CN102976892A - Method for preparing ethanol through acetic ester hydrogenation - Google Patents
Method for preparing ethanol through acetic ester hydrogenation Download PDFInfo
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- CN102976892A CN102976892A CN2012104757153A CN201210475715A CN102976892A CN 102976892 A CN102976892 A CN 102976892A CN 2012104757153 A CN2012104757153 A CN 2012104757153A CN 201210475715 A CN201210475715 A CN 201210475715A CN 102976892 A CN102976892 A CN 102976892A
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Abstract
The invention relates to a method for preparing ethanol through acetic ester hydrogenation. The method performs an acetic ester hydrogenation reaction to generate ethanol under the conditions of certain temperature, pressure, hydrogen/ester molar ratio and hydrogen circulation in a fixed-bed reactor filled with a copper-based catalyst, wherein in the copper-based catalyst, a mesoporous molecular sieve MCM-41 is used as a carrier, copper is used as an active component, and the oxide of at least one element of La and Ce is used as an auxiliary; and the MCM-41 accounts for 40-90% of the catalyst by weight, the active component copper accounts for 10-50% of the catalyst by weight, and the auxiliary accounts for 0.1-20% of the catalyst by weight. According to the method for preparing ethanol through acetic ester hydrogenation, provided by the invention, when the reaction temperature is 220 DEG C, the reaction pressure is 3MPa, the hydrogen/ester molar ratio is 30 and the mass airspeed of acetic ester is 2h<-1>, the conversion rate of acetic ester is 98.5%, and the ethanol selectivity is as high as 99.6%, thereby showing extremely high hydrogenation activity, selectivity and stability.
Description
Technical field
The present invention relates to a kind of method of acetic ester preparation of ethanol by hydrogenating.
Background technology
Ethanol is commonly called as alcohol, as a kind of important industrial chemicals, is used widely in fields such as food, medicine, chemical industry, national defence.Because the oxygen level of ethanol is up to 34.7%, thereby also can be used as methyl tertiary butyl ether (MTBE) substitute and add in the gasoline and obtain ethanol petrol, when reducing petrol consumption, can also make gasoline combustion more abundant, thereby reduce the discharging of the pollutents such as aflame CO.
Ripe alcohol production technology mainly comprises two lines.The one, adopting petroleum cracking product ethene is raw material, obtains the petroleum path of ethanol by hydration.It is raw material that an other route refers to adopt various agricultural-food, agroforestry by product and the wild plants that contain sugar, through the biological fermentation process that is hydrolyzed, ferments and make disaccharide, polysaccharide be converted into monose and be further converted to ethanol.
Because the restriction of China's national situation uses sugarcane or Maize Production alcohol fuel to be limited on a large scale, be that the alcohol production technology of raw material is not yet ripe and adopt Mierocrystalline cellulose.Based on the relatively abundant national conditions of coal in China, be subject to paying close attention to widely by synthetic gas ethanol processed.The synthetic gas of having reported directly ethanol method processed is that synthetic gas is first at Rh/SiO
2On the catalyzer under 3-10MPa and 300 ℃ of conditions reaction to generate acetaldehyde, ethanol, ethyl acetate and acetic acid be main carbon two products, then at Cu/SiO
2[JP6259632], Pd-Fe/SiO
2The CuO/Al of [JP61178940, JP61178942] or basic metal or the modification of transition metal oxides additive
2O
3Be ethanol with further hydrocrackings of by product such as acetaldehyde, ethyl acetate and acetic acid on the catalyzer such as [CN1230458A].Because the shortcomings such as this technical matters condition harshness, poor catalyst stability, selectivity are low not yet obtain large-scale application up to now.
Chinese patent CN101934228A has reported a kind of copper-based catalysts of acetic ester preparation of ethanol by hydrogenating, carrier is aluminum oxide or silicon oxide, auxiliary agent is the oxide compound of the elements such as zinc, manganese, chromium, calcium, barium, iron, nickel, magnesium, and wherein the transformation efficiency of acetic ester is up to 88%, and reaction efficiency is lower.
Chinese patent CN102327774A has reported that a kind of copper-based catalysts is applied to acetic ester preparation of ethanol by hydrogenating reaction system, its preparation method is to add silicon sol or aluminum soluble salt in the soluble salt of copper and promoter metal soluble salt mixing solutions, after stirring, under 50-95 ℃ of condition mixed solution is joined in the solution of precipitation agent, then aging, filtration, washing, drying, roasting, moulding and reduction obtain catalyzer.The institute's peak rate of conversion of controlling catalyst in the acetic ester hydrogenation reaction is 85%, and the ethanol selectivity is 91%.
It is carrier that Chinese patent CN101941887A adopts silicon oxide or aluminum oxide, copper is that the metals such as active ingredient, Zn, Mn, Cr, Ca, Ba or metal oxide are that auxiliary agent makes copper-based catalysts, selectivity in the acetic ester hydrogenation reaction is up to 99%, and transformation efficiency is up to 92%.
