CN103694382A - Preparation method of double-mould-pore-size-distribution silica-gel carrier - Google Patents
Preparation method of double-mould-pore-size-distribution silica-gel carrier Download PDFInfo
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- CN103694382A CN103694382A CN201210365806.1A CN201210365806A CN103694382A CN 103694382 A CN103694382 A CN 103694382A CN 201210365806 A CN201210365806 A CN 201210365806A CN 103694382 A CN103694382 A CN 103694382A
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Abstract
The invention discloses a preparation method of a double-mould-pore-size-distribution silica-gel carrier through two stage gel reactions by using an inorganic silicate and an inorganic acid as raw materials. In the first stage, a sol-gel technology is adopted, and silica gel pore size distribution of which ranges from 50 angstroms and 500 angstroms is prepared by adjusting the pH value, the reaction temperature and the ageing time. In the second phase, the pore size of the silica gel is adjusted by adding a ternary block copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) as a template reagent. The pore size distribution in the second phase ranges from 20 angstroms and 150 angstroms. The silica-gel carrier, the difference of the average pore sizes of which in the two stages is larger than 50 angstroms, is prepared. Olefin copolymer with wide molecular weight distribution can be obtained by polymerization by utilization of a catalyst prepared by the carrier.
Description
Technical field
The present invention relates to a kind of preparation method of polyolefin catalyst carrier, be specifically related to a kind of preparation method with bimodulus pore size distribution silica-gel carrier.
Technical background
Silica gel has industrial application widely, as siccative and support of the catalyst, comprises carrier for olefin polymerization catalyst.These olefin polymerization catalysis generally contain a kind of transition metal component with katalysis, as chromium, by high temperature oxidation, can be deposited on silicon aerosol carrier.By olefinic polymerization, control temperature of reaction, pressure, solvent, catalyzer and other polymerization technique, can prepare the polyolefin products of different molecular weight distribution and melting index.In all multi-usages of polyolefin resin, hardness, intensity and environmental stress (ESCR) are important indexs.When polyolefin molecular weight is higher, the corresponding raising of these attributes.Yet polyolefinic molecular weight is higher, the processability of its resin reduces conventionally, and the polyethylene that preparation has bimodal or a broad peak molecular weight distribution can improve especially extrusion performance of its processing characteristics.
One of polyethylene process that preparation has bimodal or broad peak molecular weight distribution is before polyvinyl resin machine-shaping or blown film, to add various auxiliary agents, but the method cost is high, and need to carry out extra processing.Two of method is melt-mixing methods, as US4598128, US4547551, WO94/22948 etc.It is that the polyethylene of two kinds of different molecular weights is carried out to physical mixed.This method is feasible, but has increased complete processing, thereby make to prepare gained resin cost, increases.Three of method is many stills series processes, as US5442018, WO95/26990, WO95/10548 etc.It is by a plurality of reactor strings together, carries out monomer polymerization under different reaction conditionss, thereby obtains the polyethylene of wide molecular weight distribution.Compare with single reaction vessel, the method complex process and cost are very high.
The another kind of method of improving High molecular weight polyethylene processing characteristics is in single reaction vessel, to adopt a kind of catalyzer to prepare polyolefine bimodal or broad peak molecular weight distribution.US Patent No. 5231066 by preparing polyethylene bimodal or broad peak molecular weight distribution by catalyst cupport to a kind of silica-gel carrier of bimodulus pore size distribution; Silica gel preparation method adopts two elementary reactions by regulating reaction solution pH value, prepares two stage mean pore sizes and at least differs
silica-gel carrier.This patent is prepared the silica-gel carrier of bimodulus pore size distribution by sol-gel process, the aperture of silica-gel carrier is subject to reaction conditions as the impact of digestion time, pH value, cause bimodulus pore size distribution to differ narrower, and particle aperture is less than normal, wide aperture peak value is generally less than
be unfavorable for using the load of the relatively large methylaluminoxane/metallocene catalyst system of molecular weight, easily cause supported catalyst mobility poor.In the process that the present invention is prepared at silica gel, by adding template reagent to control the pore radiuses and distribution of silica gel, prepare pore size distribution controlled, two stage mean pore sizes be distributed to look younger poor
bimodulus silica-gel carrier.The bimodulus pore size distribution silica gel preparing can, as the carrier of Z-N catalyzer, chromium-based catalysts and metallocene catalyst, be used for preparing bimodal or broad peak distribution polyethylene.
