CN104892361A - Method for preparing propanol through catalytic conversion of methanol - Google Patents
Method for preparing propanol through catalytic conversion of methanol Download PDFInfo
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- CN104892361A CN104892361A CN201410076449.6A CN201410076449A CN104892361A CN 104892361 A CN104892361 A CN 104892361A CN 201410076449 A CN201410076449 A CN 201410076449A CN 104892361 A CN104892361 A CN 104892361A
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- methanol
- propyl alcohol
- molecular sieve
- catalyst
- methyl alcohol
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Abstract
The invention relates to a method for preparing propanol through catalytic conversion of methanol. According to the method, methanol is directly used as a raw material, a molecular sieve supporting composite metal oxide containing two or more than two elements selected from iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium is adopted as a catalyst, and in a fixed bed reactor, methanol is subjected to catalytic conversion to prepare the propanol. According to the present invention, the method is the propanol preparing route directly adopting the methanol as the raw material, and directly adopts the domestic excess methanol as the raw material to prepare the important chemical industry raw material propanol so as to expand the downstream use of the methanol, and the catalyst is the non-noble metal catalyst and is cheap and easily-available, such that the method has important application prospects.
Description
Technical field
The present invention relates to the synthetic method of industrial chemicals, particularly relate to a kind of novel method of catalyzed conversion methanol-fueled CLC propyl alcohol, be exactly specifically take methyl alcohol as raw material, with the molecular sieve carried complex metal oxides containing two or more element in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium for catalyzer, in a hydrogen atmosphere, catalysis methanol transforms and obtains propyl alcohol on fixed-bed reactor.
Background technology
Propyl alcohol comprises n-propyl alcohol (1-propyl alcohol) and Virahol (2-propyl alcohol) two kinds of isomer, is important industrial chemicals and liquid fuel additive.The 60-70% of propyl alcohol aggregate consumption is for the production of chemical and be used as solvent, in addition, also for the additive of liquid fuel, is widely used in automobile and aviation fuel aspect.
The preparation method of propyl alcohol is mainly divided into propylene hydration method and biological fermentation process.Propylene hydration legal system is for propyl alcohol, and technical process is complicated, energy consumption is high, and multiplex acid as catalyst etching apparatus, contaminate environment, raw material faces the supply pressure of propylene.CN101774887A and CN101225018A disclosed the method that hydrogenation of propionaldehyde prepares propyl alcohol afterwards, and primarily of ethene and synthesis, it is transformed propionic aldehyde, and raw material also relies on petroleum-based resource.Be that the biological fermentation process of raw material also has application in addition with grain, but China is populous, and cultivated area is not enough, grain is not abundant, and current grain demand still exists breach.Therefore develop with grain is that the biological propyl alcohol of raw material does not tally with the national condition.Therefore, awaits development does not rely on the propyl alcohol new process for producing of petroleum resources.
Methyl alcohol is the simplest saturated monohydroxy alcohol, and methanol industry obtains in recent years and develops rapidly.According to statistics, domestic methyl alcohol overall throughput in 2010 has reached 3,500 ten thousand tons (Yu Hong, methyl alcohol production capacity surplus situation maybe will be aggravated in this year, the online weekly of chemical industry, 2011,3,8-9); But due to the underexploitation of methyl alcohol downstream use, particularly methyl alcohol toxicity, with gasoline-compatible difference etc. inherent defect, have impact on methyl alcohol to use as the large-scale promotion of vehicle fuel, cause domestic enterprise's working rate less than 40%, the production capacity of nearly 2,000 ten thousand tons is left unused, general (the Yin little Yong etc. of phenomenon of the underproduction of methanol production producer, stopping production, to some suggestion of China's methanol industry development, international petroleum economy, 2011,7,37-40; Wang Xiangqian etc., methyl alcohol imbalance of supply and demand situation will continue, chemical science and technology, 2012,6,69-71; Li Feng, the development of China's methanol industry and trend analysis, Coal Chemical Industry, 2013,1,8-12).Propyl alcohol is important industrial chemicals and liquid fuel additive, we have developed a kind of is raw material with methyl alcohol, with the molecular sieve carried complex metal oxides containing two or more element in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium for catalyzer, in hydrogen atmosphere, direct catalytic conversion methyl alcohol obtains propyl alcohol method (the variation route contrast that the traditional mode of production route of propyl alcohol and this patent provide as shown in Figure 1).
