CN1522958A - Process for manufacturing macroreticular spherical silica gel - Google Patents
Process for manufacturing macroreticular spherical silica gel Download PDFInfo
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- CN1522958A CN1522958A CNA031118887A CN03111888A CN1522958A CN 1522958 A CN1522958 A CN 1522958A CN A031118887 A CNA031118887 A CN A031118887A CN 03111888 A CN03111888 A CN 03111888A CN 1522958 A CN1522958 A CN 1522958A
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Abstract
The production method of macroporous spherical silica gel includes the following processes: placing the sodium silicate solution and dilute sulfuric acid into a mixed-rotating granulating equipment to make step-by-step reaction and jet the above-mentioned materials into air by means of nozzle of said granulating equipment, then making polycondensation to produce gel granules, then making the gel granules undergo the processes of ageing, acid soaking, water washing and drying so as to obtain the macroporous spherical silica gel product or making the gel granules undergo the processes of acid soaking, water washing, ageing, secondary acid soaking and drying so as to obtain the macroporous spherical silical gel product whose mean pore size is 10-45 nm, mean pore volume is 1.00-2.20 ml/g and mean specific area is 200-550 sq.m/g.
Description
(1) technical field
The present invention relates to the improvement of silica gel manufacture method, specifically is a kind of manufacture method of large pore spherical silica gel, and it belongs to silication worker technical field.
(2) background technology
In the prior art, generally silica gel is pressed its aperture difference, be divided into silochrom and Kiselgel A; Or, be divided into block silica gel and spherical silica gel by its shape difference.Disclosed a kind of macroporous silica gel of CN1363514A document and manufacture method thereof are arranged, and the physical and chemical performance of its silica gel is: mean pore size is at 10-60nm, average specific surface area 250-350m
2/ g, average pore volume 1.00-2.00ml/g; Its manufacture method is to generate positive silicic acid by sodium silicate solution and dilute sulphuric acid in reactor, solidify through leaving standstill-→ broken granulation-→ washing-→ processing of alkali bubble-→ steam treatment-→ soak salt to handle, handle through traditional stoving process again, make macroporous silica gel.The physical strength of this macroporous silica gel a little less than, it is when the support of the catalyst, it is very easily chipping to run into the aqueous solution, influences the catalysis result of use of catalyzer.Soak the salt treatment process and cause in the pore structure of this macroporous silica gel and have metal ion, not labile salt owing to adopting, this certainly will have influence on the catalytic activity of catalyzer.This macroporous silica gel is being used for matting agent, or during the opening agent, its result of use all can not reach requirement.
(3) technology contents
The objective of the invention is to overcome the defective of above-mentioned macroporous silica gel, a kind of manufacture method of large pore spherical silica gel is provided.Macroporous silica gel with this method manufacturing not only will have following pore structure: mean pore size is at 10-45nm, average pore volume 1.00-2.20ml/g, average specific surface area 200-550m
2/ g, and to have certain mechanical strength, meet the characteristic that water does not split.
Task of the present invention is realized by following technical scheme, developed a kind of manufacture method of large pore spherical silica gel, its by sodium silicate solution and dilute sulphuric acid in DL formula prilling granulator, carry out gradual reaction and through the nozzle ejection of this prilling granulator to air, and then polycondensation generates the gel grain, this gel grain is warp again: aging-→ the acid bubble-→ washing-→ the exsiccant art breading, thus the large pore spherical silica gel product obtained.
Described aging technique is handled, and is to place 70-200 ℃ hot water to handle this gel grain that granulation generates; Described drying process is handled, and is this gel grain of washing that warm water is handled is pulled out, and drying equipment is under 160-950 ℃ of high temperature, and oven dry is handled.
Described aging technique is handled, and is this gel grain that granulation generates was handled 0.5-48 hour through hot water thermal insulating.
Described drying process is handled, and is that this gel grain hyperthermia drying of washing after warm water is handled was handled 1 second-4 hours.
A kind of another kind of manufacture method of large pore spherical silica gel, its by sodium silicate solution and dilute sulphuric acid in DL formula prilling granulator, carry out gradual reaction and through the nozzle ejection of this prilling granulator to air, and then polycondensation generates the gel grain, this gel grain is warp again: the acid bubble-→ washing-→ aging-→ the quadratic acid bubble-→ the exsiccant art breading, thus the large pore spherical silica gel product obtained.
The another kind of manufacture method of large pore spherical silica gel of the present invention, described aging technique is handled, and is to place 120-200 ℃ hot water to handle again this gel grain of washing that warm water is handled; Described quadratic acid bubble art breading is that this gel grain after the burin-in process is immersed in 0.01-1.0% (W/t) the lower concentration acid solution; Described drying process is handled, and is this gel grain that the quadratic acid bubble is handled is pulled out, and drying equipment is under 160-950 ℃ of high temperature, and oven dry is handled.
