CN106866415A - A kind of manufacture method of alicyclic carboxylic ether - Google Patents
A kind of manufacture method of alicyclic carboxylic ether Download PDFInfo
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- CN106866415A CN106866415A CN201510918446.7A CN201510918446A CN106866415A CN 106866415 A CN106866415 A CN 106866415A CN 201510918446 A CN201510918446 A CN 201510918446A CN 106866415 A CN106866415 A CN 106866415A
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- catalyst
- ruthenium
- manufacture method
- hydrogenation
- alicyclic carboxylic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
Abstract
The present invention relates to a kind of method that the aromatic ring hydrogenation of aromatic carboxylic acid esters is prepared aliphatic carboxylic acid esters in the presence of ruthenium or ruthenium-palladium altogether supported catalyst.The present invention develops the catalyst of high activity, high selectivity using the comparatively cheap ruthenium of price for main active component, establishes the manufacture method of industrially simple alicyclic carboxylic ether.The catalyst can use intermittent reaction or continuous reaction form, high yield to obtain aimed aliphatic compounds of group.
Description
Technical field
The present invention relates to the manufacture method of alicyclic carboxylic ether.Specifically, it is related to aromatic series in the presence of noble metal catalyst
Carboxylic acid ester hydrogenation is so as to the method for manufacturing alicyclic carboxylic ether.Additionally, catalyst of the invention specifically hydrogenation catalyst ruthenium
Catalyst and the catalyst of ruthenium and palladium is loaded with altogether, be related to ruthenium and palladium on carrier surface with the particle comprising one or two elements
The catalyst that form is present.
Background technology
All it is all the time the focus that everybody pays close attention to by the method and its catalyst of the aromatic ring hydrogenation of aromatic carboxylic acid compound.Make
It is that, by the method for the aromatic ring direct hydrogenation of aromatic carboxylic acid compound, it is rhodium catalyst (non-patent literature to study at present more
1st, non-patent literature 2, patent document 1, patent document 2, patent document 3).Rhodium catalyst is used as aromatic carboxylic acid chemical combination
The hydrogenation catalyst of thing aromatic ring it is active it is high, there is no the advantage of side reaction, product yield high.Although rhodium has excellent urging
Change performance, but there are problems that when industrialized production is carried out, specially：First point, metal rhodium price is very high, industry
Catalyst high cost during production.Second point, the activity decrease speed of catalyst is fast, must continually enter during long-term use catalyst
Row activation act.The technique for being combined with activation can also be built, but requires simpler technique (specially for industrializing
Sharp document 1).Thirdly, the reaction needs the high pressure and raw material of 8MPa and the above to have certain corrosion to reactor, therefore
Investment to equipment increases.
Ruthenium is the noble metal that has hydrogenation capacity as the aromatic ring to aromatic carboxylic acid compound and cheap.Patent document 4
Ru/C catalyst is reported for application of the aromatic carboxylic acid esters in autoclave hydrogenation reaction, reaction pressure is 10MPa or so,
130 DEG C or so of temperature.When ruthenium catalyst generally being used for into the hydrogenation of aromatic series carboxylic class compound, the hydrogenation of aromatic ring is not only, also
The reduction of side chain carboxyl group can occur, it is the reducing catalyst (non-patent literature 3) of alcohol that ruthenium catalyst can serve as carboxyl reduction,
Therefore the selection rate step-down of alicyclic carboxylic ether.The reduction ratio of ester group is more difficult after carboxylic acid is esterified, so as to increased alicyclic carboxylic
The yield (patent document 5) of acid.
Wherein hydrogenation pyromellitic acid ester can be used to prepare hydrogenation pyromellitic dianhydride (HPMDA), and HPMDA is a kind of new
Alicyclic acid anhydrides, for preparing hydrogenated pyromellitic anhydride type polyimides.HPMDA in molecular structure due to not containing virtue
Fragrant race's composition, therefore there is polyimides prepared therefrom the excellent transparency, low-k and dielectric loss, height to puncture by force
Degree, low hydroscopicity and with the good adhesiveness of base material such as metal, in Aero-Space, automobile, microelectronics, large-scale integrated electricity
The fields such as road, semi-conducting material and flat-panel monitor have broad application prospects.Meanwhile, HPMDA type Kaptons
With excellent heat-resistant stability, good mechanical property and optical property, it is widely used in numerous high-tech sectors.
