CN1292005C - Silicon modified aluminium oxide and preparation, and its use in loading metallocene catalyst - Google Patents
Silicon modified aluminium oxide and preparation, and its use in loading metallocene catalyst Download PDFInfo
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- CN1292005C CN1292005C CN 03155997 CN03155997A CN1292005C CN 1292005 C CN1292005 C CN 1292005C CN 03155997 CN03155997 CN 03155997 CN 03155997 A CN03155997 A CN 03155997A CN 1292005 C CN1292005 C CN 1292005C
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- aluminum oxide
- polysiloxane
- carrier
- alkyl
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Abstract
The present invention relates to a silicon modified alumina support which comprises 10 to 30% of amorphous silicon dioxide and crystal alumina as the rest according to mass percent, wherein the amorphous silicon dioxide covers a surface layer of the crystal alumina and is bonded to the surface of the aluminum oxide through an Al-O-Si chemical bond. The support is prepared by treating the crystal alumina with a polysiloxane solution, drying and calcining. The support is suitable for being used as a support of a supported metallocene catalyst, the prepared catalyst has high polymerization activity, and the molecular weight distribution of a polymer is wide.
Description
Technical field
The present invention is a kind of alumina supporter and preparation method and application of silicon modification, specifically, be a kind ofly to carry out modification and the alumina supporter and the preparation method that obtain with polysiloxane, and the loaded metallocene polyolefin catalyst solid ingredient that makes with this carrier.
Background technology
Aluminum oxide, silicon oxide are the important catalyst carriers, are widely used in refining oil, in the production process of catalyzer such as chemical industry.Aluminum oxide is commonly used for the carrier of reforming catalyst, hydrocracking, hydrogenating desulfurization and hydrodenitrogenation catalyst owing to have suitable specific surface and pore structure, particularly gama-alumina.Owing to have different characteristic electrons and structural performance, its effect as carrier and active ingredient is also inequality with silicon oxide for aluminum oxide.It is generally acknowledged that silicon oxide is a kind of inert support, not having electronic action, aluminum oxide between carrier and the active ingredient is a kind of non-inert support, exists certain electronic action between aluminum oxide and the active ingredient, thereby can influence the performance of catalyzer significantly.Therefore, people often combine both and prepare the carrier that is suitable for.
CN1091395C discloses a kind of silica-alumina carriers, and this carrier is used for hydrogenation catalyst.Its preparation method is that pure aluminum compound or aluminium carboxylate and silicon alcoholate or silicone compounds are mixed with solution, under acidic conditions this solution is made gelinite then, extrusion molding again, and roasting makes carrier.Aluminum oxide and silicon oxide are uniform mixed state in this carrier.
CN1005683B discloses a kind of support of the catalyst, and this carrier is the structure phase with the stupalith, is the carrier phase with the porous oxides.Carrier is made up of the aluminum oxide of 50-93 weight % and the silicon-dioxide of 7-50 weight %.During preparation with the carrier precursor with after stupalith mixes, make its be dispersed in whole stupalith mutually in, again by extrusion moulding, obtain carrier.This carrier at high temperature still can keep high specific surface area.
In carried metallocene catalyst, used carrier mostly is unformed silicon oxide greatly, seldom use aluminum oxide, because of alumina surface acidity stronger, often there are not activity or activity very low after the load metallocene active ingredient, thereby need carry out modification to alumina supporter, could use after making its acid reduction.
Summary of the invention
The alumina supporter that the purpose of this invention is to provide a kind of silicon modification, silicon oxide in this carrier covers the top layer of aluminum oxide, and links with chemical bond with aluminum oxide, can effectively utilize the acidity of alumina surface, after making load active component, catalyst activity increases.
Another object of the present invention provides the carried metallocene catalyst by above-mentioned preparing carriers, and this catalyzer has high polymerization activity, and the olefin polymer that makes has wider molecular weight distribution.
