CN104109080A - Method for preparing ethanol through gas-phase catalysis hydrogenation of acetic acid - Google Patents
Method for preparing ethanol through gas-phase catalysis hydrogenation of acetic acid Download PDFInfo
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- CN104109080A CN104109080A CN201310129903.5A CN201310129903A CN104109080A CN 104109080 A CN104109080 A CN 104109080A CN 201310129903 A CN201310129903 A CN 201310129903A CN 104109080 A CN104109080 A CN 104109080A
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- acetic acid
- ethanol
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- catalytic hydrogenation
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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
Abstract
The invention relates to a method for preparing ethanol through gas-phase catalysis hydrogenation of acetic acid. A problem of low once-through conversion rate of present acetic acid hydrogenation catalysts in the ethanol production process is mainly solved. The method comprises the following steps: allowing raw materials comprising acetic acid and hydrogen to contact and react with a composite bed catalyst composed of a Pd-based catalyst and a Cu-based catalyst in a fixed bed reactor with a molar ratio of hydrogen to acetic acid of 1:(0.01-0.1) at a reaction temperature of 200-270DEG C under a reaction pressure of 0.5-5.0MPa, under a liquid volume air speed of 0.1-0.5h<-1> to generate ethanol and water; and separating to obtain an ethanol product. The method well solves the problem, and can be used in the industrial production of ethanol through acetic acid hydrogenation.
Description
Technical field
The present invention relates to a kind of method of preparing ethanol through acetic acid gas-phase catalytic hydrogenation.
Background technology
The Nonrenewable resources such as coal, oil, Sweet natural gas are fewer and feweri, many countries active development as positive in Brazil, the U.S., China etc., utilize biomass fuel alcohol production technology, to alleviate, face energy dilemma in world wide.As clean energy, ethanol not only can substitute tetraethyllead as the detonation suppressor of gasoline, can also be used as automobile fuel, greatly reduces the pollution that gasoline combustion causes.At present, 60% of ethanol production as automobile fuel in world wide, and the production method of ethanol mainly comprises biomass ferment method and take the chemical synthesis that petroleum material is raw material.Whole world recyclable fuel alliance and F.O. Licht have issued global annual ethanol production prediction on February 14th, 2011, and global ethanol production expectation in 2011 can reach 88,700,000,000 liters, to meet the demand that substitutes crude oil in global range.China Shi Yige energy expenditure big country, and be faced with the energy and environmental protection dual-pressure.Especially at dependence on foreign countries for oil up to today over half, develop ethanol and join or alternative fuel as adding, not only more and more urgent, and tool is of great significance.So far, alcohol fuel consumption accounts for 20% of China's gasoline consumption, and China has become the third-largest fuel ethanol production and the consumer nation that is only second to the U.S., Brazil.China approximately more than 95% factory owner to take grain especially corn pass through Ethanol Production by Fermentation as raw material.Along with the development of fuel ethanol industrial and the rising of demand, there is lack of raw materials, and problem becomes increasingly conspicuous, and causes staple food supply day by day nervous, and provision price is anxious to rise, and only relies on grain to supply raw materials and can not meet the Production requirement of alcohol fuel; And the raw material ethene that chemical synthesis adopts derives from petroleum resources, the objective present situation of oil starvation has limited chemical synthesis and has prepared ethanol in popularization and the development of China.In this case, carry out novel alcohol production technical research and development and seem increasingly important.
Synthetic gas is prepared the extensive attention that ethanol technology worldwide causes everybody, but there is the problem of poor selectivity in this route, if adopt synthetic gas, through acetic acid hydrogenation, produce ethanol, not only can make full use of abundant synthetic gas, and can produce the alternative fuel that country is badly in need of, ensure supply of fuel and national energy security, can greatly improve the selectivity that generates ethanol, reduce synthetic gas and directly generate the separation costs that ethanol brings.According to the preliminary statistics, about 40,000,000,000 m of coke-oven gas of the annual discharge of China
3if, be used, can produce every year 1300 ten thousand tons of ethanol, produce huge economic benefit and social benefit.The key issue existing is the exploitation for high-performance, tolerance catalyzer, and the optimization of building-up process and processing condition.
