CN109678658A - Fatty acid and/or aliphatic ester catalytic hydrodeoxygenation prepare the method with carbon number fatty alcohol - Google Patents
Fatty acid and/or aliphatic ester catalytic hydrodeoxygenation prepare the method with carbon number fatty alcohol Download PDFInfo
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- CN109678658A CN109678658A CN201910037458.7A CN201910037458A CN109678658A CN 109678658 A CN109678658 A CN 109678658A CN 201910037458 A CN201910037458 A CN 201910037458A CN 109678658 A CN109678658 A CN 109678658A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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Abstract
The present invention provides a kind of methods prepared for fatty acid and/or aliphatic ester catalytic hydrodeoxygenation with carbon number fatty alcohol, the described method includes: in the reaction vessel, in the presence of a catalyst, under 100~240 DEG C of low temperature and the low hydrogen pressure of 0.1~5MPa, make fatty acid and/or aliphatic ester carry out hydrogenation deoxidation with hydrogen to react, obtains required same carbon number fatty alcohol product.The present invention passes through the Me Jing Guo reactive metal modified as defined hereinaXbAlcThe advantages that same carbon number fatty alcohol is prepared by fatty acid and/or aliphatic ester in complex catalyst, has high conversion rate, and selectivity is good, and reaction condition is mild, catalyst stabilization, has extraordinary prospects for commercial application.
Description
Technical field
The present invention relates to technical field of compound preparation, more particularly to one kind to be catalyzed for fatty acid and/or aliphatic ester
Hydrogenation deoxidation prepares the method with carbon number fatty alcohol.
Background technique
Fatty alcohol is the basic material of the fine chemical products such as detergent, surfactant, plastic plastification, is produced by it
Fine chemical product has as many as thousands of kinds, is widely used in chemical industry, petroleum, metallurgy, weaving, machinery, mining, building, plastics, rubber
The departments such as glue, leather, papermaking, communications and transportation, food, medical and health, daily-use chemical industry and agricultural, it is continuous to its demand in recent years
Increase.
The preparation method of fatty alcohol mainly has grease direct hydrogenation the preparation method, aliphatic acid hydrogenation the preparation method, fatty acid methyl ester
Add hydrogen the preparation method.Currently, industrial mainly use CuCr catalyst, but the Cr that CuCr catalyst discharges during the preparation process6+It is right
Environment causes serious pollution.CN103664514A discloses a kind of method that fatty acid ester through hydrogenation prepares fatty alcohol, wherein
The catalyst used carries out adding hydrogen using copper zinc boron as component, by aliphatic ester in 220~260 DEG C, the pressure of 7.0~10.0MPa hydrogen
Reaction.On the one hand, the preparation method of such catalyst is influenced by factors, and is not easy to control, so that catalyst reproducibility
Difference, and react and need just to can be carried out in the high hydrogen pressure of 7MPa or more.CN102476056A discloses a kind of fatty acid methyl ester
The preparation method and application of the catalyst of catalytic hydrogenation fatty alcohol, catalyst therein is by (weight percent) 18-66% copper oxide
Perhaps one of copper oxide and zinc oxide mix 0-40% manganese oxide, nickel oxide or two kinds, 5-17% aluminium oxide and 0-
45% carrier composition, carrier are diatomite or calcium carbonate, and preparation method includes: by least two in copper, zinc, manganese, nickel, aluminium
Kind soluble-salt is dissolved in the water, and configures mixed solution；Using water or water and carrier as base fluid, sodium carbonate is added dropwise to base fluid cocurrent
Aqueous solution and mixed solution after dripping off, obtain precipitated product, through aging, be filtered, washed, dry, suppress after obtain finished product.Though
The right catalyst has good catalytic activity, is the substitute of Cu/Cr catalyst, but the preparation process of the catalyst is more numerous
Trivial, required adding ingredient is complicated, and industrial applications are more difficult.CN106140172A discloses one kind suitable for fatty acid methyl ester
Press liquid-phase hydrogenatin fatty alcohol catalyst, used in catalyst be made of copper Zinc-aluminium.In the catalyst, oxygen
Change copper is main catalytic active component, and zinc oxide is cocatalyst component, and aluminium oxide is both cocatalyst component and carrier.Its
Reaction pressure is 4MPa~8MPa, and temperature is 200 DEG C~250 DEG C, and reaction condition is more harsh, and will appear metal after reacting
It is lost, causes catalyst to be not sufficiently stable and cannot be recycled, not advantageous industrial production；In addition, the catalyst is a kind of only to fit
For the catalyst of fatty acid methyl ester, application range is smaller.
