CN103785412A - Carboxylic acid hydrogenation catalyst, preparation method and application thereof - Google Patents
Carboxylic acid hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a carboxylic acid hydrogenation catalyst containing a carrier, element cobalt and a second metal element. The element cobalt accounts for 15wt%-50wt% of the total weight of the catalyst; the second metal element is at least one selected from the group consisting of silver, copper, zinc, palladium, platinum and nickel, and accounts for 0.1wt%-25wt% of the total weight of the catalyst; and the carrier is at least one selected from silicon oxide, diatomite, calcium silicate, zirconium oxide and titanium oxide, and accounts for 20wt%-80wt% of the total weight of the catalyst. The catalyst has the advantages of high activity, high selectivity on target product, low manufacturing cost and mild reaction conditions.
Description
Technical field
The invention belongs to petrochemical field, more particularly, relate to a kind of Catalysts and its preparation method and the application that can be alcohol by high carboxylic acid yield hydro-conversion.
Background technology
It is long-standing that hydrogenation of carboxylic acids is prepared the research of alcohol, just applied for using ruthenium catalyst carboxylic acid to be converted into the method for alcohol as far back as nineteen fifty Ford etc.But due to last century petroleum resources cost comparatively cheap and the mankind are lower to sustainable development attention degree, therefore the production of alcohols adopts the technology such as olefin hydration, oxidation-hydration more.Enter after 21 century, along with the large-scale development to renewable system and oil replacement resource (coal, natural gas, shale gas, coal bed gas) etc., hydrogenation of carboxylic acids is prepared alcohol to be become and has more economy and continuable method.
The main technical difficulty that hydrogenation of carboxylic acids is prepared alcohol is to develop has high activity and catalyst optionally, reduce required reaction pressure, and catalyst need to possess the stability that has long-time use; The cost of catalyst need to be in rational scope, to guarantee its commercial value in addition.
US4104478 discloses a kind of hydrogenation of carboxylic acids catalyst and application process thereof, the catalyst using is M-rhenium bimetallic catalyst, M is the one in ruthenium, rhodium, platinum and palladium, under the condition of 170～250 ℃ and 2.0～14.0MPa, corresponding carboxylic acid is converted into fatty alcohol.But in disclosed embodiment, reaction pressure is all high in the extreme, is all greater than 7.0MPa.
US4517391 discloses the catalyst that a kind of acetic acid gas phase hydrogenation is prepared ethanol, and catalyst contains the cobalt that is no less than 50wt%, and one or more in copper, manganese, molybdenum, chromium and phosphoric acid.In unique embodiment, cobalt content is more up to 70%, and the reaction pressure of use is 300bar, and ethanol yield is 97%.This patent catalyst cobalt tenor is high, but owing to not using noble metal, cost has certain advantage, but this catalyst activity is lower, ethanol yield is 0.09kg/kg Cat/h only, consider catalyst cost still higher, and reactor will be very huge, therefore do not there is commercialization and be worth.The content of incoagulability gas phase in the unexposed tail gas of embodiment simultaneously, and material yield is lower than theoretical value.
CN1008088 discloses the loaded catalyst that a kind of hydrogenation of carboxylic acids is prepared alcohol, and the first component of catalyst is tungsten and molybdenum, and second component is the one in palladium, ruthenium and platinum, and carrier is active carbon.The noble metal that this catalyst contains 1～10wt%, with high costs; And reaction velocity is lower, the LHSV in embodiment is only 0.35h
-1, mean that space-time yield is lower than 0.26kg/m
3cat/h, reaction pressure is in an embodiment 1.0Mpa left and right.
CN201110104763.7 and CN201110103802.1 disclose a kind of acetic acid hydrogenation catalyst and application process thereof, the first active component of catalyst is tungsten and molybdenum, second component is the one in ruthenium, rhodium, platinum and palladium, carrier is active carbon or graphite, in its disclosed embodiment, reaction pressure is 7.0～10.0MPa.