US Patent No. 4517391 adopts Co catalyzer.In catalyzer, Co content is not less than 50%, and temperature in, at 230～270 ℃, under reaction pressure 27 MPa conditions, generates ethanol yield and reaches 97%.This reaction pressure is harsher, and it is more difficult that industrialization generates.
It is catalyzer that US Patent No. 2607807 adopts precious metal Ru base, and Dichlorodiphenyl Acetate hydrogenation is evaluated, and found that, under 70MPa condition, ethanol yield can reach 88%, reduces reaction pressure to 20MPa, ethanol maximum yield 41%.
It is that 1%Pd-10%Co-89%C is catalyzer that US Patent No. 7608744 adopts weight metal per-cent, and 250 ℃ of temperature of reaction, under reaction pressure 2.2MPa reaction conditions, acetic acid transformation efficiency is 18.5%, and generating ethanol selectivity is 97.5%.
US Patent No. 7608744B1 adopts precious metals pt catalyzer, and during catalyzer forms, Pt content is 1%, Co content while being 10%, 250 ℃ of temperature of reaction, and hydrogen pressure 22 bar, acetic acid transformation efficiency reaches 38%, generates ethanol selectivity and reaches 96%.
In sum, catalyzer prepared by prior art, is applied to, in the process of acetic acid Hydrogenation for ethanol, have the problem of one way acetic acid low conversion rate.
Summary of the invention
Technical problem to be solved by this invention is that existing acetic acid shortening ethanol technology processed exists catalyst severe reaction conditions, and the problem that per pass conversion is low provides a kind of new method of preparing ethanol through acetic acid shortening.The method has advantages of that acetic acid per pass conversion is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing ethanol through acetic acid gas-phase catalytic hydrogenation, take acetic acid and hydrogen as raw material, take fixed bed as reactor, adopting the multiple-hearth catalyzer of the catalyst based and catalyst based composition of Cu of Pt, is 1:(0.01～0.1 in the mol ratio of hydrogen/acetic acid), 200～270 ℃ of temperature of reaction, reaction pressure is 0.5～5.0MPa, and liquid volume air speed is 0.1～0.5 hour
-1under condition, raw material contacts with catalyzer, and reaction generates second alcohol and water, by separation, obtains alcohol product; Wherein,
Described upper bed layer catalyzer is that Pt is catalyst based, in weight percentage, comprises following component: a) 0.3～2.0%Pt, b) 75.0～95.0% SiO
2, c) 1.0～10.0% SnO
2, d) 2～10.0% Co, e) and 2.0～10.0% be selected from least one in MgO, CaO, ZnO or BaO;
Described lower bed layer catalyzer is that Cu is catalyst based, in weight percentage, comprises following component: a) 35.0～75.0% CuO, b) 3.0～30.0% ZnO, c) 1.0～10.0% Mn or its oxide compound, d) 2.0～15.0% Al
2o
3or SiO
2in at least one, e) 1.0～10.0% be selected from MgO, ZrO
2, at least one in CaO or BaO;
Upper and lower bed catalyst weight is than being 1:(0.2～5).
Preferably, upper and lower bed catalyst weight is than being 1:(0.3～3).
More preferably, upper and lower bed catalyst weight is than being 1:(0.5～2.5).
Preferably, the liquid volume air speed of acetic acid is 0.1～0.3 hour
-1.
Preferably, the mol ratio of hydrogen/acetic acid is 1:(0.01～0.05).
Preferably, in described raw material, the concentration of acetic acid is 10～100% by weight percentage.
Preferably, described hydrogenation reaction temperature is 220～260 ℃.
Preferably, described hydrogenation reaction pressure is 1.0～3.0 MPa.
Preferably, during upper bed layer Pt is catalyst based, by weight percentage: Pt consumption is 0.5～1.5%; SiO
2consumption be 80 ~ 90%, SnO
2consumption is 5～10%; Co consumption is 5～10%; At least one consumption being selected from MgO, CaO, ZnO or BaO is 5.0～10%.
