A kind of methyl acetate hydrogenation catalyst and preparation method thereofTechnical field
The present invention relates to a kind of hydrogenation catalyst and preparation method thereof, being specifically related to a kind of is raw material with the methyl acetate, and hydrogenation is produced new catalyst of ethanol and preparation method thereof.
Background technology
Ethanol (being commonly called as alcohol) is most widely used a kind of alcohol, and industrial is a kind of important organic synthesis raw material, as with ethanol ether processed, acetaldehyde, acetic acid etc.Ethanol has dissolubility widely, is important organic solvent, is used for dissolving resin, makes coating etc.75% alcohol can make protein denaturation (solidifying) immediately, pharmaceutically is being commonly used for disinfectant and anticorrisive agent.Ethanol also is widely used as the drink and food additive, and (but must be noted that: can not excess drink, in order to avoid cause alcoholism, the teenager especially should not drink alcoholic drink; Contain toxic methyl alcohol in the industrial alcohol, must not drink).
Ethanol is sufficient combustion in air, can avoid polluting, and combustion heat value is bigger, can add in the gasoline, and as vehicle fuel, the existing 20 years history of ethanol petrol is sold by the U.S., and China is promoting ethanol petrol.And by the ethanol decomposing hydrogen-production, also be following clean energy resource, as an important directions of development such as fuel cell.
Industrial ethanol mainly from petrochemical materials chemical synthesis (ethene aquation method), contain the fermentation of materials producing and ethanol in next life (mainly be wine brewing) of sugar and starch.
Generally adopt the ethene direct hydration method to produce ethanol abroad, China's ethene is in state in short supply always, objectively, has limited this method applying in China.
China's industrial alcohol is mainly derived from fermentation method production, can be divided into the starchy material fermentation alcohol (raw material that starch-containing matter such as potato class, cereal and wild plant are generally arranged by producing the raw material that uses, under microbial action, starch is hydrolyzed to glucose, further generates alcohol by culture propagation again); Ferment of molasses raw material alcohol (directly utilize the sugar in the molasses, divide nutritive salt through dilution sterilization and addition portion, borrow the effect fermentation of yeast to generate alcohol); With sulfite liquor fermenting and producing alcohol (utilize the hexose that contains in the papermaking wastewater, become alcohol at yeast effect bottom fermentation, major product is industrial alcohol).Along with the quick increase of ethanol demand, the raw material supply shortage, part enterprise adopts grain-production, causes grain price to go up, and has had influence on the even running of national food safety, national economy and the harmony of society and has stablized.
Coal ethanol processed is another kind of feasible selection.Be that raw material is produced ethanol three paths are arranged with the coal: 1. produce synthesis gas, directly obtain ethanol by synthesis gas, this technology is just being located the research and development stage at present, and difficulty is that selection of catalysts is too low; 2. first by the synthesis gas synthesizing methanol, methanol carbonyl synthesized acetic acid, the direct hydrogenation of acetic acid is produced ethanol, and this method production technology is very harsh, and large-scale production is difficulty relatively; 3. after the esterification of acetic acid process low-carbon alcohols, repeated hydrogenation obtains ethanol, compares with the direct hydrogenation of acetic acid, it is less that this method has equipment corrosion, the advantage of reduced investment, this raw materials technology is neither also non-grain of oil is the technology path of a practicable large-scale production ethanol in China.
On the other hand, because the methyl acetate of the annual by-product of China's vinylon industry more than 1,000,000 tons, raw material sources cheaply are easy to get, and with all or part of ethanol that is converted into of these methyl acetates, have both reduced the energy consumption of vinylon manufacturing enterprise, promote the development of the sector, simultaneously, this technology is neither use oil, and also non-is raw material with grain, large-scale production goes out ethanol, and economic and social benefit is very remarkable.
Summary of the invention
The object of the present invention is to provide a kind of methyl acetate hydrogenation catalyst and preparation method thereof, prepared catalyst is used for the methyl acetate hydrogenation and produces ethanol, has methyl acetate conversion ratio height, the selective good characteristics of ethanol, but industrial applications.
The present invention adopts following technical scheme:
A kind of methyl acetate hydrogenation catalyst is characterized in that, is active component with nickel and/or copper, and one or more in cobalt, zinc, iron, chromium, the silicon are co-catalyst, and aluminium oxide is carrier; Wherein active component quality percentage composition is 5-50%, and cocatalyst content is 3-40%, and all the other are carrier.
Described catalyst, makes by coprecipitation with active component, co-catalyst as support precursor with boehmite or aluminum soluble salt.
In the described catalyst, active component is nickel and/or copper, and the quality percentage composition is preferably 15-40%.
In the described catalyst, co-catalyst comprises cobalt, zinc, iron, chromium, silicon etc., can adopt wherein that one or two or more kinds element makes up, and the co-catalyst total content is preferably 15-30%(wt%).
