CN103785415B - Hydrogenation of carboxylic acids prepares the cobalt bismuth catalyst of alcohol - Google Patents
Hydrogenation of carboxylic acids prepares the cobalt bismuth catalyst of alcohol Download PDFInfo
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Abstract
The present invention relates to a kind of at least containing cobalt and bismuth catalyst and be applied to the method that hydrogenation of carboxylic acids is prepared as alcohol.In the present invention, the catalyst of use is at least containing the cobalt of 10wt% ~ 40wt% and the bismuth of 3wt% ~ 30wt% that account for overall catalyst weight.By this catalyst, under 220 ~ 300 DEG C and 0.5 ~ 4.0MPa condition, carboxylic acid can with higher than 90% be selectively converted to corresponding alcohol and ester, the catalyst activity used is high, good stability and cost is lower, and the reaction condition used is not harsh, therefore more easily realizes commercial operation.
Description
Technical field
The present invention relates to a kind of can be cobalt bismuth catalyst and the methods for making and using same thereof of alcohol by carboxylic acid height yield hydro-conversion.
Technical background
It is the important chemical reaction of a class that hydrogenation of carboxylic acids prepares alcohol, as acetic acid hydrogenation prepare ethanol, lactic acid Hydrogenation all also exists demand urgently for propane diols.This causes due to multiple reason: due to technique progress, cause the manufacturing cost of carboxylic acid to reduce, and if acetic acid is along with the maturation of methanol carbonyl method, manufacturing cost reduces; Or because raw material changes, make the manufacture of carboxylic acid have sustainability, as biomass derivatives such as lactic acid, 3-hydracrylic acids.
The Hydrogenation of carboxylic acid is long-standing for the research of alcohol, as as far back as nineteen fifty, Ford etc. have just applied for using the method that Carboxylic Acid is alcohol by ruthenium catalyst, but because petroleum resources cost in last century is comparatively cheap and the sustainable development attention degree of the mankind is lower, therefore the production of alcohols adopts the technology such as olefin hydration, oxidation-hydration more.After entering 21 century, people to the large-scale development of renewable system and oil replacement resource (coal, natural gas, shale gas, coal bed gas) etc., make hydrogenation of carboxylic acids prepare alcohol become alcohols produce have more economy and continuable method.
In fact hydrogenation of carboxylic acids is prepared alcohol and is had high challenge, main technical difficulty is to develop has high activity and optionally catalyst, reaction pressure needed for reduction, and catalyst needs to have the long-time stability used, the cost of certain catalyst needs in rational scope, to ensure its commercial value.
US4104478 discloses a kind of hydrogenation of carboxylic acids catalyst and application process thereof, the catalyst used is M-rhenium bimetallic catalyst, M is the one in ruthenium, rhodium, platinum and palladium, under the condition of 170 ~ 250 DEG C and 2.0 ~ 14.0MPa, is fatty alcohol by corresponding Carboxylic Acid.Disclosed embodiment pressure all in the extreme high (>7.0MPa).
US4517391 discloses the catalyst that a kind of acetic acid gas phase hydrogenation prepares ethanol, and catalyst contains the cobalt being no less than 50wt%, one or more in Yi Jitong, 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%.Although this proprietary catalysts 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/kgCat/h only, consider catalyst cost still higher, and reactor will be very huge, therefore do not there is commercialization and be worth.Simultaneously in the unexposed tail gas of embodiment the content of incoagulability gas phase and material yield lower than theoretical value.
CN1008088 discloses the loaded catalyst that a kind of hydrogenation of carboxylic acids prepares 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.This catalyst contains the noble metal of 1 ~ 10wt%, with high costs; And reaction velocity is lower, and (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 about 1.0Mpa.CN201110104763.7 and CN201110103802.1 discloses a kind of acetic acid hydrogenation catalyst and application process thereof, 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 embodiment disclosed in it, reaction pressure is 7.0 ~ 10.0MPa.
