CN103785417B - The Co catalysts of alcohol is prepared for carboxylic acid high-selective and hydrogenating - Google Patents
The Co catalysts of alcohol is prepared for carboxylic acid high-selective and hydrogenating Download PDFInfo
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Abstract
The present invention relates to a kind of at least containing cobalt and B catalyst and be applied to the method that hydrogenation of carboxylic acids is prepared as alcohol.In the present invention, the catalyst of use at least contains the cobalt of 10wt%～50wt% accounting for overall catalyst weight and the boron of 1.0wt% ~ 10wt%.By this catalyst, under the conditions of 220～300 DEG C and 0.5～4.0MPa, carboxylic acid can be to be selectively converted to corresponding alcohol and ester higher than 90%, the catalyst activity used is high, good stability and cost are relatively low, and the reaction condition used is the harshest, are therefore easier to realize commercial operation.
Description
Technical field
The invention belongs to chemical field, specifically, the present invention relates to one can be by carboxylic acid height yield hydro-conversion
The cobalt B catalyst of alcohol and methods for making and using same thereof.
Technical background
It is the important chemical reaction of a class that hydrogenation of carboxylic acids prepares alcohol, and such as acetic acid hydrogenation, to prepare ethanol, lactic acid Hydrogenation standby
Propylene glycol all also exists demand urgently.This causes due to multiple reasons: due to technique progress, cause carboxylic acid
Manufacturing cost reduce, if acetic acid is along with the maturation of methanol carbonyl method, manufacturing cost reduces；Or owing to raw material becomes
More so that the manufacture of carboxylic acid has sustainability, such as biomass derivatives such as lactic acid, 3-hydracrylic acids.
The Hydrogenation of carboxylic acid is long-standing for the research of alcohol, and as far back as nineteen fifty, Ford etc. has just applied for use ruthenium
Carboxylic acid is converted into the method for alcohol by catalyst, but owing to petroleum resources cost in last century is the cheapest and the mankind
Sustainable development attention degree is relatively low, therefore uses the technology such as alkene hydration, oxidation-hydration the production of alcohols more.Enter
After entering 21 century, people are to renewable system and oil replacement resource (coal, natural gas, shale gas, coal bed gas)
Deng large-scale development so that hydrogenation of carboxylic acids prepare alcohol become alcohols produce more economy and continuable method.
In fact hydrogenation of carboxylic acids is prepared alcohol and is had high challenge, and main technical difficulty is to develop and has height
The catalyst of activity and selectivity, the reaction pressure needed for reduction, and catalyst need to possess long-time use
Stability, the cost of certain catalyst needs in the range of reasonably, to ensure its commercial value.
The open a kind of hydrogenation of carboxylic acids catalyst of US4104478 and application process thereof, the catalyst of use is the double gold of M-rhenium
Metal catalyst, M is the one in ruthenium, rhodium, platinum and palladium, under conditions of 170 ~ 250 DEG C and 2.0 ~ 14.0MPa,
Corresponding carboxylic acid is converted into fatty alcohol.Disclosed embodiment pressure the highest (> 7.0MPa).
US4517391 discloses a kind of acetic acid gas phase hydrogenation and prepares the catalyst of ethanol, and catalyst contains no less than 50wt%
Cobalt, one or more in Yi Jitong, manganese, molybdenum, chromium and phosphoric acid.In unique embodiment, cobalt content
More up to 70%, the reaction pressure of use is 300bar, and ethanol yield is 97%.Although this proprietary catalysts cobalt gold
Belong to content high, but owing to not using noble metal, cost to have certain advantage, but this catalyst activity is relatively
Low, ethanol yield only 0.09kg/kg Cat/h, consider catalyst cost the highest, and reactor will
Can be the hugest, the most not there is commercialization and be worth.During embodiment is not disclosed tail gas simultaneously, incoagulability gas phase contains
Amount and material yield are less than theoretical value.
CN1008088 discloses a kind of hydrogenation of carboxylic acids and prepares the loaded catalyst of alcohol, and the first component of catalyst is tungsten
And molybdenum, second component is the one in palladium, ruthenium and platinum, and carrier is activated carbon.This catalyst contains 1 ~ 10wt%'s
Noble metal, with high costs；And reaction velocity is relatively low, and (LHSV in embodiment is only 0.35h-1, it is meant that time
Empty yield is less than 0.26kg/m3Cat/h), reaction pressure in an embodiment is about 1.0Mpa.
