CN104941634B - A kind of preparing furan through decarbonylation of furfural palladium carbon catalyst and preparation method thereof - Google Patents
A kind of preparing furan through decarbonylation of furfural palladium carbon catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of preparing furan through decarbonylation of furfural palladium carbon catalyst, the described method includes：The lead compound palladium salt or palladium salt of active component are mixed to form palladium ammino-complex solution with the salt-mixture of other precious metal salts with ammonium hydroxide, the palladium ammino-complex solution is mixed with dipping with auxiliary agent alkali metal salt and carrier active carbon, after reducing agent is added thereto to its electronation, the palladium carbon catalyst is obtained through separation of solid and liquid.The service life of the service life of catalyst provided by the invention catalyst than in the prior art is obviously prolonged, and improves the production efficiency of preparing furan through decarbonylation of furfural.The catalyst that the present invention is prepared has the characteristics of high activity, high selectivity, long lifespan and stability are good concurrently at the same time.
Description
Technical field
The present invention relates to a kind of preparing furan through decarbonylation of furfural palladium carbon catalyst and preparation method thereof.
Background technology
Furans is a kind of important organic synthesis raw material and solvent, is additionally operable to high-volume and makes the viscous of hot box process core
Mixture.Furans can be used to produce pyrroles, thiophene, tetrahydrofuran etc..Furans is etherified, and reduction obtains 2,5- dimethoxy dihydro furans
Mutter, through hydrolysis generation 2- hydroxyls-Isosorbide-5-Nitrae-butanedial, it can be used for the production of synthetic method anisodamine.Furans is etherified, reduction,
When obtaining 2,5- dimethoxy-tetrahydrofurans through catalytic hydrogenation again, butanedial is generated through hydrolysis, this is then another biology of synthesis
The raw material of alkali atropine.Furans, into obtained furan ammonium salt after salt, is cefuroxime through acetylation, methoxy amination oximate, ammonification
Important intermediate.Furans is also used for producing each sodium acetate of antiphlogistic toluoyl pyrrole, and this medicine per ton need to consume furans
4.75t.Developing catalyst of preparing furan through decarbonylation of furfural and preparation method thereof has important practical application meaning.
Furans synthesis can trace back to nineteen twenty-four earliest, US1636030 report with furancarboxylic acid decarbonylation synthesize furans, 1932
Hurds et al. is reported that US2337027, US2374149 report the synthesis of furans in succession again to decarbonylation of furfural reaction；
Five sixties of 20th century various countries' consecutive publications patents such as many patents, SU 1699601, SU 1710125, RU 2027714
It is proposed to carry out decarbonylation of furfural reaction using Pd catalyst.The seventies and eighties, research of the former Russian scholar to the reaction is more, such as
RU2027714.So far, the organic synthesis research institute of the academy of sciences of republic of Latvia still carries out the research of this respect.
At present, the decarbonylation of furfural legal system furans used in industrial production mainly has two methods, liquid phase decarbonylation method and gas phase
Decarbonylation method.Catalyst used in liquid phase is mainly Pd/C, Pd/ γ-Al2O3, Pd/ γ-Al2O3-TiO2Catalyst；Gas phase is made
Catalyst is mainly Zn-Cr-Mn, Pd/C, Pd/ γ-Al2O3。
Jung researchs show：When carrying out liquid phase decarbonylation using 5%Pd/C catalyst, react and carry out 100h at 159~162 DEG C
Afterwards, catalyst activity is down to 62.5%, and the production capacity of catalyst is 36kg/ grams of palladium of furans.
Penn Speciality Chem.Inc exploitation furfural liquid phase decarbonylation furans using nanoscale 5%Pd/ γ-
Al2O3Catalyst, the yield 70-75% of furans, when the service life 80 of catalyst is small, this is petrochina Qian Guo petrochemical industry branch company tetrahydrochysene
Furans device technique data.
