CN105709777B - The method of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol - Google Patents
The method of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol Download PDFInfo
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Abstract
The invention discloses the methods of catalyst of acetic acid hydrogenation ethyl alcohol and preparation method thereof and acetic acid hydrogenation ethyl alcohol.The catalyst of the acetic acid hydrogenation ethyl alcohol includes active component, auxiliary agent and carrier, the active component is Ni and W, on the basis of the total weight of the catalyst, the catalyst contains the auxiliary agent of W, 0.01-2 weight % of Ni, 1-20 weight % of 0.1-10 weight % and the carrier of 68-98.89 weight %.The reaction that acetic acid hydrogenation ethyl alcohol is carried out using the catalyst, can significantly improve the conversion ratio of acetic acid and the selectivity of ethyl alcohol and yield and the preparation cost for reducing catalyst.
Description
Technical field
The present invention relates to a kind of catalyst of acetic acid hydrogenation ethyl alcohol, a kind of catalyst preparing acetic acid hydrogenation ethyl alcohol
The agent of acetic acid hydrogenation alcohol catalysis and a kind of method of acetic acid hydrogenation ethyl alcohol that method and this method are prepared.
Background technique
Ethyl alcohol is basic industries raw material and important organic solvent, is mainly used for food, chemical industry, military project, medicine and other fields, has
The extensive market demand.Ethyl alcohol or a kind of free of contamination high-knock rating gasoline additive.In recent years, oil price is persistently climbed
It rises, environmental pressure is increasingly heavy, and new fungible energy source, ethyl alcohol all in the development in pluralism for seeking the energy, are developed in countries in the world
As emerging one of renewable green energy resource, can be proportionally added into gasoline as vehicle alternative fuel, in world wide
Popularization and approval are inside obtained, the U.S. sells ethanol petrol and has more than 20 years history, and Brazilian 40% light-duty vehicle is fired using ethyl alcohol
Material.
China is also constantly increasing the demand of vehicle fuel ethyl alcohol, it is contemplated that China's gasoline consumption figure is up within 2015
100000000 tons or so, if all calculated by 10% alcohol fuel of blending, the demand to alcohol fuel is up to using ethanol petrol
10000000 tons, and the production capacity of internal fuel ethyl alcohol only has 1,660,000 tons (statistical data in 2011) at present, therefore, develops fuel second
Alcohol has great market demand.
The production technology of industrial ethyl alcohol mainly uses starch saccharic fermentation method and ethylene direct hydration method at present.Wherein,
Grain or cassava prepare ethyl alcohol route and always exist " striving grain with people ", and the contradiction of " striving ground with grain " is related to comparing the energy in the long term
The even more serious Food Security of safety；Traditional exemplary fermentation method technique, the carbohydrate in cereal are hydrolyzed to first
Then carbohydrate ferments to obtain ethyl alcohol by yeast.It should about 52% carbon source be sent out in the process for yeast itself metabolic consumption, starch
Ferment method yield only has 55~60%, and energy consumption is high, and production capacity is low, and economy is extremely restricted.And ethylene hydration rule exists instead
Answer pressure big, the disadvantages of conversion ratio only has 4~5%, is less economical.Therefore non-cereal crops, Non oil-based route preparation second are developed
The technology of alcohol is effectively reduced ethyl alcohol production cost, is of great significance.
Coal is that China is most abundant, most economical and most reliable energy resources.It is added by coal production liquid fuel and height
The chemical products of value are the important components of China's oil substituted pesticides.Coal ethyl alcohol technology from scientific research angle exist with
Lower three kinds of routes: coal is through synthesis gas ethyl alcohol directly processed；Coal is through synthesising gas systeming carbinol, then methanol homologization ethyl alcohol directly processed；Coal
Through methanol acetic acid, acetic acid direct hydrogenation or the repeated hydrogenation ethyl alcohol after being esterified.Wherein synthesis gas ethanol yield directly processed is low, warp
Ji property is poor, cannot achieve industrialization in a short time；Methanol homologation traditionally uses homogeneous reaction, and pressure is high, ethanol yield
It is low, less economical, technical research blank wall in decades；And coal passes through preparation of ethanol by hydrogenating in recent years due to catalyst through acetic acid
Succeed in developing, make substantial progress, be most to be hopeful to realize industrialized coal ethyl alcohol technology path.
