CN101602012B - Mesoporous material containing aromatic hydrocarbon sulfonic acid groups as well as preparation method and application thereof - Google Patents
Mesoporous material containing aromatic hydrocarbon sulfonic acid groups as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of catalyst synthesis and provides a mesoporous material containing aromatic hydrocarbon sulfonic acid groups and a preparation method thereof. The aromatic hydrocarbon sulfonic acid groups are grafted on the outer surface and the inner hole walls of the SBA-15 mesoporous material and are directly synthesized by a one-step method, so that the mesoporous material has large hole size and a large specific surface area and is more beneficial to a catalytic reaction. The mesoporous material, which is used as a catalyst in reactions instead of sulphuric acid, has extremely high reaction activity, reduces the side reaction, improves the product purity, can be repeatedly used, generates no three wastes, has little pollution to the environment and is applied to the chemical engineering field.
Description
Technical field
The present invention relates to the catalyst synthesis technical field, be specifically related to contain the mesoporous material of aromatic hydrocarbon sulfonic acid groups.
Background technology
Butanone-ethylene ketal has peat-reek, can be used in the essence, also can be used as organic synthesis intermediate or solvent (flavor chemistry. Beijing: the .1984.250 of light industry publishing house, N H Bo Latusi; Silico-tungstic acid doped polyaniline catalyst synthesizes butanone ethylene ketal, chemical reagent, 2005,27 (2), 121～123, Yang Shuijin; Tong Wenlong; Sun Jutang).Its traditional synthetic method is synthetic under the catalysis of homogeneous catalyst inorganic acid, but this method exists side reaction many, and product purity is not high, and equipment corrosion is serious, contains a large amount of acid waste water in the post processing, causes shortcomings such as environmental pollution.Therefore, as select for use the heterogeneous catalysis of excellent catalytic effect to replace the homogeneous catalyst inorganic acid, not only can avoid above-mentioned defective, also can make heterogeneousization of homogeneous catalysis.
Synthesized a kind of new material-mesoporous material SBA-15 in 1998, this material has large aperture (6-30nm), the pore volume (1.0cm of high-sequential
3/ g), the high mechanical properties that keeps of thicker hole wall (4-6nm) and good catalysis absorption property (Triblock Copolymer Syntheses ofMesoporous Silica with Periodic 50 to 300 Angstrom Pores.D.Y.Zhao; J.L.Feng, Q.S.Huo, N.Melosh; G.H.Fredrickson; B.F.Chmelka, G.D.Stucky, Science 279 (1998) 548; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao. a kind of preparation method of mesonic pore molecular sieve carrier material, CN1341553A).Yet the mesoporous material hole wall surface has only the silicon hydroxyl, causes its chemical reactivity not high, thus big limitations the actual application value of mesoporous material.Along with going deep into to the mesopore molecular sieve application study; People begin to utilize the modifiability on mesoporous material surface gradually; The surface nature of mesoporous material is carried out organically-modified, improve its catalytic reaction activity, so that develop the application of mesoporous material in catalytic field to a greater extent.
At present, existing a lot of research and report about the mesopore molecular sieve surface modification method.Modify the difference of mode according to mesoporous material being carried out organo-functional group, these methods mainly are divided into two kinds, i.e. grafting method (but also claiming the method for grafting afterwards) behind coprecipitation (claim not only in-situ synthesis) and the covalent bond.The in-situ modification that wherein utilizes silane coupler to carry out the mesoporous material surface is the more problem of research in the mesoporous material research field.Employing in-situ synthesis such as Lim will contain (Synthesis andcharacterization of a reactive vinyl-functionalized MCM-41:probing theinternal pore structure by a bromination reaction [J] .J.Am.Chem.Soc. in the preparation of organically-modified mesoporous material of silane couplers such as sulfydryl, amino, epoxy alkyl and imidazole radicals; 1997; 119 (17): 4090-4091.Lim M H; Blanford C F, Stein A.Stucky) research group adopts in-situ synthesis will contain (Direct syntheses of ordered SBA-15mesoporous silica containing sulfonicacid groups, Chem.Mater.2000 in the preparation of organically-modified mesoporous material of sulfonic silane coupler; 12; 2448-2459D.Margolese, J.A.Melero, S.C.Christiansen; B.F.Chmelka, G.D.Stucky).
