CN1120975A - Aldose hydrogenating process and catalyst for producing sugar alcohol - Google Patents
Aldose hydrogenating process and catalyst for producing sugar alcohol Download PDFInfo
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- CN1120975A CN1120975A CN 95111830 CN95111830A CN1120975A CN 1120975 A CN1120975 A CN 1120975A CN 95111830 CN95111830 CN 95111830 CN 95111830 A CN95111830 A CN 95111830A CN 1120975 A CN1120975 A CN 1120975A
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- alditol
- sugar alcohol
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Abstract
The catalyst for hydrogenating aldose to produce sugar alcohol features its composition of: CuO 30-70 wt%, ZnO 20-60 wt%, Al2O3 2-20 wt%, oxide of alkali or alkaline-earth metal (k2O, CaO, BaO, MgO) 1-10 wt% and oxide of transition metal (CoO, MnO, MoO) 1-10 wt%. It contains no harmful material and has excellent activity, selectivity and stability.
Description
The present invention relates to the sugar alcohol technology, a kind of direct gas phase hydrogenation process and the employed catalyst of this process from alditol production high-purity sugar alcohol are provided especially.
Sugar alcohol is important industrial chemicals, and it is on copper catalyst that the furane resins made from its are widely used in industry, sugar alcohols such as casting, automobile, makes with gas phase or liquid phase alditol 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 alditol hydrogenation plant 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 alditol hydrogenation catalyst is CuO-Cr
2O
3, because containing metal chromium brings quite difficulty for the processing of operation and dead catalyst.The alditol hydrogenation sugar alcohol 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 the alditol 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 the alditol hydrogenation is produced the method for sugar alcohol and 2-methylfuran under the atmospheric pressure at 100～300 ℃, reaction pressure,
6.US Pat.2,094,975 narration alditol liquid-phase hydrogenatin, CuCr
2O
4Catalyst, second family metal oxide be as auxiliary agent, 90～175 ℃ of temperature ranges.
The alditol 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/aldehyde is than high, 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 alditol charging rate is 100 kilograms/hour, and with the hydrogen mixed feeding, reaction temperature is 50～140 ℃, reaction pressure is 60～65 atmospheric pressure, product is through after the rectifying, and in the 20mmHg vacuum distillation apparatus, 30～75 ℃ foreshot is 0.61 kilogram/hour (0.6%) of amount sternly, 99.96 kilograms/hour of 76～78 ℃/20mmHg of sugar alcohol place master's fraction (98%), at the bottom of the still 1.32 kilograms/hour (1.3%), lose 6.11 kilograms/hour (0.1%) sugar alcohol purity 99.4%.
The object of the present invention is to provide a kind of catalyst of alditol hydrogenation sugar alcohol, it does not contain any harmful substance, and excellent activity, selectivity and stability are arranged.
The invention provides a kind of catalyst of alditol hydrogenation sugar alcohol, it is characterized in that, proportioning components is:
Cupric oxide: 30-70% (WT%)
Zinc oxide: 20-60% (WT%)
Aluminium oxide: 2-20% (WT%)
Alkali metal or alkaline earth oxide (K
2O, CaO, BaO, MgO): 1-10% (WT%)
Transition metal oxide (CoO, MnO, 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 alditol production high-purity alditol, and the reaction pressure of process is 0.1～0.5MPa, 100～160 ℃ of reaction temperatures.
From Polish Pat.No.67674 and US Pat.4,261,905 patent documentations such as grade, and mostly the chemical composition of the catalyst of the alditol hydrogenation sugar 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 the alditol hydrogenation catalyst, so nontoxic, nuisanceless; The CuO-SiO that is different from the patent documentation to be reported at intact gold on the chemical composition again simultaneously
2Catalyst does not contain SiO at catalyst of the present invention
2Catalyst of the present invention and corresponding alditol gas phase hydrogenation are produced the sugar alcohol technology can directly obtain the high-purity sugar alcohol from alditol.
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 alditol hydrogenation sugar 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 alditol hydrogenation sugar alcohol 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 alditol and hydrogen and carry out gas phase hydrogenation, reaction temperature is that 140 ℃, reaction pressure are 0.1MPa, alditol charging rate 1.16 Grams Per Hours, and hydrogen flow rate 7.0 liters/hour, the alditol conversion ratio is 100%, and the sugar 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 alditol charging rate 2.1 Grams Per Hours, hydrogen 10 liters/hour, the alditol conversion ratio is 100%, sugar alcohol selectivity 99.8%.