Acetic acid is important always industrial chemicals and solvent.Several years ago, in order to develop Downstream Products of Methanol, alleviate methanol mistake
Surplus production capacity, acetic acid industry are flourished, and present China's acetate yield is caused serious superfluous situation occur.It is reported that 2011
Year China acetate yield is about 7,000,000 tons, the rate of capacity utilization 66%.Due to acetic acid market saturation, acetic acid price continued in recent years
It drops, continual exploitation acetic acid downstream product, extending acetic acid industrial chain has the very big market demand.Utilize acetic acid plus hydrogen second
Alcohol not only can solve acetic acid problem of excess production capacity, moreover it is possible to meet the growing ethyl alcohol market demand, realize economy and society
Effect two-win.Acetic acid ethyl alcohol has two process routes: acetic acid direct hydrogenation ethyl alcohol and acetic acid the repeated hydrogenation system after being esterified again
Ethyl alcohol.Wherein, the conversion ratio of acetate and ethanol selectivity are all very high in acetic acid esterified back end hydrogenation ethyl alcohol route, product point
From at low cost, catalyst researches and develops relative maturity, and development difficulty is low, but the technology path process flow is long, has half ethyl alcohol to need
Want reflux cycle, need outsourcing ethyl alcohol at driving initial stage, energy consumption is larger, and needs in addition to build acetic acid esterified device, investment compared with
It is high.
The key of acetic acid direct hydrogenation ethyl alcohol technology is to develop the catalysis of high acetic acid conversion ratio, high ethano selectivity
Agent, less due to studying, so development difficulty is larger, but in recent years, this respect is making important progress.
“Acetic Acid Reduction by H2on Bimetallic Pt–Fe Catalysts(Journal of
Catalysis 209,87-98 (2002)) " report a kind of load type bimetal catalyst Pt-Fe/SiO2.The bimetallic phase
The reducing power of Fe can be increased for single-metal reforming catalyst, intensified response activity, decomposition induction time is eliminated and avoid Fe
It generates cementite during the reaction and reaction is caused to inactivate.But the key reaction product of this catalyst is acetaldehyde, ethyl alcohol
Selectivity only up to 40%.
US20100197485A1 is disclosed in Pt-Sn/SiO2CaSiO is added in catalyst system3, 250 DEG C, 22bar,
GHSV2500h-1Under the conditions of, the selectivity of ethyl alcohol can achieve 92%, but the conversion ratio of acetic acid only has 24%.
CN103170337A discloses a kind of catalyst and preparation method thereof for producing ethyl alcohol, using bimetallic catalytic
Agent, a kind of metal are noble metal platinum, ruthenium or palladium, and another metal is iron, cobalt or tin.But bullion content is relatively high, is
2%.
Summary of the invention
The purpose of the invention is to which ethyl alcohol can be produced with high acetic acid conversion and ethanol selectivity, a kind of acetic acid is provided and is added
Catalyst of hydrogen ethyl alcohol and preparation method thereof and a kind of method of acetic acid hydrogenation ethyl alcohol.
To achieve the goals above, the present invention provides a kind of catalyst of acetic acid hydrogenation ethyl alcohol, which includes living
Property component, auxiliary agent and carrier, the active component be Ni and W, on the basis of the total weight of the catalyst, the catalyst contains
There are the auxiliary agent of W, 0.01-2 weight % of Ni, 1-20 weight % of 0.1-10 weight % and the carrier of 68-98.89 weight %.
The present invention also provides a kind of method of catalyst for preparing acetic acid hydrogenation ethyl alcohol provided by the invention, this method
Include: the presoma that (1) introduces compound containing Ni, compound containing W and auxiliary agent in the carrier, obtains catalyst precarsor；(2) by institute
It states catalyst precarsor to restore under hydrogen atmosphere, obtains the catalyst of acetic acid hydrogenation ethyl alcohol.
The present invention also provides a kind of acetic acid hydrogenation alcohol catalysis agent that method provided by the invention is prepared.
The present invention also provides a kind of methods of acetic acid hydrogenation ethyl alcohol, this method comprises: existing in hydrogen and adding hydrogen anti-
Under the conditions of answering, acetic acid is contacted with catalyst；Wherein, the catalyst is acetic acid hydrogenation alcohol catalysis provided by the invention
Agent.
