CN105709815B - A kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof - Google Patents
A kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof.This method is that the MWW type molecular sieves of little crystal grain are embedded in organic matter, and then the precursor with high temperature resistant indifferent oxide is uniformly mixed, and through molding, dry and roasting obtains toluene and ethylene selectivity alkylation catalyst.Catalyst of the present invention is combined to especially suitable for toluene and ethylene selectivity alkyl in methyl-ethyl benzene reaction process.Compared with prior art, since molecular sieve dosage is greatly lowered in catalyst, not only Catalyst Production cost significantly declines, it is thus also avoided that the discharge of intractable waste water in sieve synthesis procedure, and have the characteristics that catalytic activity is high and to methyl-ethyl benzene high selectivity.
Description
Technical field
The present invention relates to a kind of toluene and ethylene selectivity alkylation catalyst and preparation method thereof.The catalyst is used for first
Benzene is combined to ethylene selectivity alkyl in methyl-ethyl benzene reaction process.
Background technology
To methyl-ethyl benzene（PET）It is the raw materials for production of novel high polymer synthon p-methylstyrene.Novel high polymer
Material-poly- p-methylstyrene is the external high performance plastics kind developed in recent years, the various performances and polyphenyl of the polymer
Ethylene is similar, keeps good molding processibility, and excellent in proportion, heat resistance, anti-flammability, transparency and shrinking percentage etc.
In existing polystyrene plastics（Tensile strength 48MPa, elasticity modulus 2210MPa, Izod notched impact strength 16J/m, heat
95 DEG C of deformation temperature）.In addition p-methylstyrene can be with other monomer copolymerizations（Such as styrene）, the resistance to of certain polymer can be improved
Hot and anti-flammability can be largely used to the manufacture of engineering plastics, phthalic resin coating etc., thus in widespread attention.
For MCM-22 molecular sieves there are two types of independent polynary ring channel systems, one kind is two-dimentional sinusoidal waveform, the ten of intersection
Membered ring channel, section are ellipse（0.45nm*0.51nm）；Another kind is the large-scale cylindrical supercage that section is twelve-ring,
Supercage free internal space is the window of 0.71nm*0.71nm*1.82nm, these supercages and ten-ring（0.45*0.45nm）Phase
Even half twelve-ring supercage（0.71*0.71*0.91nm）It is formed in [001] crystal outer surface with the mouth for teaching big adsorption capacity
Bag, two supercages are connected by hexagonal prismoid.Since MCM-22 zeolite crystals are thin slab construction, it possesses larger
Outer surface, therefore all there is excellent catalytic performance to reactions such as alkylation, aromatisation, toluene disproportionations.
At present, it is poly- to methylbenzene second so as to limit due to being much higher than styrene to methyl-ethyl benzene monomer manufacture cost
Alkene is widely used, and is now mainly used for that polystyrene is replaced to make electrical accessorie and packaging, and be used for heatproof high field is needed to share
Illuminating equipment etc..Containing a certain amount of to methyl-ethyl benzene in usual first benzene alkylation with ethylene generation product, and the benzene that by-product is a small amount of
And mixed xylenes, wherein most toluene do not convert（Most of toluene recovery recycles）, purity is obtained by rectifying
90% or so to methyl-ethyl benzene.More than 98% is purified to methyl-ethyl benzene through further adsorbing separation or freezing and crystallizing.To methyl
Contain 50% or so p-methylstyrene in the product that ethylbenzene is generated through dehydrogenation, then the polymerization of 99 more than % of purity is obtained by rectifying
Monomer p-methylstyrene.Can be used the method similar with styrene polymerization or process for suspension polymerization production polymethylstyrene or
Comonomer as styrene etc. uses.