At Aqueous-phase hydrogenation of lactic acid to propylene glycol, in Applied Catalysis A:General 219 (2001) 89-98, Zhang etc. have studied lactic acid water Hydrogenation for propane diols, the ruthenium catalyst of working load and trickle bed reactor, wherein water content is generally 40～80% water.In the method, the water of high level can significantly increase the energy consumption while separation undoubtedly; The Ru/C that the catalyst using is 5wt%, high catalyst 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 lower than 20wt%, and in catalyst, also contains palladium and the platinum of 1wt% left and right.In disclosed embodiment, cobalt content is all lower than 10wt%.
US7863489 discloses a kind of acetic acid hydrogenation catalyst, and catalyst activity component is platinum, and auxiliary agent is tin.Catalyst can be converted into ethanol with higher yield by acetic acid, but platinum content is higher, and in the embodiment announcing, platinum content exceedes 1wt%.As everyone knows, the price of platinum is very expensive and reserves are very limited, therefore in commercial applications, will make the cost of catalyst high.Same problem is also present in another patent US7608744, and Co catalysts content is lower, is about 10wt%, and catalyst need to use precious metal additive simultaneously, and as platinum and palladium, auxiliary agent content is higher than 1wt%.
In sum, in prior art, there is some technology and commercialization problem: catalyst is with high costs and produce that the raw material supplying amount of catalyst is limited, space-time yield is low, selectively lower, reaction pressure is higher makes that operating condition is too harsh, energy consumption is too high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of cobalt metallic catalyst that contains the second metallic element and preparation method thereof and its application in monocarboxylic acid hydrogenation, and this catalyst activity is higher, and object selectivity of product is high; Manufacturing cost is comparatively cheap; Reaction condition is gentleer.
One of object of the present invention is to provide a kind of hydrogenation of carboxylic acids catalyst, it is characterized in that catalyst contains carrier, cobalt element, the second metallic element, wherein the content of cobalt element accounts for the 15wt%～50wt% of catalyst gross weight, the second metallic element is selected from least one in silver, copper, zinc, palladium, platinum, nickel, its content accounts for the 0.1wt%～25wt% of catalyst gross weight, described carrier is selected from least one of silica, diatomite, calcium silicates, zirconia, titanium oxide, and its content accounts for the 20wt%～80wt% of catalyst gross weight.
Detailed description of the present invention:
The main active component of catalyst of the present invention is cobalt, and wherein cobalt tenor accounts for the 15wt%～50wt% of catalyst gross weight, and preferred content is 20wt%～40wt%, and described cobalt tenor refers to the content of element cobalt.Those skilled in the art often think that the content of the main active component of raising can improve the activity of catalyst, but inventor is surprised to find that: when compared with low cobalt content, the activity of catalyst is lower, and more the cobalt of high-load not only makes the cost of catalyst rise, and can not improve the activity of catalyst, decline even to some extent, in the time of high level, significantly decrease; Preparation difficulty at cobalt content catalyst higher than 50wt% time increases, and as forming process etc., this will make the comparatively difficulty of commercialization of catalyst.The source of cobalt metal can be selected from water miscible nitrate, sulfate, villaumite, acetate, oxalates and bromine salt, specifically, be selected from one or more in cobalt nitrate, cobalt chloride, cobalt oxalate, cobaltous sulfate, cobalt acetate, more preferably one or more in cobalt nitrate, cobalt acetate and cobalt oxalate.
Described catalyst also contains the second metal component, this metal component can with ammonia form water soluble complex.More particularly, the second described metal component be in silver, copper, zinc, palladium, platinum, nickel one or more, account for the 0.1wt%～25.0wt% of catalyst gross weight, preferred weight range is 0.5wt%～15wt%.The source of the second metal component is at least one in water miscible nitrate, villaumite, acetate, specifically, be selected from silver nitrate, copper nitrate, copper chloride, copper sulphate, Schweinfurt green, zinc nitrate, nickel nitrate, palladium nitrate, palladium bichloride, palladium, chloroplatinic acid, platinum nitrate, ammonium chloroplatinate etc.Can greatly improve the activity of catalyst, selective and stability appropriate bimetallic adding, and reason may be many-sided: suppressed growing up of cobalt crystal grain, suppressed the oxidation of cobalt or activated carboxylic acid.In addition, with respect to additive method, the Co catalysts of preparing by steaming ammonium method, the effect that the second metal component improves catalyst reaction performance is more obvious, more embodies the present invention program's superiority.