Exploitation is the new synthesis route that propyl alcohol prepared by raw material with methyl alcohol, has expanded the downstream use of methyl alcohol, has reduced the dependence to oil; Relative to the route from the biological propyl alcohol of grain-production, from Methanol for propyl alcohol, neither strive grain with people, the methyl alcohol of China's abundant can be made full use of again, have great importance.
Summary of the invention
The object of the invention is a kind of method providing catalyzed conversion Methanol for propyl alcohol, the method is directly raw material with methyl alcohol, with the molecular sieve carried complex metal oxides containing two or more element in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium for catalyzer, in a hydrogen atmosphere, catalysis methanol transforms and obtains propyl alcohol on fixed-bed reactor.
It is the molecular sieve carried complex metal oxides comprising two or more element in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium that this patent provide catalysis methanol to transform to be prepared propyl alcohol used catalyst, wherein active ingredient is two or more in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium, and carrier is the one that molecular sieve comprises in A type molecular sieve, X-type molecular sieve, Y zeolite, β-molecular sieve, mordenite, ZSM-5, ZSM-22, ZSM-23, MCM-41.
This patent provides catalysis methanol to transform the preparation process preparing propyl alcohol loading type O composite metallic oxide catalyst used can adopt one in the precipitator method, pickling process, hydrothermal synthesis method by active constituent loading on molecular sieve carrier, wherein preferred pickling process.In metal, active component content is the 0.1-20% of carrier quality, and wherein 1-15% is better, and 1-10% is best.
The catalyzed conversion Methanol that this patent provides needs could realize in certain temperature range for propyl alcohol, requires that methyl alcohol conversion reaction temperature is on a catalyst 300-500 DEG C, preferred 350-450 DEG C.
The catalyzed conversion Methanol that this patent provides needs to carry out in a hydrogen atmosphere for propyl alcohol, requires that reaction pressure is 0.1-5MPa, preferred 2.5-5MPa.In accordance with the method for claim 1, it is fixed-bed reactor that propyl alcohol equipment therefor is prepared in the catalysis methanol conversion that this patent provides, and input mode adopts pump sample introduction, and air speed is 0.1-5h
-1, preferred 2-5h
-1.
Compared with traditional route, the invention provides the route preparing propyl alcohol and have the following advantages:
1, the present invention proposes the route of direct catalytic conversion Methanol for propyl alcohol, the method has expanded the downstream use of methyl alcohol, prepares important industrial chemicals and liquid fuel additive propyl alcohol, reduces the dependence to oil, have important application prospect;
2, catalyzer of the present invention is the molecular sieve carried complex metal oxides containing two or more element in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium, and the method adopts catalyzer to be non-precious metal catalyst, cheap and easy to get;
3, reaction process is efficient, clean, green safety.
Accompanying drawing explanation
The variation route contrast that the traditional mode of production route of Fig. 1 propyl alcohol and this patent provide;
Fig. 2 catalysis methanol transforms prepares propyl alcohol reaction after product.
With embodiment in detail the present invention is described in detail below.
Embodiment
Embodiment 1: prepare Cu-Cr/ZSM-5 catalyzer for pickling process and pickling process is described in detail in detail prepares the step of loading type O composite metallic oxide catalyst: according to Cu:Cr mol ratio=2:1, take 2.44g cupric nitrate [Cu (NO respectively
3)
23H
2o] and 2.02g(Cu:Cr mol ratio=1:1,4.04g) chromium nitrate [Cr (NO
3)
39H
2o] be raw material, be dissolved in 40ml deionized water, (wherein activity component load quantity is 0.1-20%, two-pack Cu:Cr molar ratio is 0.1-10:1 to be mixed with active component salt solution, as being respectively 2:1,1:1 at this), carrier ZSM-5 be impregnated in 24h in solution; Then solution evaporation is dry, the i.e. obtained CuCr/ZSM-5 catalyzer of 500 DEG C of roasting 4h.