Using the catalyst of acetic acid hydrogenation ethyl alcohol provided by the invention, wherein containing Ni and W as active component, and add
Adding assistant promotes to carry out the reaction of acetic acid hydrogenation ethyl alcohol, can significantly improve the conversion ratio of acetic acid and the selectivity of ethyl alcohol and receipts
Rate, specifically, acetic acid conversion are 89% or more, and 88% or more, the quality space time yield of ethyl alcohol reaches the selectivity of ethyl alcohol
912mg/ (g-cath) or more.And catalyst used in comparative example 1 is not only without so high conversion ratio, yield, and
The preparation cost of noble metal containing high level, catalyst is high.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is Ni-W-Rh-Re/Al provided by the invention2O3Catalyst carries out the reaction product of acetic acid hydrogenation ethyl alcohol
Gas chromatographic analysis map.
Fig. 2 is the Pt-Sn/SiO of the prior art2Catalyst carries out the gas-chromatography of the reaction product of acetic acid hydrogenation ethyl alcohol
Analyze map.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of catalyst of acetic acid hydrogenation ethyl alcohol, which includes active component, auxiliary agent and carrier,
The active component is Ni and W；On the basis of the total weight of the catalyst, the catalyst contains 0.1-10 weight %'s
The auxiliary agent of W, 0.01-2 weight % of Ni, 1-20 weight % and the carrier of 68-98.89 weight %.Preferably, the catalysis
Agent contains the auxiliary agent and 78.5-92.99 weight % of W, 0.01-1.5 weight % of Ni, 5-15 weight % of 2-5 weight %
Carrier.
In the present invention, the catalyst provided uses non-noble metal Ni and W as active component, can effectively improve acetic acid
Acetic acid conversion, ethanol selectivity and yield in preparation of ethanol by hydrogenating reaction.Particularly, in the catalyst Ni and W content
When within the above range, catalyst is more preferable to the improvement of acetic acid hydrogenation ethanol synthesis.Under preferable case, the weight of Ni and W
Amount is than being 1:1-10；Preferably, the weight ratio of Ni and W is 1:0.3-8.The weight ratio of regulation Ni and W can preferably improve second
The conversion ratio of acid and selectivity, the yield of ethyl alcohol.
In the case of, according to the invention it is preferred to, the carrier be aluminium oxide, silica, calcium silicates, calcium oxide, zirconium oxide and
At least one of magnesia.The carrier can have various appearances, can be powder either molding catalyst granules.It is excellent
The carrier can be prepared as the carrier granular with certain external form by selection of land, such as can be using extrusion as diameter 1-3mm, length
The bar shaped agent of 3-5mm is also possible to the spheric granules that average grain diameter is 2-5mm.The carrier preparation side that general hydrogenation reaction uses
Method and the support shapes of application are used equally for the present invention.
According to the present invention, auxiliary agent is added in the catalyst, can further promotes catalyst to obtain and improves acetic acid
The selectivity of conversion ratio and ethyl alcohol, the effect of yield.Under preferable case, the auxiliary agent be copper, rhodium, ruthenium, platinum, titanium, osmium, palladium, iridium,
At least one of tin, rhenium, iron, Jin Heyin.
According to the present invention, regulate and control the dosage relation between auxiliary agent and active component Ni and W, improvement second can be advantageously promoted
The performance of the catalyst of sour preparation of ethanol by hydrogenating.Under preferable case, the weight ratio of the total amount of Ni and W and the auxiliary agent is 0.5-
2000:1；Preferably, the total amount of Ni and W and the weight ratio of the auxiliary agent are 4-200:1.
The present invention also provides a kind of method of catalyst for preparing acetic acid hydrogenation ethyl alcohol provided by the invention, this method
Include: the presoma that (1) introduces compound containing Ni, compound containing W and auxiliary agent in the carrier, obtains catalyst precarsor；(2) by institute
It states catalyst precarsor to restore under hydrogen atmosphere, obtains the catalyst of acetic acid hydrogenation ethyl alcohol.
The presoma of compound containing Ni, compound containing W and auxiliary agent, purpose are introduced in method provided by the invention in the carrier
Be finally in order to introduce active component, specially Ni and W and auxiliary agent into the catalyst of the acetic acid hydrogenation ethyl alcohol of preparation,
It is specifically as follows at least one of copper, rhodium, ruthenium, platinum, titanium, osmium, palladium, iridium, tin, rhenium, iron, Jin Heyin.