Generally speaking, the problem of about the preparation of fatty alcohol being primarily present following aspect at present, such as industrially mainly adopt
With CuCr catalyst, but CuCr catalyst there are problems that causing seriously to pollute to environment, and other catalyst presence are such as anti-
Answer condition is harsh, preparation process is complicated, after reaction metal loss and the problems such as cannot reuse, while most of catalyst are only
Be not useable for fatty acid for aliphatic ester hydrogenation reaction itself.
Therefore, this field, which needs to develop, efficiently prepares same carbon number fatty alcohol by fatty acid and/or ester in a mild condition
The novel catalyst system that new method and stability for the method are high, can be recycled.
Summary of the invention
In view of above-mentioned, the present invention provides one kind to prepare same carbon for fatty acid and/or aliphatic ester catalytic hydrodeoxygenation
The method of number fatty alcohols, which comprises in the reaction vessel, in the presence of a catalyst, in 100~240 DEG C of low temperature and
Under the low hydrogen pressure of 0.1~5MPa, so that fatty acid and/or aliphatic ester is carried out hydrogenation deoxidation with hydrogen and react, needed for obtaining
Same carbon number fatty alcohol product,
The catalyst is the Me by reactive metal modifiedaXbAlcComplex catalyst, wherein Me indicate selected from Cu,
The metal of Co, Ni or Fe, X indicate that the oxide of the metal selected from Zn, Mg, Mn or Zr, Al indicate that the oxide of Al, a, b and c divide
Not Biao Shi the respective molar ratio of Me, X and Al and respectively 0.1~10 value；And wherein the active metal be selected from Pd,
The one or more of Ru, Pt, Co, Ir, Os, Rh, Ag and Cu.
In a preferred embodiment, based on the Me by reactive metal modifiedaXbAlcComplex catalyst
Total weight, the content of the active metal is 0.01%~10.0%, preferably 0.1%~3.0%.
In a preferred embodiment, the Me by reactive metal modifiedaXbAlcComplex catalyst makes
It is directly carried out at in-situ reducing with carrying out pre-reduction treatment in atmosphere of hydrogen before, or in the atmosphere of hydrogen of reaction vessel
Reason.
In a preferred embodiment, it is preferable that the fatty acid be selected from caproic acid, octanoic acid, capric acid, lauric acid,
It is myristic acid, 14 carbon 2- olefin(e) acids, palmitinic acid, palmitoleic acid, 16 carbon 2,4- dienoic acids, palmitic acid, oleic acid, linoleic acid, hard
One of resin acid, linolenic acid, stearic acid, arachidic acid, sinapic acid and behenic acid are a variety of；The aliphatic ester be selected from
Methyl caprate, methyl laurate, methyl hexadecanoate, ethyl oleate, methyl oleate, ethyl stearte, curcas oil, palm oil,
One of coconut oil, cottonseed oil and gutter oil are a variety of.
In a preferred embodiment, the charging mole of the catalyst and the fatty acid and/or aliphatic ester
Than for 1:1~100, preferably 1:10~100.
In a preferred embodiment, the hydrogenation deoxidation reaction carries out in the presence of solvent-free or solvent；It is excellent
Selection of land, the solvent be selected from water, acetone, n-hexane, methanol, ethyl alcohol, isopropanol, normal octane, ethyl acetate, methyl acetate,
One of dodecane and the tetradecane are a variety of.
In a preferred embodiment, hydrogenation deoxidation reaction is at 100~240 DEG C, 0.1~4MPa hydrogen depress into
Row 0.5~for 24 hours.
In a further preferred embodiment, hydrogenation deoxidation reaction is at 120~200 DEG C, 1~4MPa hydrogen pressure
1~8h of lower progress.
In a preferred embodiment, the Me by reactive metal modifiedaXbAlcComplex catalyst is as follows
Preparation: the soluble-salt of metal Me, X and Al are mixed in water by constitutive molar ratio, aqueous slkali are added then to be precipitated
Object, and sediment obtained is calcined to obtain MeaXbAlcCompound；By Me obtainedaXbAlcCompound dispersion
In a solvent, the soluble-salt of active metal is then added and is thoroughly mixed so that active metal is loaded to MeaXbAlcIt is multiple
It closes on object；By the Me obtained for having loaded active metalaXbAlcCompound drying, and obtained required by reduction treatment
The Me of reactive metal modifiedaXbAlcComplex catalyst.
In a further preferred embodiment, the aqueous slkali is sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia
Aqueous solution.
In a further preferred embodiment, the soluble-salt is nitrate, acetate or chloride salt.
