TW393443B - Granules based on pyrogenically prepared silicon dioxide, method for their preparation and use thereof - Google Patents

Description

Attachment 1 (A): 85101073; j R: ㈣-supplement p in January, i. Description of the invention (24) Brief description of the formula Figure 1 is a table and diagram according to the embodiment 1g of the present invention 4 Particle size distribution of the obtained particles. Fig. 2 shows the particle size distributions of the particles obtained according to Examples 5 to 8 of the present invention in the form of a table and a diagram. FIG. 3 shows the particle size distribution of the particles obtained according to Examples 9 to 11 of the present invention in the form of a table and a diagram. FIG. 4 is a particle size distribution of the particles obtained in accordance with Examples 12 to 14 of the present invention in the form of a table and formula. (Please read the precautions on the back before filling this page) Install [·! ----Ordered · 111111 · Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs / Consumer Cooperative, the paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) -26-1-A7 A7 Central Ministry of Economics Printed by the local shellfish consumer cooperative. B7_ V. Description of the invention (1) The present invention relates to particles mainly composed of silicon dioxide obtained by a pyrolysis method, a method for preparing the same, and a use thereof as a catalyst carrier. It is known that pyrogenic gravel or shovel (1111111311113 £ 1125 ^ 1〇-pSdie der technischen Chemie, 4th edition, volume 21) can be prepared from si C cross 4 by high temperature- or water flame hydrolysis. P. 464 (1982)). Fumed silica can be distinguished by its extremely fine particles, high specific surface area (BET), very high purity, spherical particle shape, and no holes. Because of these properties, the use of silica prepared by pyrolysis as a catalyst support has attracted increasing interest (Dr. Koth et al., Chem. Ing. Techn. 52, 628 (1980). Pyrolysis The prepared silicon dioxide can be shaped by mechanical devices, such as a spindle mill, for use in applications. It is also known that the spray-drying method can be used to form the silicon dioxide prepared by pyrolysis into sprayed particles. In order to obtain starting materials for sintered ceramic materials (DE_ A3 6

In addition, it is also known that the spray-drying method can be used to form silicon dioxide in the arc by pyrolysis to form sprayed particles, which can be used as an absorption medium or else as a catalyst carrier (DE-A 1 2 0 9 1 0 8). It is also known that the silicon dioxide produced by the pyrolysis method can be subjected to a gel method, and a spray-drying method can be performed to form particles afterwards. After being coated with chromium dioxide, these particles are used in the polymerization of ethylene (EP_A 0 0 5 0 902, US-A 4,386,016. The size of private paper is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) '"' (Please read the note f on the back before filling this page) Order A7 B7 V. Description of the invention (2) In addition, the silicon dioxide precipitated as a catalyst carrier in the catalytic polymerization of olefins Its use is also known (W0 9 1/0 9 8 8 1). These silicon dioxide spray particles, which are known to be produced by pyrolysis, have a disadvantage in that they are not the same as in the preparation of polyethylene Most suitable for use as a catalyst carrier. Therefore, the objective of the present invention is to develop sprayed particles from silicon dioxide produced by pyrolysis. * They can be used as catalyst carriers in the preparation of polyethylene. The obtained silicon dioxide-based particles have the following physical and chemical properties: (Please read the precautions on the back before filling out this page) Order the average grain size printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs : 1 0 to 1 2 0 β m Β Ε Τ Surface 稹: 40 to 4 0 mz / g pore volume: 0 • 5 to 2 • 5 ml / S Pore size distribution: pores with a diameter < 5 η m are less than 5% of the total pore volume > the rest are Medium—and huge holes PΗ Value: 3 • 6 to 8 • 5 Perforation density · 2 2 to 7 0 0 S / liter The granular material of the present invention is prepared by distributing silicon dioxide obtained by pyrolysis in water, Dry-spray it and use the Chinese National Standard (CNS) Α4 (210X297 mm) -5-A7 A7 at the paper size of 150 to this paper size .__ B7_ _ 5. Description of the invention (3) 1, The obtained particles are heated at a temperature of 100 ° C for 1 to 8 hours. The present invention also provides particles mainly composed of silicon dioxide prepared by pyrolysis, which have the following physical and chemical properties : Average grain size: 10 to 120 // m BET surface 稹: 40 to 400m2 / g pore volume 稹: 0.5 to 2.5ml / g pore size distribution: pores with a diameter < 5nm are less than 5% of the total pore volume, the rest for PH value of medium and huge pores · 3.6 to 8.5 Perforation density: 220 to 700 g / liter The granular material of the present invention is prepared by distributing silicon dioxide obtained by pyrolysis in water and spraying it dry And subjecting the resulting particles to silylation. Silanes can be used with halogenated silanes, silazane, and / or siloxanes. The following are particularly useful as toothed silanes: X3Si (CnH2n + 1) type halogenated organic silanes X = C 1, B r η = 1 to 2 0 X2 (R /) S i (C „H2n + 1) type of halogenated organic silane X = C 1-B r This paper size applies to China National Standard (CNS) A4 (210X297 mm) ( (Please read the notes on the back before filling out this page)