Changchun Polytechnic Univ. a, dragon etc. develops a kind of catalyst for producing furan by furfural liquid-phase decarbonylation and preparation, this is urged
Agent is with expression formula γ-Al2O3With MO as complex carrier, co-catalyst MO is the oxide of K, Cs or Li, and MO accounts for described
0.5~2.0wt.% of complex carrier；The active component of catalyst is Pd, and the parent of Pd is PdCl2Or Pd (NO3)2Or [Pd
(C2H3O2)2]3, Pd accounts for the 5wt.% of the complex carrier.The catalyst of the invention is prepared using dipper precipitation method, preparation
Catalyst has good activity, furfural conversion ratio 92.5%-98.2%, furans selectivity in furfural liquid phase decarbonylation reaction
85.3%-94.2%, catalyst life length, reach 100-120 it is small when.
Changchun Polytechnic Univ., dragon etc. in addition develop a kind of producing furan by furfural liquid-phase decarbonylation catalyst and preparation method and
Usage.Producing furan by furfural liquid-phase decarbonylation is with high-efficient carrier palladium catalyst with γ-Al2O3-TiO2Based on composite oxides be
Carrier, the load capacity of palladium are 2~4wt.% of carrier, and K, Cs, Ru, Li, Rh, Na, La or Ba co-catalyst are added in catalyst,
Its content is 0.5~2.0wt.%, which is prepared using electronation infusion process, has high activity, high selectivity, service life
The features such as long and stability is good.The catalyst of the invention carries out chaff under conditions of 0~0.5MPa of pressure, 180~230 DEG C of temperature
Aldehyde liquid phase decarbonylation reaction, furfural conversion ratio 90~99%, the yield 80~95% of furans, when the service life 100-120 of catalyst is small.
Changchun Polytechnic Univ., is reported a kind of preparation method of catalyst in falling sea etc., is prepared for using dipper precipitation method
Furfural liquid phase decarbonylation 4.6%Pd/ γ-Al2O3Catalyst, furans yield is 87.4% under optimum conditions, and the service life can reach
190 it is small when.
But above-mentioned decarbonylation of furfural production furans all could be improved with the catalytic efficiency and catalyst life of catalyst, especially
It is that this area needs to develop a kind of catalyst of long catalytic life while high catalytic efficiency and preparation method thereof.
The content of the invention
Therefore, the present invention provides a kind of preparation method of preparing furan through decarbonylation of furfural palladium carbon catalyst, the described method includes：
The lead compound palladium salt or palladium salt of active component are mixed to form palladium ammino-complex with the salt-mixture of other precious metal salts with ammonium hydroxide
Solution, the palladium ammino-complex solution are mixed with dipping with auxiliary agent alkali metal salt and carrier active carbon, add reducing agent pair thereto
After its electronation, the palladium carbon catalyst is obtained through separation of solid and liquid.
In the present invention, by be used in combination activated carbon for carrier, by palladium salt and ammonium hydroxide formation palladium ammino-complex solution and
The use of alkali metal salt is this multiple condition of auxiliary agent so that the service life of catalyst provided by the invention is catalyzed than in the prior art
The service life of agent is obviously prolonged, and improves the production efficiency of preparing furan through decarbonylation of furfural.The catalyst that the present invention is prepared
Have the characteristics of high activity, high selectivity, long lifespan and stability are good concurrently at the same time.
Skilled artisans will appreciate that, the palladium ammino-complex solution is mixed with auxiliary agent alkali metal salt and carrier active carbon
The order of conjunction is unrestricted in the present invention.Such as can first mix palladium ammino-complex solution with auxiliary agent alkali metal salt, then
Carrier active carbon is immersed in mixed solution；Can also first mix auxiliary agent alkali metal salt and carrier active carbon, then by its
Mixed with palladium ammino-complex solution.Even auxiliary agent alkali metal salt can just be added palladium salt before palladium ammino-complex solution is prepared
Or mix in salt, or be added into ammonium hydroxide, directly obtain the palladium ammino-complex solution of alkali metal containing salt.