In homogeneous catalyst, the concentrated sulfuric acid is acid commonly used, is a kind of homogeneous catalyst preferably, is used for catalysis ethylene glycol and butanone and obtains the spices 2-ethyl-2-methyl isophthalic acid of food industry, the reaction process of 3-ring butyl oxide link (butanone-ethylene ketal).But use sulfuric acid that the problem of environmental protection aspect is arranged.
Summary of the invention
The technical problem that the present invention will solve is:
To the deficiency of prior art, the purpose of this invention is to provide a kind of mesoporous material that contains aromatic hydrocarbon sulfonic acid groups and preparation method thereof, make that this mesoporous material specific area is big, pore volume is big, more help catalytic reaction and carry out; In replacing the reaction of sulfuric acid as catalyst, reduce side reaction, improve product purity, help environmental protection.
Product technology scheme of the present invention is:
A kind of mesoporous material that contains aromatic hydrocarbon sulfonic acid groups, said mesoporous material are at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting aromatic hydrocarbon sulfonic acid groups;
The pore volume of said mesoporous material is 1cm
3/ g～1.5cm
3/ g.
The expression formula of mesoporous material product of the present invention is SBA-Ar-SO
3H.Ar-SO wherein
3H represents aromatic hydrocarbon sulfonic acid groups, Ar-SO
3H is grafted on the outer surface and/or the inner hole wall of mesoporous material SBA-15, also promptly is grafted on the part or all of the exposed surface of SBA-15.In the present invention, the outer surface of mesoporous material SBA-15 and other groups of not grafting of inner hole wall.SBA represents mesoporous material SBA-15.
Particularly, the specific area of said mesoporous material is 630m
2/ g～800m
2/ g, the aperture is 5nm～6nm.
Particularly, said mesoporous material is outer surface and/or inner hole wall grafting 2-(the 4-sulfonic group phenyl) ethyl group at the SBA-15 mesoporous material.This moment, expression formula was
Preparation method's technical scheme of the present invention is:
May further comprise the steps:
The 1st step is with triblock copolymer EO
20PO
70EO
20, join mass concentration and be in 1%～37% the aqueous hydrochloric acid solution, in molar ratio,
Triblock copolymer EO
20PO
70EO
20: hydrochloric acid=1: 100～500,
Under 25 ℃～60 ℃ temperature, be stirred to dissolving;
Described triblock copolymer EO
20PO
70EO
20, i.e. a kind of in triblock copolymer polyethylene glycol-glycerine-polyethylene glycol.
The 2nd step added ethyl orthosilicate in a last step gained solution, under 25 ℃～80 ℃ temperature, stir more than 25 minutes; Add 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane again, under 25 ℃～80 ℃ temperature, stir more than 10 hours; In molar ratio,
Ethyl orthosilicate: 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane=10～40: 1;
The 3rd step, will go up step gained solution and place closed reaction vessel, crystallization is 10 hours～72 hours under 90 ℃～150 ℃ temperature;
In the 4th step,, obtain mesoporous material raw powder with the filtration of crystallization afterproduct, washing, drying;
The 5th step, the gained mesoporous material raw powder was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with ethanol, removed template method obtains the mesoporous material product of the aforesaid 2-of containing (4-sulfonic group phenyl) ethyl group.
With document " Direct synthesis of ordered SBA-15 mesoporous materialscontaining arenesulfonic acid groups.Melero, J.A; Stucky, G.D.; Van Grieken, R.; Morales; G.J.Mater.Chem.9 (2002) 1664 " to compare, the novel mesoporous material that the present invention proposes uses the amount of silane coupler 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane to have only report in the document half the; after carrying out organic decoration; have bigger pore volume and bigger specific area, because of the mesoporous material catalytic reaction mainly occurs in the hole, to carry out so big pore structure parameter more helps catalytic reaction in the organic decoration process.