In the case of, according to the invention it is preferred to, the compound containing Ni, compound containing W, the presoma of auxiliary agent and carrier plus
In the catalyst for entering the acetic acid hydrogenation ethyl alcohol that amount makes, with the total weight of the catalyst of the acetic acid hydrogenation ethyl alcohol
On the basis of, the catalyst contains the auxiliary agent of W, 0.01-2 weight % of Ni, 1-20 weight % of 0.1-10 weight %, and
The carrier of 68-98.89 weight %.Preferably, the catalyst contains W, 0.01- of Ni, 5-15 weight % of 2-5 weight %
The auxiliary agent of 1.5 weight % and the carrier of 78.5-92.99 weight %.
In the case of, according to the invention it is preferred to, the weight ratio of Ni and W are 1:0.1-10；Preferably, the weight ratio of Ni and W is
1:0.3-8.
In the case of, according to the invention it is preferred to, the weight ratio of the total amount of Ni and W and the auxiliary agent is 0.5-2000:1；It is preferred that
The total amount of ground, Ni and W and the weight ratio of the auxiliary agent are 4-200:1.
According to the present invention, the compound containing Ni can obtain catalyst precarsor and in step (2) for carrier can be added
In reduction under conditions of can be changed into the substance of Ni；Under preferable case, the compound containing Ni be nickel nitrate, nickel chloride and
At least one of nickel acetate.
According to the present invention, the compound containing W can obtain catalyst precarsor and in step (2) for carrier can be added
Reduction under conditions of can be changed into the substance of W.Under preferable case, the compound containing W is ammonium metatungstate or ammonium tungstate.
According to the present invention, the presoma of the auxiliary agent can obtain catalyst precarsor and step (2) for carrier can be added
In reduction under conditions of can be changed into auxiliary agent metal simple-substance substance；Under preferable case, the presoma of the auxiliary agent is
Nitrate, chloride, acetate or the oxide of auxiliary agent；The auxiliary agent be copper, rhodium, ruthenium, platinum, titanium, osmium, palladium, iridium, tin, rhenium,
At least one of iron, Jin Heyin.
According to the present invention, it is also originally intended in step (2) by the compound containing Ni in the catalyst precarsor, compound containing W
Be changed into the metal simple-substance of metallic nickel, tungsten and auxiliary agent with the presoma of auxiliary agent, i.e., the active component that substantially introduces and auxiliary agent with
Reduction-state exists.The condition of the reduction only will be before the compound containing Ni in the catalyst precarsor, compound containing W and auxiliary agent
It drives body and is changed into metal simple-substance, and the metal oxide in the carrier will not change.Under preferable case, the temperature of the reduction
It is 200-700 DEG C, the time of the reduction is 0.1-6h, and hydrogen content is 1-100 volume % in the hydrogen atmosphere, described
The volume space velocity of hydrogen atmosphere is 10-9500h-1。
In the present invention, step (2) can carry out catalyst precarsor reduction immediately after catalyst precarsor is made, can also be with
It is carried out before use (i.e. for before acetic acid hydrogenation ethanol synthesis).Since active component is easy to oxidize, and in catalyst precarsor
Active component exist in the form of an oxide, therefore to be readily transported, catalyst precarsor is restored and is carrying out second by preferred steps (2)
It is carried out before sour preparation of ethanol by hydrogenating reaction.
In the case of, according to the invention it is preferred to, the presoma of compound containing Ni, compound containing W and auxiliary agent is introduced in the carrier
Method be dipping, precipitating or mechanical mixture.
A kind of preferred embodiment of the present invention, introduces the preceding body of compound containing Ni, compound containing W and auxiliary agent in the carrier
The method of body includes: that (a) mixes compound containing Ni, compound containing W, the precursor of auxiliary agent and water, forms dipping solution；(b)
The dipping solution is saturated impregnated carrier, and aging, drying and roasting obtain catalyst precarsor；Wherein, the chemical combination containing Ni
The precursor of object, compound containing W and auxiliary agent is water solubility.
According to the present invention, aging described in step (b) can be by impregnated of the carrier of the dipping solution at normal temperature
It stands, under preferable case, the time of the aging is 0.1-10h.
According to the present invention, solvent dry described in step (b) and that roasting on the carrier after being impregnated for will adsorb
Removal, and the precursor of the compound containing Ni being adsorbed on carrier with dipping solution, compound containing W and auxiliary agent is enable to be changed into
The metal oxide of nickel oxide, tungsten oxide and auxiliary agent.Under preferable case, the temperature of the drying is 50-150 DEG C, the drying
Time be 0.5-24h；The temperature of the roasting is 300-650 DEG C, and the time of the roasting is 1-10h.
