CN101817891A - Method for preparing magnesium chloride loaded non-metallocene single active site catalyst - Google Patents
Method for preparing magnesium chloride loaded non-metallocene single active site catalyst Download PDFInfo
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- CN101817891A CN101817891A CN 200910078594 CN200910078594A CN101817891A CN 101817891 A CN101817891 A CN 101817891A CN 200910078594 CN200910078594 CN 200910078594 CN 200910078594 A CN200910078594 A CN 200910078594A CN 101817891 A CN101817891 A CN 101817891A
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Abstract
The invention discloses a method for preparing a loaded non-metallocene single active site catalyst by taking magnesium chloride as a carrier, which comprises the following steps of: (1), preparation of a magnesium chloride carrier; (2), preparation of a magnesium chloride carrier of alkyl aluminoxane; and (3), preparation of a magnesium chloride loaded non-metallocene single active site catalyst, wherein the magnesium chloride carrier is prepared by adopting a spraying method in which tetrahydrofuran is taken as a solvent. The obtained loaded non-metallocene single active site catalyst catalyzes ethylene polymerization or copolymerization with high polymerization activity. In the method, the preparation of the magnesium chloride carrier is simple; and the obtained loaded catalyst granule has good shape and adjustable size.
Description
Technical field
The present invention relates to a kind of preparation method of magnesium chloride loaded non-metallocene single site catalyst, and the application of gained catalyzer aspect olefinic polymerization.
Background technology
In the evolution of olefin polymerization catalysis, the non-cyclopentadienyl single site catalyst that nineteen nineties develops has obtained great development and concern.Particularly contain the 4th group 4 transition metal complexes (EP 0874005, WO 0155231) of phenoxy group-imine ligand, have very high catalysis in olefine polymerization activity, and can obtain the polyolefin resin of features such as functionalization, have a good application prospect.But olefinic polymerization is to carry out in homogeneous phase, and the polymkeric substance that obtains is metamict, can't use on the slurry process of widespread use or gas phase polymerization technology.
At present, relevant single site catalysts load research report is very many, wherein with SiO
2Be the research of the report of carrier (CN1174848, CN 1174849, CN 1356343, US4,808,561, US5,026,797, US5,763,543, US5,661,098) at most.Although also more (the PCT Int.Appl.99/21898 of research report for the magnesium chloride compound load metallocene catalyst; US6,455,647; J.Mol.Catal.A2002,188,123; PCT Int.Appl.2004/078804), but the cost height of preparing carriers and catalyst cupport, and the carrier particle shape is poor, uncontrollable; Though use the catalyzer of spherical magnesium chloride after can the proof load metallocene to have good particle form, but contain components such as a spot of alcohol, water, alkoxyl group in the carrier, catalyzer to load has disadvantageous effect, and the preparing carriers complexity, above drawbacks limit the industrial application of magnesium chloride loaded metallocene catalyst.
Also there is document to use carrier loaded metallocene (Polymer International, 51:417-423,2002 of containing magnesium chloride, silica gel etc.; US5962360), but activity is very low, and need add a large amount of MAO when polymerization.
Summary of the invention
One of the object of the invention is to provide a kind of magnesium chloride support preparation method of load non-metallocene single site catalysts, and the magnesium chloride support that obtains with this method has good particle form.
Two of the object of the invention is to provide a kind of preparation method of the supported non-metallocene single site catalysts with the magnesium chloride support preparation.
Three of the object of the invention is above-mentioned supported non-metallocene single site catalysts is used for vinyl polymerization or copolymerization, has high polymerization activity.
The method of a kind of magnesium chloride loaded non-metallocene single site catalyst of the present invention comprises the steps:
(1) magnesium chloride support preparation: under protection of inert gas; under the room temperature; in reactor, add a certain amount of Magnesium Chloride Anhydrous; add an amount of tetrahydrofuran (THF) then; stir and heat up its dissolving; use airtight spray-dryer to prepare spherical magnesium chloride/tetrahydrofuran (THF) particle, the D of grain diameter then
50It is 10～100 microns.
With spherical magnesium chloride/tetrahydrofuran (THF) particle vacuum-drying a few hours under heating condition, remove tetrahydrofuran (THF), through gas chromatographic analysis, do not detect tetrahydrofuran (THF) (＜0.1%wt), the spheroidal particle of the good fluidity that obtains is magnesium chloride support.