Chinese patent CN101411990A discloses a kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol copper Si catalyst, and the method is that the adding specific surface area is 600-1200m in cupric ammine complex
2In the mesoporous silica molecular sieve powder of/g, then after filtration, washing, drying, roasting, reduction, make catalyzer.
Chinese patent CN1935375A discloses a kind of for dimethyl maleate Hydrogenation 1, the catalyzer of 4-butyleneglycol, this catalyzer uses the mesopore molecular sieve MCM-41 of large specific surface as carrier impregnation Cu salts solution Kaolinite Preparation of Catalyst presoma, and then roasting has obtained the Cu/MCM-41 catalyzer.In the dimethyl maleate hydrogenation reaction, this catalyzer has higher active and higher BDO selectivity.
In view of gathering and the sintering of copper crystal grain occur the Cu-series catalyst hot conditions easily, therefore to have the copper-based catalysts of high temperature sintering resistant ability, high reactivity and highly selective be one of difficult point of acetic ester preparation of ethanol by hydrogenating technology in exploitation.
Summary of the invention
The object of the present invention is to provide a kind of method of acetic ester preparation of ethanol by hydrogenating, adopt catalyzer of the present invention to be used for the reaction of acetic ester preparation of ethanol by hydrogenating, can obtain higher alcohol production ability and ethanol selectivity, have simultaneously the long life-span, significantly reduce the production cost of ethanol.
There is a large amount of layered silicate structures in the catalyzer that the invention provides a kind of acetic ester preparation of ethanol by hydrogenating before reduction, so that the dispersity of copper increases substantially, also strengthened simultaneously thermostability, adopt simultaneously the electronics modifying function of rare-earth additive La and Ce that the valence state of copper is regulated and control, make this catalyzer not only have comparatively ideal valence distribution, also have good high temperature sintering resistant ability simultaneously.This catalyzer has increased substantially the high degree of dispersion of copper, has higher thermostability and hydrogenation activity and stability in the acetic ester hydrogenation reaction, has also significantly reduced the later separation cost when reducing waste discharge.
The preparation method of the catalyzer of a kind of acetic ester preparation of ethanol by hydrogenating provided by the invention is in the synthetic link of mesoporous silicon oxide molecular sieve, in the mesopore molecular sieve mother liquor, add active ingredient and auxiliary agent, then common aging reaction is after for some time, intensification ammonia still process, then pour into and carry out the crystallization certain hour in the crystallizing kettle, then filter, wash and dry after and roasting form catalyzer of the present invention.Adopt the method to help to improve the dispersity of copper in catalyzer, and promote the valence stability of active ingredient and crystal particle scale to stablize.
Technical scheme of the present invention:
A kind of method for the acetic ester preparation of ethanol by hydrogenating in the fixed-bed reactor that are filled with copper-based catalysts, under the condition of certain temperature, pressure, hydrogen ester mol ratio and hydrogen recycle, is carried out the acetic ester hydrogenation reaction and is generated ethanol;
Described copper-based catalysts is take mesoporous silicon oxide molecular sieve MCM-41 as carrier, and take copper as active ingredient, the oxide compound of at least a element in La, the Ce is as auxiliary agent; Each component accounts for catalyst weight per-cent: silicon oxide=50-90wt%, active ingredient copper=10-50wt%, auxiliary agent=0.1-20wt%.
The preparation method of the copper-based catalysts for the acetic ester preparation of ethanol by hydrogenating provided by the invention comprises the steps: under agitation condition, in the aqueous solution that has dissolved CTAB, slowly drip the soluble silicon source, constantly adding simultaneously alkaline solution remains between 11 ~ 11.5 the pH value, after being added dropwise to complete, continue to stir formation MCM-41 mesopore molecular sieve mother liquor; In this mother liquor, add copper ammon solution and solubility auxiliary agent presoma; After fully stirring, the rising temperature is carried out ammonia still process, when liquid phase PH valve is lower than 7, and stopped heating, cooling; With the crystallization in the stainless steel crystallizing kettle of packing into of the feed liquid after the cooling, cooling, with sedimentation and filtration, washing to neutral; Catalyzer of the present invention will be formed at last after filtration cakes torrefaction, the roasting.
Alternatively, described catalyzer intermediary hole silicon oxide MCM-41 accounts for the 60-90% of catalyst weight.Active ingredient copper accounts for the 20-40% of catalyst weight.Auxiliary agent accounts for the 1-10% of catalyst weight.
