CN103772143A - Method for preparing industrial ethanol from acetic acid - Google Patents
Method for preparing industrial ethanol from acetic acid Download PDFInfo
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- CN103772143A CN103772143A CN201410008701.XA CN201410008701A CN103772143A CN 103772143 A CN103772143 A CN 103772143A CN 201410008701 A CN201410008701 A CN 201410008701A CN 103772143 A CN103772143 A CN 103772143A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to a method for preparing ethanol, and particularly relates to a method for preparing ethanol from acetic acid. The method adopts raw materials and a catalyst, wherein the raw materials are acetic acid and hydrogen. The method is characterized in that the catalyst is a Cu-based catalyst, and the method comprises the steps of loading the Cu-based catalyst into a reactor, and reducing with hydrogen at 220-270 DEG C; feeding the hydrogen and acetic acid at a molar ratio of (10-50):1 to enable contact between the raw materials and the catalyst; reacting for 24 hours at a reaction temperature of 180-300 DEG C under a reaction pressure of 0.5-6.0MPa; reacting to generate ethanol and water when the mass air speed of the acetic acid is 0.1-0.5/h; separating the product to obtain an ethanol product. The adopted Cu-based catalyst effectively adjusts the acid-base property of the catalyst, can inhibit the generation of diethyl ether, and converts acetic acid into ethanol to the greatest degree, thus the selectivity and stability are good, and the per-pass conversion of the reaction is high; meanwhile, the reaction conditions are mild, the energy consumption is low, and a good technical effect is obtained.
Description
[technical field]
The present invention relates to a kind of method of preparing ethanol, specifically a kind of method of being prepared industrial alcohol by acetic acid.
[background technology]
Ethanol is widely used in the industries such as food, medicine, chemical industry, fuel, national defence, as a kind of very important clean fuel and gasoline detonation suppressor component, can significantly reduce the pollutant emission of burning.Combine and issued global ethanol production annual prediction report according to global recyclable fuel alliance and F.O.Licht, approximately 88,700,000,000 liters of global ethanol productions (2010 being 85,800,000,000 liters) in 2011, amplification exceedes 3%, 60% ethanol for automobile fuel.The U.S. is the first big country of current fuel ethanol production, and within 2006, U.S.'s ethanol production is 194.72 hundred million liters, and within 2007, ethanol production capacity reaches 253.88 hundred million liters/year, separately has the production capacity of 308.47 hundred million liters/year building, and aggregated capacity reaches 562.35 hundred million liters/year.Brazil is due to its advantageous raw material (sugarcane) advantage, and output is only second to the U.S., and production technique, without dispute, becomes the maximum alcohol fuel export State in the whole world, and production capacity is rapid growth also.
Traditional alcohol production mainly relies on grain fermentation, and cost is high, efficiency is low, due to the global grain balance of impact, suffers majority state opposition.Adopt biomass (Mierocrystalline cellulose) fermentation ethanol processed, abundant raw material, inexpensive, but collect defeated higher with product separation cost, and technology still needs to be further improved maturation.The operational path of coal ethanol processed is mainly divided into 3 kinds at present: the one, and synthetic gas is ethanol processed directly; The 2nd, the biological legal system ethanol of synthetic gas, with synthetic gas (comprising the waste gas containing carbon monoxide and hydrogen) through production of ethanol from microbial fermentation; The 3rd, synthetic gas is through acetic acid preparation of ethanol by hydrogenating.The biological legal system ethanol of synthetic gas, because fermentation needs to stop length, is difficult to serialization and produces, and cost is higher; Synthetic gas is ethanol processed directly, and transformation efficiency and selectivity are low, and product is mixture, needs to purify, and technology is still in development.Therefore, in the route of coal ethanol processed, synthetic gas is through the technological line of acetic acid preparation of ethanol by hydrogenating because selectivity is high, and cost is relatively low, is easy to large-scale chemical combination mass-producing, has good development prospect.
In January, 2011, Celanese company disclosed the TCXTM patented technology of utilizing platinum/tin catalyst to produce ethanol from acetic acid selective hydrogenation.The said firm represents, adopts the cost of TCXTM explained hereafter ethanol to be equivalent to the cost with the crude production gasoline of 60 dollars per bucket, and the Clear Lake planning at Texas ,Usa builds the Sweet natural gas ethanol device processed of a set of 40,000 tons/year, estimates for the end of the year 2012 and goes into operation; Mainly for the production of alcohol fuel.