The open a kind of acetic acid hydrogenation catalyst of CN201110104763.7 and CN201110103802.1 and application process thereof,
First active component of catalyst is tungsten and molybdenum, and second component is the one in ruthenium, rhodium, platinum and palladium, and carrier is for living
Property charcoal or graphite, in its disclosed embodiment, reaction pressure is 7.0 ~ 10.0MPa.
Zhang etc. have studied lactic acid aqueous phase Hydrogenation for propylene glycol, the ruthenium catalyst of use load and trickle bed reaction
Device, wherein water content is generally water (the Aqueous-phase hydrogenation of lactic acid to of 40 ~ 80%
Propylene glycol, Applied Catalysis A:General 219 (2001) 89 98).In the method, higher
This energy consumption when separation can be significantly increased undoubtedly of the water of content；The Ru/C that catalyst is 5wt% used, high urges
Agent cost makes it be not suitable for commercial operation.
CN102149662 discloses a kind of Co catalysts for acetic acid hydrogenation, and the load capacity of cobalt is less than 20wt%, and
And possibly together with palladium and the platinum of about 1wt% in catalyst.Cobalt content is below 10wt% in the embodiment disclosed.
The open a kind of acetic acid hydrogenation catalyst of US7863489, catalyst activity component is platinum, and auxiliary agent is stannum.Catalysis
Acetic acid can be converted into ethanol with higher yield by agent, but platinum content is higher, in the embodiment announced, and platinum
Content is more than 1wt%, it is well known that the price of platinum is much more expensive and reserves are very limited, therefore in commercialization
The cost that will make catalyst in application is high.Same problem exists in another patent US7608744,
Co catalysts content relatively low (~ 10wt%), catalyst needs to use precious metal additive, such as platinum and palladium, auxiliary agent simultaneously
Content is higher than 1wt%.
CN102149662 discloses a kind of acetic acid hydrogenation catalyst containing cobalt, and preparation method is infusion process, the load of cobalt
Amount is 0.1wt% ~ 20wt%, and in its disclosed embodiment, cobalt loading is at 5wt% ~ 10wt%, and uses
Auxiliary agent uses precious metal additive, and such as platinum and palladium, auxiliary agent content is higher than 1wt%, and this will make the cost pole of catalyst
It is high, or is the chromium auxiliary agent with relatively high pollution；And the conversion ratio of acetic acid is relatively low, although inventor is not
Its space-time yield disclosed, but provided by embodiment data, its space-time yield can be calculated relatively low, such as it
Disclosed cobalt-chrome catalysts, the space-time yield of ethanol is only at 82g/L/h ~ 258g/L/h.
In sum, in existing carboxylic acid technical scheme, there is some technology and commercialization problem: catalyst cost is high
High and produce that the raw material quantity delivered of catalyst is limited, space-time yield is low, selectivity is relatively low, reaction pressure is higher makes
Operating condition is excessively harsh, energy consumption is too high.
Method of the present invention, under relatively mild reaction condition, it is possible to be converted into by acetic acid with higher yield
Ethanol, and catalyst has higher space-time yield and cheap manufacturing cost.
Summary of the invention
The present invention relates to a kind of cobalt metallic catalyst used containing boron additive and monocarboxylic acid is hydrogenated to alcohol, this catalysis
The most active height of agent, selectivity height and the feature of good stability, and cost is the cheapest, and form relatively
For environmental protection.
A kind of hydrogenation of carboxylic acids of the present invention prepares the catalyst of alcohol, and described catalyst includes following component:
(1) cobalt and boron, wherein cobalt tenor accounts for the 10wt% ~ 50wt% of overall catalyst weight, and boron accounts for overall catalyst weight
1.0wt%~10wt%；
(2) oxide, described oxide is selected from silicon oxide, kieselguhr, calcium silicates, zirconium oxide, titanium oxide, oxygen
Change aluminum one or more, its content accounts for the 10wt% ~ 80wt% of overall catalyst weight；
Described hydrogenation catalyst is by co-precipitation, deposition-precipitation, ammonia still process precipitation, sol-gel and ball grinding method
In one or more combine preparation.
The detailed description of the invention is as follows:
The main active component of catalyst of the present invention is cobalt, and wherein cobalt tenor accounts for overall catalyst weight
10wt% ~ 50wt%, preferred content accounts for the 20wt% ~ 45wt% of overall catalyst weight, further preferably accounts for catalysis
25wt% ~ the 40wt% of agent gross weight；Described cobalt tenor refers to the content of element cobalt.Cobalt in catalyst contains
Amount carefully filters out through inventor: relatively low compared with the activity of low cobalt content catalyst, and this can make catalysis
The ethanol space-time yield of agent remains at low levels, owing to carboxylic acid has stronger corrosivity, therefore its direct hydrogenation
Prepare the reactor of alcohol it is generally required to use stainless steel material costly, can make when therefore space-time yield is lower
The cost obtaining reactor is high；And the cobalt of higher amount not only makes the cost increase of catalyst, and can not
Improve the activity of catalyst, declined, significantly decreased when high level.This result is
Expect: because often it is believed that raising tenor can improve the activity of catalyst.Further, inventor
Finding that the preparation difficulty of catalyst increases when cobalt content is higher than 50wt%, such as forming process etc., this will make
The commercialization obtaining catalyst is the most difficult.