The present invention also provides a kind of acetic acid hydrogenation alcohol catalysis agent that method provided by the invention is prepared.This is urged
Composition and the content of agent are as described above, this is no longer going to repeat them.
The present invention also provides a kind of methods of acetic acid hydrogenation ethyl alcohol, this method comprises: existing in hydrogen and adding hydrogen anti-
Under the conditions of answering, acetic acid is contacted with catalyst；Wherein, the catalyst is acetic acid hydrogenation alcohol catalysis provided by the invention
Agent.
In the case of, according to the invention it is preferred to, the volume space velocity of the charging of acetic acid is 0.01-6h-1, mole of hydrogen and acetic acid
Than being 200-500 DEG C for the temperature of 1-100:1, the hydrogenation reaction, the pressure of the hydrogenation reaction is 1.5-10MPa.Herein
Under reaction condition, catalyst provided by the invention can obtain the conversion ratio of better acetic acid and the selectivity of ethyl alcohol, yield.
The present invention will be described in detail by way of examples below.
The composition of catalyst is calculated by the inventory of each material in following embodiment and comparative example.
The reaction product of acetic acid hydrogenation ethyl alcohol, chromatography are analyzed by the gas chromatograph GC-2010 of Japanese Shimadzu Corporation
Condition are as follows: being furnished with chromatographic column is Innowax capillary column (column length 30m × 0.25mm × 0.5 μm) and Haysep T packed column
(5ft × 1/8), wherein Innowax capillary column uses hydrogen flame detector for separating acetic acid, lipid, alcohols and hydrocarbons
FID detection；Haysep T packed column is detected for separating hydrogen, CO and hydro carbons with thermal conductivity cell detector TCD；Full constituent logistics
Product distribution measurement is carried out by chromatograph.
Calculate acetic acid conversion, ethanol selectivity and ethyl acetate selectivity, wherein acetic acid conversion, ethanol selectivity
It is calculated as follows with ethyl acetate selectivity:
Acetic acid conversion=[(quality of acetic acid in acetic acid feed quality-liquid product)/acetic acid feed quality] × 100%；
Ethanol selectivity=(generating quality of acetic acid/all conversions quality of acetic acid consumed by ethyl alcohol) × 100%.
Ethyl acetate selectivity=(generating quality of acetic acid/all conversions quality of acetic acid consumed by ethyl acetate) ×
100%.
Embodiment 1
The present embodiment is used to illustrate the preparation method of the catalyst of acetic acid hydrogenation ethyl alcohol of the invention.
By the nickel nitrate (Chinese medicines group chemical reagent Beijing Co., Ltd, 99 weight % of purity) of 2.48g, 0.853g it is inclined
The deionized water of ammonium tungstate (Chinese medicines group chemical reagent Beijing Co., Ltd, 86 weight % of purity) and 30ml are mixed equal
It is even, obtain the dipping solution 11ml containing Ni-W；
By the radium chloride (Chinese medicines group chemical reagent Beijing Co., Ltd, 99 weight % of purity) of 0.0257g, 1.171g
The mixing of the water of rheium oxide (Chinese medicines group chemical reagent Beijing Co., Ltd, 99 weight % of purity) and 10ml, obtains containing Ru-Re's
Dipping solution；
Dipping solution saturation containing Ni-W is first impregnated into the Al of 8.9g2O3On carrier, and aging 2h is stood at room temperature, so
It is impregnated by 110 DEG C of dry 4h, 500 DEG C of roasting 4h, then with the dipping solution containing Ru-Re, and stands aging 2h at room temperature, then
Through 110 DEG C of dry 4h, 500 DEG C of roasting 4h, catalyst precarsor is made；
Catalyst precarsor is restored, reduction temperature is 350 DEG C, recovery time 4h, and hydrogen contains in hydrogen atmosphere
Amount is 5 volume %, and the volume space velocity of hydrogen atmosphere is 3000h-1, obtain catalyst A.
The composition of catalyst A are as follows: the 0.1 weight % of content of content 5 the weight %, Rh of content 5 the weight %, W of Ni, Re's
Content 0.9 weight %, Al2O389 weight % of content.
Embodiment 2
The present embodiment is used to illustrate the preparation method of the catalyst of acetic acid hydrogenation ethyl alcohol of the invention.