Traditional Friede-Crafts catalyst, the thermodynamical equilibrium that three isomers containing methyl-ethyl benzene can only be made are mixed
Object is closed, such as the AlCl of DOW companies of the U.S.3Series catalysts are reacted the product for being made and being known as vinyltoluene by toluene with pure ethylene
（Containing PET about 38%, remaining is meta position methyl-ethyl benzene）.USP4117024 uses chemical modification high silica ZSM-5 type zeolite as catalyst,
When toluene is reacted with pure ethylene, the content of PET in reaction product methyl-ethyl benzene isomers is obtained, reaches more than 90% and makes
The generation of ortho methyl group ethylbenzene is significantly inhibited, and content can level off to zero.CN1047986A, which is used, contains antimony（Or phosphorus）And magnesium
The Pentasil type Si-Al zeolite catalyst of element chemistry modifying process, although this zeolite catalyst can be directly with containing sulphur
Change the refinery tail-gas of the impurity such as hydrogen, water（Containing ethylene 10% ~ 20%）Make raw material reacted with toluene produce predominantly contraposition methyl second
The process of benzene, using antimony（Or phosphorus）And magnesium elements modification can play the role of molecular sieve surface acidity in neutralization and modulation, antimony, phosphorus
Modified to reduce molecular sieve surface strong acid center, weak acid center relative increase advantageously forms para-isomer.In addition, phosphorus
It also is able to reduce the effective dimensions in duct infall or aperture.But this processing method can be substantially reduced the work of catalyst
Property, even if reaction carries out at very high temperatures, conversion ratio is still relatively low, moreover, P elements are easier to be lost at reaction conditions,
It is also a deficiency of the technology.So the conversion of ethylene of the catalyst and to methyl-ethyl benzene selectivity all than relatively low.
CN1103607A provides ethylene and toluene reaction in a kind of catalytic cracked dry gas and produces and select type to methyl-ethyl benzene
Catalyst.The catalyst is a kind of Pentasil type catalyst containing rare earth, and carrying out the dippings such as aluminium and magnesium to molecular sieve is modified,
The amount of oxide modifier is not less than 0.25%.This processing method can be substantially reduced the activity of catalyst, even if reaction is very high
At a temperature of carry out, conversion ratio is still relatively low.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of toluene and ethylene selectivity alkylation catalyst and its system
Preparation Method.This method can avoid the activated centre of catalyst from being capped, improve catalyst activity and isomerisation selectivity with
And stability.
The toluene of the present invention and the preparation method of ethylene selectivity alkylation catalyst, including：
（1）MWW type molecular sieves are embedded in organic matter, obtain the molecular sieve of organic matter embedding；
（2）By step（1）The obtained molecular sieve of organic matter embedding mixes with the precursor of high temperature resistant indifferent oxide
Even, through molding, dry and roasting obtains toluene and ethylene selectivity alkylation catalyst.
Step（1）For the MWW types molecular sieve preferably using little crystal grain MWW type molecular sieves, average grain diameter is 0.1 ~ 1.0
Micron, preferably 0.2 ~ 0.8 micron, SiO2/Al2O3Molar ratio is 20 ~ 80, preferably 30 ~ 60.The MWW types molecular sieve can be with
Selected from various MWW structure molecular screens in the prior art, including one in MCM-22, SSZ-25, MCM-36, MCM-49 and MCM-56
Kind is a variety of, preferably one or more in MCM-22 and MCM-49 molecular sieves.The MWW types molecular sieve is in the catalyst
Mass content is 1.0% ~ 20.0%, preferably 2.0% ~ 15.0%, further preferably 2.0% ~ 10.0%.The high temperature resistant inertia
Oxide can be selected from one or more in aluminium oxide, silica, calcium oxide, zinc oxide, magnesia etc., preferably aluminium oxide
Or/and silica.The precursor of the high temperature resistant indifferent oxide refers to the corresponding hydroxide of the oxide.