The source of cobalt be selected from water miscible slaine such as nitrate, sulfate, villaumite, acetate, oxalates and
Bromide, or selected from metallic cobalt, such as cobalt metallic plate etc..More specifically water-soluble metal salt is selected from cobalt nitrate, chlorination
One or more in cobalt, cobalt oxalate, cobaltous sulfate, cobaltous acetate, more preferably cobalt nitrate, cobaltous acetate and oxalic acid
One or more in cobalt.
Boron is another kind of important composition component in catalyst of the present invention, and appropriate boron additive addition drastically increases
Selectivity of catalyst and stability, and the catalyst obtained by specific preparation method more embodies the present invention
The superiority of scheme.
After boron additive adds, catalyst stability etc. represents the index of catalyst reaction performance and is greatly improved, therein
Reason is probably many: boron improves the electronics form of cobalt or inhibits the generation etc. of carbon distribution.It is more unexpected,
The inventors discovered that, at the Co catalysts prepared by methods such as co-precipitation, deposition-precipitation and ball millings, boron additive
The effect improving catalyst reaction performance becomes apparent from.
Boron accounts for the 1wt% ~ 10wt% of overall catalyst weight, and further preferred content is to account for overall catalyst weight
1.5wt% ~ 5wt%, the content more optimized is 1.5wt% ~ 3wt%.
The source of boron is not limited, can be known all boron-containing compounds.The source of the boron optimized further
Have pure boron, boric acid, metaboric acid, sodium tetraborate, Dexol, sodium metaborate, fluoboric acid, Sodium fluoroborate,
Phenylboric acid, sodium borohydride, potassium borohydride, triethyl borate, methyl borate. etc..The compound optimized further
It is boric acid and metaboric acid.
Specific method for preparing catalyst of the present invention preferably includes in co-precipitation, deposition-precipitation and ball milling
The combination of one or more, these prepare catalyst method is those skilled in the art as existing mature technology mostly
Known, this area books all have detailed introduction, it is as written in yellow Zhong Tao that < industrial catalyst designs and opens
Send out, Gerhard professor Ertl etc. written<Preparation of Solid Catalysts>.The most of the present invention
Steaming ammonium intermediate processing, brief step is as follows: (one) by salt solubility in water, it is also possible to containing other metals
Or non-metal salt；(2) ammonia is gradually added in above-mentioned saline solution, forms cobalt ammonium complex compound with ammonia；(3)
Add other components；(4) heating up and progressively evaporated by ammonia, cobalt precipitates；(5) wash, filter；(6)
Dry, roasting.The step essence of the melted-suction method in the present invention refers to the preparation process of Raney catalyst:
(1) by fusing having the metallic cobalt of catalysis activity, bismuth and aluminum (or silicon) in a furnace, obtain is molten
Body carries out quenching cooling, is then comminuted into into uniform fine grained, dissolving the auxiliary agent being also possible to add other in step；
(2) by catalyst fines molding, forming technique can use existing well known technology, as played sheet, kneading
Extrusion, spin etc.；(3) by above-mentioned preformed catalyst sucking filtration in alkali liquor of gained, i.e. obtain obtaining catalyst.
Co catalysts with boron as auxiliary agent is the most known, and its preparation method is different from the present invention, mainly
Being to be prepared by the method for dipping, described dipping method includes incipient impregnation, repeatedly impregnating.It practice,
It is well known that the compound of boron, such as boric acid, the dissolubility in water is the most very limited amount of, therefore impregnates
The catalyst Boron contents of method the lowest (generally < 1wt%)；Owing to there is an optimization between cobalt and boron
Ratio, the most sometimes has to use reduce cobalt content, and this causes again catalyst activity to reduce.
Therefore, whilst not wishing to be restricted, preparation method of the present invention include co-precipitation, deposition-precipitation,
Why performance is more superior for ammonia still process precipitation, sol-gel and ball grinding method, it may be possible to due to: (1) these method energy
Enough easier on a catalyst plus sufficient boron, (2) boron is preferably and cobalt forms compound.
