CN1077807C - Methed and catalyst for producing sugar alcohol by furfurol hydrogenation - Google Patents
Methed and catalyst for producing sugar alcohol by furfurol hydrogenation Download PDFInfo
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- CN1077807C CN1077807C CN95112092A CN95112092A CN1077807C CN 1077807 C CN1077807 C CN 1077807C CN 95112092 A CN95112092 A CN 95112092A CN 95112092 A CN95112092 A CN 95112092A CN 1077807 C CN1077807 C CN 1077807C
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- catalyst
- hydrogenation
- furfural
- oxide
- furfuryl alcohol
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Abstract
The present invention relates to a catalyst for preparing furfuralcohol by furfural hydrogenation. The present invention is characterized in that the catalyst is prepared from the components of the proportion by weight: 30 to 70 wt% of cupric oxide, 20 to 60 wt% of zinc oxide, 2 to 20 wt% of alumina, 1 to 10 wt% of alkali metal or alkaline earth oxide (K2O, Na2O, CaO, BaO and MgO) and 1 to 10 wt% of transition metal oxide (CoO, MnO, FeO and MoO). The present invention has no harmful substances, excellent activity, excellent selectivity and excellent stability.
Description
The present invention relates to make the furfuryl alcohol technology, a kind of direct gas phase hydrogenation process and the employed catalyst of this process from furfural production high-purity furfuryl alcohol are provided especially.
Furfuryl alcohol is important industrial chemicals, and it is on copper catalyst that the furane resins made from its are widely used in industry, furfuryl alcohols such as casting, automobile, makes with gas phase or liquid phase furfural hydrogenation.Alditol is by hydrolysis such as corncobs and make.China is second-biggest-in-the-world Maize Production state, and sufficient raw material resources are arranged.The liquid-phase hydrogenatin method is because aspects such as technology and energy consumption are not so good as vapor phase method, so vapor phase method obtains very fast development recently.The industrial gas phase furfural hydrogenation device of many covers such as China Shandong Zibo Linzhou City Organic Chemical Plant, Baoding chemical industry two factories uses the import catalyst.The U.S.'s main component of import furfuraldehyde hydrogenation catalyst is CuO-Cr
2O
3, because containing metal chromium brings quite difficulty for the processing of operation and dead catalyst.The furfural hydrogenation furancarbinol catalyst and the process condition of patent documentation report are as follows:
1.British Pat.734,118 to have narrated in temperature be 80-200 ℃ of situation therapeutic method to keep the adverse qi flowing downward phase method of hydrotreating, and employed catalyst is the copper catalyst that contains 50～20% anhydrous sodium metasilicate.
2.FRG Pat.881,544 have disclosed with the cupric silicate catalysts of periodic table of elements II family element as auxiliary agent.
3.FRG Pat.835,148 have disclosed the copper catalyst that is supported on alkali-metal silicate or the silicic acid.
4.French Pat.2,250,099 have disclosed with the Cu-Al alloy is as catalyst, carries out furfural hydrogenation with syngas for synthetic ammonia that hydrogenation temperature is 100～150 ℃.
5.Polish Pat.67674 has narrated use CuO-Cr
2O
3(CuCr
2O
4) as catalyst, calcium oxide, barium monoxide, zinc oxide is as auxiliary agent, temperature is that furfural hydrogenation is produced the method for furfuryl alcohol and 2-methylfuran under the atmospheric pressure at 100～300 ℃, reaction pressure,
6.US Pat.2,094,975 narration furfural liquid-phase hydrogenatin, CuCr
2O
4Catalyst, second family metal oxide be as auxiliary agent, 90～175 ℃ of temperature ranges.
Furfuraldehyde hydrogenation catalyst can be divided into two big classes from the catalyst of documents and materials and domestic introduction, a class is with CuO-SiO
2Be main, another kind of is with CuO-Cr
2O
3Be main, more general with the latter, CuO-SiO
2The catalyst conversion ratio is on the low side, and is about 85%, and service life is short, and hydrogen is urged than height, and CuO-Cr
2O
3The subject matter of catalyst is Cr
2O
3Be proved to be extremely the carcinogenic substance of poison, all can brought injury and serious environmental to pollute aspect the processing of production, use and the dead catalyst of catalyst operating personnel.Typical alditol hydrogenation example such as U.S.Pat, 4,216,905 (1981) institutes are narrated, and the use catalyst is CuO-Cr
2O
3-CaO-graphite, catalyst particle size: 8～15 millimeters, the catalyst reactor total filling amount is 750～800 kilograms, the furfural charging rate is 100 kilograms/hour, and with the hydrogen mixed feeding, reaction temperature is 50～140 ℃, reaction pressure is 60～65 atmospheric pressure, after the rectifying of product process, in the 20mmHg vacuum distillation apparatus, 0.61 kilogram/hour of 30～75% ℃ foreshot output (0.6%), 76～78 ℃/20mmHg99.96 of furfuryl alcohol place master's fraction kilogram/hour (98%), at the bottom of the still 1.32 kilograms/hour (1.3%), lose 6.11 kilograms/hour (0.1%) furfuryl alcohol purity 99.4%.