Knowable to prior art, the preparation of HPMDA is main to be completed by following reaction：
1. Pyromellitic Acid catalytic hydrogenation obtains hydrogenating Pyromellitic Acid
2. hydrogenation Pyromellitic Acid cyclodehydration prepares HPMDA
Technology is it is important that prepare hydrogenation Pyromellitic Acid.The hydrogenation of Pyromellitic Acid belongs to the hydrogenation of aromatic ring, has to aromatic ring in theory
The catalyst for having hydrogenation activity is all applied to the hydrogenation process of Pyromellitic Acid, and current catalyst is mainly born using noble metal
Supported catalyst.Patent document 6 discloses that the preparation of hydrogenation pyromellitic acid ester.Using ruthenium, rhodium or palladium as activated centre, with
Rare earth modified compounding aluminum oxide is carrier, and preparation process is complicated.More a height of 220 DEG C and 6.0MPa of reaction temperature, pressure.Specially
Sharp document 7 discloses a kind of preparation method of electronic grade hydrogenated pyromellitic acid anhydride.Equal benzene four is hydrogenated this patent reports autoclave
The preparation method of formic acid hydrogenation, does not have particular/special requirement to catalyst, i.e., commercially available Pt/C, Pd/C, Ru/C or Rh/C.By me
Experiment find that commercially available Pt/C, Pd/C, Ru/C and Rh/C catalyst is not reached to Pyromellitic Acid ester through hydrogenation and urge well
Change effect.Patent document 8 discloses the manufacture method and the catalyst for the method for alicyclic carboxylic acid.The operating pressure of reaction
Height, compares reaction pressure basic in more than 8MPa by embodiment.And the hydrogenation of trimellitic acid is primarily related to, to equal
The explanation of benzene tetracarboxylic acid hydrogenation is little.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-63263 publications
Patent document 2：Japanese Unexamined Patent Publication 2006-83080 publications
Patent document 3：Japanese Unexamined Patent Publication 2003-286222 publications
Patent document 4：Japanese Unexamined Patent Publication 1995-158472 publications
Patent document 5：Japanese Unexamined Patent Publication 2006-045166 publications
Patent document 6：The A of Chinese patent publication No. CN 102381988
Patent document 7：The A of Chinese patent publication No. CN 103992330
Patent document 8：The A of Chinese patent publication No. CN 103502197
Non-patent literature
Non-patent literature 1：Journal of Organic Chemistry, 1966, volume 31, p.3438-3439
Non-patent literature 2：Chemistry a European Journal, 2009, volume 15, p.6953-6963
Non-patent literature 3：Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis
The content of the invention
Present invention aims to use the comparatively cheap noble ruthenium of price, exploitation activity is equal or higher with rhodium catalyst and not
The phenomenon that the activity for producing rhodium catalyst common is reduced, establishes the manufacture method of industrially simple alicyclic carboxylic ether.
Due to the catalytic capability of above-mentioned ruthenium, therefore the cheap ruthenium catalyst directly sold using market is instead of rhodium catalyst
Difficult.As a result the present inventor has found that addition palladium is used as second composition in order to be conducted in-depth research as principal component using ruthenium
Ruthenium and palladium is coexisted in the catalyst, be derived from overcoming rhodium, the catalyst of the problem of ruthenium catalyst, so as to develop the present invention.
That is, the present invention relates to following [1]~[6] alicyclic carboxylic acid manufacture method and the catalyst of [7]~[10].
A kind of manufacture method of alicyclic carboxylic ether, the use support type of load two kinds of elements of ruthenium and palladium as active component with ruthenium or altogether
Catalyst, by the aromatic ring hydrogenation of aromatic carboxylic acid esters, so as to obtain alicyclic carboxylic ether.
Wherein, catalyst is supported on carriers ruthenium or is loaded with two kinds of catalyst of element of ruthenium and palladium altogether, and the mass loading amount of wherein ruthenium is
The mass loading amount of 0.5-20%, wherein palladium is 0.1-20%.
Wherein, hydrogenation is carried out in liquid solvent, as hydrogenation reaction dissolvent be selected from water, methyl alcohol, ethanol, normal propyl alcohol,
Isopropanol, butanol and ethyl acetate it is one kind or two or more.
Wherein, the carrier of catalyst is selected from activated carbon, aluminum oxide, ceria, titanium dioxide, silica and sieve and silica-sesquioxide
One kind or two or more combining form.
Wherein, aromatic carboxylic acid esters are phthalic acid ester, isophthalic acid ester, terephthalate, trimellitate, equal benzene three
It is one kind or two or more in acid esters or pyromellitic ester.
Wherein the alcohol of the ester group of aromatic carboxylic acid esters is methyl alcohol, ethanol, normal propyl alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol, penta
It is one kind or two or more in alcohol.
Wherein, hydrogenation mode is batch reactor or fixed bed reactors.
Wherein, hydrogenation condition is that reaction temperature is 20~200 DEG C, and reaction pressure is 1.0~15MPa, and the reaction time is 1-600
min。
Wherein, mass concentration of the aromatic carboxylic acid esters in reaction dissolvent is 1%~50%, and wherein reactant is dissolved in solvent or suspends
In solvent.
Wherein, aromatic carboxylic acid esters are 10~10000 relative to the quality of active component.
Brief description of the drawings
Fig. 1 is the XRD spectrum of Ru/C catalyst
Fig. 2 is catalyst transmission electron microscope picture
Fig. 3 is catalyst energy spectrum diagram
Fig. 4 is fixed bed reaction conversion versus time relation
Specific embodiment
As long as the compound with ester group is just not particularly limited on the aromatic carboxylic acid esters aromatic ring used in this reaction, can make
Use known aromatic carboxylic acid esters.