-6-A7 B7 V. Description of the invention (4) R = fluorenyl η = 1 to 2 0 X (R /) 2S i (CnH2n + 1) type of halogenated organosilane X = C 1 · B r R = courtyard η = 1 to 2 0 X a S i (CH2) R > type of halogenated organosilane X = C 1, B rm = 0.1 to 2 0 R / = alkyl, aryl (such as _CeH5) -C4F9 , — 〇cf2-chf-cf3, — CeF13 '-0-CF2-CHF2 —N Η 2' _ N 3 · — SCN, _ CH = CH 2 * -0 0 C (CH 3) c = CH 2 -〇 CH2-CH (0) CH 2 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) -NH-CO-N-CO-(CH2) 5

I_I -NH-COO-CHa *-NH-C00-CH2-CH3,-NH-(CH 2) a S i (OR) 3 -Sx- (CH2) 3S i (OR) 3 (R) X 2 S i Type of halogenated organic silane X = C 1. B r This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ~ Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of the invention (5 ) R = alkyl m = 0 · 1 to 2 0 R > = alkyl, aryl (eg —CeH5) —C4F9, —ocf2_chf — CF3, —C β F i3 * — 0 — CF2_CHF2 -NH2, one N3 , One SCN, one CH = CH2, -00C (CH3) c = ch2 -0CH2— CH (0) CH 2 -NH-CO-N-CO-(CH2) 5 I-1 -nh-coo-ch3,- nh-coo-ch2 CH 3 '-NH-(CH 2) 3 si (OR) 3 —S x — (CH 2) 3 S i (OR) 3 (R) 2XS i (CH2) m— R — Halogenated organosilane X = C 1. B r R = alkyl m = 〇 · 1 to 2 Ο R > = alkyl, aryl (such as _CeH5) -C4Fe,-OCF2-CHF-CF3, _C6F13, _0_CF2_CHF2- NH2,-N3,-SCN,-CH = CH2, -0 0 C (CH 3) c = CH 2 -0 CH 2- CH (0) CH 2 -NH-C 0-N-C 0-(CH 2 ) 5 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back before filling this page), book r-8-A7 Printed by B7 Consumer Products Cooperative of the Central Samples Bureau of the Ministry of Economic Affairs 5. Description of invention (6) -nh -coo-ch3,-nh-coo-ch2 C Η 3 *-Ν Η-(C Η 2) 3 si (OR) 3 -Sx- (CH2) 3S i (0 R) a Organic silanes of the alkoxysilane (R0) 3Si (C „H2n + 1) type R = alkyl η = 1 to 2 0 (R, (RO) ySi (C nH 2n + 1) R = alkyl R / = Alkyl η = 1 to 2 0 χ + y = 3 x = 1, 2 y = 1, 2 (RO) 3S i (CH2) m-R > type of organosilane R = fluorenyl η = 0 · 1 to 2 0 R > = alkyl, aryl (eg-CeH5) -C4F9, -OCF2-CHF-CF3, -C e F 13 * — 0—CF2— CHF2 _ NH 2 * _ N 3 · One SCN '~ CH = CH 2 '-0 0 C (CH 3) c = CH 2 (Please read the precautions on the reverse side before filling out this page) -II. Order " · This paper size is free to use China National Standards (CNS) A4 Specifications (210X297 mm) A7 B7 printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (7) -0CH2-CH (0) ch2 —NH— C0 — N— CO — (C H 2) 5

I_I -NH-COO-CHa '-NH-C00-CH2 -CH3,-NH — (CH2) 3S i (0 R) a -Sx- (CH2) 3Si (OR) 3 (R ") x (R 0 ) y S i (CH 2) m- R ^ R 〃 = alkyl x + y = 2 x = 1, 2 y = 1, 2 R ~ = alkyl, aryl (eg —CeH5) -C4F9 >-0CF2 -CHF-CF3'- C 6 F i3 * — 0 — CF2— CHF2 -NH2, one N3, one SCN, one CH = CH2, -0 0 C (CH 3) c = CH 2 -0CH2-CH (0) CH 2 —NH-CO-N— CO-(CH 2) 5 I_! -Nh-coo-ch3 ·-nh-coo-ch2 —CH3, -NH- (CH2) 3Si (0 R) 3 -Sx- ( CH2) 3S i (OR) 3 is more preferably a silicon oxidant using silane Si 108 [CH3〇) 3-Si-CeH17] and trimethoxyoctylsilane. The following substances are particularly useful as silazane: This paper is sized for China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page) Order-10-V. Description of the invention ( 8) R, R2Si- N -SiR2R (Η A7 B7 type silamine courtyard R = courtyard R > = alkyl, vinyl and such as hexamethyldisilazane. The following materials are particularly useful as siloxy Alkane: D3, D4, D5 type cyclopolysiloxane (pc), such as octamethylcyclotetrasiloxane (D4) lysiloxane