Preferably, during lower bed layer Cu is catalyst based, by weight percentage: the consumption of CuO is 35.0～70.0%; The consumption of ZnO is 5.0～25.0%; The consumption of Mn or its oxide compound is 5.0 ~ 10.0%, Al
2o
3or SiO
2in at least one consumption be 5.0～10.0%; Be selected from MgO, ZrO
2, at least one the consumption in CaO or BaO is 5.0～10.0%.
The catalyst based preparation method of upper bed layer Pt comprises the following steps: adopt pickling process by the Mg that is selected from of aequum
2+, Ca
2+, Zn
2+, Ba
2+in at least one solubility solution impregnation at SiO
2surface, is dried and obtains carrier by 400～1000 ℃ of roastings; According to the method for incipient impregnation, by the SnCl of aequum
4solution impregnation is on carrier, and dry, roasting obtains SnO
2the carrier of modifying; Adopt the method for dipping, by the Pt that contains of aequum
2+solution impregnation is on carrier, and dry, roasting obtains Pt catalyzer; Adopt the method for dipping, by the Co that contains of aequum
2+water/ethanolic soln is immersed on Pt catalyzer, and after being dried, roasting obtains Pt-Co catalyzer again.
The catalyst based preparation method of lower bed layer Cu comprises the following steps: the silicon sol of requirement is added in required water gaging, heated and stirred forms solution I, being selected from containing at least one and Mn soluble species in Cu, Zn, Al, Mg, Zr, Ca or Ba of aequum added in required water gaging and dissolved, form solution II, solution III will be formed after aequum sodium carbonate solution, solution II and solution III splash in solution I simultaneously, after dripping completely, obtain slurries I, slurries I after filtration, washing, dry after after 300～600 ℃ of roastings, after moulding, obtain catalyzer.
Acetic acid shortening generates in the process of ethanol, contingent side reaction is a lot, and main side reaction comprises: the ethanol of generation further reacts generation ethyl acetate with acetic acid, the ethanol generation ethene that further dewaters, the further hydrogenation of ethene generates ethane, and acetic acid partial hydrogenation forms acetaldehyde.Therefore, the acid site quantity of catalyzer need to be mated well with active centre.When simple employing Pd base or Pt base catalyst, reaction conversion ratio is low, and the ethyl acetate that part generates is simultaneously difficult to further hydrogenation generation ethanol, therefore generates ethanol selectivity not high.The Pt the present invention relates to is catalyst based, by introducing at least wherein a kind of to Al of MgO, CaO, ZnO or BaO
2o
3carrier is modified, and has reduced the acidity of carrier, effectively suppresses the generation of ether.By introducing SnO
2improve the mode of action of Pt and carrier, effectively improved the dispersity of Pt, improved catalytic activity.The quantity at catalyst acid center and strength of acid regulate by kind and the content of oxide compound, thereby make that the Pt of preparation is catalyst based has good selectivity and stability, and the Cu the present invention relates to is catalyst based, by introducing MgO, ZrO
2, at least one in CaO or BaO modify catalyzer, reduced the acidity of carrier, make the ethanol and the reaction raw materials acetic acid that in reaction process, generate further react the possibility attenuating that forms ethyl acetate, be conducive to improve the selectivity of reaction, cross and introduce appropriate ZnO, improve the dispersity of catalyzer, be conducive to improve the catalyst based hydrogenation activity of Cu.Adopt composite bed catalyzer, at upper bed layer, a part of acetic acid is transformed, generate ethanol and ethyl acetate, when reaction raw materials touches Cu catalyzer, remaining acetic acid content reduces, reduced the corrosion of acetic acid to Cu catalyzer, Cu catalyzer has good ester through hydrogenation activity and selectivity, can improve the selectivity that generates ethanol.Adopt two kinds of methods that catalyzer is compound, effectively improved active selectivity and the stability of catalyzer.