Specifically, aromatic monocarboxylate's ester such as benzoic ether can be exemplified；Phthalic acid ester, isophthalic acid ester, to benzene
Dicarboxylic acid esters, 1,2- naphthalene dicarboxylic acids ester, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids ester, 1,8- naphthalene dicarboxylic acids ester, 2,3- naphthalene dicarboxylic acids ester, 2,6- naphthalenes
Dicarboxylic ester, 1,5- naphthalene dicarboxylic acids ester, 2,7- naphthalene dicarboxylic acids ester, 2,2 '-diphenyl dicarboxylic acid ester, 3,3 '-diphenyl dicarboxylic acid
The aromatic dicarboxylic acid esters such as ester, 4,4 '-diphenyl dicarboxylic acid ester；Benzene-1,2,3-tricarboxylic acid ester, trimellitate, trimesic acid ester, 1,2,4-
The aromatic tricarboxylic acids esters such as naphthalene tricarboxylic ester, 2,5,7- naphthalene tricarboxylic esters；Mellophanic acid ester, prehnitic acid ester, pyromellitic ester,
3,3 ' 4,4 '-biphenyltetracarboxyacid acid ester, Isosorbide-5-Nitrae, aromatic tetracarboxylic acid's ester such as 5,8- naphthalene tetracarboxylic acid esters, 2,3,6,7- naphthalene tetracarboxylic acid esters；
The aromatic series pentacarboxylic acid ester such as benzene pentacarbonic acid's ester；Aromatic series hexacarboxylic acid ester such as benzene hexacarboxylic acid ester etc..Methyl alcohol, second are may be selected from into ester alcohol class
Alcohol, propyl alcohol, butanol etc..They can be used alone or appropriately combined use two or more.
Wherein, there are 2~4 aromatic dicarboxylic acid ester, aromatic tricarboxylic acids ester, the aromatic series four of ester group preferably on phenyl ring
Carboxylate, specifically Methyl Benzene-o-dicarboxylate, M-phthalic acid methyl esters, terephthalic acid (TPA) methyl esters, trimellitic acid methyl esters,
Trimesic acid methyl esters, PMA ethyl ester.They can be used alone or appropriately combined use two or more.
Reaction dissolvent can be suitably used in hydrogenation of the invention, as long as reaction dissolvent dissolving aromatic carboxylic acid esters, no
Reaction is hindered just to be not particularly limited.
Specifically, water outlet can be enumerated；Methyl alcohol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, 2- methyl isophthalic acids-
The alcohols of propyl alcohol etc；Anaesthetie Ether, Di Iso Propyl Ether, n-butyl ether, cyclopentyl-methyl ether, t-butyl methyl ether, THF it
The ethers of class；The esters of methyl acetate, ethyl acetate etc；The ketone of acetone, MEK etc.These, it is preferred to water,
Methyl alcohol, ethanol, 1- propyl alcohol, 2- propyl alcohol.They can be used alone or appropriately combined use two or more.
In hydrogenation, aromatic carboxylic acid esters are soluble in be suspended in a solvent in solvent, for concentration also without spy
Do not limit.With aromatic carboxylic acid esters relative to aromatic carboxylic acid esters and the summation meter of solvent, the concentration of specific aromatic carboxylic acid esters
Preferably 1~50 weight %, more preferably 2~40 weight %, more preferably 2~20 weight %.
As long as the catalyst containing ruthenium and palladium used in hydrogenation makes ruthenium and palladium either or both of which coexist in catalyst just
Without limitation.Specifically, the catalyst that will be loaded with ruthenium can be included and/or the catalysis that the catalyst of palladium is mixed is loaded with
It is loaded with the catalyst of one or both of ruthenium and palladium in agent, carrier altogether, preferably supported on carriers ruthenium and both ruthenium and palladium is urged
Agent.
In the present invention preferably, existed using the load ruthenium on carrier surface or the particle shape comprising both, i.e. ruthenium and palladium
Both co-exist in same intragranular ruthenium-palladium supported catalyst altogether.Both ruthenium and palladium are co-existed in same particle, pressed close to each other, by
This shows high activity and selection rate for the hydrogenation of the aromatic ring of aromatic carboxylic acid esters.
The size of the particle coexisted for the ruthenium and palladium on ruthenium-palladium altogether carrier surface of supported catalyst, as long as both ruthenium and palladium coexist
Just it is not particularly limited.When the size of the particle of commonly known carried metal is larger, the external surface area of particle diminishes, and is loaded
Metal can not be effectively used to reaction.Supported catalyst is same altogether for ruthenium-palladium of the invention, when the size of the particle of metal is larger,
The external surface area of particle diminishes, and the metal for being loaded can not be effectively used to reaction.It is anti-in order to metal is efficiently used for into hydrogenation
Should, the small particle of particle diameter is suitable, preferably 1-50nm, more preferably 1-15nm.The particle diameter can be by transmitted electron
The methods such as microscope and simply determine.