Application process technical scheme of the present invention is: be used for 2-ethyl-2-methyl isophthalic acid, as catalyst, replace sulfuric acid of the prior art in the preparation feedback process of 3-ring butyl oxide link.
This reaction is a reaction raw materials with ethylene glycol and butanone, in molar ratio,
Ethylene glycol: butanone=1: 1～10,
Mesoporous material with the above-mentioned 2-of containing (4-sulfonic group phenyl) ethyl group is a catalyst,
Under 120 ℃～150 ℃ temperature, stirring reaction 1 hour～72 hours, after reactant liquor was cooled to room temperature, centrifugation obtained liquid product: 2-ethyl-2-methyl isophthalic acid, 3-encircles butyl oxide link;
The vacuum drying 1 hour～24 hours under 25 ℃～200 ℃ temperature of the solid product of centrifugation, the catalyst that obtains reclaiming.
2-ethyl-2-methyl isophthalic acid, 3-encircles butyl oxide link, also can claim butanone-ethylene ketal, has peat-reek, can be used in the essence of food industry, also can be used as the intermediate or the solvent of organic synthesis.Prior art uses sulfuric acid as Preparation of Catalyst butanone-ethylene ketal, and sulfuric acid constantly is consumed, and can not recycle.
Utilize
of the present invention butanone and ethylene glycol to be carried out catalytic reaction as catalyst; Butanone conversion ratio 95%; 2-ethyl-2-methyl isophthalic acid; The selectivity 100% of 3-ring butyl oxide link (butanone-ethylene ketal), yield 95%.
When the catalyst that reclaims after the above-mentioned reaction reuses, butanone conversion ratio 96%, 2-ethyl-2-methyl isophthalic acid, 3-ring butyl oxide link (butanone-ethylene ketal) 100%, yield 96%.And quadric catalysis post catalyst reaction
still keeps the distinctive orderly hexagonal hole road structure of mesoporous material SBA-15, sees Fig. 1 and Fig. 2.
The technical scheme that another kind of product of the present invention contains the macroporous/mesoporous material of aromatic hydrocarbon sulfonic acid groups is:
Said mesoporous material is at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting aromatic hydrocarbon sulfonic acid groups;
The pore volume of said mesoporous material is 1cm
3/ g～1.5cm
3/ g, specific area is 500m
2/ g～650m
2/ g, the aperture is 7nm～13nm.
Macroporous/mesoporous material product and aforementioned mesoporous material product have common trait aspect grafting aromatic hydrocarbon sulfonic acid groups and the pore volume, and difference is that the aperture is bigger.
The expression formula of macroporous/mesoporous material product of the present invention is SBA-Ar-SO
3H.Ar-SO wherein
3H represents aromatic hydrocarbon sulfonic acid groups, Ar-SO
3H is grafted on the outer surface and/or the inner hole wall of mesoporous material SBA-15.SBA represents mesoporous material SBA-15.
Usually, macroporous/mesoporous material is outer surface and/or inner hole wall grafting 2-(the 4-sulfonic group phenyl) ethyl group at the SBA-15 mesoporous material.This moment, expression formula was
Preparation method's technical scheme of macroporous/mesoporous material of the present invention is:
May further comprise the steps:
The 1st step is with triblock copolymer EO
20PO
70EO
20, join mass concentration and be in 1%～37% the aqueous hydrochloric acid solution, in molar ratio,
Triblock copolymer EO
20PO
70EO
20: hydrochloric acid=1: 100～500,
Under 25 ℃～60 ℃ temperature, be stirred to dissolving;
Described triblock copolymer EO
20PO
70EO
20, i.e. a kind of in triblock copolymer polyethylene glycol-glycerine-polyethylene glycol.