In a further preferred embodiment, for dispersing the MeaXbAlcThe solvent of compound be water,
Ethyl alcohol, acetone, diethyl ether, toluene or dimethylbenzene.
In a preferred embodiment, the complex catalyst is recycled.
The present invention prepares the method with carbon number fatty alcohol, has high conversion rate, and selectivity is good, and reaction condition is mild, catalysis
Agent preparation is convenient, and stability is good and the advantages that can be recycled, with extraordinary prospects for commercial application.Particularly, of the invention
Method by using the Me through reactive metal modifiedaXbAlcCompound solid catalysis system, can be in relative low temperature, low-pressure section
Under part, large-scale fatty acid and/or aliphatic ester can be efficiently converted to required same carbon number fatty alcohol, such as this hair
The feed stock conversion of bright method is up to 99.9%, and with the selectivity of carbon number product fatty alcohol up to 99.6%.Meanwhile making
With the Me through reactive metal modifiedaXbAlcCompound solid catalysis system, repeatedly catalytic activity is still able to maintain after circulation, is solved
Me beforeaXbAlcThe metal loss problem of catalyst.Method of the invention has easy to operate, good catalyst activity, conversion ratio
The advantages that height, selectivity is excellent, and stability is good；After the completion of reaction, solid-liquid two-phase laminated flow is convenient, and catalyst can be multiple
It uses, and catalytic activity and stability still keep good.In addition, using method of the invention, in reaction process raw material without
Decarbonylation and decarboxylation, so as to improve Atom economy and reduce carbon emission.
Specific embodiment
The present invention relates to a kind of sides prepared for fatty acid and/or aliphatic ester catalytic hydrodeoxygenation with carbon number fatty alcohol
Method, the method includes the Me in reactive metal modifiedaXbAlcUnder complex catalyst catalytic action, make fatty acid and/or rouge
Fat acid esters carries out hydrogenation deoxidation with hydrogen and reacts, and required same carbon number fatty alcohol is obtained under lower temperature and pressure.More specifically
Ground, the method comprise the steps that in the reaction vessel, in the presence of a catalyst, in 100~240 DEG C of low temperature and 0.1~5MPa
Low hydrogen pressure under, so that fatty acid and/or aliphatic ester and hydrogen is carried out hydrogenation deoxidation and react, obtain required same carbon number rouge
Fat alcohol product.
In the method for the invention, reaction vessel is not specially required, as long as can be realized hydrogenation deoxidation of the invention
Reaction, can be used any reaction vessel well known in the art, such as can be reaction kettle commonly used in the art.For this
The reaction vessel of sample can match the agitating device of such as magnetic agitation and the heating device of such as oil bath heating, and
For providing the nitrogen cylinder of inert atmosphere and providing hydrogen reaction atmosphere and the hydrogen cylinder of pressure etc..
In the method for the invention, the reaction raw materials used are that (the two may each comprise naturally for fatty acid and/or aliphatic ester
Grease).As used in this article, fatty acid is containing one or more carboxyls, preferably the aliphatic carboxylic only containing a carboxyl
Acid, and aliphatic ester can be the ester such as fatty acid methyl ester or fatty-acid ethyl ester of aforementioned fatty acids.Although the present invention for
The structure and carbon atom number of used fatty acid and/or aliphatic ester are not particularly limited, but preferably, the fatty acid used
And/or the saturated or unsaturated C6~C22 fatty acid of aliphatic ester or aliphatic ester；More particularly, the fatty acid used can be with
It is selected from caproic acid, octanoic acid, capric acid, lauric acid, myristic acid, 14 carbon 2- olefin(e) acids, palmitinic acid, palmitoleic acid, 16 carbon 2,4-
In dienoic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, linolenic acid, stearic acid, arachidic acid, sinapic acid and behenic acid
It is one or more；The aliphatic ester is selected from methyl caprate, methyl laurate, methyl hexadecanoate, ethyl oleate, oleic acid first
One of ester, ethyl stearte, curcas oil, palm oil, coconut oil, cottonseed oil and gutter oil are a variety of.Particularly, work as institute
When the fatty acid or ester raw material used contains unsaturated bond such as ethylene linkage, after hydrogenation deoxidation reaction of the invention, obtain
The fatty alcohol product of saturation.
In the method for the invention, cover above-mentioned fatty acid and/or fatty acid as the same carbon number fatty alcohol of reaction product
The reaction product that the catalytic hydrodeoxygenation of ester through the invention reacts, including catalytic hydrodeoxygenation reaction through the invention
The fatty alcohol of acquisition can be certain single fatty alcohol, be also possible to a variety of fatty alcohols.In addition, in the present invention, as
The fatty alcohol of reaction product, carbon atom number by as reaction raw materials fatty acid and/or aliphatic ester determine, i.e. its carbon atom
Number range usually may be 6~22 carbon atoms.As used in this article, term " same to carbon number " refers to and used raw material
The carbon number of fatty acid is identical, or identical as the carbon number of fatty acid in the feedstock fat acid esters used.
