CN107970934A - A kind of furfural hydrogenation 2- methylfurans method for preparing catalyst and catalyst - Google Patents

A kind of furfural hydrogenation 2- methylfurans method for preparing catalyst and catalyst Download PDF

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Publication number
CN107970934A
CN107970934A CN201610921945.6A CN201610921945A CN107970934A CN 107970934 A CN107970934 A CN 107970934A CN 201610921945 A CN201610921945 A CN 201610921945A CN 107970934 A CN107970934 A CN 107970934A
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Prior art keywords
catalyst
absolute ethyl
ethyl alcohol
cuo
carrier
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苗小培
者东梅
冯海强
杨化浩
武鹏
刘玉春
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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
    • B01J23/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of 2 methylfuran method for preparing catalyst of furfural hydrogenation system.Including：1) first absolute ethyl alcohol and polyethylene glycol are mixed and then ethyl orthosilicate is added in uniformly mixed absolute ethyl alcohol polyethylene glycol/deionized water/ammonium hydroxide and reaction is hydrolyzed, centrifuged, obtain carrier S iO2；2) carrier S iO2Mix with CuO precursor solutions, alkaline solution, add in the lump in reaction flask, the pH value for controlling reaction is 58, continuously stir 0.5 3.5 it is small when, CuO SiO will be made after precipitation filtering, dry, roasting2Catalyst fines.The preparation method of the present invention is simple, and catalyst is pollution-free, and composition is simple, catalytic activity and high selectivity, service life length.

Description

A kind of furfural hydrogenation 2- methylfurans method for preparing catalyst and catalyst
Technical field
The present invention relates to 2- methylfuran preparation method fields, further say, be to be related to a kind of furfural hydrogenation 2- first Base furans method for preparing catalyst and catalyst.
Background technology
2- methylfurans are a kind of important organic synthesis intermediates, can be used as solvent, are widely used in synthesis medicine, agriculture Medicine and solution polymerization process.The production method of 2- methylfurans have it is a variety of, since furfural catalytic hydrogenation method yield is high and raw material It is easy to get, therefore actual industrial production all uses this method.About 150,000 tons or so of China's furfural annual output, but domestic dosage is seldom, More than 90% inexpensively exports, and economic benefit is relatively low.Therefore, develop and improve furfural deep process technology needs to complying with international market , to make full use of renewable resource, realize that higher economic benefit is particularly significant.
2- methylfurans are that only the carbonyl of furfural is made choice to be hydrogenated with obtained product, mainly using hydrogenation capability compared with Weak Cu series catalysts.The catalyst that production 2- methylfurans use both at home and abroad at present mainly has three classes：The first kind is chromous acid Copper catalyst, although catalyst activity is preferably, heat conductivility difference easily causes reaction " temperature runaway ", sintering of catalyst, crystal grain Aggregation, activity reduces, stability is poor, and contains Cr+6Ionic soil is serious；Second class copper alloy catalyst, mainly Cu-Al Alloy, such catalyst choice is good, but prepares difficulty, of high cost, and activity is unstable, needs separating for several times to regenerate；Three classes are Metal oxide catalyst, main component are metal oxide CuO, Cr2O3、Al2O3, BaO, ZnO etc. and graphite it is mixed using machinery It is legal compressing obtained.
Recent domestic adds the alkali or alkaline earth metal such as Cr, Ca, Ba, Mg, Zn as helping by active component of Cu The research that loaded catalyst is made in catalyst is Main way, such as Chinese patent CN101422731A, CN The numerous patents such as 104383929A, CN 103007942 are all that CuO is carried on carrier S iO2Or Al2O3On, but gold must be added Belong to auxiliary agent to improve the dispersiveness of catalyst, on the one hand complicate catalyst composition, on the other hand some metals can bring dirt Dye.Therefore the key for improving furfural hydrogenation production technology should be inexpensive, efficient, the free of contamination environment-friendly catalyst of exploitation, this To development China using the renewable resources such as agricultural and sideline product as raw material fine chemicals industry, promote Green Chemistry process technology Develop significant.