The invention still further relates to described Preparation of catalysts method, can adopt the coprecipitation preparation.Adopt coprecipitation to prepare described catalyst, comprise the steps:
1) according to composition, with catalyst activity component nickel and/or copper soluble-salt, the soluble-salt of one or more the above elements in co-catalyst cobalt, zinc, iron, chromium or the silicon, Weighing adds a certain amount of deionized water, stirs to make its whole dissolvings.
2) add the soluble-salt solution of a certain amount of boehmite or aluminium in the solution of step 1) preparation, under agitation, add precipitating reagent, to carrier, obtaining solid content is the 15%-40% slip with active component and co-catalyst co-precipitation.
3) step 2) slip that obtains is overanxious, dry, or spray-drying.
4) with dried catalyst, 300-450 ℃ of roasting 4～8 h in air atmosphere, or program is warmed up to 300-450 ℃ (3-10 ℃/min) and keep 8～12h, obtain catalyst precarsor in air atmosphere.
5) above-mentioned gained catalyst precarsor activates 12-48h at 200-400 ℃ in the pure hydrogen of normal pressure, makes described hydrogenation catalyst.
In the step 1), total concentration of metal ions is 0.5-6.0mol/l in the solution.
Step 2) in, described precipitating reagent is NaOH (potassium), sodium carbonate (potassium) or sodium acid carbonate (potassium), preferred sodium carbonate (potassium).
Preferably spray drying in the described step 3).250-410 ℃ of spray-drying feeding temperature, drop temperature 80-160 ℃.
Described catalyst is mainly used in by the methyl acetate hydrogenation and produces ethanol, can be used for still formula or fixed-bed process for preparing.For example, in fixed bed reactors, its typical reaction process condition: temperature is 150-300 ℃, is preferable with 160-300 ℃, and pressure is 0.1-10.0MPa, be preferable with 2.0 –, 8.0 MPa, atmosphere is pure hydrogen, and the hydrogenating materials methyl acetate has two kinds, and a kind of can be that volume ratio is methyl acetate and the methyl alcohol of 3:1, another kind can be that the methyl acetate percentage composition is 93%(wt%), all the other are the mixed liquor of water, methyl acetate liquid air speed 0.2-5.0h-1, the conversion ratio of methyl acetate is more than 82%, and is selective more than 90%.
Methyl acetate hydrogenation catalyst of the present invention can be used for methyl acetate catalysis hydrogenation preparing ethanol synthesis, and this catalyst has high catalytic activity and selective under lower temperature and pressure.Methyl acetate hydrogenation catalyst of the present invention is used for suitability for industrialized production, can reduce the production cost of coal ethanol processed, realize the large-scale industrial production of non-oil or grain raw material ethanol, and catalyst stability is good, long service life.Adopt catalyst of the present invention, the methyl acetate hydrogenation catalyst prepares ethanol, methyl acetate conversion ratio 〉=82%, selective 〉=90% of ethanol.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with the specific embodiment, but is limited by claim.
The specific embodiment
Embodiment 1
Nickel nitrate 120.40g adds a certain amount of zinc nitrate, and the adding aluminum nitrate is support precursor, adds 1000ml distilled water wiring solution-forming, drips certain density soda ash solution, co-precipitation, and washing and filtering is at 100 ℃ of drying 10 h.400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back the ortho states catalyst.The content of metallic nickel is 10wt% in the catalyst, and cocatalyst content is 20wt%.
Get above-mentioned catalyst 5.0g, (the two volume ratio=1:3) is raw material, and catalytic hydrogenation in fixed bed reactors, reaction condition are 200 ℃, 5.0M Pa, liquid air speed 1.0h with methyl alcohol and methyl acetate-1, hydrogen gas space velocity 1500 h-1, the sampling chromatography, the methyl acetate conversion ratio is 82.6%, ethanol selectively be 91.5%.
Embodiment 2
Copper nitrate 150.40g adds a certain amount of zinc nitrate and chromic nitrate, adds 1000ml distilled water wiring solution-forming, adds a certain amount of boehmite support precursor, drips certain density soda ash solution, co-precipitation, and washing and filtering is at 100 ℃ of drying 10 h.400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back the ortho states catalyst.The content of metallic copper is 20wt% in the catalyst, and cocatalyst content is 25wt%.
Get above-mentioned catalyst 5.0g, (the two volume ratio=1:3) is raw material, and catalytic hydrogenation in fixed bed reactors, reaction condition are 200 ℃, 5.0M Pa, liquid air speed 1.0h with methyl alcohol and methyl acetate-1, hydrogen gas space velocity 1500 h-1, the sampling chromatography, the methyl acetate conversion ratio is 82.4%, ethanol selectively be 95.5%.
