CN103785414B - Hydrogenation of carboxylic acids catalyst, preparation method and application thereof - Google Patents

Hydrogenation of carboxylic acids catalyst, preparation method and application thereof Download PDF

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CN103785414B
CN103785414B CN201210429720.0A CN201210429720A CN103785414B CN 103785414 B CN103785414 B CN 103785414B CN 201210429720 A CN201210429720 A CN 201210429720A CN 103785414 B CN103785414 B CN 103785414B
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hydrogenation
carboxylic acids
characterized
catalyst
described
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CN201210429720.0A
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CN103785414A (en
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黄龙
王国清
田保亮
戴伟
李宝芹
杨溢
唐国旗
彭晖
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Abstract

The present invention relates to a kind of hydrogenation of carboxylic acids catalyst, this catalyst contains carrier, cobalt element, group vib element, wherein the content of cobalt element accounts for the 15wt% ~ 50wt% of overall catalyst weight, group vib element is selected from least one in molybdenum, tungsten, chromium, its content accounts for the 0.5wt% ~ 15wt% of overall catalyst 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 overall catalyst weight.This catalyst activity is higher, and object selectivity of product is high, and manufacturing cost is comparatively cheap, and reaction condition is gentleer.

Description

Hydrogenation of carboxylic acids catalyst, preparation method and application thereof

Technical field

The invention belongs to petrochemical field, more particularly, relating to a kind of can be Catalysts and its preparation method and the application of alcohol by carboxylic acid height yield hydro-conversion.

Background technology

The research that hydrogenation of carboxylic acids prepares alcohol is long-standing, has just applied for using the method that Carboxylic Acid is alcohol by ruthenium catalyst as far back as nineteen fifty Ford etc.But because petroleum resources cost in last century is 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.After entering 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 prepares alcohol to be become and has more economy and continuable method.

The main technical difficulty that hydrogenation of carboxylic acids prepares alcohol is to develop has high activity and optionally catalyst, the reaction pressure needed for reduction, and catalyst needs to have the long-time stability used; The cost of catalyst needs in rational scope, to ensure its commercial value in addition.

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.But reaction pressure is high all in the extreme in the embodiment disclosed, be all greater than 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%.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.The simultaneously content of incoagulability gas phase in the unexposed tail gas of embodiment, and material yield is 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, 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 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.

At Aqueous-phasehydrogenationoflacticacidtopropyleneglycol, in AppliedCatalysisA:General219 (2001) 89 – 98, 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 of 40 ~ 80%.In the method, the energy consumption when water of high level significantly can increase separation undoubtedly; 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, and 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, and Co catalysts content is lower, is about 10wt%, and catalyst needs to use precious metal additive simultaneously, and as platinum and palladium, auxiliary agent content is higher than 1wt%.

In sum, there is some technology and commercialization problem in prior art: 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.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of cobalt metallic catalyst containing group vib element and preparation method thereof and its application in monocarboxylic acid hydrogenation, this catalyst activity is higher, object selectivity of product is high, and manufacturing cost is comparatively cheap, and reaction condition is gentleer.

An object of the present invention is to provide a kind of hydrogenation of carboxylic acids catalyst, this catalyst contains carrier, cobalt element, group vib element, wherein the content of cobalt element accounts for the 15wt% ~ 50wt% of overall catalyst weight, group vib element is selected from least one in molybdenum, tungsten, chromium, its content accounts for the 0.5wt% ~ 15wt% of overall catalyst 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 overall catalyst 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 overall catalyst weight, and preferred content is 20wt% ~ 40wt%.Described cobalt tenor refers to the content of element cobalt.Those skilled in the art often think that the content improving main active component can improve the activity of catalyst, but inventor is surprised to find that: lower compared with the activity of catalyst during low cobalt content, and more the cobalt of high-load not only makes the cost increase of catalyst, and the activity of catalyst can not be improved, decline even to some extent, significantly decrease when high level; Increase in the preparation difficulty of cobalt content higher than catalyst when 50wt%, as forming process etc., this will make the commercialization of catalyst comparatively difficult.

The source of cobalt metal can be selected from water miscible nitrate, sulfate, villaumite, acetate, oxalates and bromine salt, specifically, be selected from cobalt nitrate, cobalt chloride, cobalt oxalate, cobaltous sulfate, cobalt acetate one or more, be more preferably in cobalt nitrate, cobalt acetate and cobalt oxalate one or more.

