CN105712840A - Method for producing high-carbon primary alcohols by catalytic conversion of ethanol - Google Patents
Method for producing high-carbon primary alcohols by catalytic conversion of ethanol Download PDFInfo
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Abstract
The present invention provides a method for producing high-carbon primary alcohols by catalytic conversion of ethanol. Even-number-carbon primary alcohols are prepared in a fixed bed by catalytic conversion of ethanol by use of transition metal-compound oxide as a catalyst prepared by co-precipitation method. Compared with the prior art, a raw material used in the method is bio-ethanol, the bio-ethanol has the advantages of being rich in reserves, environmentally friendly, green, pollution-free and the like, the prepared even-number-carbon primary alcohols include butanol, hexanol and octanol, and have the advantages of being highly-economical, wide in use ways, and the like. In addition, in the process, the catalyst is low in price, the reaction selectivity is high, stability is good, products are easy to separate, and the method has important economic value and potential industrial prospects.
Description
Technical field
The present invention relates to bioenergy development technique field, particularly relate to a kind of method that high carbon primary alcohol is prepared in alcohol catalysis conversion.
Background technology
Along with the fast development of the exhaustion of Fossil fuel, the aggravation of environmental pollution and fermentation technique, ethanol causes the extensive attention of people as a kind of novel energy chemistry platform chemicals.By 2010, the yield of ethanol reached 60,000,000,000 liters.Current most ethanol is mainly used in oil product and adds, thus part replaces fuel oil.But, based on the restriction that safety and solvent are compatible, ethanol addition in oil product is limited, can only be less than 10%, and what this was serious constrains development and the application of ethanol.
Corresponding, the higher alcohols such as butanol have higher adding proportion, and do not affect the normal operation of available engine.Meanwhile, the low molecule idol carbon alcohol such as butanol, hexanol is also a class intermediate chemical, thus is widely used in the various fields such as perfume additive, medicine intermediate, life sciences, and tool has been widely used and industrialization potential.
The even carbon alcohol such as green butanol has two kinds of preparation methoies, a kind of method for biomass direct fermentation, is called for short ABE technique, and this process primary product is ethanol, butanol and acetone.This process reaction time is long, reaction efficiency is low, enzyme relatively costly.Another kind of method is that the even carbon alcohol such as butanol are prepared in catalysis ethanol conversion.Detailed process is shown in aforesaid equation, and the most important process of this process is " by means of hydrogen ".First ethanol dehydrogenation on a catalyst, dissociating, then through aldol condensation, the hydrogen on last catalyst is then added in product to generate the single methanols such as butanol.Under current catalyst system, this reaction ethanol conversion is low, and its dehydrogenation rate is relatively slow, affects the carrying out of subsequent reactions.Meanwhile, ethanol is susceptible in molecule or intermolecular dehydration generates ethylene or ether, thus reducing the selectivity of product.It addition, metal is easily reunited, is grown up in reaction, thus causing catalysqt deactivation.
Purpose provided by the invention is to provide a kind of method that high carbon primary alcohol is prepared in alcohol catalysis conversion, the method can significantly improve the yield of even carbon alcohol, reduce the generation of by-product in course of reaction, stability and the service life of catalyst are improved significantly, the method have simple to operate, catalyst cost is low, good stability, reaction efficiency advantages of higher.
Summary of the invention
It is an object of the invention to provide a kind of method that high carbon primary alcohol is prepared in alcohol catalysis conversion.The method have simple to operate, catalyst cost is low, economical and practical, high, the low power consumption and other advantages that produces even carbon alcohol efficiency.
For achieving the above object, the technical step that the present invention takes is:
Adopting metal-composite oxides is catalyst, it is achieved high carbon primary alcohol is prepared in alcohol catalysis conversion.The formula of catalyst is M-MgO-Al2O3, M is one or more combinations in Ni, Co, Cu, Zn；MgO-Al2O3In the mol ratio of Mg and Al be 1～5:1；The content of M mass is 10-80%；Catalytic conversion reaction carries out in fixed bed reactors, and the temperature of reaction is 180-350 DEG C, and product is taken out of fixed bed reactors by carrier gas.
The catalyst that this reaction adopts is prepared by coprecipitation, and detailed process is as follows:
The soluble nitrate of metal M, Mg, Al of formula ratio is dissolved in deionized water, obtain the saline solution containing M, Mg, Al, M, Mg, Al total concentration in saline solution is 0.02-2mol/L, the aqueous slkali that compound concentration is 0.05-1mol/L is placed in 20～50 DEG C of water-baths, under agitation isopyknic metal salt solution is slowly added in alkali liquor, alkali liquor has Precipitation gradually；Fully after precipitation, the pH of regulation system is 9～11, then bath temperature rises to 50～80 DEG C, and crystallization 1～24h at such a temperature, after the material after crystallization is sequentially passed through filtration, washing, drying and processing, obtains brucite precursor；The brucite precursor obtained original position hydrogen reduction reaction in the reactor processes, and can obtain metallic catalyst；
Alkali in aqueous slkali is mol ratio is NaOH and the Na of 0.5～1.5:12CO3Aqueous solution；M is one or more combinations in Ni and Co, Cu, Zn.