Embodiment 2: 10ml Cu-Cr/ZSM-5(wherein Cu:Cr mol ratio=2:1 that laboratory is synthesized, active metal component charge capacity is 10%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 350 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 2h
-1, reaction pressure is 0.5MPa.After reacting balance, sample by Agilent7890A-5973C GC-MS combined instrument and HP-5 chromatogram column analysis product composition (as shown in Figure 2), mainly propyl alcohol (comprising n-propyl alcohol and Virahol), a small amount of ethanol, propyl carbinol and isopropylcarbinol also detected, by Agilent7890A to reaction product quantitative analysis simultaneously.The selectivity calculating propyl alcohol in product in conjunction with gas chromatographic analysis result is 87.5%.
Embodiment 3: 10ml Cu-Cr/ZSM-23(wherein Cu:Cr mol ratio=1:1 that laboratory is synthesized, active metal component charge capacity is 10%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 380 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 2.5h
-1, reaction pressure is 2.0MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 75.3%.
Embodiment 4: (its preparation process is with embodiment 1 for the 10ml Fe-V/ β synthesized in laboratory, just active metallic element is different) (wherein Fe:V mol ratio=1:1, active metal component charge capacity is 8%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 400 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 3h
-1, reaction pressure is 4.0MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 38.7%.
Embodiment 5: its preparation process of 10ml Fe-W/Y(of being synthesized in laboratory is with embodiment 1, just active metallic element is different) (wherein Fe:W mol ratio=1:1, active metal component charge capacity is 5%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 400 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 2.5h
-1, reaction pressure is 2.5MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 22.6%.
Embodiment 6: (its preparation process is with embodiment 1 for the 10ml Fe-Co/ mordenite synthesized in laboratory, just active metallic element is different) (wherein Fe:Co mol ratio=1:1, active metal component charge capacity is 4%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 350 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 2.5h
-1, reaction pressure is 2.0MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 48.9%.
Embodiment 7: its preparation process of 10ml Cu-Mn/ZSM-22(of being synthesized in laboratory is with embodiment 1, just active metallic element is different) (wherein Cu:Mn=2:1, active metal component charge capacity is 5%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 450 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 3h
-1, reaction pressure is 2MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 72.6%.
Embodiment 8: its preparation process of 10ml Mn-W/ZSM-5(of being synthesized in laboratory is with embodiment 1, just active metallic element is different) (Mn:W mol ratio=5:1, active metal component charge capacity is 8%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 420 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 3.5h
-1, reaction pressure is 3.0MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 53.6%.、
Embodiment 9: its preparation process of 10ml Cu-Co/MCM-41(of being synthesized in laboratory is with embodiment 1, just active metallic element is different) (Cu:Co mol ratio=10:1, active metal component charge capacity is 10%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 450 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 2.5h
-1, reaction pressure is 2.0MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 60.6%.
Embodiment 10: its preparation process of 10ml Cu-Cr/ZSM-22(of being synthesized in laboratory is with embodiment 1, just active metallic element is different) (Cu:Co mol ratio=10:1, active metal component charge capacity is 10%) granules of catalyst loading fixed-bed reactor, pass into hydrogen after air in nitrogen replacement system, and temperature of reaction is risen to 380 DEG C.With pump methyl alcohol passed into reactor and catalyst exposure reacts, the Feed space velocities of methyl alcohol is 5h
-1, reaction pressure is 2.5MPa.After reacting balance, according to the methods analyst product in embodiment 2, the selectivity obtaining propyl alcohol is 89.2%.
The above; be only the specific embodiment of part of the present invention; but protection scope of the present invention is not limited in this; also not because the precedence of each embodiment causes any restriction to the present invention; anyly be familiar with person skilled in the art of the present invention in the technical scope that the present invention reports; can carry out easily changing or replacing, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention is not limited only to above embodiment, should be as the criterion with the protection domain of claim.
