g and 0.0456g wiring solution-forming as impregnating in carrier, after standing 4h respectively The dry moisture of 60 DEG C of stirrings is placed in tube furnace 400 DEG C of roasting 2h in a nitrogen atmosphere, is cooled to room temperature and is placed on after dry 550 DEG C of roasting 4h, obtain 20%WO in Muffle furnace3/MCM-41.It weighs and is impregnated according to the platinum acid chloride solution of certain metering ratio The 20%WO prepared3/ MCM-41 stands the dry moisture of 60 DEG C of stirrings after 4h, after dry, is placed in 400 DEG C of roastings in Muffle furnace 2h is burnt, 5%Pt-5%WO is obtained3/MCM-41。
Embodiment 2
Ammonium metatungstate is weighed respectively and citric acid 0.1062g and 0.0921g are impregnated in MCM-41, other conditions and implementation Example 1 is identical, prepares 5%Pt-10%WO3/MCM-41。
Embodiment 3
Ammonium metatungstate is weighed respectively and citric acid 0.2125g and 0.1824g are impregnated in MCM-41, other conditions and implementation Example 1 is identical, prepares 5%Pt-20%WO3/MCM-41。
Embodiment 4
Ammonium metatungstate is weighed respectively and citric acid 0.3186g and 0.2736g are impregnated in MCM-41, other conditions and implementation Example 1 is identical, prepares 5%Pt-30%WO3/MCM-41。
Embodiment 5
Ammonium metatungstate is weighed respectively and citric acid 0.425g and 0.3648g are impregnated in MCM-41, other conditions and embodiment 1 is identical, prepares 5%Pt-40%WO3/MCM-41。
Embodiment 6
Ammonium metatungstate is weighed respectively and citric acid 0.6375g and 0.5472g are impregnated in MCM-41, other conditions and implementation Example 1 is identical, prepares 5%Pt-60%WO3/MCM-41。
Embodiment 7
It weighs and is impregnated in the 20%WO prepared according to the rhodium chloride solution of certain metering ratio3/ MCM-41, other Part is same as Example 1, prepares 5%Rh-20%WO3/MCM-41。
Embodiment 8
Evaluating catalyst of the invention carries out in batch reactor, and experimentation is as follows: first by 0.25g catalyst 350 DEG C of reductase 12 h at hydrogen flow rate 50mL/min.Then it is taken after 5% tetrahydrofurfuryl alcohol aqueous solution 20g, 200 DEG C of reaction 12h Fluid sample out carries out quantitative analysis to resulting reaction solution using gas-chromatography, as a result as follows:
From result above it may be concluded that 5%Pt-WO3Work as WO in/MCM-413Load capacity be 30% when show most Good activity, works as WO3When load capacity is below or above 20%, conversion ratio has different degrees of decline, therefore explanation works as WO3's When load capacity is 20%, WO3Dispersion degree be best.5%Rh-20%WO3/ MCM-41 is in 170 DEG C of reaction 12h, conversion ratio Reach 84.4% and 90.8% with selectivity.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although reference Invention is explained in detail for previous embodiment, those skilled in the art should understand that: it still can be right Technical solution documented by foregoing embodiments is modified or equivalent replacement of some of the technical features；And this It modifies or replaces, the spirit and model of technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution It encloses.

Claims (8)

1. a kind of biomass loaded catalyst for adding hydrogen for open loop, which is characterized in that it is A-WO3/ MCM-41 support type is urged Agent, wherein component A is one of Pt element and Rh element.
2. the biomass loaded catalyst according to claim 1 for adding hydrogen for open loop, which is characterized in that elements A Load capacity is 0.5-10%, WO3Mass percentage be 5-60%.
3. a kind of preparation method for the biomass loaded catalyst for adding hydrogen for open loop characterized by comprising
Ammonium metatungstate and citric acid wiring solution-forming are added to the medium volume impregnation of carrier MCM-41, through first dry, the first roasting It is impregnated again with the soluble salt solutions of A after burning, through the second dry roast with second obtains that the biomass of hydrogen is added to load for open loop Type catalyst；
Wherein component A is one of Pt element and Rh element.
4. the preparation method of the biomass loaded catalyst according to claim 3 for adding hydrogen for open loop, feature exist In the described first dry temperature is 60-120 DEG C.
5. the preparation method of the biomass loaded catalyst according to claim 3 for adding hydrogen for open loop, feature exist In the temperature of first roasting is 300-600 DEG C.
6. the preparation method of the biomass loaded catalyst according to claim 3 for adding hydrogen for open loop, feature exist In, by ammonium metatungstate and citric acid wiring solution-forming specifically include by ammonium metatungstate and citric acid by W element and citric acid mole Than 1:1 wiring solution-forming.
7. the preparation method of the biomass loaded catalyst according to claim 1 for adding hydrogen for open loop, feature exist In the described second dry temperature is 60-120 DEG C.
8. the preparation method of the biomass loaded catalyst according to claim 1 for adding hydrogen for open loop, feature exist In the temperature of second roasting is 300-600 DEG C.
CN201811574650.1A 2018-12-21 2018-12-21 Biomass supported catalyst for ring-opening hydrogenation and preparation method thereof Active CN109590013B (en)

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Citations (5)

* 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
CN104507896A (en) * 2012-04-27 2015-04-08 纳幕尔杜邦公司 Production of alpha, omega-diols
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

Patent Citations (5)

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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
CN104507896A (en) * 2012-04-27 2015-04-08 纳幕尔杜邦公司 Production of alpha, omega-diols
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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Title
SHIXIANG FENG，ET AL: ""Selective hydrogenolysis of tetrahydrofurfuryl alcohol on Pt/WO3/ZrO2 catalysts: Effect of WO3 loading amount on activity"", 《CATALYSIS TODAY》 *
SHUICHI KOSO，ET AL: ""Promoting effect of Mo on the hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Rh/SiO2"", 《JOURNAL OF CATALYSIS》 *
ZHIQIANGWANG，ET AL: ""Chemoselective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Ir-MoOx/SiO2 catalyst"", 《JOURNAL OF ENERGY CHEMISTRY》 *
滕宏程: ""钨基催化剂制备及其催化纤维素加氢反应研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

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