In described catalyst, contain oxide component, its content accounts for the 20wt%～80wt% of catalyst gross weight.Described oxide component is selected from one or more in silica, zirconia, titanium oxide, preferential oxidation silicon.These oxides mainly play the effect of carrier, not only play a supporting role, and can also assist the dispersion of active component or the activation of carboxylic acid.The critical index such as structural behaviour, product and the raw material that therefore these carriers affect catalyst diffusion, mechanical strength, activity and stability therein.
Described silica support can be selected from waterglass precipitate method, SiO 2 powder, teos hydrolysis, Ludox etc.Described waterglass precipitate method refers to take waterglass as raw material, adds acidic precipitation agent or ion precipitation agent, as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, calcium nitrate, zirconyl nitrate, zirconium oxychloride, magnesium nitrate, cobalt nitrate etc. in waterglass.Precipitating reagent adds the white jelly of rear formation, uses or the precipitation method of carrying out other components on this basis add after washing for several times.Described SiO 2 powder can pass through dry after chemical deposition, waterglass precipitate after ball milling obtain or Ludox spraying is dry etc. that method obtains, its size is selected from 10nm～500 μ m; As the gross porosity microballoon silica that Haiyang Chemical Plant, Qingdao produces, average pore size is 8.0～12.0nm, and specific area is 300～600m2/g, and pore volume is 0.8～1.1ml/g; The precipitated silica that and for example Guangzhou people chemical plant produces, dioxide-containing silica %>=95.0, fineness (325 screen residue) %≤1.8, specific area is 400～600m
2/ g or active carbon white; The and for example aerosil AEROSIL 200 of goldschmidt chemical corporation, its specific surface is 200m
2/ g; The and for example dry silicon dioxide microsphere obtaining of self-control spraying, specific surface is 400～500m
2/ g, is of a size of 2～30 μ m.SiO 2 powder can add as carrier in precipitation or deposition-precipitation method.Ethyl orthosilicate is to prepare in catalyst of the present invention and use in sol-gel process.Ludox, as liquid-state silicon source, can directly use in the precipitation system that enters precipitation, the deposition-precipitation method.
Described diatomite is a kind of natural porous material, mainly by unbodied SiO
2form and contain a small amount of Fe
2o
3, CaO, MgO, Al
2o
3and organic impurities, there is special porous structure.As the diatomite of governor Bai Xian green hill, Jilin source diatomite company production.
Described Zirconia carrier is selected from powder zirconia material or obtains by the precipitation of zirconates.Powder zirconia size is selected from 10nm～500 μ m, and specific surface is greater than 20m
2/ g.The sediment of zirconates can be realized according to following approach: first zirconium oxychloride is dissolved in water, adds subsequently the highly basic such as caustic soda, the gel finally sediment washing and filtering being obtained; Or use zirconyl nitrate as zirconium source, the gel that adds the rear washing and filtering of caustic soda precipitation to obtain.Above-mentioned gel is joined in other sediments, or add as the carrier of deposition-precipitation after above-mentioned gel is worn into powder after super-dry.
Titanium dioxide carrier in the present invention can be commercially available titanium dioxide, as the P25 of goldschmidt chemical corporation, also can adopt the method preparation of liquid-phase precipitation, as adopt titanium tetrachloride or titanium sulfate as titanium source, add urea, ammoniacal liquor, sodium carbonate or caustic soda etc. as precipitating reagent, also can adopt organic metatitanic acid as butyl titanate hydrolysis preparation.
