CN1047100C - Catalyst for furfural gas-phase hydrogenization synthetizing 2-methyl furan - Google Patents
Catalyst for furfural gas-phase hydrogenization synthetizing 2-methyl furan Download PDFInfo
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- CN1047100C CN1047100C CN 95111759 CN95111759A CN1047100C CN 1047100 C CN1047100 C CN 1047100C CN 95111759 CN95111759 CN 95111759 CN 95111759 A CN95111759 A CN 95111759A CN 1047100 C CN1047100 C CN 1047100C
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Abstract
The present invention relates to a catalyst used for gas phase synthesis of 2-methyl furan by furfural. The catalyst is prepared from aluminum oxides, cupric oxides and chromium oxides as main catalytic ingredients, alkali metal, alkaline earth metal and other elements. The catalyst has the advantages of high yield, fewer byproducts, long lifespan, etc., and the catalyst can be widely used in the industrial production of 2-methyl furan.
Description
The present invention relates to the synthetic catalyst of 2-methylfuran, the particularly catalyst of relevant furfural gas-phase catalytic hydrogenation Synthetic 2-methylfuran.
The 2-methylfuran is a kind of important organic chemical industry's intermediate, and solvent is widely used in synthetic medicine, agricultural chemicals and solution polymerization process; Also can be used for producing organic chemical industry's products such as pentadiene, pentanediol, acetyl, propyl alcohol and ketone thereof, 2-methyltetrahydrofuran, in medical industry, the 2-methylfuran is medicine and Cobastabs such as synthetic phosphoric acid hydrogen quinoline, primaquine phosphate
1Deng important source material.Normal in the past 1,3-pentadiene oxidation or the furfuryl alcohol hydrogenation of adopting of process route of producing the 2-methylfuran synthesizes; But the side reaction of these process routes is many, and 2-methylfuran yield is low, only about 70%, and Russian Patent SU941366 has reported with cupric oxide-chromium oxide/graphite or aluminium oxide and has made catalyst; The technology of furfural gas-phase catalytic hydrogenation system 2-methylfuran, but the catalyst manufacturing cost height of this patent, the product reaction is after 1200 hours, and yield only is 90%, and the accessory substance of this technology is more in addition, the separation difficulty of post processing.For overcoming the shortcoming that exists in the above-mentioned technology, reach in producing 2-methylfuran process product yield height, purpose that accessory substance is few, the present inventor has invented a kind of new catalyst of furfural gas-phase catalytic hydrogenation Synthetic 2-methylfuran.
The objective of the invention is to realize by following technical scheme.In furfural gas-phase catalytic hydrogenation Synthetic 2-methylfuran process, with a kind of new catalyst, its composition is by weight percentage: CuO 5～15%, Cr
2O
30.5～5%, Al
2O
380～90%, 0.01～2% at least a oxide that is selected from alkali metal and alkaline-earth metal, 0.01～2% at least a oxide that is selected from P, Bi, Ce, Mo, Zn, Cr, B, Co.
The oxide of alkali metal and alkaline-earth metal is K in catalyst of the present invention
2O, Na
2O, CaO, BaO, MgO, their suitable content ranges are 0.5～1% (wt), the weight percentage preferred range of the oxide of at least a P of being selected from, Bi, Ce, Mo, Zn, Cr, B, Co is 0.04～1%.The catalyst of the application of the invention is 0.25～0.40hr in air speed
-1Reaction pressure is a normal pressure, reaction temperature is under 230～240 ℃ of conditions, furfural gas phase hydrogenation reaction after turning round 1200 hours continuously, the conversion ratio of its furfural can reach 99～100%, and selectivity reaches more than 95%, the yield of 2-methylfuran can reach 92.5～94%, the result shows after testing in addition, in the product except that containing a spot of 2-methyltetrahydrofuran, furfuryl alcohol, no tetrahydrofurfuryl alcohol; Pentanediol accessory substance, product are easy to separate and purify.
Be equipped with in the 2-methylfuran course of reaction at preparation by furfural gas phase hydrogenation, adopt catalyst of the present invention, selectivity, the yield of 2-methylfuran all are enhanced, and accessory substance is few, even suppressed the generation of by-product tetrahydrofurfuryl alcohol, pentanediol, obtained good effect.
