CN102408304B - 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
Relate to a kind of aldehyde Hydrogenation herein for method and the application thereof of alcohol.
Background technology
Aldehyde hydrogenation is the important method of preparing monohydroxy-alcohol and polyvalent alcohol in industry.As industry for a long time of development, hydrogen atom source be the reducing substances (as formic acid, alcohol, hydrazine hydrate etc.) of hydrogen or hydrogen atoms.The former is the method for the aldehyde hydrogenation of existing main flow, is mainly used in scale operation alcohols, need to use metal catalyst, and the latter usually uses in synthetic medicine, organic intermediate etc. are small-sized, the metal catalyst of use or basic catalyst.Situation for 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 for alcohol, object selectivity of product has vital meaning 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 are wherein as more difficult in acetal and product formation separated, and this causes aldehyde hydrogenation process middle and lower reaches must have complicated separable programming.
Therefore, reduce the side reactions such as etherificate and condensation and not only can improve the yield of catalyzer, and the by product that enters downstream reduces and to mean that downstream separation energy consumption can significantly reduce, even can realize the simplification of downstream process, the quality of product can be improved simultaneously.
Aldehydes can be polymerized to the surface that superpolymer covers catalyzer by condensation reaction can cover hydrogenation activity position, reduces catalyst activity; Also can stop up 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 is usually extremely important or major cause (Xiao Da Zhu and Hanns Hofmann, Applied Catalysis A:General, Volume 155, and Issue 2,31July 1997, Pages 179-194).The life-span of extending catalyst can promote efficiency, energy consumption and the economic benefit of reaction unit to improving the efficiency of device.
US Patent No. 4762817 has been introduced a kind of method of aldehyde hydrogenation, and the catalyzer chief component of use is Cu and Zn, and adds the mixture of basic metal, transition metal or basic metal and transition metal as auxiliary agent.Wherein basic metal can be one or more in Na, K, Li, Ce, and it adds massfraction is 0.05%～7.0%, preferably 0.3%～3.5%; Transition metal as the add-on of Ni, Co or its mixture be 0.15%～5.0%, preferably 1.0%～4.0%.The Main Function of these auxiliary agents is the side reactions that reduce in hydrogenation, 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 aldehyde hydrogenating catalyst, it is characterized in that adopting alkaline-earth metal Mg as auxiliary agent.In catalyzer, the metal Ni massfraction of reduction-state is 25%～50%, the Ni massfraction of oxidation state is that 10%～35%, MgO massfraction is that 4%～12%, 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
3and (or) SiO
2, diatomite is as carrier.
The Ni introducing in EP394842 A1 is aldehyde hydrogenating catalyst, except having added Cu, has also added the 3rd component Zr and the 4th component Mo.This catalyzer is to adopt coprecipitation method preparation, and before reduction, in oxide catalyst, the massfraction of each component is: NiO 20%～75%, ZrO
210%～75%, CuO 5%～50%, MoO
30.1%～5%.
Above-mentioned technological method all raising to a certain degree the selectivity of object product, reduced the side reactions such as condensation, etherificate, but along with the improving constantly and the consideration of industry member to downstream energy consumption of product quality requirement, the selectivity of object product 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 reduce the side reaction such as condensation, etherificate in aldehyde hydrogenation reaction, reduce catalyst surface carbon distribution simultaneously and generate cost and the energy consumption for alcohols all has great importance to aldehyde Hydrogenation.
Summary of the invention
For meeting current people, to improving aldehyde, be hydrogenated to the selectivity of alcohol and the two aspect requirements in extending catalyst work-ing life, the present invention proposes a kind of method, can effectively improve the object selectivity of product of hydrogenation process, simultaneously method of the present invention also has that the growing amount of carbon distribution on catalyzer is little, the feature of long service life.
