CN102976892B - Method for preparing ethanol through acetic ester hydrogenation - Google Patents
Method for preparing ethanol through acetic ester hydrogenation Download PDFInfo
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- CN102976892B CN102976892B CN201210475715.3A CN201210475715A CN102976892B CN 102976892 B CN102976892 B CN 102976892B CN 201210475715 A CN201210475715 A CN 201210475715A CN 102976892 B CN102976892 B CN 102976892B
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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 and in gasoline, obtain ethanol petrol, in reducing petrol consumption, can also make gasoline combustion more abundant, thereby reduce the discharge 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.An other route refers to that adopting various sugary agricultural-food, agroforestry by product and wild plant is raw material, through the biological fermentation process that is hydrolyzed, ferments and make disaccharide, polysaccharide be converted into monose and be further converted to ethanol.
Due to the restriction of China's national situation, use on a large scale sugarcane or Maize Production alcohol fuel to be limited to, and adopt the alcohol production technology that Mierocrystalline cellulose is raw material not yet ripe.The national conditions of relatively enriching based on coal in China, have been 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 catalyzer, under 3-10MPa and 300 DEG C of conditions, reaction generates carbon two products that acetaldehyde, ethanol, ethyl acetate and acetic acid are master, 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
3on catalyzer such as [CN1230458A], be ethanol by further hydrocrackings of by product such as acetaldehyde, ethyl acetate and acetic acid.Due to the shortcoming such as this technical matters condition harshness, poor catalyst stability, selectivity be low, not yet obtain up to now large-scale application.
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 DEG C of condition, mixed solution is joined in the solution of precipitation agent, then aging, filter, washing, dry, roasting, moulding and reduction obtain catalyzer.The peak rate of conversion of institute's controlling catalyst in acetic ester hydrogenation reaction is 85%, and 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 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 in cupric ammine complex, to add specific surface area be 600-1200m
2in the mesoporous silica molecular sieve powder of/g, then after filtration, washing, dry, roasting, reduction, make catalyzer.
Chinese patent CN1935375A discloses a kind of for dimethyl maleate Hydrogenation 1, the catalyzer of 4-butyleneglycol, this catalyzer is with 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 Cu/MCM-41 catalyzer.In dimethyl maleate hydrogenation reaction, this catalyzer has higher active and higher BDO selectivity.
In view of gathering and the sintering of copper crystal grain easily occur Cu-series catalyst hot conditions, 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 for the reaction of acetic ester preparation of ethanol by hydrogenating, can obtain higher alcohol production ability and ethanol selectivity, have the longer life-span simultaneously, significantly reduce the production cost of ethanol.
Before reduction, 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, the dispersity of copper is increased substantially, also strengthened thermostability simultaneously, adopt the electronics modifying function of rare-earth additive La and Ce to regulate and control the valence state of copper simultaneously, make this catalyzer not only there is comparatively ideal valence distribution, also there is 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 acetic ester hydrogenation reaction, has also significantly reduced 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 mesopore molecular sieve mother liquor, add active ingredient and auxiliary agent, then after common aging reaction for some time, intensification ammonia still process, then pour in crystallizing kettle and carry out crystallization certain hour, after then filtering, wash and being dried and roasting form catalyzer of the present invention.Adopt the method to contribute 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:
For a method for 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, carry out acetic ester hydrogenation reaction and generate ethanol;
Described copper-based catalysts is taking mesoporous silicon oxide molecular sieve MCM-41 as carrier, taking copper as active ingredient, taking the oxide compound of at least one element in La, Ce 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 acetic ester preparation of ethanol by hydrogenating provided by the invention comprises the steps: under agitation condition, in the aqueous solution of CTAB, slowly drip soluble silicon source toward having dissolved, constantly add alkaline solution remains between 11 ~ 11.5 pH value simultaneously, 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, rising temperature is carried out ammonia still process, when liquid phase PH valve is lower than 7 time, stops heating, cooling; Pack the feed liquid after cooling in stainless steel crystallizing kettle crystallization, cooling, sedimentation and filtration, washing is extremely neutral; Finally catalyzer of the present invention will be formed after filtration cakes torrefaction, 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, slowly drip soluble silicon source toward having dissolved in the aqueous solution of CTAB, constantly add NaOH simultaneously pH value is remained between 11-11.5, after being added dropwise to complete, stir 0.5-2h formation MCM-41 mesopore molecular sieve mother liquor;
2) select a kind of soluble precursor of copper to be dissolved in ammoniacal liquor;
3) select one or both soluble precursor of auxiliary agent to be mixed with the aqueous solution;
4) by step 2) in solution and the solution in step 3) pour in the mother liquor of step 1), under room temperature, stir 4-24 h;
5) slurry of the generation in step 4) is increased the temperature to 50-100 DEG C carry out ammonia still process, when liquid phase PH valve is lower than 7 time, stop heating;
6) pack stainless steel crystallizing kettle into, then crystallization 24-72 h at 80-140 DEG C;
7) by after cooling the stainless steel crystallizing kettle in step 6), sedimentation and filtration, washing is extremely neutral;
8) filter cake in step 7) is dry under 50-120 DEG C of condition;
9) by after dried filter cake pulverizes in step 8), at 350-600 DEG C, after roasting, form catalyzer of the present invention.