Catalyst of the present invention is also optionally with one or more in IB race, palladium, platinum, ruthenium, rhenium
Element, as auxiliary agent, accounts for the 0wt% ~ 10wt% of overall catalyst weight；It is preferably selected from silver, copper, palladium, ruthenium, rhenium
One or more elements as auxiliary agent, further preferably one or more elements in silver, copper and rhenium are as helping
Agent, preferred one in silver and copper.
Silver and copper tenor account for the 0wt% ~ 10wt% of overall catalyst weight, more preferably in the range of 0.2 ~ 5wt%.
The source of silver metal is silver nitrate, and the source of copper can be metallic copper, copper nitrate, copper chloride, Schweinfurt green, oxalic acid
One or more in copper.The addition manner of silver and copper can be various: as in precipitation, deposition-precipitation, steaming
Add after the ammonium sedimentation method or sol-gel process are dissolved together with cobalt salt；Catalyst precursor adds,
In the dried filter cake obtained in precipitation, deposition-precipitation, the steaming ammonium sedimentation method or sol-gel or xerogel,
Or in the material after Roasting Decomposition；Or add beating the formative stage such as sheet or extrusion；Or with cobalt liquor
During dipping add, or with cobalt salt step impregnation；Melting process adds together with cobalt metal.
Catalyst in the present invention can also be possibly together with alkali metal or alkaline-earth metal, described alkali metal or alkaline-earth metal
Content accounts for the 0wt ~ 30wt% of catalyst total amount.More specifically, described alkali metal or alkaline-earth metal selected from potassium,
One or more in sodium, calcium, magnesium, barium, content accounts for the 0wt ~ 15wt% of catalyst total amount, further preferred
Scope is 0wt% ~ 10wt%.Alkali and alkaline earth metal ions source can be water miscible nitrate, carbonate, chlorine
Salt, phosphate, sulfate, acetate, fluoride, hydroxide etc..More specifically, alkali metal and alkaline earth
Metal source selected from potassium hydroxide, potassium nitrate, potassium carbonate, potassium acetate, potassium fluoride, potassium phosphate, sodium hydroxide,
Sodium nitrate, sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, sodium acetate, calcium nitrate, dalcium biphosphate, nitre
One or more in acid magnesium, magnesium phosphate, barium nitrate.
The feed postition of alkali and alkaline earth metal ions element can any one in the in the following manner: dipping,
Add after kneading, precipitation, deposition-precipitation or sol-gel process dissolve together with cobalt salt；At blended, ball
Mill, the method such as melted add together with cobalt salt or substep adds；Dipping, precipitation, deposition-precipitation or
In sol-gel process, respectively or substep adds with cobalt salt；Catalyst precursor adds, such as precipitation, sinks
In the dried filter cake obtained in long-pending-precipitation or sol-gel or xerogel, or the material after Roasting Decomposition
In；Or add beating the formative stage such as sheet or extrusion.
Catalyst is possibly together with some oxide components, whilst not wishing to do any restriction, but inventor thinks that these aoxidize
Thing primarily serves the effect of carrier, described oxide component selected from silicon oxide, aluminium oxide, kieselguhr, calcium silicates,
Zirconium oxide, titanium oxide one or more, its content accounts for the 10wt% ~ 80wt% of overall catalyst weight.It practice,
These carriers are not only to play a supporting role, additionally it is possible to assist dispersion or the activation of carboxylic acid of active component, therefore
These carriers affect the diffusion wherein of the texture property of catalyst, product and raw material, mechanical strength, activity and
The critical index such as stability.
Support Silica can be selected from waterglass precipitate method, SiO 2 powder, teos hydrolysis, Ludox
Deng.Described SiO 2 powder can be by after chemical deposition, waterglass precipitate dried ball milling obtain,
Or the method such as Ludox spray drying obtains, its size is selected from 10nm ~ 500 μm；Such as Qingdao Haiyang chemical industry
Factory produce gross porosity microsphere silicon dioxide (average pore size is 8.0-12.0nm, and specific surface area is 300 ~ 600m2/g,
Pore volume is 0.8 ~ 1.1ml/g), the precipitated silica (silicon dioxide (SiO that and for example Guangzhou people chemical plant produces2)
Content % >=95.0, fineness (325 screen residue) %≤1.8, specific surface area is 400 ~ 600m2/ g) or
Active carbon white, and for example the aerosil AEROSIL 200 of goldschmidt chemical corporation, its specific surface is 200m2/ g,
And for example self-control is spray-dried the silicon dioxide microsphere obtained, and specific surface is 400 ~ 500m2/ g, a size of 2 ~ 30 μm.