The present invention relates to that in a kind of aldehyde, Hydrogenation is for the method for alcohols, concrete grammar is as follows: take aldehyde as raw material, and 20 ℃～300 ℃ of temperature of reaction, reactor pressure 0.1MPa～7.0MPa, the weight space velocity of aldehyde is 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, the silane group process silylanizing processing grafting on the catalyzer described in it is characterized in that.With respect to existing method, method of the present invention has the two obvious advantages in aspect: 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, the present inventor finds by utilizing silane group in grafting can significantly reduce the by product that the reactions such as etherificate and condensation cause containing on the carrier supported catalyst of hydroxyl.The inventor also finds that it is the surface hydroxyl quantity of catalyzer that carbon distribution has very close relationship, although also there is no strict proof at present, but 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 theoretically, the silane group that catalyst surface has has hydrophobicity, a little less than oh group absorption, therefore can reduce the absorption of the rear alcohol of reaction, further reduces the follow-up side reaction after alcohol generates.The present invention completes after inferring based on above discovery and theory.
Concrete technical scheme is as follows:
Aldehyde of the present invention selects Hydrogenation for the method for alcohol, is to take aldehyde as raw material, at the weight space velocity of 20 ℃～300 ℃ of temperature of reaction, reaction pressure 0.1MPa～7.0MPa and aldehyde, is 0.02h
-1～20h
-1under, 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 processed grafting through silylanizing.
Preferably, described metal active group is at least one in palladium, nickel, platinum, copper and cobalt, and its percentage ratio that accounts for catalyzer gross weight is 0.05wt%～70wt%.More preferably, described metal active constituent is at least one in copper, cobalt and nickel, and its percentage ratio that accounts for catalyzer gross weight is 0.5wt%～60wt%.Further preferably, described metal active group is at least one in copper and mickel, and its percentage ratio that accounts for 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, described metal promoter A ShiIA family, at least one metallic element in IIAZu He VA family, and its content is the 0.01wt%～10wt% of catalyzer gross weight.More preferably, described metal promoter a is at least one 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, in the above-mentioned various catalyzer schemes that do not contain metal promoter a and contain metal promoter a, described catalyzer also contains metal promoter b, at least one metallic element in described metal promoter Shi IB family, IIB family, IIIB family and group vib, its content is the 0.01wt%～30wt% of catalyzer gross weight.More preferably, described metal promoter b comprises at least one in silver, gold, zinc, lanthanum, cerium, chromium, molybdenum and tungsten, and its content is the 0.5wt%～25wt% of catalyzer gross weight.
In order further to improve the catalytic performance of catalyzer, above-mentionedly do not containing metal promoter a and b, only containing metal promoter a, only containing metal promoter b and contain in the various catalyzer schemes of metal promoter a and b simultaneously, described catalyzer also contains non-metal assistant d, described non-metal assistant d is at least one non-metallic element in IIIA family, IVAHe VA family, and its content is the 0.01wt%～8wt% of catalyzer gross weight.More preferably, described metal promoter d is at least one in boron, phosphorus, sulphur, selenium, fluorine, chlorine and iodine, and its content is the 0.1wt%～4wt% of catalyzer gross weight.
Catalyzer of the present invention can be used any carrier, but from the industrial application situation of hydrogenation of unsaturated hydrocarbons, preferably 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 diatomite or two or more mixture in them;
In catalyzer of the present invention, described silane group is processed grafting through silylanizing, more preferably described silane group be take silicomethane base as raw material grafting by silylanizing method, described silane group accounts for the 0.05wt%～25wt% of catalyzer gross weight, more preferably 0.1wt%～15wt%.