China is gasoline production and the country of consumption of the world's second largest, and the output of China's gasoline in 2011 reaches 8141.1 ten thousand tons, and apparent consumption amount reaches 7738.0 ten thousand tons, estimates that the year two thousand twenty gasoline consumption will reach 1.2 hundred million tons, and diesel oil demand is 2.33 hundred million tons.The feature of China's energy structure is: rich coal, oil-poor, weak breath, and coal resources in China total amount is 5.6 trillion tons, wherein proven reserve are 1,000,000,000,000 tons, account for 11% of world's total reserves, and oil, Sweet natural gas only account for global share and are respectively 2.4%, 1.2%.Chinese primary energy source in 2010 is produced and is formed: raw coal 77.4%, crude oil 9.7%, 4.3%, electric power 8.6% of Sweet natural gas.At Waste Era of Oil, replacement of fuel is ensure national energy security and reduce costs one of effective way.Research shows, uses E10 vehicle-use alcohol gasoline (ethanol 10%), and octane value can improve 3%, can reduce discharging CO25～30%, reduces discharging CO2 approximately 10%.Therefore, development ethanol petrol to improving environment, to realize Sustainable development significant.
Approximately 3,000,000 tons of ethanol of the at present annual consumption of China, and with average annual 8%～10% speed rapid growth.Carry out and completed the pilot of alcohol fuel year June in June, 2002 to 2003, in February, 2004, eight departments such as National Development and Reform Committee combine and have promulgated " vehicle-use alcohol gasoline expands pilot scheme " and " vehicle-use alcohol gasoline expansion pilot work detailed rules for the implementation ", using promoting the use of the strategic act of ethanol petrol as country.China's biofuel ethanol technology is ripe at present, and Heilungkiang, Jilin, Liaoning, Henan, Anhui 5 provinces and Hubei, Hebei, Shandong, some areas, Jiangsu are substantially realized vehicle-use alcohol gasoline and substituted regular unleaded.Domestic more than 95% ethanol adopts grain fermentative Production, along with the development of fuel ethanol industrial and the continuous growth of demand, causes staple food supply day by day nervous, and price is anxious to rise, and production cost rises.The development of following alcohol fuel should " not striven grain with people, not strive ground with grain ".
I can add 10% ethanol at regulation in gasoline now, if calculate in this ratio, extend to the whole country, and China's alcohol fuel demand is about 6.6 × 106t/a (being 6.6 × 107t/a by China's gasoline demand).And the main just 1.42 × 106t/a (in table 1) of 5 fuel ethanol production enterprise overall throughputs of current China, therefore the market potential of alcohol fuel is huge.
Table 1 China main fuel alcohol production conditions of the enterprise (ten thousand tons/year)
The production method of ethanol mainly contains fermentation method and chemical method.The main raw material of fermentation method is farm crop, by utilizing the amylofermentation in farm crop to obtain ethanol.Chemical method is mainly take ethene as raw material, produces ethanol by ethylene hydration.The production of China's ethanol, mainly take fermentation method as main, accounts for 96.5% of ethanol total amount.Can find out from the statistics of table 1, China's Ethanol Production by Fermentation main raw material concentrates on corn and wheat.Compared with alcohol fuel first U.S. of big producing country.China's Fuel Ethanol Production Cost is higher, and ethanol per ton need consume 3.3 tons of corns and 1.5 tons of coals, and the production cost of ethanol is more than 8000 yuan.
Along with maintaining sustained and rapid growth of national economy, the demand of following ethanol will significantly improve, if ethanol petrol is popularized application at home in an all-round way, estimate that the demand of national alcohol fuel in 2015 is by 10 million ton, therefore developing ethanol new synthesis technology is cheaply the task of top priority.Domestic at present still in laboratory or the pilot scale stage.
Meanwhile, be accompanied by the development of fiber, coating, tamanori industry, China's acetic acid industry production capacity Rapid Expansion, within 2010, China's accumulative total is produced 383.80 ten thousand tons, Glacial acetic acid, increase by 29.29% on a year-on-year basis, obviously supply exceed demand for acetic acid production, and Business Economic Benefit declines to a great extent.Within 2011, national polyvinyl alcohol production capacity reaches 87.7 ten thousand tons, approximately 1,450,000 tons of by-product ritalins, because ritalin market capacity is very limited, most enterprise can only be used by hydrolysis, Separation and Recovery acetic acid and methanol loop, retrieving arrangement technical process complexity, invest highly, energy consumption is high, the thick ritalin of minority producer direct marketing.Therefore develop acetic acid/ritalin preparation of ethanol by hydrogenating technology and not only there is raw material and the market advantage, and can promote the benefit of relevant industries to promote.