Zhang etc. have studied lactic acid aqueous phase Hydrogenation for propane diols, the ruthenium catalyst of working load and trickle bed reactor, wherein water content is generally the water (Aqueous-phasehydrogenationoflacticacidtopropyleneglycol, AppliedCatalysisA:General219 (2001) 89-98) of 40 ~ 80%.In the method, this energy consumption when significantly can increase separation undoubtedly of water of high level; The Ru/C that the catalyst used 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 lower than 20wt%, and also contains palladium and the platinum of about 1wt% in catalyst.Cobalt content is all lower than 10wt% in the embodiment disclosed.
US7863489 discloses a kind of acetic acid hydrogenation catalyst, and catalyst activity component is platinum, and auxiliary agent is tin.Acetic acid can be converted into ethanol with higher yield by catalyst, but platinum content is higher, in the embodiment announced, platinum content is more than 1wt%, as everyone knows, the price of platinum is very expensive and reserves are very limited, and the cost of catalyst therefore will be made in commercial applications high.Same problem is also present in another patent US7608744, Co catalysts content lower (~ 10wt%), and catalyst needs to use precious metal additive simultaneously, and as platinum and palladium, auxiliary agent content is higher than 1wt%.
CN102149662 discloses a kind of acetic acid hydrogenation catalyst containing cobalt, preparation method is infusion process, the load capacity of cobalt is 0.1wt% ~ 20wt%, in embodiment disclosed in it, cobalt loading is at 5wt% ~ 10wt%, and the auxiliary agent used uses precious metal additive, as platinum and palladium, auxiliary agent content is higher than 1wt%, and this will make the cost of catalyst extremely high, or for having the chromium auxiliary agent compared with high pollution; And the conversion ratio of acetic acid is lower, although inventor's its space-time yield unexposed, the embodiment data provided by it, can calculate its space-time yield lower, cobalt-chrome catalysts disclosed in it, and 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 is with high costs and produce that the raw material supplying amount of catalyst is limited, space-time yield is low, selective lower, reaction pressure is higher makes that operating condition is too harsh, energy consumption is too high.
Method of the present invention, under relatively mild reaction condition, with higher yield, acetic acid can be converted into 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 containing bismuth auxiliary agent that uses and monocarboxylic acid is hydrogenated to alcohol catalyst, this catalyst not only has the feature of active high, selective height and good stability, and cost is comparatively cheap, and forms comparatively environmental protection.
A kind of hydrogenation of carboxylic acids of the present invention prepares the catalyst of alcohol, and described catalyst comprises following component:
(1) containing cobalt and bismuth, wherein cobalt tenor accounts for the 10wt% ~ 50wt% of overall catalyst weight, and bismuth metal accounts for the 0.1wt% ~ 50wt% of overall catalyst weight;
(2) oxide, described oxide be selected from silica, diatomite, calcium silicates, zirconia, titanium oxide, aluminium oxide one or more, its content accounts for the 10wt% ~ 80wt% of overall catalyst weight;
Described hydrogenation catalyst passes through dipping, co-precipitation, deposition-precipitation, ammonia still process precipitation, sol-gel, dissolves for one or more in suction filtration after alloy and ball grinding method 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 the 10wt% ~ 50wt% of overall catalyst weight, and preferred content accounts for the 15wt% ~ 45wt% of overall catalyst weight, preferably accounts for the 10wt% ~ 40wt% of overall catalyst weight further; Described cobalt tenor refers to the content of element cobalt.The content of Co catalysts is through that inventor carefully filters out: lower compared with the activity of catalyst during low cobalt content, this can make the ethanol space-time yield of catalyst remain at low levels, because carboxylic acid has stronger corrosivity, therefore the reactor that its direct hydrogenation prepares alcohol generally needs the stainless steel material used costly, and the cost of reactor can be made when therefore space-time yield is lower high; And more the cobalt of high-load not only makes the cost increase of catalyst, and the activity of catalyst can not be improved, even make activity decline to some extent, significantly decrease when high level.This result is unexpected: because often it is believed that improving tenor can improve the activity of catalyst.Further, inventor finds to increase in the preparation difficulty of cobalt content higher than catalyst when 50wt%, and as forming process etc., this will make the commercialization of catalyst comparatively difficult.