Summary of the invention
The object of this invention is to provide a kind of method of preparing bimodulus pore size distribution silica-gel carrier, for the preparation of thering is bimodal or broad peak molecular weight distribution polyethylene catalysts and resin thereof.In the present invention, adopted for two stages by different process, the first stage adopts sol-gel technology, by regulating pH value, temperature of reaction and digestion time, prepares pore size distribution and exists
extremely
between silica gel, mean pore size exists
extremely
between; Subordinate phase, by adding terpolymer as template reagent, regulates and controls subordinate phase pore, and subordinate phase pore size distribution exists
extremely
between, mean pore size exists
extremely
between, prepare two stage mean pore sizes and differ by more than
silica-gel carrier.Polymerization catalyst prepared by gained carrier obtains the olefin polymer of wide molecular weight distribution.Concrete preparation method is as follows:
It is main raw material that inorganic silicate and mineral acid are take in the present invention, by two stage gel reactions, prepares bimodulus silica gel,
(1) using inorganic silicic acid salt brine solution that concentration is 10%-40% dioxide-containing silica as mother liquor, at 20 ℃ of-80 ℃ of inorganic acid aqueous solutions that are 2%-12% by concentration, add in mother liquor, to reaction solution pH value be 8-10, reaction 0.5-2h, system obtains silica dioxide gel, then be warming up to 70-100 ℃, aging 2-24 hour, obtains first stage pore size distribution and exists
extremely
between silica gel, mean pore size exists
extremely
between;
(2) silica dioxide gel system pH value in (1) is adjusted to 0.5-2, the ternary block polymer that adds the polyethylene oxide-poly(propylene oxide)-polyethylene oxide (PEO-PPO-PEO) of molecular weight between 1000-20000, PEO-PPO-PEO concentration is controlled between 1%-15%, adding carbonatoms is the Organic Alcohol of 2-6, and the ratio of add-on and water is between 1:100-1:4;
(3) at 20 ℃-80 ℃, add above-mentioned inorganic silicic acid reactant salt, when PH rises to 2.5-4, keep 0.5-2h, be warming up to 70-100 ℃ of aging 0.5-24 hour, obtain pore size distribution and exist
extremely
silica gel, mean pore size exists
extremely
between;
(4) silica hydrogel obtained above through deionized water wash, filtration and dry after obtain the silica gel of bimodulus pore size distribution.
The present invention's inorganic silicate used can be potassium silicate or water glass, generally adopts liquid silicic acid sodium solution, i.e. water glass, and molecular formula is Na
2o.nSiO
2, wherein n is modulus, generally between 2.4-3.3.Mineral acid raw material can adopt sulfuric acid, nitric acid or hydrochloric acid etc., and generally adopting the vitriol oil is raw material.
PH value in reaction process of the present invention is regulated by mineral acid, generally by adding sulphuric acid soln to control.
In the present invention, generally inorganic silicate solution preparation is become to the aqueous solution containing 10%-40% dioxide-containing silica; Inorganic acid solution is generally mixed with the solution of 2%-12%.