The alumina supporter of silicon modification provided by the invention, the soft silica that wherein contains 10-30 quality %, all the other are crystalline aluminum oxide, and described soft silica covers the top layer of crystalline aluminum oxide, and are connected in the surface of aluminum oxide by Al-O-Si chemical bond key.
The present invention adopts polysiloxane solution that crystalline aluminum oxide is carried out modification, makes the crystalline aluminum oxide surface form a kind of unformed silicon oxide layer.Link by chemical bond between silicon oxide and the aluminum oxide, the two characteristic electron and structural performance organically combined, form a kind of new carrier.Described preparing carriers is simple, only needs to handle crystalline aluminum oxide at low temperatures with the polysiloxane of proper viscosity and gets final product.The carrier of the present invention's preparation, the load metallocene active ingredient can obtain the polyolefine solid catalyst.This catalyzer is used for olefin polymerizating activity and reaches 1.9 * 10
7Gram/(mole zirconium hour), the polyolefin products molecular weight distribution that makes reaches 5.18.
Description of drawings
Fig. 1 makes the infrared spectrogram of carrier for example 1 of the present invention.
Fig. 2 makes the infrared spectrogram of carrier for example 2 of the present invention.
Fig. 3 is that example 1 of the present invention makes carrier
27AlNMR figure.
Fig. 4 is that example 2 of the present invention makes carrier
27AlNMR figure.
Fig. 5 is that example 1 of the present invention makes carrier
34SiNMR figure.
Fig. 6 is that example 2 of the present invention makes carrier
34SiNMR figure.
Embodiment
The present invention selects for use has certain crystal formation, the aluminum oxide of specific surface and pore structure, with polysiloxane it being carried out modification handles, after roasting, can form unformed silicon oxide on the surface of crystalline aluminum oxide, and aluminum oxide still can keep original crystal formation, specific surface and pore structure feature, formed unformed silicon oxide links to each other with aluminum oxide by the Al-O-Si key, but and the part acid sites on capping oxidation aluminium surface, thereby, can make the alumina supporter after the modification have suitable activity, the active ingredient of load polyolefin catalyst preferably, particularly metallocene active ingredient.
Crystalline aluminum oxide described in the carrier of the present invention can be the aluminum oxide of various crystallization types, the aluminum oxide of preferred γ, δ or η crystal formation, more preferably gama-alumina.
The specific surface area of described carrier is a 30-500 rice
2/ gram, preferred 100-400 rice
2/ gram, aperture are 10-500 nanometer, preferred 10-200 nanometer, and pore volume is 0.2-6.0 milliliter/gram, preferred 0.2-3.0 milliliter/gram.
The shape of described carrier can be sphere, clavate or particulate state, and grain size is the 1-1000 nanometer, preferred 3-300 nanometer.
The preparation method of the alumina supporter of silicon modification provided by the invention, comprise polysiloxane is dissolved in and make polysiloxane solution in the organic solvent, again crystalline aluminum oxide is placed polysiloxane solution, stir down and handled 0.5-24 hour, dry then, roasting, described polysiloxane has following structural formula:
In the formula, R
1, R
2Be selected from hydrogen, C respectively
1-C
6Alkyl, C
6-C
8Aryl, hydroxyl, carboxyl or nitro, R
3Be the modification group, be selected from amino, carboxyl, hydroxyl or have C
4-C
30The alkyl that replaces of amido, m is the integer of 5-40, the integer of preferred 5-15, n is the integer of 0-40, the integer of preferred 0-10.
The viscosity of the polysiloxane that uses in the described method is for being 600-1000 centipoise, R in its structural formula
1, R
2Can be identical or different, preferred hydrogen, methyl, ethyl, phenyl or hydroxyl.Preferred polysiloxane is polydimethylsiloxane, polymethy ethylsiloxane, poly-diphenyl siloxane or poly-methyl hydroxyl siloxanes.Also can select the polysiloxane of modification for use, the modification radicals R
3The alkyl that preferred amino, amido replace, in the alkyl that amido replaces, the alkyl carbon atoms number can be 1-8, and preferred amido is a quadrol.The alkyl that preferred amido replaces is quadrol propyl group (C
3H
6-NHCH
2CH
2NH
2).