In the method for the invention, the catalyst used is the Me by reactive metal modifiedaXbAlcComplex catalyst,
Wherein Me indicates that the metal for being selected from Cu, Co, Ni or Fe, X indicate that the oxide of the metal selected from Zn, Mg, Mn or Zr, Al indicate Al
Oxide, a, b and c respectively indicate the value of the respective molar ratio of Me, X and Al and respectively 0.1~10, which can be small
Number or integer；And wherein the active metal be selected from Pd, Ru, Pt, Co, Ir, Os, Rh, Ag and Cu one kind or
It is several.In certain embodiments, catalyst of the invention can be supported on active metal MeXAl compound (wherein a, b and
C can be any desired value) on the form of loaded catalyst " active metal/MeXAl " indicate, such as Pd of the invention
Modified one example of catalyst can be referred to as Pd/MeaXbAlc.In the present invention, active metal can pass through all of routine
As infusion process loads on MeXAl compound.
In the method for the invention, it is preferable that based on the Me Jing Guo reactive metal modifiedaXbAlcComplex catalyst it is total
Weight, the content for modified active metal are 0.01%~10.0%, preferably 0.1%~3.0%.
In the method for the invention, it is preferable that by the Me of reactive metal modifiedaXbAlcComplex catalyst is using it
It is preceding that pre-reduction treatment is carried out in atmosphere of hydrogen, or directly carried out at prereduction in situ in the atmosphere of hydrogen of reaction vessel
Reason, thereby further ensures that metal Me and is in its activated state for modified active metal, and the catalyst has
Complete catalytic activity.
In the method for the invention, although being not particularly limited, it is preferable that the catalyst that uses and raw fatty acid and/
Or the raw materials components mole ratio of aliphatic ester can be 1:1~100, preferably 1:10~100.
In the method for the invention, since the raw fatty acid used or aliphatic ester itself may be used as solvent, so
Hydrogenation deoxidation reaction can carry out in the presence of solvent-free or solvent.Preferably, there are solvent, what is used is molten
Agent can be selected from water, acetone, n-hexane, methanol, ethyl alcohol, isopropanol, normal octane, ethyl acetate, methyl acetate, dodecane and
One of tetradecane is a variety of.
Preferably, hydrogenation deoxidation reaction is at 100~240 DEG C, and the pressure of 0.1~4MPa hydrogen carries out 0.5~for 24 hours.More preferably exist
120~200 DEG C, the pressure of 1~4MPa hydrogen carries out 1~8h.
In the method for the invention, the modified complex catalyst used can pass through any method system of this field
It is standby.For example, the Me of the invention by reactive metal modifiedaXbAlcComplex catalyst can be prepared as follows:
Firstly, the soluble-salt of metal Me, X and Al are mixed in water by constitutive molar ratio, then for example in beaker
Aqueous slkali is added to obtain sediment, and sediment obtained is forged for example in Muffle furnace at such as 300~600 DEG C
It burns to obtain MeaXbAlcCompound；
Then, by Me obtainedaXbAlcCompound is dispersed in suitable solvent, and the solubility of active metal is then added
Salt is simultaneously thoroughly mixed so that active metal is loaded to MeaXbAlcOn compound；
Finally, by the Me obtained for having loaded active metalaXbAlcCompound for example removes solvent by rotary evaporation
Later, such as in 60~100 DEG C of baking oven it dries, and obtains required reactive metal modified by reduction treatment
MeaXbAlcComplex catalyst.
In catalyst preparation of the invention, the aqueous slkali used is mainly used for adjusting the pH of reaction system, and in fact
Example can be sodium hydroxide, potassium hydroxide, sodium carbonate or ammonia spirit etc..
In catalyst preparation of the invention, the soluble-salt used can be the nitrate of respective metal, acetate or
This is not particularly limited in chloride salt etc., as long as it can be dissolved in solvent used in reaction system.
In catalyst preparation of the invention, it is used to disperse Me to what is usedaXbAlcThe solvent of compound does not limit especially
System, such as can be water, ethyl alcohol, acetone, diethyl ether, toluene or dimethylbenzene etc..
The Me of the invention through reactive metal modified prepared by the above methodaXbAlcComplex catalyst not only has
Good catalytic activity, and excellent in stability, and can be recycled for multiple times.