The preparation method of the copper-based catalysts of a kind of acetic ester preparation of ethanol by hydrogenating provided by the invention is through following steps:
1) under agitation condition, in the aqueous solution that has dissolved CTAB, slowly drip the soluble silicon source, constantly add simultaneously NaOH the pH value is remained between the 11-11.5, after being added dropwise to complete, stir 0.5-2h and form MCM-41 mesopore molecular sieve mother liquor;
2) select a kind of soluble precursor of copper to be dissolved in the ammoniacal liquor;
3) select one or both soluble precursor of auxiliary agent to be mixed with the aqueous solution;
4) with step 2) in solution and the solution in the step 3) pour in the mother liquor of step 1), stir 4-24 h under the room temperature;
5) slurry of the generation in the step 4) is increased the temperature to 50-100 ℃ carry out ammonia still process, when liquid phase PH valve is lower than 7, stopped heating;
6) the stainless steel crystallizing kettle of packing into is then at 80-140 ℃ of lower crystallization 24-72 h;
7) with after the cooling of the stainless steel crystallizing kettle in the step 6), that sedimentation and filtration, washing is extremely neutral;
8) filter cake in the step 7) is dry under 50-120 ℃ of condition;
9) with after dried filter cake pulverizes in the step 8), after 350-600 ℃ of lower roasting, form catalyzer of the present invention.
Wherein, the soluble silicon source is a kind of in tetraethoxy, the water glass or two kinds.
Described auxiliary agent is the soluble salt of La, Ce, for example: nitrate, muriate or acetate.
The step that the method that a kind of acetic ester preparation of ethanol by hydrogenating is provided provided by the invention comprises:
1) will prepare load on copper-based catalysts moulding on the MCM-41 molecular sieve after put into fixed-bed reactor, be 5-10%H in volume ratio
2/ N
2Reduce in the atmosphere, reduction temperature 350-500 ℃, recovery time 2-24 hour;
2) after reduction finishes, with pure hydrogen displacement whole system, adjust temperature of reaction to 160-260 ℃, pressure is 1.0-4.0MPa, and the acetic ester mass space velocity is 0.5-3 h
-1, the material that contains acetic ester passes through and enters reactor and hydrogen reaction generation ethanol after vaporizing chamber is vaporized;
3) product separates through the laggard promoting the circulation of qi liquid of condensation, and liquid-phase product is collected products pot, gas phase through the supercharger supercharging after circulation enter reactor and react, the mole hydrogen ester is than being 20-200; Fresh hydrogen is replenished automatically according to pressure change.
Described acetic ester comprises one or both in ritalin and the vinyl acetic monomer.
The described acetic ester material that contains can also include one or both solvents in ethanol and the methyl alcohol.
Described circulation gas phase composite comprises hydrogen, acetate in minute ester and ethanol, and volume ratio is: 100:0.01-0.2:0.01-0.2.
Described circulation gas phase composite comprises hydrogen, acetate in minute ester, ethanol and methyl alcohol, and volume ratio is: 100:0.01-0.2:0.01-0.2:0.01-0.4.
Step 2) described temperature of reaction is 180-240 ℃.
Step 2) described reaction pressure is 2-4MPa.
The mole hydrogen ester of the described reaction of step 3) is than being 20-100.
The present invention adopts ammonia still process-crystallization method that copper is loaded on the mesoporous silicon oxide molecular sieve, adopts simultaneously La, Ce that the valence distribution of copper in the catalyzer and specific surface area and pore size distribution are regulated and control, thereby has significantly improved the anti-caking power of catalyzer.
Preformed catalyst of the present invention is used for the reaction of acetic ester preparation of ethanol by hydrogenating, is 220 ℃ in temperature of reaction, and reaction pressure is 3MPa, and mole hydrogen ester ratio is 50, and the acetic ester mass space velocity is 1.2h
-1The time, the vinyl acetic monomer transformation efficiency is 98.6%, and the ethanol selectivity is up to 99.6%, and the ethanol space-time yield reaches 628g/L.h, shows high hydrogenation activity and selectivity.
The present invention is in conjunction with the unique texture in the mesopore molecular sieve MCM-41 forming process, adopt the method that ammonia still process-the crystallization method combines to prepare the copper silica-base catalyst, the method impels copper and silicon can more form more stable layered silicate structure, thereby has increased substantially the high degree of dispersion of copper.The gained catalyzer has higher thermostability and hydrogenation activity and stability in the acetic ester hydrogenation reaction.Adopt this catalyzer to carry out acetic ester preparation of ethanol by hydrogenating reaction, under optimal conditions, the ethyl acetate transformation efficiency reaches in 98.6% the situation, and the ethanol selectivity reaches 99.6%, has also significantly reduced the later separation cost when reducing waste discharge.In addition, this catalyzer steady running 1500 hours, activity does not have considerable change, illustrates that this catalyzer has good thermostability.
Description of drawings
Fig. 1. the mould examination stability of acetic ester preparation of ethanol by hydrogenating catalyzer.
Fig. 2. the low temperature nitrogen adsorption desorption curve of acetic ester preparation of ethanol by hydrogenating catalyzer.