In the present invention, the reducing agent is selected from formaldehyde, sodium borohydride, hydrazine hydrate and hydrogen, and the electronation time is 1-
10h, electronation preferably carry out in a heated state.And further included after the solid-liquid separation step of the present invention using deionized water
The step of washing the catalyst.
In a kind of specific embodiment, activated carbon of the present invention is more than 1000m for specific surface area2/ g, large pore volume
In the wood activated charcoal that 1.0ml/g, average pore size are more than 1.5nm, particle mean size is 200-300 mesh.The activated carbon can lead to
Cross commercially available acquisition.
In a kind of specific embodiment, in step " palladium ammino-complex solution and auxiliary agent alkali metal salt and Carriers Active
Charcoal be mixed with dipping " in, first alkali metal salt and activated carbon and water are mixed and stirred for reacting, evaporated under reduced pressure remove water after, then by its
It is mixed with dipping with palladium ammino-complex solution.
In the present invention, the carrier active carbon before being mixed with active component and/or auxiliary agent preferably first using nitric acid into
Row pretreatment.
In a kind of specific embodiment, other noble metals are selected from platinum and rhodium, and in the mixing salt palladium and its
The molar ratio of its noble metal is 1：0.001~0.5.In a kind of specific embodiment, palladium load capacity is 0.5- in catalyst
10.0wt%, the load capacity of other noble metals is 0-5.0wt%.
Preferably, the alkali metal salt is cesium salt, and concentration of the alkali metal salt in maceration extract is 0.2~1.5wt%.
In a kind of specific embodiment, concentration of the alkali metal salt in maceration extract is 0.4~1.0wt%.
Preferably, the alkali metal salt be the acetate of alkali metal, oxalates, citrate and one kind in carbonate or
It is a variety of.In a kind of embodiment, the alkali carbonate is selected from cesium carbonate, potassium carbonate, sodium carbonate and lithium carbonate；Institute
State alkali metal acetate and be selected from cesium acetate, potassium acetate, sodium acetate and lithium acetate；The alkali-metal citrate is selected from citric acid
Caesium, potassium citrate, sodium citrate and lithium citrate；The alkaline metal oxalate is selected from cesium oxalate, potassium oxalate, sodium oxalate and oxalic acid
Lithium.
In a kind of highly preferred embodiment, the alkali metal salt is cesium acetate.
In a kind of embodiment, the palladium salt is palladium, palladium nitrate, chlorine Asia palladium acid, palladium bichloride and chlorine Asia palladium
One or more in sour sodium.Other precious metal salts are, for example, one kind in chloroplatinic acid, platinum nitrate, rhodium nitrate and rhodium acetate
It is or a variety of.
In a kind of highly preferred embodiment, the palladium salt is palladium.
In the present invention, after forming palladium ammino-complex solution using palladium, the performance of gained catalyst is better than other palladiums
The performance for the catalyst that salt is formed, when especially combined use cesium acetate is auxiliary agent, the catalytic capability of gained catalyst is strong, and urges
The agent service life is extremely long.
The present invention also provides a kind of preparing furan through decarbonylation of furfural palladium carbon catalyst, to be prepared using method as described above
's.
From the present invention and the catalyst application effect comparative illustration described in the prior art, or it is catalyzed from comparative example
The comparative illustration of agent application effect, the microstructure certainty and the prior art of the catalyst obtained using the preparation method of the present invention
In palladium-carbon catalyst it is different.Only because catalyst structure and/or property are different, it could be catalyzed under identical reaction conditions
Activity and catalyst life are substantially distinguished from the prior art.
The present invention also provides a kind of method of preparing furan through decarbonylation of furfural, and including the use of catalyst as described above makes furfural exist
Continuous decarbonylation under liquid phase.