Embodiment
To further illustrate the present invention, detailed description is provided to the present invention below with reference to embodiment.
Unless otherwise specified, process and step involved in following embodiments are conventional process and step, are made
Reagent and equipment commercially obtain, and do not use directly after further treatment.
The preparation of catalyst
Preparation example 1:Pd/Cu6Zn3Al1The preparation of complex catalyst
In beaker, in the ratio that Cu:Zn:Al molar ratio is 6:3:1 by Cu (NO3)2·3H2O、Zn(NO3)2·6H2O and
Al(NO3)3·9H2O is dissolved in 150mL deionized water at 80 DEG C.Then, Na is added2CO3Aqueous solution is until mixture solution
PH be about 8.By the mixture solution by magnetic stirring apparatus stir about 1 hour, then aging 15 hours at 80 DEG C, and
Solid sediment is obtained by filtering.Resulting solid is washed with deionized and dry 30 small in 105 DEG C of drying box
When, it is then calcined 6 hours in 350 DEG C of Muffle furnace, thus obtains Cu6Zn3Al1Compound；
By 1.0g Cu achieved above6Zn3Al1Compound is placed in a beaker, and acetone is added, and is passed through under magnetic stirring
Then the solution of the 0.0007g palladium chloride of dissolution in acetone is added dropwise to 45 DEG C in heating water bath, and continue stirring for 24 hours.So
Vacuum rotary steam has been loaded the Pd/Cu of metal Pd to remove solvent and dry in 80 DEG C of baking oven afterwards6Zn3Al1Compound；
The modified composite of acquisition can directly carry out pre-reduction treatment in nitrogen atmosphere before the use or directly add
It is added in reaction system and carries out reduction treatment, thus obtain the required Cu modified through active metal Pd of the present invention6Zn3Al1It is compound
Object catalyst, and wherein based on the total weight of the complex catalyst, the content of active metal Pd is that 0.1wt% (thus should
Complex catalyst is expressed as Pd/Cu6Zn3Al1)。
Preparation example 2:Ag/Cu3Mn6Al1The preparation of complex catalyst
By the preparation process similar with preparation example 1, the Ag/Cu that Ag load capacity is 1.0% is prepared3Mn6Al1It is compound
Object catalyst.
Preparation example 3:Pd/Fe1Zn4Al5The preparation of complex catalyst
By the preparation process similar with preparation example 1, the Pd/Fe that Pd load capacity is 0.3% is prepared1Zn4Al5It is compound
Object catalyst.
Preparation example 4:Pt/Ni3Mn6Al1The preparation of complex catalyst
By the preparation process similar with preparation example 1, the Pt/Ni that Pt load capacity is 0.5% is prepared3Mn6Al1It is compound
Object catalyst.
Preparation example 5:Pd/Co3Zn6Al1The preparation of complex catalyst
By the preparation process similar with preparation example 1, the Pd/Co that Pd load capacity is 0.3% is prepared3Zn6Al1It is compound
Object catalyst.
Preparation example 6: active metal Ru modified MeaXbAlcThe preparation of complex catalyst
By the preparation process similar with preparation example 1, the Me of a variety of different metal components and different mol ratio is preparedaXbAlc
Compound, and further it is prepared for the Me being modified by active metal Ru as shown in table 1 belowaXbAlcComplex catalysts
Agent, wherein the load capacity of active metal Ru is 0.3% (based on modified MeaXbAlcThe total weight of complex catalyst).
Preparation example 7: the Me of other reactive metal modifiedsaXbAlcThe preparation of complex catalyst
By the preparation process similar with preparation example 1, it is prepared for a variety of different metal components and different mol ratio
MeaXbAlcCompound, and further it is prepared for the Me of various other reactive metal modifieds as shown in table 2 belowaXbAlc
Complex catalyst, wherein the load capacity of active metal (is based on modified Me 0.1~3.0% respectivelyaXbAlcCompound is urged
The total weight of agent).
For the application from fatty acid (ester) preparation with carbon number fatty alcohol
Application examples 1: active metal Ru modified MeaXbAlcComplex catalyst is catalyzed the preparation of fatty acid (ester) hydrogenation deoxidation
Fatty alcohol
In the reaction kettle of 25mL, prepared shown in the table 1 of addition 50mg oleic acid and 5mg by preparation example 6 each
0.3%Ru/MeaXbAlcComplex catalyst (before use, these complex catalysts respectively in closed reactor in hydrogen
Under atmosphere room temperature carry out prereduction 3h), then be added 10mL n-hexane, under 2MPa nitrogen atmosphere, be heated to 200 DEG C and
Under the conditions of magnetic agitation, 8h is reacted.After reaction, it is cooled to room temperature, and after being vented emptying, with n-hexane dilute reaction solution,
By being centrifugated out catalyst solid, thus to obtain reaction solution, and gas chromatographic analysis is carried out to the reaction solution of acquisition.