The content of the invention
To solve produced problem in the prior art, the present invention provides a kind of furfural hydrogenation 2- methylfuran catalyst Preparation method and catalyst.Preparation method is simple, and catalyst is pollution-free, and composition is simple, and catalytic activity and high selectivity, use the longevity Life length.
In order to overcome the problems such as 2- methylfurans catalyst contains Cr pollutions, stability is poor, yield is not high in the prior art, this Invention provides a kind of CuO and is carried on single dispersing SiO2The method for preparing catalyst of particle, gained CuO catalyst crystallite dimensions are small (50-70nm), catalytic activity are high；(metallic copper dispersion degree uses N to dispersion degree up to 0.62The chemiadsorption measure of O), stability By force.
An object of the present invention is to provide a kind of furfural hydrogenation 2- methylfuran method for preparing catalyst.
The described method includes：
1) first by absolute ethyl alcohol and polyethylene glycol mix then by ethyl orthosilicate be added to uniformly mixed absolute ethyl alcohol- Reaction is hydrolyzed in polyethylene glycol/deionized water/ammonium hydroxide, centrifuges, obtains carrier S iO2；
Absolute ethyl alcohol and polyethylene glycol volume ratio are：3:1~1:2；
The volume ratio of absolute ethyl alcohol-polyethylene glycol/deionized water/ammonium hydroxide is：100:2:(1~6)；
The volume ratio of absolute ethyl alcohol/polyethylene glycol and ethyl orthosilicate is 100：(1~4)；
2) carrier S iO2Mix with CuO precursor solutions, alkaline solution, add in the lump in reaction flask, control the pH of reaction Be worth for 5-8, continuously stir 0.5-3.5 it is small when, CuO-SiO will be made after precipitation filtering, dry, roasting2Catalyst fines；
Carrier S iO2Mass ratio with CuO precursor solutions, alkaline solution is：(6~20):(5~15):(1~2)；It is preferred that For (8~17):(6~13):(1~2).
It is preferred that：
In step (1), reaction is hydrolyzed in water bath with thermostatic control, water bath with thermostatic control temperature is 25 DEG C~80 DEG C, reaction time 6- 24h, preferably 12h.
Centrifugation rotating speed is 3000~10000rpm, preferably 6500rpm.
The copper oxide precursor solution is copper nitrate, copper chloride or copper sulphate；
The alkaline solution is ammonium hydroxide, ammonium carbonate or sodium carbonate
Preparation method further includes：
3) graphite is added to be uniformly mixed after lubricating, compression molding.
Key of the present invention is by preparing single dispersing carrier, improving the dispersiveness of CuO, effectively increase catalyst specific surface Product, so as to improve furfural conversion ratio and 2- methylfurans selectivity.In addition the addition of carrier can improve the machinery of catalyst by force Degree and wearability, extend its service life.
The second object of the present invention is to provide a kind of catalyst prepared by the method.
CuO contents are 20-35wt%, carrier S iO2Content is 65-80wt%；
The present invention product technology scheme be：
One) carrier S iO is prepared2
Ethyl orthosilicate is added in uniformly mixed deionized water/absolute ethyl alcohol-PEG/ ammonium hydroxide reaction is hydrolyzed, Up to carrier S iO2。
Two) catalyst of uO containing support C is prepared
Take the carrier S iO of a certain amount of above-mentioned preparation2Mixed with CuO precursor solutions, alkaline solution, add reaction flask in the lump In, the pH value for controlling reaction is 5-8, continuously stir 0.5-3.5 it is small when, CuO catalysis will be made after precipitation filtering, dry, roasting Agent powder, then adds graphite to be uniformly mixed after lubricating, compression molding.
The copper oxide precursor solution is copper nitrate, copper chloride, copper sulphate, is preferably copper nitrate.