(2) preparation of the magnesium chloride support of alkylaluminoxane: under rare gas element such as nitrogen protection; the magnesium chloride support that obtains in (1) step is added in the reactor; add solvent; be dispersed into suspension; add alkylaluminoxane; be warming up to 30～80 ℃; preferred 40～60 ℃; stirring reaction 3～6 hours, then for several times with solvent wash, vacuum-drying; obtain the magnesium chloride support that contains alkylaluminoxane of good fluidity; wherein solvent can adopt aromatic hydrocarbons or aliphatic hydrocarbon, as toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene etc., and preferred toluene.
(3) preparation of magnesium chloride loaded non-metallocene single site catalyst: under rare gas element such as nitrogen protection; the magnesium chloride support that contains alkylaluminoxane that will prepare in (2) step; join and make slurries in the solvent; the solution of non-cyclopentadienyl single site catalyst precursor slowly is added drop-wise in these slurries; under 0～40 ℃; reacted 1～120 minute; can obtain the supported non-metallocene single site catalysts; slurries can be directly used in polyreaction; or the gained reactant removed desolvate; obtain the solid supported non-metallocene single site catalyst of good fluidity after the washing drying; described solvent is a toluene; benzene; dimethylbenzene; hexane; heptane; hexanaphthenes etc. are selected toluene; hexane or both mixture the bests.
Above-mentioned alkylaluminoxane general structure is:
Wherein R represents C
1～C
12Alkyl is preferably methyl, a represents 4～30 integer, is preferably 10～30 integer.Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta (MAO), improved methylaluminoxane (MMAO).In the load non-metallocene single site catalysts, the aluminium weight content is 1～50%, is preferably 1～15%.
Be meant the metal complexes shown in general formula 1 and 2 at above-mentioned non-cyclopentadienyl single site catalyst precursor,
General formula 1
Wherein, R
1Be selected from and replace or unsubstituted C
1-C
20Aliphatic group or C
6-C
30Aryl radical,
R
2-R
6Identical or different, be hydrogen atom, halogen atom, C
1-C
20Aliphatic group, C
3-C
20Cyclic hydrocarbon radical or C
6-C
20Aryl radical, arbitrary hydrogen or carbon atom can be randomly replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atoms on the described alkyl,
Wherein, M is the transition metal of the 4th family or the 5th family in the periodic table of elements, and n is the integer of 1-3,
X be selected from hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido a kind of when n be 2 or when bigger, a plurality of X groups can be identical or different;
N is the integer that satisfies the M valence state, m is＞and 1 integer;
General formula 2
Wherein:
M is the transition metal of 3-11 family in the periodic table of elements, and n is＞1 integer, and m is the integer that satisfies the M valence state, and X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido; R
1-R
8Identical or different, be hydrogen atom, halogen atom, C
1-C
20Aliphatic group, C
3-C
20Cyclic hydrocarbon radical or C
6-C
20Aryl radical, arbitrary hydrogen on its described alkyl or carbon atom can randomly be replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atoms; R
9-R
10Identical or different, be selected from replacement or unsubstituted C
1-C
20Aliphatic group or C
6-C
30Aryl radical; R
1-R
10In two or more groups can be keyed to ring mutually; Y is a bridge joint group, is C
1-C
20Aliphatic group or C
6-C
20Aryl radical, the arbitrary hydrogen on its described alkyl or carbon atom can randomly be replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atoms;
In the supported non-metallocene single site catalysts, the weight content of central metal M counts 0.01～5%, is preferably 0.05～2%.
The catalyzer for preparing in the magnesium chloride loaded non-metallocene single site catalyst method of the present invention can be applied on the different polymerization processs, as vapour phase polymerization and slurry polymerization etc.The equal polymerization or the copolymerization that can be used for alkene are specially adapted to that ethylene homo closes or the copolymerization of ethene and other alpha-olefin, and wherein alpha-olefin adopts propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
The catalyzer for preparing in the magnesium chloride loaded non-metallocene single site catalyst method of the present invention can be directly used in olefinic polymerization, as is applied in the gas-phase polymerization process; Also can add aluminum alkyl catalyst and be used for olefinic polymerization, particularly in aq slurry process, add aluminum alkyls and can remove impurity in the system, improve polymerization activity to a certain extent, make promotor and need not add expensive MAO.
Wherein the employed solvent of polymerization is selected from alkane, aromatic hydrocarbon or halohydrocarbon.A kind of in preferred hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, the ethylene dichloride or their mixture most preferably are a kind of in hexane, toluene, the heptane or their mixture.