-I. L ·-HIJn It 1 ^ 1 1 --- ^-:: t I— I (Please read the precautions on the back before filling in this page J Order ch3 ch3

Si 〇 / N O CH3

N

Si

Si 〆 H3C 〇 0 CH3 Si ch3 / ^ ch3 Shellfish consumer cooperation cooperation printed by the Central Bureau of Standards of the Ministry of Economy The following types of polysiloxane or silicone oil

Y-0- R 'I • m R " 1 _ 1 Si-0 I-1 Si-0 I 1 R, 1 R… m _ · n- Y This paper is based on China National Standard (CNS) A4 specifications ( 2 丨 0X297mm) -11-B7 V. Description of the Invention (9)

m = 0 * 1, 2 * 3 9… 〇〇η = 0 1 1, 2 »3» • · · oo u = 0 > 1, 2 3 1 • · ·… oo Y = C Η 3, Η- C η Η 2 η Ten 1 n = 1 to 2 0 Υ = S i (C Η 3) 3 S i (c H 3) 2H, S i (C Η 3) 2 0 Η > S i (c H 3 ) 2 (〇c HS i (C Η 3) 2 (C ηΗ 2 n + 1) n = 1 to 2 0 R = alkyl 9 aryl (C Η 2) n — N Η 2, HR courtyard, aromatic (CH 2) n — NH 2 'HR • Uncle radical, aryl (CH 2) n NH 2' HR * »» = = alkyl, aryl, CC Η 2) n--N Η 2, H (Please read the precautions on the back before filling out this page) Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China. The present invention also provides particles based on silica prepared by pyrolysis, which have the following physical and chemical properties: average Grain size: 10 to 120 // m BET surface area: 40 to 400m2 / g pore volume: 0 • 5 to 2 • 5 m 1 / S pore size distribution: pores with a diameter < 5 η m are less than 5 in the total pore volume % 9 the rest are medium — and huge holes Hole carbon content: 0 • 3 to 1 5 • 0 weight% P Η value: 3 • 6 to 8 • 5 perforation density: 2 2 0 to 7 0 0 S / liter The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 12 Seal A7 B7, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (ίο) The granular material of the present invention should have medium-sized and large holes, among which the medium-sized holes are contained in the entire hole volume Occupies 10 to 80%. The carbon content of the granular material of the present invention is between 0.3 and 15.0% by weight. The particle size distribution of the granular material of the present invention is 80% by volume, which will be greater than 8 m, and 80% by volume, which will be less than 96 # m. In a preferred system of the present invention, pores having a size of less than 5 Am occupy at most 5% of the total pore volume. The granular material of the present invention is prepared by dispersing silicon dioxide obtained by pyrolysis in water, spraying and drying the other particles, and heating the obtained particles to a temperature of 150 to 1, 100 ° C for 1 to 8 hours. And then silylation on each other. The silylation can be carried out as described above with respect to the halogenated silane, alkoxysilane, silamine and / or silane. The invention also provides a method for preparing the main particles of silicon dioxide obtained by pyrolysis, which is characterized in that the silicon dioxide obtained by pyrolysis is more preferably made of silicon tetrachloride by flame hydrolysis. The prepared silicon dioxide is distributed in water and spray-dried. The obtained particles can be selectively heated at 150 to 1, 100 ° C for 1 to 8 hours, and / or siliconized. The distribution liquid in water has a silicon dioxide concentration of 5 to 25% by weight. The spray-drying method can be performed at a temperature of 200 to 600 ° C. Rotary spraying device or spray spraying device can be used for this purpose. The heating of the particles can be carried out on a fixed bed such as a kiln, and on a moving bed. Please read the notes on the back before filling this page) 'Binding-13-Printed by A7 __B7 of the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 5. Description of the Invention (11) Such as a rotary dryer. The silylation can be carried out as described above with a halogenated silane, alkoxysilane, silamane and / or silane, in which the silylating agent is selectively soluble in an organic solvent like ethanol. It is better to use silane i 108 [(CH30) 3-S i-C8H17], trimethoxyoctylsilane as the silylating agent. The silylation is carried out by spraying the particulate material together with the silylating agent, and then heat-treating the mixture at a temperature of 105 to 400 ° C for 1 to 6 hours. In another alternative method, the particles are silanized by treating the particulate material with a silylating agent in the form of a vapor, and then subjecting the mixture at a temperature of 200 to 800 ° C for 0.5 to 6 hours. Heat treatment. The heat treatment can be performed in a protective gas like nitrogen. Silaneization can be carried out in a flail or batch mode in a heatable mixer and dryer equipped with a spraying facility. Examples of suitable devices are plowshare mixers, rotary disk dryers or fluidized bed dryers. Physical and chemical variables of the particles, such as specific surface area, particle size distribution, pore volume, compacted density and concentration of silanol groups, pore distribution and P Η value-can be changed within a certain upper and lower limits by spraying the starting material, The