Step（1）The organic species can be in starch and polyvinyl alcohol one or more, the polyethylene
The degree of polymerization of alcohol is 1500 ~ 2500, and alcoholysis degree is more than 85%, preferably 90% ~ 99%.The starch is water soluble starch,
Molecular weight is 20000 ~ 100000, the starch be precipitated as one kind in cornstarch, tapioca and potato starch or
It is a variety of, preferably cornstarch.Step（1）The process that may be used with the method for organic matter embedding molecular sieve is as follows：It will be organic
Object is mixed with water, and MWW type molecular sieves are suspended in wherein, is then granulated, molecular sieve is made to be embedded in organic matter, wherein making
Grain method can be vacuum spray drying method, boiling granulation method, centrifugal granulation or extrusion―spherozation etc., preferably vacuum
Spray drying process.In vacuum spray drying method, vacuum degree is generally 0.01 ~ 0.05MPa, and drying temperature is 50 ~ 150 DEG C, dry
Time is 1 ~ 24 hour, i.e., suspension obtained above is carried out vacuum spray drying, form small dry particle.Step
（1）In the molecular sieve of the organic matter embedding of gained, the mass ratio of organic matter and molecular sieve is 20:1~1:1, preferably 10:1~5:
1.Step（1）The grain size of the molecular sieve of the organic matter embedding of gained is 10 ~ 100 microns.
Step（2）The molding can be selected according to practical application, such as spherical, strip or other special-shaped particles,
Preferably strip.Step（2）The drying condition is：80 ~ 150 DEG C of drying temperature, 5 ~ 20 hours drying times, the roasting
Burning is carried out in oxygenous atmosphere, and the condition of roasting is：400 ~ 650 DEG C of calcination temperature, roasting time 5 ~ 20 hours.Purpose is
By organic matter oxidation removal at high temperature, the duct i.e. reaction channel of needs is released.
Toluene of the present invention is to generate toluene and ethylene selectivity alkylation with ethylene selectivity alkylation process
To the technical process of methyl-ethyl benzene.The process conditions of use are generally as follows：Toluene/ethylene molar ratio 1：1~10：1, reaction temperature
It is 350 DEG C ~ 450 DEG C, 1 ~ 10h of volume space velocity during liquid-1, reaction pressure is 0.8MPa ~ 3MPa.
The toluene of the present invention is to use first to embed molecular sieve organic matter with ethylene selectivity alkylation catalyst,
Then catalyst is mixed with high temperature resistant inert inorganic oxide again, can makes molecular sieve distribution more uniform in this way, may be used also
So that the more active center distributions of catalyst can avoid the activated centre of catalyst from being capped in this way in pore passage structure, when
When reactant is by catalyst duct, directly efficiently contacts and react with the catalytic active species in its duct, and by
Small in active particle, orifice throat length is short, and product can be diffused out quickly, avoid deep reaction, improves the choosing of target product
Selecting property.Compared with prior art, the method for the present invention is used for toluene in ethylene selectivity alkylation process, not only having and urging
It is high and the features such as to methyl-ethyl benzene high selectivity to change activity, and Catalyst Production cost significantly declines, while avoid point
The characteristics of discharge of intractable waste water in son sieve building-up process.
Specific embodiment
The technology of the present invention is described further, but should not be construed as being limited to this range below by embodiment.This
In invention, wt% is mass fraction.
In the present invention, the grain size of molecular sieve uses SEM（Scanning electron microscope）Mode measure, silica alumina ratio
It is to be measured using chemical analysis.
Little crystal grain MCM-22 used in this experiment is reference literature（Petrochemical industry the 33rd phase in 2004）The method of report
Synthesis obtains, and average grain diameter is 0.6 micron.
The conversion ratio and the selectivity to methyl-ethyl benzene that key data involved in the present embodiment has ethylene, it is specific to calculate
Method is as follows：
Conversion of ethylene=[（Into the weight of weight-reactor outlet ethylene of reactor ethylene）/ into reactor ethylene
Weight] × 100%
Selective to methyl-ethyl benzene=（Reactor outlet is to the weight of weight/reactor outlet methyl-ethyl benzene of methyl-ethyl benzene
Amount）×100%
Embodiment 1
A kind of preparation process of catalyst of the present invention is as follows：
（1）By 90 grams of water-soluble cornstarch（Molecular weight is 35000）It is dissolved in 300 grams of water, then adds in 10 under room temperature
Gram MCM-22 molecular sieves（Grain size is 0.6 micron, SiO2/Al2O3Molar ratio is 35）, uniform suspension is sufficiently stirred into, is passed through
Vacuum spray drying（Vacuum degree 0.03MPa, drying temperature are 60 DEG C, drying time 5h）, it is 80 to obtain average particle diameter
The molecular sieve of the starch embedding of micron.
