CN103372435B - A kind of ethyl acetate preparation of ethanol by hydrogenating Catalysts and its preparation method - Google Patents
A kind of ethyl acetate preparation of ethanol by hydrogenating Catalysts and its preparation method Download PDFInfo
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- CN103372435B CN103372435B CN201210119122.3A CN201210119122A CN103372435B CN 103372435 B CN103372435 B CN 103372435B CN 201210119122 A CN201210119122 A CN 201210119122A CN 103372435 B CN103372435 B CN 103372435B
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Abstract
The present invention relates to a kind of ethyl acetate preparation of ethanol by hydrogenating Catalysts and its preparation method, catalyst weight ratio consists of Cu: Si: Ni=10 ~ 50: 2 ~ 5: 0.002 ~ 0.01; The preparation method of this catalyst comprises and adds sodium carbonate liquor by after copper nitrate solution dilution, obtain Kocide SD precipitate slurry, washing is precipitated filter cake after removing sodium salt after filtration, add a certain amount of water and Ludox making beating, slurries are obtained after certain hour dipping, roasting after drying, is obtaining cylindric ethyl acetate hydrogenation catalyst through compressing tablet.The advantages such as compared with prior art, be studied in fixed bed reactors to catalyst of the present invention, experimental result shows to have the higher hydrogenation activity of hydrogenation to ethyl acetate, the selective height of ethanol, and the life-span is long.
Description
Technical field
The present invention relates to one and relate to catalyst material and preparation method thereof, especially relate to a kind of ethyl acetate preparation of ethanol by hydrogenating Catalysts and its preparation method.
Background technology
As everyone knows, preparing C2 (acetylene, ethene, ethanol, acetic acid etc.) by coal or synthesis gas is the important of Coal Chemical Industry or C1 chemistry, and one of most valuable task.Industrial production generally adopts acetylene from calcium carbide, MTO, carbonylation method acetic acid, but, also there is no economically viable C1 alcohol production route.
The production line of ethanol is all take grain as the fermentation method of raw material substantially, and by the impact of a price high position, its production cost is higher.3 tons of corns, 1 ton of alcohol, current corn price more than 2000 yuan, therefore, alcohol price is rational more than 6000 yuan/ton.In addition, blending amount 10% in ethanol-gasoline, and gas price is close to 10,000 yuan/ton, therefore, alcohol price is also rational at 7000 yuan/ton.
Research and development take coal as the ethanol synthetic route of raw material will be competitive economically.But there is thermodynamic (al) restriction by one-step method from syngas synthesizing alcohol, although catalyst remains rhodium system, its efficiency is very low, and IP prospecting is little.Also be an approach by MTO via ethylene hydration method, but generally can not consider, because the value of ethene is far above ethanol; Calcium carbide synthesis acetylene, rehydrated hydrogenation also can obtain ethanol, and cost of material is still higher, and is high energy consumption route.
China's acetic acid production capacity it is reported more than 7,000,000 yuan/year, estimates that 2013 close to 9,000,000 tons, but demand deficiency 5,000,000 tons, and therefore, production capacity surplus is very serious, the utilization of capacity only 50%.In recent years, drop in acetic acid price one road.Recent months, other chemicals prices are all higher, and acetic acid price maintenance low level, and the price of ethanol continues to increase to nearest 6800 yuan/ton from 4000 yuan/ton in this year, within 1 year, amount of increase reaches 70%; And price one tunnel of acetic acid maintains between 3000-3500 yuan/ton.Exploitation ethyl acetate preparation of ethanol by hydrogenating route, its production cost, compared with existing grain fermentative routes, has good competitive advantage.
Summary of the invention
Object of the present invention is exactly provide a kind of preparation method and the application thereof that are applicable to the ethyl acetate preparing methanol by hydrogenation catalyst of fixed bed reactors to overcome by the thermodynamics restriction of one-step method from syngas synthesizing alcohol and the shortcoming such as the inefficiency of rhodium series catalysts and costliness, this preparation method's production cost is low, simple to operate, be convenient to control, pollute few.
Object of the present invention can be achieved through the following technical solutions:
A kind of ethyl acetate preparation of ethanol by hydrogenating catalyst, the content of this catalyst is made up of following component and weight ratio: Cu: Si: Ni=10 ~ 50: 2 ~ 5: 0.002 ~ 0.01.