Therefore the feasibility that, acetic acid/acetic ester preparation of ethanol by hydrogenating technique possesses skills economically.Exploitation acetic acid/acetic ester Hydrogenation is for ethanol technology, formation meets the coal-based ethanol maximization complete set technology of the independent intellectual property right of China's characteristic, for the economic benefit that promotes acetic acid and polyvinyl alcohol industry, scale operation alternative fuel, ensure national energy security, there is great strategic significance and good development prospect.
According to Thailand of Britain can Rong Quanqiu chemistry corporate statistics, 2012, the effective capacity of China's acetic acid was 7,520,000 tons, and acetic acid demand is only 4,000,000 tons of left and right.Yima, henan Province gasification plant, Yangtze River, Chongqing acetyl Chemical Co., Ltd., Anhui Dingyuan salt chemical engineering, Ningxia English Z-TEK Ning Dong coal-based chemical company limited, Inner Mongol Wuhai coal industrys etc. are all by the acetic acid project of going into operation in the near future new.Although the scale of vinyl acetate between to for plastic, acetic ester, PTA production capacity will continue steady-state growth, but under serious superfluous acetic acid production capacity precursor, also unable by acetic acid consumption, if can maximize for ethanol by acetic acid Hydrogenation, further utilize problem by what be conducive to alleviate current acetic acid, provide a feasible approach for realizing ethanol preparation.
In US4517391 patent, adopt Co catalyzer for acetic acid hydrogenation reaction.In catalyzer, Co content is not less than 50%, and temperature in, at 230～270 ℃, under reaction pressure 27MPa condition, generates ethanol yield and reaches 97%.This reaction pressure is harsher, and it is more difficult that industrialization generates.
It is catalyzer that US2607807 patent is used Ru base, found that, under 70MPa condition, carry out acetic acid hydrogenation, ethanol yield can reach 88%, reduces reaction pressure to 20MPa, ethanol maximum yield 41%.
US7608744B1 patent adopts Pt catalyst series, and in catalyzer composition, Pt content is 1%, Co content while being 10%, 250 ℃ of temperature of reaction, and hydrogen pressure 22bar, acetic acid transformation efficiency reaches 38%, generates ethanol selectivity and reaches 96%, Pt catalyst series cost costliness.
To sum up can find, prior art is applied in the process of acetic acid Hydrogenation for ethanol, and condition harshness is answered in existence, per pass conversion is low causes the problem that energy consumption is high, and catalyzer is with high costs.
[summary of the invention]
The technical problem to be solved by this invention severe reaction conditions that is existing acetic acid hydrogenation catalyst in preparation ethanol process, per pass conversion be low causes the problem that energy consumption is high, the problem with high costs with catalyzer, the invention provides a kind of new method of preparing ethanol.The method has advantages of catalyst reaction mild condition, catalyst activity is high, cost is low.
For solving the problems of the technologies described above, the present invention adopts technical scheme as follows: comprise raw material and catalyzer, raw material is acetic acid and hydrogen, it is characterized in that catalyzer adopts Cu catalyst based, described Cu is catalyst based to be made up of following component by weight percentage: 15.0～40.0%Cu or its oxide compound, 10.0～25.0%Zn or its oxide compound, 1.0～10.0%Mn or its oxide compound, 1.0～15.0%Al
2o
3, 15.0～40%SiO
2, 0.5～5.0% is selected from least one in Co, Ce, La, Mg, Ba or its oxide compound; Fill in reactor catalyst based Cu, after 220～270 ℃ of hydrogen reducings, by hydrogen and acetic acid with mol ratio 10～50:1 charging, raw material contacts with catalyzer, it is 180～300 ℃ in temperature of reaction, reaction pressure is 0.5～6.0MPa, reaction times 24h, and acetic acid quality air speed is 0.1～0.5h
-1condition under, reaction generates second alcohol and water, obtains alcohol product by product separation.
