CN1046100C - Furancarbinol catalyst by furol gas phase catalytic hydrogenation - Google Patents
Furancarbinol catalyst by furol gas phase catalytic hydrogenation Download PDFInfo
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- CN1046100C CN1046100C CN94101975A CN94101975A CN1046100C CN 1046100 C CN1046100 C CN 1046100C CN 94101975 A CN94101975 A CN 94101975A CN 94101975 A CN94101975 A CN 94101975A CN 1046100 C CN1046100 C CN 1046100C
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- furfural
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Abstract
The present invention provides a catalyst for preparing furfuralcohol by furfural gas-phase hydrogenation. The present invention is prepared from 30 to 52 wt% of CuO, 28 to 56 wt% of Cr2O3, 5 to 15 wt% of CaO and 2 to 14 wt% of oxide in the VIII group, and an amount of zincum can be added in the present invention. The present invention can operate for more than 1300 hours under the conditions that the reaction temperature is from 90 to 170 DEG C, the pressure is less than 0.5MPa, the feeding load of furfural is 0.1 to 0.65g of furfural per catalyst. G. h, and the molar ratio of hydrogen to furfural is 1: (7 to 62); the conversion rate of the furfural still keeps more than 95%, and the treating capacity of the furfural by one gram of the catalyst for preparing furfuralcohol by furfural gas-phase hydrogenation can reach as high as 450 grams.
Description
The invention belongs to the preparation of furfuryl alcohol, be specifically related to a kind of catalyzer of furfural gas-phase catalytic hydrogenation system furfuryl alcohol.
Furfural shortening system furfuryl alcohol, that adopts at present has two kinds of methods: i.e. vapor phase process and liquid phase method.Liquid phase method generally is at 180-210 ℃, middle pressure (5-8MPa) or high pressure (more than the 10MPa) hydrogenation.Higher and the material back-mixing of liquid phase method temperature of reaction the deep hydrogenation of furfuryl alcohol takes place easily, so by product is more, the raw material consumption height, and used copper, chromium-based catalysts are discharged reactor with hydrogenation products, can not regenerate chromium seriously polluted.Vapor phase process generally is below 170 ℃, hydrogenation under normal pressure or the low pressure condition, and this method is paid reaction and is reduced, because catalyzer is also renewable with the product discharge, so eliminated catalyst contamination basically.Vapor phase process hydrogenation catalyst system therefor is seen so that cupric oxide series more, generally be with copper, chromium is main active constituent, Na in addition, Si, promotor such as Ca or Ba constitutes, intelligent as the groove scape, " research of hydrogenation of furfural system furfuryl alcohol catalyzed reaction " (TaiYuan Industry University's journal that Ye Peirong writes, 1987 the 3rd phases, P52), with by Zhang Xiaoyan, Lu Yun, " furfural gas-phase catalytic hydrogenation system furfuryl alcohol " (Beijing chemical industry journal that Liu Rong merit three people write jointly, 1988 the 15th volumes, the 4th phase, P15) two pieces of documents provide the laboratory report of Cu-Si catalyzer and DHK-I type catalyzer (do not disclose the concrete composition of catalyzer in the literary composition, estimation is the Cu-Cr series catalysts) respectively.In the former report, the author mentions catalyzer the treatment capacity of furfural is up to 340Kg (furfural)/Kg (urging) abroad, and 300g (furfural)/g (urging) is only accomplished in their experiment.Then be provided in the latter's the laboratory report and guarantee that the maximum load that the furfural transformation efficiency reaches 95% catalyzer when above is 0.125g furfural/g catalyzer h, this shows that the common drawback of above-mentioned catalyzer is that the load of catalyzer is lower, the life-span is shorter.
The object of the present invention is to provide a kind of Cu-series catalyst of improved hydrogenation of furfural system furfuryl alcohol, this catalyzer has higher load and life-span.