conditions during heating and silylation vary. The granules of the invention can be used as supports for polymerization catalysts * especially as catalysts for the production of polyethylene. The advantages of the particles of the present invention are high purity, high thermal stability, low concentration of silanol groups, the shape of primary particles is microspheres and all pores (please read the notes on the back before filling this page) *? τ%: This paper uses China National Standard (CNS) A4 (210X297 mm) -14-__ B7_ V. Description of the invention (12) Less than 5% of holes in the volume exist < 5 nm diameter of. The invention additionally provides the use of particles as a catalyst support, especially for the preparation of polymerization catalysts. In a preferred system of the invention, the particles of the invention can be used as catalysts for the manufacture of catalysts for the production of polyethylene. Carrier. EXAMPLES The silicon dioxide obtained by the pyrolysis method used has the following physical and chemical properties. (Please read the notes on the back before filling in this page) The printed paper size of the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs of the People's Republic of China applies the Chinese national standard (CNS> A4 specification (210X297 mm) A7 B7 Invention Description (13 Ministry of Economy The Central Government Bureau of Standards and Consumers Cooperatives printed gas silicon 90 gas silicon 130 gas silicon 150 gas silicon 200 gas silicon 300 gas silicon 380 gas silicon 0X 50 CAS registration number 112945-52-5 (previous number S |: 7631-86 -9) Effect on water Loose white powder surface area BET) m2 / g 90 ± 15 130 ± 25 150 ± 15 200 ± 25 300 soil 30 380 ± 30 50 soil 15 average pore diameter of primary particles mm 20 16 14 12 7 7 • 40 Overdensity density 2) The normal person is g / 1 and the contractor is g / 1. Gamma " V, estimated Ι ·· 80 is estimated to be 50 estimated to be 120 estimated to be 50 estimated to be Π0 estimated to be 50 Estimated 120 Estimated 50 Estimated 120 Estimated 50 Estimated 120 Estimated 130 Weight loss on drying 3 > (105 hours at 1C)% < 1.0 < 1.5 < 0.59) < 1.5 < 1.5 < 1.5 < 1.5 Weight loss during combustion 4) 7) (2 hours at 1,000 ° c)% < 1 < 1 & l t; 1 < 1 < 2 < 2.5 < 1 pHfiS) (¢ 4% in aqueous distribution solution) > 3.6-4.5 3.6-4.3 3.6-4.3 3.6-4.3 3.6-4.3 36-4.3 3.6-43 Si02 '>% > 99,8 > 99.8 > 99.8 > 99,8 > 99.8 > 99.8 > 99.8 miscellaneous')% < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.08 Fe20 ,,)% < 0.003 < 0.003 < 0.003 < 0.003 < 0,003 < 0.003 < 0.01 Ti02% < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 < 0.03 HC1,) n)% < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 < 0.025 Those who have been sieved out of size (according to Mocker, 45 μπι)% < 0.05 < 0.05 < 0.05 < 0,05 < 0.05 < 0.05 0.2 2) According to ISO 787 / XI, JIS K 5101 / 丨 8 (unscreened) 3) According to DIN ISO 787/1 丨 .ASTM D 28 (UIS KL 5101/21 4) According to DIN 55921, ASTM D 1208, JIS KK 5101/23 5) According to DIN ISO 787 / IX, ASTM D 1208, MS K 5101/24. 6) According to DIN ISO787 / XVm, JIS K 5101 / 20, 7) Relatively dried material at 丨 05 ° C for 2 hours • 8) Relatively dried material at 1000 " C for 2 hours Special moisture resistance Packaging i: i〇) in water: acetic acid solution 丨: 丨 I ;, 11) HC1 content in the composition after burning weight loss (please read the precautions on the back before filling this page) Order fc applies China National Standard (CNS) A4 (210X297 mm) _ _ B7 V. Description of the invention (14) The preparation of silicon dioxide is to spray liquid silicon compounds into an oxygen-hydrogen flame composed of hydrogen and air. The situation is to use silicon tetrachloride. This substance is hydrolyzed to silicon dioxide and hydrochloric acid by the water formed during the hydrogen-oxygen reaction. After moving away from the flame, the silicon dioxide will enter a so-called condensation zone, in which the first-stage gas silicon (Aerosi 1) particles and the first-stage gas silicon clot will sinter together. At this stage, the product in the form of an aerosol is separated from the accompanying gaseous material in the cyclone, and is then reconditioned with water-heated air. Using this process can reduce the residual hydrochloric acid content to 0.025%. Since the bulk density of the silicon dioxide obtained at the end of the process is only about 15 g / 1, a subsequent vacuum compression is required, so a compacted density of about 501 or more can be established. The particle size of silicon dioxide can be changed by reaction conditions such as flame temperature, hydrogen and oxygen ratio, placement of silicon tetrachloride, residence time in the flame or length of condensation path, etc. The BET surface radon is determined according to DIN 66 131 using nitrogen. Dumpling Packing for Shellfish Consumer Cooperation of the Central Bureau of Procurement, Ministry of Economic Affairs (Please read the notes on the back before filling this page)