In technique scheme:
In raw material, acetic acid is with the form charging of pure acetic acid or acetum, and the concentration of acetic acid is 50～100% by weight percentage, and inlet amount is 0.2～0.6ml/min, hydrogen flowing quantity 3500～5000ml/min.
On processing parameter, the mass space velocity preferable range of acetic acid is 0.1～0.4h
-1; The mol ratio preferable range of hydrogen/acetic acid is 20～40:1; Described hydrogenation reaction temperature preferable range is 220～260 ℃; Reaction pressure preferable range is 1.0～4.0MPa;
Catalyzer is by weight percentage: Cu or its oxide compound consumption preferable range are 15.0～35.0%; The preferable range of Zn or its oxide compound consumption is 15.0～20.0%; Al
2o
3consumption preferable range is 5.0～15.0%; SiO
2consumption preferable range is 15.0～30.0%; At least one the consumption preferable range being selected from Co, Ce, La, Mg, Ba or its oxide compound is 1.0～5.0%.
Kaolinite Preparation of Catalyst comprises the following steps: 40% silicon sol and 15% aluminium colloidal sol are heated to 70-85 ℃ of formation solution 1 in 1.0-1.2L in water, or take a certain amount of Al
2o
3join and in 1.0L, in water, be heated to 80 ℃ and form solution 1; Being selected from containing Cu, Zn, Co, Ce, La, Mg, Ba, Al and Mn solubility thing of aequum is dissolved in 1.0L water, and in 75-80 ℃ of oil bath, heated and stirred forms solution 2; Take 1.0mol/L aqueous sodium carbonate or 1.0mol/L wet chemical or ammoniacal liquor as solution 3; Solution 2 and solution 3 splash in solution 1 simultaneously and control pH value 6.5-10 and is precipitated thing, obtain Cu after dripping completely catalyst based through filtering, after washing, dry, roasting, moulding.
Owing to generating in the process of ethanol at acetic acid hydrogenation, may there is multiple side reaction, as: acetic acid Partial hydrogenation generates acetaldehyde, ethanol and acetic acid that direct hydrogenation generates generate vinyl acetic monomer by esterification, the ethanol generation ethene that further dewaters, the further hydrogenation of ethene generates ethane, also may generate sec-butyl alcohol etc. by coupling.Therefore, designing suitable catalyzer, to adopt suitable processing condition be to realize acetic acid to select Hydrogenation for the key of ethanol.While adopting Pt catalyst based, reaction conversion ratio is low.And the Cu the present invention relates to is catalyst based, by introducing CoO, CeO
2, the oxide compound one at least wherein such as MgO, CaO, BaO modifies catalyzer, effectively regulate the acid-basicity of catalyzer, can suppress the generation of ether, farthest acetic acid is converted into ethanol, quantity by regulating catalyst acid site and strength of acid be by the kind of oxide compound, thereby make that the Cu of preparation is catalyst based has good selectivity and stability.
Use method provided by the invention, at 245 ℃ of entrance temperature of reaction, reaction pressure 3.0MPa, raw materials quality air speed is 0.3h
-1, under the reaction conditions that the mol ratio of hydrogen and acetic acid is 25.0:1, be applied to acetic acid and select Hydrogenation for ethanol, in the time that acetic acid transformation efficiency is 92%, the selectivity that generates ethanol reaches 96.5%, and reaction per pass conversion is high, simultaneous reactions mild condition, energy consumption is low, has obtained good technique effect.
[embodiment]
Below by embodiment, the present invention is further elaborated.
Embodiment 1
Proportionally take 60.0g40% silicon sol and in 1.0L, in water, be heated to 80 ℃ of formation solution 1; Take 121.5gCu (NO
3)
23H
2o, 73.5g Zn (NO
3)
26H
2o, 10.6g La (NO
3)
36H
2o, 5.1g Ba (NO
3)
2, 36.8g Al (NO
3)
39H
2o, weight percent are 50%Mn (NO
3)
2solution 8.2g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Take 106.0g anhydrous sodium carbonate in beaker, add distilled water to 1L, it is solution 3 that stirring and dissolving is made into 1.0mol/L aqueous sodium carbonate.Solution 2 and solution 3 drip in solution 1 simultaneously, and keeping pH is that 7.0 left and right are precipitated thing, filter and are precipitated thing.Throw out drying, roasting moulding obtain catalyzer 1(and are by weight percentage: 40%CuO-20%ZnO%-4%Lal
2o
3-5%Al
2o
3-3%BaO-4%MnO
2-24%SiO
2)
Load this catalyzer 50g in reactor, after 250 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.4ml/min, hydrogen flowing quantity 3500ml/min, temperature of reaction is controlled at 240 ℃, and reaction pressure 1.5MPa, after reaction 24h, acetic acid transformation efficiency 91.5%, generates ethanol selectivity 94.5%.