SiO 2 powder can add as carrier in precipitation or deposition-precipitation.Described waterglass directly sinks
Shallow lake method refers to waterglass as raw material, adds acidic precipitation agent or ion precipitation agent in waterglass, as sulphuric acid,
Hydrochloric acid, nitric acid, acetic acid, calcium nitrate, zirconyl nitrate, zirconium oxychloride, magnesium nitrate, cobalt nitrate etc..Precipitant adds
Forming white gum thing after entering, washing uses the most afterwards or carries out the sedimentation method of other components on this basis and adds
Enter.Tetraethyl orthosilicate is to use in sol-gel process prepares the catalyst of the present invention.Ludox is as liquid-state silicon
Source, can be used directly in the precipitation system entering precipitation, deposition-precipitation.
Support Silica or aluminium oxide are also likely to be in the catalyst prepared as melted-suction method as bonding
Agent adds so that the catalyst fines of gained can be shaped to the shape needed for the present invention.
The shape of catalyst of the present invention can be diversified, such as spherical, strip, column, ring
Shape etc., size is between 0.3 ~ 15mm, and more preferably between 1 ~ 10mm, the requirement of this size is main
It is to design according to fixed bed reactors of the present invention, in order to be beneficial to install, reduce the requirements such as bed layer pressure.
These knowledge are known to professional and technical personnel.
Described zirconia material source is for powder body zirconia material or by the precipitation of zirconates.Powder body aoxidizes
Zirconium size is selected from 10nm ~ 500 μm, and specific surface is more than 20m2/g.The precipitation of zirconates can be real according to following approach
Existing: first zirconium oxychloride to be dissolved in water, be subsequently added the highly basic such as caustic soda, finally precipitate is washed
The gel being filtrated to get；Or using zirconyl nitrate as zirconium source, after adding caustic soda precipitation, washing and filtering obtains
The gel obtained.Above-mentioned gel is joined in other precipitate, or by above-mentioned gel through dried
After wearing into powder body, the carrier as deposition-precipitation adds.
Titanium oxide in the present invention can be some satisfactory commercially available titanium dioxide, such as goldschmidt chemical corporation
P25, it would however also be possible to employ prepared by the method for liquid-phase precipitation, if employing titanium tetrachloride or titanium sulfate are as titanium source,
Add carbamide, ammonia, sodium carbonate or caustic soda etc. as precipitant, it would however also be possible to employ organic metatitanic acid such as titanium
Acid butyl ester hydrolysis preparation.
Catalyst is also possible to containing thulium, and its oxide content accounts for catalyst total amount
0wt~8wt%；Described rare earth element selects the one in lanthanum or cerium, and it is total that its oxide content accounts for catalyst
0wt ~ the 5wt% of amount.The rare earth element adding trace can make cobalt by reducing incoagulable gas content
Selectivity of catalyst obtains a certain degree of raising.
Catalyst is also possible to containing one or more inorganic non-metallic elements, and content accounts for catalyst total amount
0wt~5wt%.More specifically, described inorganic non-metallic element one in phosphorus, fluorine, content accounts for
0wt ~ the 2wt% of catalyst total amount.The addition of these inorganic non-metallic elements, have along with other auxiliary agents
Addition and enter catalyst system, such as potassium fluoride.
Heretofore described is the method for fatty alcohol by organic carboxyl acid hydro-conversion, its concrete principle be by
Monocarboxylic acid gasification also mix with hydrogen, or entrance hydrogenation reactor after being gasified in hydrogen by monocarboxylic acid
In, and contact with catalyst of the present invention and be converted into fatty alcohol and water.
The reactor of Catalyst packing is fixed bed reactors, more preferably shell and tube reactor, more specifically and
Speech, is by Catalyst packing in pipe, and filling heat-conducting medium between pipe, such as conduction oil or water etc., so
It is more conducive to the removal of reaction heat.Those skilled in the art all knows this technical key point, such as every pipe filling
Amount need to keep consistent etc..
The catalyst of the present invention when being applied in hydrogenation of carboxylic acids, need by its fully reduction activation make absolutely
Most of cobalt is all reduced to zero valence state before carrying out hydrogenation reaction, and the mode of activation can be at intensification bar
Hydrogen, use reducing agent such as sodium borate etc. or the method using ionizing radiation it is passed through under part.These methods
All it is well known to those skilled in the art.