Alduronic gas-phase hydrogenation to prepare alditol catalyzer of the present invention is the Cu-series catalyst that contains copper, chromium, calcium, and the weight percentage ranges of its composition is:
CuO 30-52
Cr
2O
3 28-56
CaO 5-15
The VIII family metal oxide is selected from nickel, palladium or platinum 2-14
In above-mentioned catalyzer, can also add an amount of zinc to improve selectivity of catalyst, the weight percentage ranges of its composition is:
CuO 30-52
Cr
2O
3 28-46
CaO 5-15
The VIII family metal oxide is selected from nickel, palladium or platinum 2-14
ZnO 2-10
Described VIII family metal oxide can be nickel, palladium or platinum, though palladium and platinum have good catalytic activity, owing to cost an arm and a leg, thereby consider the cheap nickel of the many employings of its price factor in actual applications.The present invention recommends following two kinds of catalyzer, and the weight percentage ranges of its composition is:
A. CuO 39-45
Cr
2O
540-50
CaO 5-12
NiO 6-12
B. CuO 39-45
Cr
2O
340-50
CaO 5-12
NiO 6-12
ZuO 3-7
Catalyzer of the present invention can adopt precipitator method preparation, is about to be mixed with solution after the metal-salt dissolving, and post precipitation forms throw out filtration, drying, roasting, moulding.The granularity of catalyzer can be selected according to the size and the processing condition of reactor, generally at the 10-20 order.
Furancarbinol catalyst by furol gas phase catalytic hydrogenation of the present invention is that to add calcium, zinc and VIII family element in the catalyzer of copper chromium system be auxiliary agent, and the especially adding of VIII family element makes catalyzer obtain promoting significantly.Catalyzer of the present invention is at temperature of reaction 90-10 ℃, below the pressure 0.5MPa, furfural feed loading 0.1-0.65g furfural/catalyzer .g.h, hydrogen and furfural mol ratio are 1: under the operational conditions of 7-62, but continuous operation 1300/ hour, the furfural transformation efficiency still remains on more than 95%, and the furfural treatment capacity of every gram catalyzer can be up to 450 grams.This shows that catalyzer of the present invention is better than all catalyzer at present, thereby is with a wide range of applications and industrial utility value.
Embodiment 1
Take by weighing cupric nitrate 85.0 grams, chromium nitrate 165.8 grams, nitrocalcite 17.7 grams, nickelous nitrate 24.5 grams are dissolved in the 800ml distilled water, are mixed with solution.Mixing obtains precipitation with alkaline precipitating agent under agitation condition with this solution, aging 1 hour then.Throw out after filtration, about 110 ℃ dry 12 hours, and, must about 70 gram particle degree be 10-20 purpose copper, chromium, calcium, nickel catalyst, hereinafter to be referred as No. 1 catalyzer at 3-5 hour aftershaping of 350 ℃ of left and right sides roastings.
Embodiment 2
Take by weighing cupric nitrate 85.0 grams, chromium nitrate 151.1 grams, nitrocalcite 17.7 grams, nickelous nitrate 24.5 grams, zinc nitrate 10.2 grams are dissolved in the 800ml distilled water and are mixed with solution.Preparation of catalysts such as embodiment 1.Making about 70 gram particle degree at last is 10-20 purpose copper, chromium, calcium, nickel, zinc system catalyst, hereinafter to be referred as No. 2 catalyzer.
Embodiment 3
Evaluating catalyst.Get No. 1 or No. 2 catalyzer 27 grams granularity 10-20 order, about 26 milliliters of volume, pack into 12 millimeters of internal diameters, in the high 530 millimeters stainless steel reactor, furfural is thrown the vaporizer inlet into micro pump, feed vaporizing chamber with mix the back from the hydrogen in the steel cylinder, enter reactor then.At temperature of reaction 120-150 ℃, normal pressure, furfural feed loading 0.19-0.58g (furfural)/cat (g) .hr, hydrogen and furfural mol ratio are to react under the condition of 10-20, reacted gas obtains liquid product after condensation.Utilize gas-chromatography to carry out quantitative analysis, tail gas emptying.Two kinds of catalyst performances see the following form with the relation in reaction times.Reaction times 23 12 19 22 (hr) catalyzer transforms to select to transform to select to transform to select to transform to select to transform selects numbering forthright forthright
(％) (％) (％) (％) (％) (％) (％) (％) (％) (％) 1 100 94.5 100 95.8 100 98.0 100 98.5 99.4 98.5 2 100 95.0 100 96.0 100 98.3 100 98.8 99.8 99.4
From table, can find out, owing to add an amount of zinc element, slightly improve selectivity of catalyst in No. 2 catalyzer.