The object of the present invention is to provide a kind of catalyst of furfural hydrogenation system furfuryl alcohol, it does not contain any harmful substance, and excellent activity, selectivity and stability are arranged.
The invention provides a kind of catalyst of furfural hydrogenation system furfuryl alcohol, it is characterized in that, proportioning components is:
| Cupric oxide: | 30—70％WT |
| Zinc oxide: | 20—60％WT |
| Aluminium oxide: | 2—20％WT |
Be selected from K
2O, Na
2The alkali metal of one of O, CaO, BaO, MgO or alkaline earth oxide: 1-10%WT
Be selected from the transition metal oxide of one of CoO, MnO, FeO, MoO: 1-10%WT.
The Preparation of catalysts method is to adopt the feasible coprecipitation method preparation of industry usually.All catalyst preparation process may be summarized to be following several steps:
1. metal salt solution 2. in and 3. 4. 5. roasting of drying of filtration washing of co-precipitation
Catalyst of the present invention can be used for common gas phase hydrogenation process from furfural production high-purity furfural, and the reaction pressure of process is a normal pressure, 80～200 ℃ of reaction temperatures.
From PolishPat.No.67674, and USPat.4,261,905 patent documentations such as grade, and mostly the chemical composition of the catalyst of the furfural hydrogenation system furfuryl alcohol of industrial extensive employing at present is CuO, Cr
2O
3Be main; Employing CuO/SiO is also arranged
2The patent report of System Catalyst is as U.S.Pat.4, and 85,022 (Jan.22,1980) the present invention does not contain crome metal in furfuraldehyde hydrogenation catalyst, so nontoxic, nuisanceless; The CuO-SiO that is being different from the patent documentation fully on the chemical composition to be reported again simultaneously
2Catalyst does not contain SiO at catalyst of the present invention
2Catalyst of the present invention and corresponding furfural hydrogasification producing furancarbinol technology can directly obtain the high-purity furfuryl alcohol from furfural.
In a word, the invention has the advantages that the catalyst Nonpoisonous, non-environmental-pollution, avoided the U.S. Catalysts Cu O-Cr that (Shandong Zibo Linzhou City Organic Chemical Plant, Baoding chemical industry two factories) use in the present furfural hydrogenation system furfuryl alcohol commercial plant
2O
3In the crome metal murder by poisoning and the environmental pollution that cause, simultaneously this catalyst also have active high, series of advantages such as the low and hydrogen/aldehyde of reaction temperature is than low, and energy consumption is low.
Below by embodiment in detail the present invention is described in detail:
Embodiment 1: with 20.5 gram copper nitrates, 49.3 gram zinc nitrates, 18.4 gram aluminum nitrates, 51.1 gram magnesium nitrates and 5.2 gram nitric acid molybdenums, be dissolved in 280 ml distilled waters, adding under the thermal agitation, use Na
2Co
3PH=7～8 that neutralize, then with after the washing of precipitate in 110 ℃ baking oven dry 6 hours, 400 ℃ of calcinations 4 hours in Muffle furnace are then played the sheet moulding to catalyst fines at last, just obtain the furfural hydrogenation furancarbinol catalyst.
Embodiment 2: the catalyst that makes use-case 1 preparation, on small-sized gas phase fixed-bed reactor, catalyst amount 5.89 grams, granularity 20～40 orders are in 160～300 ℃ of temperature ranges, behind hydrogen reducing, add furfural and hydrogen and carry out gas phase hydrogenation, reaction temperature is that 140 ℃, reaction pressure are 0.1MPa, furfural charging rate 1.16 Grams Per Hours, and hydrogen flow rate 7.0 liters/hour, the furfural conversion ratio is 100%, and the furfuryl alcohol selectivity is 99.8%.
Embodiment 3: on the device with example 2, catalyst amount and reduction step are also with example 1, and reaction temperature is 137 ℃, reaction pressure 0.1MPa, and furfural charging rate 2.1 Grams Per Hours, hydrogen 10 liters/hour, the furfural conversion ratio is 100%, furfuryl alcohol selectivity 99.8%.
Embodiment 4: use same catalyst, at φ
InOn the reactor of 23mm, catalyst uses 770 milliliters, bed height 1.6m, and reaction temperature: 120～145 ℃, reactor inlet pressure 0.14MPa, reactor outlet pressure 0.12MPa, furfural 0.083 milliliter of/milliliter catalyst that feeds intake.Hour, hydrogen/furfural (molecular proportion)=32, under the condition of hydrogen circulation, successive reaction 1000 hours, the furfural conversion ratio is 98.8%.Furfuryl alcohol selectivity 98.3%, 2-methylfuran selectivity is 1.7%.