Described catalyst is also containing group vib element, and described group vib element is at least one in molybdenum, tungsten and chromium, accounts for the 0.5wt% ~ 15.0wt% of overall catalyst weight, and preferred weight range is 1.0wt% ~ 10.wt%.The source of molybdenum can be selected from water-soluble molybdenum hydrochlorate, as the one in ammonium molybdate, sodium molybdate, potassium molybdate, magnesium molybdate, or the complex compound of molybdenum, as citric acid molybdenum etc.

Water soluble salt or salt solvable after adding alkaline auxiliary solvent can be selected, as ammonium tungstate, ammonium metatungstate, Zinc Tungstate, sodium tungstate, potassium tungstate etc. in the source of tungsten.

The source of chromium can be selected from water soluble salt or salt solvable after adding acid cosolvent, as ammonium dichromate, sodium dichromate, potassium bichromate, barium chromate, chromic anhybride, sodium chromate, potassium chromate, magnesium chromate, chromic nitrate, chromic acetate, chromium+oxalic acid etc.

Molybdenum, tungsten and chromium belong to group vib element, second component as catalyst can improve the performance indications of the catalyst such as the activity of catalyst, selective and stability significantly, and reason wherein may be many-sided: inhibit growing up or having activated carboxylic acid of cobalt crystal grain.In addition, relative to infusion process, the Co catalysts prepared by co-precipitation, deposition-precipitation or sol-gel process, the effect of its performance improvement is more obvious, more embodies the superiority of the present invention program.

Containing oxide component in described catalyst, its content accounts for the 20wt% ~ 80wt% of overall catalyst weight.Described oxide component be selected from silica, zirconia, titanium oxide one or more, 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.Therefore these carriers affect structural behaviour, the critical index such as product and raw material diffusion wherein, mechanical strength, activity and stability of catalyst.

Described silica support can be selected from waterglass precipitate method, SiO 2 powder, teos hydrolysis, Ludox etc.It is raw material that described waterglass precipitate 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.After described SiO 2 powder can pass through chemical deposition, waterglass precipitate drying, the method such as ball milling acquisition or Ludox spraying dry obtains, and its size is selected from 10nm ~ 500 μm; 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 ~ 600m 2/ g, pore volume is 0.8 ~ 1.1ml/g; The and for example precipitated silica of Guangzhou people chemical plant production, 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 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.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.

Described diatomite is a kind of natural porous material, primarily of unbodied SiO 2form and contain a small amount of Fe 2o 3, CaO, MgO, Al 2o 3and organic impurities, there is special porous configuration.As the diatomite that governor Bai Xian green hill, Jilin source diatomite company produces.

Described Zirconia carrier is selected from powder zirconia material or is obtained by the precipitation of zirconates.Powder zirconia size is selected from 10nm ~ 500 μm, and specific surface is greater than 20m 2/ g.The sediment 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 dioxide carrier in the present invention can be 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.

The preparation method of described catalyst is selected from least one in coprecipitation, deposition-precipitation and sol-gel process.Coprecipitation, deposition-precipitation and sol-gel process Kaolinite Preparation of Catalyst are well known to those skilled in the art as existing mature technology, detailed introduction is all had in the books of this area, as Huang Zhongtao " the industrial catalyst design and development " shown, " PreparationofSolidCatalysts " that professor GerhardErtl etc. show.

Catalyst of the present invention can also containing silver salt as auxiliary agent, and silver element content accounts for the 0.1wt% ~ 10wt% of overall catalyst weight, and scope is more preferably 0.2wt% ~ 2wt%, and preferred scope is 0.2wt% ~ 0.5wt% further; The source of silver element is silver nitrate.The addition manner of silver salt can be various, adds after dissolving together with cobalt salt in 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.In the Co catalysts prepared by co-precipitation, deposition-precipitation or sol-gel process, adding silver salt, to improve the effect of catalyst reaction performance more obvious.

Described catalyst can also contain alkali metal or alkali earth metal, and described alkali metal or alkali earth metal content account for the 0.1wt% ~ 15wt% of overall catalyst weight.Specifically, described alkali metal or alkali earth metal be selected from potassium, sodium, calcium, magnesium, barium one or more, content accounts for the 0.2wt% ~ 10wt% of overall catalyst weight.The source of alkali and alkaline earth metal ions element can be water miscible nitrate, carbonate, villaumite, phosphate, sulfate, acetate, fluoride, hydroxide etc.Specifically, its 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 the compound containing alkali and alkaline earth metal ions element can be selected from any one under type: add after dissolving together with cobalt salt in precipitation, deposition-precipitation or sol-gel process; Add respectively with cobalt salt in 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.