In silylanizing process, the silicomethane base that silylanizing process to be used is preferably a kind of in organosilane, organo-siloxane, organosilazanes and organic oxosilane or two or more mixture in them; A kind of in organo-siloxane and organosilazanes or their mixture 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 furfuryl alcohol, 2,2-methylol butyraldehyde Hydrogenation is hydrogenated to 1,3-PD for TriMethylolPropane(TMP), 3-HPA or glucose hydrogenation is 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, if oxide compound or mixed oxide are (as 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 (as gac), shale soil (as kaolin and diatomite), mesoporous material (as MCM-41, SBA-15 etc.), carbonate (as calcium carbonate etc.).Solid support material can also be by Al
2o
3, TiO
2, V
2o
5, SiO
2, ZnO, SnO
2be carried on at least one in MgO the complex carrier forming on inertial base, described inertial base comprises metal base and pottery.For example, the solid support material that the catalyzer in the present invention is used 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 diatomite or two or more mixture in them.If needed, various carriers can mix use.Mixture in the present invention not only can their mechanical mixture, can be also the mixed oxide that has chemical bond to exist, as Al
2o
3-SiO
2.Solid support material during loaded catalyst that ' carrier ' as herein described not only refers to obtain for pickling process, ion exchange method and spraying method etc., and can also refer to the supporter (or having people to be referred to as structural promoter) of the unsupported catalysts such as coprecipitation method, kneading method.
The metal catalyst that the preparation method of any known catalyzer in this area obtains can be applied in method of 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 in the present invention, except silane group part, be exemplified below: Ni/Al
2o
3, Cu-Zn/Al
2o
3, Cu-Cr/SiO
2, Pd-Ni/ diatomite, 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 surperficial grafting situation of catalyzer, still, according to the principle of the molecular structure of silylating reagent and Silanization reaction, can make rational supposition to the form of silane group.Existence form after the grafting of several silane groups of below giving an example wherein on catalyzer:
Described silane group can be explained with following general formula (1):
Wherein, substituent R
1, R
2and R
3can be identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc., simultaneously according to the option demand reacting, alkyl can also be aromatic, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
Described silane group can also be explained with following general formula (2):
Substituent R wherein
1, R
2, R
4and R
5can be identical or different alkyl independently of one another, such as 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 oxygen, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
Described silane group can also be explained with following general formula (3):
Substituent R wherein
1and R
2can be identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc., simultaneously according to the option demand reacting, alkyl can also be aromatic, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
The mode that metal component loads on carrier can be multiple, for example, by the salt of metallic element or the solution of oxide compound or suspension, flood, then dry.Dry post-heating to 300 ℃～600 ℃ of roastings are metal oxide, 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 of oxide compound or suspension flood, then dry, can also use a kind of reductive agent after dry metal component is converted into zero-valent metal state in whole or in part.The reductive agent using comprises hydrogen, hydrogeneous gas, polyvalent alcohol or hydrazine, gas and the polyvalent alcohol of handy hydrogen, and reductive agent can be reduced to active metallic compound on corresponding metal or compared with the compound of suboxide valency.In addition, metal component also can load on carrier by the mode of spraying, metal or metallorganics evaporation, uniform deposition.Above to metal component carrying method be for example just metal component load on explanation catalyzer, those skilled in the art can be at an easy rate by conversion step to realize the load of metal component and adding of auxiliary agent, these do not affect essence of the present invention.
Auxiliary agent can load on carrier to realize the Hydrogenation that improves catalyzer by the above-mentioned carrying method identical with metal component.The joining day of auxiliary agent can be before active metal load, add afterwards or together with active metal.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 catalyzer.
Because silylating reagent has higher reactive behavior, so the concrete reaction in silanization treating processes is not still come to a conclusion completely.According to Silanization reaction, in chromatogram, apply the empirical principle obtaining, in silylation treating processes, silane group by silylanizing method, the hydroxyl on silicomethane base and catalyst surface is carried out to condensation reaction and grafting to catalyst surface.The principle that the organo-siloxane of take is silicomethane base raw material is exemplified below:
Grafting process can be carried out in liquid phase solvent, and effectively solvent can be a kind of in ketone, ether, hydrocarbon and ester, preferably ether and hydro carbons.Particularly, effectively solvent can be a kind of or mixed solvent in toluene, benzene, dimethylbenzene, hexanaphthene, normal hexane, heptane, ether, methyl-phenoxide, tetrahydrofuran (THF), whiteruss, the saturated gasoline of hydrogenation, the saturated diesel oil of hydrogenation, sherwood oil.Grafting process generally need to be controlled temperature at 30 ℃～320 ℃, is preferably 50 ℃～180 ℃.