Fig. 3. the mesoporous pore size distribution curve of acetic ester preparation of ethanol by hydrogenating catalyzer.
Fig. 4. the micropore size distribution curve of acetic ester preparation of ethanol by hydrogenating catalyzer.
Embodiment
The invention will be further described below by specific embodiment, but they do not impose any restrictions the present invention.And particularly point out, the reagent that uses among the embodiment and equipment are commercially available except offering some clarification on the source.
Embodiment 1:
The catalyzer preparation
Weighing 11 g CTAB(cetyl trimethylammonium bromides) place the beaker of 270 g water and fully dissolving, add the TEOS(tetraethoxy of 51.4 g); Then add the NaOH of 2.2g, make the pH value between 11-11.5; Improve behind the bath temperature to 80 ℃ and stir the mother liquor that 2 H-shapeds become the MCM-41 molecular sieve; Weighing 15.2g Cu (NO
3)
23H
2The ammoniacal liquor of O and 51.7ml25% joins in the 150ml water and is made into copper ammon solution; Under the room temperature copper ammon solution is poured in the mother liquor of MCM-41 molecular sieve and stirred 4h; Weighing 0.53g La(NO
3)
36H
2O joins in this slurry; Afterwards warming-in-water to 80 ℃ is made ammonia volatilization, stopped heating when the pH value is lower than 7; Subsequently this slurry is packed in the stainless steel crystallizing kettle, and 120 ℃ of lower crystallization 24 hours; Taking-up cooling after crystallization is finished, filtration, washing are to neutral; Then at 120 ℃ of lower dry 6 h; Becoming the copper charge capacity at 500 ℃ of lower roasting 6 H-shapeds at last is 20%, La
2O
3Charge capacity is 1% catalyzer, is labeled as 20Cu-1La-MCM-41.Adopt low temperature nitrogen physical adsorption appearance (Tristar3000 and ASAP2020, U.S. Micromeritics company) that this catalyzer adsorption desorption performance and pore size distribution are characterized, the result sees respectively Fig. 2,3 and 4.
Evaluating catalyst
The catalyzer compressing tablet for preparing is sieved into the 40-60 order, and the 0.8g that then weighs puts into the fixed bed isothermal reactor, uses 20%H
2/ N
2Reduce in the atmosphere, gas gross is controlled at 200ml/min, 400 ℃ of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust about temperature to 215 ℃, pressure is 2.5MPa, and a mole hydrogen ester ratio is 50, and ethyl acetate (EAC) liquid mass air speed is 1.5 h
-1, adopt the charging of liquid phase high-pressure pump.The gas chromatographic analysis product composition of being separated by 1 hour and taking a sample and adopting fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result sees Table 1.
Embodiment 2
The catalyzer preparation
Weighing 11 g CTAB place the beaker of 270 g water and fully dissolving, add the TEOS of 59.4g; Then add the NaOH of 2.2g, make the pH value between 11-11.5; Improve behind the bath temperature to 80 ℃ and stir the mother liquor that 2 H-shapeds become the MCM-41 molecular sieve; Weighing 7.6g Cu (NO
3)
23H
2The ammoniacal liquor of O and 25.8ml 25% joins in the 150ml water and is made into copper ammon solution; Under the room temperature copper ammon solution is poured in the mother liquor of MCM-41 molecular sieve and stirred 4h; Weighing 1.06g La(NO
3)
36H
2O joins in this slurry; Afterwards warming-in-water to 80 ℃ is made ammonia volatilization, stopped heating when the pH value is lower than 7; Subsequently this slurry is packed in the stainless steel crystallizing kettle and 120 ℃ of lower crystallization 24 hours; Taking-up cooling after crystallization is finished, filtration, washing are to neutral; Then at 120 ℃ of lower dry 6 h, becoming the copper charge capacity at 500 ℃ of lower roasting 6 H-shapeds at last is 10%, La
2O
3Charge capacity is 2% catalyzer, is labeled as 10Cu-2La-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet for preparing is sieved into the 40-60 order, and the 0.8g that then weighs puts into the fixed bed isothermal reactor, uses 20%H
2/ N
2Reduce in the atmosphere, gas gross is controlled at 200ml/min, 400 ℃ of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust about temperature to 215 ℃, pressure is 2.5MPa, and a mole hydrogen ester ratio is 50, and ethyl acetate (EAC) liquid mass air speed is 1.2 h
-1, adopt the charging of liquid phase high-pressure pump.The gas chromatographic analysis product composition of being separated by 1 hour and taking a sample and adopting fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result sees Table 1.