The source of cobalt metal can be selected from water miscible slaine as nitrate, sulfate, villaumite, acetate, oxalates and bromine salt, or is selected from metallic cobalt, as cobalt metallic plate etc.Water-soluble metal salt is selected from one or more in cobalt nitrate, cobalt chloride, cobalt oxalate, cobaltous sulfate, cobalt acetate more specifically, is more preferably one or more in cobalt nitrate, cobalt acetate and cobalt oxalate.
Bismuth is another kind of important composition component in catalyst of the present invention, and appropriate bismuth auxiliary agent adds the activity drastically increasing catalyst, selective and stability, and more embodies the superiority of the present invention program by the catalyst that specific preparation method obtains.
After bismuth auxiliary agent adds, the index that catalyst activity and stability etc. represent catalyst reaction performance significantly improves, and reason wherein may be many-sided: bismuth improves the electronics form of cobalt or activated carboxylic acid.More unexpected, the present inventor finds, by co-precipitation, deposition-precipitation with dissolve the Co catalysts that after for alloy prepared by suction filtration, the effect that bismuth auxiliary agent improves catalyst reaction performance is more obvious.
Bismuth metal accounts for the 0.1wt% ~ 50wt% of overall catalyst weight, and preferred content accounts for the 1wt% ~ 40wt% of overall catalyst weight further, and the content more optimized is 3wt% ~ 30wt%.
Not limiting the source of bismuth, can be known all bismuth-containing compounds.There are bismuth metal, bismuth oxide, bismuth nitrate, novismuth, basic bismuth carbonate, bismuth chloride, Bismuth Oxychloride and organo-bismuth etc. in the source of the bismuth of further optimization.
Method for preparing catalyst of the present invention can be obtained by existing catalyst preparation technology, as the method such as infusion process, ion-exchange, blending method, kneading method, co-precipitation, deposition-precipitation, steaming ammonium precipitation, melting-suction filtration, ball milling and sol-gel.Preferred method comprises one or more the combination in co-precipitation, deposition-precipitation, steaming ammonium precipitation, melting-suction filtration, ball milling and sol-gel, these Kaolinite Preparation of Catalyst methods are well known to those skilled in the art as existing mature technology mostly, detailed introduction is all had in the books of this area, as Huang Zhongtao the < industrial catalyst design and development > that shows, the <PreparationofSolidCatalysts> that professor GerhardErtl etc. show.Wherein steaming ammonium intermediate processing of the present invention, concise and to the point step is as follows: salt solubility in water, also may be contained other metals or non-metal salt by (one); (2) ammoniacal liquor is progressively added in above-mentioned salting liquid, form cobalt ammonium complex compound with ammonia; (3) other components are added; (4) heat up and progressively evaporated by ammonia, cobalt precipitates; (5) wash, filter; (6) dry, roasting.The step essence of the melting-suction method in the present invention refers to the preparation process of Raney catalyst: (one) is by will having the fusion of the metallic cobalt of catalytic activity, bismuth and aluminium (or silicon) in a furnace, the melt obtained carries out quench cooled, then be crushed into uniform fine grained, dissolve in step the auxiliary agent that also may add other; (2) catalyst fines is shaping, forming technique can adopt existing known technology, as beaten sheet, mediating extrusion, spin etc.; (3) by above-mentioned preformed catalyst suction filtration in alkali lye of gained, catalyst can be obtained.
The present invention further preferred method for preparing catalyst be co-precipitation, deposition-precipitation and dissolving for one or more of suction filtration after alloy combine.
Catalyst of the present invention also containing one or more elements be selected from IB race, palladium, platinum, ruthenium, rhenium as auxiliary agent, account for the 0wt% ~ 10wt% of overall catalyst weight; Preferably be selected from one or more elements in silver, copper, palladium, ruthenium, rhenium as auxiliary agent, one or more elements further preferably in silver, copper and rhenium as auxiliary agent, the preferred one be selected from silver and copper.