Described polysiloxane should be dissolved in and be used further to handle aluminum oxide after suitable organic solvent is made solution, and described solvent is selected from ether, ketone, alcohol, organic acid, alkane, aromatic hydrocarbons or halohydrocarbon, preferred ketone compounds, more preferably acetone.
The mass ratio of polysiloxane and solvent is 1 in the described polysiloxane solution: 1-20, preferred 1: 2-10, more preferably 1: 2.5-5.0.
The inventive method is to place polysiloxane solution to handle crystalline aluminum oxide, and treatment temp is 10-50 ℃, is preferably 15-30 ℃, and the treatment time is 0.1-8.0 hour, preferred 0.1-4.0 hour.Crystalline aluminum oxide is 1 with the solid-liquid ratio of polysiloxane solution during processing: the 3-15 grams per milliliter.
The crystal formation of crystalline aluminum oxide is γ, δ or η type in the described silicon method of modifying, preferred gama-alumina.The shape of aluminum oxide can be excellent type, ball-type or particulate state, and its particle size range is the 1-1000 nanometer, preferred 3-300 nanometer.The surface-area of aluminum oxide is a 30-500 rice
2/ gram, preferred 60-400 rice
2/ gram, aperture are 0.5-500 nanometer, preferred 0.8-200 nanometer, and pore volume is 0.2-6.0 milliliter/gram, preferred 0.2-3.0 milliliter/gram.
The solid that aforesaid method obtains after aluminum oxide is handled with polysiloxane need carry out drying, roasting then, and drying temperature is 100-200 ℃, and the time is 0.5-6.0 hour, and maturing temperature is 400-900 ℃, and the time is 1-8 hour.The roasting sectional carries out, temperature from low to high, as prepare when crystalline aluminum oxide is gama-alumina in the carrier, first section maturing temperature is 200-400 ℃, second section maturing temperature is 400-600 ℃, the 3rd section maturing temperature is 600-800 ℃, but final maturing temperature should be no more than the top temperature that required aluminum oxide crystalline phase exists.
Modified aluminium oxide supports of the present invention is applicable to the carrier as the carried metallocene catalyst solid ingredient.Described carried metallocene catalyst comprises the alumina supporter of silicon modification provided by the invention and general formula is (Cp ')
2MX
2The metallocene active ingredient, Cp ' is selected from the above-mentioned group that cyclopentadienyl, indenyl, fluorenyl or alkyl replace in the described general formula, described substituted alkyl can be one or more, is selected from C
1～C1
2Alkyl; M is selected from any one in the IVB family element; X is selected from halogen.
In the described metallocene general formula, preferred cyclopentadienyl of Cp ' or C
1～C
6The cyclopentadienyl that alkyl replaces, substituent number can be one or more, preferred titanium of M or zirconium, the preferred chlorine of X.Preferred metallocene is two (cyclopentadienyl) zirconium dichloride, two (cyclopentadienyl) titanium dichloride, two (butyl cyclopentadiene) titanium dichloride, two (butyl cyclopentadiene) zirconium dichloride, two (pentamethyl-cyclopentadiene) zirconium dichloride or two (pentamethyl-cyclopentadiene) titanium dichloride.