The grafting of silane group also can be by another kind of way: silicomethane base form with gas or fine droplet under the carrying of carrier gas is contacted with catalyzer, thereby complete, the silylation of catalyzer is processed.The carrier gas of using can be a kind of in nitrogen, air, hydrogen, oxygen, carbonic acid gas and argon gas or two or more mixture in them.In the limited Catalyst Production factory of some conditions, in absence lower time of carrier gas, contacts the grafting of carrying out silane group after also silicomethane base can being heated to be to steam with catalyzer.During grafting, temperature is controlled at 60 ℃～450 ℃, preferably at 85 ℃～280 ℃ by this method.
Silicomethane base can be selected from organosilane, organo-siloxane, at least one in organosilazanes and organic oxosilane, for example, Union carbide A-162 for example, dimethyldiethoxysilane, trimethylammonium diethoxy silane, ethyl triethoxysilane, diethyl 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 diethyl disilazane, 1, 3-phenylbenzene tetramethyl-disilazane etc.
Silane group is very large 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 completely, and when coverage is too high, thereby may cause the Adsorption of polymerization covering catalyst between silane, reduce the activity of catalyzer, therefore need to control the content of silane group in catalyzer, generally account for catalyzer total mass 0.05wt%～25wt%, be preferably 0.1wt%～15wt%.The coverage of silane group can be by regulating the methods such as silicomethane base raw material, silylanizing treatment time, silylanizing treatment temp, carrier gas kind and flow velocity (vapor phase process) and solvent (liquid phase method) to realize point-device control.When using gas phase silylanizing, silicomethane base raw material at beds residence time general control at 0.001 second～400 seconds.The vapor phase process overall operation time, saving running cost and operating time can also regulate silicomethane base material concentration to realize at 1 minute～80 hours.And when using liquid phase method, the scope control of the time residence time was at 0.5 second～24 hours.
On hydrogenation catalyst of the present invention, the coverage of the silane group of grafting can be confirmed the amount of carbon atom of catalyst surface by using x-ray photoelectron power spectrum (XPS) to analyze, thus gauging surface coverage; Also can use infrared instrument (IR) to observe the functional group of catalyst surface, as pass through-CH
3characteristic peak (～2970cm
-1) gauging surface silane level of coverage, by the characteristic peak (～3750cm of-OH
-1) calculate catalyst surface hydroxyl residual content.Can be by organic carbon/elemental carbon (OC/EC) thus the quantitative organic carbon content of analyser accurately obtains the silylation quality on catalyzer.
As everyone knows, aldehyde hydrogenating catalyst generally need to carry out pre-treatment before use.Catalyzer of the present invention needs pre-treatment before use, and pre-treatment is to be mainly corresponding active state or by the impurity removal adsorbing on catalyzer by catalyst reduction.Reduction pretreatment can adopt hydrogen, hydrogen-containing gas, CO or hydrazine metal oxide on catalyzer to be reduced to the metal of zeroth order or lower valency.Above-described these pre-treatment are all known as the professionals.
Method of the present invention is applied to aldehyde Hydrogenation for the reaction member of 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 furfuryl alcohol, 2,2-methylol butyraldehyde Hydrogenation for TriMethylolPropane(TMP), 3-HPA be hydrogenated to 1,3-PD, glucose hydrogenation is sorbyl alcohol.
Catalyzer is applicable to the reaction of the systems such as gas-liquid phase-solid phase three-phase system, vapor solid and gas phase-supercritical phase-liquid phase-solid phase.Particularly, in hydrogenation process, the form of aldehyde gas phase exists, and now between aldehyde, hydrogen (or hydrogen gas) and the solid-phase catalyst as raw material, forms gas phase-solid phase two-phase system; Meanwhile, aldehyde also can most of form with liquid phase exist, and forms gas-liquid phase-solid phase three-phase system with hydrogen (or 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, tetrahydrofuran (THF), dioxa six rings, now between raw material aldehyde, solvent phase, hydrogen (or mixed gas of hydrogen) and solid-phase catalyst, form gas-liquid phase-solid phase three-phase system.