Comparative example:
The relevant comparative example of the present invention sees Table 1:
| Catalyst | Reaction temperature (℃) | Alditol conversion ratio (%) | Selectivity (%) | |
| U.S.Pat 4,185,022 | CuO/SiO 2 | 120～150 | 100 | 98 |
| U.S.Pat 4,261,905 | CuO-Cr 2O 3 | 50～140 | 100 | 98 |
| The present invention | CuO-ZnO- Sl 2O 3 | 120～140 | 100 | 99.8 |
Claims (2)
1. the catalyst of a furfural hydrogenation system furfuryl alcohol is characterized in that, proportioning components is:
Be selected from K
2O, Na
2The alkali metal of one of O, CaO, BaO, MgO or alkaline earth oxide: 1-10%WT
Be selected from the transition metal oxide of one of CoO, MnO, FeO, MoO: 1-10%WT.
2. the method for a furfural hydrogenation system furfuryl alcohol is to adopt the gas phase hydrogenation process, it is characterized in that adopting the described catalyst of claim 1, and the reaction pressure of process is a normal pressure, 80～200 ℃ of reaction temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112092A CN1077807C (en) | 1995-10-31 | 1995-10-31 | Methed and catalyst for producing sugar alcohol by furfurol hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112092A CN1077807C (en) | 1995-10-31 | 1995-10-31 | Methed and catalyst for producing sugar alcohol by furfurol hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149507A CN1149507A (en) | 1997-05-14 |
| CN1077807C true CN1077807C (en) | 2002-01-16 |
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ID=5079314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95112092A Expired - Fee Related CN1077807C (en) | 1995-10-31 | 1995-10-31 | Methed and catalyst for producing sugar alcohol by furfurol hydrogenation |
Country Status (1)
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102584C (en) * | 2000-05-12 | 2003-03-05 | 石油大学(华东) | Catalyst and process for preparing tetrahydrofurfuryl alcohol |
| CN100358627C (en) * | 2005-06-06 | 2008-01-02 | 周焕文 | Furfuraldehyde hydrogenation catalyst and method for preparing the same |
| CN101343264B (en) * | 2008-08-29 | 2010-05-12 | 河南宏业化工有限公司 | Method for pre-heating furfural and catalyst in furylcarbinol preparation and special equipment thereof |
| US9084990B2 (en) * | 2009-07-17 | 2015-07-21 | Southwest Nanotechnologies, Inc. | Catalyst and methods for producing multi-wall carbon nanotubes |
| CN102302937A (en) * | 2011-07-06 | 2012-01-04 | 上海焦化有限公司 | Catalyst for preparing neopentyl glycol by hydrogenation of hydroxypivalaldehyde and preparation method thereof |
| CN105056958B (en) * | 2015-08-21 | 2017-12-26 | 宁波海越新材料有限公司 | A kind of preparation method of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst |
| CN105399705B (en) * | 2015-12-28 | 2018-02-13 | 中国石油大学(北京) | A kind of method that furfuryl alcohol is prepared using hydrogen transfer reaction |
| CN107376929A (en) * | 2017-08-09 | 2017-11-24 | 南京工业大学 | Catalytic combustion catalyst, preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0261603A2 (en) * | 1986-09-23 | 1988-03-30 | BASF Aktiengesellschaft | Process for the preparation of furan by decarbonylation of furfural |
| CN1066610A (en) * | 1991-05-13 | 1992-12-02 | 陕西省渭南市东方化工厂 | Cobalt skeleton catalyst for hydrogenation and preparation method thereof |
| CN1107079A (en) * | 1994-02-19 | 1995-08-23 | 中国科学院山西煤碳化学研究所 | Furancarbinol catalyst by furol gas phase catalytic hydrogenation |
| EP0669163A1 (en) * | 1994-02-02 | 1995-08-30 | Degussa Aktiengesellschaft | Formed copper catalysator for the selective hydrogenation of furfural to furfuryl-alcohol |
-
1995
- 1995-10-31 CN CN95112092A patent/CN1077807C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0261603A2 (en) * | 1986-09-23 | 1988-03-30 | BASF Aktiengesellschaft | Process for the preparation of furan by decarbonylation of furfural |
| CN1066610A (en) * | 1991-05-13 | 1992-12-02 | 陕西省渭南市东方化工厂 | Cobalt skeleton catalyst for hydrogenation and preparation method thereof |
| EP0669163A1 (en) * | 1994-02-02 | 1995-08-30 | Degussa Aktiengesellschaft | Formed copper catalysator for the selective hydrogenation of furfural to furfuryl-alcohol |
| CN1107079A (en) * | 1994-02-19 | 1995-08-23 | 中国科学院山西煤碳化学研究所 | Furancarbinol catalyst by furol gas phase catalytic hydrogenation |
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| Publication number | Publication date |
|---|---|
| CN1149507A (en) | 1997-05-14 |
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