The manufacture method of the catalyst containing ruthenium and palladium for being used in hydrogenation, as long as can coexist in both ruthenium and palladium
Just do not limited in catalyst, as long as both ruthenium and palladium can preferably co-existed in just not having in the same particle on carrier surface
It is restricted, except ruthenium and palladium can also add other compositions.Ion-exchange, dipping can be included as specific preparation method
Method, precipitation method etc., preferably infusion process and the precipitation method.
When ruthenium and palladium is loaded altogether, for making metal be also not particularly limited in the order of supported on carriers.Specifically, can arrange
Enumerate while the method for being loaded, method for being loaded successively etc..
After catalyst is contained ruthenium and palladium, it is also possible to carry out suitable drying, calcining, reduction according to preparation method.
Ruthenium and the amount of palladium for containing in catalyst are not limited.When tenor is few, increase the catalyst for hydrogenation
；Conversely, when tenor is more, reducing the catalyst for hydrogenation.Specifically, the total content of metal
Preferably 0.5~20 weight %, more preferably 0.5~5 weight %.Metal amount to load capacity can by XRF and
ICP-AES analyzes to determine.
Do not limited for the ruthenium and the ratio of palladium in the metal that contains in catalyst.Specific every kind of ratio is respectively preferably
1~99 weight %, more preferably 20~80 weight %.
For the carrier of catalyst, if can carried metal be just not particularly limited, for carrier shape (such as powder,
Products formed etc.), the physical property (such as specific surface area, average pore size etc.) of carrier also do not limit.Specifically, work can be exemplified
Property charcoal, aluminum oxide, zirconium oxide, ceria, titanium dioxide, silica, silica-alumina, zeolite, oxidation
Chromium, tungsten oxide, ion exchange resin, synthesis sorbing material etc..These, it is preferred to activated carbon, aluminum oxide, zirconium oxide,
Ceria, titanium dioxide, silica, they can be used alone or are suitably used in mixed way two or more.Additionally,
For the particle diameter (average grain diameter) of carrier, 1 μm~300 are preferably in the case of being reacted in reactor or suspension bed
μm, 0.3mm~10mm is preferably in the case of being reacted in fixed bed.
Catalytic amount for being used in hydrogenation is not limited, it is contemplated that the content of metal and the aromatic carboxylic acid for reacting
The amount of ester and the appropriate determination in the way of reaching the goal response time.
Temperature for hydrogenation is not limited, and reaction speed diminishes when temperature is too low, the time required for terminating hydrogenation
Elongated, conversely, reaction speed becomes big when temperature is too high, the time required for terminating hydrogenation shortens, but the alicyclic carboxylic of target
The selection rate step-down of acid esters.Can be reacted within the temperature range of 40~220 DEG C, preferably 50~170 DEG C of temperature
Degree scope.
Hydrogen Vapor Pressure for hydrogenation is not particularly limited, and reaction speed diminishes when Hydrogen Vapor Pressure is low, terminates hydrogenation institute
The time of needs is elongated, conversely, when Hydrogen Vapor Pressure is high, the time required for terminating hydrogenation shortens, but device pressure-resistant rule
The investment to device such as lattice becomes big.Specifically, can be to carry out hydrogenation in the range of 1~15MPa in Hydrogen Vapor Pressure,
Preferably 3~9MPa.
Hydrogenation is not limited to the reaction formation of batch (-type), continous way etc.When target output is a small amount of, the system of batch (-type) is built
Technique is made, when yield is a large amount of, the manufacturing process of continous way is built.
The catalyst used in hydrogenation can't see larger activity reduction in batch (-type) during every secondary response, even if therefore not entering
The activation act of row catalyst can also be recycled.In continous way, even if more than 1200 hours continuously run,
Can't see larger activity reduction.
Implement the present invention by as implied above, enabling with simple technique and industrially advantageous approach manufacture alicyclic ring
Race's carboxylate.
Embodiment
Below, by embodiment, the present invention will be described in more detail, but the present invention is not by any restriction of these examples.
Embodiment 1
1.35g ruthenic chlorides (Ru contents 37%) are made to be dissolved in 40mL water.By the powdered SiO of 9.5g2It is scattered in 60g
20min is stirred in water, the aqueous solution of above-mentioned ruthenium is dropped into SiO2Stirred 1 hour in suspension.With the NaOH aqueous solution (matter
Amount fraction is 10 20%) to adjust solution ph.Thereafter, 10mLNaBH is added4The aqueous solution (mass fraction 10%) is stirred
Mix 0.5 hour.Filter and wash the Ru/SiO for obtaining that mass fraction is 5%2Catalyst.