Wherein, soluble silicon source is a kind of in tetraethoxy, water glass or two kinds.
Described auxiliary agent is the soluble salt of La, Ce, for example: nitrate, muriate or acetate.
The step that provides a kind of method of acetic ester preparation of ethanol by hydrogenating to comprise provided by the invention:
1) by prepare load on the copper-based catalysts moulding on MCM-41 molecular sieve after put into fixed-bed reactor, be 5-10%H in volume ratio
2/ N
2in atmosphere, reduce, reduction temperature 350-500 DEG C, recovery time 2-24 hour;
2) after reduction finishes, with pure hydrogen displacement whole system, adjust temperature of reaction to 160-260 DEG C, pressure is 1.0-4.0MPa, and acetic ester mass space velocity is 0.5-3 h
-1, the material that contains acetic ester enters reactor after vaporizing chamber vaporization and hydrogen reaction generates ethanol;
3) product is through the laggard row gas-liquid separation of condensation, and liquid-phase product is collected products pot, and gas phase circulates and enters reactor and react after supercharger supercharging, and mole hydrogen ester is than being 20-200; Fresh hydrogen is supplemented automatically according to pressure change.
Described acetic ester comprises one or both in ritalin and vinyl acetic monomer.
Described contain acetic ester material and can also include one or both solvents in ethanol and 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 DEG C.
Step 2) described reaction pressure is 2-4MPa.
Mole hydrogen ester of the reaction described in step 3) is than being 20-100.
The present invention adopts ammonia still process-crystallization method that copper is loaded on mesoporous silicon oxide molecular sieve, adopts valence distribution to copper in catalyzer of La, Ce and specific surface area and pore size distribution to regulate and control simultaneously, thereby has significantly improved the anti-caking power of catalyzer.
Preformed catalyst of the present invention, for the reaction of acetic ester preparation of ethanol by hydrogenating, is 220 DEG C in temperature of reaction, and reaction pressure is 3MPa, and a mole hydrogen ester ratio is 50, and acetic ester mass space velocity is 1.2h
-1time, vinyl acetic monomer transformation efficiency is 98.6%, and ethanol selectivity is up to 99.6%, and 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 mesopore molecular sieve MCM-41 forming process, the method that adopts ammonia still process-crystallization method to combine is prepared 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.Gained catalyzer has higher thermostability and hydrogenation activity and stability in acetic ester hydrogenation reaction.Adopt this catalyzer to carry out the reaction of acetic ester preparation of ethanol by hydrogenating, under optimal conditions, ethyl acetate transformation efficiency reaches in 98.6% situation, and ethanol selectivity reaches 99.6%, has also significantly reduced 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.
Brief description of the 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
Below by specific embodiment, the invention will be further described, but they do not impose any restrictions the present invention.And particularly point out, the reagent using in embodiment and equipment, except clearly stating source, are commercially available.
