CN102408304A - Method for preparing alcohols by selectively hydrogenating aldehydes - Google Patents
Method for preparing alcohols by selectively hydrogenating aldehydes Download PDFInfo
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Abstract
The invention relates to a method for preparing alcohols by selectively hydrogenating aldehydes, belonging to hydrogenation technologies. In order to meet the requirements of people on two aspects, i.e. the improving of the selectivity on preparing the alcohols by hydrogenating the aldehydes and the prolonging of the service life of a catalyst currently, the method proposes that: the aldehydes are taken as raw materials; the reaction temperature is 20-300 DEG C; the reaction pressure is 0.1-7.0 MPa; the weight space velocity of the aldehydes is 0.02-20 h<-1>; the aldehydes and hydrogen gas are in contact with a hydrogenation catalyst; and the aldehydes are produced into corresponding alcohols through selectively hydrogenating. In the method, the hydrogenation catalyst comprises a carrier, a metal active component and silane groups; the silane groups are grafted through a silylanizing treatment; and the content of the silane groups in the total weight of the catalyst is 0.05 wt% to 25 wt%. Compared with the existing method, with the adoption of the catalyst in the method provided by the invention, the selectivity is high, the amount of byproducts, such as ethers, esters and acetals is greatly lowered; and meanwhile, the generation amount of carbon deposit is little, so that the catalyst has longer service life.
Description
Technical field
This paper relates to a kind of method and application thereof of aldehyde hydrogenation preparing alcohol.
Background technology
Aldehyde hydrogenation is the important method for preparing monohydroxy-alcohol and polyvalent alcohol in the industry.As for a long time industry of development, Wasserstoffatoms the source be the reducing substances (like formic acid, alcohol, Hydrazine Hydrate 80 etc.) of hydrogen or hydrogen atoms.The former is the method for the aldehyde hydrogenation of existing main flow, is mainly used in the scale operation alcohols, need to use metal catalyst, and the latter usually uses the metal catalyst of use or basic catalyst in synthesizing in that medicine, organic intermediate etc. are small-sized.For the situation of hydrogen as hydrogen source, the metal catalyst of use has numerous species, and its active ingredient has copper, nickel, cobalt and noble metal platinum, ruthenium, palladium etc., wherein in industry, is mainly copper-based catalysts and nickel-base catalyst.
Commercial run for aldehyde hydrogenation preparing alcohol; The purpose selectivity of product all has great important to economic benefit, Environmental Protection Level and the energy consumption of device: this is because in the process of aldehyde hydrogenation, the condensation from condensation, aldehyde and alcohol of aldehyde, etc. react (Xueqin Wang, Ramzi Y.Salehb; Umit S.Ozkana; Journal of Catalysis, 2005,231 (1): 20-32); Many by products wherein such as acetal and product form difficulty to be separated, and this causes aldehyde hydrogenation process middle and lower reaches that complicated separable programming possibly must be arranged.
Therefore; Reduce the yield that side reactions such as etherificate and condensation not only can improve catalyzer; And the by product that gets into downstream reduces and means that the downstream separation energy consumption can significantly reduce, even can realize the simplification of downstream process, and the quality of product can be improved simultaneously.
Aldehydes can be polymerized to the surface that superpolymer covers catalyzer through condensation reaction can cover the hydrogenation activity position, reduces catalyst activity; Also can stop up the duct simultaneously, reduce the spread coefficient of catalyzer, further reduce the reactivity worth of catalyzer; Therefore, for the inactivation of aldehyde hydrogenating catalyst, carbon distribution usually is very important or major cause (Xiao Da Zhu and Hanns Hofmann; Applied Catalysis A:General, Volume 155, and Issue 2; 31July 1997, Pages 179-194).Prolong life of catalyst and can promote efficient, energy consumption and the economic benefit of reaction unit efficient the raising device.
U.S. Pat 4762817 has been introduced a kind of method of aldehyde hydrogenation, and the catalyzer of use mainly consists of Cu and Zn, and the mixture of adding basic metal, transition metal or basic metal and transition metal is as auxiliary agent.Wherein basic metal can be one or more among Na, K, Li, the Ce, and it adds massfraction is 0.05%～7.0%, preferably 0.3%～3.5%; The add-on of transition metal such as Ni, Co or its mixture is 0.15%～5.0%, preferably 1.0%～4.0%.The main effect of these auxiliary agents is the side reactions that reduce in the hydrogenation, the generation ethers and the carboxylate of trying one's best few.In the time of in being applied to butyraldehyde, the amount of by product butyl butyrate is 0.05wt% only
DE43100538 discloses a kind of aldehyde method of hydrotreating, and the Ni of use is an aldehyde hydrogenating catalyst, it is characterized in that adopting earth alkali metal Mg as auxiliary agent.The metal Ni massfraction of going back ortho states in the catalyzer is 25%～50%; The Ni massfraction of oxidation state is 10%～35%, and the MgO massfraction is 4%～12%, and the NaO massfraction is 1%～5%; Total Ni massfraction is 40%～70%, and the reduction ratio of nickel reaches 50%～80%.This catalyzer adopts Al
2O
3(or) SiO
2, zeyssatite is as carrier.