In the present invention, subordinate phase is used terpolymer as template reagent, and this template reagent is polyethylene oxide-poly(propylene oxide)-polyethylene oxide (PEO-PPO-PEO) ternary block polymer, and its general formula is HO (C
2h
4o)
a(C
3h
6o)
b(C
2h
4o)
ch, wherein a and c are 2-130, b is 15-150.Be used for regulating the pore size of silica gel, PEO-PPO-PEO terpolymer substrate concentration is between 1%-15%, and preferably, between 5%-12%, PEO-PPO-PEO concentration is too low, and pore is less; PEO-PPO-PEO excessive concentration, may cause the silica gel particle pattern of production poor, as generated the network-like silica gel being cross-linked with each other.Ternary PEO-PPO-PEO molecular weight is between 1000-20000, preferred 2000-15000, include but not limited to that the commercially available F68(of BASF AG relative molecular mass is about 6000), F127(relative molecular mass is about 12000), and the P123(of Adrich company relative molecular mass is about 5800) etc.In subordinate phase silica gel preparation process, adding carbonatoms is the Organic Alcohol of 2-6, as ethanol, n-propyl alcohol, Virahol, n-butyl alcohol, amylalcohol, hexanol, hexalin etc., the saturated alcohol that preferably carbonatoms is 2-4, as ethanol, the mass percent of add-on and water is between 1:100-1:4, preferably between 1:50-1:10, as pore-creating agent.
Without special instruction, in this patent, the concentration of material all refers to mass percentage concentration.
Bimodulus pore size distribution silica slurry prepared by two stages of using in the present invention, can be used existing washing, drying process to prepare the silica gel product with bimodulus pore size distribution.In the present invention, use Plate Filtration, drying process with atomizing to prepare the silica gel with bimodulus pore size distribution.After silica hydrogel is filtered, use flame filter press, with deionized water, hydrogel is washed, foreign ion is washed off, then add water to prepare the 2-20% silicon-dioxide aqueous solution, then spray dry, the inlet temperature of spray-dryer is controlled at 250-400 ℃, generally remains on 270-350 ℃ and is advisable.The silica gel product pore volume obtaining after spraying is dry is between 1.0-2.0 ml/g; Specific surface area is between 200-400 meters squared per gram.
The silica gel of bimodulus pore size distribution prepared by the inventive method, two stage mean pore sizes differ by more than
adopt the catalyzer that this bimodulus silica gel makes as carrier can be for the preparation of bimodal or broad peak molecular weight distribution polyethylene, thereby improve poly processing characteristics.
In the present invention, silica dioxide granule aperture, specific surface area and pore volume are tested by Nova2000e tester.Bimodulus pore size distribution silicon-dioxide obtains dV (d) by BJH absorption method and characterizes with aperture (d) curve, and silicon-dioxide pore volume and specific surface area are tested by BET method.
accompanying drawing explanation
Fig. 1 is embodiment 1 bimodulus pore size distribution silica-gel carrier DV (d) and aperture d graphic representation;
Fig. 2 is embodiment 2 bimodulus pore size distribution silica-gel carrier DV (d) and aperture d graphic representation;
Fig. 3 is embodiment 3 bimodulus pore size distribution silica-gel carrier DV (d) and aperture d graphic representation;
Fig. 4 is embodiment 6 bimodulus pore size distribution silica-gel carrier DV (d) and aperture d graphic representation;
Fig. 5 is comparative example 7 bimodulus pore size distribution silica-gel carrier DV (d) and aperture d graphic representation;
Fig. 6 is comparative example 8 bimodulus pore size distribution silica-gel carrier DV (d) and aperture d graphic representation.
embodiment
Embodiment 1
At 40 ℃, 5% sulphuric acid soln is dropped to the sodium silicate solution that content is 20% silicon-dioxide, until PH is 8.5-9, form silicon dioxide gel, continue to stir 0.5 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 80 ℃, aging 7 hours.After aging, cool the temperature to room temperature, drip 5% sulphuric acid soln to PH be 0.5-1, standing 3 hours, then add ethanol and F68PEO-PPO-PEO ternary block polymer, stir F68 is fully dissolved, ethanol and water ratio are 1:10, and F68 add-on is total solution 10%, at 30 ℃, drip the sodium silicate solution of 20% silicon-dioxide, until pH rises to 3, obtain subordinate phase gel, rising temperature to 80 ℃, aging 6 hours, obtain bimodulus silica dioxide gel slurries.Use deionized water after plate-and-frame filter press washing 3 times, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 330 ℃ and 150 ℃, after being dried, obtains bimodulus silica supports.First stage aperture peak value is
subordinate phase peak value is
dV (d) is shown in Fig. 1 with aperture d curve.