The condition of gas chromatographic analysis are as follows: GC99 gas-chromatography, fid detector, capillary chromatographic column (HP-5 30m ×
0.320mm × 0.25 μm), temperature programming, is warming up to 160 DEG C with the heating rate of 5 DEG C/min, and keep by 100 DEG C of post case initial temperature
3 minutes.Carrier gas is 99.99% high pure nitrogen, flow velocity 1mL/min.
The results are shown in Table 1 for gas chromatographic analysis after used catalyst and its reaction, wherein conversion ratio and yield
Calculation it is as follows:
Table 1
Application examples 2: the Me of the reactive metal modified of variety classes and load capacityaXbAlcComplex catalyst is catalyzed fatty acid
(ester) hydrogenation deoxidation prepares fatty alcohol
In addition to using methyl laurate substitution oleic acid as reaction raw materials, prepared using as shown in table 2 by preparation example 7
Various complex catalysts and use normal octane as solvent and diluent except, with process identical with application examples 1 into
Row reaction and interpretation of result, wherein the results are shown in Table 2 for the gas chromatographic analysis after used catalyst and its reaction.
Table 2
| Catalyst | Modified metal load capacity (%) | Feed stock conversion (%) | Fatty alcohol yield (%) |
| Pd/Cu6Zn3Al1 | 0.6 | 96.8 | 96.7 |
| Pd/Cu6Mg1Al3 | 1 | 99.1 | 98.6 |
| Ag/Cu1Zn4Al5 | 0.3 | 98.3 | 98.1 |
| Ru/Fe5Mg3Al2 | 0.1 | 96.2 | 96.1 |
| Os/Cu4Zn5Al1 | 1.5 | 98.7 | 97.9 |
| Pd/Ni2Zn2Al3 | 0.1 | 99.8 | 99.2 |
| Co/Cu6Mn3Al1 | 0.3 | 99.2 | 98.2 |
| Co/Cu4Mg5Al1 | 2 | 97.1 | 96.3 |
| Ru/Cu1Mn5Al4 | 0.1 | 96.8 | 96.6 |
| Pd/Ni2Mn7Al1 | 1 | 96.4 | 96.3 |
| Co/Cu2.5Mn3Al1 | 0.1 | 96.6 | 96.4 |
| Pd/Cu6Zr3Al1 | 0.1 | 97.4 | 96.3 |
| Ru/Ni2Zr3Al3 | 0.3 | 99.4 | 99.2 |
| Ru/Cu1Zr4Al5 | 0.5 | 98.5 | 97.9 |
| Pt/Cu3Zr6Al1 | 1 | 96.4 | 95.9 |
| Co/Cu4Zr5Al1 | 0.3 | 97.5 | 96.9 |
| Ag/Co6Zn3Al1 | 2.5 | 98.1 | 97.6 |
| Pd/Ni5Zn4Al1 | 0.1 | 95.5 | 95.0 |
| Ru/Co4Zn5Al1 | 1 | 99.0 | 98.2 |
| Os/Co3Zn6Al1 | 2 | 96.3 | 95.9 |
| Ir/Fe2Zn7Al1 | 0.3 | 96.1 | 95.8 |
| Os/Co1Zn4Al5 | 2 | 99.5 | 98.9 |
| Ru/Co6Zr3Al1 | 1 | 98.0 | 97.9 |
| Pt/Co5.5Zr3Al1 | 3 | 100.0 | 99.2 |
| Ru/Fe4Mg3Al2,5 | 0.3 | 99.9 | 99.8 |
| Pd/Co2Zr6Al2 | 2.5 | 97.6 | 96.1 |
| Pd/Fe1Zr3Al6 | 3 | 99.6 | 98.7 |
| Ag/Co1Zr4Al5 | 0.5 | 100.0 | 99.6 |
| Pt/Co6Mn3Al1 | 1.5 | 96.7 | 95.7 |
| Os/Ni5Mg3Al2 | 1 | 99.1 | 98.6 |
| Pt/Co4Mn4Al2 | 1 | 98.3 | 98.1 |
| Pd/Co3Mn6Al1 | 3 | 96.2 | 94.4 |
| Ru/Fe2Mn3Al5 | 1.5 | 98.7 | 97.9 |
| Pt/Co1Mg3Al6 | 0.1 | 99.8 | 99.2 |
Application examples 3: fatty alcohol is prepared using differential responses raw material hydrogenation deoxidation
In addition to using differential responses raw material as shown in Table 3 below, and use the Ag/ prepared in preparation example 2
Cu3Mn6Al1Except complex catalyst (wherein Ag load capacity be 1.0%), react with the identical process of application examples 9 and
Interpretation of result, wherein the results are shown in Table 3 for the gas chromatographic analysis after used reaction raw materials and its reaction.