The condition that the catalyst of the present invention is used for the continuous decarbonylation production furans of furfural liquid phase is as follows：0~0.5MPa of pressure, temperature
180~230 DEG C, 200~300r/min of mixing speed are spent, first batch of catalyst charge is 0.5~2wt% of furfural quality, and
A small amount of antioxidant or polymerization inhibitor are added in the reaction.
Embodiment
Provided herein is following examples to illustrate the present invention, but cannot be regarded as limitations on the claims.
Embodiment 1
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, after being washed with deionized,
It is dry.
2) by 1.25gPd (NO3)2·2H2O is hybridly prepared into palladium ammino-complex aqueous solution (40g) with ammonium hydroxide, adds 0.36g
Cesium acetate, is added rapidly in the activated carbon of above-mentioned gained after mixing, and stirs 4.0h.
3) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 5%Pd/C catalyst, moisture content
61.5%.
Embodiment 2
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, after being washed with deionized,
It is dry.
2) by 0.63gPd (NO3)2·2H2O is hybridly prepared into palladium ammino-complex aqueous solution (40g) with ammonium hydroxide, adds 0.18g
Potassium citrate, is added rapidly in the activated carbon of above-mentioned gained after mixing, and stirs 4.0h.
3) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 2.5%Pd/C catalyst, moisture content
59.5%.
Embodiment 3
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, after being washed with deionized,
It is dry.
2) by 0.83gPdCl2Palladium ammino-complex aqueous solution (40g) is hybridly prepared into ammonium hydroxide, adds 0.36g sodium carbonate,
It is added rapidly to after mixing in the activated carbon of above-mentioned gained, and stirs 4.0h.
3) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 5%Pd/C catalyst, moisture content
61.5%.
Embodiment 4
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, after being washed with deionized,
It is dry.
2) by 0.83gPdCl2, 0.26g six is hydrated chloroplatinic acid and ammonium hydroxide is hybridly prepared into palladium ammino-complex aqueous solution
(40g), adds 0.36g cesium acetates, is added rapidly to after mixing in the activated carbon of above-mentioned gained, and stir 4.0h.
3) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 5%Pd/C catalyst, moisture content
61.9%.
Embodiment 5
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, after being washed with deionized,
It is dry.
2) by 1.25gPd (NO3)2·2H2O, 0.20gRh (NO3)2Palladium ammino-complex aqueous solution is hybridly prepared into ammonium hydroxide
(40g), adds 0.33g sodium oxalates, is added rapidly to after mixing in the activated carbon of above-mentioned gained, and stir 4.0h.
3) at 80 DEG C, 3.0ml hydrazine hydrates are added, and stir reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 5%Pd/C catalyst, moisture content
61.1%.
Embodiment 6
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, after being washed with deionized,
It is dry.
2) by 1.055gPd (C2H3OO)2Palladium ammino-complex aqueous solution (40g) is hybridly prepared into ammonium hydroxide, adds 0.4g vinegar
Sour caesium, is added rapidly in the activated carbon of above-mentioned gained after mixing, and stirs 4.0h.
3) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 5%Pd/C catalyst, moisture content
60.9%.
Embodiment 7
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, after being washed with deionized,
The cesium acetate solution of 36ml mass fractions 1.0% is added, stirs 2h, 40 DEG C are dried under reduced pressure.
2) by 1.055gPd (C2H3OO)2Palladium ammino-complex aqueous solution (40g) is hybridly prepared into ammonium hydroxide, is added rapidly to
In the activated carbon of above-mentioned gained, and stir 4.0h.
3) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 5%Pd/C catalyst, moisture content
61.5%.Comparative example 1~7
Other conditions of comparative example 1~7 are identical with 1~7 difference of embodiment, but active component palladium not with ammonium hydroxide network
Close.