Embodiment 4: use same catalyst, at Ф
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, alditol 0.083 milliliter of/milliliter catalyst that feeds intake.Hour, hydrogen/alditol (molecular proportion)=32, under the condition of hydrogen circulation, successive reaction 1000 hours, the alditol conversion ratio is 98.8%.Sugar 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- ?SI 2O 3 | ??120～140 | ????100 | ??99.8 |
Claims (2)
1. the catalyst of an alditol hydrogenation sugar alcohol, it is characterized in that proportioning components is: cupric oxide: 30-70% (WT%) zinc oxide: 20-60% (WT%) aluminium oxide: 2-20% (WT%) alkali metal or alkaline earth oxide (K
2O, CaO, BaO, MgO): 1-10% (WT%) transition metal oxide (CoO, MnO, MoO): 1-10% (WT%)
2. the method for an alditol hydrogenation sugar 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 0.1～0.5MPa, 100～160 ℃ of reaction temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111830A CN1081082C (en) | 1995-06-28 | 1995-06-28 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111830A CN1081082C (en) | 1995-06-28 | 1995-06-28 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1120975A true CN1120975A (en) | 1996-04-24 |
| CN1081082C CN1081082C (en) | 2002-03-20 |
Family
ID=5079073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111830A Expired - Fee Related CN1081082C (en) | 1995-06-28 | 1995-06-28 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
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|---|---|
| CN (1) | CN1081082C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095400C (en) * | 1999-12-08 | 2002-12-04 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone by gas-phase normal-pressure hydrogenation of maleic anhydride and its use |
| CN1101262C (en) * | 1999-09-29 | 2003-02-12 | 中国石油化工集团公司 | Process for preparing Cu-contained catalyst |
| CN1122567C (en) * | 1998-03-26 | 2003-10-01 | 中国科学院大连化学物理研究所 | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture |
| CN102249854A (en) * | 2011-07-06 | 2011-11-23 | 上海焦化有限公司 | Two-step-method hydrogenation process for preparing neopentyl glycol |
| 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 |
| CN105618063A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst for preparation of beta-diol form beta-diketone by hydrogenation |
| CN106749120A (en) * | 2017-01-13 | 2017-05-31 | 中国石油化工股份有限公司 | The method that furfural hydrogenation prepares furfuryl alcohol |
| CN106810516A (en) * | 2017-01-13 | 2017-06-09 | 中国石油化工股份有限公司 | The preparation method of furfuryl alcohol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2732250B1 (en) * | 1977-07-16 | 1978-07-06 | Muhr & Bender | Fastening device for fastening railroad tracks on railway sleepers |
| CN1031178C (en) * | 1991-05-13 | 1996-03-06 | 陕西省渭南市东方化工厂 | Raney cobalt hydrogenation catalyst for producing furfuryl alcohol and preparation method thereof |
-
1995
- 1995-06-28 CN CN95111830A patent/CN1081082C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122567C (en) * | 1998-03-26 | 2003-10-01 | 中国科学院大连化学物理研究所 | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture |
| CN1101262C (en) * | 1999-09-29 | 2003-02-12 | 中国石油化工集团公司 | Process for preparing Cu-contained catalyst |
| CN1095400C (en) * | 1999-12-08 | 2002-12-04 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone by gas-phase normal-pressure hydrogenation of maleic anhydride and its use |
| CN102249854A (en) * | 2011-07-06 | 2011-11-23 | 上海焦化有限公司 | Two-step-method hydrogenation process for preparing neopentyl glycol |
| 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 |
| CN102249854B (en) * | 2011-07-06 | 2014-02-19 | 上海焦化有限公司 | Two-step-method hydrogenation process for preparing neopentyl glycol |
| CN105618063A (en) * | 2014-11-04 | 2016-06-01 | 中国石油化工股份有限公司 | Catalyst for preparation of beta-diol form beta-diketone by hydrogenation |
| CN105618063B (en) * | 2014-11-04 | 2018-08-17 | 中国石油化工股份有限公司 | It is a kind of for beta-diketon Hydrogenation for beta-diol catalyst |
| CN106749120A (en) * | 2017-01-13 | 2017-05-31 | 中国石油化工股份有限公司 | The method that furfural hydrogenation prepares furfuryl alcohol |
| CN106810516A (en) * | 2017-01-13 | 2017-06-09 | 中国石油化工股份有限公司 | The preparation method of furfuryl alcohol |
| CN106749120B (en) * | 2017-01-13 | 2019-04-23 | 中国石油化工股份有限公司 | The method that furfural hydrogenation prepares furfuryl alcohol |
| CN106810516B (en) * | 2017-01-13 | 2019-04-26 | 中国石油化工股份有限公司 | The preparation method of furfuryl alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1081082C (en) | 2002-03-20 |
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