The Ni that introduces among the EP394842 A1 is an aldehyde hydrogenating catalyst, except that having added Cu, has also added the 3rd component Zr and the 4th component Mo.This catalyzer is to adopt the coprecipitation method preparation, and the massfraction of each component is in the oxide catalyst before reduction: NiO 20%～75%, ZrO
210%～75%, CuO 5%～50%, MoO
30.1%～5%.
Above-mentioned technological method all to a certain degree raising the purpose product selectivity, reduced side reactions such as condensation, etherificate, but along with product quality requirement improve constantly and industry member to the consideration of downstream energy consumption, the purpose product selectivity still needs to improve.The raising in catalyzer work-ing life is to reducing production costs also highly significant.
In sum, develop a kind of method and promptly reduce side reaction such as condensation, etherificate in the aldehyde hydrogenation reaction, reduce the catalyst surface carbon distribution simultaneously and generate and will the cost and the energy consumption of aldehyde hydrogenation preparing alcohols all be had great importance.
Summary of the invention
For satisfying present people to improving the selectivity and the two aspect requirements in work-ing life of prolongation catalyzer that aldehyde is hydrogenated to alcohol; The present invention proposes a kind of method; Can improve the purpose selectivity of product of hydrogenation process effectively, simultaneously method of the present invention has also that the growing amount of carbon distribution on the catalyzer is little, the characteristics of long service life.
The present invention relates to the method for hydrogenation preparing alcohols in a kind of aldehyde, concrete grammar is following: with aldehyde raw material, and 20 ℃～300 ℃ of temperature of reaction, reactor pressure 0.1MPa～7.0MPa, the weight space velocity of aldehyde are 0.02h
-1～20h
-1, aldehyde contacts with hydrogenation catalyst with hydrogen, and aldehyde is selected to be hydrogenated to alcohol, and described hydrogenation catalyst contains carrier, metal active constituent palladium, silane group, it is characterized in that the silane group on the described catalyzer is handled grafting through silylanizing.With respect to existing method, method of the present invention has two aspect remarkable advantages: the selectivity that aldehyde is hydrogenated to alcohol is high, and aldehyde significantly reduces from side reactions such as condensation, aldol condensation, etherificates; Catalyst surface carbon distribution growing amount is little, has longer work-ing life.
Although agnogenio, contriver of the present invention finds through utilizing on the carrier supported catalyst of hydroxyl that silane group can significantly reduce the by product that reactions such as etherificate and condensation cause in the grafting containing.The inventor also finds have very by carbon distribution, and confidential relation is the surface hydroxyl quantity of catalyzer; Although also there is not strict proof at present; But the contriver thinks that after theory is inferred the reactive hydrogen on the surface hydroxyl of catalyzer has promoter action for aldehyde from condensation, aldol condensation, etherification reaction, and the reactive hydrogen quantity on methyl-monosilane rear catalyst surface significantly reduces.Infer that theoretically the silane group that catalyst surface has has hydrophobicity, a little less than oh group absorption, therefore can reduce the absorption of reaction back alcohol, further reduce the follow-up side reaction after alcohol generates.The present invention is based on above discovery and infers what accomplished the back with theoretical.
Concrete technical scheme is following:
Aldehyde of the present invention is selected the method for hydrogenation preparing alcohol, is to be raw material with aldehyde, is 0.02h at the weight space velocity of 20 ℃～300 ℃ of temperature of reaction, reaction pressure 0.1MPa～7.0MPa and aldehyde
-1～20h
-1Down, aldehyde contacts with hydrogenation catalyst with hydrogen, and aldehyde is selected to be hydrogenated to alcohol, and described hydrogenation catalyst contains carrier, metal active constituent palladium and silane group, and described silane group is handled grafting through silylanizing.
Preferably, described metal active group is at least a in palladium, nickel, platinum, copper and the cobalt, and its percentage ratio that accounts for the catalyzer gross weight is 0.05wt%～70wt%.More preferably, described metal active constituent is at least a in copper, cobalt and the nickel, and its percentage ratio that accounts for the catalyzer gross weight is 0.5wt%～60wt%.Further preferably, described metal active group is at least a in the copper and mickel, and its percentage ratio that accounts for the catalyzer gross weight is 5wt%～50wt%.
In order to improve the catalytic performance of catalyzer; In above-mentioned various catalyzer schemes; Described catalyzer also contains metal promoter a, and described metal promoter A is at least a metallic element in IA family, IIA family and the VA family, and its content is the 0.01wt%～10wt% of catalyzer gross weight.More preferably, described metal promoter a is at least a metallic element of potassium, calcium, magnesium, barium, bismuth, and its content is the 0.1wt%～6wt% of catalyzer gross weight.