Use catalyzer provided by the invention and processing condition, in the situation of upper and lower bed catalyzer usage quantity 1:2, at 240 ℃ of entrance temperature of reaction, reaction pressure 2. 5 MPa, raw material cumulative volume air speed is 0.2 h
-1, under the reaction conditions that the mol ratio of hydrogen and acetic acid is 40.0, be applied to acetic acid shortening and prepare ethanol, when acetic acid transformation efficiency is 90%, the selectivity that generates ethanol reaches 96.5%, catalyst activity selectivity is good, and simultaneous reactions mild condition has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[catalyzer 1]
Catalyzer 1, by 50 g silicon-dioxide and Mg
2+content is 3.0% aqueous solution incipient impregnation, after dry, roasting, obtains the carrier I that MgO modifies, and this carrier is adopted and contains 3.94% Sn
4+solution impregnation, after super-dry, roasting, obtain SnO
2the carrier II that-MgO modifies, it consists of: 5%MgO-5%SnO
2-90%SiO
2; By 1.0 g Pt (NH
3)
4cl
2solution is dissolved in water/ethanolic soln that 56.0 g mass ratioes are 1:1, according to the method for incipient impregnation, solution I is immersed in carrier II, and after being dried, at 400～700 ℃, roasting obtains Pt catalyzer; According to the method for incipient impregnation, by a certain amount of 5% Co that contains
2+ethanolic soln is immersed on Pt catalyzer, and after being dried, at 500 ℃, roasting obtains catalyzer 1, and it forms in Table 1.
[catalyzer 2～5]
According to each step Kaolinite Preparation of Catalyst in catalyzer 1, just change each material and form, it forms in Table 1.
[catalyzer 6]
Catalyzer 6, takes 330.0 g Cu (NO
3)
23H2O, 55 g Zn (NO
3)
26H
2o, 48 g Mg (NO
3)
26H
2o, 55 g Al (NO
3)
29H
2o, 50.0 g weight percents are 50%Mn (NO
3)
2solution is dissolved in 1.0 L water in the lump, adds 50 g 40% silicon sol in 80 ℃ of oil baths after heated and stirred 2 h, continues to stir 1 H-shaped and becomes solution I.To dripping 1.0 mol/L aqueous sodium carbonates to the pH value of mixing solutions in solution I, be 8.0 formation solution II, the washing after aging 4 hours at 80 ℃ of solution II, filter and be precipitated thing.Throw out is dried 24 hours through 120 ℃, 500 ℃ of roastings 2 hours, obtains catalyzer 6.
[catalyzer 7～10]
According to catalyzer 6 each step Kaolinite Preparation of Catalysts, just change each material and form, it forms in Table 1.
The composition of each catalyzer of table 1
[embodiment 1-12]
According to upper and lower bed catalyzer in table 2, form and ratio, take pure acetic acid as raw material, 240 ℃ of temperature of reaction, hydrogen pressure 2.5 MPa, H
2with acetic acid mol ratio be 30, acetic acid liquid phase feed volume space velocity 0.2 h
-1condition under, catalyst activity and stability are checked and rated, it the results are shown in Table 2.
[comparative example]
According to US Patent No. 7608744B1, prepare Pt catalyzer, during catalyzer forms, Pt content is that 1%, Co content is 10%, take pure acetic acid as raw material, 245 ℃ of temperature of reaction, and hydrogen pressure 2.5 MPa, H
2with acetic acid mol ratio be 30, liquid phase feed volume space velocity 0.2 h
-1condition under, catalyst activity and stability are checked and rated, it the results are shown in Table 2.
The acetic acid hydrogenation reaction performance of table 2 different catalysts
As seen from Table 2, the catalyzer of bed up and down and the filling method thereof with method provided by the invention, prepared, be 0.2 h in 240 ℃ of temperature of reaction, 2.5 MPa, the total air speed of raw material volume
-1, under the reaction conditions that hydrogen and acetic acid mol ratio are 30.0, be applied to acetate catalyst hydrogenation reaction, there is good hydrogenation activity, to compare with the catalyzer providing in comparative example, hydrogenation activity selectivity is good.
Adopt catalyzer 4 and catalyzer 6, according to the ratio of 1:2, load by weight percentage, under different technology conditions, the catalytic performance of this composite catalyst is checked and rated, the results are shown in Table 3.
Acetic acid catalytic hydrogenation catalyst evaluation result under table 3 differential responses condition
From table 2,3 can find out, this technology is applied to acetic acid gas-phase catalytic hydrogenation and prepares ethanol, at 220～260 ℃ of temperature of reaction, reaction pressure 1.0～3.0 MPa, and acetic acid liquid air speed 0.1～0.4 h
-1under condition, the activity of catalyzer is good, has obtained good technique effect.