Comparative example 8
1) 10g activated carbons (dry weight) carrier is taken, which is pre-processed with nitric acid, is washed, it is dry.
2) by 0.83gPdCl2Palladium ammino-complex solution (40g) is hybridly prepared into ammonium hydroxide, is added rapidly to by pre- place
In the activated carbon of reason, and stir 4.0h.
3) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
4) cool down, stand overnight, filter, spend ion-cleaning to filtrate neutrality, obtain 5%Pd/C catalyst, moisture content
60.6%.
Comparative example 9
Other conditions of comparative example 9 are identical with comparative example 8, but active component palladium is not complexed with ammonium hydroxide.
Comparative example 10
1) by 1.055gPd (C2H3OO)2Palladium ammino-complex aqueous solution (40g) is hybridly prepared into ammonium hydroxide, adds 0.4g vinegar
Sour caesium, is added rapidly in commercially available 10g alumina supports after mixing, and stirs 4.0h.
2) at 80 DEG C, 2ml formaldehyde is added, and stirs reduction 4h；
3) cool down, stand overnight, filter, it is neutral to filtrate to spend ion-cleaning, obtains 5%Pd/ aluminium oxide catalysts, aqueous
Rate 60.9%.
Comparative example 11
Other conditions of comparative example 11 are identical with comparative example 10, but active component palladium is not complexed with ammonium hydroxide.
Corresponding catalyst in 1.0g examples detailed above is respectively put into reaction kettle, is subsequently poured into 100g furfurals, is added few
Antioxidant and polymerization inhibitor are measured, under conditions of 0~0.5MPa of pressure, 180-230 DEG C of temperature, 100~200r/min of mixing speed
Carry out the continuous decarbonylation reaction of furfural liquid phase.Polymer concentration in kettle, reaction terminating.In reaction of the present invention, work as polymer
When concentration is more than 4.0%, although catalyst is not apparent from inactivating, because polymer concentration is high, residue is excessively sticky in kettle, catalysis
Agent will be difficult to recycle, and be calculated as the terminal in the service life of catalyst at this time.Acquired results are shown in Table 1.
Table 1
It can be seen that from 1 embodiment 1~7 of table with the result of corresponding comparative example 1~7 in the present invention and be using activated carbon
When carrier and use alkali metal salt are auxiliary agent, active component will cause using palladium salt and using the difference of the ammonium hydroxide complex compound of palladium salt
The catalytic performance and catalyst service life significant difference of catalyst.And it can be seen that from the result of comparative example 8~11 when catalysis
When in agent without using auxiliary agent, or when the carrier of catalyst is changed to aluminium oxide by activated carbon, if palladium salt is formed palladium ammonia complexing
Thing is not notable to the catalytic performance of catalyst and the influence of service life.
Situation in embodiment 1~6 is as it can be seen that the active component presoma of catalyst is most preferably acetic acid in the present invention
Palladium, secondly palladium nitrate.Auxiliary agent is equally most preferably cesium acetate, secondly other cesium salts (use the corresponding catalyst of cesium salt
Performance is substantially better than using sodium salt and the corresponding catalyst performance of sylvite).Be used in the present invention active component for palladium or
Palladium ammino-complex prepared by palladium nitrate, auxiliary agent uses cesium salt, and when carrier uses activated carbon, the service life of gained catalyst can be with
Break through 200 it is small when in addition significantly exceed, while every gram of palladium can effectively be catalyzed decarbonylation of furfural generation furans amount maximum it is reachable
88.5g, this is unusual significant progress for this area.