The alkaline solution is ammonium hydroxide, ammonium carbonate, sodium carbonate, is preferably ammonium hydroxide.
In contrast test, carrier elects Ludox, powder silica as.
The essential distinction of the present invention and the prior art are：The present invention provides a kind of pollution-free, high activity, high receipts The CuO catalyst of rate, stabilization, composition are simple.
The beneficial effects of the invention are as follows：The mechanical strength of catalyst and wearability are improved by means of carrier, extending it makes With the service life, active component CuO by being carried on well dispersed Nano-meter SiO_2 by the catalyst2On, wherein CuO contents are 20- 35wt%, carrier S iO2Content is 65-80wt%, and specific surface area of catalyst can be improved under the conditions of without other auxiliary agents, enhancing Catalytic activity and selectivity, prolong the service life.
The present invention has following advantage compared with prior art：
1. the catalyst is free of toxicity chromium, environmentally protective.
2. the catalyst furfural conversion ratio is 100%, 2- methylfurans high selectivity up to 94.5%.
3. the catalyst is CuO-SiO2, composition is simple, is easy to industrial applications.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
Carrier S iO2Preparation
100ml absolute ethyl alcohols/PEG (V are sequentially added into flask:V=2:1), 2ml deionized waters, 4ml ammonium hydroxide (25wt%), after 40 DEG C of water bath with thermostatic control constant temperature, is rapidly added the positive silicic acid second of 3ml under 150rpm mixing speeds into flask Ester, reaction 12h stop, 2ml ammonium chlorides are then added dropwise into solution, are centrifuged under 6500rpm rotating speeds, water/absolute ethyl alcohol Up to SiO when drying 12 is small at 120 DEG C after washing2Solid powder.The preparation of CuO catalyst
Weigh 25.52g SiO2Solid, with 1:1 water/absolute ethyl alcohol dissolving, with 15gCu (NO3)2It is miscible to be gone in 200ml In ionized water, adding 12ml ammonium hydroxide (25wt%) with continuous stirring, [ammonium hydroxide density is 0.91g/mL at room temperature, its quality is 2.73g], the pH value for controlling reaction is 6, continues to stir 2h in 40 DEG C of insulations, and filtering precipitation, is washed with water, absolute ethyl alcohol, When 120 DEG C of dryings 12 are small, then in Muffle furnace when 350 DEG C of roastings 4 are small, after then the graphite of addition 5wt% is to lubricate It is uniformly mixed, compression molding.In gained catalyst：Active component CuO accounts for the 20% of gross weight, carrier S iO2Account for gross weight 80%.
Catalyst activity evaluation uses following methods：In stainless steel reactor, by the preformed catalyst in 270 DEG C of temperature It is lower with nitrogen hydrogen mixture reduction 6 it is small when.It is in reaction condition：220 DEG C of reaction temperature, normal pressure, liquid air speed 0.4hr-1, hydrogen Under conditions of aldehyde molar ratio 15, through the small trial operations of 1200h, furfural conversion ratio is selectively for 100%, 2- methylfurans 94.5%.
Embodiment 2
Carrier S iO2Preparation
100ml absolute ethyl alcohols/PEG (V are sequentially added into flask:V=1:1), 2ml deionized waters, 2ml ammonium hydroxide (25wt%), after 35 DEG C of water bath with thermostatic control constant temperature, is rapidly added the positive silicic acid second of 2ml under 150rpm mixing speeds into flask Ester, reaction 12h stop, 2ml ammonium chlorides are then added dropwise into solution, are centrifuged under 8000rpm rotating speeds, water/absolute ethyl alcohol Up to SiO when drying 12 is small at 120 DEG C after washing2Solid powder.The preparation of CuO catalyst
Weigh 25g SiO2Solid, with 1:1 water/absolute ethyl alcohol dissolving, with 30gCu (NO3)2It is miscible in 200ml deionizations In water, adding 12ml ammonium hydroxide (25wt%) with continuous stirring, [ammonium hydroxide density is 0.91g/mL at room temperature, its quality is 2.73g], the pH value for controlling reaction is 6, continues to stir 2h in 40 DEG C of insulations, and filtering precipitation, is washed with water, absolute ethyl alcohol, When 120 DEG C of dryings 12 are small, then in Muffle furnace when 350 DEG C of roastings 4 are small, after then the graphite of addition 5wt% is to lubricate It is uniformly mixed, compression molding.In gained catalyst：Active component CuO accounts for the 35% of gross weight, carrier S iO2Account for gross weight 65%.