By four ammino platinum nitrates (the Chinese medicines group chemical reagent north of the nickel nitrate of 1g, the ammonium metatungstate of 0.853g, 0.002g
Capital Co., Ltd, 99 weight % of purity), stannous acetate (Chinese medicines group chemical reagent Beijing Co., Ltd, the purity 99 of 0.04g
Weight %), the deionized water of 0.01g dilute hydrochloric acid (0.1mol/L) (Beijing chemical reagents corporation, analyze pure) and 10ml mixes and stirs
It mixes uniformly, obtains the dipping solution 11ml containing Ni-W-Pt-Sn；
Above-mentioned dipping solution saturation is impregnated into the SiO of 9.3g2On carrier, and aging 4h is stood at room temperature, it is dry through 110 DEG C
Catalyst precarsor is made in dry 4h, 700 DEG C of roasting 4h；
Catalyst precarsor is restored, reduction temperature is 400 DEG C, recovery time 6h, and hydrogen contains in hydrogen atmosphere
Amount is 20 volume %, and the volume space velocity of hydrogen atmosphere is 3500h-1, obtain catalyst B.
The composition of catalyst B are as follows: content 0.01 the weight %, Sn of content 5 the weight %, Pt of content 2 the weight %, W of Ni
Content 0.2 weight %, SiO292.79 weight % of content.
Embodiment 3
The present embodiment is used to illustrate the preparation method of the catalyst of acetic acid hydrogenation ethyl alcohol of the invention.
Copper nitrate (Chinese medicines group chemical reagent Beijing of the nickel nitrate of 0.149g, the ammonium metatungstate of 1.71g, 0.381g
Co., Ltd, 99 weight % of purity), stannous chloride (Chinese medicines group chemical reagent Beijing Co., Ltd, 99 weight of purity of 0.38g
Amount %) and the deionized water of 10ml be mixed evenly, obtain the dipping solution 11ml containing Ni-W-Cu-Sn；
Above-mentioned dipping solution saturation is impregnated into the ZrO of 8.67g2On carrier, and aging 4h is stood, through 110 DEG C of dry 4h,
Catalyst precarsor is made in 500 DEG C of roasting 4h；
Catalyst precarsor is restored, reduction temperature is 500 DEG C, recovery time 2h, and hydrogen contains in hydrogen atmosphere
Amount is 60 volume %, and the volume space velocity of hydrogen atmosphere is 2500h-1, obtain catalyst C.
Catalyst C composition are as follows: the 1 weight % of content of content 10 the weight %, Cu of content 0.3 the weight %, W of Ni, Sn's
Content 2 weight %, ZrO286.7 weight % of content.
Embodiment 4
The present embodiment is used to illustrate the preparation method of the catalyst of acetic acid hydrogenation ethyl alcohol of the invention.
The palladium nitrate of the nickel nitrate of 2g, the ammonium metatungstate of 12.8g, 0.125g, (Chinese medicines group chemical reagent Beijing is limited
Company, 99 weight % of purity), the rheium oxide (Chinese medicines group chemical reagent Beijing Co., Ltd, 99 weight % of purity) of 0.065g
It is mixed evenly with the deionized water of 10ml, obtains the dipping solution 11ml containing Ni-W；
Above-mentioned dipping solution saturation is impregnated into the MgO-Al of 8.9g2O3On complex carrier, and aging 3h is stood, through 110 DEG C
Dry 4h, 500 DEG C of roasting 4h, are made catalyst precarsor；
Catalyst precarsor is restored, reduction temperature is 350 DEG C, recovery time 4h, and hydrogen contains in hydrogen atmosphere
Amount is 5 volume %, and the volume space velocity of hydrogen atmosphere is 3000h-1, obtain catalyst D.
Catalyst D composition are as follows: content 0.5 the weight %'s, Re of content 6 the weight %, Pt of content 4 the weight %, W of Ni contains
Measure 0.5 weight %, MgO-Al2O389 weight % of content.
Comparative example 1
Weigh the SnCl of 0.19g2·2H2O is dissolved in the ethyl alcohol of 9.3ml, forms the dipping solution containing Sn；
Maceration extract is impregnated into the SiO of 10g2Carrier, dry 5h, 500 DEG C of roasting 5h at 110 DEG C, obtains load Sn's
Silica support.
The four ammino platinum nitrates for weighing 0.2g, are dissolved in 8ml deionized water, after mixing evenly bear dipping solution
It is downloaded on the silica support containing Sn, 110 DEG C of dry 5h, 500 DEG C of roasting 5h obtain the SiO of supporting Pt and each autoxidisable substance of Sn2
Carrier, i.e. catalyst precarsor.