Embodiment 3
The catalyzer preparation
Weighing 11 g CTAB place the beaker of 270 g water and fully dissolving, add the TEOS of 40g; Then add the NaOH of 2.2g, make the pH value between 11-11.5; Improve behind the bath temperature to 80 ℃ and stir the mother liquor that 2 H-shapeds become the MCM-41 molecular sieve; Weighing 22.8g Cu (NO
3)
23H
2The ammoniacal liquor of O and 77.5ml25% joins in the 150ml water and is made into copper ammon solution; Under the room temperature copper ammon solution is poured in the mother liquor of MCM-41 molecular sieve and stirred 4 h; Weighing 2.7g La(NO
3)
36H
2O joins in this slurry; Afterwards warming-in-water to 80 ℃ is made ammonia volatilization, stopped heating when the pH value is lower than 7; Subsequently this slurry is packed in the stainless steel crystallizing kettle and 120 ℃ of lower crystallization 24 hours; Taking-up cooling after crystallization is finished, filtration, washing are to neutral; Then at 120 ℃ of lower dry 6 h; Becoming the copper charge capacity at 500 ℃ of lower roasting 6 H-shapeds at last is 30%, La
2O
3Charge capacity is 5% catalyzer, is labeled as 30Cu-5La-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet for preparing is sieved into the 40-60 order, and the 0.8g that then weighs puts into the fixed bed isothermal reactor, uses 20%H
2/ N
2Reduce in the atmosphere, gas gross is controlled at 200ml/min, 400 ℃ of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust about temperature to 220 ℃, pressure is 3MPa, and a mole hydrogen ester ratio is 30, and ethyl acetate (EAC) liquid mass air speed is 2h
-1, adopt the charging of liquid phase high-pressure pump.The gas chromatographic analysis product composition of being separated by 1 hour and taking a sample and adopting fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result sees Table 1.
Embodiment 4
The catalyzer preparation
Weighing 11 g CTAB place the beaker of 270 g water and fully dissolving, add the TEOS of 34.4g; Then add the NaOH of 2.2g, make the pH value between 11-11.5; Improve behind the bath temperature to 80 ℃ and stir the mother liquor that 2 H-shapeds become the MCM-41 molecular sieve; Weighing 30.4g Cu (NO
3)
23H
2The ammoniacal liquor of O and 103.4ml25% joins in the 150ml water and is made into copper ammon solution; Under the room temperature copper ammon solution is poured in the mother liquor of MCM-41 molecular sieve and stirred 4h; Weighing 0.27g La(NO
3)
36H
2O joins in this slurry; Afterwards warming-in-water to 90 ℃ is made ammonia volatilization, stopped heating when the pH value is lower than 7; Subsequently this slurry is packed in the stainless steel crystallizing kettle and 120 ℃ of lower crystallization 24 hours; Taking-up cooling after crystallization is finished, filtration, washing are to neutral; Then at 120 ℃ of lower dry 6 h; Becoming the copper charge capacity at 500 ℃ of lower roasting 6 H-shapeds at last is 40%, La
2O
3Charge capacity is 0.5% catalyzer, is labeled as 40Cu-0.5La-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet for preparing is sieved into the 40-60 order, and the 0.8g that then weighs puts into the fixed bed isothermal reactor, uses 20%H
2/ N
2Reduce in the atmosphere, gas gross is controlled at 200ml/min, 400 ℃ of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust about temperature to 220 ℃, pressure is 3MPa, and a mole hydrogen ester ratio is 30, and ethyl acetate (EAC) liquid mass air speed is 2 h
-1, adopt the charging of liquid phase high-pressure pump.The gas chromatographic analysis product composition of being separated by 1 hour and taking a sample and adopting fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result sees Table 1.
Embodiment 5
The catalyzer preparation
Weighing 11 g CTAB place the beaker of 270 g water and fully dissolving, add the TEOS of 43.3g; Then add the NaOH of 2.2g, make the pH value between 11-11.5; Improve behind the bath temperature to 80 ℃ and stir the mother liquor that 2 H-shapeds become the MCM-41 molecular sieve; Weighing 22.8g Cu (NO
3)
23H
2The ammoniacal liquor of O and 77.5ml25% joins in the 150ml water and is made into copper ammon solution; Under the room temperature copper ammon solution is poured in the mother liquor of MCM-41 molecular sieve and stirred 4 h; Weighing 0.1g Ce (NO
3)
36H
2O joins in this slurry; Afterwards warming-in-water to 80 ℃ is made ammonia volatilization, stopped heating when the pH value is lower than 7; Subsequently this slurry is packed in the stainless steel crystallizing kettle and 120 ℃ of lower crystallization 24 hours; Taking-up cooling after crystallization is finished, filtration, washing are to neutral; Then at 120 ℃ of lower dry 6 h; Becoming the copper charge capacity at 500 ℃ of lower roasting 6 H-shapeds at last is 30%, CeO
2Charge capacity is 0.2% catalyzer, is labeled as 30Cu-0.2Ce-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet for preparing is sieved into the 40-60 order, and the 0.8g that then weighs puts into the fixed bed isothermal reactor, uses 20%H
2/ N
2Reduce in the atmosphere, gas gross is controlled at 200ml/min, 400 ℃ of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust about temperature to 200 ℃, pressure is 3MPa, and a mole hydrogen ester ratio is 50, and methyl acetate (MAC) liquid mass air speed is 2 h
-1, adopt the charging of liquid phase high-pressure pump.Product is after condensation and gas-liquid separation, and gas phase enters reactor reaction through the supercharger circulation.The gas chromatographic analysis product composition of being separated by and getting the liquid sample in 1 hour and adopting fid detector, and calculate MAC transformation efficiency and ethanol selectivity.Reaction result sees Table 1.