Prepare a method for ethyl acetate hydrogenation catalyst, the method comprises the following steps:
(1) in sodium carbonate liquor, add copper nitrate solution form sediment slurry, precipitation endpoint pH is 5 ~ 8, and precipitation temperature is 20 ~ 90 degrees Celsius, obtains co-precipitation filter cake after filtration, precipitation;
(2) deionized water making beating is added in co-precipitation filter cake, obtain the slurries of solid content 5 ~ 19wt%, then add the Ludox of 20%, molar concentration is the nickel nitrate solution of 0.02 ~ 0.1 mol/L, flood 1 ~ 6 hour under 10 ~ 60 degrees Celsius, obtain pulp;
(3) pulp is sent in baking oven dry under 100 ~ 200 degrees Celsius;
(4) powder obtained after drying is carried out roasting, sintering temperature is 200 ~ 600 degrees Celsius, and roasting time is 1 ~ 8 hour, namely prepares ethyl acetate hydrogenation catalyst.
Pulp concentration described in step (2) is 10 ~ 20wt%.
The specific area of the ethyl acetate hydrogenation catalyst prepared is 300 ~ 450m
2/ g, pore volume is 0.6 ~ 1.0ml/g.
The analysis test method that the present invention is used: the specific area of finished product cylinder catalyst, pore volume and pore-size distribution measure: adopt low-temperature nitrogen adsorption method, specific area is BET specific surface area; The distribution of particles of finished product cylinder catalyst, adopts laser particle size analyzer to obtain catalyst particle size distributed data; Scanning electron microscopic observation catalyst surface pattern.
Compared with prior art, the present invention has the following advantages:
1. the present invention adopts Cu-series catalyst, and raw material is easy to get, cheap.
2. the present invention adopts sodium carbonate as precipitating reagent, and because sodium carbonate and copper nitrate solution are all quantitatively add, precipitation reaction is simple to operate, reacted pH value precise control, and reaction temperature is low, can react at normal temperatures, and specificity of catalyst favorable reproducibility.
3. adopt pressed disc method shaping in method for preparing catalyst provided by the present invention, simple to operate, be suitable for suitability for industrialized production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
The copper nitrate solution getting 8kg 40% adds in reactor, at room temperature forms sediment slurry by the ammoniacal liquor of 5% instillation copper nitrate solution in rapid stirring, and pH value is that 7.5 stoppings drip ammoniacal liquor, obtains co-precipitation filter cake after filtration, washing.Co-precipitation filter cake is moved in beaker, adds deionized water 10 liters and pull an oar with the acidic silicasol of 4kg 20%, weigh Ni (NO
3)
22g is dissolved in deionized water and is made into 0.5 liter of solution, adds in above-mentioned slurries, stirs and makes it abundant mixing, be heated to 70 degrees Celsius, stir 120 minutes.It is dry that the slurries obtained put into the baking oven of 120 degrees Celsius, and 450 degrees Celsius of roastings 2 hours, obtain the final catalyst of 2.1kg, above catalyst called after A.
Embodiment 2
The copper nitrate solution getting 7.5kg 40% adds in reactor, at room temperature forms sediment slurry by the carbonic hydroammonium of 5% instillation copper nitrate solution in rapid stirring, and pH value is that 7.5 stoppings drip, and obtains co-precipitation filter cake after filtration, washing.Co-precipitation filter cake is moved in beaker, adds deionized water 10 liters and pull an oar with the acidic silicasol of 3.8kg 20%, weigh Ni (NO
3)
2be made into 0.5 liter of solution in 0.75g honor deionized water, add in above-mentioned slurries, stir and make it abundant mixing, be heated to 70 degrees Celsius, stir 120 minutes.It is dry that the slurries obtained put into the baking oven of 150 degrees Celsius, and 450 degrees Celsius of roastings 2 hours, obtain the final catalyst of 2.0kg, above catalyst called after B.