Catalyst precarsor is restored, reduction temperature is 350 DEG C, recovery time 4h, and hydrogen contains in hydrogen atmosphere
Amount is 5 volume %, and the volume space velocity of hydrogen atmosphere is 3000h-1, obtain catalyst E.
The composition of catalyst E are as follows: content 1 the weight %, SiO of content 1 the weight %, Sn of Pt298 weight % of content.
Embodiment 5
The method that the present embodiment is used to illustrate acetic acid hydrogenation ethyl alcohol provided by the invention.
The catalyst A of 1g is put into the reaction that acetic acid hydrogenation ethyl alcohol is carried out in fixed bed reactors, the temperature of reaction is
275 DEG C, the pressure of reaction is 2.5MPa, and the volume space velocity of the charging of acetic acid is 0.72h-1, the molar ratio of hydrogen and acetic acid is 6:
1。
Reaction product is taken out and is condensed, is formed with the product liquid that chromatographic obtains, obtained gas-chromatography
Analysis of spectra is as shown in Figure 1.
Acetic acid conversion, ethanol selectivity and the ethyl acetate of the reaction of acetic acid hydrogenation ethyl alcohol are selective to be the results are shown in Table
1。
Embodiment 6
The method that the present embodiment is used to illustrate acetic acid hydrogenation ethyl alcohol provided by the invention.
The catalyst A of 1g is put into the reaction that acetic acid hydrogenation ethyl alcohol is carried out in fixed bed reactors, the temperature of reaction is
300 DEG C, the pressure of reaction is 1.5MPa, and the volume space velocity of the charging of acetic acid is 1.5h-1, the molar ratio of hydrogen and acetic acid is 4:1.
Reaction product is taken out and is condensed, is formed, is obtained similar with Fig. 1 with the product liquid that chromatographic obtains
Gas chromatographic analysis spectrogram.
Acetic acid conversion, ethanol selectivity and the ethyl acetate of the reaction of acetic acid hydrogenation ethyl alcohol are selective to be the results are shown in Table
1。
Embodiment 7
The method that the present embodiment is used to illustrate acetic acid hydrogenation ethyl alcohol provided by the invention.
The catalyst A of 1g is put into the reaction that acetic acid hydrogenation ethyl alcohol is carried out in fixed bed reactors, the temperature of reaction is
250 DEG C, the pressure of reaction is 3MPa, and the volume space velocity of the charging of acetic acid is 0.5h-1, the molar ratio of hydrogen and acetic acid is 8:1.
Reaction product is taken out and is condensed, is formed, is obtained similar with Fig. 1 with the product liquid that chromatographic obtains
Gas chromatographic analysis spectrogram.
Acetic acid conversion, ethanol selectivity and the ethyl acetate of the reaction of acetic acid hydrogenation ethyl alcohol are selective to be the results are shown in Table
1。
Embodiment 8-10 and comparative example 2
According to the method for embodiment 5, the difference is that, catalyst B, C, D, E alternative catalysts A are used respectively.
The product liquid that catalyst E is reacted is with carrying out gas chromatographic analysis, obtained gas chromatographic analysis
Spectrogram is as shown in Figure 2.
Acetic acid conversion, ethanol selectivity and the ethyl acetate of the reaction of acetic acid hydrogenation ethyl alcohol are selective to be the results are shown in Table
1。
Table 1
From the reaction result in above-mentioned table 1 and Fig. 1-2: in the acetic acid hydrogenation ethyl alcohol using catalyst of the present invention
In reaction, acetic acid conversion reaches 88% or more, and in reaction product, ethanol selectivity reaches 89% or more, ethyl acetate selection
Property 10% hereinafter, the quality space time yield of ethyl alcohol can reach 912mg/ (g-cath) or more, considerably beyond art-recognized
Make acetic acid direct hydrogenation ethanol have economic feasibility 200mg/ (g-cath) ethanol yield critical value.
Compare Fig. 1 and Fig. 2, it can be found that: using the catalyst of the present invention of embodiment 1, in the reaction product of embodiment 5,
Ethanol selectivity is very high, and ethyl acetate is selectively lower；And existing catalyst in comparative example 1 is used, and in reaction product, ethyl alcohol choosing
Selecting property is low, and ethyl acetate selectivity is then higher.This explanation: catalyst of the present invention produces second particularly suitable for acetic acid direct hydrogenation
The technique of alcohol has good ethanol selectivity.And there is no the appearance of original acetic acid in Fig. 1, illustrate that acetic acid participates in well
Reaction.