In the above-mentioned carried metallocene catalyst, the content of metallocene active ingredient is counted 0.1-1.5 quality % with metal.Elder generation is suspended in the alumina supporter of silicon modification in the unreactive hydrocarbons solvent during preparation, adds the metallocene active ingredient again, stirs down fully contact, except that desolvating, promptly gets loaded catalyst after the drying.Preferable methods is earlier to handle described carrier with methylaluminoxane (MAO), and the dosage of MAO is counted 0.5-50 times of carrier quality with aluminium during processing, and the temperature of processing is 20-100 ℃.In the catalyst preparation process, the preferred C of the unreactive hydrocarbons solvent of use
6-C
10Alkane or C
6-C
8Aromatic hydrocarbons, it is 1 that its dosage should make the solid-liquid ratio: the 10-80 grams per milliliter.The mol ratio of aluminium is 1 in metallocene that adds during load and the methylaluminoxane: 50-500.
Carried metallocene catalyst provided by the invention is applicable to the Primary Catalysts of olefinic polymerization, and promotor is an alkylaluminoxane, and preferred promotor is a methylaluminoxane.The mol ratio of metal is 20-2000 in Al during polymerization in the promotor and the Primary Catalysts, preferred 25-1000.Polymerization temperature is 10-110 ℃, and preferred 20-100 ℃, pressure is 0.1-8.0MPa, preferred 0.1-1.0MPa.
Catalyzer of the present invention is applicable to the homopolymerization of alkene or the copolyreaction of alkene and alpha-olefin.Suitable olefinic monomer is C
3～C
8Alpha-olefin, as ethene, propylene, butylene, hexene or vinylbenzene, the preferred butylene of comonomer, hexene or octene.Polymerization methods can be slurry polymerization or gas phase mass polymerization.
Further specify the present invention below by example.But the present invention is not limited to this.
Example 1
The alumina supporter of following examples preparation silicon modification of the present invention.
Get 5.0 gram particles and directly be the 60-100 micron, specific surface area is 245 meters
2γ-the Al of/gram
2O
3Place 100 milliliters crucible, adding by 2.05 gram viscosity is polydimethyl siloxane fluid and 10 milliliters of solution that acetone is made into of 620 centipoises, and 25 ℃ were stirred 15 minutes down, and the paste that obtains was at room temperature left standstill 4 hours, got white powder.All substituting groups are methyl in the described polydimethyl siloxane fluid, and m is 8, and n is zero.
With above-mentioned white powder 200 ℃ of dryings 1 hour, then in 400 ℃ of roastings 1 hour, again 600 ℃ of roastings 1 hour, at last 800 ℃ of roastings 1 hour.Obtain the alumina supporter a of silicon modification.The content that fluorometry records silicon oxide in this carrier is 10.6 quality %.The physico-chemical property of carrier a sees Table 1, infrared spectra,
27AlNMR and
34The spectrogram of SiNMR is seen Fig. 1, Fig. 3 and Fig. 5 respectively.
Example 2
Get 5.0 gram particles and directly be the 40-80 micron, specific surface area is 235 meters
2γ-the Al of/gram
2O
3Place 100 milliliters of crucibles, adding by 3.2 gram viscosity is amino-modified silicone oil and 12 milliliters of solution that acetone is made into of 650 centipoises, and 30 ℃ were stirred 15 minutes, and described amino-modified silicone oil has following structural formula, and wherein m is 13, and n is 7.Get white paste after the stirring, this paste was left standstill 4 hours in room temperature, get white powder.
With above-mentioned white powder in 150 ℃ of roastings 1 hour, 400 ℃ of roastings 1 hour, 550 ℃ of roastings 2 hours at last 700 ℃ of roastings 0.5 hour, obtain the alumina supporter b of silicon modification.The content of silicon oxide is 29.5 quality % among the carrier b, and the physico-chemical property of carrier b sees Table 1, infrared spectra,
27AlNMR and
34The spectrogram of SiNMR is seen Fig. 2, Fig. 4 and Fig. 6 respectively.
By Fig. 1, infrared spectra shown in Figure 2 as can be known, the carrier of the present invention's preparation is at 1040cm
-1Stronger absorption peak has appearred in the place.Show to have formed the Al-O-Si key in the carrier, that is to say that silicon oxide and aluminum oxide are the form banded with chemical bond.