Embodiment 1
With Powdered 10 gram cupric oxide, 3 gram chromium oxide, 84.5 gram aluminium oxide, potassium oxide 0.7 gram sodium oxide molybdena 0.3 gram, magnesia 0.5 gram, phosphorous, bismuth, zinc, oxide mixture 1 gram of molybdenum, add in the agitating device mixing together, in agitating device, after fully mixing evenly, in agitator, add sesbania powder 3 grams, active carbon 3 grams, salpeter solution, treat each component mix after with this material extrusion, pelletizing becomes 6.4 ± 0.1 millimeters of external diameters, 2.5 ± 0.1 millimeters of internal orifice dimensions, high 6.4 ± 0.1 millimeters Raschig ring, then with its under 110 ℃ of conditions the oven dry after, roasting 2 hours under 500 ℃ of conditions again, finished catalyst, its bulk density is 0.70 grams per milliliter.
Carry out evaluating catalyst in tubular reactor, reactor is a stainless steel, 20 millimeters of internal diameters, and long 500 millimeters, be seated in the reactor constant temperature zone after the catalyst chopping, hydrogen enters the gasification blender after the spinner flowmeter metering; After gasification mixes the gasification blender with the furfural that transports from measuring pump, enter beds again and react after economizer bank is preheated to reaction temperature, product enters gas-liquid separator after condenser condenses, contain 2-methylfuran and H in the gained product liquid
2O; Tail gas emptying.
Reaction temperature is 238 ℃, and pressure is normal pressure, and the raw material furfural is 100 grams, and the liquid phase air speed is 0.3 hour
-1, after reacting 5 hours, sample analysis, the 2-methylfuran is 84.14 grams in its product, and furfuryl alcohol is 1.38 grams, and 2 methyltetrahydrofurans are 0.13 gram; Tetrahydrofurfuryl alcohol is zero, and pentanediol is zero; Furfural is zero, and its furfural conversion ratio is 100% as calculated, and selectivity is 98.5%, and yield is 98.5%.This catalyst is after turning round 1200 hours continuously, and its reaction yield is 94.2%.
Embodiment 2
Method according to example 1 prepares catalyst and investigates evaluate catalysts.
Wherein catalyst consists of: cupric oxide 5 grams, chromium oxide 5 grams, aluminium oxide 88.6 grams, potassium oxide 0.4 gram, barium monoxide 0.2 gram, calcium oxide 0.2 gram, the oxide mixture 0.6 that contains phosphorus, cerium, cobalt restrains, in temperature is 235 ℃, and pressure is normal pressure, and the liquid phase air speed is 0.35 hour
-1Investigate under the condition and estimate, drop into furfural 100 grams, sample analysis after 5 hours contains 2-methylfuran 82.95 grams in the product, furfuryl alcohol 2.13 grams, and 2-methyl tetrahydrochysene furan is ridiculed 0.27 gram: tetrahydrofurfuryl alcohol, pentanediol are respectively zero; Furfural is 0.5 gram, and as calculated, its furfural conversion ratio is 99.5%, and selectivity is 97.6%, and its product yield is 97.1%, and this catalyst is after turning round 1200 hours continuously, and its reaction yield is 92.9%.
Embodiment 3
Method according to example 1 prepares catalyst and investigates evaluate catalysts.
Wherein catalyst consists of: cupric oxide 15 grams, and chromium oxide 1.0 grams, aluminium oxide 80.5 grams, mixture 2 grams of potassium oxide and calcium oxide, the oxide mixture 1.5 that contains phosphorus, cerium, boron restrains, and is 230 ℃ in temperature, and pressure is normal pressure, and the liquid phase air speed is 0.25 hour
-1Under the condition, investigate and estimate, drop into furfural 100 grams, sample analysis after 5 hours, contain 2-methylfuran 81.09 grams in the product, furfuryl alcohol 3.85 grams, the 2-methyltetrahydrofuran is 0.44 gram: tetrahydrofurfuryl alcohol and pentanediol are respectively zero: furfural is 0.8 gram, as calculated, its furfural conversion ratio is 99.2%, and selectivity of product is 95.7%, and product yield is 94.9%, this catalyst is after moving 1200 hours continuously, and its product reaction yield is 92.5%.
Embodiment 4
Method according to example 1 prepares catalyst and investigates evaluate catalysts.