Described catalyst can also contain thulium, and its oxide content accounts for the 0.1wt% ~ 8wt% of overall catalyst weight; Described thulium selects the one in lanthanum or cerium, and its oxide content preferably accounts for the 0.5wt% ~ 5wt% of overall catalyst weight.The rare earth element adding trace can reduce incoagulable gas content and make the selective raising obtained 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 overall catalyst weight.Specifically, described inorganic non-metallic element is selected from the one in phosphorus, boron, fluorine, and content accounts for the 0.3wt% ~ 2wt% of overall catalyst weight.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.

Another object of the present invention is to provide a kind of method above-mentioned catalyst application being prepared alcohol in hydrogenation of carboxylic acids.Specifically, be monocarboxylic acid is gasified 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, preferred shell and tube reactor.Specifically, be 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.

Monocarboxylic acid hydrogenation is prepared as to the reaction of alcohol, hydrogen gas 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 choice of the present invention is higher, therefore incoagulable gas selective lower than 10% in accessory substance, lower than 5% when more excellent, lower than 2% in further optimization situation.

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 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 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 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.

Catalyst of the present invention can be widely used in monocarboxylic acid hydrogenation and be prepared as 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 monocarboxylic acid is one in acetic acid and propionic acid or mixture.Preferred monocarboxylic acid is acetic acid further.

Method of the present invention, when after monocarboxylic 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 application thereof can ensure that Carboxylic Acid is that total selection rate 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 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 run under wider operation condition, broadening action pane.

Detailed description of the invention

With embodiment, the present invention is described below, but and unrestricted invention scope.

Embodiment 1

Get the cobalt nitrate aqueous solution 1 liter of 1mol/L, add ammonium molybdate 9.5 grams and lanthanum nitrate 7.5g 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-21.

Embodiment 2

Get the cobalt nitrate aqueous solution 1 liter of 1.5mol/L, add cerous nitrate 6.0 grams and chromic nitrate 4 grams wherein, abundant dissolving, when stirring, at the titania powder 60 grams adding goldschmidt chemical corporation production, (model is P25, particle diameter is for being greater than 150 orders), the solid-liquid that contains of gained is called solution I.The ammonium metatungstate solution 250ml(W content be dissolved in ammoniacal liquor is about 1.5wt%) be solution II; The sodium carbonate liquor of 20wt% is solution III.Solution II is poured into after in solution I and precipitate, about finally using solution III to regulate pH value to 6.7.Carry out subsequently washing and filter and obtain a moister filter cake; Place after 1 hour dry spray into the BAS 25ml containing 0.1wt% in this filter cake after.By dry cake Roasting Decomposition aftershaping, obtain catalyst CHZ-22.

Embodiment 3

Be dissolved in 800ml normal propyl alcohol by being respectively 240g and 15g through the cobalt nitrate of super-dry process and chromic nitrate under Elevated Temperature Conditions, temperature controls, at 50 ~ 60 DEG C, slowly to add ethyl orthosilicate 300g, prepares the ethyl orthosilicate containing cobalt and chromium after purifying.Get and above-mentioned be dissolved in ethanol containing cobalt and chromium ethyl orthosilicate 100g, after adding water 600ml and red fuming nitric acid (RFNA) 5.0g, place under 75 DEG C of conditions and obtain gel in 6 hours.In above-mentioned gel, add 20ml silver nitrate aqueous solution (60mgAg/ml) and stirring to pulp, slurry spray drying is obtained tiny microballoon.After the particle of above-mentioned microballoon screening removing more than 300 μm, 400 DEG C of roastings, beat the shaping rear acquisition catalyst CHZ-23 of sheet by above-mentioned powder.

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-24.

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-25.

Embodiment 4

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.;

Table 1 reaction condition and result

As can be seen from Table 1, catalyst activity of the present invention is high, selective height.

Embodiment 5

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 2 reaction condition and result

As can be seen from Table 2, catalyst activity of the present invention is high, selective height.

Claims (25)