Embodiment 6
The catalyzer preparation
Weighing 11 g CTAB place the beaker of 270 g water and fully dissolving, add the Na of 61.6g
2SiO
3.9H
2O; Then add the NaOH of 2.2g, make the pH value between 11-11.5; Improve behind the bath temperature to 80 ℃ and stir the mother liquor that 2 H-shapeds become the MCM-41 molecular sieve; Weighing 15.2g Cu (NO
3)
23H
2The ammoniacal liquor of O and 51.7ml25% joins in the 150ml water and is made into copper ammon solution; Under the room temperature copper ammon solution is poured in the mother liquor of MCM-41 molecular sieve and stirred 4 h; Weighing 5g Ce (NO
3)
36H
2O joins in this slurry; Afterwards warming-in-water to 80 ℃ is made ammonia volatilization, stopped heating when the pH value is lower than 7; Subsequently this slurry is packed in the stainless steel crystallizing kettle and 120 ℃ of lower crystallization 24 hours; Taking-up cooling after crystallization is finished, filtration, washing are to neutral; Then at 120 ℃ of lower dry 6 h; Becoming the copper charge capacity at 500 ℃ of lower roasting 6 H-shapeds at last is 20%, CeO
2Charge capacity is 10% catalyzer, is labeled as 20Cu-10Ce-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet for preparing is sieved into the 40-60 order, and the 0.8g that then weighs puts into the fixed bed isothermal reactor, uses 20%H
2/ N
2Reduce in the atmosphere, gas gross is controlled at 200ml/min, 400 ℃ of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust about temperature to 210 ℃, pressure is 3MPa, and a mole hydrogen ester ratio is 50, and methyl acetate liquid mass air speed is 1.3h
-1, adopt the charging of liquid phase high-pressure pump.The gas chromatographic analysis product composition of being separated by and getting the liquid sample in 1 hour and adopting fid detector, and calculate MAC transformation efficiency and ethanol selectivity.Reaction result sees Table 1.
Embodiment 7
The catalyzer preparation
Weighing 5.5kg CTAB places the reactor of 130L water and fully dissolving, adds the TEOS of 25.7kg; Then add the NaOH of 1.1kg, make the pH value between 11-11.5; Improve in the still behind the liquidus temperature to 80 ℃ and stir the mother liquor that 4 H-shapeds become the MCM-41 molecular sieve; Weighing 7.6kg Cu (NO
3)
23H
2The ammoniacal liquor of O and 26L25% joins in the 135L water and is made into copper ammon solution; Copper ammon solution is squeezed in the mother liquor of MCM-41 molecular sieve with impeller pump under the room temperature and stirred 4h; Weighing 266g La(NO
3)
36H
2O joins in this reactor; Afterwards temperature in the kettle is risen to 80 ℃ and make ammonia volatilization, stopped heating when the pH value is lower than 7; In confined conditions temperature is increased to subsequently 120 ℃ of lower crystallization 24 hours; Cooling, filtration after crystallization is finished, wash to water and be neutral; Then in baking oven, descend dry 6 h in 120 ℃; Becoming the copper charge capacity at 500 ℃ of lower roasting 6 H-shapeds at last is 20%, La
2O
3Charge capacity is 1% catalyzer.
Evaluating catalyst
The catalyzer for preparing is beaten the cylindrical particle that sheet is shaped to Φ 3*3mm, and the 47g that then weighs puts into the fixed bed mould examination reactor that internal diameter is 27mm, uses 20%H
2/ N
2Reduce in the atmosphere, gas gross is controlled at 10L/min, 400 ℃ of reduction temperatures, 10 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust about bed core temperature to 220 ℃, pressure is 3MPa, and a mole hydrogen ester ratio is 50, and ethyl acetate (EAC) liquid mass air speed is 1.2 h
-1, adopt the charging of liquid phase high-pressure pump.Product is after condensation and gas-liquid separation, and gas phase enters reactor reaction through the supercharger circulation.Fresh hydrogen is replenished automatically according to pressure change.The gas chromatographic analysis product composition of being separated by and getting the liquid sample in 1 hour and adopting fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result sees Table 1.The reaction stability data are seen Fig. 1.