Embodiment 2
1.35g ruthenic chlorides (Ru contents 37%) are made to be dissolved in 40mL water.9.5g active carbon powders are scattered in 60g
20min is stirred in water, the aqueous solution of above-mentioned ruthenium is dropped into SiO2Stirred 1 hour in suspension.With the NaOH aqueous solution (matter
Amount fraction is 11 20%) to adjust solution ph.Thereafter, 5mL formalins (mass fraction 30%) is added, is heated up
To 90 DEG C, constant temperature 2 hours, cooling.Filter and wash the Ru/C catalyst for obtaining that mass fraction is 5%.
Its XRD is as shown in Figure 1.Diffraction maximum without obvious ruthenium.
Embodiment 3
1.35g ruthenic chlorides (Ru contents 37%) and 0.83g palladium bichlorides is set to be dissolved in 60mL deionized waters.By aluminium oxide granule
It is added in above-mentioned solution in grain (30-40 mesh) 50g.60 DEG C of revolvings of heating water bath, make ruthenic chloride and palladium bichloride be supported on oxygen
Change on aluminium.Aluminum oxide containing precious metal salt is dried 2 hours at 150 DEG C, is calcined 4 hours at 400 DEG C in air atmosphere,
Reduced 4 hours at last 250 DEG C of hydrogen, obtain ruthenium-palladium supported catalyst (1 weight %Ru-1 weight %Pd/Al altogether2O3)。
The transmission electron microscope image of the common supported catalyst of ruthenium-palladium that will be prepared using the method is shown in Fig. 2.Nothing on carrier surface
Obvious particle.Ruthenium, the coexisting state of palladium in the particle are analyzed with EDX, Fig. 3 is shown the result in.
Embodiment 4
1.35g ruthenic chlorides (Ru contents 37%) and 0.83g palladium bichlorides is set to be dissolved in 60mL deionized waters.By silica
It is added in above-mentioned solution in grain (10-20 mesh) 100g.60 DEG C of revolvings of heating water bath, are supported on ruthenic chloride and palladium bichloride
On silica.Silica containing precious metal salt is dried 2 hours at 120 DEG C, is calcined 4 hours at 400 DEG C in air atmosphere,
Reduced 4 hours at last 250 DEG C of hydrogen, obtain ruthenium-palladium supported catalyst (0.5 weight %Ru-0.5 weight %Pd/SiO altogether2)。
Embodiment 5
2.70g ruthenic chlorides (Ru contents 37%) and 1.66g palladium bichlorides is set to be dissolved in 60mL deionized waters.By activated carbon
It is added in above-mentioned solution in grain (20-40 mesh) 50g.60 DEG C of revolvings of heating water bath, make ruthenic chloride and palladium bichloride be supported on work
On property charcoal.Activated carbon containing precious metal salt is dried 2 hours at 120 DEG C and is cooled down, be redispersed in 60mL deionized waters,
Add 25mLNaBH4The aqueous solution (mass fraction 10%), stirs 30min, filtration washing, last 120 DEG C of dryings.By
This prepares ruthenium-palladium supported catalyst (2 weight %Ru-2 weight %Pd/C) altogether.
Embodiment 6
1.35g ruthenic chlorides (Ru contents 37%) are made to be dissolved in 40mL water.9.5g active carbon powders are scattered in 60g
20min is stirred in water, is stirred 1 hour during the aqueous solution of above-mentioned ruthenium is dropped into SiO2 suspensions.With the NaOH aqueous solution (matter
Amount fraction is 11 20%) to adjust solution ph.Thereafter, the 2mL hydrazines aqueous solution (mass fraction 50%) are diluted to 10mL
After drop in above-mentioned solution and stir 2 hours.Filter and wash the Ru/C catalyst for obtaining that mass fraction is 5%.
Embodiment 7
1.35g ruthenic chlorides (Ru contents 37%) and 0.83g palladium bichlorides is set to be dissolved in 60mL deionized waters.By 19g oxygen
Change during titanium powder is scattered in 60g water and stir 20min, the aqueous solution of above-mentioned ruthenium is dropped into SiO2Stirred 1 hour in suspension.
It is 11 with the NaOH aqueous solution (mass fraction is 20%) regulation solution ph.Thereafter, 10mL formalin (matter is added
Amount fraction 30%), it is warming up to 90 DEG C, constant temperature 2 hours, cooling.Filter and wash and obtain (2.5 weight %Ru-2.5 weight %Pd/
TiO2) catalyst.