Silver and copper tenor account for the 0wt% ~ 10wt% of overall catalyst weight, and scope is more preferably 0 ~ 5wt%.The source of silver metal is silver nitrate, and the source of copper can be one or more in metallic copper, copper nitrate, copper chloride, Schweinfurt green, cupric oxalate.Silver can be various with the addition manner of copper: add after dissolving together with cobalt salt in precipitation, deposition-precipitation, the steaming ammonium precipitation method or sol-gel process; Add in catalyst precursor, as in filter cake after the drying that obtains in precipitation, deposition-precipitation, the steaming ammonium precipitation method or sol-gel or xerogel, or in material after Roasting Decomposition; Or add beating the formative stage such as sheet or extrusion; Or add when flooding with cobalt liquor, or with cobalt salt step impregnation; Add together with cobalt metal in melting process.
Catalyst in the present invention can also contain alkali metal or alkaline-earth metal, and described alkali metal or alkaline earth metal content account for the 0wt ~ 30wt% of catalyst total amount.More specifically, be selected from potassium, sodium, calcium, magnesium, barium one or more, content accounts for the 0wt ~ 15wt% of catalyst total amount, and preferred scope is 0wt% ~ 10wt% further.Alkali and alkaline earth metal ions source can be water miscible nitrate, carbonate, villaumite, phosphate, sulfate, acetate, fluoride, hydroxide etc.More 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.
The feed postition of alkali and alkaline earth metal ions element can be selected from any one under type: add after dissolving together with cobalt salt in dipping, kneading, precipitation, deposition-precipitation or sol-gel process; Add together with cobalt salt in the method such as blended, ball milling, melting or add step by step; Add respectively or step by step with cobalt salt in dipping, precipitation, deposition-precipitation or sol-gel process; Add in catalyst precursor, as in filter cake after the drying that obtains in precipitation, deposition-precipitation or sol-gel or xerogel, or in material after Roasting Decomposition; Or add beating the formative stage such as sheet or extrusion.
Catalyst is also containing oxide component, although do not want to do any restriction, but inventor thinks that these oxides mainly play the effect of carrier, described oxide component be selected from silica, aluminium oxide, diatomite, calcium silicates, zirconia, titanium oxide one or more, its content accounts for the 10wt% ~ 80wt% of overall catalyst weight.In fact, these carriers are not only play a supporting role, can also assist the dispersion of active component or the activation of carboxylic acid, therefore these carriers affect texture property, the critical index such as product and raw material diffusion wherein, mechanical strength, activity and stability of catalyst.
Support Silica can be selected from waterglass precipitate method, SiO 2 powder, teos hydrolysis, Ludox etc.Described SiO 2 powder can be obtained by methods such as rear ball milling acquisition dry after chemical deposition, waterglass precipitate or Ludox spraying dry, and its size is selected from 10nm ~ 500 μm; As the gross porosity microballoon silica (average pore size is 8.0-12.0nm, and specific area is 300 ~ 600m2/g, and pore volume is 0.8 ~ 1.1ml/g) that Haiyang Chemical Plant, Qingdao produces, the precipitated silica (silica (SiO of and for example Guangzhou people chemical plant production
2) content %>=95.0, fineness (325 screen residue) %≤1.8, specific area is 400 ~ 600m
2/ g) or active carbon white, and for example the aerosil AEROSIL200 of goldschmidt chemical corporation, its specific surface is 200m
2/ g, and for example make the silicon dioxide microsphere that spraying dry obtains by oneself, specific surface is 400 ~ 500m
2/ g, is of a size of 2 ~ 30 μm.SiO 2 powder can add as carrier in precipitation or deposition-precipitation.It is raw material that described waterglass direct precipitation method refers to waterglass, 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 rear formation white gum thing, washs the precipitation method using or carry out on this basis other components for several times and adds.Ethyl orthosilicate prepares in catalyst of the present invention in sol-gel process to use.Ludox, as liquid-state silicon source, can directly use in the precipitation system entering precipitation, deposition-precipitation.