Catalyst activity evaluation uses following methods：In stainless steel reactor, by the preformed catalyst in 270 DEG C of temperature It is lower with nitrogen hydrogen mixture reduction 6 it is small when.It is in reaction condition：220 DEG C of reaction temperature, normal pressure, liquid air speed 0.4hr-1, hydrogen Under conditions of aldehyde molar ratio 15, through the small trial operations of 1200h, furfural conversion ratio is selectively for 100%, 2- methylfurans 93.2%.
Embodiment 3
Carrier S iO2Preparation
100ml absolute ethyl alcohols/PEG (V are sequentially added into flask:V=3:1), 2ml deionized waters, 4ml ammonium hydroxide (25wt%), after 50 DEG C of water bath with thermostatic control constant temperature, is rapidly added the positive silicic acid second of 4ml under 150rpm mixing speeds into flask Ester, reaction 12h stop, 2ml ammonium chlorides are then added dropwise into solution, are centrifuged under 6000rpm rotating speeds, water/absolute ethyl alcohol Up to SiO when drying 12 is small at 120 DEG C after washing2Solid powder.
The preparation of CuO catalyst
Weigh 26g SiO2Solid, with 1:1 water/absolute ethyl alcohol dissolving, with 20gCu (NO3)2It is miscible in 200ml deionizations In water, adding 12ml ammonium hydroxide (25wt%) with continuous stirring, [ammonium hydroxide density is 0.91g/mL at room temperature, its quality is 2.73g], the pH value for controlling reaction is 6, continues to stir 2h in 40 DEG C of insulations, and filtering precipitation, is washed with water, absolute ethyl alcohol, When 120 DEG C of dryings 12 are small, then in Muffle furnace when 350 DEG C of roastings 4 are small, after then the graphite of addition 5wt% is to lubricate It is uniformly mixed, compression molding.In gained catalyst：Active component CuO accounts for the 25% of gross weight, carrier S iO2Account for gross weight 75%.
Catalyst activity evaluation uses following methods：In stainless steel reactor, by the preformed catalyst in 270 DEG C of temperature It is lower with nitrogen hydrogen mixture reduction 6 it is small when.It is in reaction condition：220 DEG C of reaction temperature, normal pressure, liquid air speed 0.4hr-1, hydrogen Under conditions of aldehyde molar ratio 15, through the small trial operations of 1200h, furfural conversion ratio is selectively for 100%, 2- methylfurans 93.8%.
Comparative example 1
Weigh 15gCu (NO3)2, it is miscible in 200ml deionized waters with 25.5g Ludox, add with continuous stirring 12ml ammonium hydroxide (25wt%), the pH value for controlling reaction are 6, continue to stir 2h, filtering precipitation, with water, anhydrous second in 40 DEG C of insulations Alcohol washs, and when 120 DEG C of dryings 12 are small, then in Muffle furnace when 350 DEG C of roastings 4 are small, the graphite for then adding 5wt% is used To be uniformly mixed after lubrication, compression molding.