Method of hydrotreating of the present invention, reaction temperature is 180 ~ 350 DEG C, more preferably 220 ~ 300 DEG C,
Selectivity of catalyst change is less within the range, maintains higher level.When reaction temperature is relatively low, carboxylic
Acid conversion ratio is relatively low, and this makes circulating consumption increase；And during reaction temperature continuation rising, by-product is especially
The amount of incoagulable gas product such as ethane is significantly increased.
Being prepared as alcohol for monocarboxylic acid hydrogenation, hydrogen gas consumption is 2 with the mol ratio of carboxylic acid in theory, but
For maintaining subsequent reactions pressure and catalyst life, carboxylic acid is 4:1 ~ 40:1 with the molar ratio of hydrogen, more excellent
Ratio is 6:1 ~ 25:1, and further Optimal Ratio is 8:1 ~ 20:1.From reactor thick product out through gas
After liquid/gas separator, the hydrogen of excess can recycle.
The catalyst choice used in the present invention is higher, and therefore in by-product, the selectivity of incoagulable gas is low
In 15%, more excellent in the case of less than 10%, less than 5% in the case of optimizing further.
The hydrogenation of carboxylic acid is typical compressive reaction, and the reaction pressure that the present invention uses is 0.3 ~ 8.0MPa, more
Preferably reaction pressure is 0.5 ~ 4.0MPa, and the reaction pressure optimized further is 1.0 ~ 2.5MPa.The present invention
The reaction pressure used, much lower relative to reaction pressure disclosed in many hydrogen addition technologies before, this makes instead
Answer condition gentleer, and reduce cost.
In the method, the volume space velocity of carboxylic acid is 0.1 ~ 5.0h-1；Preferred volume space velocity is 0.2 ~ 2.0h-1。
According to factory, air speed really wishes that extraction product composition is relevant with later separation ability, the present invention is in force
Be not restricted, this be due to: when air speed is higher, although acetic acid conversion ratio is relatively low, but ethanol and acetic acid
The productivity of ethyl ester and increasing on the contrary, particularly ethyl acetate selectivity can improve；When air speed is relatively low, vinegar
Acid conversion ratio is high, but the productivity of ethanol may reduce, therefore for having separating power and wishing many
Produce the factory of ethyl acetate, can use high-speed operator scheme, and for the less work of later separation ability
Factory, can use low-speed to operate.Catalyst of the present invention, at 0.3 ~ 1.0h-1Inside can ensure that acetic acid
Conversion ratio higher than 50%, preferred be higher than 75%, further preferred higher than 90%.
The composite can be widely applied to monocarboxylic Hydrogenation for alcohol, specifically, described monocarboxylic acid
One in acetic acid, propanoic acid, butanoic acid, lactic acid, 3-hydracrylic acid, itaconic acid or mixture.This
A little carboxylic acids derive from reproducible biomass resource, such as lactic acid, 3-hydracrylic acid, benzoic acid, acetic acid/propanoic acid
Deng mix acid liquor etc., it is also possible to derive from other oil replacement resources, such as acetic acid.It is furthermore preferred that it is described
Carboxylic acid is the one in acetic acid and propanoic acid or mixture.Further preferred carboxylic acid is acetic acid.
Method of the present invention, after hydrogen contacts with catalyst with carboxylic acid, product is in addition to alcohol, also
Have other by-products of trace, be mainly derived from (1) decarboxylation/decarbonylation product include carbon monoxide, carbon dioxide,
Alkane；(2) ketonization product；(3) alkyd/aldehyde condensation products；(4) dehydration product etc..For example,
For acetic acid preparation of ethanol through hydrogenation, product except main by ethanol and ethyl acetate in addition to, also acetaldehyde, ether,
Butanol, acetone, isopropanol, dimethoxym ethane, methane, ethane, propane, carbon monoxide, carbon dioxide etc..
Catalyst and method thereof that the present invention describes can ensure that carboxylic acid is converted into alcohol and the total of corresponding ester selects greatly
In 70%, the situation that more optimizes is more than 85%, and situation about optimizing further is more than 90%.
Relative to prior art, the hydrogenation of carboxylic acids catalyst of the present invention and method thereof have the advantage that simultaneously
(1) catalyst activity is higher, and purpose selectivity of product is high；
(2) catalyst manufacturing cost is the cheapest so that investment and operating cost reduce；
(3) reaction condition is gentleer, can run under wider operation condition, broadening operation window
Mouthful.
Embodiment
Following example are that citing more detailed to the present invention describes, but the invention is not limited in that these are real
Execute example.