In order to improve the catalytic performance of catalyzer; Do not contain metal promoter a and contain in the various catalyzer schemes of metal promoter a above-mentioned; Described catalyzer also contains metal promoter b; Described metal promoter is at least a metallic element in IB family, IIB family, IIIB family and the group vib, and its content is the 0.01wt%～30wt% of catalyzer gross weight.More preferably, described metal promoter b comprises at least a in silver, gold, zinc, lanthanum, cerium, chromium, molybdenum and the tungsten, and its content is the 0.5wt%～25wt% of catalyzer gross weight.
In order further to improve the catalytic performance of catalyzer; Above-mentioned do not contain metal promoter a and b, only contain metal promoter a, only contain metal promoter b and containing simultaneously in the various catalyzer schemes of metal promoter a and b; Described catalyzer also contains non-metal assistant d; Described non-metal assistant d is at least a non-metallic element in IIIA family, IVA and the VA family, and its content is the 0.01wt%～8wt% of catalyzer gross weight.More preferably, described metal promoter d is at least a in boron, phosphorus, sulphur, selenium, fluorine, chlorine and the iodine, and its content is the 0.1wt%～4wt% of catalyzer gross weight.
Catalyzer of the present invention can use any carrier, but sees from the industrial application situation of hydrogenation of unsaturated hydrocarbons, and preferred described carrier is selected from Al
2O
3, Fe
2O
3, TiO
2, V
2O
5, SiO
2, ZnO, SnO
2, ZrO
2, a kind of in MgO, gac, kaolin and the zeyssatite or two or more mixture in them;
In catalyzer of the present invention; Said silane group is handled grafting through silylanizing; More preferably said silane group is the raw material grafting through the silylanizing method with the silicomethane base; Described silane group accounts for the 0.05wt%～25wt% of catalyzer gross weight, more preferably 0.1wt%～15wt%.
In the silylanizing process, the silicomethane base that silylanizing handle to be used is preferably a kind of in organosilane, organo-siloxane, organosilazanes and the organic oxosilane or two or more mixture in them; A kind of or their mixture in organo-siloxane and the organosilazanes more preferably.
Preferably; Described method is applied to: hydrogenation of propionaldehyde is that n-propyl alcohol, hydrogenation of n-butyraldehyde are that propyl carbinol, octenal are hydrogenated to that octanol, enanthaldehyde are hydrogenated to enanthol, hydrogenation of furfural is a furfuryl alcohol, 2; 2-methylol butyraldehyde hydrogenation preparing TriMethylolPropane(TMP), 3-hydroxy propanal are hydrogenated to 1, and ammediol or glucose hydrogenation are sorbyl alcohol.
Preferably, described method is carried out under following reaction conditions: the weight space velocity 0.1h of 50 ℃～260 ℃ of temperature of reaction, reaction pressure 0.1MPa～5.0MPa and aldehyde
-1～3h
-1
Preferably, the mol ratio of hydrogen and aldehyde is 1～200.
In described catalyzer, any known cellular solid can be as the carrier of metal catalyst in the inventive method, like oxide compound or mixed oxide (like Al
2O
3, Fe
2O
3, TiO
2, V
2O
5, SiO
2, ZnO, SnO
2, ZrO
2, MgO, SiO
2-Al
2O
3, ZrO
2-SiO
2), in SiC, carbon material (like gac), shale soil (like kaolin and zeyssatite), the mesoporous material (like MCM-41, SBA-15 etc.), carbonate (like lime carbonate etc.).Solid support material can also be with Al
2O
3, TiO
2, V
2O
5, SiO
2, ZnO, SnO
2With at least a complex carrier that forms on the inertial base that is carried among the MgO, described inertial base comprises metal base and pottery.For example, the solid support material that uses of the catalyzer among the present invention is Al
2O
3, Fe
2O
3, TiO
2, V
2O
5, SiO
2, ZnO, SnO
2, ZrO
2, a kind of in MgO, SiC, gac, kaolin and the zeyssatite or two or more mixture in them.If desired, various carrier can mix use.Mixture among the present invention not only can their mechanical mixture, also can be the mixed oxide that has chemical bond to exist, like Al
2O
3-SiO
2Solid support material when ' carrier ' as herein described not only refers to be used for loaded catalyst that pickling process, ion exchange method and spraying method etc. obtain, and can also refer to the supporter (perhaps the someone is referred to as structural promoter) of unsupported catalysts such as coprecipitation method, kneading method.
The metal catalyst that any known Preparation of catalysts method in this area obtains can be applied in the method for the present invention, and they comprise, for example, and coprecipitation method, pickling process, kneading method, spraying method, ion exchange method, sol-gel method etc.The preferred method for preparing catalyst of method of the present invention is pickling process, coprecipitation method, pressed disc method and ion exchange method.
As the composition of the hydrogenation catalyst among the present invention, except that the silane group part, be exemplified below: Ni/Al
2O
3, Cu-Zn/Al
2O
3, Cu-Cr/SiO
2, Pd-Ni/ zeyssatite, Ru/TiO
2, Ni-B/Al
2O
3, Cu-Co-Zn/MgAl
2O
4, Ni-Cu/SiO
2, Cu-Zn-K/ gac, Cu-Zn-Pd/TiO
2
Catalyzer described in the present invention also contains silane group, accounts for catalyzer total mass 0.05wt%-25wt%, is preferably 0.1wt%-15wt%.
