CN1308986A - Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde - Google Patents
Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde Download PDFInfo
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- CN1308986A CN1308986A CN 00132855 CN00132855A CN1308986A CN 1308986 A CN1308986 A CN 1308986A CN 00132855 CN00132855 CN 00132855 CN 00132855 A CN00132855 A CN 00132855A CN 1308986 A CN1308986 A CN 1308986A
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- catalyst
- furaldehyde
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Abstract
An efficient carried noble metal catalyst used for preparing furan by gas-phase decarbonylation of furaldehyde contains Al2O3-TiO2 composite as carrier, as well as Pt (0.4-0.7 Wt.%) and K2O or Cs2O or MgO or CaO or BaO (0.5-2 Wt.%), and is prepared by impregnation method. Its advantages are high activity, high conversion up to 80-97% and high selectivity up to 85-92%.
Description
The present invention relates to a kind of preparing furan by gas-phase decarbonylation of furaldehyde loaded noble metal catalyst and preparation method thereof.
Furfural gas phase decarbonylation base system furans is a present domestic production furans method commonly used, and technology is comparatively ripe.Forefathers once used ZnO-Cr
2O
3, ZnO-Cr
2O
3-MnO
2, ZnO-CdO-MnO-Al
2O
3Deng oxide catalyst.But because the less poor stability of its production capacity, the service condition harshness, and can cause environmental pollution and be eliminated gradually.The sixties rise, and Ouaker Oats company proposes the Pd catalyst is applied to this decarbonylation reaction.Patents such as SU1699601, SU1710125, RU2027714 also propose to use this decarbonylation reaction of Pd catalyst, and its catalytic activity and selectivity all reach more than 90%, but the load capacity of noble metal is generally greater than 1%.In recent years, because the continuous rise of Pd price makes the higher Pd catalyst of load capacity not be suitable for large-scale industrial production.
At present few about the report that the Pt catalyst is applied to this decarbonylation reaction.DE3632255 discloses a kind of Al of being carried on
2O
3On the Pt catalyst, active constituent is by the Na of 0.75%Pt weight and 0.01～10% weight
2O or Cs
2O forms.In temperature is 300～350 ℃, and hydrogen and furfural mol ratio are that the conversion ratio of catalyst can reach more than 70% under 0.75 the condition, and average selectivity reaches 90%.
The object of the invention provides the Catalysts and its preparation method of a kind of high activity, high selectivity decarbonylation of furfural production furans.
Catalyst carrier of the present invention is Al
2O
3-TiO
2Composite oxides.Active constituent is by 0.4～0.7% weight Pt, 0.5～2.0% weight K
2O or Cs
2O or MgO or CaO or BaO form.
Catalyst of the present invention adopts immersion process for preparing, it is characterized in that elder generation is immersed in Al with the saline solution of Pt
2O
3-TiO
2On the composite oxides, in 100～120 ℃ of dryings, 450～600C roasting, the saline solution with K or Cs or Mg or Ca or Ba is immersed on the carrier again, and in 100～120 ℃ of dryings, uses N at last
2-H
2, 450 ℃ of following reduction activations, make catalyst.
The mutually deserved salt of the used Pt of the present invention can be chloroplatinic acid or platinum tetrachloride or acetylacetone,2,4-pentanedione platinum.Used K or Cs or Mg or Ca or Ba salt can be chloride or nitrate or acetate.This catalyst used carrier is Al
2O
3-TiO
2Composite oxides.
The present invention makes the furfural of working solution for handling through decompression distillation that catalyst adopts, and working solution and hydrogen is plug flow from up to down, under normal pressure, 280 ℃, and liquid air speed 0.9h
-1(volume space velocity), hydrogen and furfural mol ratio are 0.5～2.0, and reaction conversion ratio reaches 80～97%, and selectivity can reach 85～92%.
Embodiment 1: adopt 20gAl
2O
3-TiO
2Carrier, its shape and size are 20～50 purpose particles.With 20.3ml concentration is the H of 0.00592gPt/ml
2PtCl
6Solution is poured the above-mentioned Al of 20g into
2O
3-TiO
2In the carrier, in 100～120 ℃ of dry 3h, 450～600 ℃ of roasting 3h, after the cooling, impouring 20ml contains 0.21gKNO
3Solution, 100～120 ℃ of dry 3h use N at last
2-H
2, air speed 300h
-1, 450 ℃ of following reduction 3h can make required catalyst.
The above-mentioned catalyst of 10ml is packed in the stainless steel reactor of φ 10, and under 280 ℃, normal pressure, the liquid air speed is 0.9h
-1(volume space velocity), the mol ratio of furfural and hydrogen are 1, and the conversion ratio of reaction is 85%, and selectivity is 92%
Embodiment 2: the Preparation of catalysts method is with routine l, and different is, and dipping adopts for the second time is that 20ml is dissolved with 0.14gCsNO
3Solution, and dry, reduction makes required catalyst.
Adopt this catalyst 10ml, use the condition identical with embodiment 1, reaction conversion ratio is 97%, and selectivity is 88%.