（3）Take 25 grams of steps（2）The molecular sieve of the starch embedding of preparation and 118 grams（Butt 76wt%）Aluminium hydroxide, that is, SB
Powder is sufficiently mixed, and then adds in the salpeter solution of a concentration of 0.1mol/L of 85mL, and abundant kneading makes paste plastic,
Forming diameter is the cylindrical bars of 1.5mm on banded extruder, and the cylindrical bars are 16 hours dry at 100 DEG C, then in air atmosphere
In 550 DEG C of roastings obtain catalyst of the present invention within 4 hours.Catalyst forms, in terms of mass fraction, MCM-22：2.5%th, aluminium oxide：
Surplus.
10mL catalyst is taken, is packed into the miniature flow reactor of fixed bed after being diluted with 10mL quartz sands and carries out catalysis work
Property evaluation.Process conditions are as follows：Toluene/ethylene molar ratio 4, reaction temperature is 400 DEG C, reaction pressure 2.0MPa, during with liquid
Volume space velocity 5h-1Into raw material, evaluating catalyst is carried out, negates and the product of 4 hours is answered to be analyzed, the selection of toluene and ethylene
Property alkylation in reaction result be shown in Table 1.
Embodiment 2
With embodiment 1, the difference lies in content of material in each step to carry out a kind of embodiment of catalyst of the present invention
Adjustment, MCM-49（Grain size is 0.8 micron, SiO2/Al2O3Molar ratio is 40）Replace MCM-22 molecular sieves, obtain catalyst group
Into, in terms of mass fraction, MCM-49：3.0%th, aluminium oxide：Surplus.Evaluation results are shown in Table 1.
Embodiment 3
With embodiment 1, the difference lies in content of material in each step to carry out a kind of embodiment of catalyst of the present invention
The mass ratio of adjustment, starch and molecular sieve is 5:1, it is prepared into the molecule for the starch embedding that average particle diameter is 50 microns
Sieve.Obtain catalyst composition, in terms of mass fraction, MCM-22：10%th, aluminium oxide：Surplus.Evaluation results are shown in Table 1.
Embodiment 4
A kind of embodiment of catalyst of the present invention is with embodiment 1, and the difference lies in steps（1）It is middle to replace chlorine with palladium bichloride
Platinic acid, and content of material is adjusted in each step, and the mass ratio of starch and molecular sieve is 10:1, it is prepared into average
The molecular sieve of the starch embedding of a diameter of 100 microns of grain obtains catalyst composition, in terms of mass fraction, MCM-22：5.0%th, oxygen
Change aluminium：Surplus.Evaluation results are shown in Table 1.
Embodiment 5
A kind of embodiment of catalyst of the present invention is with embodiment 1, and the difference lies in steps（1）In be additionally added palladium bichloride,
And content of material is adjusted in each step, and the mass ratio of starch and molecular sieve is 2:1, it is straight to be prepared into average grain
Diameter is the molecular sieve of 70 microns of starch embedding, obtains catalyst composition, in terms of mass fraction, Pd：0.15%、MCM-22：
5.5%th, aluminium oxide：Surplus.Evaluation results are shown in Table 1.
Embodiment 6
A kind of embodiment of catalyst of the present invention is with embodiment 1, and the difference lies in steps（2）In use polyvinyl alcohol（It is poly-
Right is 1800, alcoholysis degree 98%）Replace water soluble starch, content of material is adjusted in each step, polyvinyl alcohol with
The mass ratio of molecular sieve is 5:1, the molecular sieve for the polyvinyl alcohol embedding that average particle diameter is 50 microns is prepared into, is catalyzed
Agent forms, in terms of mass fraction, MCM-22：8%th, aluminium oxide：Surplus.Evaluation results are shown in Table 1.