Embodiment 4
Get catalyzer No. 2, other condition is with embodiment 3.At temperature of reaction 90-170 ℃, 0.5Mpa below, furfural feed loading 0.30-0.38g (furfural)/cat. (g) .hr, under the condition of hydrogen and furfural mol ratio 1: 20-45, its the active not obviously decline in 1300 hours of this catalyzer continuous operation, transformation efficiency still can keep 95%, and the every gram catalyst treatment furfural amount of accumulative total reaches 450 grams.
Claims (4)
1. an alduronic gas-phase hydrogenation to prepare alditol catalyzer contains copper, chromium, calcium in the catalyzer, it is characterized in that the weight percentage ranges of its composition is:
CuO 30-52
Cr
2O
3 28-56
CaO 5-15
The VIII family metal oxide is selected from nickel, palladium or platinum 2-14.
2. catalyzer as claimed in claim 1 is characterized in that and can add zinc element in above-mentioned catalyzer, and the weight percentage ranges of its composition is:
CuO 30-52
Cr
2O
3 28-46
CaO 5-15
The VIII family metal oxide is selected from nickel, palladium or platinum 2-14
ZnO 2-10。
3. catalyzer as claimed in claim 1 is characterized in that the composition weight percentage ranges of described catalyzer is:
CuO 39-45
Cr
2O
340-50
CaO 5-12
NiO 6-12。
4. catalyzer as claimed in claim 1 or 2 is characterized in that the composition weight percentage ranges of described catalyzer is:
CuO 39-45
Cr
2O
340-50
CaO 5-12
NiO 6-12
ZnO 3-7。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94101975A CN1046100C (en) | 1994-02-19 | 1994-02-19 | Furancarbinol catalyst by furol gas phase catalytic hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94101975A CN1046100C (en) | 1994-02-19 | 1994-02-19 | Furancarbinol catalyst by furol gas phase catalytic hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1107079A CN1107079A (en) | 1995-08-23 |
| CN1046100C true CN1046100C (en) | 1999-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94101975A Expired - Fee Related CN1046100C (en) | 1994-02-19 | 1994-02-19 | Furancarbinol catalyst by furol gas phase catalytic hydrogenation |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077807C (en) * | 1995-10-31 | 2002-01-16 | 中国科学院大连化学物理研究所 | Methed and catalyst for producing sugar alcohol by furfurol hydrogenation |
| CN100438976C (en) * | 2005-12-07 | 2008-12-03 | 南化集团研究院 | Catalyst for alduronic gas-phase hydrogenation to prepare alditol and preparing method |
| CN102247860A (en) * | 2011-08-03 | 2011-11-23 | 中国地质大学（武汉） | Method for preparing hydrogenation catalyst by loading copper oxide on silica gel carrier |
| CN107445923B (en) * | 2017-08-23 | 2019-12-13 | 深圳名飞远科技有限公司 | process for preparing furfuryl alcohol by hydrogenation of furfural |
| CN110563674B (en) * | 2019-07-25 | 2023-05-05 | 宏业生物科技股份有限公司 | Device and method for preparing furfuryl alcohol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956459A (en) * | 1972-05-18 | 1976-05-11 | American Cyanamid Company | Process for the elimination of pollutants in exhaust gases |
| JPS55154921A (en) * | 1979-05-22 | 1980-12-02 | Nippon Petrochem Co Ltd | Purification of olefin |
| CN1054060A (en) * | 1989-12-21 | 1991-08-28 | 联合碳化化学品及塑料有限公司 | With the hydrogenation that copper-aluminium-other metal catalyst carries out |
-
1994
- 1994-02-19 CN CN94101975A patent/CN1046100C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956459A (en) * | 1972-05-18 | 1976-05-11 | American Cyanamid Company | Process for the elimination of pollutants in exhaust gases |
| JPS55154921A (en) * | 1979-05-22 | 1980-12-02 | Nippon Petrochem Co Ltd | Purification of olefin |
| CN1054060A (en) * | 1989-12-21 | 1991-08-28 | 联合碳化化学品及塑料有限公司 | With the hydrogenation that copper-aluminium-other metal catalyst carries out |
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|---|---|
| CN1107079A (en) | 1995-08-23 |
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