The concentration of catalyzer when polymerization for preparing in the magnesium chloride loaded non-metallocene single site catalyst method of the present invention is 1 * 10
-8Mol～1 * 10
-3Mol, preferred concentration range for are 1 * 10
-8Mol～1 * 10
-5Mol.
Polymerization temperature is-78 ℃-100 ℃, is preferably 0 ℃-90 ℃.
Polymerization pressure is 0.01-10.0MPa, preferred 0.01-2.0MPa.
The present invention compared with prior art has following advantage:
1, magnesium chloride support preparation method of the present invention is simple, and the granules of catalyst form that obtains is good, and catalyst particle size is adjustable.
2, the catalyzer for preparing in the magnesium chloride loaded non-metallocene single site catalyst method of the present invention has very high vinyl polymerization catalytic activity.
3, the catalyzer for preparing in the magnesium chloride loaded non-metallocene single site catalyst method of the present invention is used for olefinic polymerization and obtains the resin powder and have good particle form, and the tap density height goes for slurry process and vapor phase process polymerization technique.
Employed analysis and characterization instrument is as follows among the present invention:
1, GC (gas-chromatography) characterizes: measure the content of THF in the carrier, its tetrahydrofuran (THF) minimum detectable activity is 0.1%-wt;
2, ICP (plasma emission spectrum) characterizes: the weight percent of metal in the quantitative assay carried catalyst.The P1000 type ICP-AES plasma emission spectrometer that instrument selection U.S. PE company produces.
3, the sign of polymericular weight and molecular weight distribution: molecular weight and distribution thereof are measured by gel permeation chromatography (GPC), and instrument adopts Waters Alliance GPCV 2000, and solvent is 1,2,4-trichlorobenzene, sample concentration are 1mg/ml, and solvent flow rate is 1.0ml/min; Measuring temperature is 150 ℃.Each sample measurement secondary.
Embodiment
Embodiment 1
Under the nitrogen protection; in glass reactor; add 25.21 gram Magnesium Chloride Anhydrouss under the room temperature, add 700 milliliters of dried tetrahydrofuran (THF)s then, start stirring; be warming up to 65 ℃; stirring and dissolving 5 hours guarantees that magnesium chloride dissolves fully, prepares spherical magnesium chloride/tetrahydrofuran (THF) particle by Buchi B-290 spraying drying instrument then; content of tetrahydrofuran 23wt%, particle diameter are D
50It is 16 microns.
Spherical magnesium chloride/tetrahydrofuran (THF) particle 100 ℃ of following vacuum-dryings 2 hours, again 300 ℃ of following vacuum-dryings 10 hours, is obtained the spherical magnesium chloride support of good fluidity,, fail to detect tetrahydrofuran (THF) through gas chromatographic analysis.
Under nitrogen protection; get the above-mentioned magnesium chloride support that obtains 4.72 grams and add in the glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; MAO (methylaluminoxane) toluene solution that adds 28 milliliters of 10wt%; be warming up to 50 ℃, stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then; use hexane wash then; vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of methylaluminoxane.
Under nitrogen protection; with the magnesium chloride support that contains methylaluminoxane 2.12 grams that obtain previously; join in the glass reactor; add 35 milliliters of dried toluene and make slurries, will be dissolved in 20 milliliters of toluene 0.145 gram two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride ((L1)
2ZrCl
2, it is synthetic sees Chinese patent application 200610137778, its structure is as follows) drips of solution be added in the reactor, 30 ℃ of reactions 30 minutes, use 35 milliliters of toluene wash then, vacuum-drying obtains supported non-metallocene single site catalysts A.Characterize through ICP, in the catalyst A, the Zr weight content is 0.51%, and the Al weight content is 14.8%.
Embodiment 2
Preparation spherical magnesium chloride/tetrahydrofuran (THF) particle on pilot plant.
Under the nitrogen protection; in reactor; add 7.2 kilograms of Magnesium Chloride Anhydrouss under the room temperature, add 200 liters of dried tetrahydrofuran (THF)s then, start stirring; be warming up to 65 ℃; stirring and dissolving 7 hours guarantees that magnesium chloride dissolves fully, prepares spherical magnesium chloride/tetrahydrofuran (THF) particle by pilot scale spray-dryer (per hour 3 kilograms of bearer capabilities) then; content of tetrahydrofuran 31wt%, particle diameter are D
50It is 26 microns.
Spherical magnesium chloride/tetrahydrofuran (THF) particle 200 grams 100 ℃ of following vacuum-dryings 2 hours, again 300 ℃ of following vacuum-dryings 10 hours, are obtained the magnesium chloride support of good fluidity,, fail to detect tetrahydrofuran (THF) through gas chromatographic analysis.