Embodiment 1:
Catalyzer preparation
Weigh 11 g CTAB(cetyl trimethylammonium bromides) be placed in the beaker of 270 g water and fully dissolve, add the TEOS(tetraethoxy of 51.4 g); Then add the NaOH of 2.2g, make pH value between 11-11.5; After improving bath temperature to 80 DEG C and stir 2 H-shapeds and become the mother liquor of MCM-41 molecular sieve; Weigh 15.2g Cu (NO
3)
23H
2the ammoniacal liquor of O and 51.7ml25%, joins in 150ml water and is made into copper ammon solution; Under room temperature, copper ammon solution poured in the mother liquor of MCM-41 molecular sieve and stirred 4h; Weigh 0.53g La(NO
3)
36H
2o joins in this slurry; Afterwards warming-in-water to 80 DEG C is made to ammonia volatilization, when pH value stops heating lower than 7 time; Subsequently this slurry is packed in stainless steel crystallizing kettle, and at 120 DEG C crystallization 24 hours; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6 h at 120 DEG C; Finally at 500 DEG C roasting 6 H-shapeds to become copper charge capacity be 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, Micromeritics company of the U.S.) to characterize this catalyzer adsorption desorption performance and pore size distribution, result is shown in respectively Fig. 2,3 and 4.
Evaluating catalyst
The catalyzer compressing tablet preparing is sieved into 40-60 order, and the 0.8g that then weighs puts into fixed bed isothermal reactor, uses 20%H
2/ N
2in atmosphere, reduce, gas gross is controlled at 200ml/min, 400 DEG C of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust temperature to 215 DEG C left and right, 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.Be separated by and within 1 hour, sample and adopt the gas chromatographic analysis product composition of fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 2
Catalyzer preparation
Weigh 11 g CTAB and be placed in the beaker of 270 g water and fully dissolve, add the TEOS of 59.4g; Then add the NaOH of 2.2g, make pH value between 11-11.5; After improving bath temperature to 80 DEG C and stir 2 H-shapeds and become the mother liquor of MCM-41 molecular sieve; Weigh 7.6g Cu (NO
3)
23H
2the ammoniacal liquor of O and 25.8ml 25%, joins in 150ml water and is made into copper ammon solution; Under room temperature, copper ammon solution poured in the mother liquor of MCM-41 molecular sieve and stirred 4h; Weigh 1.06g La(NO
3)
36H
2o joins in this slurry; Afterwards warming-in-water to 80 DEG C is made to ammonia volatilization, when pH value stops heating lower than 7 time; Subsequently this slurry is packed in stainless steel crystallizing kettle and at 120 DEG C into crystallization 24 hours; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6 h at 120 DEG C, finally at 500 DEG C roasting 6 H-shapeds to become copper charge capacity be 10%, La
2o
3charge capacity is 2% catalyzer, is labeled as 10Cu-2La-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet preparing is sieved into 40-60 order, and the 0.8g that then weighs puts into fixed bed isothermal reactor, uses 20%H
2/ N
2in atmosphere, reduce, gas gross is controlled at 200ml/min, 400 DEG C of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust temperature to 215 DEG C left and right, 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.Be separated by and within 1 hour, sample and adopt the gas chromatographic analysis product composition of fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 3
Catalyzer preparation
Weigh 11 g CTAB and be placed in the beaker of 270 g water and fully dissolve, add the TEOS of 40g; Then add the NaOH of 2.2g, make pH value between 11-11.5; After improving bath temperature to 80 DEG C and stir 2 H-shapeds and become the mother liquor of MCM-41 molecular sieve; Weigh 22.8g Cu (NO
3)
23H
2the ammoniacal liquor of O and 77.5ml25%, joins in 150ml water and is made into copper ammon solution; Under room temperature, copper ammon solution poured in the mother liquor of MCM-41 molecular sieve and stirred 4 h; Weigh 2.7g La(NO
3)
36H
2o joins in this slurry; Afterwards warming-in-water to 80 DEG C is made to ammonia volatilization, when pH value stops heating lower than 7 time; Subsequently this slurry is packed in stainless steel crystallizing kettle and at 120 DEG C into crystallization 24 hours; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6 h at 120 DEG C; Finally at 500 DEG C roasting 6 H-shapeds to become copper charge capacity be 30%, La
2o
3charge capacity is 5% catalyzer, is labeled as 30Cu-5La-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet preparing is sieved into 40-60 order, and the 0.8g that then weighs puts into fixed bed isothermal reactor, uses 20%H
2/ N