Support Silica or aluminium oxide also may be add as binding agent in the catalyst prepared as melting-suction method, make the catalyst fines of gained can be shaped to shape required for the present invention.
The shape of catalyst of the present invention can be diversified, as spherical, strip, column, ring-type etc., size is between 0.3 ~ 15mm, more preferably between 1 ~ 10mm, the requirement of this size mainly designs according to fixed bed reactors of the present invention, with convenient installation, reduces the requirements such as bed layer pressure.These knowledge are known by professional and technical personnel.
Described zirconia material source is powder zirconia material or the precipitation by zirconates.Powder zirconia size is selected from 10nm ~ 500 μm, and specific surface is greater than 20m
2/ g.The precipitation of zirconates can realize according to following approach: be first dissolved in water by zirconium oxychloride, add the highly basic such as caustic soda subsequently, finally by gel that sediment washing and filtering obtains; Or use zirconyl nitrate as zirconium source, the gel that after adding caustic soda precipitation, washing and filtering obtains.Above-mentioned gel is joined in other sediments, or the carrier that above-mentioned gel is worn into as deposition-precipitation after powder after super-dry is added.
Titanium oxide in the present invention can be some satisfactory commercially available titanium dioxide, as the P25 of goldschmidt chemical corporation, also the method for liquid-phase precipitation can be adopted to prepare, as adopted titanium tetrachloride or titanium sulfate as titanium source, add urea, ammoniacal liquor, sodium carbonate or caustic soda etc. as precipitating reagent, organic metatitanic acid also can be adopted as butyl titanate hydrolysis preparation.
Catalyst also may contain thulium, and its oxide content accounts for the 0wt ~ 8wt% of catalyst total amount; Described rare earth element selects the one in lanthanum or cerium, and preferably its oxide content accounts for the 0wt ~ 5wt% of catalyst total amount.The rare earth element adding trace can make the selective raising obtained to a certain extent of Co catalysts by reducing incoagulable gas content.
Catalyst is also containing one or more inorganic non-metallic elements, and content accounts for the 0wt ~ 5wt% of catalyst total amount.More specifically, described inorganic non-metallic element is selected from the one in phosphorus, boron, fluorine, and content accounts for the 0wt ~ 2wt% of catalyst total amount.Adding of these inorganic non-metallic elements, what have enters catalyst system along with adding of other auxiliary agents, as potassium fluoride.Have plenty of and added by extra mode, add the mode that can adopt and be added by boric acid aqueous solution in filter cake as boron.
Described in the present invention is the method for fatty alcohol by organic carboxyl acid hydro-conversion, its concrete principle is by monocarboxylic acid gasification and mixes with hydrogen, or enter in hydrogenation reactor after monocarboxylic acid is gasified in hydrogen, and be converted into fatty alcohol and water with catalyst exposure of the present invention.
The reactor of Catalyst packing is fixed bed reactors, is more preferably shell and tube reactor, more specifically, is by Catalyst packing in pipe, and filling heat-conducting medium between pipe, as conduction oil or water etc., be more conducive to shifting out of reaction heat like this.Those skilled in the art all knows this technical key point, as every root pipe loadings need be consistent.
Catalyst of the present invention is when being applied in hydrogenation of carboxylic acids, need by its fully reduction activation make most cobalt all be reduced to zero valence state before carrying out hydrogenation reaction, the mode of activation can be under Elevated Temperature Conditions, pass into hydrogen, use reducing agent as Boratex etc. or the method adopting ionizing radiation.These methods are all known by those skilled in the art.
Method of hydrotreating of the present invention, reaction temperature is 180 ~ 350 DEG C, is more preferably 220 ~ 300 DEG C, less in the selective change of this scope inner catalyst, maintains higher level.When reaction temperature is lower, Carboxylic Acid leads lower, and this makes circulating consumption increase; And during reaction temperature continuation rising, the accessory substance especially amount of incoagulable gas product as ethane significantly increases.