The pore volume is calculated from the sum of the volume of micro-, medium one and huge pores. Huge- and medium holes were measured by recording the N 2 isotherms and evaluating them using the methods of B E T, de Boer and Barrett, Joyner, and Halenda. D > The huge pores at 30 nm were measured by the Hg porosity method. In order to measure the huge holes *, the samples were dried in a drying oven at 1000 ° C for 15 hours' and vented at room temperature and under vacuum. In order to determine the micro and medium holes, the sample is at 100 ° C. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). -17-Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs A7 B7 5. In the drying oven of the description of invention (15), the drying method is performed for 15 hours, and the exhaust is performed for 1 hour under 2000 and vacuum. The silanol group concentration was measured by the lithium alanine method. The S i 0H group interacts with L i A 1 H4, and the amount of ammonia gas formed during the reaction is measured by pressure. Principles of measurement Weigh the particulate material and add it to a four-necked flask. Vacuum the bottle and heat the oil bath to 150 ° C. The temperature in the bottle (controlled by the internal thermometer) raises the temperature of the oil to approximately 130 ° C. The pressure during the initial treatment was recorded using a pressure measuring device P I2 (TM2 1 0, purchased from Ley bo Id, measuring range 10 3 to 10 3 mbar). Desorption of water can be monitored by pressure measurement. After the end of the initial treatment (at the end temperature of 30 minutes), the pressure that must be reached is less than 10 2 mbar. After the initial treatment is completed, the evacuated bottle is separated from the vacuum element by closing the stop valve and allowed to return to normal temperature. The actual measurement is based on the amount of L i A 1 H4 solution added to the bottle via the dropping funnel, and the pressure rise is measured by the hydrogen formed. If the volume of the bottle is known, the number of Η 2 can be calculated from the ideal gas law. Pressure is recorded using a digital measuring device (PIi) (MKS Instrument PR-2000) with a measuring range between 0 and 1 bar. The L i A 1 H4 solution (2% L i A 1 114 dissolved in diethylene glycol dimethyl ether) was vented before the experiment was carried out in order to remove any components that would volatilize at any time, which would cause errors in the pressure test. For this purpose, the Chinese National Standard (CNS) 8-4 specification (210X297 mm) is applied at this paper size. 18---n I— n —1 n il nnn I n ϋ IIT --------- I--III (Please read the notes on the back before filling out this page) Ministry of Economic Affairs, Central Bureau of quasi-bureau, Shellfish consumer cooperation, Du printed A7 _B7_ V. Description of the invention (16) The second vacuum pump is used for dripping The pressure above the solution in the funnel dropped to vapor pressure (3.7 mbar at 22 ° C), so the liquid would boil. Perform a blank measurement without the sample to test whether the solution has sufficient oxygen evolution. When measuring the hydrogen pressure, the vapor pressure of the solution is used for correction. Solution: First, the device was calibrated by measuring the volume of the dropping funnel equipped with a frosted stopper and accurately measuring the volume of the liter. As long as the stop valve is obtained by the following tests, the contents of the reaction bottle will include all connection points: Connect an air-filled drip funnel to the evacuated bottle. The pressure cancellation between the two containers is then achieved by opening the stopper of the drip funnel. The established pressure is indicated by a digital measuring device. The volume of the reaction vessel is obtained by mass balance. In this arrangement, a volumetric VR equal to 243.8 ml is obtained. The mole number of hydrogen formed is obtained from the following equation: n = ^ RT V repair JH. = Vr-V 囲-V »Liquid P is the pressure increase of the reaction flask. This value is corrected by an amount corresponding to the solvent vapor pressure (37 mbar at 22 ° C). Vapor pressure at room temperature, which is very different from 22 ° C, is obtained from a vapour pressure gauge. Choosing a weighed sample helps to obtain a P value between 2000 and 800 mbar. At this time, slight changes in vapor pressure due to temperature changes will have almost no effect on the results (please read the precautions on the back before filling this page).--Π 4 This paper size applies to China National Standard (CNS) 8-4 specifications. (210X 297mm) -19-A7 B7_ V. Description of the invention (17) Effect. The capacity of the reaction vessel is corrected by subtracting the capacity of the solid material and the capacity of the added solution. The former is obtained by weighing proportions, while the density and the latter are read by dropping funnels. The density of the silanol groups is finally obtained from the following equation:

η · N L d =-

F Lohschmidt number F: The surface sample of the weighed solid material is processed as follows: heating at 120 ° C and 0.2 mbar for 1 hour: cooling to 60 ° C; adding LiAlH4; after 10 minutes , Read out the rising pressure difference 9 The seal of the Consumer Affairs Cooperative of the Central Government Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

A Particle size distribution was measured with a laser optical particle size analyzer, Cilas Granulame-tre715. Perforation capacity is measured in accordance with ASTM D 4164-88 *

Window: Perforated volume meter STAV 2003 purchased from Engelsmann, according to DIN 53194, section 5.2, b-f. This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 OXW7 mm) -20- Printed by the Central Bureau of Standards, the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, 袈 Α7 Β7 V. Description of the invention (18) 250 ml measuring cylinder, scale mark is 2 ml balance, the maximum error upper limit is ± 0.1. The count is set to 1,000 beeps. Deduct the weight of the graduated cylinder. Place the particulate material into the graduated cylinder 'up to a mark of 250 ml. Record the weight of the sample (± 0.1 g). Place the measuring cylinder in the volume meter and turn on the device. End of piercing: the device will automatically cut off after 100 beeps. The volume of the perforated body reads an accurate value of 1 liter. 簏 E: The weighted part of the granular material, expressed in grams. V: Volume reading, expressed in milliliter. W: Moisture content, expressed as reset%. ( Measured according to the instruction P 0 〇1) EX (100-W) Perforation density-VX 1 0 0 When the hydrophobic catalyst support is in a solution of water: ethanol 1: 1, the P P value is 4% aqueous cloth solution. This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0 × 297 mm) ----; ---.-- {装 -------, ΤΓ --- ^ ---- 4 " (Please read the precautions on the back before filling this page) -21-A7 ____B7__ V. Description of the invention (I9) The preparation of the particles of the present invention allows the silica obtained by pyrolysis to be completely distributed in distilled water. The rotor / stator principle operates with distributed clots in this process. The formed suspension was spray-dried. A filter or cyclone is used to settle the final product. The sprayed particles are heated in a muffle furnace. The spray-dried and selectively heated granules are placed in a mixer for the silylation process and, under intensive mixing, can be selectively mixed with water and then with silane Si 1 0 8 (trimethoxyoctyl) Silane) or HMD S (Hexamethyldisilazane) spraying together. After spraying, the material is mixed for 15 to 30 minutes or more, and then heated to 100 to 4 0 0 ° C for 1 To 4 hours. The water used can be acidified, such as hydrochloric acid, to change the pΗ value from 7 to 1. The silylating agent used can be dissolved in solvents such as ethanol ) Α4 size (210'〆297mm) -22-A7 V. Description of invention (20) Printing and dyeing examples of the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Printing and dyeing Examples for comparison 1 2 3 4 For comparison 5 Initial gas silicon 380 380 380 380 380 Spray drying data 2 kg (kg) 10 10 105 105 15 Gas silicon volume (kg) 1.5 1.5 14.7 14.7 1.5 Atomization using turntable turntable turntable turntable turntable operation RC) 380 380 380 440 380 waste gas ( 〇 105 105 105 108 105 Precipitation filter filter Filter filter Cyclone heating data (hour / ° c)--2/700 2/700-Surface modification data reagent Si 108 Si 108 HMDS • Quantity [g / 100 g of air sand] 25 25 20-water content [g / 100 g of air silicon]--5 5-heating time (hours) 2 2 4-brewing ΓΟ-120 120 140-physical and chemical properties it'- ^ ΕΤ surface area (meter 2 / g) 350 197 189 212 277 Pore volume (ml / g) 2.09 1.69 1.55 1.68 1.69 Pore volume of holes < 5 rnn (% of total nd 1.8 ndndnd grinding amount) Medium pores (ml / g) 2-30 nm 1.34 1.04 1.12 1.17 0.66 yOnm's huge holes (ml / g) 0.75 0.65 0.43 0.51 1.03 ite50 _ 38 40 66 53 39 Barn volume (g / l) 320 390 420 370 260 • Ϋ? ·: _ 4.7 5.0 5.6 7.2 4.8 mm%-10.9 10.4 3.8-Concentration of Alcohol-Based Countries (millimolar OH / g) 1.80 1.18 0.74 0.37 1.50 (Please read the precautions on the back before filling out this page). Packing-* νβ This paper is applicable to the national standard (CNS) 〉 A4 size (210X297mm) -23-