The 2nd step added 1 gram～5 grams, 1,3,5 mesitylene in a last step gained solution, under 25 ℃～80 ℃ temperature, stir more than 25 minutes;
The 3rd step added ethyl orthosilicate in a last step gained solution, under 25 ℃～80 ℃ temperature, stir more than 25 minutes;
The 4th step, will go up a step gained solution and place closed reaction vessel, crystallization is 10 hours～72 hours under 90 ℃～150 ℃ temperature;
In the 5th step,, obtain the former powder of macroporous/mesoporous material with the filtration of crystallization afterproduct, washing, drying;
In the 6th step, the former powder of gained macroporous/mesoporous material was washed 10 hours～80 hours removed template method with ethanol under 90 ℃～120 ℃ temperature;
The 7th step; The former powder of gained macroporous/mesoporous material was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with acetone and 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane, obtain the macroporous/mesoporous material product of the described 2-of containing (4-sulfonic group phenyl) ethyl group
The invention has the beneficial effects as follows:
The mesoporous material that contains aromatic hydrocarbon sulfonic acid groups of the present invention has the big and big characteristics of specific area of pore volume, more helps catalytic reaction and carries out, in the butanone-ethylene ketal course of reaction of preparation; Has high reaction activity; Can reduce side reaction, improve product purity, and can use repeatedly; Do not have the three wastes fully, environmental pollution is little.Preparation method of the present invention utilizes one-step method directly to synthesize to contain the mesoporous material of 2-(4-sulfonic group phenyl) ethyl group, and dosage of silane coupling agent is few.
Description of drawings
Fig. 1 is the XRD spectra of mesoporous material of the present invention before and after catalytic reaction.
Fig. 2 is the pore structure figure of mesoporous material of the present invention before and after catalytic reaction.
Fig. 3 is a mesoporous material of the present invention
29Si CPMAS NMR spectrogram.
Fig. 4 is the graph of pore diameter distribution of mesoporous material of the present invention before and after catalytic reaction.
Fig. 5 is the XRD spectra of macroporous/mesoporous material of the present invention.
Fig. 6 is a macroporous/mesoporous material of the present invention
29Si CPMAS NMR spectrogram.
The specific embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention does not receive the restriction of these embodiment, and scope of the present invention proposes in claims.
Conversion ratio of the following example and selectivity, result's calculating of analyzing according to gas chromatography-mass spectrography gets.In the computational process, confirming of each concrete material is to provide according to given mass spectrogram and the standard spectrogram contrast that is input in the computer.
Embodiment 1, a kind of preparation that contains the mesoporous material of 2-(4-sulfonic group phenyl) ethyl group:
With 4.0 gram triblock copolymer EO
20PO
70EO
20(commercial goods; Abbreviate P123 as) join in the solution of 120ml hydrochloric acid (mass concentration 37%) and 6ml water, under 40 ℃ of temperature, be stirred to P123 and dissolve fully, again the 8.2ml ethyl orthosilicate is joined in the above-mentioned solution; Under 40 ℃ of temperature, stirred 45 minutes; In solution, add 1.3 gram 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silanes again, after stirring 24 hours under 40 ℃ of temperature, solution is transferred in the teflon-lined agitated reactor; Crystallization is after 24 hours under 100 ℃ of temperature, and solution is filtered, washs, obtains mesoporous material raw powder after the drying.Mesoporous material raw powder was under refluxad washed 24 hours with ethanol, obtain containing in the skeleton mesoporous material product
of 2-(4-sulfonic group phenyl) ethyl group
Embodiment 2,2-ethyl-2-methyl isophthalic acid, and the preparation of 3-ring butyl oxide link:
With mesoporous material
150 ℃ of following vacuum drying 6 hours; After being cooled to room temperature, take by weighing 0.3 the gram, take by weighing again 21.6 the gram butanone and 22.3 the gram ethylene glycol put into the 100ml there-necked flask successively; Add water knockout drum and condenser pipe; Divide in reflux under the condition of water and stirred 4 hours, be cooled to room temperature after, solid-liquid is centrifugalized; Utilize gas chromatographic analysis product liquid phase ingredient; Butanone conversion ratio 95%, 2-ethyl-2-methyl isophthalic acid, the selectivity 100% of 3-ring butyl oxide link (butanone-ethylene ketal); Yield 95%; Solid catalyst mesoporous material
is 150 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, utilize again after the recovery.