In described catalyst, it is preferable that the weight of metal is the 10-50wt% of total catalyst weight.
Described ethanol is the water content ethanol less than 20wt%.
Carrier gas is one or more in nitrogen, argon, helium, and in reactor, gas pressure is 0.1-10MPa, and the mass space velocity of catalytic reaction is 0.2-20h-1。
In described reaction, preferred reaction temperature is 225-280 DEG C.
Preferred carrier gas is nitrogen, it is preferable that gas pressure is 2-5MPa, it is preferable that gas flow rate is 10-60ml/min；The preferred mass air speed of catalytic reaction is 0.5-5h-1。
Described high carbon primary alcohol is one or more in butanol, hexanol, capryl alcohol, certain herbaceous plants with big flowers alcohol.
Present invention have the advantage that
1. the even carbon alcohol such as ethanol production is big, source is sufficient, the butanol that this process generates have a wide range of applications in the field such as fuel, chemicals.
2. catalyst is easily prepared, and cost is low, good stability, and product can be easily separated use, and whole process has good economy and practicality, meets the requirement of sustainable development, is with a wide range of applications in biomass convert.
Below by specific embodiment, the present invention is described in detail, but present disclosure is not construed as limiting by these embodiments.
Detailed description of the invention
Embodiment 1
The preparation of catalyst
Weigh 0.04mol nitric acid M (M be in Ni and Co, Cu, Zn one or more) and 0.08mol magnesium nitrate (Mg (NO3)2·6H2O), 0.02mol aluminum nitrate (Al (NO3)3·9H2O) it is dissolved in 100mL deionized water, makes solution A.Separately weigh 0.12mol natrium carbonicum calcinatum (Na2CO3) be dissolved in 60mL deionized water, mix with the NaOH solution of 20mL3M, obtain solution B.Solution B is placed in 35 DEG C of water-baths, under intense agitation, solution A is added wherein with the speed of 3mL/min, and adding a small amount of NaOH solution, to regulate pH be 10.Crystallization 18h in 65 DEG C of water-baths will be deposited in.Through filtering, after washing, by sample 80 DEG C of drying.
Comparative example 1
Infusion process prepares Al2O3The Ni catalyst of load:
Weigh 6.27gNi (NO3)2·6H2O is dissolved in 10mL deionized water, separately weighs 0.74gAl2O3Under agitation adding in above-mentioned nickelous nitrate solution, dried by excessive moisture after dipping, the sample obtained is roasting 2h at 300 DEG C.After above-mentioned gained roasting, sample uses 10%H at 500 DEG C2/ He reduces 1h, obtains infusion process Ni catalyst based.
Embodiment 2
Catalyzed conversion experiment carries out in fixed bed reactors, and actual conditions is as follows: catalyst precursor 2g embodiment 1 prepared, and joins in fixed bed reactors, online hydrogen reducing, and hydrogen flow rate is 60ml/min, and reduction temperature is 600 DEG C, reduction event 2h.
Lowering the temperature after reduction, pass into nitrogen, pressure is 3MPa, and gas flow rate is 20ml/min.It is raised to reaction temperature to pump into raw material reaction, liquid product and gas-phase product and use gas chromatographic analysis respectively.
Embodiment 3
The different catalysts of comparative example 1 and embodiment 1 preparation, converts the result of the even carbon alcohol of preparation by the condition alcohol catalysis of embodiment 2:
Under table 1 different catalysts, alcohol catalysis converts the reaction result (atmosphere is argon for concentration of alcohol 98wt%, charging rate 0.1ml/min, reaction temperature 250 DEG C, catalyst quality 2.2g) of the even carbon alcohol of preparation
From response data it will be seen that the catalyst that relatively prepared by infusion process, adopting Ni, Cu, Co catalyst prepared by coprecipitation to show significantly high conversion ratio and selectivity in ethanol conversion, even carbon alcohol yield is more than 60%.
Embodiment 4
Under differential responses temperature conditions (all the other are with embodiment 2), the reaction result of the even carbon alcohol of ethanol conversion preparation:
When table 2 differential responses, (catalyst is Ni-MgO-Al prepared by embodiment 1 to the result of the even carbon alcohol of alcohol catalysis conversion preparation2O3, charging rate 0.1ml/min, atmosphere is nitrogen, catalyst quality 2.2g)
From response data it will be seen that reaction is not had a great impact by ethanol containing a certain amount of water.In time improving reaction temperature, the conversion ratio of ethanol increases, but even carbon alcohol yield declines to some extent, but is held at more than 50%.
Embodiment 5
The stability of catalyst.
(catalyst is Co-MgO-Al prepared by embodiment 1 to the test of table 3 catalyst stability2O3, charging rate 0.05ml/min, atmosphere is nitrogen, and mass space velocity is 3h-1, concentration of alcohol 98wt%)
As shown in table 3, catalyst prepared by coprecipitation has higher stability, uses 3 days rear catalyst activity not to be decreased obviously.