Embodiment 3: the Preparation of catalysts method is with example 1, and what dipping adopted for the second time is that 20ml is dissolved with 0.74gMg (NO
3)
2Solution, and dry, reduction makes required catalyst.
Adopt this catalyst 10ml, use the condition identical with embodiment 1, reaction conversion ratio is 82%, and selectivity is 86%.
Embodiment 4: the Preparation of catalysts method is with example 1, and what dipping adopted for the second time is that 20ml is dissolved with 0.59gCa (NO
3)
2Solution, and dry, reduction makes required catalyst.
Adopt this catalyst 10ml, use the condition identical with embodiment 1, reaction conversion ratio is 81%, and selectivity is 87.8%.
Embodiment 5: the Preparation of catalysts method is with example 1, and what dipping adopted for the second time is that 20ml is dissolved with 0.34gBa (NO
3)
2Solution, and dry, reduction makes required catalyst.
Adopt this catalyst 10ml, use the condition identical with embodiment 1, reaction conversion ratio is 83%, and selectivity is 88.3%.
Claims (4)
1. a preparing furan by gas-phase decarbonylation of furaldehyde catalyst is characterized in that carrier is Al
2O
3-TiO
2Composite oxides, active constituent are by 0.4～0.7% weight Pt, 0.5～2.0% weight K
2O or Cs
2O or MgO or CaO or BaO form.
2. Preparation of catalysts method as claimed in claim 1 adopts immersion process for preparing, it is characterized in that elder generation is immersed in Al with the saline solution of platinum
2O
3-TiO
2On the composite oxides, in 100～120 ℃ of dryings, 450～600 ℃ of roastings, the saline solution with K or Cs or Mg or Ca or Ba is immersed on the carrier again, and in 100～120 ℃ of dryings, uses N at last
2-H
2, 450 ℃ of reduction activations make catalyst.
3. method as claimed in claim 2, the salt that it is characterized in that platinum are chloroplatinic acid or platinum tetrachloride or acetylacetone,2,4-pentanedione platinum.
4. method as claimed in claim 2 is characterized in that the salt of K or Cs or Mg or Ca or Ba, can be chloride or nitrate or acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132855 CN1095397C (en) | 2000-11-09 | 2000-11-09 | Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132855 CN1095397C (en) | 2000-11-09 | 2000-11-09 | Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1308986A true CN1308986A (en) | 2001-08-22 |
| CN1095397C CN1095397C (en) | 2002-12-04 |
Family
ID=4595431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00132855 Expired - Fee Related CN1095397C (en) | 2000-11-09 | 2000-11-09 | Catalyst for preparing furan by gas-phase decarbonylation of furaldehyde |
Country Status (1)
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|---|---|
| CN (1) | CN1095397C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000569A (en) * | 2010-09-19 | 2011-04-06 | 长春工业大学 | Catalyst for producing furan by furfural liquid-phase decarbonylation and preparation method |
| CN102482248A (en) * | 2009-08-31 | 2012-05-30 | 纳幕尔杜邦公司 | Decarbonylation process |
| CN102993139B (en) * | 2007-11-30 | 2015-09-16 | 三菱化学株式会社 | The preparation method of furan compound |
| CN111298818A (en) * | 2019-11-14 | 2020-06-19 | 天津大学 | Palladium and platinum catalyst, preparation thereof and application thereof in reaction for preparing furan from furfural |
| CN115845837A (en) * | 2022-10-10 | 2023-03-28 | 河南省生物基材料产业研究院有限公司 | Furan catalyst prepared by furfural gas-phase continuous decarbonylation and preparation method thereof |
-
2000
- 2000-11-09 CN CN 00132855 patent/CN1095397C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993139B (en) * | 2007-11-30 | 2015-09-16 | 三菱化学株式会社 | The preparation method of furan compound |
| CN102482248A (en) * | 2009-08-31 | 2012-05-30 | 纳幕尔杜邦公司 | Decarbonylation process |
| CN102482248B (en) * | 2009-08-31 | 2015-05-20 | 纳幕尔杜邦公司 | Decarbonylation process |
| CN102000569A (en) * | 2010-09-19 | 2011-04-06 | 长春工业大学 | Catalyst for producing furan by furfural liquid-phase decarbonylation and preparation method |
| CN111298818A (en) * | 2019-11-14 | 2020-06-19 | 天津大学 | Palladium and platinum catalyst, preparation thereof and application thereof in reaction for preparing furan from furfural |
| CN111298818B (en) * | 2019-11-14 | 2023-07-25 | 天津大学 | Palladium and platinum catalyst, preparation thereof and application thereof in furfuraldehyde preparation reaction |
| CN115845837A (en) * | 2022-10-10 | 2023-03-28 | 河南省生物基材料产业研究院有限公司 | Furan catalyst prepared by furfural gas-phase continuous decarbonylation and preparation method thereof |
| CN115845837B (en) * | 2022-10-10 | 2024-07-12 | 河南省生物基材料产业研究院有限公司 | Furfural catalyst prepared by continuous decarbonylation of furfural in gas phase and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1095397C (en) | 2002-12-04 |
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