Embodiment 8:
Except reaction pressure adopted 2MPa, other were with outside the embodiment 8, and reaction result sees Table 1.
Embodiment 9:
Except reaction pressure adopted 1MPa, other were with outside the embodiment 8, and reaction result sees Table 1.
Embodiment 10:
Except temperature of reaction adopted 205 ℃, other were with outside the embodiment 8, and reaction result sees Table 1.
Embodiment 11:
Except temperature of reaction adopted 185 ℃, other were with outside the embodiment 8, and reaction result sees Table 1.
Embodiment 12:
Except temperature of reaction adopted 235 ℃, other were with outside the embodiment 8, and reaction result sees Table 1.
Embodiment 13:
Except reaction mole hydrogen ester ratio adopts 20, other are with outside the embodiment 8, and reaction result sees Table 1.
Embodiment 14:
Except reaction mole hydrogen ester ratio adopts 10, other are with outside the embodiment 8, and reaction result sees Table 1.
Embodiment 15:
Be 215 ℃ except adopting methyl acetate to replace ethyl acetate and temperature, other are with outside the embodiment 8, and reaction result sees Table 1.
Table 1 acetic acid second (first) ester through hydrogenation ethanol synthesis result processed
| Embodiment | Raw material | Temperature, ℃ | Pressure, MPa | Mole hydrogen ester ratio | Air speed, h -1 | Transformation efficiency | Selectivity | Space-time yield, g/L.h |
| Embodiment 1 | Ethyl acetate | 215 | 2.5 | 50 | 1.5 | 98.8% | 99.8% | -- |
| Embodiment 2 | Ethyl acetate | 215 | 2.5 | 50 | 1.2 | 95.5% | 99.5% | -- |
| Embodiment 3 | Ethyl acetate | 220 | 3 | 30 | 2 | 98.5% | 99.6% | -- |
| Embodiment 4 | Ethyl acetate | 220 | 3 | 30 | 2 | 97.2% | 99.2% | -- |
| Embodiment 5 | |
200 | 3 | 50 | 2 | 88.6% | 99.5% | -- |
| Embodiment 6 | Methyl acetate | 210 | 3 | 50 | 1.3 | 98.7% | 99.4% | -- |
| Embodiment 7 | Ethyl acetate | 220 | 3 | 50 | 1.2 | 98.6% | 99.6% | 628.34 |
| Embodiment 8 | Ethyl acetate | 220 | 2 | 50 | 1.2 | 97.5% | 99.8% | 622.58 |
| Embodiment 9 | Ethyl acetate | 220 | 1 | 50 | 1.2 | 75.7% | 99.8% | 483.37 |
| |
Ethyl acetate | 205 | 3 | 50 | 1.2 | 96.5% | 100.0% | 617.42 |
| Embodiment 11 | Ethyl acetate | 185 | 3 | 50 | 1.2 | 61.8% | 100.0% | 395.41 |
| Embodiment 12 | Ethyl acetate | 235 | 3 | 50 | 1.2 | 98.8% | 99.8% | 630.88 |
| Embodiment 13 | Ethyl acetate | 220 | 3 | 20 | 1.2 | 96.5% | 99.9% | 616.81 |
| Embodiment 14 | Ethyl acetate | 220 | 3 | 10 | 1.2 | 87.1% | 99.8% | 556.17 |
| Embodiment 15 | Methyl acetate | 215 | 3 | 50 | 1.2 | 98.4% | 99.5% | 372.47 |
Claims (10)
1. the method for an acetic ester preparation of ethanol by hydrogenating is characterized in that the step that it comprises:
1) will prepare load on copper-based catalysts moulding on the MCM-41 molecular sieve after put into fixed-bed reactor, be 5-10%H in volume ratio
2/ N
2Reduce in the atmosphere, reduction temperature 350-500 ℃, recovery time 2-24 hour;
2) after reduction finishes, with pure hydrogen displacement whole system, adjust temperature of reaction to 160-260 ℃, pressure is 1.0-4.0MPa, and the acetic ester mass space velocity is 0.5-3 h
-1, the material that contains acetic ester passes through and enters reactor and hydrogen reaction generation ethanol after vaporizing chamber is vaporized;
3) product separates through the laggard promoting the circulation of qi liquid of condensation, and liquid-phase product is collected products pot, gas phase through the supercharger supercharging after circulation enter reactor and react, the mole hydrogen ester is than being 20-200.
2. in accordance with the method for claim 1, it is characterized in that described acetic ester is one or both in ritalin and the vinyl acetic monomer.
3. in accordance with the method for claim 1, it is characterized in that the described acetic ester material that contains also includes one or both solvents in ethanol and the methyl alcohol.
4. in accordance with the method for claim 1, it is characterized in that described circulation gas phase composite comprises hydrogen, acetate in minute ester and ethanol, volume ratio is: 100:0.01-0.2:0.01-0.2.
