CN102382216B - Preparation method of silica gel carrier for ethylene polymerization catalyst - Google Patents
Preparation method of silica gel carrier for ethylene polymerization catalyst Download PDFInfo
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- CN102382216B CN102382216B CN 201110137699 CN201110137699A CN102382216B CN 102382216 B CN102382216 B CN 102382216B CN 201110137699 CN201110137699 CN 201110137699 CN 201110137699 A CN201110137699 A CN 201110137699A CN 102382216 B CN102382216 B CN 102382216B
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Abstract
The invention discloses a preparation method of a silica gel carrier for an ethylene polymerization catalyst. The preparation method is characterized by comprising the process steps: 1) diluting industrial sodium silicate; dropping 15-35% sulfuric acid solution at an initial temperature of 10-40 DEG C, reacting for 1-3 hours, adjusting the PH value to 2-4, and keeping the final pH value to 4-5; 2) heating to 50-60 DEG C, adding a complexing agent of which the addition amount is 10-15% of silica, and keeping the temperature for 30-60 minutes; 3) heating to a final temperature ranging from 80-100 DEG C, adding a surfactant of which the addition amount is 1-3wt% of silica, and keeping the temperature for 1-5 hours; 4) washing with deionized water to ensure that the weight content of sodium ions is below 0.05%; 5) adding deionized water in the filter cake, keeping the content of silica to 8-15%, pulping with a high-speed dispersion machine in 2000-2500rpm, and stirring for 20-30 minutes; 6) performing spray drying at 400-600 DEG C, wherein the outlet temperature is kept to 90-100 DEG C and the water content is kept below 10%; and 7) grading the product with air flow to control the average particle size to 30-50mu m and obtain the carrier.
Description
Technical field
The present invention relates to catalysis technical field, be a kind of preparation method of silica gel carrier for ethylene polymerization catalyst.
Background technology
In the polythene production process, the polymerization efficiency of its catalyzer is extremely important, and in the ethylene rolymerization catalyst preparation process, silica gel is widely used as a kind of efficient support of the catalyst at present.
Report such as US5231066, US5895770, US5372983 etc. about the existing a lot of patents of preparation method that are used for polyolefin catalyst large pore volume silica-gel carrier.Patent US3652215,3652216 disclosed methods are that water glass is neutralized with sulfuric acid, then washing, again with the organic solvent washing of pulling an oar, then dry, calcine and obtain specific surface 200-500m
2/ g, silica-gel carrier, the recovery of the method solvent is to hinder industrialized key. Yao Pei flood etc. discloses a kind of preparation method of silica-gel carrier among the patent CN1403486, when the preparation hydrogel, employing is take part dilute silicate solution as mother liquor, and dilute silicate solution and mineral acid add in the reactor that mother liquor is housed simultaneously, treats to regulate when partial gel occurs the mother liquor PH5-8.5 water-sol and is converted into hydrogel fully, through the silica-gel carrier that aging, washing, drying obtain, specific surface area: 200-400m
2/ g, pore volume: 1.0-2.0ml/g pore size distribution
Introduced a kind of preparation method of macroporous particle silica gel in CN02127599, described method is because pore volume only has 0.8-1.1ml/g to be not suitable for doing the use of ethylene rolymerization catalyst carrier.Because employed catalyzer must be a kind of efficient polymerizing catalyst in the ethylene polymerisation process, therefore, be mainly three aspects for the requirement of silica-gel carrier.1, chemical purity, 2, pore property, 3, size-grade distribution.These three conditions must all will satisfy, and could use as the ethylene rolymerization catalyst carrier.Therefore, we have invented the preparation method of suitable ethylene rolymerization catalyst silica-gel carrier.
Summary of the invention:
The objective of the invention is to adopt industrial metasilicate is raw material, a kind of preparation method of suitable silica gel carrier for ethylene polymerization catalyst is provided, adopt the method, the silica-gel carrier of producing, its chemical purity, the overall target such as pore volume and specific surface area is excellent, thereby can be as the ethylene rolymerization catalyst carrier.