Described catalyst can also contain alkali metal or alkaline-earth metal, and described alkali metal or alkaline earth metal content account for the 0.1wt%～10wt% of catalyst total amount.Specifically, described alkali metal or alkaline-earth metal are selected from one or more in potassium, sodium, calcium, magnesium, barium, and content accounts for the 0.2wt%～5wt% of catalyst total amount.Alkali and alkaline earth metal ions source can be water miscible nitrate, carbonate, villaumite, phosphate, sulfate, acetate, fluoride, hydroxide etc.Specifically, alkali and alkaline earth metal ions source is selected from one or more in potassium hydroxide, potassium nitrate, potash, potassium acetate, potassium fluoride, potassium phosphate, NaOH, sodium nitrate, sodium carbonate, sodium acid carbonate, sodium chloride, sodium sulphate, sodium acetate, calcium nitrate, calcium dihydrogen phosphate, magnesium nitrate, magnesium phosphate, barium nitrate.
Described catalyst can also contain thulium, and its oxide content accounts for the 0.1wt%～8wt% of catalyst total amount; Described thulium is selected the one in lanthanum or cerium, and its oxide content preferably accounts for the 0.5wt%～5wt% of catalyst total amount.Add micro-rare earth element can reduce incoagulable gas content and make selective the raising to a certain extent of Co catalysts.
Described catalyst can also contain one or more inorganic non-metallic elements, and content accounts for the 0.1wt%～5wt% of catalyst total amount.Specifically, described inorganic non-metallic element is selected from the one in phosphorus, boron, fluorine, and content accounts for the 0.3wt%～2wt% of catalyst total amount.Adding of these inorganic non-metallic elements, what have is accompanied by adding of other auxiliary agents and enters catalyst system, as potassium fluoride.Have plenty of by extra mode and add, as adopted adding of boron, boric acid aqueous solution is added to the mode in filter cake.
The concise and to the point step of the steaming ammonium precipitation method of the present invention is as follows: (1) is dissolved in the water cobalt salt and the second slaine, also may contain other metals or non-metal salt; (2) ammoniacal liquor is progressively added in above-mentioned salting liquid, form complex compound with ammonia, as cuprammonium complex, cobalt ammonium complex compound, silver-colored ammonium complex compound etc.; (3) add other components, for example carrier and alkaline earth metal component; (4) heat up and progressively ammonia is evaporated, cobalt and other components precipitate; (5) washing, filtration; (6) dry, roasting.Above-mentioned steps has just been enumerated some steps necessarys wherein, and order do not have strict requirement, and professional and technical personnel can add some steps or change number of times the essence that does not change invention as required.
The mode that adds of alkali and alkaline earth metal ions element can be selected from any one in following mode: in precipitation process, add respectively with cobalt salt; In catalyst precursor, add respectively, as in precipitation, obtain dry after in filter cake, or in material after Roasting Decomposition; Or add beating the formative stage such as sheet or extrusion.
Another object of the present invention is to provide and a kind of above-mentioned catalyst is applied to the method that hydrogenation of carboxylic acids is prepared alcohol.Specifically, be that monocarboxylic acid is gasified and mixed with hydrogen, or enter in hydrogenation reactor after monocarboxylic acid is gasified in hydrogen, and contact and be converted into fatty alcohol and water with catalyst of the present invention.
The reactor of Catalyst packing is fixed bed reactors, preferably shell and tube reactor.Specifically, be by Catalyst packing in pipe, and filling heat-conducting medium between pipe, as conduction oil or water etc., is more conducive to shifting out of reaction heat like this.Those skilled in the art all knows this technical key point, as every pipe loadings need be consistent etc.
Catalyst of the present invention is in the time being applied in hydrogenation of carboxylic acids, need to by its fully reduction activation make most cobalts carrying out being all reduced to zeroth order state before hydrogenation reaction, the mode of activation can be under Elevated Temperature Conditions, to pass into hydrogen, use reducing agent as Boratex etc. or adopt the method for ionizing radiation.These methods are all by those skilled in the art is known.
Method of hydrotreating of the present invention, reaction temperature is 180～350 ℃, more preferably 220～300 ℃, less in the selective variation of this scope inner catalyst, maintain higher level.When reaction temperature is lower, carboxylic acid conversion ratio is lower, and this increases circulating consumption; And reaction temperature is while continuing to raise, accessory substance especially incoagulable gas product significantly increases as the amount of ethane.