With the mesoporous material of recycling
150 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, take by weighing 0.3g; Take by weighing again 21.6 the gram butanone and 22.3 the gram ethylene glycol put into the 100ml there-necked flask successively; Add water knockout drum and condenser pipe, divide in reflux under the condition of water and stirred 4 hours, be cooled to room temperature after; Solid-liquid is centrifugalized; Utilize gas chromatographic analysis product liquid phase ingredient, butanone conversion ratio 96%, 2-ethyl-2-methyl isophthalic acid; The selectivity 100% of 3-ring butyl oxide link (butanone-ethylene ketal), yield 96%.
Embodiment 4, a kind of preparation that contains the macroporous/mesoporous material of 2-(4-sulfonic group phenyl) ethyl group:
4.0 gram triblock copolymer P123 are joined in the solution of 120ml hydrochloric acid (mass concentration 37%) and 6ml water; Under 40 ℃, being stirred to P123 dissolves fully; 1,3,5 mesitylene of 1.5g are joined in the above-mentioned solution; After 40 ℃ are stirred 2 hours down, again the 8.2ml ethyl orthosilicate is joined in the above-mentioned solution; After 40 ℃ are stirred 24 hours down, solution is transferred in the teflon-lined agitated reactor, 100 ℃ of following crystallization are after 24 hours, through obtaining the former powder of macroporous/mesoporous material after filtration, washing, the drying in baking oven.The former powder of macroporous/mesoporous material was under refluxad washed 24 hours with ethanol, obtain macroporous/mesoporous material.At last macroporous/mesoporous material was under refluxad washed 24 hours with acetone and 1.3 gram 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silanes, after filtration and drying, obtain containing in the skeleton macroporous/mesoporous material product of phenylbenzimidazole sulfonic acid base.
Comparative Examples 1:
Take by weighing 21.6 the gram butanone and 22.3 the gram ethylene glycol put into the 100ml there-necked flask successively; Add water knockout drum and condenser pipe; Divide in reflux under the condition of water and stirred 4 hours, be cooled to room temperature after, solid-liquid is centrifugalized; Utilize gas chromatographic analysis product liquid phase ingredient, do not see to measure other products.
Fig. 1 provides
carries out the XRD spectra before and after the catalytic reaction as catalyst.A is the XRD spectra of
, and b is the XRD spectra of quadric catalysis reacted
.Low-angle spectrum peak by XRD spectra occurs can be known;
has the hexagonal hole road structure of the peculiar sequential 2 D of mesoporous material SBA-15, and order mesoporous structure still remains unchanged after carrying out twice catalytic reaction.
Fig. 2 is the pore structure sketch map of
before and after the catalytic reaction; A is the pore structure sketch map of
, and b is the pore structure sketch map of quadric catalysis reacted
.Can know by figure,
and carry out the reacted pore structure of quadric catalysis and still keep the distinctive hexagonal hole of mesoporous material road structure.This result is consistent with the result of XRD.
Fig. 3 does
29Si CPMAS NMR spectrogram, wherein a is that SBA-15, b be not for passing through catalytic reaction
C is for after reclaiming once more after the catalytic reaction
29Si CPMAS NMR spectrogram.Can find out by spectrogram, before and after mesoporous material of the present invention uses
29In the Si CPMAS NMR spectrogram, promptly among b and the c, (SiO)
2Si (OH)
2Go out peak position (Q among the figure
2The position), (SiO)
3Si (OH) goes out peak position (Q among the figure
3The position) and (SiO)
4Si goes out peak position (Q among the figure
4The position), i.e. three kinds of peak positions that go out that connect skeleton Si are with coincideing of SBA-15.Compare with SBA-15, except above-mentioned three peaks, the spectrogram of b and c new peak all occurs at 55ppm and 60ppm place, and these two emerging spectrum peaks can belong to T
m(T
m=RSi (OSi)
m(OH)
3-m, m=1-3; T
2At δ=-55 and T
3δ=-60ppm).These two emerging spectrum peaks show that
group successfully is grafted on the skeleton of SBA-15, and
skeleton structure is not destroyed after the catalytic reaction.