Embodiment 8
2.02g ruthenic chlorides (Ru contents 37%) and 0.42g palladium bichlorides is set to be dissolved in 60mL deionized waters.By aluminium oxide granule
It is added in above-mentioned solution in grain (30-40 mesh) 50g.60 DEG C of revolvings of heating water bath, make ruthenic chloride and palladium bichloride be supported on oxygen
Change on aluminium.Aluminum oxide containing precious metal salt is dried 2 hours at 150 DEG C, is calcined 4 hours at 400 DEG C in air atmosphere,
Reduced 4 hours at last 250 DEG C of hydrogen, obtain ruthenium-palladium supported catalyst (1.5 weight %Ru-0.5 weight %Pd/Al altogether2O3)。
Embodiment 9
2.7g ruthenic chlorides (Ru contents 37%) are made to be dissolved in 60mL deionized waters.By alumina particle (30-40 mesh)
It is added in 50g in above-mentioned solution.60 DEG C of revolvings of heating water bath, make ruthenic chloride and palladium bichloride load on alumina.To contain
The aluminum oxide of precious metal salt is dried 2 hours at 150 DEG C, is calcined 4 hours at 400 DEG C in air atmosphere, 250 DEG C of last hydrogen
Lower reduction 4 hours, obtains ruthenium-palladium supported catalyst (2 weight %Ru/Al altogether2O3)。
Embodiment 10
The Ru/C powder for adding Pyromellitic Acid tetra-ethyl ester 1.0g, embodiment 2 to prepare in the SUS316 autoclaves of 50ml
Last catalyst 25mg, ethanol 10mL.Nitrogen (1MPa) is replaced three hydrogen and replaces three times (1MPa), and pressurized with hydrogen is extremely
4MPa, stirs and rises high-temperature to 90 DEG C.The pressure after starting 2 hours that heats up, without significant change, stops reaction.Reaction solution
It is analyzed through gas chromatograph, now the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 100%, hydrogenation Pyromellitic Acid tetra-ethyl ester
Selectivity is 97% (mole %).
Embodiment 11
The Ru/SiO for adding Pyromellitic Acid tetra-ethyl ester 10.0g, embodiment 1 to prepare in the SUS316 autoclaves of 300ml2
Fine catalyst 0.25g, ethanol 100mL.Three hydrogen are replaced with nitrogen (1MPa) replace three times (1MPa), hydrogen
4MPa is forced into, high-temperature to 70 DEG C is stirred and rise.The pressure after starting 2 hours that heats up, without significant change, stops reaction.
Reaction solution is analyzed through gas chromatograph, and now the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 91% (mole %), hydrogenates equal benzene
The selection rate of tetracarboxylic acid tetra-ethyl ester is 99% (mole %).
Embodiment 12
The Ru/SiO for adding Pyromellitic Acid tetra-ethyl ester 10.0g, embodiment 1 to prepare in the SUS316 autoclaves of 300ml2
Fine catalyst 0.25g, water 100mL.Three hydrogen being replaced with nitrogen (1MPa) and replacing three times (1MPa), hydrogen adds
4MPa is depressed into, high-temperature to 80 DEG C is stirred and rise.The pressure after starting 2 hours that heats up, without significant change, stops reaction.Instead
Liquid is answered to be analyzed through gas chromatograph, now the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 92% (mole %), hydrogenates equal benzene four
The selection rate of formic acid tetra-ethyl ester is 97.3% (mole %).
Embodiment 13
The Ru/SiO for adding Pyromellitic Acid tetra-ethyl ester 10.0g, embodiment 1 to prepare in the SUS316 autoclaves of 300ml2
Fine catalyst 0.25g, ethanol 100mL.Three hydrogen are replaced with nitrogen (1MPa) replace three times (1MPa), hydrogen
4MPa is forced into, high-temperature to 50 DEG C is stirred and rise.The pressure after starting 2 hours that heats up, without significant change, stops reaction.
Reaction solution is analyzed through gas chromatograph, and now the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 89% (mole %), hydrogenates equal benzene
The selection rate of tetracarboxylic acid tetra-ethyl ester is 99.3% (mole %).
Catalyst is filtered out, the catalyst for reclaiming is not activated, rejoin reactant, repeated under above-mentioned the same terms
Carry out catalyst and apply mechanically performance test.To reaction 11 times Pyromellitic Acid ethyl ester conversion ratio be 95% (mole %),
The average selection rate for hydrogenating Pyromellitic Acid tetra-ethyl ester is 98.6% (mole %).
Embodiment 14
Powder prepared by Pyromellitic Acid tetra-ethyl ester 10.0g, embodiment 4 is added to urge in the SUS316 autoclaves of 300ml
Agent 0.25g, water 100mL.Replace three hydrogen with nitrogen (1MPa) and replace three times (1MPa), pressurized with hydrogen to 4MPa,
Stir and rise high-temperature to 80 DEG C.The pressure after starting 2 hours that heats up, without significant change, stops reaction.Reaction solution is through gas phase
Chromatograph is analyzed, and now the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 100% (mole %), hydrogenation Pyromellitic Acid tetrem
The selection rate of ester is 98% (mole %).
Embodiment 15
1.0 weights prepared by embodiment 3 are filled in internal diameter 10mm φ, the SUS316 reaction tubes of length 100mm
Amount %Ru-1.0 weight %Pd/ particulate alumina catalyst 5g.250 DEG C of reduction of hydrogen in-situ, are cooled to temperature for 150 DEG C
Afterwards, the pressure for increasing hydrogen is 4MPa, and Pyromellitic Acid tetra-ethyl ester (mass fraction is 10%) ethanol solution is with 1.2mL/min
In pumping into reaction tube, hydrogen flow rate 30mL/min.React 1200 hours after starting, can't see turning for Pyromellitic Acid ethyl ester
The reduction of rate, it is 98% (mole %) left and right, equal benzene tetramethyl that the selection rate of Pyromellitic Acid tetra-ethyl ester is hydrogenated in course of reaction
It is as shown in Figure 4 that the conversion ratio of sour tetra-ethyl ester changes over time curve.