7 B V. Description of the invention (21) Example 6 printed by the Shellfish Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs 7 7 8 Controlled 9 10 Initial air sand 300 300 300 0 X 50 0 X 50 Spray drying data H2o amount ( Kg) 15 105 105 10 10 Air sand volume (kg) 1.5 14.7 14.7 1.5 1.5 Atomization using a turntable single nozzle double _ turntable turntable operation away from ΓΟ 380 440 440 380 380 exhaust gas temperature (.105 105 108 105 105 precipitation cyclone Filter filter cyclone cyclone heating data (hours / ° c) 2/700 surface modification data reagent HMDS Si 108 HMDS HMDS quantity [g / 100g gas silicon] 15 25 20-3 water volume [g / 100g gas silicon ] 5 5 5--Heating time (hours) 4 2 4 5 m. Ro 140 120 140-140 Physical and chemical properties BET surface area (m2 / g) 222 180 195 46 41 Pore volume (ml / g) 1.79 1.49 1.51 0.73 0.68 pores < 5 nm pore volume (% of all pores nd 1.7 1.5 nd 1.2% of pore volume) medium pores (mL / g) of 2-3nm 0.78 0.60 0.60 0.08 0.09 > 30nm huge pores (mL / Gram 1.01 0.89 0.91 0.65 0.59 Particle size d5Vm) 32 40 43 21 21 Perforation volume (g / l) 290 320 300 540 570 pH 値 6 5.2 6.9 5.3 7.4 Carbon content% 2.7 9.3 3.3-0.5 Silanol group concentration (millimolar) OH / g) 0.61 1.15 0.40 0.29 0.14 (Please read the notes on the back before filling in this page) -se This paper size uses the Chinese National Standard (CNS) A4 specification (2 丨 OX 297 mm) B7 V. Description of the invention (22) Example of printing by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs for comparison 11 12 for comparison 13 14 Initial gas silicon 130 130 200 200 Spray drying data H2o amount (kg) 15 115 15 15 Air sand amount (kg) 1.5 1.5 1.5 1.5 Atomization using turntable turntable turntable turntable operating temperature (. 〇 380 380 380 380 Exhaust gas M (. 105 105 105 105 105 Precipitation cyclone cyclone cyclone spin title heating data (hour / ° C)---Surface modification data reagent HMDS HMDS quantity [g / 100g gas silicon] -5-7 Water content [g / 100g of silicon gas]----Heating time (hours)-5-5 mt co-140-140 Physical and chemical properties BET surface area (m2 / g) 131 111 196 153 Pore volume ( Ml / g) 1.92 1.62 2.25 2.04 pore volume of the 5 run (% of total pore volume) nd 1.7 nd 0.9 2-30 run medium pore (ml / g) 0.24 0.24 0.46 0.47 > 30mn (Ml / g) 1.68 1.38 1.79 1.57 Vertical diameter d50 (μηι) 20 20 14 14 Perforation volume (g / l) 250 280 230 240 pH 値 4.8 7.3 4.8 7.2 Carbon content%-1.3-1.7 Concentration of salanol groups ( Millimolar OH / g) 0.83 0.44 1.16 0.56 ----- ^ --- Γ ---- (Please read the notes on the back before filling out this page) Order i.feN_ This paper size applies Chinese national standards ( CNS) A4 specification (210X297 mm) -25-A7 ___B7 _ V. Description of invention (23) Basis The particle size distributions of the particles obtained in Examples 1 to 14 are shown in tables and graphs in Figures 1 to 4. Examples 1, 5, 9, 11 and 13 are comparative examples of the prior art (DE-A 3 6 1 1 449 Liu). The granules of the present invention are used as catalysts for the preparation of polyethylene. [The example of coating the window with cutting sauce refers to the active ingredient titanium. The catalyst can achieve the following results during the polymerization of ethylene: (This page)) Example of production of printed catalysts on a carrier by the Central Ministry of Economic Affairs of the Central Bureau of Quasi-Continent Bureau of Industrial Engineering. Production of kilograms of PE per gram of titanium. Comments on Examples 1 2 9 2 Use only the spray-dried carrier as in Example 1. Hip Example 2 3 6 9 The chemically-treated carrier as in Example 4 Example 3 3 7 6 The heat-treated and chemically-treated carrier as in Example 6 This paper applies Chinese National Standard (CNS) A4 specifications (210X297) 26) Appendix I (A): 85101073 year; j R: ㈣-supplement p in January, i. Description of the invention (24) Brief description of the formula Figure 1 shows the implementation of the invention in the form of tables and diagrams Particle size distribution of the particles obtained in Example 1g 4. Fig. 2 shows the particle size distributions of the particles obtained according to Examples 5 to 8 of the present invention in the form of a table and a diagram. FIG. 3 shows the particle size distribution of the particles obtained according to Examples 9 to 11 of the present invention in the form of a table and a diagram. FIG. 4 is a particle size distribution of the particles obtained in accordance with Examples 12 to 14 of the present invention in the form of a table and formula. (Please read the precautions on the back before filling this page) Install [·! ----Ordered · 111111 · Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by a consumer cooperative. The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -26-1-