Embodiment 1
Take the cobalt nitrate aqueous solution 1 liter of 1mol/L, add the precipitation two that people chemical plant, Guangzhou produces wherein
Silicon oxide 40g(silicon dioxide (SiO2) content % >=95.0, fineness (325 screen residue) %≤1.8,
Specific surface area is 400 ~ 600m2/ g), it is warming up to 60 degree, in the case of high degree of agitation, adds 20wt%'s
Aqueous sodium carbonate to pH value is 9.0.Progressively it is warming up to 85 DEG C, after constant temperature keeps 2 hours, adds nitre
Acid lanthanum 3.0g, continues constant temperature and is cooled to room temperature after 2 hours, be slowly added into boric acid 6.0g.Washing and filtering,
And be dried overnight and obtain dry cake, after this filter cake sprays into the silver nitrate solution 10ml containing 0.1wt%
Pelletize.Play sheet molding by after particle Roasting Decomposition, obtain catalyst CHZ-91.
Embodiment 2
Take the cobalt nitrate aqueous solution 1 liter of 1.2mol/L, add silver nitrate 1.0 grams and copper nitrate 10.2 wherein
Gram, after fully dissolving, in the case of high degree of agitation, add strong aqua ammonia (containing NH3Mass percent is about 28%)
0.6L, forms transparent complex solution.Being warming up to 70 DEG C, constant temperature, after 2 hours, is slowly added into 500g
In the sodium silicate solution of dilution in (dioxide-containing silica about 10wt%), at above-mentioned slurry species, then drip
Add calcium nitrate solution 100ml(calcium nitrate concentration 1.0mol/L), and continue to stir constant temperature 12 hours, add
Progressively slurry material is cooled to room temperature after boric acid 8g.By above-mentioned slurry thing filtration washing, and it is dried overnight
Obtain dry cake.Play sheet molding by after filter cake Roasting Decomposition, obtain catalyst CHZ-92.
Comparative example 1
Take 30 grams of silica supports (Haiyang Chemical Plant, Qingdao, water absorption rate is about 0.9g/g), by 60 grams of nitre
Acid cobalt and 1g silver nitrate are soluble in water, are prepared by the method combining repeatedly dipping-co-impregnation-incipient impregnation
Obtain presoma, and the 400 DEG C of roastings of this presoma are obtained catalyst CHZ-93.
Comparative example 2
According to method disclosed in CN200980134837.2, it is prepared for the silicon dioxide carried cobalt that a calcium is modified
-platinum catalyst, cobalt loading is 10wt% and platinum load capacity 0.85wt%.This catalyst is CHZ-94.
Embodiment 3
Above-mentioned catalyst is evaluated in fixed bed reactors, for acetic acid preparation of ethanol through hydrogenation, filling
Amount is 10ml, uses the quartz sand dilution of 1:1, uses pure hydrogen reduction, the reduction highest temperature before use
Degree is 450 ~ 500 DEG C, and concrete reaction condition and reaction result are as shown in table 1.
In the present embodiment, acetic acid conversion ratio and ethanol selectivity are according to the carbon molar content meter of each component
Calculate and obtain.
Other products have: acetaldehyde, ethane, methane, carbon monoxide, carbon dioxide, acetic acid aldehyde, acetone,
Propanol etc.；
Embodiment 4
Above-mentioned catalyst is evaluated in fixed bed reactors, is hydrogenated with for lactic acid (20wt% aqueous solution)
Preparing 1,2-PD, loadings is 10ml, uses the quartz sand dilution of 1:1, uses pure before use
Hydrogen reducing, reduction maximum temperature is 450 ~ 500 DEG C, institute in concrete reaction condition and reaction result such as table 2
Show.
In the present embodiment, rotational rate of lactic acid and 1,2-PD selectivity contain according to the carbon Mole percent of each component
Amount calculates and obtains.Other by-products include: normal propyl alcohol, isopropanol, 2-hydroxy-propionaldehyde, propane, ethane,
Carbon monoxide, carbon dioxide, ethanol, pentanedione etc..
Table 1
Table 2
Claims (17)
1. a hydrogenation of carboxylic acids prepares the catalyst of alcohol, it is characterised in that described catalyst includes following component:
(1) cobalt and boron, wherein cobalt tenor accounts for 10wt%～50wt% of overall catalyst weight, and it is total that boron accounts for catalyst
1.0wt%～10wt% of weight；
(2) oxide, described oxide selected from silicon oxide, zirconium oxide, titanium oxide, the one of aluminium oxide or
Multiple, its content accounts for 10wt%～80wt% of overall catalyst weight；
Described hydrogenation catalyst is by co-precipitation, deposition-precipitation, ammonia still process precipitation, sol-gel and ball milling side
One or more in method combine preparation.