Claims (8)
1. the method that high carbon primary alcohol is prepared in an alcohol catalysis conversion, it is characterised in that: adopting transition metal-composite oxides is catalyst, it is achieved high carbon primary alcohol is prepared in alcohol catalysis conversion；The formula of catalyst is M-MgO-Al2O3, M is one or more combinations in Ni, Co, Cu, Zn；MgO-Al2O3The mol ratio of middle Mg and Al is 1～5:1；M mass content is 10-80%, and catalytic conversion reaction carries out in fixed bed reactors, and the temperature of reaction is 180-350 DEG C, and product is taken out of fixed bed reactors by carrier gas.
2. in accordance with the method for claim 1, it is characterised in that: the catalyst that this reaction adopts is prepared by coprecipitation, and detailed process is as follows:
The soluble nitrate of metal M, Mg, Al of formula ratio is dissolved in deionized water, obtain the saline solution containing M, Mg, Al, M, Mg, Al total concentration in saline solution is 0.02-2mol/L, the aqueous slkali that compound concentration is 0.05-1mol/L is placed in 20～50 DEG C of water-baths, under agitation isopyknic metal salt solution is slowly added in alkali liquor, alkali liquor has Precipitation gradually；Fully after precipitation, the pH of regulation system is 9～11, then bath temperature rises to 50～80 DEG C, and crystallization 1～24h at such a temperature, after the material after crystallization is sequentially passed through filtration, washing, drying and processing, obtains brucite precursor；The brucite precursor obtained original position hydrogen reduction reaction in the reactor processes, and can obtain metallic catalyst；
Alkali in aqueous slkali is mol ratio is NaOH and the Na of 0.5～1.5:12CO3Aqueous solution；M is one or more combinations in Ni, Co, Cu, Zn.
3. in accordance with the method for claim 1, it is characterised in that: in described catalyst, the preferred weight of metal M is the 10-50% of total catalyst weight.
4. in accordance with the method for claim 1, it is characterised in that: described ethanol is the water content ethanol less than 20wt%.
5. in accordance with the method for claim 1, it is characterised in that: carrier gas is one or more in nitrogen, argon, helium, and in reactor, gas pressure is 0.1-10MPa, and the mass space velocity of catalytic reaction is 0.2-20h-1。
6. in accordance with the method for claim 1, it is characterised in that: in described reaction, preferred reaction temperature is 225-280 DEG C.
7. the condition described in claim 5, it is characterised in that: preferably carrier gas is nitrogen, it is preferable that gas pressure is 2-5MPa, it is preferable that gas flow rate is 10-60ml/min；The preferred mass air speed of catalytic reaction is 0.5-5h-1。
8. in accordance with the method for claim 1, it is characterised in that: described high carbon primary alcohol is one or more in butanol, hexanol, capryl alcohol, certain herbaceous plants with big flowers alcohol.
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| CN106732602A (en) * | 2016-11-22 | 2017-05-31 | 中国科学院青岛生物能源与过程研究所 | A kind of direct hydrogenolysis of catalysis biomass furfural prepares the catalyst and preparation method of pentanediol |
| CN107983356A (en) * | 2017-12-07 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and preparation method and application for synthesizing higher order branched alcohol |
| CN108043403A (en) * | 2017-12-07 | 2018-05-18 | 中国科学院山西煤炭化学研究所 | A kind of synthesis higher alcohols catalyst and preparation method and application |
| CN108855127A (en) * | 2017-05-15 | 2018-11-23 | 中国石油天然气股份有限公司 | A kind of hydrogenation catalyst and preparation method thereof |
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| CN108863716A (en) * | 2018-05-08 | 2018-11-23 | 北京化工大学 | A kind of method that highly selective catalysis ethanol conversion prepares n-butanol and higher alcohol |
| CN110227471A (en) * | 2019-06-26 | 2019-09-13 | 北京化工大学 | A kind of methanol/ethanol intersects C-C key coupling catalyst and preparation method thereof |
| CN110711578A (en) * | 2019-10-24 | 2020-01-21 | 中国科学院大连化学物理研究所 | Catalyst for preparing C4-C8 higher alcohol by ethanol conversion, and preparation method and application thereof |
| CN111217673A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for high-energy utilization of ethanol |
| CN113145155A (en) * | 2021-03-09 | 2021-07-23 | 广东工业大学 | Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof |
| CN113492009A (en) * | 2020-04-03 | 2021-10-12 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN113578327A (en) * | 2021-08-31 | 2021-11-02 | 浙江师范大学 | Catalyst for preparing butanol by ethanol coupling and preparation method and application thereof |
| CN115228471A (en) * | 2022-07-28 | 2022-10-25 | 大连理工大学 | Catalyst for preparing butanol and/or higher alcohol by ethanol coupling, preparation method and application thereof |
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