Under nitrogen protection; get the above-mentioned magnesium chloride support that obtains 4.63 grams and add in the glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; MAO (methylaluminoxane) toluene solution that adds 28 milliliters of 10wt%; be warming up to 50 ℃, stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then; use hexane wash then; vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of methylaluminoxane.
Under nitrogen protection; with the magnesium chloride support that contains methylaluminoxane 2.39 grams that obtain previously; join in the glass reactor; add 35 milliliters of dried toluene and make slurries; to be dissolved in 20 milliliters of toluene 0.161 gram two-drips of solution of [N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride is added in the reactor, 30 ℃ of reactions 30 minutes, uses 35 milliliters of toluene wash then; vacuum-drying obtains supported non-metallocene single site catalysts B.Characterize through ICP, in the catalyst B, the Zr weight content is 0.57%, and the Al weight content is 15.6%.
Embodiment 3
Under nitrogen protection; get magnesium chloride support 3.62 grams that obtain among the embodiment 3 and add in the glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; MAO (methylaluminoxane) toluene solution that adds 21 milliliters of 10wt%; be warming up to 50 ℃, stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then; use hexane wash then; vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of methylaluminoxane.
Under nitrogen protection, the magnesium chloride support that contains methylaluminoxane 2.25 grams with obtaining previously join in the glass reactor, add 35 milliliters of dried toluene and make slurries, will be dissolved in 0.195 gram (L2) in 20 milliliters of toluene
3Zr
2Cl
4The drips of solution of (its structure is as follows, synthesizes and sees Chinese patent application 200410086388.8) is added in the reactor, 30 ℃ of reactions 30 minutes, uses 35 milliliters of toluene wash then, and vacuum-drying obtains supported non-metallocene single site catalysts C.Characterize through ICP, among the catalyzer C, the Zr weight content is 0.46%, and the Al weight content is 13.4%.
Embodiment 4～6 high-pressure ethylene polymerization experiment
High-pressure ethylene polymerization experiment process is as follows:
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then, adding along with hexane, triethyl aluminum (TEA) hexane solution of 2 milliliter of 1 mol is added, then add 50～100 milligrams of the supported non-metallocene single site catalysts that the foregoing description makes, be warming up to 80 ℃, pressure is risen to and keeps 1.0MPa, reacted 1 hour.After polyreaction finished, the polyethylene particle powder was collected in cooling, weighs.
Concrete polymerization result is listed in the table 1.
Table 1, supported non-metallocene single site catalysts polymerization result
Claims (8)
1. the method for a magnesium chloride loaded non-metallocene single site catalyst is characterized in that, comprises the steps:
(1) magnesium chloride support preparation: under protection of inert gas; under the room temperature; in reactor, add a certain amount of Magnesium Chloride Anhydrous; add an amount of tetrahydrofuran (THF) then; stir and heat up its dissolving; use airtight spray-dryer to prepare spherical magnesium chloride/tetrahydrofuran (THF) particle, the D of grain diameter then
50It is 10～100 microns;
With spherical magnesium chloride/tetrahydrofuran (THF) particle vacuum-drying a few hours under heating condition, remove tetrahydrofuran (THF), through gas chromatographic analysis, do not detect tetrahydrofuran (THF) (＜0.1%wt), the spheroidal particle of the good fluidity that obtains is magnesium chloride support;
(2) preparation of the magnesium chloride support of alkylaluminoxane: under rare gas element such as nitrogen protection, the magnesium chloride support that obtains in (1) step is added in the reactor, add solvent, be dispersed into suspension, add alkylaluminoxane, be warming up to 30～80 ℃, stirring reaction 3～6 hours, then for several times with solvent wash, vacuum-drying, obtain the magnesium chloride support that contains alkylaluminoxane of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene;
(3) preparation of magnesium chloride loaded non-metallocene single site catalyst: under rare gas element such as nitrogen protection; the magnesium chloride support that contains alkylaluminoxane that will prepare in (2) step; join and make slurries in the solvent; the solution of non-cyclopentadienyl single site catalyst precursor slowly is added drop-wise in these slurries; under 0～40 ℃; reacted 1～120 minute; obtain the supported non-metallocene single site catalysts; slurries can be directly used in polyreaction; or the gained reactant removed desolvate; obtain the solid supported non-metallocene single site catalyst of good fluidity after the washing drying, described solvent is a toluene; benzene; dimethylbenzene; hexane; heptane; hexanaphthene.