Fig. 3 and Fig. 4's
27The AlNMR spectrum shows that further carrier a and b all have γ-Al
2O
3Crystal formation.
Fig. 5 and Fig. 6's
34The SiNMR spectrum shows that then the silicon oxide among carrier a and the b is unformed silicon oxide.
Example 3
Method by example 1 prepares carrier c, the different 2.8 gram viscosity that are to use are that the phenylbenzene silicone oil and the acetone of 820 centipoises is mixed with modified solution, obtain the alumina supporter c of silicon modification after drying, the roasting, silica content wherein is 17.8 quality %, and physico-chemical property sees Table 1.All substituting groups are phenyl in the described phenylbenzene silicone oil, and m is 12, and n is zero.
Example 4
Following examples preparation carried metallocene catalyst.
Get the silicon modified aluminium oxide supports a that 2.0 gram examples 1 make; under nitrogen protection, move into and be equipped with in 250 milliliters of there-necked flasks that stir magneton; adding 50 milliliters of (77.5mmol) aluminium content is the toluene solution of the methylaluminoxane of 10 quality %, stirs 1 hour under the room temperature.
Under nitrogen protection, in above-mentioned there-necked flask, add two (cyclopentadiene) zirconium dichloride of 0.1 gram (0.327mmol).The temperature of control in the flask is 65 ℃, continues to stir 2 hours, and then, under nitrogen protection, filtration under diminished pressure, resistates wash with 30 milliliters toluene and normal hexane successively.70 ℃ of drying under reduced pressure 2 hours, the flaxen carried metallocene catalyst A of 1.86 grams.Ultimate analysis (ICP/AES) shows that the Zr content of catalyst A is 0.42 quality %.
Example 5
Method by example 4 prepares catalyst B, the different carrier b that is to use example 2 preparations, and zirconium content is 0.38 quality % in the catalyst B that makes.
Example 6
Method by example 4 prepares catalyzer C, the different carrier c that is to use example 2 preparations, and the metallocene active ingredient is two (cyclopentadiene) titanium dichloride, titanium content is 0.36 quality % among the catalyzer C that makes.
Example 7-9
The polymerization of the metallocene catalyst of following case expedition the present invention preparation.
300 milliliters of reactors with after the polymer grade ethylene displacement, are added 150 milliliters of purified normal hexanes, 1.5 ml concns are the toluene solution of the MAO of 10 quality %, 45 milligrams of loaded catalysts successively.Feed continuously ethylene gas, the maintenance ethylene pressure is 0.7MPa, 60 ℃ of polymerizations 1 hour.With the ethanolic soln termination reaction of hydrochloric acid, filter water, washing with alcohol successively, dry metallocene PE under the vacuum.Each example catalyst system therefor and activity thereof and polymer property see Table 1.
Table 1
| Instance number | Bearer number | Specific surface area, rice 2/ gram | Pore volume, milliliter/gram | Pore size distribution range, nanometer |
| 1 | a | 222 | 0.66 | 40-180 |
| 2 | b | 217 | 0.58 | 30-110 |
| 3 | c | 225 | 0.82 | 50-90 |
Table 2
| Instance number | The catalyzer numbering | Catalytic activity, gram/mole M hour | Polyethylene | ||
| Mw | Mw/Mn | Fusing point, ℃ | |||
| 7 | A | 2.48×10 7 | 877000 | 3.66 | 133.96 |
| 8 | B | 1.9×10 7 | 624000 | 5.18 | 128.82 |
| 9 | C | 6.24×10 6 | 352000 | 4.21 | 119.41 |
M is zirconium or titanium
Claims (13)
1, a kind of alumina supporter of silicon modification, the soft silica that wherein contains 10-30 quality %, all the other are crystalline aluminum oxide, described soft silica covers the top layer of crystalline aluminum oxide, and be connected in the surface of aluminum oxide by Al-O-Si chemical bond key, this carrier specific surface area is a 100-400 rice
2/ gram, aperture are that 10-200 nanometer, pore volume are 0.2-6.0 milliliter/gram.