Alcohol is prepared as monocarboxylic acid hydrogenation, the mol ratio of hydrogen gas consumption and carboxylic acid is 2 in theory, but for maintaining subsequent reactions pressure and catalyst life, the molar ratio of hydrogen and carboxylic acid is 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.
The catalyst choice used in the present invention is higher, therefore incoagulable gas selective lower than 15% in accessory substance, lower than 10% when more excellent, lower than 5% in further optimization situation.
The hydrogenation of carboxylic acid is typical compressive reaction, and the reaction pressure that the present invention uses is 0.3 ~ 8.0MPa, and preferred reaction pressure is 0.5 ~ 4.0MPa, and the reaction pressure optimized further is 1.0 ~ 2.5MPa.The reaction pressure that the present invention uses, relative to reaction pressure disclosed in many hydrogen addition technologies is much lower before, this makes reaction condition gentleer, and reduces 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.Air speed is actual is wish that extraction product composition is relevant with later separation ability according to factory, the present invention is not restricted in force, this be due to: when air speed is higher, although acetic acid conversion ratio is lower, but the productive rate of ethanol and ethyl acetate and increasing on the contrary, particularly ethyl acetate is selective can improve; When 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 can be adopted to operate.Catalyst of the present invention, at 0.3 ~ 1.0h
-1in can ensure that the conversion ratio of acetic acid is higher than 50%, preferred higher than 75%, preferred higher than 90% further.
The present invention can be widely used in monocarboxylic Hydrogenation for alcohol, and specifically, described monocarboxylic acid is selected from one in acetic acid, propionic acid, butyric acid, lactic acid, 3-hydracrylic acid, itaconic acid or mixture.These carboxylic acids derive from reproducible biomass resource, as mix acid liquors etc. such as lactic acid, 3-hydracrylic acid, benzoic acid, acetic acid/propionic acid, also can derive from other oil replacement resources, as acetic acid.Preferred, described organic acid is one in acetic acid and propionic acid or mixture.Preferred organic acid is acetic acid further.
Method of the present invention, when after carboxylic acid and hydrogen and catalyst exposure, 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 preparation of ethanol through hydrogenation, product, except primarily of except ethanol and ethyl acetate, also has acetaldehyde, ether, butanols, acetone, isopropyl alcohol, dimethoxym ethane, methane, ethane, propane, carbon monoxide, carbon dioxide etc.The catalyst that the present invention describes and method thereof can ensure that Carboxylic Acid is that total selection of alcohol and corresponding ester is greater than 70%, and situation of more optimizing is greater than 85%, and situation about optimizing further is greater than 90%.
Relative to prior art, hydrogenation of carboxylic acids catalyst of the present invention and method thereof have the following advantages simultaneously:
(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 run under wider operation condition, broadening action pane.
Embodiment
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.
Embodiment 1
Get the cobalt nitrate aqueous solution 1 liter of 1.5mol/L, add five water bismuth nitrate 20g wherein, adding that 20wt% sodium carbonate liquor carries out being precipitated to pH value is about 9.0, stirs 2 hours, obtain presoma I under the condition of heating.
10g red fuming nitric acid (RFNA) and 6g four water-calcium nitrate are added in 300ml water, to join in the sodium silicate solution of 500g dilution in (dioxide-containing silica is about 10wt%) lentamente, form white depositions, use high-power agitator to stir sediment and form slurry thing, these slurry materials are joined in presoma I, continues aging 1 hour in the condition stirred.Washing and filtering, and dried overnight obtains dry cake, sprays into granulation after the liquor argenti nitratis ophthalmicus 15ml containing 0.1wt% in this filter cake.Shaping by beating sheet after particle Roasting Decomposition, obtain catalyst CHZ-71.