Claims (10)
1. a method of preparing ethanol through acetic acid gas-phase catalytic hydrogenation, take acetic acid and hydrogen as raw material, take fixed bed as reactor, adopt the multiple-hearth catalyzer of the catalyst based and catalyst based composition of Cu of Pt, mol ratio at hydrogen/acetic acid is 1:(0.01～0.1), 200～270 ℃ of temperature of reaction, reaction pressure is 0.5～5.0MPa, liquid volume air speed is 0.1～0.5 hour
-1under condition, raw material contacts with catalyzer, and reaction generates second alcohol and water, by separation, obtains alcohol product; Wherein,
Described upper bed layer catalyzer is that Pt is catalyst based, in weight percentage, comprises following component: a) 0.3～2.0%Pt, b) 75.0～95.0% SiO
2, c) 1.0～10.0% SnO
2, d) 2～10.0% Co, e) and 2.0～10.0% be selected from least one in MgO, CaO, ZnO or BaO;
Described lower bed layer catalyzer is that Cu is catalyst based, in weight percentage, comprises following component: a) 35.0～75.0% CuO, b) 3.0～30.0% ZnO, c) 1.0～10.0% Mn or its oxide compound, d) 2.0～15.0% Al
2o
3or SiO
2in at least one, e) 1.0～10.0% be selected from MgO, ZrO
2, at least one in CaO or BaO;
Upper and lower bed catalyst weight is than being 1:(0.2～5).
2. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, is characterized in that upper and lower bed catalyst weight than being 1:(0.3～3).
3. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 2, is characterized in that upper and lower bed catalyst weight than being 1:(0.5～2.5).
4. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, the liquid volume air speed that it is characterized in that acetic acid is 0.1～0.3 hour
-1.
5. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, the mol ratio that it is characterized in that hydrogen/acetic acid is 1:(0.01～0.05).
6. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, the concentration that it is characterized in that acetic acid in described raw material is 10～100% by weight percentage.
7. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, is characterized in that described hydrogenation reaction temperature is 220～260 ℃.
8. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, is characterized in that described hydrogenation reaction pressure is 1.0～3.0 MPa.
9. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, is characterized in that upper bed layer Pt is catalyst based, by weight percentage: Pt consumption is 0.5～1.5%; SiO
2consumption be 80 ~ 90%, SnO
2consumption is 5～10%; Co consumption is 5～10%; At least one consumption being selected from MgO, CaO, ZnO or BaO is 5.0～10%.
10. the method for preparing ethanol through acetic acid gas-phase catalytic hydrogenation according to claim 1, is characterized in that lower bed layer Cu is catalyst based, by weight percentage: the consumption of CuO is 35.0～70.0%; The consumption of ZnO is 5.0～25.0%; The consumption of Mn or its oxide compound is 5.0 ~ 10.0%, Al
2o
3or SiO
2in at least one consumption be 5.0～10.0%; Be selected from MgO, ZrO
2, at least one the consumption in CaO or BaO is 5.0～10.0%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437486A (en) * | 2014-11-03 | 2015-03-25 | 北京联合大学 | Catalytic combustion catalyst for hydrochloric ether and preparation method of catalytic combustion catalyst |
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|---|---|---|---|---|
| CN102149662A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Ethanol production from acetic acid utillizing a cobalt catalyst |
| CN102229520A (en) * | 2011-04-25 | 2011-11-02 | 江苏索普（集团）有限公司 | Method for preparing alcohol by acetic acid gas phase hydrogenation |
| CN102690170A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing ethanol by acetic acid gas phase hydrogenation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149662A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Ethanol production from acetic acid utillizing a cobalt catalyst |
| CN102690170A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing ethanol by acetic acid gas phase hydrogenation |
| CN102229520A (en) * | 2011-04-25 | 2011-11-02 | 江苏索普（集团）有限公司 | Method for preparing alcohol by acetic acid gas phase hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437486A (en) * | 2014-11-03 | 2015-03-25 | 北京联合大学 | Catalytic combustion catalyst for hydrochloric ether and preparation method of catalytic combustion catalyst |
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