Claims (7)
1. a catalyzed conversion Methanol is for the method for propyl alcohol, it is characterized in that: take methyl alcohol as raw material, with the molecular sieve carried complex metal oxides containing more than two or three element in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium for catalyzer, in a hydrogen atmosphere, catalysis methanol transforms and obtains propyl alcohol on fixed-bed reactor.
2. in accordance with the method for claim 1; it is characterized in that: it is that the complex metal oxides comprising more than two or three element in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium is carried on molecular sieve carrier that propyl alcohol loaded catalyst used is prepared in catalysis methanol conversion; wherein active ingredient is more than two or three in iron, cobalt, manganese, copper, molybdenum, vanadium, tungsten and chromium, and the atomic molar ratio between any two kinds of metals is 0.1 ~ 10:1;
Carrier is one or two or more kinds that molecular sieve comprises in A type molecular sieve, X-type molecular sieve, Y zeolite, β-molecular sieve, mordenite, ZSM-5, ZSM-22, ZSM-23, MCM-41.
3. according to the method described in claim 1 or 2, it is characterized in that: catalysis methanol transforms the preparation process preparing propyl alcohol loading type O composite metallic oxide catalyst used can adopt one in the precipitator method, pickling process, hydrothermal synthesis method by active constituent loading on carrier, wherein preferred pickling process.
4. according to the method described in claim 1 or 2, it is characterized in that: catalysis methanol transforms prepares ethanol loaded catalyst used, and in metal, active component content is the 0.1-20% of catalyst quality, and wherein 1-15% is better, and 1-10% is best.
5. according to the method described in claim 1 or 2, it is characterized in that: material benzenemethanol conversion reaction temperature is on a catalyst 300-500 DEG C, preferred 350-450 DEG C.
6. according to the method described in claim 1 or 5, it is characterized in that: catalyzed conversion methyl alcohol carries out in a hydrogen atmosphere, reaction pressure is 0.1-5MPa, preferred 2.5-5MPa.
7. in accordance with the method for claim 1, it is characterized in that: it is fixed-bed reactor that propyl alcohol equipment therefor is prepared in catalysis methanol conversion, and input mode adopts pump sample introduction, and air speed is 0.1-5h
-1, preferred 2-5h
-1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429766A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Method of producing carbon monoxide and hydrogen using methanol and reactor used |
| CN101341110A (en) * | 2005-12-16 | 2009-01-07 | 巴特尔纪念研究院 | Alcohol synthesis from co or co2 |
| WO2013072228A1 (en) * | 2011-11-18 | 2013-05-23 | Haldor Topsøe A/S | Process for the preparation of higher alcohols |
| CN103121922A (en) * | 2007-07-09 | 2013-05-29 | 阿尔比马尔公司 | Methods and apparatus for producing alcohols from syngas |
| WO2014001597A1 (en) * | 2012-06-29 | 2014-01-03 | Abengoa Bioenergía Nuevas Tecnologías, S.A. | Method for obtaining higher alcohols |
-
2014
- 2014-03-04 CN CN201410076449.6A patent/CN104892361A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429766A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Method of producing carbon monoxide and hydrogen using methanol and reactor used |
| CN101341110A (en) * | 2005-12-16 | 2009-01-07 | 巴特尔纪念研究院 | Alcohol synthesis from co or co2 |
| CN103121922A (en) * | 2007-07-09 | 2013-05-29 | 阿尔比马尔公司 | Methods and apparatus for producing alcohols from syngas |
| WO2013072228A1 (en) * | 2011-11-18 | 2013-05-23 | Haldor Topsøe A/S | Process for the preparation of higher alcohols |
| WO2014001597A1 (en) * | 2012-06-29 | 2014-01-03 | Abengoa Bioenergía Nuevas Tecnologías, S.A. | Method for obtaining higher alcohols |
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Application publication date: 20150909 |
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