In the type of reactor, method of the present invention can be used any one or the two or more combinations in fixed bed, fluidized-bed, slurry state bed, moving-bed, Magnetic suspension float bed, reaction rectification bed.
The reaction conditions of the method for the invention need to be controlled, and temperature of reaction is 20 ℃～300 ℃ in the method for the invention, reaction pressure 0.1MPa～7.0MPa, and the weight space velocity of aldehyde is 0.02h
-1～20h
-1.Described temperature of reaction refers to temperature of reactor, the pressure that described reaction pressure is reactor, 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
-1.The stable control of reaction pressure, temperature of reaction and air speed is that current professional and technical personnel is known.
With respect to existing aldehyde hydrogen addition technology, the method that aldehyde hydrogenation of the present invention is prepared alcohols has the following advantages:
(1) method by product of the present invention is few, has higher object selectivity, downstream separation process simplification and Energy Intensity Reduction.The silane group of the catalyst surface using due to the inventive method can obviously suppress aldehyde from side reactions such as condensation, aldol condensation and etherificates, and object selectivity of product obtains height; The silane group that catalyst surface has simultaneously has hydrophobicity, a little less than oh group absorption, therefore can reduce the absorption of the rear alcohol of reaction, further reduces the follow-up side reaction after alcohol generates; Due to the significantly reduction of amount of by-products, the separating unit in downstream can be simplified, and energy consumption also obtains and reduces thus.
(2) generation that can suppress significantly polymkeric substance of catalyzer described in method of the present invention, thus the carbon distribution generating on catalyzer, the work-ing life of significantly improving catalyzer reduced;
(3) method of the present invention only need to be replaced catalyzer, and the manufacture of described catalyzer can major part 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
350 grams of catalyzer (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 thermogravimetric analyzer), catalyzer is packed in fixed-bed reactor (diameter 15mm, length 400mm are with two temperature to show reference mark).At temperature of reactor, be stabilized in after 80 ℃, the hydrogen of the trimethylammonium methoxyl group alkane containing 2vol% is passed in reactor, flow control is at 300ml/min, 80 ℃ are warming up to 120 ℃ after maintaining 2h, after temperature-stable, keep within 1 hour, stopping entering the hydrogen containing trimethylammonium methoxyl group alkane, fill into nitrogen cooling, obtain catalyzer Cat-1.
By Fourier's infrared spectrometric analyzer (FTIR), compare Ni-Mo-K/Al
2o
3and Cat-1, the characteristic peak (～2970cm of the methyl on Cat-1
-1) be obviously better than Ni-Mo-K/Al
2o
3, and the characteristic peak (～3750cm of hydroxyl
-1) be obviously weaker than Ni-Mg/Al
2o
3, this illustrates Ni-Mo-K/Al
2o
3on part of hydroxyl by silylation, replaced.ICP-AES elemental analyser is analyzed Si content, and in quantitatively rear Cat-1, Si content is 1.7wt%; By the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser, be 2.21wt%, the silylation mass percent on catalyzer is 5.41wt% accordingly simultaneously.
Comparative example 1
The trifolium shape Ni-Cr-Mo-K/Al of cut-off footpath 3mm
2o
350 grams of catalyzer (Beijing Chemical Research Institute produces, and catalyzer is identical with embodiment 1), pack catalyzer in one fixed-bed reactor (diameter 15mm, length 400mm are with two temperature to show reference mark) into.At temperature of reactor, be stabilized in after 80 ℃, hydrogen is passed in reactor, flow control is at 300ml/min, and 80 ℃ are warming up to 120 ℃ after maintaining 2h, keep stopping entering hydrogen in 1 hour after temperature-stable, fill into nitrogen cooling, obtain catalyzer Cat-2.
By Fourier's infrared spectrometric analyzer (FTIR), compare Ni-Cr-Mo-K/Al
2o
3and Cat-2, Cat-2 and Ni-Cr-Mo-K/Al
2o
3on equal to obvious 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.ICP-AES elemental analyser is analyzed Si content, and in quantitatively rear Cat-2, Si content is 0.001wt%; Pass through the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser lower than instrument lower limit simultaneously.