Silane group still imperfectly understands in the grafting situation on the surface of catalyzer, still, can make rational supposition to the form of silane group according to the molecular structure of silylating reagent and the principle of Silanization reaction.Following wherein the existence form of several kinds of silane groups after the grafting on the catalyzer for example:
Described silane group can be used following general formula (1) statement:
Wherein, substituent R
1, R
2And R
3Can be identical or different alkyl independently of one another; For example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc.; Simultaneously according to the option demand that reacts; Alkyl can also be aromatic, and another covalent linkage of the Sauerstoffatom of the last connection of Si is connected on the catalyzer, the covalent linkage through this Sauerstoffatom with the silane group grafting on catalyzer.
Described silane group can also be used following general formula (2) statement:
Substituent R wherein
1, R
2, R
4And R
5Can be identical or different alkyl independently of one another, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc., according to the option demand of reaction, alkyl can also be aromatic, substituent R simultaneously
3Be a kind of in chlorine, nitrogen and the oxygen, another covalent linkage of the Sauerstoffatom of the last connection of Si is connected on the catalyzer, the covalent linkage through this Sauerstoffatom with the silane group grafting on catalyzer.
Described silane group can also be used following general formula (3) statement:
Substituent R wherein
1And R
2Can be identical or different alkyl independently of one another; For example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc.; Simultaneously according to the option demand that reacts; Alkyl can also be aromatic, and another covalent linkage of the Sauerstoffatom of the last connection of Si is connected on the catalyzer, the covalent linkage through this Sauerstoffatom with the silane group grafting on catalyzer.
The mode that metal component loads on the carrier can be multiple, for example floods through the salt of metallic element or the solution or the suspension-s of oxide compound, and is dry then.Dry post-heating to 300 ℃～600 ℃ of roastings are MOX, and the atmosphere of roasting can be air, nitrogen, oxygen, argon gas or their mixture.The another kind of method of metal component load is that the salt of metallic element or the solution or the suspension-s of oxide compound flood, and is dry then, can also use a kind of reductive agent after the drying with all or part of zero-valent metal attitude that is converted into of metal component.The reductive agent that uses comprises hydrogen, hydrogenous gas, polyvalent alcohol or hydrazine, the gas and the polyvalent alcohol of handy hydrogen, and reductive agent can be reduced to corresponding metal or than the compound of suboxide valency with active metallic compound.In addition, metal component also can load on the carrier through the mode of spraying, metal or metallorganics evaporation, uniform deposition.More than to the metal component carrying method be for example just metal component load on the explanation catalyzer, this professional can be at an easy rate through conversion step with the load that realizes metal component and the adding of auxiliary agent, these do not influence essence of the present invention.
Auxiliary agent can load on the carrier to realize improving the hydrogenation performance of catalyzer through the above-mentioned carrying method identical with metal component.The joining day of auxiliary agent can be before the reactive metal load, perhaps add with reactive metal afterwards.The adding of auxiliary agent can also be in the moulding process of carrier.In the moulding process of carrier, the salt of metal promoter or oxide compound can add, and are dispersed on the catalyzer.
Because silylating reagent has high reaction activity and high, so the concrete reaction in the silylanization treating processes is not still come to a conclusion completely.In chromatogram, use the empirical principle that obtains according to Silanization reaction, in the siloyl group treating processes, silane group through the silylanizing method hydroxyl on silicomethane base and the catalyst surface is carried out condensation reaction and grafting to catalyst surface.The principle that with the organo-siloxane is silicomethane base raw material is exemplified below:
The grafting process can be carried out in liquid phase solvent, and effectively solvent can be a kind of in ketone, ether, hydrocarbon and the ester, preferred ether and hydro carbons.Particularly, effectively solvent can be a kind of or mixed solvent in toluene, benzene, YLENE, hexanaphthene, normal hexane, heptane, ether, methyl-phenoxide, THF, whiteruss, the saturated gasoline of hydrogenation, the saturated diesel oil of hydrogenation, the sherwood oil.The grafting process generally needs controlled temperature at 30 ℃～320 ℃, is preferably 50 ℃～180 ℃.
The grafting of silane group also can be through another kind of way: silicomethane base form with gas or fine droplet under the carrying of carrier gas is contacted with catalyzer, thereby accomplish the silylation of catalyzer is handled.The carrier gas of using can be a kind of in nitrogen, air, hydrogen, oxygen, carbonic acid gas and the argon gas or two or more mixture in them.In the limited Catalyst Production factory of some conditions, in absence following time of carrier gas, also can be heated to be the silicomethane base behind the steam and contact the grafting of carrying out silane group with catalyzer.During grafting, temperature is controlled at 60 ℃～450 ℃, preferably at 85 ℃～280 ℃ by this method.