Embodiment 7
A kind of embodiment of catalyst of the present invention is with embodiment 1, and the difference lies in steps（3）It is middle to replace hydrogen-oxygen with silica gel
Change aluminium, content of material is adjusted in each step, and the mass ratio of starch and molecular sieve is 8:1, it is straight to be prepared into average grain
Diameter is the molecular sieve of 80 microns of starch embedding, obtains catalyst composition in terms of mass fraction, MCM-22：1.0%th, silica：It is remaining
Amount.Evaluation results are shown in Table 1.
Comparative example 1
Aluminium hydroxide, that is, SB powder, MCM-22 molecular sieves and sesbania powder are sufficiently mixed, then added in appropriate a concentration of
The salpeter solution of 0.1mol/L, abundant kneading make paste plastic, the circle of a diameter of 1.5mm are squeezed out on banded extruder
Column, cylindrical bars are 16 hours dry at 100 DEG C, and then 550 DEG C of roastings obtain catalyst in 4 hours in air atmosphere, are made
Catalyst forms, in terms of mass fraction, MCM-22：65%th, aluminium oxide：Surplus.With embodiment 1, evaluation result is shown in Table evaluation condition
1。
Comparative example 2
With comparative example 1, the difference lies in obtained catalyst to form with implementation the preparation method of this comparative example catalyst
Example 1, in terms of mass fraction, i.e. MCM-22：2.5%th, aluminium oxide：Surplus.Evaluation condition is with embodiment 1, and evaluation results are shown in Table 1.
Comparative example 3
With comparative example 1, the difference lies in obtained catalyst to form with implementation the preparation method of this comparative example catalyst
Example 2, in terms of mass fraction, MCM-49：3.0%th, aluminium oxide：Surplus.Evaluation condition is with embodiment 1, and evaluation results are shown in Table 1.
The evaluation result of 1 different catalysts of table
| Embodiment is numbered | Conversion of ethylene, % | To methyl-ethyl benzene selectivity, % |
| Embodiment 1 | 97.8 | 93.8 |
| Embodiment 2 | 98.8 | 95.3 |
| Embodiment 3 | 97.9 | 96.1 |
| Embodiment 4 | 98.1 | 95.8 |
| Embodiment 5 | 97.6 | 93.4 |
| Embodiment 6 | 97.9 | 95.7 |
| Embodiment 7 | 98.2 | 96.1 |
| Comparative example 1 | 96.5 | 77.5 |
| Comparative example 2 | 75.1 | 35.6 |
| Comparative example 3 | 65.3 | 30.9 |
From the results shown in Table 1, catalyst of the present invention is generated in the alkylated reaction of toluene and ethylene to methyl
The selectivity of ethylbenzene all reaches more than 93%, hence it is evident that higher than the result of comparative example.
Claims (20)
1. the preparation method of a kind of toluene and ethylene selectivity alkylation catalyst, including：
（1）MWW type molecular sieves are embedded in organic matter, obtain the molecular sieve of organic matter embedding；The organic matter, which is selected from, to form sediment
It is one or more in powder and polyvinyl alcohol；In the molecular sieve of the organic matter embedding of gained, the mass ratio of organic matter and molecular sieve
It is 20:1~1:1；
（2）By step（1）The obtained molecular sieve of organic matter embedding is uniformly mixed with the precursor of high temperature resistant indifferent oxide, is passed through
Molding, dry and roasting, obtains toluene and ethylene selectivity alkylation catalyst.
2. according to the method for claim 1, it is characterised in that the MWW types molecular sieve uses little crystal grain MWW type molecular sieves,
Average grain diameter is 0.1 ~ 1.0 micron.
3. according to the method for claim 2, it is characterised in that the MWW types molecular sieve uses little crystal grain MWW type molecular sieves,
Average grain diameter is 0.2 ~ 0.8 micron.
4. according to the method described in claims 1 or 2, it is characterised in that the SiO of the MWW types molecular sieve2/Al2O3Molar ratio is
20~80。
5. according to the method for claim 4, it is characterised in that the SiO of the MWW types molecular sieve2/Al2O3Molar ratio for 30 ~
60。
6. according to the method described in any one in claim 1-3, it is characterised in that the MWW types molecular sieve is selected from MCM-
22nd, it is one or more in SSZ-25, MCM-36, MCM-49 and MCM-56.