Embodiment 16
The Ru/SiO for adding trimellitic acid triethyl 10.0g, embodiment 1 to prepare in the SUS316 autoclaves of 300ml2
Fine catalyst 0.25g, ethanol 100mL.Three hydrogen are replaced with nitrogen (1MPa) replace three times (1MPa), hydrogen
4MPa is forced into, high-temperature to 70 DEG C is stirred and rise.The pressure after starting 2 hours that heats up, without significant change, stops reaction.
Reaction solution is analyzed through gas chromatograph, and now the conversion ratio of trimellitic acid triethyl is 98% (mole %), hydrogenates inclined benzene
The selection rate of tricarboxylic acid triethyl is 98% (mole %).
Embodiment 17
3,3 ' 4, the methyl esters 10.0g of 4 '-bibenzene tetracarboxylic four, embodiment are added in the SUS316 autoclaves of 300ml
1 Ru/SiO for preparing2Fine catalyst 0.25g, ethanol 100mL.Three hydrogen are replaced with nitrogen (1MPa) to replace three times
(1MPa), pressurized with hydrogen stirs and rises high-temperature to 90 DEG C to 6MPa.Heat up start 2 hours after pressure without obvious
Change, stops reaction.Reaction solution is analyzed through gas chromatograph, now 3,3 ' 4, the methyl esters of 4 '-bibenzene tetracarboxylic four turn
Rate is 92% (mole %), hydrogenation 3,3 ' 4, and the selection rate of the methyl esters of 4 '-bibenzene tetracarboxylic four is 98% (mole %).
Comparative example 1
Pyromellitic Acid tetra-ethyl ester 10.0g, 5 weight %Ru/ carbon of commodity are added in the SUS316 autoclaves of 300ml
Powder (Xi'an system) catalyst 0.25g, ethanol 100mL.Three hydrogen are replaced with nitrogen (1MPa) replace three times (1MPa),
Pressurized with hydrogen stirs and rises high-temperature to 80 DEG C to 4MPa.The pressure after starting 2 hours that heats up, without significant change, stops anti-
Should.Reaction solution is analyzed through gas chromatograph, and now the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 80% (mole %), hydrogenation
The selection rate of Pyromellitic Acid tetra-ethyl ester is 98% (mole %).
The catalyst for reclaiming is not activated, reaction is repeated under the same conditions.Reaction the 4th Pyromellitic Acid tetrem
The conversion ratio of ester is 24%, and the average selection rate for hydrogenating Pyromellitic Acid ethyl ester is 98% (mole %).
Comparative example 2
5 weights for adding Pyromellitic Acid tetra-ethyl ester 10.0g, embodiment 6 to prepare in the SUS316 autoclaves of 300ml
Amount %Ru/ carbon dust catalyst 0.25g, ethanol 100mL.Three hydrogen are replaced with nitrogen (1MPa) replace three times (1MPa),
Pressurized with hydrogen stirs and rises high-temperature to 80 DEG C to 4MPa.The pressure after starting 2 hours that heats up, without significant change, stops anti-
Should.Reaction solution is analyzed through gas chromatograph, and now the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 33% (mole %), hydrogenation
The selection rate of Pyromellitic Acid tetra-ethyl ester is 98% (mole %).
Comparative example 3
Filled according to 1.5 recorded with embodiment 8 in internal diameter 10mm φ, the SUS316 reaction tubes of length 100mm
Weight %Ru-0.5 weight %Pd/Al2O3Catalyst 5g.250 DEG C of reduction of hydrogen in-situ, are cooled to temperature after 150 DEG C, to increase
The pressure of hydrogenation is 4MPa, and Pyromellitic Acid tetra-ethyl ester (mass fraction is 10%) ethanol solution is with 1.2mL/min pumps
In entering reaction tube, hydrogen flow rate 30mL/min.React 2 hours after starting, the conversion ratio of Pyromellitic Acid tetra-ethyl ester is 98%,
The selection rate for hydrogenating Pyromellitic Acid tetra-ethyl ester is 92% (mole %).After reaction 6 hours, the conversion of Pyromellitic Acid tetra-ethyl ester
Rate is 40%, and the selection rate for hydrogenating Pyromellitic Acid tetra-ethyl ester is 93% (mole %).
Comparative example 4
Filled in internal diameter 10mm φ, the SUS316 reaction tubes of length 100mm according to identical with what embodiment 9 was recorded
2.0 weight %Ru/ particulate alumina catalyst 5g prepared by method.250 DEG C of reduction of hydrogen in-situ, are cooled to temperature for 150 DEG C
Afterwards, the pressure for increasing hydrogen is 4MPa, and Pyromellitic Acid tetra-ethyl ester (mass fraction is 10%) ethanol solution is with 1.2mL/min
In pumping into reaction tube, hydrogen flow rate 30mL/min.React 2 hours after starting, the conversion ratio of Pyromellitic Acid ethyl ester is 22%,
The selection rate for hydrogenating Pyromellitic Acid ethyl ester is 80% (mole %).