In addition, the preparation process of only catalyst is slightly different in embodiment 6 and embodiment 7, be in embodiment 6 carrier at the same time
Mixed with active component and auxiliary agent, and in embodiment 7 be carrier elder generation and auxiliary agent hybrid reaction, then reacted with active component.From this
The contrast situation of two embodiments, which can be seen that the catalyst performance that both approaches are prepared, certain difference, it is clear that
The latter is method for preparing catalyst more excellent in the present invention.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this area
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of preparation method of preparing furan through decarbonylation of furfural palladium carbon catalyst, the described method includes：Active component it is precursor
Compound palladium salt or palladium salt and the salt-mixture of other precious metal salts are mixed to form palladium ammino-complex solution, the palladium ammonia complexing with ammonium hydroxide
Thing solution is mixed with dipping with auxiliary agent alkali metal salt and carrier active carbon, after adding reducing agent thereto to its electronation, through solid
The isolated palladium carbon catalyst of liquid；The alkali metal salt is cesium salt, and the alkali metal salt is acetate, the oxalic acid of alkali metal
One or more in salt, citrate and carbonate.
2. method according to claim 1, it is characterised in that step " palladium ammino-complex solution and auxiliary agent alkali metal salt and
Carrier active carbon is mixed with dipping " in, first alkali metal salt and activated carbon and water are mixed and stirred for reacting, are removed water in evaporated under reduced pressure
Afterwards, then by itself and palladium ammino-complex solution it is mixed with dipping.
3. method according to claim 1, it is characterised in that other noble metals are selected from platinum and rhodium, and the mixing salt
The molar ratio of middle palladium and other noble metals is 1：0.001~0.5.
4. according to any one the method in claims 1 to 3, it is characterised in that and alkali metal salt is dense in maceration extract
Spend for 0.2~1.5wt%.
5. according to any one the method in claims 1 to 3, it is characterised in that the alkali metal salt is cesium acetate.
6. according to any one the method in claims 1 to 3, it is characterised in that the palladium salt for palladium, palladium nitrate,
One or more in chlorine Asia palladium acid, palladium bichloride and sodium chloropalladite.
7. method according to claim 6, it is characterised in that the palladium salt is palladium.
8. according to any one the method in claims 1 to 3, it is characterised in that the reducing agent is selected from formaldehyde, hydroboration
Sodium, hydrazine hydrate and hydrogen, electronation time are 1-10h.
9. according to any one the method in claims 1 to 3, it is characterised in that the activated carbon is more than for specific surface area
1000m2The wood activated charcoal that/g, pore volume are more than 1.0ml/g, average pore size is more than 1.5nm, particle mean size is 200-300 mesh.
10. according to any one the method in claims 1 to 3, it is characterised in that the carrier active carbon with activearm
Divide and/or auxiliary agent mixing is first pre-processed using nitric acid before.
A kind of 11. preparing furan through decarbonylation of furfural palladium carbon catalyst, for using such as any one the method in claim 1~10
It is prepared.
12. a kind of method of preparing furan through decarbonylation of furfural, including the use of catalyst as claimed in claim 11 makes furfural in liquid phase
Continuous decarbonylation down.
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| CN105771982A (en) * | 2016-04-25 | 2016-07-20 | 张玲 | Method for preparing 5-hydroxymethyl furfural decarbonylation catalyst |
| CN107970928B (en) * | 2016-10-24 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of preparing furan through decarbonylation of furfural catalyst, preparation method and application |
| WO2019030289A1 (en) * | 2017-08-10 | 2019-02-14 | Shell Internationale Research Maatschappij B.V. | Method for preparing a catalyst and method for producing 1,4-butanediol and/or tetrahydrofuran from furan |
| CN111450845B (en) * | 2020-04-28 | 2023-06-23 | 济南同誉新材料科技有限公司 | Preparation method and application of PdCu bimetallic catalyst |
| CN112759567A (en) * | 2020-12-25 | 2021-05-07 | 安徽金轩科技有限公司 | Device and method for preparing furan by furfural gas-phase decarbonylation |
| CN113786840B (en) * | 2021-08-24 | 2024-02-06 | 河南省生物基材料产业研究院有限公司 | Composite catalyst for preparing furoic acid by oxidizing furfural and preparation method thereof |
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