7. according to the method for claim 6, it is characterised in that the MWW types molecular sieve is selected from MCM-22 and MCM-49 molecules
It is one or more in sieve.
8. according to the method for claim 1, it is characterised in that the mass content of the MWW types molecular sieve in the catalyst is
1.0%~20.0%。
9. according to the method for claim 8, it is characterised in that the mass content of the MWW types molecular sieve in the catalyst is
2.0%~15.0%。
10. according to the method for claim 1, it is characterised in that the high temperature resistant indifferent oxide be selected from aluminium oxide or/
And silica.
11. according to the method for claim 1, it is characterised in that the degree of polymerization of the polyvinyl alcohol is 1500 ~ 2500, alcoholysis
For degree more than 85%, the starch is water soluble starch, and molecular weight is 20000 ~ 100000.
12. according to the method for claim 11, it is characterised in that the starch is cornstarch, tapioca and Ma Ling
It is one or more in sweet potato starch.
13. according to the method for claim 1, it is characterised in that step（1）It is used with the method for organic matter embedding molecular sieve
Process it is as follows：Organic matter with water is mixed, MWW type molecular sieves are suspended in wherein, is then granulated, embeds molecular sieve
In organic matter, wherein prilling process is vacuum spray drying method, boiling granulation method, centrifugal granulation or extrusion-spheronization pelletizing
Method.
14. according to the method for claim 13, it is characterised in that step（1）Prilling process is vacuum spray drying method, very
Reciprocal of duty cycle is 0.01 ~ 0.05MPa, and drying temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 24 hour.
15. according to the method for claim 1, it is characterised in that step（1）In the molecular sieve of the organic matter embedding of gained, have
The mass ratio of machine object and molecular sieve is 10:1~5:1.
16. according to the method for claim 1, it is characterised in that step（1）The grain of the molecular sieve of the organic matter embedding of gained
Diameter is 10 ~ 100 microns.
17. according to the method for claim 1, it is characterised in that step（2）The drying condition is：Drying temperature 80 ~
150 DEG C, 5 ~ 20 hours drying times, the roasting is carried out in oxygenous atmosphere, and the condition of roasting is：Calcination temperature
400 ~ 650 DEG C, roasting time 5 ~ 20 hours.
18. a kind of toluene and ethylene selectivity alkylation catalyst, it is characterised in that using any side of claim 1 ~ 17
It is prepared by method.
19. a kind of toluene and ethylene selectivity alkylation, it is characterised in that using the catalyst described in claim 18.
20. according to the method for claim 19, it is characterised in that the toluene is with ethylene selectivity alkylation process
Toluene and ethylene selectivity alkylation are generated into the technical process to methyl-ethyl benzene, reaction condition is as follows：Toluene/ethylene molar
Than 1：1~10：1, reaction temperature is 350 DEG C ~ 450 DEG C, 1 ~ 10h of volume space velocity during liquid-1, reaction pressure is 0.8MPa ~ 3MPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101563159A (en) * | 2006-12-21 | 2009-10-21 | 埃克森美孚化学专利公司 | A catalyst composition, the method of manufacturing, and the process of use thereof in aromatics alkylation |
| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| CN103301889A (en) * | 2012-03-15 | 2013-09-18 | 山西腾茂科技有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN103801385A (en) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080058566A1 (en) * | 2006-09-05 | 2008-03-06 | Fina Technology, Inc. | Processes for reduction of alkylation catalyst deactivation utilizing low silica to alumina ratio catalyst |
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- 2014-12-02 CN CN201410716665.2A patent/CN105709815B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101563159A (en) * | 2006-12-21 | 2009-10-21 | 埃克森美孚化学专利公司 | A catalyst composition, the method of manufacturing, and the process of use thereof in aromatics alkylation |
| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| CN103301889A (en) * | 2012-03-15 | 2013-09-18 | 山西腾茂科技有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN103801385A (en) * | 2012-11-13 | 2014-05-21 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition |
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