Embodiment 2
The strip Cu-Cr/ZrO of cut-off footpath 3mm
2-Al
2o
315 grams of catalyzer (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 thermogravimetric analyzer), catalyzer is packed in a 500ml there-necked flask, there-necked flask is placed in oil bath, and a bite in there-necked flask connects cooling coil, and a bite jointing temp meter connects opening for feed flatly.First in there-necked flask, pour 80ml p-Xylol into, and will be stabilized in after 110 ℃ at temperature of reactor, by passing in reactor of the hexa methyl silazane containing 8ml.110 ℃ are warming up to 140 ℃ after maintaining 1h, keep cooling after 1 hour after temperature-stable, take out catalyzer 160 ℃ of dry 3h in baking oven, obtain catalyzer Cat-3.
By Fourier's infrared spectrometric analyzer (FTIR), compare Cu-Cr/ZrO
2-Al
2o
3and Cat-3, the characteristic peak (～2970cm of the methyl on Cat-3
-1) be obviously better than Cu-Cr/ZrO
2-Al
2o
3, and the characteristic peak (～3750cm of hydroxyl
-1) be obviously weaker than Cu-Cr/ZrO
2-Al
2o
3, this illustrates Cu-Cr/ZrO
2-Al
2o
3on part of hydroxyl by silylation, replaced.ICP-AES elemental analyser is analyzed Si content, and in quantitatively rear Cat-3, Si content is 1.1wt%; By the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser, be 1.50wt%, the silylation mass percent on catalyzer is about 3.55wt% accordingly simultaneously.
Comparative example 2
The strip Cu-Cr/ZrO of cut-off footpath 3mm
2-Al
2o
315 grams of catalyzer (Beijing Chemical Research Institute produces, identical with embodiment 2), pack catalyzer in one 500ml there-necked flask into, and there-necked flask is placed in oil bath, and a bite in there-necked flask connects cooling coil, and a bite jointing temp meter connects opening for feed flatly.First in there-necked flask, pour 80ml p-Xylol into, and be warming up to 140 ℃ after will maintaining 1h after temperature of reactor is stabilized in 110 ℃, after temperature-stable, keep cooling after 1 hour, take out catalyzer 160 ℃ of dry 3h in baking oven, obtain catalyzer Cat-4.
By Fourier's infrared spectrometric analyzer (FTIR), compare Cu-Cr/ZrO
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.ICP-AES elemental analyser is analyzed Si content, and in quantitatively rear Cat-4, Si content is 0.003wt%; By the quantitative organic carbon content of organic carbon/elemental carbon (OC/EC) analyser, be 0.01wt% simultaneously.
Embodiment 3
The catalyzer of embodiment 1 and comparative example 1 is applied to respectively to 3-HPA hydrogenation.Hydrogenator is 100ml isothermal fixed bed, catalyzer 10.0g.The processing condition of hydrogenation reaction are as table 1 (selectivity refers to 1,3-PD selectivity).After finishing, reaction 1500h compares carbon deposition quantity by TG-MS combination.
Under reaction conditions, form as shown in table 1,3-HPA liquid hourly space velocity 2.0h wherein
-1, hydrogen and 3-HPA mol ratio be 8.0, water content 380ppm.
Result is as shown in table 1, tests and shows with respect to existing method, and method object 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 example 1
Carbon deposition quantity is measured: TG-MS combination instrument, in the air atmosphere of 30ml/min, 10 ℃/Min of temperature rise rate, from room temperature to 450 ℃ and maintain 1 hour, according to CO in mass spectrum
2the weightless peak position of thermogravimetric carbon distribution quantitative according to the weightless result of thermogravimetric is determined at peak.