Be prepared as the reaction of alcohol for monocarboxylic acid hydrogenation, hydrogen consumption and monocarboxylic mol ratio are 2 in theory, but for maintaining subsequent reactions pressure and catalyst life, hydrogen and monocarboxylic molar ratio are 4: 1～40: 1, more ratio of greater inequality is 6: 1～25: 1, and further Optimal Ratio is 8: 1～20: 1.From reactor thick product out, after gas-liquid separator, excessive hydrogen can recycle.
Catalyst selectivity of the present invention is higher, therefore in accessory substance incoagulable gas selectively lower than 10%, in more excellent situation lower than 5%, in further optimization situation lower than 2%.
The reaction pressure of method of hydrotreating of the present invention is 0.3～8.0MPa, and preferred reaction pressure is 0.5～4.0MPa, and the reaction pressure of further optimizing is 1.0～2.5MPa.The reaction pressure that the present invention uses, with respect to the disclosed reaction pressure of many hydrogen addition technologies is much lower before, this makes reaction condition gentleer, and has reduced cost.
In method of the present invention, monocarboxylic volume space velocity is 0.1～5.0h
-1; Preferred volume space velocity is 0.2～2.0h
-1.Air speed is actual is to wish that according to factory extraction product composition is relevant with later separation ability, the present invention is not restricted in force, this be due to: in the time that air speed is higher, although acetic acid conversion ratio is lower, but the productive rate of ethanol and ethyl acetate and can increasing on the contrary, particularly ethyl acetate selectively can improve; In the time that air speed is lower, acetic acid conversion ratio is high, but the productive rate of ethanol may reduce, therefore for having separating power and wishing the factory of voluminous ethyl acetate, high-speed operator scheme can be adopted, and for the less factory of later separation ability, low-speed operation can be adopted.Catalyst of the present invention, at 0.3～1.0h
-1the interior conversion ratio that can guarantee acetic acid is higher than 50%, preferred higher than 75%, further preferably higher than 90%.
Catalyst of the present invention can be widely used in monocarboxylic acid hydrogenation and be prepared as alcohol, and particularly, described monocarboxylic acid is selected from one or the mixture in acetic acid, propionic acid, butyric acid, lactic acid, 3-hydracrylic acid, itaconic acid.These carboxylic acids derive from reproducible biomass resource, as mix acid liquors such as lactic acid, 3-hydracrylic acid, benzoic acid, acetic acid/propionic acid etc., also can derive from other oil replacement resources, as acetic acid.Preferred, described monocarboxylic acid is one or the mixture in acetic acid and propionic acid.Further preferred monocarboxylic acid is acetic acid.
Method of the present invention, after contacting with catalyst with hydrogen when monocarboxylic acid, product, except alcohol, also has other accessory substances of trace, is mainly derived from (1) decarboxylation/decarbonylation product and comprises carbon monoxide, carbon dioxide, alkane; (2) ketonization product; (3) alkyd/aldehyde condensation products; (4) dehydration product etc.For example, for acetic acid Hydrogenation, for ethanol, product by ethanol and ethyl acetate, also has acetaldehyde, ether, butanols, acetone, isopropyl alcohol, dimethoxym ethane, methane, ethane, propane, carbon monoxide, carbon dioxide etc. except mainly.The catalyst that the present invention describes and application thereof can guarantee that carboxylic acid is converted into alcohol and is greater than 70% with total selection rate of corresponding ester, and more optimization situation is greater than 85%, and situation about further optimizing is greater than 90%.
With respect to prior art, hydrogenation of carboxylic acids catalyst of the present invention and application thereof have the following advantages:
(1) catalyst activity is higher, and object selectivity of product is high;
(2) catalyst manufacturing cost is comparatively cheap, and investment and operating cost are reduced;
(3) reaction condition is gentleer, can under wider operation condition, move, broadening action pane.