2in atmosphere, reduce, gas gross is controlled at 200ml/min, 400 DEG C of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust temperature to 220 DEG C left and right, 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.Be separated by and within 1 hour, sample and adopt the gas chromatographic analysis product composition of fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 4
Catalyzer preparation
Weigh 11 g CTAB and be placed in the beaker of 270 g water and fully dissolve, add the TEOS of 34.4g; Then add the NaOH of 2.2g, make pH value between 11-11.5; After improving bath temperature to 80 DEG C and stir 2 H-shapeds and become the mother liquor of MCM-41 molecular sieve; Weigh 30.4g Cu (NO
3)
23H
2the ammoniacal liquor of O and 103.4ml25%, joins in 150ml water and is made into copper ammon solution; Under room temperature, copper ammon solution poured in the mother liquor of MCM-41 molecular sieve and stirred 4h; Weigh 0.27g La(NO
3)
36H
2o joins in this slurry; Afterwards warming-in-water to 90 DEG C is made to ammonia volatilization, when pH value stops heating lower than 7 time; Subsequently this slurry is packed in stainless steel crystallizing kettle and at 120 DEG C into crystallization 24 hours; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6 h at 120 DEG C; Finally at 500 DEG C roasting 6 H-shapeds to become copper charge capacity be 40%, La
2o
3charge capacity is 0.5% catalyzer, is labeled as 40Cu-0.5La-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet preparing is sieved into 40-60 order, and the 0.8g that then weighs puts into fixed bed isothermal reactor, uses 20%H
2/ N
2in atmosphere, reduce, gas gross is controlled at 200ml/min, 400 DEG C of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust temperature to 220 DEG C left and right, 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.Be separated by and within 1 hour, sample and adopt the gas chromatographic analysis product composition of fid detector, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 5
Catalyzer preparation
Weigh 11 g CTAB and be placed in the beaker of 270 g water and fully dissolve, add the TEOS of 43.3g; Then add the NaOH of 2.2g, make pH value between 11-11.5; After improving bath temperature to 80 DEG C and stir 2 H-shapeds and become the mother liquor of MCM-41 molecular sieve; Weigh 22.8g Cu (NO
3)
23H
2the ammoniacal liquor of O and 77.5ml25%, joins in 150ml water and is made into copper ammon solution; Under room temperature, copper ammon solution poured in the mother liquor of MCM-41 molecular sieve and stirred 4 h; Weigh 0.1g Ce (NO
3)
36H
2o joins in this slurry; Afterwards warming-in-water to 80 DEG C is made to ammonia volatilization, when pH value stops heating lower than 7 time; Subsequently this slurry is packed in stainless steel crystallizing kettle and at 120 DEG C into crystallization 24 hours; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6 h at 120 DEG C; Finally at 500 DEG C roasting 6 H-shapeds to become copper charge capacity be 30%, CeO
2charge capacity is 0.2% catalyzer, is labeled as 30Cu-0.2Ce-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet preparing is sieved into 40-60 order, and the 0.8g that then weighs puts into fixed bed isothermal reactor, uses 20%H
2/ N
2in atmosphere, reduce, gas gross is controlled at 200ml/min, 400 DEG C of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust temperature to 200 DEG C left and right, 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 gas-liquid separation, and gas phase enters reactor reaction through supercharger circulation.The gas chromatographic analysis product composition of getting liquid sample for 1 hour and adopting fid detector of being separated by, and calculate MAC transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 6
Catalyzer preparation
Weigh 11 g CTAB and be placed in the beaker of 270 g water and fully dissolve, add the Na of 61.6g
2siO
3.9H
2o; Then add the NaOH of 2.2g, make pH value between 11-11.5; After improving bath temperature to 80 DEG C and stir 2 H-shapeds and become the mother liquor of MCM-41 molecular sieve; Weigh 15.2g Cu (NO
3)
23H
2the ammoniacal liquor of O and 51.7ml25%, joins in 150ml water and is made into copper ammon solution; Under room temperature, copper ammon solution poured in the mother liquor of MCM-41 molecular sieve and stirred 4 h; Weigh 5g Ce (NO
3)
36H
2o joins in this slurry; Afterwards warming-in-water to 80 DEG C is made to ammonia volatilization, when pH value stops heating lower than 7 time; Subsequently this slurry is packed in stainless steel crystallizing kettle and at 120 DEG C into crystallization 24 hours; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6 h at 120 DEG C; Finally at 500 DEG C roasting 6 H-shapeds to become copper charge capacity be 20%, CeO
2charge capacity is 10% catalyzer, is labeled as 20Cu-10Ce-MCM-41.