Table 3
Note: since raw material curcas oil, palm oil, cottonseed oil and the gutter oil sheet used is as mixture, reaction
Product afterwards is also corresponding a variety of fatty alcohol mixtures.
Application examples 4: fatty alcohol is prepared by fatty acid (ester) hydrogenation deoxidation under the conditions of differential responses
In addition to using ethyl stearte to replace oleic acid as reaction raw materials, the Pd/Fe prepared by preparation example 3 is used1Zn4Al5
Complex catalyst (Pd load capacity is 0.3%), uses n-dodecane as solvent and diluent, and using as in the following table 4
Shown in except reaction condition, to be reacted with the identical process of application examples 1 and interpretation of result, wherein used in react item
The results are shown in Table 4 for gas chromatographic analysis after part and its reaction.
Table 4
Application examples 5: differential responses solvent and it is solvent-free under fatty alcohol prepared by fatty acid (ester) hydrogenation deoxidation.
In addition to using methyl oleate to replace oleic acid as reaction raw materials, the Pt/Ni prepared by preparation example 4 is used3Mn6Al1It is multiple
Mixture catalyst (Pt load capacity be 0.5%), and using different solvents (and being used as diluent) as shown in Table 5 below or
Except solvent, to be reacted with the identical process of application examples 1 and interpretation of result, wherein used in solvent and its anti-
The results are shown in Table 5 for gas chromatographic analysis after answering.
Table 5
| Solvent | Feed stock conversion (%) | Fatty alcohol yield (%) |
| Water | 98.3 | 98.1 |
| N-hexane | 98.9 | 98.4 |
| First fatty alcohol | 98.1 | 96.9. |
| Second fatty alcohol | 99.0 | 98.4 |
| Isopropyl fatty alcohol | 97.9 | 97.3 |
| Normal octane | 98.9 | 97.9 |
| Ethyl acetate | 98.7 | 98.0 |
| Dodecane | 97.9 | 96.8 |
| The tetradecane | 97.9 | 97.2 |
| Nothing | 95.6 | 94.0 |
Application examples 6: the recycling performance evaluation of catalyst
According to the similar program of preparation example 1, Co is obtained3Zn6Al1Compound, and as control, by the Co3Zn6Al1It is multiple
It closes object and is used as comparative catalyst without reactive metal modified as described in the present invention.
In addition to using methyl caprate to replace oleic acid as reaction raw materials, respectively using above-mentioned comparative catalyst and by preparation example
The Pd/Co of 5 preparations3Zn6Al1Except complex catalyst (Pd load capacity is 0.3%), with process identical with application examples 1 progress
Reaction and interpretation of result, and the above-mentioned catalyst isolated is reused five times respectively, wherein the gas-chromatography after reaction
Analyze result difference as shown in table 6 and table 7.
Table 6
Table 7
It can be seen that according to the result of above 1~table of table 5 and urged by the compound using reactive metal modified of the invention
Agent, the present invention can be produced by fatty acid or aliphatic ester by the fatty alcohol that same carbon number is prepared in catalytic hydrodeoxygenation
Object, and there is good feed stock conversion and selectivity of product and yield.In addition, can be clear according to the result of table 6 and table 7
Chu finds out, the catalyst of the present invention after reactive metal modified has excellent stability, catalytic activity and can be recycled
Property.
Method and core concept of the invention that the above embodiments are only used to help understand.Further for this skill
For the those of ordinary skill in art field, under the premise of not departing from the present invention, can also to the present invention carry out it is several improvement and
Modification, these are improved and the modified protection scope for also falling into the claims in the present invention.
Claims (10)
1. a kind of method for fatty acid and/or the preparation of aliphatic ester catalytic hydrodeoxygenation with carbon number fatty alcohol, the method
Include: in the reaction vessel, in the presence of a catalyst, under 100~240 DEG C of low temperature and the low hydrogen pressure of 0.1~5MPa,
Make fatty acid and/or aliphatic ester carry out hydrogenation deoxidation with hydrogen to react, obtain required same carbon number fatty alcohol product,
The catalyst is the Me by reactive metal modifiedaXbAlcComplex catalyst, wherein Me indicates to be selected from Cu, Co, Ni
Or the metal of Fe, X indicate that the oxide of the metal selected from Zn, Mg, Mn or Zr, Al indicate that the oxide of Al, a, b and c distinguish table
Show the value of the respective molar ratio of Me, X and Al and respectively 0.1~10；And wherein the active metal be selected from Pd, Ru,
The one or more of Pt, Co, Ir, Os, Rh, Ag and Cu.