Embodiment 2
At 50 ℃, 5% sulphuric acid soln is dropped to the sodium silicate solution that content is 20% silicon-dioxide, until PH is 9-9.5, form silicon dioxide gel, continue to stir 1 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 90 ℃, aging 5 hours.After aging, cool the temperature to room temperature, drip 5% sulphuric acid soln to PH be 0.5-1, standing 1 hour, then add ethanol and F68PEO-PPO-PEO ternary block polymer, stir F68 is fully dissolved, ethanol and water ratio are 1:5, F68 add-on is 12% of total solution, at 35 ℃ of sodium silicate solutions that drip 20% silicon-dioxide, until pH rises to 3.5, obtain subordinate phase gel, rising temperature to 80 ℃, aging 6 hours, obtains bimodulus silica dioxide gel slurries.Use deionized water after plate-and-frame filter press washing 4 times, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 350 ℃ and 150 ℃, after being dried, obtains bimodulus silicon-dioxide.First stage aperture peak value is
subordinate phase peak value is
dV (d) is shown in Fig. 2 with aperture d curve.
Embodiment 3
At 40 ℃, 8% sulphuric acid soln is dropped to the sodium silicate solution that content is 15% silicon-dioxide, until PH is 8.5-9, form silicon dioxide gel, continue to stir 0.5 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 70 ℃, aging 7 hours.After aging, cool the temperature to room temperature, drip 8% sulphuric acid soln to PH be 0.5-1, standing 3 hours, then add n-butyl alcohol and F68PEO-PPO-PEO ternary block polymer, stir F68 is fully dissolved, n-butyl alcohol and water ratio are 1:4, F68 add-on is 8% of total solution, at 35 ℃ of sodium silicate solutions that drip 20% silicon-dioxide, until pH rises to 3.5, obtain subordinate phase gel, rising temperature to 90 ℃, aging 6 hours, obtains bimodulus silica dioxide gel slurries.Use deionized water after plate-and-frame filter press washing 3 times, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 330 ℃ and 150 ℃, after being dried, obtains bimodulus silica supports.First stage aperture peak value is
subordinate phase peak value is
dV (d) is shown in Fig. 3 with aperture d curve.
Embodiment 4
At 40 ℃, 5% sulphuric acid soln is dropped to the sodium silicate solution that content is 20% silicon-dioxide, until PH is 8.5-9, form silicon dioxide gel, continue to stir 0.5 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 80 ℃, aging 7 hours.After aging, cool the temperature to room temperature, drip 5% sulphuric acid soln to PH be 0.5-1, standing 3 hours, then add ethanol and F127PEO-PPO-PEO ternary block polymer, stir F127 is fully dissolved, ethanol and water ratio are 1:10, and F127 add-on is total solution 10%, at 50 ℃, drip the sodium silicate solution of 20% silicon-dioxide, until pH rises to 3, obtain subordinate phase gel, rising temperature to 80 ℃, aging 6 hours, obtain bimodulus silica dioxide gel slurries.Use deionized water after plate-and-frame filter press washing 3 times, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 330 ℃ and 150 ℃, after being dried, obtains bimodulus silica supports.First stage aperture peak value is
subordinate phase peak value is
Embodiment 5
At 30 ℃, 5% sulphuric acid soln is dropped to the sodium silicate solution that content is 20% silicon-dioxide, until PH is 8.5-9, form silicon dioxide gel, continue to stir 1 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 80 ℃, aging 7 hours.After aging, cool the temperature to room temperature, drip 5% sulphuric acid soln to PH be 0.5-1, standing 3 hours, then add n-hexyl alcohol and P123PEO-PPO-PEO ternary block polymer, stir P123 is fully dissolved, n-hexyl alcohol and water ratio are 1:5, and P123 add-on is total solution 15%, at 30 ℃, drip the sodium silicate solution of 20% silicon-dioxide, until pH rises to 3, obtain subordinate phase gel, rising temperature to 70 ℃, aging 8 hours, obtain bimodulus silica dioxide gel slurries.Use deionized water after plate-and-frame filter press washing 3 times, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 330 ℃ and 150 ℃, after being dried, obtains bimodulus silica supports.First stage aperture peak value is