2. the method for magnesium chloride loaded non-metallocene single site catalyst according to claim 1 is characterized in that, described alkylaluminoxane general formula is:
Wherein R represents C
1～C
12Alkyl, a are represented 4～30 integer, and in the load non-metallocene single site catalysts, the aluminium weight content is 1～50%.
3. the method for magnesium chloride loaded non-metallocene single site catalyst according to claim 2, it is characterized in that described alkylaluminoxane wherein R is a methyl, a represents 10～30 integer, in the load non-metallocene single site catalysts, the aluminium weight content is 1～15%.
4. the method for magnesium chloride loaded non-metallocene single site catalyst according to claim 3 is characterized in that, described alkylaluminoxane is methylaluminoxane (MAO), improved methylaluminoxane (MMAO).
5. the method for magnesium chloride loaded non-metallocene single site catalyst according to claim 1 is characterized in that, in the preparation of magnesium chloride support of (2) step alkylaluminoxane, add alkylaluminoxane after, be warming up to 40～60 ℃; Solvent for use is a toluene; In the preparation of the magnesium-supported non-cyclopentadienyl single site catalyst of (3) one-step chlorination, solvent for use is toluene, hexane or both mixtures.
6. the method for magnesium chloride loaded non-metallocene single site catalyst according to claim 1 is characterized in that, described non-cyclopentadienyl single site catalyst precursor is meant the metal complexes shown in general formula 1 and 2,
General formula 1
In general formula 1, R
1Be selected from and replace or unsubstituted C
1-C
20Aliphatic group or C
6-C
30Aryl radical, R
2-R
6Identical or different, be hydrogen atom, halogen atom, C
1-C
20Aliphatic group, C
3-C
20Cyclic hydrocarbon radical or C
6-C
20Aryl radical, arbitrary hydrogen or carbon atom are randomly replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atoms on the described alkyl;
Wherein, M is the transition metal of the 4th family or the 5th family in the periodic table of elements, and n is the integer of 1-3,
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, when n is 2 or when bigger, a plurality of X groups are identical or different;
N is the integer that satisfies the M valence state, m is＞and 1 integer;
General formula 2
In general formula 2:
M is the transition metal of 3-11 family in the periodic table of elements, and n is＞1 integer, and m is the integer that satisfies the M valence state, and X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido; R
1-R
8Identical or different, be hydrogen atom, halogen atom, C
1-C
20Aliphatic group, C
3-C
20Cyclic hydrocarbon radical or C
6-C
20Aryl radical, arbitrary hydrogen on its described alkyl or carbon atom are randomly replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atoms; R
9-R
10Identical or different, be selected from replacement or unsubstituted C
1-C
20Aliphatic group or C
6-C
30Aryl radical; R
1-R
10In the optional ring that is keyed to mutually of two or more groups; Y is a bridge joint group, is C
1-C
20Aliphatic group or C
6-C
20Aryl radical, the arbitrary hydrogen on its described alkyl or carbon atom randomly replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atoms;
In the supported non-metallocene single site catalysts, the weight content of central metal M is 0.01～5%.
7. the method for magnesium chloride loaded non-metallocene single site catalyst according to claim 6 is characterized in that, in the described non-cyclopentadienyl single site catalyst, the weight content of central metal M is 0.05～2%.
8. the application of magnesium chloride loaded non-metallocene single site catalyst in olefinic polymerization for preparing in the method for claim 1～7 kind of any described magnesium chloride loaded non-metallocene single site catalyst.
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| CN109843938A (en) * | 2016-10-27 | 2019-06-04 | 尤尼威蒂恩技术有限责任公司 | The method for preparing molecular catalyst |
| CN112759679A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst and preparation and application thereof |
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| JP3322643B2 (en) * | 1998-10-19 | 2002-09-09 | 丸善石油化学株式会社 | Solid catalyst for olefin polymerization and method for producing olefin polymer using the same |
| CN101172988B (en) * | 2006-10-31 | 2011-03-23 | 中国石油化工股份有限公司 | Magnesium chloride loaded metallocene catalyst component, prepare method and application of the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109843938A (en) * | 2016-10-27 | 2019-06-04 | 尤尼威蒂恩技术有限责任公司 | The method for preparing molecular catalyst |
| CN109843938B (en) * | 2016-10-27 | 2022-09-30 | 尤尼威蒂恩技术有限责任公司 | Process for preparing molecular catalysts |
| CN112759679A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst and preparation and application thereof |
| CN112759679B (en) * | 2019-11-01 | 2023-02-28 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst and preparation and application thereof |
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