Embodiment 2
Get the cobalt nitrate aqueous solution 1 liter of 1.0mol/L, add five water bismuth nitrate 18g gram and lanthanum nitrate 3.1g wherein, adding 50g after dissolving through the diatomite (Beijing Chemical Research Institute is self-produced) refined fully stirs, after add urea, being warming up to 80 degree, to be slowly hydrolyzed into pH value be about 6.5, by above-mentioned slurry thing filtration washing, and dried overnight obtains dry cake, and spray dilutes phosphoric acid liquid 10ml on filter cake.Shaping by beating sheet after filter cake Roasting Decomposition, obtain catalyst CHZ-72.
Comparative example 1
Get 30 grams of silica supports (Haiyang Chemical Plant, Qingdao, water absorption rate is about 0.9g/g), by 60 grams of cobalt nitrates and 1g silver nitrate soluble in water, prepare presoma by the method combining repeatedly dipping-total immersion stain-incipient impregnation, and by this presoma 400 DEG C of roastings acquisition catalyst CHZ-73.
Comparative example 2
According to method disclosed in CN200980134837.2, prepared 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-74.
Embodiment 3
Evaluated in fixed bed reactors by above-mentioned catalyst, for acetic acid preparation of ethanol through hydrogenation, loadings is 10ml, adopt the quartz sand dilution of 1:1, before use adopt pure hydrogen reduction, reduction maximum temperature be 450 ~ 500 DEG C, concrete reaction condition and reaction result as shown in table 1.
In the present embodiment, acetic acid conversion ratio and ethanol selectivity calculate according to the carbon molar content of each component and obtain.
Other products have: acetaldehyde, ethane, methane, carbon monoxide, carbon dioxide, acetic acid aldehyde, acetone, propyl alcohol etc.
Embodiment 4
Above-mentioned catalyst is evaluated in fixed bed reactors, for lactic acid (the 20wt% aqueous solution) Hydrogenation for 1,2-propane diols, loadings is 10ml, adopt the quartz sand dilution of 1:1, before use adopt pure hydrogen reduction, reduction maximum temperature be 450 ~ 500 DEG C, concrete reaction condition and reaction result as shown in table 2.
In the present embodiment, rotational rate of lactic acid and the selective carbon molar content according to each component of 1,2-PD calculate and obtain.Other accessory substances comprise: normal propyl alcohol, isopropyl alcohol, 2-hydroxy-propionaldehyde, propane, ethane, carbon monoxide, carbon dioxide, ethanol, pentanedione etc.
Table 1
Table 2
Claims (16)
1. hydrogenation of carboxylic acids prepares a catalyst for alcohol, it is characterized in that, described catalyst comprises following component:
(1) containing cobalt and bismuth, wherein cobalt tenor accounts for the 10wt% ~ 50wt% of overall catalyst weight, and bismuth metal accounts for the 0.1wt% ~ 50wt% of overall catalyst weight;
(2) oxide, described oxide be selected from silica, diatomite, calcium silicates, zirconia, titanium oxide, aluminium oxide one or more, its content accounts for the 10wt% ~ 80wt% of overall catalyst weight;
Described hydrogenation catalyst by dipping, co-precipitation, deposition-precipitation, ammonia still process precipitation, sol-gel, be molten into after alloy in suction filtration and ball grinding method one or more combine and prepare;
Also containing at least one in alkali metal or alkaline-earth metal, thulium and inorganic non-metallic element in described catalyst, wherein, the content of described alkali metal or alkaline-earth metal accounts for the 0wt ~ 30wt% of catalyst total amount, the oxide content of described thulium accounts for the 0wt ~ 8wt% of catalyst total amount, and the content of described inorganic non-metallic element accounts for the 0wt ~ 5wt% of catalyst total amount.
2. catalyst according to claim 1, is characterized in that, in described catalyst, cobalt tenor accounts for the 15wt% ~ 45wt% of overall catalyst weight, and bismuth metal accounts for the 1wt% ~ 40wt% of overall catalyst weight; Described catalyst is by co-precipitation, deposition-precipitation, ammonia still process precipitation and one or more combination preparations after being molten into alloy in suction filtration method.