Embodiment 3
The copper nitrate solution getting 7kg 40% adds in reactor, at room temperature forms sediment slurry by the sodium carbonate liquor of 5% instillation copper nitrate solution in rapid stirring, and pH value is that 6.5 stoppings drip sodium carbonate liquor, obtains co-precipitation filter cake after filtration, washing.Co-precipitation filter cake is moved in beaker, adds deionized water 30 liters and pull an oar with the acidic silicasol of 3.3kg 20%, weigh Ni (NO
3)
2be made into 1 liter of solution in 0.50g honor deionized water, add in above-mentioned slurries, stir and make it abundant mixing, be heated to 70 degrees Celsius, stir 120 minutes.It is dry that the slurries obtained put into the baking oven of 120 degrees Celsius, and 500 degrees Celsius of roastings 2 hours, obtain the final catalyst of 1.8kg, above catalyst called after C.
Embodiment 4
The copper nitrate solution getting 6.5 liter 40% adds in reactor, at room temperature forms sediment slurry by the sodium carbonate liquor of 5% instillation copper nitrate solution in rapid stirring, and pH value is that 7.0 stoppings drip ammoniacal liquor, obtains co-precipitation filter cake after filtration, washing.Co-precipitation filter cake is moved in beaker, adds deionized water 30 liters and pull an oar with the acidic silicasol of 10Kg20%, weigh Ni (NO
3)
2be made into 1 liter of solution in 0.45g honor deionized water, add in above-mentioned slurries, stir and make it abundant mixing, be heated to 70 degrees Celsius, stir 120 minutes.It is dry that the slurries obtained put into the baking oven of 120 degrees Celsius, and 550 degrees Celsius of roastings 2 hours, obtain the final catalyst of 3.1kg, above catalyst called after D.
Detailed physical property analysis is carried out to the catalyst of preparation, the results are shown in Table 1
The performance indications of table 1 embodiment catalyst
| Catalyst is named | Pore-size distribution (20 ~ 80) nm% | BET specific surface area m 2/g | Pore volume ml/g |
| A | 33.52 | 350.21 | 0.7256 |
| B | 33.67 | 360.22 | 0.7412 |
| C | 37.63 | 370.43 | 0.7968 |
| D | 38.51 | 390.21 | 0.8021 |
The ethyl acetate hydrogenation reaction evaluation experimental of catalyst carries out on the fixed-bed reactor of laboratory.Every gram of catalyst (60 ~ 80 order) uses 100ml/min10%H at ambient pressure
2/ N
2gaseous mixture reduces, and temperature was warming up to 220 degrees Celsius by 180 degrees Celsius through 2 hours, and stablized reduction at this temperature 14 hours.After reduction, start evaluation response, reaction pressure is 3.0MPa, and temperature is 210 ~ 230 degrees Celsius, and liquid hourly space velocity (LHSV) is 0.5 ~ 1.0g (ethyl ester)/gcath, and hydrogen ester ratio is 30 ~ 60, and evaluation result lists in table 2.
Table 2 (liquid hourly space velocity (LHSV) is 1.0g (ethyl ester)/gcath, and hydrogen ester ratio is 60)
From table 2, stack up says this catalyst under the above-described reaction conditions, in fixed bed reactors, have higher reactivity equally, and good selective, when temperature is 210 degrees Celsius, and ethanol selective higher more stable.
Table 3 (liquid hourly space velocity (LHSV) is 1.0g (ethyl ester)/gcath, and hydrogen ester ratio is 30., reaction temperature 210 degrees Celsius)
From table 3, reducing hydrogen ester ratio is 30, and the conversion ratio of ethyl acetate is in a slight decrease, has higher reactivity equally in fixed bed reactors, and good selective, ethanol selective higher more stable.
Embodiment 5
Prepare a method for ethyl acetate hydrogenation catalyst, the method comprises the following steps:
(1) in sodium carbonate liquor, add copper nitrate solution form sediment slurry, precipitation endpoint pH is 5, and precipitation temperature is 20 degrees Celsius, obtains co-precipitation filter cake after filtration, precipitation;
(2) deionized water making beating is added in co-precipitation filter cake, obtain the slurries of solid content 5wt%, then add the Ludox of 20%, molar concentration is the nickel nitrate solution of 0.02 mol/L, flood 6 hours under 10 degrees Celsius, obtain the pulp that concentration is 10wt%;
(3) pulp is sent in baking oven dry under 100 degrees Celsius;
(4) powder obtained after drying is carried out roasting, sintering temperature is 200 degrees Celsius, roasting time is 8 hours, namely ethyl acetate hydrogenation catalyst is prepared, the content of this catalyst is made up of following component and weight ratio: Cu: Si: Ni=10: 2: 0.002, and the specific area of the ethyl acetate hydrogenation catalyst prepared is 300m
2/ g, pore volume is 0.6ml/g.