Fig. 4 is
graph of pore diameter distribution before and after the catalytic reaction; Can find out that by graph of pore diameter distribution
has narrow pore-size distribution; This is consistent with the result of bibliographical information; Document is seen " Science 279 (1998) 548 for Triblock Copolymer Syntheses of Mesoporous Silica withPeriodic 50 to 300 Angstrom Pores.D.Y.Zhao; J.L.Feng, Q.S.Huo, N.Melosh; G.H.Fredrickson; B.F.Chmelka, G.D.Stucky ".And after the quadric catalysis reaction; Sample
pore size distribution curve remains unchanged basically, and peak shape is narrow and symmetrical.This explanation quadric catalysis reaction does not destroy the pore structure of sample.This is consistent with XRD diffraction result.
Fig. 5 is the XRD spectra before and after the macroporous/mesoporous material grafting.C is the XRD spectra of macropore SBA-15, and d is the macropore SBA-Ar-SO behind the graft reaction
3The XRD spectra of H.Macropore SBA-15 and macropore SBA-Ar-SO can be known in low-angle spectrum peak by XRD spectra occurs
3H has the hexagonal hole road structure of the peculiar sequential 2 D of mesoporous material SBA-15.
Fig. 6 is macropore SBA-15 (c) and macropore SBA-Ar-SO
3H's (d)
29Si CPMAS NMR spectrogram can be found out macropore SBA-15 (c) and macropore SBA-Ar-SO by spectrogram
3H's (d)
29In the Si CPMASNMR spectrogram (SiO)
2Si (OH)
2(Q
2The position), (SiO)
3Si (OH) (Q
3The position) and (SiO)
4Si (Q
4The position) three kinds connect skeleton Si go out the identical of peak position and SBA-15.SBA-15 compares with macropore, except above-mentioned three peaks, and macropore SBA-Ar-SO
3H's
29Si MAS NMR spectrogram all occurs new peak 55 with the 60ppm place, and these two emerging spectrum peaks can belong to T
m(T
m=RSi (OSi)
m(OH)
3-m, m=1-3; T
2At δ=-55 and T
3δ=-60ppm).These two emerging spectrum peaks show that
group successfully is grafted on the skeleton of macropore SBA-15.
Table 1 be before
catalytic reaction (sample a) with catalytic reaction after the pore structure parameter of (sample b); Can know by table; Mesoporous material
H is after the quadric catalysis reaction; Pore volume and specific area all reduce to some extent; And pore wall thickness increases, and this explanation reactant in catalytic reaction process enters in the duct of mesoporous material.It then is because due to the reactant that the part hole wall is entered into the mesoporous material duct in catalytic reaction process bursts that last aperture slightly increases.
Table 1 pore structure parameter table
Table 2 is macropore SBA-15 (sample c) and macropore SBA-Ar-SO
3The pore structure parameter of H (sample d) can know that by table macroporous/mesoporous material SBA-15 is behind graft reaction, and specific area and aperture reduce to some extent, and this explanation organic group in process of grafting enters into the skeleton of mesoporous material.
Table 2 pore structure parameter table
Claims (1)
1. the application of mesoporous material in catalytic reaction that contains aromatic hydrocarbon sulfonic acid groups is characterized in that:
With ethylene glycol and butanone is reaction raw materials, in molar ratio,
Ethylene glycol: butanone=1: 1～10,
With the mesoporous material that contains aromatic hydrocarbon sulfonic acid groups is catalyst,
Under 120 ℃～150 ℃ temperature, stirring reaction 1 hour～72 hours after reactant liquor is cooled to room temperature, centrifugalizes, and obtains liquid product: 2-ethyl-2-methyl isophthalic acid, and 3-encircles butyl oxide link;
The vacuum drying 1 hour～24 hours under 25 ℃～200 ℃ temperature of the solid product of centrifugation, the catalyst that obtains reclaiming;
The said mesoporous material that contains aromatic hydrocarbon sulfonic acid groups is at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting 2-(4-sulfonic group phenyl) ethyl group; The said pore volume that contains the mesoporous material of aromatic hydrocarbon sulfonic acid groups is 1cm
3/ g～1.5cm
3/ g, specific area is 630m
2/ g～800m
2/ g, the aperture is 5nm～6nm.
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| CN1735459A (en) * | 2003-01-13 | 2006-02-15 | Ucb公司 | Hydrogenation catalysts |
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