Embodiment 2
Proportionally take 78.0g40% silicon sol and 46.7g15% aluminium colloidal sol and in 1.0L, in water, be heated to 80 ℃ of formation solution 1; Take a certain amount of 91.13g Cu (NO
3)
23H
2o, 73.50g Zn (NO
3)
26H
2o, 19.4g Co (NO
3)
26H
2o, 8.54gBa (NO
3)
2, weight percent is 50%Mn (NO
3)
2solution 14.4g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Take 106g anhydrous sodium carbonate in beaker, add distilled water to 1L, it is solution 3 that stirring and dissolving is made into 1.0mol/L aqueous sodium carbonate.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 7.5 left and right are precipitated thing, filter and are precipitated thing.Throw out drying, roasting moulding obtain catalyzer 2(and are by weight percentage: 30%CuO-20%ZnO%-5%CoO-7%Al
2o
3-5%BaO-7%MnO
2-31%SiO
2)
Load this catalyzer 50g in reactor, after 250 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.4ml/min, hydrogen flowing quantity 4000ml/min, temperature of reaction is controlled at 250 ℃, and reaction pressure 2.5MPa, after reaction 24h, acetic acid transformation efficiency 92.5%, generates ethanol selectivity 95.2%.
Embodiment 3
Proportionally take 100g40% silicon sol and 100g15% aluminium colloidal sol and in 1.3L, in water, be heated to 75 ℃ of formation solution 1; Take 75.94g Cu (NO
3)
23H
2o, 91.84g Zn (NO
3)
26H
2o, 19.4g Co (NO
3)
26H
2o, 2.52gCe (NO
3)
26H
2o, Ba (NO
3)
2, weight percent is 50%Mn (NO
3)
2solution 14.4g is dissolved in 1.0L water, and in 75 ℃ of oil baths, heated and stirred forms solution 2.Take 106g anhydrous sodium carbonate in beaker, add distilled water to 1L, it is solution 3 that stirring and dissolving is made into 1.0mol/L aqueous sodium carbonate.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 6.5 left and right are precipitated thing, filter and are precipitated thing.Drying precipitate, roasting moulding obtain catalyzer 3(and are by weight percentage: 25%CuO-25%ZnO%-5%CoO-1%CeO
2-15%Al
2o
3-5%BaO-7%MnO
2-17%SiO
2)
Load this catalyzer 50g in reactor, after 230 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.4ml/min, hydrogen flowing quantity 4500ml/min, temperature of reaction is controlled at 250 ℃, and reaction pressure 3.0MPa, after reaction 24h, acetic acid transformation efficiency 93.5%, generates ethanol selectivity 95.3%.
Embodiment 4
Proportionally take 162.5g40% silicon sol and 134.0g15% aluminium colloidal sol and in 1.2L, in water, be heated to 85 ℃ of formation solution 1; Take 182.3g Cu (NO
3)
23H
2o, 147.0gZn (NO
3)
26H
2o, 64.1g Mg (NO
3)
26H
2o, 38.8gCo (NO
3)
26H
2o, 17.1g Ba (NO
3)
2, weight percent is 50%Mn (NO
3)
2solution 16.5g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Take ammoniacal liquor as solution 3.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 10 left and right are precipitated thing, and 95 ℃ of solvent evaporated are precipitated thing.Throw out obtains catalyzer 4(and is by weight percentage through washing, dry, roasting moulding: 30%CuO-20%ZnO%-5%CoO-5%MgO-10%Al
2o
3-5%BaO-2%MnO
2-13%SiO
2)
Load this catalyzer 50g in reactor, after 240 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.4ml/min, hydrogen flowing quantity 4000ml/min, temperature of reaction is controlled at 250 ℃, and reaction pressure 4.0Mpa, after reaction 24h, acetic acid transformation efficiency 90.5%, generates ethanol selectivity 94.8%.