Embodiment 6
Prepare a method for ethyl acetate hydrogenation catalyst, the method comprises the following steps:
(1) in sodium carbonate liquor, add copper nitrate solution form sediment slurry, precipitation endpoint pH is 8, and precipitation temperature is 90 degrees Celsius, obtains co-precipitation filter cake after filtration, precipitation;
(2) deionized water making beating is added in co-precipitation filter cake, obtain the slurries of solid content 19wt%, then add the Ludox of 20%, molar concentration is the nickel nitrate solution of 0.1 mol/L, flood 1 hour at 60 c, obtain the pulp that concentration is 20wt%;
(3) pulp is sent in baking oven dry at 200 degrees celsius;
(4) powder obtained after drying is carried out roasting, sintering temperature is 600 degrees Celsius, roasting time is 1 hour, namely ethyl acetate hydrogenation catalyst is prepared, the content of this catalyst is made up of following component and weight ratio: Cu: Si: Ni=50: 5: 0.01, and the specific area of catalyst is 450m
2/ g, pore volume is 1.0ml/g.
Claims (3)
1. prepare a method for ethyl acetate hydrogenation catalyst, it is characterized in that, the method comprises the following steps:
(1) in sodium carbonate liquor, add copper nitrate solution form sediment slurry, precipitation endpoint pH is 5 ~ 8, and precipitation temperature is 20 ~ 90 degrees Celsius, obtains co-precipitation filter cake after filtration, precipitation;
(2) deionized water making beating is added in co-precipitation filter cake, obtain the slurries of solid content 5 ~ 19wt%, then add the Ludox of 20%, molar concentration is the nickel nitrate solution of 0.02 ~ 0.1 mol/L, flood 1 ~ 6 hour under 10 ~ 60 degrees Celsius, obtain pulp;
(3) pulp is sent in baking oven dry under 100 ~ 200 degrees Celsius;
(4) powder obtained after drying is carried out roasting, sintering temperature is 200 ~ 600 degrees Celsius, roasting time is 1 ~ 8 hour, namely prepare ethyl acetate hydrogenation catalyst, the content of this catalyst is made up of following component and weight ratio: Cu ︰ Si ︰ Ni=10 ~ 50 ︰ 2 ~ 5 ︰ 0.002 ~ 0.01.
2. a kind of method preparing ethyl acetate hydrogenation catalyst according to claim 1, is characterized in that, the pulp concentration described in step (2) is 10 ~ 20wt%.
3. a kind of method preparing ethyl acetate hydrogenation catalyst according to claim 1, is characterized in that, the specific area of the ethyl acetate hydrogenation catalyst prepared is 300 ~ 450m
2/ g, pore volume is 0.6 ~ 1.0mL/g.
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| CN1695803A (en) * | 2005-04-01 | 2005-11-16 | 上海兖矿能源科技研发有限公司 | Iron based catalyst prepared in use for Fischer-Tropsch synthesis under high temperature, and preparation method |
| CN101301612A (en) * | 2008-05-27 | 2008-11-12 | 神华集团有限责任公司 | Nickelic Fischer-Tropsch synthetic iron-based catalyst and preparation thereof |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
| CN101934228A (en) * | 2010-09-30 | 2011-01-05 | 江苏丹化煤制化学品工程技术有限公司 | Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof |
| CN102327774A (en) * | 2011-07-06 | 2012-01-25 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
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- 2012-04-20 CN CN201210119122.3A patent/CN103372435B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1695803A (en) * | 2005-04-01 | 2005-11-16 | 上海兖矿能源科技研发有限公司 | Iron based catalyst prepared in use for Fischer-Tropsch synthesis under high temperature, and preparation method |
| CN101301612A (en) * | 2008-05-27 | 2008-11-12 | 神华集团有限责任公司 | Nickelic Fischer-Tropsch synthetic iron-based catalyst and preparation thereof |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
| CN101934228A (en) * | 2010-09-30 | 2011-01-05 | 江苏丹化煤制化学品工程技术有限公司 | Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof |
| CN102327774A (en) * | 2011-07-06 | 2012-01-25 | 山东华鲁恒升化工股份有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic ester and preparation method and application of catalyst |
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