The specific embodiment
With embodiment, the present invention is described below, but and unrestricted invention scope.Embodiment 1
Get 1 liter of the cobalt nitrate aqueous solution of 1mol/L, add therein 7.5 grams of 1.68 grams of silver nitrates and zinc nitrates, after fully dissolving, the in the situation that of high degree of agitation, add concentrated ammonia liquor (containing NH
3mass percent is about 28%) 0.5L, form transparent complex solution.In above-mentioned complex solution, add people chemical plant, Guangzhou produce precipitated silica 40g (specific area is 400～600m for dioxide-containing silica %>=95.0, fineness (325 screen residue) %≤1.8
2/ g).Progressively be warming up to 85 ℃, constant temperature keeps, after 2 hours, adding lanthanum nitrate 3.0g, continues constant temperature 2 hours.By above-mentioned slurry state thing filtration washing, and dried overnight obtains dry cake, and on filter cake spray dilution phosphoric acid liquid 10ml.By playing sheet moulding after filter cake Roasting Decomposition, obtain catalyst CHZ-31.
Embodiment 2
Get 0.8 liter of the cobalt nitrate aqueous solution of 1.5mol/L, add therein 5.8 grams of 2.0 grams of silver nitrates and copper nitrates, after fully dissolving, the in the situation that of high degree of agitation, add concentrated ammonia liquor (containing NH
3mass percent is about 28%) 0.6L, form transparent complex solution.Be warming up to 70 ℃, after constant temperature 2 hours, join lentamente in the sodium silicate solution of 500g dilution in (the about 10wt% of dioxide-containing silica), at above-mentioned slurry state species, drip again calcium nitrate solution 100ml (calcium nitrate concentration 1.0mol/L), and continue to stir constant temperature 12 hours.By above-mentioned slurry state thing filtration washing, and dried overnight obtains dry cake.By playing sheet moulding after filter cake Roasting Decomposition, obtain catalyst CHZ-32.
Comparative example 1
Get 30 grams of silica supports (Haiyang Chemical Plant, Qingdao, water absorption rate is about 0.9g/g), by soluble in water to 60 grams of cobalt nitrates and 1g silver nitrate, by preparing presoma in conjunction with the method for dipping-total immersion stain-incipient impregnation repeatedly, and by 400 ℃ of roastings acquisition catalyst CHZ-33 of this presoma.Comparative example 2
According to the disclosed method of CN200980134837.2, prepare the silicon dioxide carried cobalt-platinum catalyst of a calcium modification, cobalt loading is 10wt% and platinum load capacity 0.85wt%.This catalyst is CHZ-34.Embodiment 3
Above-mentioned catalyst is evaluated in fixed bed reactors, and for acetic acid Hydrogenation, for ethanol, loadings is 10ml, adopt the quartz sand dilution of 1: 1, adopt before use pure hydrogen reduction, reduction maximum temperature is 450～500 ℃, and concrete reaction condition and reaction result are as shown in table 1.
In the present embodiment, acetic acid conversion ratio and ethanol selectively calculate and obtain according to the carbon molar content of each component.
Other products
Table 1 reaction condition and result
As can be seen from Table 1, catalyst activity of the present invention is high, selectively high.
Embodiment 4
Above-mentioned catalyst is evaluated in fixed bed reactors, be used for lactic acid (the 20wt% aqueous solution) Hydrogenation for 1,2-propane diols, loadings is 10ml, adopt the quartz sand dilution of 1: 1, adopt before use pure hydrogen reduction, reduction maximum temperature is 450～500 ℃, and concrete reaction condition and reaction result are as shown in table 2.
In the present embodiment, rotational rate of lactic acid and 1,2-PD selectively calculate and obtain according to the carbon molar content of each component.Other accessory substances comprise: normal propyl alcohol, isopropyl alcohol, 2-hydroxyl-propionic aldehyde, propane, ethane, carbon monoxide, carbon dioxide, ethanol, pentanedione etc.
Table 2 reaction condition and result
As can be seen from Table 2, catalyst activity of the present invention is high, selectively high.