Wherein catalyst consists of: cupric oxide 8 grams, chromium oxide 0.5 gram, aluminium oxide 89.48 grams, potassium oxide, sodium oxide molybdena, barytic mixture 0.02 gram, the mixture 2 that contains phosphorus, cerium, zinc oxide restrains, 240 ℃ of temperature, pressure is normal pressure, and the liquid phase air speed is 0.35 hour
-1Under the condition, investigate and estimate, drop into furfural 100 grams, sample analysis after 5 hours contains 2-methylfuran 83.71 grams in the product, furfuryl alcohol 1.63 grams, and 2-methyl tetrahydrochysene furan is ridiculed 0.20 gram: tetrahydrofurfuryl alcohol and pentanediol are zero; Furfural is 0.2 gram, and as calculated, its furfural conversion ratio is 99.8%, and selectivity of product is 98.2%, and the product yield is 98.0%, and this catalyst is after turning round 1200 hours continuously, and its product yield is 93.8%.
Embodiment 5
Method according to example 1 prepares catalyst and investigates evaluate catalysts.
Wherein catalyst consists of: cupric oxide 12 grams, chromium oxide 2 grams, aluminium oxide 84.76 grams, mixture 1.2 grams of potassium oxide, magnesia, calcium oxide, the mixture 0.04 that contains phosphorus, cerium oxide restrains, 240 ℃ of temperature, pressure is normal pressure, and the liquid phase air speed is 0.30 hour
-1Under the condition, investigate and estimate, drop into furfural 100 grams, sample analysis after 5 hours contains 2-methylfuran 83.37 grams in the product, furfuryl alcohol 1.93 grams, 2-methyltetrahydrofuran 0.18 gram; Tetrahydrofurfuryl alcohol and pentanediol are zero: furfural is 0.3 gram, and as calculated, its furfural conversion ratio is 99.7%, and selectivity of product is 97.9%, and the product yield is 97.6%, and this catalyst is after turning round 1200 hours continuously, and its product yield is 93.4%.
Claims (4)
1. one kind is used for furfural gas-phase catalytic hydrogenation Synthetic 2-methylfuran catalyst, and its composition is by weight percentage: CuO 5～15%, Cr
2O
30.5～5%, Al
2O
380～90%, 0.01～2% at least a oxide that is selected from alkali metal and alkaline-earth metal, 0.01～2% at least a oxide that is selected from P, Bi, Ce, Mo, Zn, B, Co.
2. according to the described catalyst that is used for furfural gas-phase catalytic hydrogenation Synthetic 2-methylfuran of claim 1, the oxide that it is characterized in that being selected from alkali metal and alkaline-earth metal is K
2O, Na
2O, CaO, BaO, MgO.
3. according to the described catalyst that is used for furfural gas-phase catalytic hydrogenation Synthetic 2-methylfuran of claim 1, it is characterized in that at least a percentage by weight that is selected from the oxide of alkali metal and alkaline-earth metal is 0.5～1%.
4. according to the described catalyst that is used for furfural gas-phase catalytic hydrogenation Synthetic 2-methylfuran of claim 1, the percentage by weight that it is characterized in that the oxide of at least a P of being selected from, Bi, Ce, Mo, Zn, B, Co is 0.04～1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95111759 CN1047100C (en) | 1995-09-15 | 1995-09-15 | Catalyst for furfural gas-phase hydrogenization synthetizing 2-methyl furan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95111759 CN1047100C (en) | 1995-09-15 | 1995-09-15 | Catalyst for furfural gas-phase hydrogenization synthetizing 2-methyl furan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1145274A CN1145274A (en) | 1997-03-19 |
| CN1047100C true CN1047100C (en) | 1999-12-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95111759 Expired - Fee Related CN1047100C (en) | 1995-09-15 | 1995-09-15 | Catalyst for furfural gas-phase hydrogenization synthetizing 2-methyl furan |
Country Status (1)
| Country | Link |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089035C (en) * | 2000-08-04 | 2002-08-14 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde and its application |
| JP5484321B2 (en) * | 2007-07-02 | 2014-05-07 | ビーエーエスエフ ソシエタス・ヨーロピア | Process for the production of methyltetrahydrofuran from furfural over two catalysts in a structured packed bed in one step |
| CN101961652B (en) * | 2010-10-14 | 2013-06-26 | 来安县迅能催化剂有限公司 | Catalyst for preparing 2-methyl furan through gas phase hydrogenation of furfural and preparation method thereof |
| CN104549319B (en) * | 2013-10-24 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method of preparing 2-methylfuran by gas-phase hydrogenation of furaldehyde |
| CN115779915B (en) * | 2022-11-15 | 2023-08-29 | 山东一诺生物质材料有限公司 | Catalyst for producing 2-methyl furan by using furfuryl alcohol |
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1995
- 1995-09-15 CN CN 95111759 patent/CN1047100C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1145274A (en) | 1997-03-19 |
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