1. a hydrogenation of carboxylic acids catalyst, it is characterized in that catalyst contains carrier, cobalt element, group vib element and silver element, wherein the content of cobalt element accounts for the 15wt% ~ 50wt% of overall catalyst weight, group vib element is selected from least one in molybdenum, tungsten, chromium, its content accounts for the 0.5wt% ~ 15wt% of overall catalyst weight, the content of described silver element accounts for the 0.1wt% ~ 10wt% of overall catalyst 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 overall catalyst weight.
2. hydrogenation of carboxylic acids catalyst according to claim 1, is characterized in that described catalyst is prepared by coprecipitation, deposition-precipitation or sol-gel process.
3. hydrogenation of carboxylic acids catalyst according to claim 1, it is characterized in that described silver element derives from silver nitrate, silver content accounts for the 0.2wt% ~ 2wt% of overall catalyst weight.
4. hydrogenation of carboxylic acids catalyst according to claim 3, is characterized in that described silver element content accounts for the 0.2wt% ~ 0.5wt% of overall catalyst weight.
5. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, it is characterized in that described cobalt element derives from water miscible nitrate, sulfate, villaumite, acetate, oxalates and bromine salt, its content accounts for the 20wt% ~ 40wt% of overall catalyst 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 1 and 2, is characterized in that described molybdenum element derives from the complex compound of water miscible molybdate or molybdenum.
8. hydrogenation of carboxylic acids catalyst according to claim 7, is characterized in that described molybdenum element derives from the one in ammonium molybdate, sodium molybdate, potassium molybdate, magnesium molybdate, citric acid molybdenum.
9. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, is characterized in that described W elements derives from water-soluble or solvable after adding alkaline auxiliary solvent salt.
10. hydrogenation of carboxylic acids catalyst according to claim 9, is characterized in that described W elements derives from ammonium tungstate, ammonium metatungstate, Zinc Tungstate, sodium tungstate, potassium tungstate.
11. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, is characterized in that described chromium element source is in water miscible or solvable after adding acid cosolvent salt.
12. hydrogenation of carboxylic acids catalyst according to claim 11, is characterized in that the described one of chromium element source in ammonium dichromate, sodium dichromate, potassium bichromate, barium chromate, chromic anhybride, sodium chromate, potassium chromate, magnesium chromate, chromic nitrate, chromic acetate, chromium+oxalic acid.
13. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, it is characterized in that described catalyst also containing thulium, its oxide content accounts for the 0.1wt% ~ 8wt% of overall catalyst weight.
14. hydrogenation of carboxylic acids catalyst according to claim 13, it is characterized in that described thulium is lanthanum or cerium, its oxide content accounts for the 0.5wt% ~ 5wt% of overall catalyst weight.
15. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, it is characterized in that described catalyst also containing at least one inorganic non-metallic element, its content accounts for the 0.1wt% ~ 5wt% of overall catalyst weight.
16. hydrogenation of carboxylic acids catalyst according to claim 15, it is characterized in that described inorganic non-metallic element is selected from the one in phosphorus, boron, fluorine, its content accounts for the 0.3wt% ~ 2wt% of overall catalyst weight.
17. hydrogenation of carboxylic acids catalyst according to claim 1 and 2, it is characterized in that described catalyst also containing alkali metal or alkali earth metal, its content accounts for the 0.1wt% ~ 15wt% of overall catalyst weight.
18. hydrogenation of carboxylic acids catalyst according to claim 17, it is characterized in that described alkali metal or alkali earth metal are at least one in potassium, sodium, calcium, magnesium, barium, its content accounts for the 0.2wt% ~ 10wt% of overall catalyst weight.
19. hydrogenation of carboxylic acids catalyst according to claim 17, is characterized in that described alkali metal or alkali earth metal derive from water miscible nitrate, carbonate, villaumite, phosphate, sulfate, acetate, fluoride, hydroxide.
20. hydrogenation of carboxylic acids catalyst according to claim 17, 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 21. claim 1-20 at monocarboxylic acid Hydrogenation for the application in the reaction of alcohol.
The application in the reaction of alcohol prepared by 22. hydrogenation of carboxylic acids catalyst according to claim 21 at acetic acid hydrogenation.
The application of 23. hydrogenation of carboxylic acids catalyst according to claim 21 or 22, it is characterized in that monocarboxylic acid, hydrogen-containing gas become after mist with hydrogenation of carboxylic acids catalyst exposure, be converted into alcohol and water, hydrogen and monocarboxylic molar ratio are 4:1 ~ 40:1, reaction temperature is 180 ~ 350 DEG C, reaction pressure is 0.3 ~ 8.0MPa, and monocarboxylic volume space velocity is 0.1 ~ 5.0h -1.
The application of 24. hydrogenation of carboxylic acids catalyst according to claim 23, it is characterized in that hydrogen and monocarboxylic molar ratio are 6:1 ~ 25:1, reaction temperature is 220 ~ 300 DEG C, and reaction pressure is 0.5 ~ 4.0MPa, and monocarboxylic volume space velocity is 0.2 ~ 2.0h -1.
The application of 25. hydrogenation of carboxylic acids catalyst according to claim 24, it is characterized in that hydrogen and monocarboxylic molar ratio are 8:1 ~ 20:1, reaction pressure is 1.0 ~ 2.5MPa, and monocarboxylic volume space velocity is 0.3 ~ 1.0h -1.
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