The silicomethane base can be selected from least a in organosilane, organo-siloxane, organosilazanes and the organic oxosilane; For example; For example Union carbide A-162, dimethyldiethoxysilane, trimethylammonium diethoxy silane, ethyl triethoxysilane, diethylammonium diethoxy silane, triethyl-ethoxy-silicane alkane, ethyl trimethoxy silane, butyl triethoxyl silane, dimethyl-one ethyl methoxy silane, dimethyl-one phenyl ethoxy silane, tripropyl methoxy silane, trimethylchlorosilane, dimethyldichlorosilane(DMCS), dimethyl-one propyl chloride silane, dimethylbutyl chlorosilane, dimethyl-isopropyl chloride silane, tributyl chlorosilane, hexamethyldisilazane, heptamethyldisilazane, tetramethyl-disilazane, 1; 3-dimethyl-diethylammonium disilazane, 1,3-phenylbenzene tetramethyl-disilazane etc.
Silane group is very big to catalyzer water resisting property of the present invention and anti-carbon performance impact in the coverage of catalyst surface.When coverage is low; Water resisting property and anti-carbon performance can not be brought into play fully, and when coverage is too high, thereby the surfactivity position that may cause polymerization covering catalyst between silane; Reduce activity of such catalysts; Therefore need the content of control silane group in catalyzer, generally account for catalyzer total mass 0.05wt%～25wt%, be preferably 0.1wt%～15wt%.The coverage of silane group can realize point-device control through regulating silicomethane base raw material, silylanizing treatment time, silylanizing treatment temp, carrier gas kind and flow velocity (vapor phase process) and solvent methods such as (liquid phase methods).When using the gas phase silylanizing, silicomethane base raw material generally was controlled at 0.001 second～400 seconds in the beds residence time.Save operation cost and running time can also be regulated silicomethane base material concentration and realize at 1 minute～80 hours the vapor phase process overall operation time.And when using liquid phase method, the scope of the time residence time was controlled at 0.5 second～24 hours.
The coverage of the silane group of grafting can be analyzed through using x-ray photoelectron power spectrum (XPS) on the hydrogenation catalyst of the present invention, confirms the amount of carbon atom of catalyst surface, thus the gauging surface coverage; Also can use infrared appearance (IR) to observe the functional group of catalyst surface, as passing through-CH
3Characteristic peak (～2970cm
-1) gauging surface silane level of coverage, through the characteristic peak (～3750cm of-OH
-1) calculate catalyst surface hydroxyl residual content.Can be through organic carbon/elemental carbon (OC/EC) thus the quantitative organic carbon content of analyser accurately obtains the siloyl group quality on the catalyzer.
As everyone knows, aldehyde hydrogenating catalyst generally need carry out pre-treatment before use.Catalyzer of the present invention needs pre-treatment before use, and pre-treatment mainly is to be corresponding active state or with the impurity removal that adsorbs on the catalyzer with catalyst reduction.The reduction pre-treatment can adopt hydrogen, hydrogen-containing gas, CO or hydrazine MOX on the catalyzer to be reduced to the metal of zeroth order or lower valency.Above-described these pre-treatment all are to know for this professional.
Method of the present invention is applied to the reaction member of aldehyde hydrogenation preparing alcohols; The reaction member of advantageous applications has: hydrogenation of propionaldehyde is that n-propyl alcohol, hydrogenation of n-butyraldehyde are that propyl carbinol, octenal are hydrogenated to that octanol, enanthaldehyde are hydrogenated to enanthol, hydrogenation of furfural is a furfuryl alcohol, 2; 2-methylol butyraldehyde hydrogenation preparing TriMethylolPropane(TMP), 3-hydroxy propanal are hydrogenated to 1, and ammediol, glucose hydrogenation are sorbyl alcohol.
Catalyzer is applicable to the reaction of gas phase-liquid phase-solid phase three-phase system, gas-solid phase and gas phase-supercritical phase-systems such as liquid phase-solid phase.Particularly, in hydrogenation process, the form of aldehyde gas phase exists, and form gas phase-solid phase two-phase system between aldehyde, hydrogen (perhaps hydrogen gas) and the solid-phase catalyst as raw material this moment; Simultaneously, aldehyde also can most of form with liquid phase exist, and forms gas phase-liquid phase-solid phase three-phase system with hydrogen (perhaps hydrogen gas), solid-phase catalyst etc.In the process of hydrogenation; Can also introduce one liquid phase as solvent phase; As solvent can be ethers, alcohols, furans or water; Preferably have water, methyl alcohol, propyl alcohol, butanols, THF, dioxa six rings, form gas phase-liquid phase-solid phase three-phase system between raw material aldehyde, solvent phase, hydrogen (the perhaps mixed gas of hydrogen) and solid-phase catalyst at this moment.
On the type of reactor drum, method of the present invention can be used any one the perhaps two or more combination in fixed bed, fluidized-bed, slurry attitude bed, moving-bed, Magnetic suspension float bed, the reaction rectification bed.