Embodiment 5
Proportionally take 54g Al
2o
3join and in 1.0L, in water, be heated to 80 ℃ and form mixed solutions 1; Take 151.9gCu (NO
3)
23H
2o, 147.0g Zn (NO
3)
26H
2o, 38.8g Co (NO
3)
26H
2o, 35.3gCe (NO
3)
26H
2o weight percent is 50%Mn (NO
3)
2solution 57.6g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Preparation 1.0mol/L aqueous sodium carbonate is solution 3.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 7.5 left and right are precipitated thing, filter and are precipitated thing.Throw out is through super-dry, and it is 25%CuO-20%ZnO%-5%CoO-4%CeO by weight percentage that roasting, moulding obtain catalyzer 5(
2-7%CeO
2-5%BaO-7%MnO
2-27%Al
2o
3)
Load this catalyzer 40g in reactor, after 220 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.4ml/min, hydrogen flowing quantity 4000ml/min, temperature of reaction is controlled at 220 ℃, and reaction pressure 5.0Mpa, after reaction 24h, acetic acid transformation efficiency 90.5%, generates ethanol selectivity 93.8%.
Embodiment 6
Proportionally take 97.5g40% silicon sol and 15% aluminium colloidal sol 70.0g and in 1.0L, in water, be heated to 80 ℃ of formation solution 1; Take 136.7g Cu (NO
3)
23H
2o, 110.2g Zn (NO
3)
26H
2o, 29.1g Co (NO
3)
26H
2o, 5.1gBa (NO
3)
2, weight percent is 50%Mn (NO
3)
2solution 61.7g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Preparation 1.0mol/L wet chemical is solution 3.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 7.5 left and right are precipitated thing, filter and are precipitated thing.It is 30%CuO-20%ZnO%-5%CoO-7%Al by weight percentage that throw out drying, roasting obtain catalyzer 6(
2o
3-2%BaO-10%MnO
2-26%SiO
2)
Load this catalyzer 40g in reactor, after 250 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.2ml/min, hydrogen flowing quantity 4000ml/min, temperature of reaction is controlled at 260 ℃, and reaction pressure 3.5Mpa, after reaction 24h, acetic acid transformation efficiency 95.2%, generates ethanol selectivity 93.2%.
Embodiment 7
Proportionally take 67.5g40% silicon sol and in 1.2L, in water, be heated to 85 ℃ of formation solution 1; Take 91.1g Cu (NO
3)
23H
2o, 73.5g Zn (NO
3)
26H
2o, 32.1Mg (NO
3)
26H
2o, 19.4g Co (NO
3)
26H
2o, 8.5gBa (NO
3)
2, weight percent is 50%Mn (NO
3)
2solution 16.5g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Take ammoniacal liquor as solution 3.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 10 left and right are precipitated thing, is heated to 90 ℃ of evaporates to dryness and is precipitated thing.Throw out obtains catalyzer 7(and is by weight percentage through washing, roasting, moulding: 30%CuO-20%ZnO%-5%CoO-5%MgO-5%BaO-8%MnO
2-27%SiO
2)
Load this catalyzer 40g in reactor, after 250 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.4ml/min, hydrogen flowing quantity 4000ml/min, temperature of reaction is controlled at 260 ℃, and reaction pressure 2.0Mpa, after reaction 24h, acetic acid transformation efficiency 87.5%, generates ethanol selectivity 91.2%.
Embodiment 8
Proportionally take 125.0g40% silicon sol and 15% aluminium colloidal sol 200g and in 1.5L, in water, be heated to 70 ℃ of formation solution 1; Take 182.3g Cu (NO
3)
23H
2o, 110.2g Zn (NO
3)
26H
2o, 25.2g Ce (NO
3)
26H
2o, 17.1gBa (NO
3)
2, weight percent is 50%Mn (NO
3)
2solution 41.2g is dissolved in 1.0L water in the lump, and in 70 ℃ of oil baths, heated and stirred forms solution 2.Preparation 1.5mol/L aqueous sodium carbonate is solution 3.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 8.0 left and right are precipitated thing, filter and are precipitated thing.Throw out is through super-dry, roasting, and it is 30%CuO-15%ZnO%-5%CeO by weight percentage that moulding obtains catalyzer 8(
2-15%Al
2o
3-5%BaO-5%MnO
2-25%SiO
2)
Load this catalyzer 50g in reactor, after 250 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.5ml/min, hydrogen flowing quantity 5000ml/min, temperature of reaction is controlled at 260 ℃, and reaction pressure 4.0Mpa, after reaction 24h, acetic acid transformation efficiency 93.5%, generates ethanol selectivity 94.7%.