Evaluating catalyst
The catalyzer compressing tablet preparing is sieved into 40-60 order, and the 0.8g that then weighs puts into fixed bed isothermal reactor, uses 20%H
2/ N
2in atmosphere, reduce, gas gross is controlled at 200ml/min, 400 DEG C of reduction temperatures, 4 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust temperature to 210 DEG C left and right, 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 getting liquid sample for 1 hour and adopting fid detector of being separated by, and calculate MAC transformation efficiency and ethanol selectivity.Reaction result is in table 1.
Embodiment 7
Catalyzer preparation
Weigh 5.5kg CTAB and be placed in the reactor of 130L water and fully dissolve, add the TEOS of 25.7kg; Then add the NaOH of 1.1kg, make pH value between 11-11.5; After improving liquidus temperature to 80 in still DEG C and stir 4 H-shapeds and become the mother liquor of MCM-41 molecular sieve; Weigh 7.6kg Cu (NO
3)
23H
2the ammoniacal liquor of O and 26L25%, joins in 135L water and is made into copper ammon solution; Under room temperature, with impeller pump, copper ammon solution squeezed in the mother liquor of MCM-41 molecular sieve and stirred 4h; Weigh 266g La(NO
3)
36H
2o joins in this reactor; Afterwards temperature in the kettle is risen to 80 DEG C and make ammonia volatilization, when pH value stops heating lower than 7 time; In confined conditions temperature is increased to subsequently at 120 DEG C to crystallization 24 hours; Cooling after crystallization completes, filter, wash to water and be neutral; Then in baking oven, at 120 DEG C, be dried 6 h; Finally at 500 DEG C roasting 6 H-shapeds to become copper charge capacity be 20%, La
2o
3charge capacity is 1% catalyzer.
Evaluating catalyst
The catalyzer preparing is beaten to sheet and is shaped to the cylindrical particle of Φ 3*3mm, the 47g that then weighs puts into the fixed bed mould examination reactor that internal diameter is 27mm, uses 20%H
2/ N
2in atmosphere, reduce, gas gross is controlled at 10L/min, 400 DEG C of reduction temperatures, 10 hours recovery times.After reduction finishes, with pure hydrogen exchange system, and adjust bed core temperature to 220 DEG C left and right, 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 gas-liquid separation, and gas phase enters reactor reaction through supercharger circulation.Fresh hydrogen is supplemented automatically according to pressure change.The gas chromatographic analysis product composition of getting liquid sample for 1 hour and adopting fid detector of being separated by, and calculate EAC transformation efficiency and ethanol selectivity.Reaction result is in table 1.Reaction stability data are shown in Fig. 1.
Embodiment 8:
Except reaction pressure adopts 2MPa, other are with outside embodiment 8, and reaction result is in table 1.
Embodiment 9:
Except reaction pressure adopts 1MPa, other are with outside embodiment 8, and reaction result is in table 1.
Embodiment 10:
Except temperature of reaction adopts 205 DEG C, other are with outside embodiment 8, and reaction result is in table 1.
Embodiment 11:
Except temperature of reaction adopts 185 DEG C, other are with outside embodiment 8, and reaction result is in table 1.
Embodiment 12:
Except temperature of reaction adopts 235 DEG C, other are with outside embodiment 8, and reaction result is in table 1.
Embodiment 13:
Except reaction mole hydrogen ester is than adopting 20, other are with outside embodiment 8, and reaction result is in table 1.
Embodiment 14:
Except reaction mole hydrogen ester is than adopting 10, other are with outside embodiment 8, and reaction result is in table 1.
Embodiment 15:
Be 215 DEG C except adopting methyl acetate to replace ethyl acetate and temperature, other are with outside embodiment 8, and reaction result is in table 1.