The present invention is a kind of preparation method of silica gel carrier for ethylene polymerization catalyst, it is characterized in that:
Processing step comprises:
1, industrial metasilicate being added deionized water, to be diluted to concentration be that the mass content of silicon-dioxide is the 8-15% aqueous solution; Dripping mass content under initial temperature 10-40 ℃ is the sulphuric acid soln of 15-35%, fully reacts 1-3 hour. regulation system PH to 2-4, and keeping the final pH value of regulating is 4-5;
2, being warming up to 50-60 ℃ and adding complexing agent, be incubated 30-60 minute. complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), sodium oxalate; The complexing agent add-on is the 10-15% of silicon-dioxide;
3, be warming up to outlet temperature 80-100 ℃, add tensio-active agent; Be incubated 1-5 hour. tensio-active agent is selected from nonionogenic tenside T-20, T-80 and penetrating agent JFC, one or more, the add-on of tensio-active agent is the 1-3% of silicon-dioxide quality content;
4, utilize deionized water to wash above-mentioned slip,, being washed to the sodium ion mass content is below 0.05%;
5, the filter cake after the above-mentioned washing is added deionized water, keep dioxide-containing silica 8-15%; Pull an oar under 2000-2500 rev/min with high speed dispersor, stirred 20-30 minute;
6, drying, drying mode adopts spraying drying: temperature keeps 400-600 ℃; Temperature out keeps 90-100 ℃, keeps moisture content below 10%;
7, adopting air classification is 30-50 μ m with dried control of product mean particle size, namely gets carrier of the present invention.
The index that obtains the finished product is:
Silicon-dioxide: greater than 99.7%; Pore volume: 1.5-1.8ml/g; Specific surface area:
280-350m
2/g；
Mean particle size 40-50 μ m.
Kind and the content purpose that reach the pore property of the chemical purity of regulating product and product of foregoing invention by regulating initial temperature, complexing agent and tensio-active agent.
The preferred technical solution of the present invention: it is characterized in that:
Processing step comprises:
1, industrial metasilicate being added deionized water, to be diluted to concentration be that the mass content of silicon-dioxide is the 8-12% aqueous solution; Dripping mass content under initial temperature 10-35 ℃ is the sulphuric acid soln of 15-35%, fully reacts 1-2 hour. regulation system PH to 3-4, and keeping the final pH value of regulating is 4-4.5;
2, being warming up to 50-60 ℃ and adding complexing agent, be incubated 40-60 minute. complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), sodium oxalate; The complexing agent add-on is the 10-15% of silicon-dioxide;
3, be warming up to outlet temperature 80-100 ℃, add tensio-active agent; Be incubated 2-4 hour. tensio-active agent is selected from nonionogenic tenside T-20, T-80 and penetrating agent JFC, one or more, the add-on of tensio-active agent is the 1-2% of silicon-dioxide quality content;
4, utilize deionized water to wash above-mentioned slip,, being washed to the sodium ion mass content is below 0.05%;
5, the filter cake after the above-mentioned washing is added deionized water, keep dioxide-containing silica 8-15%; Pull an oar under 2000-2500 rev/min with high speed dispersor, stirred 20-30 minute;
6, drying, drying mode adopts spraying drying: temperature keeps 400-600 ℃; Temperature out keeps 90-100 ℃, keeps moisture content below 10%;
7, adopting air classification is 30-50 μ m with dried control of product mean particle size, namely gets carrier of the present invention.
The invention has the advantages that: can select common industrial sodium silicate as the silicon source, raw material is easy to get, low price. the silica-gel carrier of preparation, and product purity is high, and whole technological process need not to use strict raw materials technology,
Reaction times of the present invention is 2-5 hour.In reaction process, add complexing agent product carried out the purification of product, and in the Hydrothermal Synthesis process, add tensio-active agent, the surface hydroxyl of silica gel with carry out graft reaction, prevented the contraction in aperture, thereby silica gel structure be fixed up at last.The present invention adopts the prepared special silica-gel carrier dioxide-containing silica of common raw material greater than 99.7%.