Embodiment 9
Proportionally take 40% silicon sol 25.0g and 15% aluminium colloidal sol 66.7g and in 0.8L, in water, be heated to 80 ℃ of formation solution 1; Take 136.7g Cu (NO
3)
23H
2o, 55.1g Zn (NO
3)
26H
2o, 19.4g Co (NO
3)
26H
2o, 8.5gBa (NO
3)
2, weight percent is 50%Mn (NO
3)
2solution 41.1g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Preparation 1.0mol/L sodium carbonate and 1.0ml salt of wormwood mixing solutions are solution 3.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 7.5 left and right are precipitated thing, filter and are precipitated thing.Throw out is through super-dry, roasting, and it is 45%CuO-15%ZnO%-5%CoO-10%Al by weight percentage that moulding obtains catalyzer 9(
2o
3-5%BaO-10%MnO
2-10%SiO
2)
Load this catalyzer 40g in reactor, after 270 ℃ of hydrogen reducings, keep inlet amount as 0.6ml/min take weight percent 50% ethanol acetate solution as raw material, hydrogen flowing quantity 4000ml/min, temperature of reaction is controlled at 240 ℃, and reaction pressure 2.5Mpa, after reaction 24h, acetic acid transformation efficiency 95.5%, generates ethanol selectivity 89.2%.
Embodiment 10
Proportionally take 175.0g40% silicon sol and in 1.0L, in water, be heated to 80 ℃ of formation solution 1; Take 212.6g Cu (NO
3)
23H
2o, 73.5g Zn (NO
3)
26H
2o, 38.8g Co (NO
3)
26H
2o, 17.1g Ba (NO
3)
2, 102.9g Al (NO
3)
39H
2o, weight percent are 50%Mn (NO
3)
2solution 41.2g is dissolved in 1.0L water in the lump, and in 80 ℃ of oil baths, heated and stirred forms solution 2.Take 17% ammoniacal liquor as solution 3.Solution 2 and solution 3 drop in solution 1 simultaneously, and keeping pH is that 10 left and right are precipitated thing, evaporates liquid and is precipitated thing.By drying precipitate, it is 35%CuO-10%ZnO%-5%CoO-7%Al by weight percentage that roasting obtains catalyzer 10(
2o
3-5%BaO-3%MnO
2-35%SiO
2)
Load this catalyzer 50g in reactor, after 220 ℃ of hydrogen reducings, keeping inlet amount take pure acetic acid as raw material is 0.5ml/min, hydrogen flowing quantity 4000ml/min, temperature of reaction is controlled at 250 ℃, after reaction 24h, acetic acid transformation efficiency 92.5%, generates ethanol selectivity 90.2%.
Can find out by above embodiment, the catalyzer and the processing condition that adopt the method to provide, acetic acid per pass conversion reaches 95%, generates ethanol selection high, and reaction conditions easily reaches, and has realized good technique effect.
Claims (7)
1. prepared the method for industrial alcohol by acetic acid for one kind, comprise raw material and catalyzer, raw material is acetic acid and hydrogen, it is characterized in that catalyzer adopts Cu catalyst based, described Cu is catalyst based to be made up of following component by weight percentage: 15.0～40.0%Cu or its oxide compound, 10.0～25.0%Zn or its oxide compound, 1.0～10.0%Mn or its oxide compound, 1.0～15.0%Al
2o
3, 15.0～40%SiO
2, 0.5～5.0% is selected from least one in Co, Ce, La, Mg, Ba or its oxide compound; Fill in reactor catalyst based Cu, after 220～270 ℃ of hydrogen reducings, by hydrogen and acetic acid with mol ratio 10～50:1 charging, raw material contacts with catalyzer, it is 180～300 ℃ in temperature of reaction, reaction pressure is 0.5～6.0MPa, reaction times 24h, and acetic acid quality air speed is 0.1～0.5h
-1condition under, reaction generates second alcohol and water, obtains alcohol product by product separation.