The reaction conditions of the method for the invention need be controlled, and temperature of reaction is 20 ℃～300 ℃ in the method for the invention, and reaction pressure 0.1MPa～7.0MPa, the weight space velocity of aldehyde are 0.02h
-1～20h
-1Described temperature of reaction refers to temperature of reactor, and described reaction pressure is the pressure of reactor drum, and the weight space velocity of aldehyde is the aldehyde raw material weight of the catalyzer institute hydrotreatment of unit mass in the unit time.The reaction conditions of the inventive method is preferably: 50 ℃～260 ℃ of temperature of reaction, reaction pressure 0.1MPa～5.0MPa, the weight space velocity 0.1h of aldehyde
-1～8h
-1Reaction pressure, temperature of reaction and air speed stable is controlled to be that present professional and technical personnel knows.
With respect to existing aldehyde hydrogen addition technology, the method for aldehyde hydrogenation hydrogenation preparing alcohols of the present invention has the following advantages:
(1) method by product of the present invention is few, has higher purpose selectivity, and downstream separation process simplification and energy consumption reduce.Because the silane group of the employed catalyst surface of the inventive method can obviously suppress aldehyde from side reactions such as condensation, aldol condensation and etherificates, the purpose selectivity of product obtains height; The silane group that the while catalyst surface has has hydrophobicity, a little less than oh group absorption, therefore can reduce the pure absorption in reaction back, further reduces the follow-up side reaction after alcohol generates; Because the significantly reduction of amount of by-products, the separating unit in downstream can obtain simplifying, energy consumption also obtains to reduce thus.
(2) generation that can suppress polymkeric substance significantly of catalyzer described in the method for the present invention, thus the carbon distribution that generates on the catalyzer reduced, significantly improve work-ing life of catalyzer;
(3) method of the present invention only need be replaced catalyzer, and the manufacturing of said catalyzer can most of utilize existing catalyst technology and equipment, and industry is amplified simple, and the relative prior art investment of cost is less;
Embodiment
Following examples are to more detailed the describing for example of the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
The trifolium shape Ni-Cr-Mo-K/Al of cut-off footpath 3mm
2O
3Catalyzer 50 grams (volume 72ml, the mass percentage content of Ni, Cr, Mo and K is respectively 22%, 8%, 4.5% and 2.2%, and surplus is Al
2O
3, weightless 1.9wt% when temperature rises to 500 ℃ on the thermogravimetric analyzer), catalyzer is packed in the fixed-bed reactor (diameter 15mm, length 400mm are with two temperature to show reference mark).After temperature of reactor is stabilized in 80 ℃; The hydrogen that will contain the trimethylammonium methoxyl group alkane of 2vol% feeds in the reactor drum; Flow control is at 300ml/min, and 80 ℃ are warming up to 120 ℃ after keeping 2h, keep stopping to get in 1 hour the hydrogen that contains trimethylammonium methoxyl group alkane behind the temperature-stable; Mend the nitrogen cooling, obtain catalyzer Cat-1.
Compare Ni-Mo-K/Al through Fourier's infrared spectrometric analyzer (FTIR)
2O
3And Cat-1, the characteristic peak (～2970cm of the methyl that Cat-1 is last
-1) obviously be better than Ni-Mo-K/Al
2O
3, and the characteristic peak (～3750cm of hydroxyl
-1) obviously be weaker than Ni-Mg/Al
2O
3, this explains Ni-Mo-K/Al
2O
3On part of hydroxyl replaced by siloyl group.The ICP-AES elemental analyser is analyzed Si content, and quantitatively Si content is 1.7wt% among the Cat-1 of back; Be 2.21wt% through the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser simultaneously, the siloyl group mass percent on the catalyzer is 5.41wt% in view of the above.
Comparative Examples 1
The trifolium shape Ni-Cr-Mo-K/Al of cut-off footpath 3mm
2O
3Catalyzer 50 gram (Beijing Chemical Research Institute produces, and catalyzer is identical with embodiment 1) is packed catalyzer in one fixed-bed reactor (diameter 15mm, length 400mm are with two temperature demonstration reference mark) into.After temperature of reactor is stabilized in 80 ℃, hydrogen is fed in the reactor drum, flow control is at 300ml/min, and 80 ℃ are warming up to 120 ℃ after keeping 2h, keep stopping to get in 1 hour hydrogen behind the temperature-stable, mend the nitrogen cooling, obtain catalyzer Cat-2.
Compare Ni-Cr-Mo-K/Al through Fourier's infrared spectrometric analyzer (FTIR)
2O
3And Cat-2, Cat-2 and Ni-Cr-Mo-K/Al
2O
3On all do not have a tangible methyl characteristic peak (～2970cm
-1), and the characteristic peak (～3750cm of hydroxyl
-1) burn and to be weaker than Ni-Cr-Mo-K/Al
2O
3.The ICP-AES elemental analyser is analyzed Si content, and quantitatively Si content is 0.001wt% among the Cat-2 of back; Be lower than the instrument lower limit through the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser simultaneously.