Embodiment:
Embodiment-,
The preparation dioxide-containing silica is 8% sodium silicate solution 1Kg, formulation content is 35% sulphuric acid soln 172g, react 35 ℃ of temperature, reaction times is controlled at 1 hour, keep final PH4-4.5, be warming up to 50 ℃ and add disodium ethylene diamine tetraacetate 8g, be incubated 40 minutes. be warming up to again 80 ℃, add tensio-active agent T-201.6g, be incubated 4 hours, washing above-mentioned slip, to make the sodium ion mass content be below 0.05%, with high speed dispersor at 2500 rev/mins, with the filter cake after above-mentioned the washing making beating, and adding tap water, to adjust silicon-dioxide quality concentration be 15%, and spray-dried and size classification mean particle size 40-50 μ m obtains moisture less than 10% silica-gel carrier again.Its experimental data such as table one
The physical and chemical performance table of table one, silica-gel carrier embodiment 1
Embodiment two,
The preparation dioxide-containing silica is 10% sodium silicate solution 1Kg, formulation content is 25% sulphuric acid soln 300g, react 25 ℃ of temperature, reaction times is controlled at 1 hour, keep final PH4-4.5, be warming up to 50 ℃ and add ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) 10g, be incubated 40 minutes. be warming up to again 90 ℃, add tensio-active agent T-802g, be incubated 4 hours, washing above-mentioned slip, to make the sodium ion mass content be below 0.05%, with high speed dispersor at 2500 rev/mins, with the filter cake after above-mentioned the washing making beating, and adding tap water, to adjust silicon-dioxide quality concentration be 12%, and spray-dried and size classification mean particle size 40-50 μ m obtains moisture less than 10% silica-gel carrier again.Its experimental data such as table two
The physical and chemical performance table of table two, silica-gel carrier embodiment 2
Embodiment three,
The preparation dioxide-containing silica is 12% sodium silicate solution 1Kg, formulation content is 20% sulphuric acid soln 450g, react 15 ℃ of temperature, reaction times is controlled at 2 hours, keep final PH4-4.5, be warming up to 50 ℃ and add ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) and each 9g of sodium oxalate, be incubated 50 minutes. be warming up to again 90 ℃, add tensio-active agent T-20 and each 1.2g of JFC, be incubated 3 hours, washing above-mentioned slip, to make the sodium ion mass content be below 0.05%, with high speed dispersor at 2500 rev/mins, with the filter cake after above-mentioned the washing making beating, and adding tap water, to adjust silicon-dioxide quality concentration be 10%, and spray-dried and size classification mean particle size 40-50 μ m obtains moisture less than 10% silica-gel carrier again.
Its experimental data such as table three;
The physical and chemical performance table of table three, silica-gel carrier embodiment 3
Claims (2)
1. the preparation method of a silica gel carrier for ethylene polymerization catalyst, it is characterized in that: processing step comprises:
1) industrial metasilicate being added deionized water, to be diluted to concentration be that the mass content of silicon-dioxide is the 8-15% aqueous solution; Dripping mass content under initial temperature 10-40 ℃ is the sulphuric acid soln of 15-35%, fully reacts 1-3 hour; Regulation system pH to 2-4, keeping final pH value of regulating is 4-5;
2) be warming up to 50-60 ℃ and add complexing agent, be incubated 30-60 minute; Complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), sodium oxalate;
The complexing agent add-on is the 10-15% of silicon-dioxide;
3) be warming up to outlet temperature 80-100 ℃, add tensio-active agent; Be incubated 1-5 hour; Tensio-active agent is selected from one or more of nonionogenic tenside T-20, T-80 and penetrating agent JFC, and the add-on of tensio-active agent is the 1-3% of silicon-dioxide quality content;
4) utilize deionized water to wash above-mentioned slip, being washed to the sodium ion mass content is below 0.05%;
5) filter cake after the above-mentioned washing is added deionized water, keep dioxide-containing silica 8-15%; Pull an oar under 2000-2500 rev/min with high speed dispersor, stirred 20-30 minute;
6) drying, drying mode adopts spraying drying: temperature keeps 400-600 ℃; Temperature out keeps 90-100 ℃, keeps moisture content below 10%;
7) adopting air classification is 30-50 μ m with dried control of product mean particle size, namely gets carrier;
The index that obtains the finished product is:
Silicon-dioxide: greater than 99.7%; Pore volume: 1.5-1.8ml/g; Specific surface area:
280-350m
2/g；
Mean particle size 40-50 μ m.