3. catalyst according to claim 1, is characterized in that, in described catalyst, cobalt tenor accounts for the 10wt% ~ 40wt% of overall catalyst weight, and bismuth metal accounts for the 3wt% ~ 30wt% of overall catalyst weight.
4. catalyst according to claim 1, is characterized in that, described oxide is selected from the one in silica, diatomite and calcium silicates.
5. catalyst according to claim 1, is characterized in that, described catalyst also optionally containing one or more elements be selected from IB race, palladium, platinum, ruthenium, rhenium as auxiliary agent, its content accounts for the 0wt% ~ 10wt% of overall catalyst weight.
6. catalyst according to claim 5, is characterized in that, described auxiliary agent is selected from one or more elements in silver, copper, palladium, ruthenium, rhenium.
7. catalyst according to claim 6, is characterized in that, described auxiliary agent is selected from one or more elements in silver, copper, rhenium.
8. catalyst according to claim 7, is characterized in that, described catalyst promoter is silver and/or copper.
9. catalyst according to claim 1, is characterized in that, described alkali metal or alkaline-earth metal be selected from potassium, sodium, calcium, magnesium, barium one or more, its content accounts for the 0wt ~ 15wt% of catalyst total amount.
10. catalyst according to claim 1, is characterized in that, described thulium is lanthanum or cerium, and its oxide content accounts for the 0wt ~ 5wt% of catalyst total amount.
11. catalyst according to claim 1, is characterized in that, described inorganic non-metallic element is selected from the one in phosphorus, boron, fluorine, and its content accounts for the 0wt-2wt% of catalyst total amount.
12. 1 kinds of carboxylic acid gas phase hydrogenations prepare the method for alcohol, it is characterized in that, in fixed bed reactors, carboxylic acid steam mixes with hydrogen-containing gas and is converted into alcohol and water after hydrogenation catalyst haptoreaction, the mol ratio of hydrogen and carboxylic acid is 4:1 ~ 40:1, reaction temperature is 180 ~ 350 DEG C, and reaction pressure is 0.3 ~ 8.0MPa, and the volume space velocity of carboxylic acid is 0.1 ~ 5.0h
-1;
Described hydrogenation catalyst is the catalyst described in claim 1 ~ 11 any one, and the described carboxylic acid for hydrogenation is monocarboxylic acid.
13. carboxylic acid gas phase hydrogenations according to claim 12 prepare the method for alcohol, it is characterized in that, the mol ratio of hydrogen and carboxylic acid is 8:1 ~ 20:1, and reaction temperature is 220 ~ 300 DEG C, and reaction pressure is 0.5 ~ 4.0MPa, and the volume space velocity of carboxylic acid is 0.2 ~ 2.0h
-1.
14. carboxylic acid gas phase hydrogenations according to claim 12 prepare the method for alcohol, it is characterized in that, the described carboxylic acid for hydrogenation is one in acetic acid, propionic acid, butyric acid, lactic acid, 3-hydracrylic acid, benzoic acid or mixture.
15. carboxylic acid gas phase hydrogenations according to claim 14 prepare the method for alcohol, it is characterized in that, described carboxylic acid is one in acetic acid, propionic acid or mixture.
16. carboxylic acid gas phase hydrogenations according to claim 15 prepare the method for alcohol, it is characterized in that, described carboxylic acid is acetic acid.
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| WO2016175745A1 (en) | 2015-04-27 | 2016-11-03 | Celanese International Corporation | Ruthenium-bismuth mixed oxide hydrogenation catalysts and processes for producing ethanol |
| US9540297B2 (en) | 2015-04-27 | 2017-01-10 | Celanese International Corporation | Ruthenium-bismuth mixed oxide hydrogenation catalysts and processes for producing ethanol |
| CN109622025B (en) * | 2019-01-17 | 2021-08-17 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl glycolate and preparation method and application thereof |
| CN110975877B (en) * | 2019-11-25 | 2021-09-21 | 华南理工大学 | Quenching modification method for improving electrocatalytic performance of metal oxide, prepared metal oxide electrocatalyst and application |
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