Claims (21)
1. a hydrogenation of carboxylic acids catalyst, it is characterized in that catalyst contains carrier, cobalt element, the second metallic element, wherein the content of cobalt element accounts for the 15wt%～50wt% of catalyst gross weight, the second metallic element is selected from least one in silver, copper, zinc, palladium, platinum, nickel, its content accounts for the 0.1wt%～25wt% of catalyst gross weight, described carrier is selected from least one of silica, diatomite, calcium silicates, zirconia, titanium oxide, and its content accounts for the 20wt%～80wt% of catalyst gross weight.
2. hydrogenation of carboxylic acids catalyst according to claim 1, is characterized in that described catalyst makes by ammonia still process method, comprises the following steps: (1) is dissolved in the water cobalt salt and the second slaine; (2) ammoniacal liquor is progressively added in above-mentioned salting liquid, form complex compound with ammonia; (3) add carrier; (4) heat up, progressively by ammonia evaporation, solid constituent precipitation; (5) washing, filtration; (6) dry, roasting.
3. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, is characterized in that the second described metallic element derives from least one in water miscible nitrate, villaumite, acetate, and its content accounts for the 0.5wt%～15wt% of catalyst gross weight.
4. hydrogenation of carboxylic acids catalyst according to claim 3, is characterized in that the second described metallic element derives from silver nitrate, copper nitrate, copper chloride, copper sulphate, Schweinfurt green, zinc nitrate, nickel nitrate, palladium nitrate, palladium bichloride, palladium, chloroplatinic acid, platinum nitrate, ammonium chloroplatinate.
5. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, is characterized in that described cobalt element derives from water miscible nitrate, sulfate, villaumite, acetate, oxalates and bromine salt, and its content accounts for the 20wt%～40wt% of catalyst gross weight.
6. hydrogenation of carboxylic acids catalyst according to claim 5, is characterized in that the source of described cobalt element is selected from least one in water miscible cobalt nitrate, cobalt chloride, cobalt oxalate, cobaltous sulfate, cobalt acetate.
7. hydrogenation of carboxylic acids catalyst according to claim 6, is characterized in that the source of described cobalt element is selected from least one in water miscible cobalt nitrate, cobalt oxalate, cobalt acetate.
8. hydrogenation of carboxylic acids catalyst according to claim 1, is characterized in that described carrier is silica.
9. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, is characterized in that described catalyst also contains thulium, and its oxide content accounts for the 0.1wt%～8wt% of catalyst total amount.
10. hydrogenation of carboxylic acids catalyst according to claim 9, is characterized in that described thulium is lanthanum or cerium, and its oxide content accounts for the 0.5wt%～5wt% of catalyst total amount.
11. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, is characterized in that described catalyst also contains at least one inorganic non-metallic element, and its content accounts for the 0.1wt%～5wt% of catalyst total amount.
12. hydrogenation of carboxylic acids catalyst according to claim 11, is characterized in that described inorganic non-metallic element is selected from the one in phosphorus, boron, fluorine, and its content accounts for the 0.3wt%～2wt% of catalyst total amount.
13. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, is characterized in that described catalyst also contains alkali metal or alkali earth metal, and its content accounts for the 0.1wt%～10wt% of catalyst total amount.
14. hydrogenation of carboxylic acids catalyst according to claim 13, is characterized in that described alkali metal or alkali earth metal are at least one in potassium, sodium, calcium, magnesium, barium, and its content accounts for the 0.2wt%～5wt% of catalyst total amount.
15. hydrogenation of carboxylic acids catalyst according to claim 13, is characterized in that described alkali metal or alkali earth metal derive from water miscible nitrate, carbonate, villaumite, phosphate, sulfate, acetate, fluoride, hydroxide.
16. hydrogenation of carboxylic acids catalyst according to claim 15, is characterized in that described alkali metal or alkali earth metal derive from least one in potassium hydroxide, potassium nitrate, potash, potassium acetate, potassium fluoride, potassium phosphate, NaOH, sodium nitrate, sodium carbonate, sodium acid carbonate, sodium chloride, sodium sulphate, sodium acetate, calcium nitrate, calcium dihydrogen phosphate, magnesium nitrate, magnesium phosphate, barium nitrate.
The described hydrogenation of carboxylic acids catalyst of one of 17. claim 1-16 at monocarboxylic acid Hydrogenation for the application in the reaction of alcohol.