2. it is characterized in that in accordance with the method for claim 1:
Processing step comprises:
1) industrial metasilicate being added deionized water, to be diluted to concentration be that the mass content of silicon-dioxide is the 8-12% aqueous solution; Dripping mass content under initial temperature 10-35 ℃ is the sulphuric acid soln of 15-35%, fully reacts 1-2 hour; Regulation system pH to 3-4, keeping final pH value of regulating is 4-4.5;
2) be warming up to 50-60 ℃ and add complexing agent, be incubated 40-60 minute; Complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA), sodium oxalate;
The complexing agent add-on is the 10-15% of silicon-dioxide;
3) be warming up to outlet temperature 80-100 ℃, add tensio-active agent; Be incubated 2-4 hour; Tensio-active agent is selected from one or more of nonionogenic tenside T-20, T-80 and penetrating agent JFC, and the add-on of tensio-active agent is the 1-2% of silicon-dioxide quality content;
4) utilize deionized water to wash above-mentioned slip, being washed to the sodium ion mass content is below 0.05%;
5) filter cake after the above-mentioned washing is added deionized water, keep dioxide-containing silica 8-15%;
Pull an oar under 2000-2500 rev/min with high speed dispersor, stirred 20-30 minute;
6) drying, drying mode adopts spraying drying: temperature keeps 400-600 ℃; Temperature out keeps 90-100 ℃, keeps moisture content below 10%;
7) adopting air classification is 30-50 μ m with dried control of product mean particle size, namely gets carrier.
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| CN103464216B (en) * | 2013-09-26 | 2015-08-19 | 中国海洋石油总公司 | The method for making of acetic acid and the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of butylene |
| CN106111097A (en) * | 2016-06-27 | 2016-11-16 | 中国海洋石油总公司 | A kind of preparation method of high-purity column chromatography silica gel |
| CN113583159A (en) * | 2021-09-14 | 2021-11-02 | 无锡玖汇科技有限公司 | Supported polyolefin catalyst and preparation method thereof |
| CN113583160A (en) * | 2021-09-14 | 2021-11-02 | 无锡玖汇科技有限公司 | Preparation method of composite carrier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403486A (en) * | 2001-09-03 | 2003-03-19 | 中国石油天然气股份有限公司 | Prepn of silica gel carrier |
| CN1472138A (en) * | 2002-08-02 | 2004-02-04 | 中国科学院大连化学物理研究所 | Method for preparing macroporous particle silica gel |
| CN1803600A (en) * | 2005-12-16 | 2006-07-19 | 厦门大学 | Preparation method of silica gel carrier |
| CN102002120A (en) * | 2010-09-20 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing special silica gel carrier with large pore volume and large specific surface area |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403486A (en) * | 2001-09-03 | 2003-03-19 | 中国石油天然气股份有限公司 | Prepn of silica gel carrier |
| CN1472138A (en) * | 2002-08-02 | 2004-02-04 | 中国科学院大连化学物理研究所 | Method for preparing macroporous particle silica gel |
| CN1803600A (en) * | 2005-12-16 | 2006-07-19 | 厦门大学 | Preparation method of silica gel carrier |
| CN102002120A (en) * | 2010-09-20 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing special silica gel carrier with large pore volume and large specific surface area |
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