Compared with existing similar catalyst, catalyst provided by the invention can be such that acetic acid conversion and ethanol selectivity obtains
It is significantly increased, moreover, noble metal usage amount is reduced, and catalytic life is extended in catalyst preparation process, makes
It obtains catalyst of the present invention and there is preferable economy using the acetic acid direct hydrogenation ethanol of catalyst of the present invention.
Claims (12)
1. a kind of catalyst of acetic acid hydrogenation ethyl alcohol, which includes active component, auxiliary agent and carrier, the active component
For Ni and W, on the basis of the total weight of the catalyst, the catalyst contains Ni, 1-20 weight % of 0.1-10 weight %
W, 0.01-2 weight % auxiliary agent and 68-98.89 weight % carrier；
Wherein, the preparation method of the catalyst includes:
(1) presoma for introducing compound containing Ni, compound containing W and auxiliary agent in the carrier, obtains catalyst precarsor；
(2) catalyst precarsor is restored under hydrogen atmosphere, obtains the catalyst of acetic acid hydrogenation ethyl alcohol.
2. catalyst according to claim 1, wherein the carrier is aluminium oxide, silica, calcium silicates, calcium oxide, oxygen
Change at least one of zirconium and magnesia.
3. catalyst according to claim 1, wherein the auxiliary agent be copper, titanium, tin, rhenium, iron, rhodium, ruthenium, platinum, osmium, palladium,
At least one of iridium, Jin Heyin.
4. catalyst according to any one of claim 1-3, wherein the weight ratio of Ni and W is 1:0.1-10.
5. catalyst according to any one of claim 1-3, wherein the weight ratio of the total amount of Ni and W and the auxiliary agent
For 0.5-2000:1.
6. a kind of method for the catalyst for preparing acetic acid hydrogenation ethyl alcohol of any of claims 1-5, this method packet
It includes:
(1) presoma for introducing compound containing Ni, compound containing W and auxiliary agent in the carrier, obtains catalyst precarsor；
(2) catalyst precarsor is restored under hydrogen atmosphere, obtains the catalyst of acetic acid hydrogenation ethyl alcohol.
7. according to the method described in claim 6, wherein, the compound containing Ni is in nickel nitrate, nickel chloride and nickel acetate
It is at least one；The compound containing W is ammonium metatungstate or ammonium tungstate；The presoma of the auxiliary agent is the nitrate of auxiliary agent, chlorination
Object, acetate or oxide；The auxiliary agent is at least one in copper, rhodium, ruthenium, platinum, titanium, osmium, palladium, iridium, tin, rhenium, iron, gold and silver
Kind.
8. according to the method described in claim 6, wherein, before introducing compound containing Ni, compound containing W and auxiliary agent in the carrier
The method of body includes:
(a) compound containing Ni, compound containing W, the precursor of auxiliary agent and water are mixed, forms dipping solution；
(b) dipping solution is saturated impregnated carrier, and aging, drying and roasting obtain catalyst precarsor；
Wherein, the precursor of the compound containing Ni, compound containing W and auxiliary agent is water solubility.
9. according to the method described in claim 8, wherein, the time of the aging is 0.1-10h；The temperature of the drying is
50-150 DEG C, the time of the drying is 0.5-24h；The temperature of the roasting is 300-650 DEG C, and the time of the roasting is 1-
10h。
10. the temperature of the reduction is 200-700 DEG C according to the method described in claim 6, wherein, the time of the reduction
For 0.1-6h, hydrogen content is 1-100 volume % in the hydrogen atmosphere, and the volume space velocity of the hydrogen atmosphere is 10-
9500h-1。
11. the acetic acid hydrogenation alcohol catalysis agent that method described in any one of claim 6-10 is prepared.
12. a kind of method of acetic acid hydrogenation ethyl alcohol, this method comprises: hydrogen exist and hydrogenation conditions under, by acetic acid
It is contacted with catalyst；Wherein, the catalyst is acetic acid hydrogenation alcohol catalysis described in any one of claim 1-5 and 11
Agent.
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| CN102614914A (en) * | 2012-03-07 | 2012-08-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing ethanol by acetic acid hydrogenation, preparation method and application thereof |
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| CN102614914A (en) * | 2012-03-07 | 2012-08-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing ethanol by acetic acid hydrogenation, preparation method and application thereof |
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