Catalyst the most according to claim 1, it is characterised in that in described catalyst, cobalt tenor accounts for
20wt%～45wt% of overall catalyst weight, boron accounts for 1.5wt%～3wt% of overall catalyst weight.
Catalyst the most according to claim 1, it is characterised in that optionally with choosing in described catalyst
One or more elements in IB race, palladium, platinum, ruthenium, rhenium are as auxiliary agent, and it accounts for overall catalyst weight
0wt%～10wt%.
4. want the catalyst described in 3 according to right, it is characterised in that described auxiliary agent selected from silver, copper, palladium, ruthenium,
One or more elements in rhenium.
Catalyst the most according to claim 4, it is characterised in that described auxiliary agent is in silver, copper and rhenium
One or more elements.
Catalyst the most according to claim 5, it is characterised in that described auxiliary agent is silver and/or copper.
Catalyst the most according to claim 1, it is characterised in that described catalyst is optionally with alkali gold
Belonging to or alkaline-earth metal, its content accounts for 0wt～30wt% of catalyst total amount.
Catalyst the most according to claim 7, it is characterised in that described alkali metal or alkaline-earth metal are selected from
One or more in potassium, sodium, calcium, magnesium, barium, its content accounts for 0wt～15wt% of catalyst total amount.
Catalyst the most according to claim 1, it is characterised in that described catalyst is optionally with rare earth
Metallic element, its content accounts for 0wt～8wt% of catalyst total amount.
Catalyst the most according to claim 9, it is characterised in that described thulium be lanthanum or
Cerium, its content accounts for 0wt～5wt% of catalyst total amount.
11. catalyst according to claim 1, it is characterised in that described catalyst is optionally with removing
Inorganic non-metallic element outside boron element, its content accounts for 0wt～5wt% of catalyst total amount.
12. catalyst according to claim 11, it is characterised in that described inorganic non-metallic element is phosphorus
And/or fluorine, its content accounts for 0wt～2wt% of catalyst total amount.
The method that 13. 1 kinds of carboxylic acid gas phase hydrogenations prepare alcohol, it is characterised in that in fixed bed reactors, carboxylic acid steams
Vapour mixes with hydrogen-containing gas and is converted into alcohol and water after hydrogenation catalyst haptoreaction, wherein the rubbing of hydrogen and carboxylic acid
That ratio is 4:1～40:1, and reaction temperature is 180～350 DEG C, and reaction pressure is 0.3～8.0MPa, the volume of carboxylic acid
Air speed is 0.1～5.0h-1；
Described hydrogenation catalyst is the catalyst described in claim 1～12 any one, and described being used for adds
The carboxylic acid of hydrogen is monocarboxylic acid.
14. methods preparing alcohol according to hydrogenation of carboxylic acids as claimed in claim 13, it is characterised in that hydrogen and carboxylic
The molar ratio of acid is 8:1～20:1, and reaction temperature is 220～300 DEG C, and reaction pressure is 0.5～4.0MPa, carboxylic
The volume space velocity of acid is 0.2～2.0h-1。
15. according to the method described in claim 13 or 14, it is characterised in that described carboxylic acid be acetic acid, third
One in acid, butanoic acid, lactic acid, 3-hydracrylic acid, benzoic acid or mixture.
16. methods according to claim 15, it is characterised in that described carboxylic acid is in acetic acid, propanoic acid
One or mixture.
17. methods according to claim 16, it is characterised in that described carboxylic acid is acetic acid.
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| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
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| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104478A (en) * | 1977-11-23 | 1978-08-01 | Ashland Oil, Inc. | Catalytic hydrogenation of fatty acids |
| CN86102420A (en) * | 1985-04-13 | 1986-10-08 | Bp化学有限公司 | The method of carboxylic acid alcohols production by hydrogenation |
| CN102149662A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Ethanol production from acetic acid utillizing a cobalt catalyst |
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2012
- 2012-10-31 CN CN201210429995.4A patent/CN103785417B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104478A (en) * | 1977-11-23 | 1978-08-01 | Ashland Oil, Inc. | Catalytic hydrogenation of fatty acids |
| CN86102420A (en) * | 1985-04-13 | 1986-10-08 | Bp化学有限公司 | The method of carboxylic acid alcohols production by hydrogenation |
| CN86102452A (en) * | 1985-04-13 | 1986-12-03 | Bp化学有限公司 | By hydrogenation of carboxylic acids preparation alcohol |
| CN102149662A (en) * | 2008-07-31 | 2011-08-10 | 国际人造丝公司 | Ethanol production from acetic acid utillizing a cobalt catalyst |
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