Claims (1)

A8 B8 C8 D8 The member of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, printed a member of Zou Jing, clearly stated whether the amended bismuth will be changed, the content is 6, the scope of patent application 1 Appendix 1 No. 85101073 Patent String Request 1 Chinese String Please revise the scope of the patent. V {I Please 1 I June 1988 First Read 1 | Read 1 Back 1 Side | of 1 1 • A kind of particles mainly composed of sand dioxide obtained by pyrolysis method. 1 Ψ 1 has the following physicochemical properties 1 '1 Average grain size 1 0 to 12 0 β m 4 (Write' IBET surface area 4 0 to 4 0 0 m 2 / g shell 1 1 Pore volume 0 * 5 To 2 • 5 m 1 / g ί 1 pore diameter & <5 η m Less than 5% of the product t Order I the rest are medium — and huge holes 1 1 IP Η value 3 6 to 8 5 1 1 perforation density · 2 2 0 to 7 0 0 g / liter 1 1 2 — seed month 3 to prepare as The method of claim Λ 1 for the granules of the patent scope is characterized in that the silicon dioxide obtained by the pyrolysis method is distributed in water and spray-dried at 1 I, and the obtained granules are heated to 15 0 to I 1, 1 0 0 ° C for 1 to 8 hours 0 1 .II 3 — a method 1 for preparing particles such as those in the patent claim 1, which is characterized by the distribution of silica obtained by pyrolysis Spraying and drying in water, and siliconizing the obtained particles 0 1 4 • A method 1 | for preparing particles such as the first item in the patent scope, which is characterized by using a pyrolysis method The obtained silica is distributed in water and the size of 1 1 paper is suitable. China National Ladder Standard (CNS) A4 specification (210X297 mm) A8 B8 C8 D8 Compensation printed by member of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy Scope 1 Attachment 1 No. 85101073 Patent String Request 1 Chinese String Request Patent Scope Amendment V {I Please 1 I Republic of China 1986 Submitted First Read 1 | Read 1 Back 1 Side | No. 1 1 Granules based on sand dioxide obtained by the solution. It has the following physical and chemical properties. 1 '1 The average grain size 1 0 to 12 0 β m 4 (Write' IBET surface area 4 0 to 4 0 0 m 2 / g shell 1 1 hole volume 0 * 5 to 2 • 5 m 1 / g ί 1 pore size distribution diameter &lt; 5 The holes of η m are less than 5% of the total volume of the holes in the whole part I. The order I is medium and the rest are medium—and the huge holes 1 1 IP Η value 3 6 to 8 5 1 1 perforation density · 2 2 0 to 7 0 0 g / liter 1 1 2 — month 3 method for preparing granules such as those in the patent claim 1, characterized in that the silicon dioxide obtained by pyrolysis is distributed in water and 1 I is spray-dried and dried The granules obtained are heated to 150 to I 1, 1 0 0 ° C for 1 to 8 hours 0 1 .II 3-a method 1 for preparing granules as described in item 1 of the Chinese patent application, characterized in that The silica dioxide produced by the pyrolysis method is distributed in water and spray-dried, and the obtained particles are siliconized. 0 1 4 • A method 1 for preparing particles such as the first item in the patent scope | , Which is characterized by the second Silicon oxide is distributed in water and 1 1 paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ABCD 393448 6. Spraying and drying range for patent application, and heating the obtained particles to 150 to 1,100 ° C for 1 to 8 hours and subsequent silylation. 5. A method for preparing particles mainly composed of silicon dioxide obtained by pyrolysis as described in item 1 of the scope of patent application, which is characterized in that silicon dioxide obtained by pyrolysis is more preferably The silicon dioxide prepared from the silicon tetrachloride by the flame hydrolysis method is distributed in water, and the spray drying method is performed to selectively heat the obtained particles to 150 to 1,100 ° C for 1 to 8 hours and / or Carrying out silanization · 6 · The granules according to item 1 of the scope of patent application are used as catalyst carriers, especially for preparing polymerization catalysts. 7. The granule according to item 1 of the patent application, which is used as a catalyst carrier for the manufacture of a catalyst for the production of polyethylene. --------- pack ---: --- ΓΙ1Τ ---- -^ (Please read the notes on the back first, and then this page) The paper size printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -2-