Embodiment 2
The strip Cu-Cr/ZrO of cut-off footpath 3mm
2-Al
2O
3Catalyzer 15 grams (Beijing Chemical Research Institute produces, volume 14ml, and the mass percentage content of Cu and Mg is respectively 20.1% and 12.8%, and surplus is ZrO
2-Al
2O
3, weightless 1.8wt% when temperature rises to 500 ℃ on the thermogravimetric analyzer), catalyzer to be packed in the 500ml there-necked flask, there-necked flask places in the oil bath, and a bite in the there-necked flask connects cooling coil, and a bite jointing temp meter connects opening for feed flatly.At first in there-necked flask, pour the 80ml p-Xylol into, and will be after temperature of reactor is stabilized in 110 ℃, will contain in the feeding reactor drum of hexa methyl silazane of 8ml.110 ℃ are warming up to 140 ℃ after keeping 1h, keep cooling after 1 hour behind the temperature-stable, take out catalyzer 160 ℃ of dry 3h in baking oven, obtain catalyzer Cat-3.
Compare Cu-Cr/ZrO through Fourier's infrared spectrometric analyzer (FTIR)
2-Al
2O
3And Cat-3, the characteristic peak (～2970cm of the methyl that Cat-3 is last
-1) obviously be better than Cu-Cr/ZrO
2-Al
2O
3, and the characteristic peak (～3750cm of hydroxyl
-1) obviously be weaker than Cu-Cr/ZrO
2-Al
2O
3, this explains Cu-Cr/ZrO
2-Al
2O
3On part of hydroxyl replaced by siloyl group.The ICP-AES elemental analyser is analyzed Si content, and quantitatively Si content is 1.1wt% among the Cat-3 of back; Be 1.50wt% through the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser simultaneously, the siloyl group mass percent on the catalyzer is about 3.55wt% in view of the above.
Comparative Examples 2
The strip Cu-Cr/ZrO of cut-off footpath 3mm
2-Al
2O
3Catalyzer 15 gram (Beijing Chemical Research Institute produces, and is identical with embodiment 2) is packed catalyzer in the one 500ml there-necked flask into, and there-necked flask places in the oil bath, and a bite in the there-necked flask connects cooling coil, and a bite jointing temp meter connects opening for feed flatly.At first in there-necked flask, pour the 80ml p-Xylol into, and be warming up to 140 ℃ after will after temperature of reactor is stabilized in 110 ℃, keeping 1h, keep cooling after 1 hour behind the temperature-stable, take out catalyzer 160 ℃ of dry 3h in baking oven, obtain catalyzer Cat-4.
Compare Cu-Cr/ZrO through Fourier's infrared spectrometric analyzer (FTIR)
2-Al
2O
3And Cat-4, Cat-4 and Cu-Cr/ZrO
2-Al
2O
3On the characteristic peak (～2970cm of the methyl that all do not have
-1), and the characteristic peak (～3750cm of hydroxyl
-1) and Cu-Cr/ZrO
2-Al
2O
3Close.The ICP-AES elemental analyser is analyzed Si content, and quantitatively Si content is 0.003wt% among the Cat-4 of back; Be 0.01wt% through the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser simultaneously.
Embodiment 3
The catalyzer of embodiment 1 and Comparative Examples 1 is applied to 3-hydroxy propanal hydrogenation respectively.Hydrogenator is a 100ml isothermal fixed bed, catalyzer 10.0g.The processing condition of hydrogenation reaction such as table 1 (selectivity refers to 1, the ammediol selectivity).Reaction 1500h finishes the back and compares carbon deposition quantity through thermogravimetric-mass spectrometry.
Reaction conditions is formed as shown in table 1 down, wherein 3-hydroxy propanal liquid hourly space velocity 2.0h
-1, hydrogen and 3-hydroxy propanal mol ratio be 8.0, water cut 380ppm.
The result is as shown in table 1, and experiment shows that with respect to existing method method purpose selectivity of the present invention is high, and catalyst surface carbon distribution amount is low, and deactivation rate is low.
The catalyst reactivity worth of table 1 embodiment 1 and Comparative Examples 1
Carbon deposition quantity is measured: thermogravimetric-GC-MS, in the air atmosphere of 30ml/min, 10 ℃/Min of temperature rise rate is from room temperature to 450 ℃ and kept 1 hour, according to CO in the mass spectrum
2The weightless peak position of thermogravimetric carbon distribution and quantitative according to the weightless result of thermogravimetric is confirmed at the peak.
Embodiment 4
The catalyzer of embodiment 2 Comparative Examples 2 is applied to the reaction of butyraldehyde liquid-phase hydrogenatin respectively, and wherein hydrogen reactor is a 50ml isothermal fixed bed, catalyzer 8.0g.The processing condition of hydrogenation reaction such as table 2 (selectivity make a comment or criticism butanols selectivity).Reaction 1200h finishes the back and compares carbon deposition quantity through thermogravimetric-mass spectrometry.The result is shown in table two, and experiment shows that with respect to prior art method selectivity of the present invention is high, and catalyst surface carbon distribution amount is low, and deactivation rate is low.