subordinate phase peak value is
Embodiment 6
At 40 ℃, 5% sulphuric acid soln is dropped to the sodium silicate solution that content is 20% silicon-dioxide, until PH is 8-8.5, form silicon dioxide gel, continue to stir 0.5 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 80 ℃, aging 7 hours.After aging, cool the temperature to room temperature, drip 5% sulphuric acid soln to PH be 0.5-1, standing 3 hours, then add ethanol and F127PEO-PPO-PEO ternary block polymer, stir F127 is fully dissolved, ethanol and water ratio are 1:4, and F127 add-on is total solution 5%, at 30 ℃, drip the sodium silicate solution of 20% silicon-dioxide, until pH rises to 3, obtain subordinate phase gel, rising temperature to 80 ℃, aging 6 hours, obtain bimodulus silica dioxide gel slurries.Use deionized water after plate-and-frame filter press washing 3 times, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 330 ℃ and 150 ℃, after being dried, obtains bimodulus silica supports.First stage aperture peak value is
subordinate phase peak value is
dV (d) is shown in Fig. 4 with aperture d curve.
Comparative example 7
At 40 ℃, 5% sulphuric acid soln is dropped to the sodium silicate solution that content is 20% silicon-dioxide, until PH is 8.5-9, form silicon dioxide gel, continue to stir 0.5 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 80 ℃, aging 7 hours.After aging, cool the temperature to room temperature, drip 5% sulphuric acid soln to PH be 0.5-1, standing 3 hours, then drip the sodium silicate solution of 20% silicon-dioxide, until pH rises to 4, obtain subordinate phase gel, rising temperature to 80 ℃, aging 6 hours, obtains bimodulus silica dioxide gel slurries.Use deionized water after plate-and-frame filter press washing 3 times, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 350 ℃ and 150 ℃, after being dried, obtains bimodulus silica supports.First stage aperture peak value is
subordinate phase peak value is
dV (d) is shown in Fig. 5 with aperture d curve.
Comparative example 8
At 40 ℃, 5% sulphuric acid soln is dropped to the sodium silicate solution that content is 20% silicon-dioxide, until PH is 8.5-9, form silicon dioxide gel, continue to stir 0.5 hour, colloidal sol is hardened to silica dioxide gel, then temperature is risen to 80 ℃, aging 7 hours.After aging, cool the temperature to room temperature, drip 5% sulphuric acid soln to PH be 2, standing 6 hours, use deionized water after plate-and-frame filter press washing 3-4 time, use GLP-150 type Highspeedcentrifugingandsprayingdrier to be dried, spray-drier out temperature is respectively 350 ℃ and 150 ℃, after being dried, obtains single mode pore size distribution silica supports.Aperture peak value is
dV (d) is shown in Fig. 6 with aperture d curve.
The preparation of embodiment 9 catalyzer
Under nitrogen protection, in a flask, add bimodulus silica gel and the 65 grams of methylene dichloride in 5.6 grams of routine 1-8, prepared, stir.Then the dichloromethane solution (1.23 mg/ml) that adds 50 milliliters of chromium acetates, stirs under room temperature 1 hour.After stopping stirring, standing, upper strata is colorless clear liquid, shows that chromium acetate all loads on carrier.Continue to stir, heating, all vapors away methylene dichloride, and the chromium-based catalysts obtaining, at 50-70 ℃, is dried 30 minutes under nitrogen protection, obtains the free-pouring catalyst fines of purple.The catalyst fines obtaining is activated to 8 hours at 800 ℃.In catalyzer, chromium content is 1%.
The silica supports of preparing in example 1-8 example (comprising bimodulus silica supports), and Sylopol 955 silica gel are prepared chromium-based catalysts according to identical operation above.Sylopol 955 silica gel are not bimodulus silica gel.