Table 1 acetic acid second (first) ester through hydrogenation ethanol synthesis result processed
| Embodiment | Raw material | Temperature, DEG C | 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 | Methyl acetate | 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 |
| Embodiment 10 | 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 (9)
1. a method for acetic ester preparation of ethanol by hydrogenating, is characterized in that the step that it comprises:
1) by prepare load on the copper-based catalysts moulding on MCM-41 molecular sieve after put into fixed-bed reactor, be 5-10%H in volume ratio
2/ N
2in atmosphere, reduce, reduction temperature 350-500 DEG C, recovery time 2-24 hour;
2) after reduction finishes, with pure hydrogen displacement whole system, adjust temperature of reaction to 160-260 DEG C, pressure is 1.0-4.0MPa, and acetic ester mass space velocity is 0.5-3h
-1, the material that contains acetic ester enters reactor after vaporizing chamber vaporization and hydrogen reaction generates ethanol;
3) product is through the laggard row gas-liquid separation of condensation, and liquid-phase product is collected products pot, and gas phase circulates and enters reactor and react after supercharger supercharging, and mole hydrogen ester is than being 20-200;
Described copper-based catalysts is taking mesoporous silicon oxide molecular sieve MCM-41 as carrier, taking copper as active ingredient, taking the oxide compound of at least one element in La, Ce as auxiliary agent; Each component accounts for catalyst weight per-cent: silicon oxide=50-90wt%, and active ingredient copper=10-50wt%, auxiliary agent=0.1-20wt%, each weight percentages of components sum is 100%;
The preparation method of described copper-based catalysts is:
1), by measuring tetraethoxy or water glass and cetyl trimethylammonium bromide aqueous solution, with NaOH adjust pH=11-11.5, at 80 DEG C, stirring reaction 0.5-2h, forms MCM-41 mesopore molecular sieve mother liquor;
2), under room temperature, add successively at least one the soluble salt aqueous solution in copper ammon solution and La, Ce; And stirring reaction 4h;
3) 80 DEG C of heating make ammonia volatilization, when pH value stops heating lower than 7 time;
4) crystallization 24 hours at 120 DEG C; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6h at 120 DEG C; Finally roasting 6h at 500 DEG C.
2. in accordance with the method for claim 1, it is characterized in that described acetic ester is one or both in ritalin and 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 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 DEG C.
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 step 3) mole hydrogen ester of described reaction is than being 20-100.
9. for a method for acetic ester preparation of ethanol by hydrogenating, it is characterized in that the step that it comprises:
1) by prepare load on the copper-based catalysts moulding on MCM-41 molecular sieve after put into fixed-bed reactor, be 5-10%H in volume ratio
2/ N
2in atmosphere, reduce, reduction temperature 350-500 DEG C, recovery time 2-24 hour;
2) after reduction finishes, with pure hydrogen displacement whole system, adjust temperature of reaction to 220 DEG C, pressure is 3MPa, and acetic ester mass space velocity is 1.2h
-1, the material that contains acetic ester enters reactor after vaporizing chamber vaporization and hydrogen reaction generates ethanol;
3) product is through the laggard row gas-liquid separation of condensation, and liquid-phase product is collected products pot, and gas phase circulates and enters reactor and react after supercharger supercharging, and a mole hydrogen ester ratio is 50;
Described copper-based catalysts is taking mesoporous silicon oxide molecular sieve MCM-41 as carrier, taking copper as active ingredient, taking the oxide compound of at least one element in La, Ce as auxiliary agent; Each component accounts for catalyst weight per-cent: silicon oxide=50-90wt%, and active ingredient copper=10-50wt%, auxiliary agent=0.1-20wt%, it is 100% that each component accounts for catalyst weight per-cent sum;
The preparation method of described copper-based catalysts is:
1), by measuring tetraethoxy or water glass and cetyl trimethylammonium bromide aqueous solution, with NaOH adjust pH=11-11.5, at 80 DEG C, stirring reaction 0.5-2h, forms MCM-41 mesopore molecular sieve mother liquor;
2), under room temperature, add successively at least one the soluble salt aqueous solution in copper ammon solution and La, Ce; And stirring reaction 4h;
3) 80 DEG C of heating make ammonia volatilization, when pH value stops heating lower than 7 time;
4) crystallization 24 hours at 120 DEG C; After crystallization completes taking-up cooling, filter, washing is to neutral; Then dry 6h at 120 DEG C; Finally roasting 6h at 500 DEG C.
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