Hydrogenation of carboxylic acids catalyst described in 18. claims 17 is prepared the application in the reaction of alcohol at acetic acid hydrogenation.
19. according to the application of the hydrogenation of carboxylic acids catalyst described in claim 17 or 18, it is characterized in that contacting with hydrogenation of carboxylic acids catalyst after monocarboxylic acid, hydrogen-containing gas become mist, be converted into alcohol and water, hydrogen and monocarboxylic molar ratio are 4: 1～40: 1, reaction temperature is 180～350 ℃, reaction pressure is 0.3～8.0MPa, and monocarboxylic volume space velocity is 0.1～5.0h
-1.
The application of 20. hydrogenation of carboxylic acids catalyst according to claim 19, it is characterized in that hydrogen and monocarboxylic molar ratio are 6: 1～25: 1, reaction temperature is 220～300 ℃, and reaction pressure is 0.5～4.0MPa, and monocarboxylic volume space velocity is 0.2～2.0h
-1.
The application of 21. hydrogenation of carboxylic acids catalyst according to claim 20, is characterized in that hydrogen and monocarboxylic molar ratio are 8: 1～20: 1, and reaction pressure is 1.0～2.5MPa, and monocarboxylic volume space velocity is 0.3～1.0h
-1.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| CN105536802A (en) * | 2015-12-17 | 2016-05-04 | 中国科学院上海高等研究院 | Micro-nano structure copper-based catalyst and preparation method and application thereof |
| CN105566059A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for preparing ethanol and co-producing mixed solvent through acetic acid hydrogenation |
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| CN107321357A (en) * | 2017-05-24 | 2017-11-07 | 沈阳三聚凯特催化剂有限公司 | A kind of preparation method and applications of acetic acid hydrogenation catalyst |
| CN107486210A (en) * | 2016-06-12 | 2017-12-19 | 河南中宏清洁能源股份有限公司 | A kind of catalyst for acetic acid one-step method ethanol and preparation method thereof |
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| CN114073963A (en) * | 2020-08-13 | 2022-02-22 | 国家能源投资集团有限责任公司 | Method for preparing ethanol by acetic acid hydrogenation, catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof |
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| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9458072B2 (en) | 2014-04-28 | 2016-10-04 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| CN105566060A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for preparing ethanol through acetic acid hydrogenation |
| CN105566063A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Ethanol preparation method |
| CN105566059A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for preparing ethanol and co-producing mixed solvent through acetic acid hydrogenation |
| CN105566060B (en) * | 2014-10-14 | 2019-02-19 | 中国石油化工股份有限公司 | The method of acetic acid preparation of ethanol through hydrogenation |
| CN105536802A (en) * | 2015-12-17 | 2016-05-04 | 中国科学院上海高等研究院 | Micro-nano structure copper-based catalyst and preparation method and application thereof |
| CN107282104A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The catalyst synthesized for 1,4 cyclohexane dimethanol |
| CN107282104B (en) * | 2016-04-12 | 2020-02-07 | 中国石油化工股份有限公司 | Catalyst for synthesizing 1, 4-cyclohexanedimethanol |
| CN107486210A (en) * | 2016-06-12 | 2017-12-19 | 河南中宏清洁能源股份有限公司 | A kind of catalyst for acetic acid one-step method ethanol and preparation method thereof |
| CN107321357A (en) * | 2017-05-24 | 2017-11-07 | 沈阳三聚凯特催化剂有限公司 | A kind of preparation method and applications of acetic acid hydrogenation catalyst |
| CN114073963A (en) * | 2020-08-13 | 2022-02-22 | 国家能源投资集团有限责任公司 | Method for preparing ethanol by acetic acid hydrogenation, catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof |
| CN114433128A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Furfural hydrogenation catalyst, preparation method and application thereof, and method for preparing furfuryl alcohol by furfural gas-phase hydrogenation |
| CN113559879A (en) * | 2021-07-27 | 2021-10-29 | 大连理工大学 | Low-temperature synthesis method and application of corrosion-resistant high-entropy alloy nano-catalyst |
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