Catalyzer is used for vinyl polymerization:
In a slurry polymerization reactor, catalyzer is carried out to ethene slurry polymerization.
2.0 liters of dry Trimethylmethanes are joined in nitrogen replacement and dried 5 liters of stainless steel autoclaves, then add 5 milliliters of triethyl aluminum TEA(1.3 mol/L), stirring velocity is 450 revs/min, then adds 0.2 gram of above-mentioned catalyzer, passes into ethene and makes reactor internal pressure remain on 4.0MPa, ethene volumetric molar concentration is 17%, at 105 ℃, stir under 450 revs/min of conditions polymerization 1 hour, termination reaction, be cooled to room temperature, after being dried, obtain polyethylene product.The performance data of gained polyethylene product is in Table 1.
Silicon-dioxide physical property result table 1
。
Claims (3)
1. a silica-gel carrier preparation method, take inorganic silicate and mineral acid as main raw material, by two stage gel reactions, prepares bimodulus silica gel, it is characterized in that mainly comprising the following steps:
(1) using inorganic silicic acid salt brine solution that concentration is 10%-40% dioxide-containing silica as mother liquor, at 20 ℃ of-80 ℃ of inorganic acid aqueous solutions that are 2%-12% by concentration, add in mother liquor, to reaction solution pH value be 8-10, reaction 0.5-2h, system obtains silica dioxide gel, then be warming up to 70-100 ℃, aging 2-24 hour, obtains first stage pore size distribution and exists
extremely
between silica gel, mean pore size exists
extremely
between;
(2) silica dioxide gel system pH value in (1) is adjusted to 0.5-2, add the polyethylene oxide-poly(propylene oxide)-polyethylene oxide ternary block polymer of molecular weight between 1000-20000, ternary block polymer concentration is controlled between 1%-15%, adding carbonatoms is the Organic Alcohol of 2-6, and the ratio of add-on and water is between 1:100-1:4;
(3) at 20 ℃-80 ℃, add above-mentioned inorganic silicic acid reactant salt, when PH rises to 2.5-4, keep 0.5-2h, be warming up to 70-100 ℃ of aging 0.5-24 hour, obtain pore size distribution and exist
extremely
silica gel, mean pore size exists
extremely
between;
(4) silica hydrogel obtained above through deionized water wash, filtration and dry after obtain the silica gel of bimodulus pore size distribution.
2. silica-gel carrier preparation method according to claim 1, is characterized in that described inorganic silicate is selected from potassium silicate, water glass.
3. silica-gel carrier preparation method according to claim 1, is characterized in that described mineral acid is selected from sulfuric acid, nitric acid, hydrochloric acid.
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| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
| CN105330769A (en) * | 2014-06-13 | 2016-02-17 | 中国石油化工股份有限公司 | Supported polyethylene catalyst ingredient and preparation method thereof, and supported polyethylene catalyst and application thereof |
| CN106467579A (en) * | 2015-08-17 | 2017-03-01 | 中国石油化工股份有限公司 | Macropore two dimension double hole channel spherical complex carrier and the composite containing polyethylene catalysts and their preparation method and application |
| CN106467582A (en) * | 2015-08-17 | 2017-03-01 | 中国石油化工股份有限公司 | Macropore two dimension the spherical complex carrier of straight channels and the composite containing polyethylene catalysts with and its preparation method and application |
| CN113277523A (en) * | 2021-06-01 | 2021-08-20 | 钦州东辰材料科技有限公司 | Preparation method of silica gel carrier for olefin polymerization catalyst |
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| CN105175586A (en) * | 2014-06-13 | 2015-12-23 | 中国石油化工股份有限公司 | Meso-porous composite material, preparation method thereof, catalyst ingredient preparation method, and polyethylene preparation method |
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| CN113277523A (en) * | 2021-06-01 | 2021-08-20 | 钦州东辰材料科技有限公司 | Preparation method of silica gel carrier for olefin polymerization catalyst |
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