Embodiment 4
The catalyzer of embodiment 2 comparative examples 2 is applied to respectively to the reaction of butyraldehyde liquid-phase hydrogenatin, wherein hydrogen reactor is 50ml isothermal fixed bed, catalyzer 8.0g.The processing condition of hydrogenation reaction are as table 2 (selectivity make a comment or criticism butanols selectivity).After finishing, reaction 1200h compares carbon deposition quantity by TG-MS combination.Result as shown in Table 2, is tested and is shown with respect to prior art, and 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 example 2
Carbon deposition quantity is measured: TG-MS combination instrument, in the air atmosphere of 30ml/min, 10 ℃/Min of temperature rise rate, from room temperature to 450 ℃ and maintain 1 hour, according to CO in mass spectrum
2the weightless peak position of thermogravimetric carbon distribution quantitative according to the weightless result of thermogravimetric is determined at peak.
Claims (15)
1. aldehyde selects Hydrogenation for a method for alcohol, it is characterized in that, take aldehyde as raw material, at the weight space velocity of 20 ℃～300 ℃ of temperature of reaction, reaction pressure 0.1MPa～7.0MPa and aldehyde, is 0.02h
-1～20h
-1under, aldehyde contacts with hydrogenation catalyst with hydrogen, aldehyde selects to be hydrogenated to alcohol, described hydrogenation catalyst contains carrier, metal active constituent and silane group, described metal active constituent is at least one in palladium, nickel, platinum, copper and cobalt, its percentage ratio that accounts for catalyzer gross weight is 0.05wt%～70wt%, and described silane group is processed grafting through silylanizing, and it accounts for the 0.1wt%～15wt% of catalyzer gross weight.
2. the method for claim 1, is characterized in that, described metal active constituent is at least one in copper, cobalt and nickel, and its percentage ratio that accounts for catalyzer gross weight is 0.5wt%～60wt%.
3. method as claimed in claim 2, is characterized in that, described metal active group is at least one in copper and mickel, and its percentage ratio that accounts for catalyzer gross weight is 5wt%～50wt%.
4. the method for claim 1, is characterized in that, described catalyzer also contains metal promoter a, described metal promoter a ShiIA family, at least one metallic element in IIAZu He VA family, and its content is the 0.01wt%～10wt% of catalyzer gross weight.
5. method as claimed in claim 4, is characterized in that, described metal promoter a is at least one metallic element of potassium, calcium, magnesium, barium, bismuth, and its content is the 0.1wt%～6wt% of catalyzer gross weight.
6. the method as described in claim 1 or 4, it is characterized in that, described catalyzer also contains metal promoter b, at least one metallic element in described metal promoter b Shi IB family, IIB family, IIIB family and group vib, and its content is the 0.01wt%～30wt% of catalyzer gross weight.
7. method as claimed in claim 6, is characterized in that, described metal promoter b comprises at least one in silver, gold, zinc, lanthanum, cerium, chromium, molybdenum and tungsten, and its content is the 0.5wt%～25wt% of catalyzer gross weight.
8. the method as described in claim 1 or 4, it is characterized in that, described catalyzer also contains non-metal assistant d, and described non-metal assistant d is at least one non-metallic element in IIIA family, IVAHe VA family, and its content is the 0.01wt%～8wt% of catalyzer gross weight.
9. method as claimed in claim 8, is characterized in that, described non-metal assistant d is at least one in boron, phosphorus, sulphur and selenium, and its content is the 0.1wt%～4wt% of catalyzer gross weight.
10. 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 diatomite or two or more mixture in them.
11. the method for claim 1, is characterized in that, the silicomethane base that silylanizing process to be used is a kind of in organosilane, organo-siloxane, organosilazanes and organic oxosilane or two or more mixture in them.
12. methods as claimed in claim 11, is characterized in that, the silicomethane base that silylanizing process to be used is a kind of in organo-siloxane and organosilazanes or their mixture.
13. 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 furfuryl alcohol, 2,2-methylol butyraldehyde Hydrogenation is hydrogenated to 1,3-PD for TriMethylolPropane(TMP), 3-HPA or glucose hydrogenation is sorbyl alcohol.
14. the method for claim 1, 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
-1～3h
-1.
15. methods as described in claim 1 or 14, is characterized in that, the mol ratio of hydrogen and aldehyde is 1～200.
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