Embodiment 3
Copper nitrate 150.40g adds a certain amount of zinc nitrate, cobalt nitrate and aluminum nitrate, adds 1000ml distilled water wiring solution-forming, drips certain density soda ash solution, co-precipitation, and washing and filtering is at 100 ℃ of drying 10 h.400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back the ortho states catalyst.The content of metallic copper is 20wt% in the catalyst, and cocatalyst content is 30wt%.
Get above-mentioned catalyst 5.0g, (the two volume ratio=1:3) is raw material, and catalytic hydrogenation in fixed bed reactors, reaction condition are 200 ℃, 5.0M Pa, liquid air speed 1.0h with methyl alcohol and methyl acetate-1, hydrogen gas space velocity 1000 h-1, the sampling chromatography, the methyl acetate conversion ratio is 85.4%, ethanol selectively be 97.5%.
Embodiment 4
Copper nitrate 150.40g adds certain amount of ferric nitrate and zinc nitrate, adds 1000ml distilled water wiring solution-forming, adds a certain amount of boehmite support precursor, drips certain density soda ash solution, co-precipitation, and washing and filtering is at 100 ℃ of drying 10 h.400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back the ortho states catalyst.The content of metallic copper is 30wt% in the catalyst, and cocatalyst content is 30wt%.
Get above-mentioned catalyst 5.0g, (the two volume ratio=1:3) is raw material, and catalytic hydrogenation in fixed bed reactors, reaction condition are 200 ℃, 5.0M Pa, liquid air speed 1.0h with methyl alcohol and methyl acetate-1, hydrogen gas space velocity 1000 h-1, the sampling chromatography, the methyl acetate conversion ratio is 83.4%, ethanol selectively be 90.5%.
Embodiment 5
Copper nitrate 150.40g adds a certain amount of chromic nitrate, zinc nitrate and aluminum nitrate, adds 1000ml distilled water wiring solution-forming, drips certain density soda ash solution, co-precipitation, and washing and filtering is at 100 ℃ of drying 10 h.400 ℃ of roasting 4 h in air atmosphere obtain catalyst precarsor.Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back the ortho states catalyst.The content of metallic copper is 30wt% in the catalyst, and cocatalyst content is 30wt%.
Get above-mentioned catalyst 5.0g, (the two volume ratio=1:3) is raw material, and catalytic hydrogenation in fixed bed reactors, reaction condition are 200 ℃, 5.0M Pa, liquid air speed 1.0h with methyl alcohol and methyl acetate-1, hydrogen gas space velocity 1000 h-1, the sampling chromatography, the methyl acetate conversion ratio is 83.8%, ethanol selectively be 92.5%.
Embodiment 6
Get the catalyst 5.0g of embodiment 5 preparation, with 93%(wt%) methyl acetate, all the other be that the mixed liquor of water is raw material, catalytic hydrogenation in fixed bed reactors, reaction condition are 190 ℃, 5.0M Pa, the fast 1.0h of liquid air-1, hydrogen gas space velocity 1000 h-1, the sampling chromatography, the methyl acetate conversion ratio is 83.5%, ethanol selectively be 90.4%.
Embodiment 7
Copper nitrate 18000.56 g add a certain amount of zinc nitrate, aluminum nitrate and nickel nitrate, add 100000ml distilled water wiring solution-forming, drip certain density soda ash solution, under agitation, to carrier, obtaining solid content is the 15%-40% slip with active component and co-catalyst co-precipitation.
The slip spray-drying, 250-410 ℃ of spray-drying feeding temperature, drop temperature 80-160 ℃.
Employing far-infrared dryer calcining, with the catalyst after the spray-drying, program is warmed up to 400 ℃ (3-10 ℃/min) and keep 12h, obtain catalyst precarsor in air atmosphere.
Catalyst precarsor carries out reduction activation 4 h in 400 ℃, the pure hydrogen of normal pressure, obtain going back the ortho states catalyst.The content of metallic copper is 30wt% in the catalyst, and cocatalyst content is 30wt%.
Get above-mentioned catalyst 50.0ml, (the two volume ratio=1:3) is raw material, and catalytic hydrogenation in fixed bed reactors, reaction condition are 200 ℃, 5.0M Pa, liquid air speed 1.0h with methyl alcohol and methyl acetate-1, hydrogen gas space velocity 1000 h-1, the sampling chromatography, the methyl acetate conversion ratio is 90.4%, ethanol selectively be 98.5%.
Embodiment 8
Get the catalyst 50.0ml that embodiment 7 makes, with 93%(wt%) methyl acetate, all the other are that the mixed liquor of water is raw material, catalytic hydrogenation in fixed bed reactors, reaction condition are 190 ℃, 5.0M Pa, liquid air speed 1.0h-1, hydrogen gas space velocity 1000 h-1, the sampling chromatography, the methyl acetate conversion ratio is 88.5%, ethanol selectively be 95.6%.