The catalyst reactivity worth of table 2 embodiment 2 and Comparative Examples 2
Carbon deposition quantity is measured: thermogravimetric-GC-MS, in the air atmosphere of 30ml/min, 10 ℃/Min of temperature rise rate is from room temperature to 450 ℃ and kept 1 hour, according to CO in the mass spectrum
2The weightless peak position of thermogravimetric carbon distribution and quantitative according to the weightless result of thermogravimetric is confirmed at the peak.
Claims (18)
1. an aldehyde is selected the method for hydrogenation preparing alcohol, it is characterized in that, and with aldehyde raw material, be 0.02h at the weight space velocity of 20 ℃～300 ℃ of temperature of reaction, reaction pressure 0.1MPa～7.0MPa and aldehyde
-1～20h
-1Down, aldehyde contacts with hydrogenation catalyst with hydrogen, and aldehyde is selected to be hydrogenated to alcohol, and described hydrogenation catalyst contains carrier, metal active constituent and silane group, and described silane group is handled grafting through silylanizing.
2. the method for claim 1 is characterized in that, described metal active constituent is at least a in palladium, nickel, platinum, copper and the cobalt, and its percentage ratio that accounts for the catalyzer gross weight is 0.05wt%～70wt%.
3. method as claimed in claim 2 is characterized in that, described metal active constituent is at least a in copper, cobalt and the nickel, and its percentage ratio that accounts for the catalyzer gross weight is 0.5wt%～60wt%.
4. hydrogenation catalyst as claimed in claim 3 is characterized in that, described metal active constituent is at least a in the copper and mickel, and its percentage ratio that accounts for the catalyzer gross weight is 5wt%～50wt%.
5. the method for claim 1 is characterized in that, described catalyzer also contains metal promoter a, and described metal promoter A is at least a metallic element in IA family, IIA family and the VA family, and its content is the 0.01wt%～10wt% of catalyzer gross weight.
6. method as claimed in claim 5 is characterized in that, described metal promoter a is at least a metallic element of potassium, calcium, magnesium, barium, bismuth, and its content is the 0.1wt%～6wt% of catalyzer gross weight.
7. like claim 1 or 5 described hydrogenation catalysts; It is characterized in that; Described catalyzer also contains metal promoter b, and described metal promoter is at least a metallic element in IB family, IIB family, IIIB family and the group vib, and its content is the 0.01wt%～30wt% of catalyzer gross weight.
8. method as claimed in claim 7 is characterized in that, described metal promoter b is at least a in silver, gold, zinc, lanthanum, cerium, chromium, molybdenum and the tungsten, and its content is the 0.5wt%～25wt% of catalyzer gross weight.
9. like claim 1,5 or 7 described methods; It is characterized in that; Described catalyzer also contains non-metal assistant d, and described non-metal assistant d is at least a non-metallic element in IIIA family, IVA and the VA family, and its content is the 0.01wt%～8wt% of catalyzer gross weight.
10. method as claimed in claim 9 is characterized in that, described metal promoter d is at least a in boron, phosphorus, sulphur, selenium, fluorine, chlorine and the iodine, and its content is the 0.1wt%～4wt% of catalyzer gross weight.
11. the method for claim 1 is characterized in that, described carrier is selected from Al
2O
3, Fe
2O
3, TiO
2, V
2O
5, SiO
2, ZnO, SnO
2, ZrO
2, a kind of in MgO, gac, kaolin and the zeyssatite or two or more mixture in them;
12. the method for claim 1 is characterized in that, described silane group accounts for the 0.05wt%～25wt% of catalyzer gross weight.
13. method as claimed in claim 12 is characterized in that, described silane group accounts for the 0.1wt%～15wt% of catalyzer gross weight.
14. the method for claim 1 is characterized in that, silylanizing is handled the silicomethane base use and is a kind of in organosilane, organo-siloxane, organosilazanes and the organic oxosilane or two or more mixture in them.
15. method as claimed in claim 14 is characterized in that, silylanizing is handled the silicomethane base use and is a kind of in organo-siloxane and the organosilazanes or their mixture.
16. the method for claim 1; It is characterized in that; Described method is applied to: hydrogenation of propionaldehyde is that n-propyl alcohol, hydrogenation of n-butyraldehyde are that propyl carbinol, octenal are hydrogenated to that octanol, enanthaldehyde are hydrogenated to enanthol, hydrogenation of furfural is a furfuryl alcohol, 2; 2-methylol butyraldehyde hydrogenation preparing TriMethylolPropane(TMP), 3-hydroxy propanal are hydrogenated to 1, and ammediol or glucose hydrogenation are sorbyl alcohol.
17., it is characterized in that described method is carried out under following reaction conditions: the weight space velocity 0.1h of 50 ℃～260 ℃ of temperature of reaction, reaction pressure 0.1MPa～5.0MPa and aldehyde like claim 1 described method
-1～3h
-1
18., it is characterized in that the mol ratio of hydrogen and aldehyde is 1～200 like claim 1 or 17 described methods.
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