2,, it is characterized in that described crystalline aluminum oxide is the aluminum oxide of γ, δ or η crystal formation according to the described carrier of claim 1.
3,, it is characterized in that described aluminum oxide is a gama-alumina according to the described carrier of claim 2.
4, the preparation method of the described carrier of a kind of claim 1, comprise polysiloxane is dissolved in and make polysiloxane solution in the organic solvent, again crystalline aluminum oxide is placed polysiloxane solution, stir down and handled 0.5-24 hour, dry then, roasting, described polysiloxane has following structural formula:
In the formula, R
1, R
2Be selected from hydrogen, C respectively
1-C
6Alkyl, C
6-C
8Aryl, hydroxyl, carboxyl or nitro, R
3Be selected from C
4-C
30Alkyl or the alkyl that replaces of amido, m is the integer of 5-40, n is the integer of 0-40.
5, in accordance with the method for claim 4, it is characterized in that R in the described polysiloxane structure formula
1, R
2Be selected from hydrogen, methyl, ethyl or hydroxyl respectively, R
3Propyl group for the quadrol replacement.
6, according to claim 4 or 5 described methods, the viscosity that it is characterized in that described polysiloxane is the 600-1000 centipoise, and m is the integer of 5-15 in the described polysiloxane structure formula, and n is the integer of 0-10.
7, in accordance with the method for claim 4, it is characterized in that described temperature with polysiloxane solution processing crystalline aluminum oxide is 10-50 ℃.
8, in accordance with the method for claim 4, it is characterized in that described organic solvent is an acetone.
9, in accordance with the method for claim 4, it is characterized in that the mass ratio of polysiloxane and solvent is 1 in the described polysiloxane solution: 2-10, crystalline aluminum oxide is 1 with the solid-liquid ratio of polysiloxane solution: the 3-15 grams per milliliter.
10, in accordance with the method for claim 4, it is characterized in that described drying temperature is 100-200 ℃, maturing temperature is 400-900 ℃, and roasting time is 1-8 hour.
11, a kind of carried metallocene catalyst comprises with the alumina supporter of the described silicon modification of claim 1 and general formula is (Cp ')
2MX
2The metallocene active ingredient, Cp ' is selected from the above-mentioned group that cyclopentadienyl, indenyl, fluorenyl or alkyl replace in the described general formula, described substituted alkyl can be one or more, is selected from C
1～C
12Alkyl; M is selected from any one in the IVB family element; X is selected from halogen.
12,, it is characterized in that Cp ' is selected from cyclopentadienyl or C in the described metallocene general formula according to the described catalyzer of claim 11
1-C
6The cyclopentadienyl that alkyl replaces, M is selected from titanium or zirconium, and X is selected from chlorine.
13,, it is characterized in that the content of metallocene active ingredient in the described catalyzer is counted 0.1-1.5 quality % with metal according to the described catalyzer of claim 11.
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|---|---|---|---|
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090098032A1 (en) * | 2007-10-11 | 2009-04-16 | Basf Catalysts Llc | Methods of making aluminosilicate coated alumina |
| CN101797520B (en) * | 2010-03-19 | 2011-11-09 | 山西大学 | Aluminum doped organic/inorganic hybrid clay catalyst, and preparation method and application thereof |
| CN102286115B (en) * | 2010-06-21 | 2013-02-13 | 中国石油天然气股份有限公司 | Olefin polymerization loaded metallocene catalyst and preparation method thereof |
| CN114433040B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | High-activity hydrotreating catalyst and preparation method and application thereof |
| CN114349885B (en) * | 2021-12-03 | 2023-11-07 | 国家能源集团宁夏煤业有限责任公司 | Preparation method of catalyst carrier, supported catalyst and application thereof |
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