5. in accordance with the method for claim 1, it is characterized in that described circulation gas phase composite comprises hydrogen, acetate in minute ester, ethanol and methyl alcohol, volume ratio is: 100:0.01-0.2:0.01-0.2:0.01-0.4.
6. in accordance with the method for claim 1, it is characterized in that step 2) described temperature of reaction is 180-240 ℃.
7. in accordance with the method for claim 1, it is characterized in that step 2) described reaction pressure is 2-4MPa.
8. in accordance with the method for claim 1, it is characterized in that the mole hydrogen ester of the described reaction of step 3) is than being 20-100.
9. method that is used for the acetic ester preparation of ethanol by hydrogenating is characterized in that the step that it comprises:
1) will prepare load on copper-based catalysts moulding on the MCM-41 molecular sieve after put into fixed-bed reactor, be 5-10%H in volume ratio
2/ N
2Reduce in the atmosphere, reduction temperature 350-500 ℃, recovery time 2-24 hour;
2) after reduction finishes, with pure hydrogen displacement whole system, adjust temperature of reaction to 220 ℃, pressure is 3MPa, and the acetic ester mass space velocity is 1.2h
-1, the material that contains acetic ester passes through and enters reactor and hydrogen reaction generation ethanol after vaporizing chamber is vaporized;
3) product separates through the laggard promoting the circulation of qi liquid of condensation, and liquid-phase product is collected products pot, gas phase through the supercharger supercharging after circulation enter reactor and react, a mole hydrogen ester ratio is 50.
10. according to claim 1 or 9 described methods, it is characterized in that described copper-based catalysts is take mesoporous silicon oxide molecular sieve MCM-41 as carrier, take copper as active ingredient, the oxide compound of at least a element in La, the Ce is as auxiliary agent; Each component accounts for catalyst weight per-cent: silicon oxide=50-90wt%, active ingredient copper=10-50wt%, auxiliary agent=0.1-20wt%; The preparation method:
1) by measuring tetraethoxy or water glass and cetyl trimethylammonium bromide aqueous solution, with NaOH adjust pH=11-11.5, at 80 ℃, stirring reaction 0.5-2h forms MCM-41 mesopore molecular sieve mother liquor;
2) under the room temperature, add successively at least a soluble salt aqueous solution among copper ammon solution and La, the Ce; And stirring reaction 4h;
3) heat 80 ℃ and make ammonia volatilization, stopped heating when the pH value is lower than 7;
4) 120 ℃ of lower crystallization 24 hours; Taking-up cooling after crystallization is finished, filtration, washing are to neutral; Then at 120 ℃ of lower dry 6 h; At last at 500 ℃ of lower roasting 6 h.
?
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103265402A (en) * | 2013-05-21 | 2013-08-28 | 江苏金聚合金材料有限公司 | Method for reducing energy consumption in technological process of preparing ethyl alcohol through acetic ester hydrogenation |
| CN105399605A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Method for preparing ethanol through acetate hydrogenation |
| CN106431809A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Synthesis method of ethylbenzene |
| CN109225190A (en) * | 2018-09-04 | 2019-01-18 | 华东师范大学 | A kind of self-supporting hydrogenation catalyst and its preparation method and application |
| CN116041145A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for producing ethanol |
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| WO2009077720A1 (en) * | 2007-12-17 | 2009-06-25 | Bp P.L.C. | Process for the production of alcohol from a carbonaceous feedstock |
| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof |
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| WO2009077720A1 (en) * | 2007-12-17 | 2009-06-25 | Bp P.L.C. | Process for the production of alcohol from a carbonaceous feedstock |
| CN101856615A (en) * | 2010-06-04 | 2010-10-13 | 天津大学 | Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265402A (en) * | 2013-05-21 | 2013-08-28 | 江苏金聚合金材料有限公司 | Method for reducing energy consumption in technological process of preparing ethyl alcohol through acetic ester hydrogenation |
| CN105399605A (en) * | 2014-09-16 | 2016-03-16 | 中国石油化工股份有限公司 | Method for preparing ethanol through acetate hydrogenation |
| CN105399605B (en) * | 2014-09-16 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method of acetate preparation of ethanol by hydrogenating |
| CN106431809A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Synthesis method of ethylbenzene |
| CN106431809B (en) * | 2015-08-12 | 2019-01-25 | 中国石油化工股份有限公司 | The synthetic method of ethylbenzene |
| CN109225190A (en) * | 2018-09-04 | 2019-01-18 | 华东师范大学 | A kind of self-supporting hydrogenation catalyst and its preparation method and application |
| CN109225190B (en) * | 2018-09-04 | 2021-06-15 | 华东师范大学 | Self-supporting hydrogenation catalyst and preparation method and application thereof |
| CN116041145A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for producing ethanol |
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