2. a kind of method of being prepared industrial alcohol by acetic acid according to claim 1, is characterized in that: temperature of reaction is 220～260 ℃; Reaction pressure is 1.0～4.0MPa.
3. a kind of method of being prepared industrial alcohol by acetic acid according to claim 1, is characterized in that: the mass space velocity of acetic acid is 0.1～0.4h
-1; The mol ratio of hydrogen and acetic acid is 20～40:1.
4. according to a kind of method of being prepared industrial alcohol by acetic acid described in claim 1 or 3, it is characterized in that: in raw material, acetic acid is with the form charging of pure acetic acid or acetum, the concentration of acetic acid is 50～100% by weight percentage, inlet amount is 0.2～0.6ml/min, hydrogen flowing quantity 3500～5000ml/min.
5. a kind of method of being prepared industrial alcohol by acetic acid according to claim 1, is characterized in that: described Cu is catalyst based to be made up of following component by weight percentage: 15.0～35.0%Cu or its oxide compound; 15～20.0%Zn or its oxide compound; 1.0～10.0%Mn or its oxide compound; 5.0～15.0%Al
2o
3; 15.0～30.0%SiO
2; 1.0～5.0% are selected from least one in Co, Ce, La, Mg, Ba or its oxide compound.
6. a kind of method of being prepared industrial alcohol by acetic acid according to claim 1, it is characterized in that: the catalyst based preparation of described Cu comprises the following steps: 40% silicon sol and 15% aluminium colloidal sol are heated to 70-85 ℃ of formation solution 1 in 1.0-1.2L in water, or take a certain amount of Al
2o
3join and in 1.0L, in water, be heated to 80 ℃ and form solution 1; Being selected from containing Cu, Zn, Co, Ce, La, Mg, Ba, Al and Mn solubility thing of aequum is dissolved in 1.0L water, and in 75-80 ℃ of oil bath, heated and stirred forms solution 2; Take 1.0mol/L aqueous sodium carbonate or 1.0mol/L wet chemical or ammoniacal liquor as solution 3; Solution 2 and solution 3 splash in solution 1 simultaneously and control pH value 6.5-10 and is precipitated thing, obtain Cu after dripping completely catalyst based through filtering, after washing, dry, roasting, moulding.
7. a kind of method of being prepared industrial alcohol by acetic acid according to claim 6, is characterized in that: by aequum to be selected from containing Cu, Zn, Co, Ce, La, Mg, Ba, Al and Mn solubility thing be Cu (NO
3)
23H
2o, Zn (NO
3)
26H
2o, Co (NO
3)
26H
2o, Ce (NO
3)
26H
2o, La (NO
3)
36H
2o, Mg (NO
3)
26H
2o, Ba (NO
3)
2, Al (NO
3)
29H
2o, weight percent are 50%Mn (NO
3)
2solution.
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|---|---|---|---|---|
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| CN107486210A (en) * | 2016-06-12 | 2017-12-19 | 河南中宏清洁能源股份有限公司 | A kind of catalyst for acetic acid one-step method ethanol and preparation method thereof |
| CN108707060A (en) * | 2018-07-14 | 2018-10-26 | 太原理工大学 | A kind of technique using dissociated methanol in-situ reducing acetic acid ethyl alcohol |
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| CN103170337A (en) * | 2013-02-27 | 2013-06-26 | 厦门大学 | Catalyst for producing ethanol and preparation method thereof |
| US20130211150A1 (en) * | 2012-02-10 | 2013-08-15 | Celanese International Corporation | Chemisorption of Ethyl Acetate During Hydrogenation of Acetic Acid to Ethanol |
| CN103331167A (en) * | 2013-07-19 | 2013-10-02 | 新地能源工程技术有限公司 | Catalyst for directly preparing ethanol from acetic acid, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| US9458072B2 (en) | 2014-04-28 | 2016-10-04 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| CN107486210A (en) * | 2016-06-12 | 2017-12-19 | 河南中宏清洁能源股份有限公司 | A kind of catalyst for acetic acid one-step method ethanol and preparation method thereof |
| CN108707060A (en) * | 2018-07-14 | 2018-10-26 | 太原理工大学 | A kind of technique using dissociated methanol in-situ reducing acetic acid ethyl alcohol |
| CN108707060B (en) * | 2018-07-14 | 2022-03-18 | 太原理工大学 | Process for preparing ethanol by in-situ reduction of acetic acid by cracking methanol |
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