Compared with embodiment 13 by comparative example 1 and see that Ru/C catalyst prepared by our method adds in Pyromellitic Acid tetra-ethyl ester
Activity and life-span in hydrogen reaction is apparently higher than presently commercially available catalyst.Greatly reduce the catalysis of cyclohexanetetracarboxylic acid ester production
Agent cost, and reaction yield is high, reduces separation costs.In fixed bed reaction, work of the bimetallic ratio to catalyst
Property have significant impact, when being less than 1: 3 using monometallic ruthenium and Pd: Ru ratio, catalyst activity and life-span substantially reduce, preferably double
Metal Pd, Ru alloys are that catalyst and Pd: Ru ratio are between 1: 3~5: 1.Catalyst prepared by preferred embodiment 3 can be continuous
1200 hours catalysis activities of production can at least produce 1550g target products without substantially reduction by calculating every gram of catalyst.
Claims (10)
1. a kind of manufacture method of alicyclic carboxylic ether, it is characterised in that：Use with ruthenium or common load
Two kinds of elements of ruthenium and palladium are the loaded catalyst of active component, by the aromatic ring of aromatic carboxylic acid esters
Hydrogenation, so as to obtain alicyclic carboxylic ether.
2. the manufacture method of alicyclic carboxylic ether according to claim 1, wherein, catalyst
It is supported on carriers ruthenium or is loaded with two kinds of catalyst of element of ruthenium and palladium, the wherein quality of ruthenium altogether
Load capacity is 0.5-20%；When loading altogether, wherein the mass loading amount of palladium is 0.1-20%.
3. the manufacture method of alicyclic carboxylic ether according to claim 1, wherein, hydrogenation is anti-
Should be carried out in liquid solvent, as hydrogenation reaction dissolvent be selected from water, methyl alcohol, ethanol,
Normal propyl alcohol, isopropanol, butanol and ethyl acetate it is one kind or two or more.
4. the manufacture method of alicyclic carboxylic ether according to claim 1 and 2, wherein, urge
The carrier of agent be selected from activated carbon, aluminum oxide, ceria, titanium dioxide, silica and
One kind or two or more combining form in sieve and silica-sesquioxide.
5. the manufacture method of alicyclic carboxylic ether according to claim 1, wherein, aromatic series
Carboxylate be phthalic acid ester, isophthalic acid ester, terephthalate, trimellitate,
It is one kind or two or more in trimesic acid ester or pyromellitic ester.
6. the manufacture method of alicyclic carboxylic ether according to claim 1 or 5, wherein fragrance
The alcohol of the ester group of race's carboxylate be methyl alcohol, ethanol, normal propyl alcohol, isopropanol, butanol, isobutanol,
It is one kind or two or more in the tert-butyl alcohol, amylalcohol.
7. the manufacture method of alicyclic carboxylic ether according to claim 1, wherein, hydrogenation is anti-
It is batch reactor or fixed bed reactors to answer mode；Wherein, aromatic carboxylic acid esters relative to
The mass ratio of active component is 10~10000 in catalyst.
8. the manufacture method of alicyclic carboxylic ether according to claim 1, wherein, hydrogenation is anti-
It is that reaction temperature is 20~200oC, and reaction pressure is 1.0~15MPa, during reaction to answer condition
Between be 1-600min.
9. the manufacture method of the alicyclic carboxylic ether according to claim 1 or 3, wherein, virtue
Mass concentration of the fragrant race's carboxylate in reaction dissolvent is 1%~50%, and wherein reactant is dissolved in
In solvent or it is suspended in solvent.
10. the manufacture method of alicyclic carboxylic ether according to claim 1, wherein, hydrogen pressure
Power is 1.0~15MPa.
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| CN108947842A (en) * | 2018-08-21 | 2018-12-07 | 大连理工大学 | A kind of method that ruthenium rhenium bimetallic catalytic dimethyl terephthalate (DMT) adds hydrogen to prepare 1,4 cyclohexanedicarboxylic acid dimethyl ester |
| CN113332977A (en) * | 2021-05-25 | 2021-09-03 | 哈尔滨工业大学（深圳） | Catalyst for phthalate hydrogenation catalytic reaction and preparation method and application thereof |
| CN114096508A (en) * | 2021-08-23 | 2022-02-25 | 河北海力香料股份有限公司 | Preparation method of 3,3',4,4' -dicyclohexyltetracarboxylic acid and treatment method of acidic wastewater |
| CN115445609A (en) * | 2022-09-30 | 2022-12-09 | 浙江工业大学 | Active carbon-loaded ruthenium catalyst and preparation method and application thereof |
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