Catalyst activity evaluation uses following methods：In stainless steel reactor, by the preformed catalyst in 270 DEG C of temperature It is lower with nitrogen hydrogen mixture reduction 6 it is small when.It is in reaction condition：220 DEG C of reaction temperature, normal pressure, liquid air speed 0.4hr-1, hydrogen Under conditions of aldehyde molar ratio 15, furfural conversion ratio is that 90.1%, 2- methylfurans selectivity is 83.7%, small trial run time< 700h。

Claims (7)

  1. A kind of 1. furfural hydrogenation 2- methylfuran method for preparing catalyst, it is characterised in that the described method includes：
    1) first absolute ethyl alcohol and polyethylene glycol are mixed and then ethyl orthosilicate is added to uniformly mixed absolute ethyl alcohol-poly- second Reaction is hydrolyzed in glycol/deionized water/ammonium hydroxide, centrifuges, obtains carrier S iO2；
    The volume ratio of absolute ethyl alcohol and polyethylene glycol is：3:1~1:2；
    The volume ratio of absolute ethyl alcohol-polyethylene glycol/deionized water/ammonium hydroxide is：100:2:(1~6)；
    The volume ratio of absolute ethyl alcohol/polyethylene glycol and ethyl orthosilicate is 100：(1~4)；
    2) carrier S iO2Mix, add in the lump in reaction flask, the pH value for controlling reaction is 5- with CuO precursor solutions, alkaline solution 8, continuously stir 0.5-3.5 it is small when, CuO-SiO will be made after precipitation filtering, dry, roasting2Catalyst fines；
    Carrier S iO2Mass ratio with CuO precursor solutions, alkaline solution is：(6~20):(5~15):(1~2).
  2. 2. furfural hydrogenation 2- methylfuran method for preparing catalyst as claimed in claim 1, it is characterised in that：
    The volume ratio of absolute ethyl alcohol-polyethylene glycol/deionized water/ammonium hydroxide is：100:2:(2~4)；
    Carrier S iO2Mass ratio with CuO precursor solutions, alkaline solution is：(8~17):(6~13):(1~2).
  3. 3. furfural hydrogenation 2- methylfuran method for preparing catalyst as claimed in claim 1, it is characterised in that：
    Step (1), is hydrolyzed reaction in water bath with thermostatic control, bath temperature is 25 DEG C~80 DEG C, reaction time 6-24h.
  4. 4. furfural hydrogenation 2- methylfuran method for preparing catalyst as claimed in claim 3, it is characterised in that：
    It is 3000~10000rpm that step (1), which centrifuges rotating speed,.
  5. 5. furfural hydrogenation 2- methylfuran method for preparing catalyst as claimed in claim 1, it is characterised in that the method Including：
    The copper oxide precursor solution is copper nitrate, copper chloride or copper sulphate；
    The alkaline solution is ammonium hydroxide, ammonium carbonate or sodium carbonate.
  6. 6. the furfural hydrogenation 2- methylfuran method for preparing catalyst as described in one of Claims 1 to 5, it is characterised in that：
    3) graphite is added to be uniformly mixed after lubricating, compression molding.
  7. A kind of 7. catalyst prepared by method as described in one of Claims 1 to 5, it is characterised in that：
    CuO contents are 20-35wt%, carrier S iO2Content is 65-80wt%.
CN201610921945.6A 2016-10-21 2016-10-21 A kind of furfural hydrogenation 2- methylfurans method for preparing catalyst and catalyst Pending CN107970934A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111085203A (en) * 2019-08-20 2020-05-01 中国科学院广州能源研究所 Method for preparing 2-methylfuran by catalyzing hydrogenation of furfural
CN113457675A (en) * 2021-05-26 2021-10-01 郑州大学 Catalyst for preparing 2-methylfuran through furfural gas-phase hydrogenation and preparation method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111085203A (en) * 2019-08-20 2020-05-01 中国科学院广州能源研究所 Method for preparing 2-methylfuran by catalyzing hydrogenation of furfural
CN113457675A (en) * 2021-05-26 2021-10-01 郑州大学 Catalyst for preparing 2-methylfuran through furfural gas-phase hydrogenation and preparation method thereof
CN113457675B (en) * 2021-05-26 2022-06-24 郑州大学 Catalyst for preparing 2-methylfuran through furfural gas-phase hydrogenation and preparation method thereof

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