2. the method according to claim 1, wherein based on the Me by reactive metal modifiedaXbAlcIt is multiple
The total weight of mixture catalyst, the content of the active metal are 0.01%~10.0%, preferably 0.1%~3.0%.
3. the method according to claim 1, wherein the Me by reactive metal modifiedaXbAlcCompound
Catalyst carries out pre-reduction treatment in atmosphere of hydrogen before the use, or directly carries out in the atmosphere of hydrogen of reaction vessel
In-situ reducing processing.
4. the method according to claim 1, wherein the fatty acid and/or aliphatic ester are saturation or insatiable hunger
C6~C22 the fatty acid and/or aliphatic ester of sum；Preferably, the fatty acid be selected from caproic acid, octanoic acid, capric acid, lauric acid,
It is myristic acid, 14 carbon 2- olefin(e) acids, palmitinic acid, palmitoleic acid, 16 carbon 2,4- dienoic acids, palmitic acid, oleic acid, linoleic acid, hard
One of resin acid, linolenic acid, stearic acid, arachidic acid, sinapic acid and behenic acid are a variety of；The aliphatic ester be selected from
Methyl caprate, methyl laurate, methyl hexadecanoate, ethyl oleate, methyl oleate, ethyl stearte, curcas oil, palm oil,
One of coconut oil, cottonseed oil and gutter oil are a variety of.
5. the method according to claim 1, wherein the catalyst and the fatty acid and/or aliphatic ester
Raw materials components mole ratio be 1:1~100, preferably 1:10~100.
6. the method according to claim 1, wherein hydrogenation deoxidation reaction is solvent-free or with the presence of solvent
Lower progress；Preferably, the solvent is selected from water, n-hexane, methanol, ethyl alcohol, isopropanol, normal octane, ethyl acetate, acetic acid first
One of ester, dodecane and tetradecane are a variety of.
7. the method according to claim 1, wherein the hydrogenation deoxidation reaction time be 0.5~for 24 hours.
8. the method according to claim 1, wherein the Me by reactive metal modifiedaXbAlcCompound
Catalyst is prepared as follows:
The soluble-salt of metal Me, X and Al are mixed in water by constitutive molar ratio, aqueous slkali is added then to be precipitated
Object, and sediment obtained is calcined to obtain MeaXbAlcCompound；
By Me obtainedaXbAlcCompound disperses that the soluble-salt of active metal is then added in a solvent and is sufficiently stirred
Mixing is to load to Me for active metalaXbAlcOn compound；
By the Me obtained for having loaded active metalaXbAlcCompound drying, and required work is obtained by reduction treatment
The metal-modified Me of propertyaXbAlcComplex catalyst.
9. according to the method described in claim 8, it is characterized in that, the aqueous slkali is sodium hydroxide, potassium hydroxide, sodium carbonate
Or ammonia spirit；The soluble-salt is nitrate, acetate or chloride salt；For dispersing the MeaXbAlcCompound
The solvent is water, ethyl alcohol, acetone, diethyl ether, toluene or dimethylbenzene.
10. the method according to claim 1, wherein the complex catalyst is recycled.
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| CN112221501A (en) * | 2020-11-10 | 2021-01-15 | 西华大学 | Hydrogenation catalyst, preparation method thereof and method for preparing fatty alcohol by catalysis |
| CN112642441A (en) * | 2020-12-10 | 2021-04-13 | 西安凯立新材料股份有限公司 | Catalyst for preparing 1,2, 4-butanetriol through catalytic hydrogenation and preparation method and application thereof |
| CN115090292A (en) * | 2022-05-06 | 2022-09-23 | 北京化工大学 | Preparation method of cobalt-zinc bimetallic alloy catalyst and application of cobalt-zinc bimetallic alloy catalyst in catalyzing fatty acid methyl ester and fatty acid hydrodeoxygenation reaction |
| CN117607320A (en) * | 2024-01-19 | 2024-02-27 | 中国农业科学院北京畜牧兽医研究所 | Method for measuring content of 88 fatty acids in milk and application thereof |
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| CN117607320B (en) * | 2024-01-19 | 2024-04-16 | 中国农业科学院北京畜牧兽医研究所 | Method for measuring content of 88 fatty acids in milk and application thereof |
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