The another kind of manufacture method of large pore spherical silica gel of the present invention, described aging technique is handled, and is this gel grain of washing that warm water is handled was handled 0.5-48 hour through hot water thermal insulating again.
The another kind of manufacture method of large pore spherical silica gel of the present invention, described quadratic acid bubble art breading is that this gel grain after the burin-in process was soaked 2-16 hour in the lower concentration acid solution.
The another kind of manufacture method of large pore spherical silica gel of the present invention, described drying process is handled, and is that this gel grain hyperthermia drying after the quadratic acid bubble is handled was handled 1 second-4 hours.
The another kind of manufacture method of large pore spherical silica gel of the present invention, described drying process is handled, be this gel grain after the quadratic acid bubble is handled under 500-850 ℃ of high temperature, oven dry was handled 1 second-4 hours.
The another kind of manufacture method of large pore spherical silica gel of the present invention, described quadratic acid bubble art breading, selected acid is: sulfuric acid, nitric acid, hydrochloric acid, formic acid, a kind of in the acetic acid.
The invention has the advantages that: because two kinds of manufacture method of macroporous silica gel of the present invention all in aging technique is handled, place 70-200 ℃ hot water to heat-treat the gel grain.This high-temperature heat treatment aging technique has stronger reaming effect than warm water (25-40 ℃) burin-in process of traditional adhesive-preparing technology.Because two kinds of manufacture method of macroporous silica gel of the present invention all in drying process was handled, under 160-950 ℃ of high temperature, handled 1 second-4 hours with the gel grain by oven dry.This hyperthermia drying treatment process is more much higher than the bake out temperature (120-150 ℃) of traditional adhesive-preparing technology, it has the effect of partially sintering, can improve the surperficial frame strength of silicon particle widely, make this silicon particle when running into water, can resist the impact of capillary pressure, and be unlikely broken.Therefore this hyperthermia drying treatment process of the present invention makes macroporous silica gel of the present invention have water tolerance.Because two kinds of manufacture method of macroporous silica gel of the present invention have all adopted sour bubble art breading, and do not adopt alkali bubble technology, so just having reduced metal ion remains in the silica gel hole, cooperate the hyperthermia drying treatment process again, make the acid that remains in the silica gel space can decompose volatilization or burning, make noresidue in the finished product macroporous silica gel, thereby improved the use properties of the catalytic activity of this macroporous silica gel that is used as support of the catalyst.Therefore, macroporous silica gel of the present invention is specially adapted to as support of the catalyst, matting agent, opening agent, beer filtration medium, paper additive etc.
(4) embodiment
Protection scope of the present invention not only is confined to following examples.The embodiment of two kinds of manufacture method of large pore spherical silica gel of the present invention has illustrated advantage of the present invention.
Large pore spherical silica gel manufacture method of the present invention is on the basis of traditional adhesive-preparing technology equipment, and preparation contains SiO
217 ± 0.5% sodium silicate solution and content are that 20 ± 0.5% sulphuric acid soln is in the DL formula prilling granulator of ZL95233839.4 patented product, carry out gradual reaction and through the nozzle ejection of this prilling granulator to air, and then polycondensation generates the gel grain, this gel grain is warp again: aging: hot water temperature 70-200 ℃ down insulation handle 0.5-48 hour-→ the acid bubble: in content is the sulphuric acid soln of 3-3.5%, soak 4-6 hour-→ washing: with 30-70 ℃ warm water washing to pH value 2.2-7.5-→ drying: under 200-950 ℃ of high temperature, oven dry was handled 1 second-4 hours, thereby obtained the large pore spherical silica gel product.Specific embodiment sees Table 1.
Table 1: large pore spherical silica gel manufacture method main technique condition embodiment and pore structure thereof
The another kind of manufacture method of large pore spherical silica gel of the present invention is on the basis of traditional adhesive-preparing technology equipment, and preparation contains SiO
217 ± 0.5% sodium silicate solution and content are that 20 ± 0.5% sulphuric acid soln is in the DL formula prilling granulator of ZL95233839.4 patented product, carry out gradual reaction and through the nozzle ejection of this prilling granulator to air, and then polycondensation generates the gel grain, this gel grain is warp again: acid bubble: in content is the sulphuric acid soln of 3-3.5%, soak 4-6 hour-→ washing: with 30-70 ℃ warm water washing to pH value 6.0 or more-→ aging: hot water temperature 120-200 ℃ down insulation handle 0.5-48 hour-→ quadratic acid steeps: content be immersion 2-6 hour in the acid solution of 0.01-1.0% (W/t)-→ drying: under 200-950 ℃ of high temperature, oven dry was handled 1 second-4 hours, thereby obtained the large pore spherical silica gel product.Specific embodiment sees Table 2.
Table 2: another kind of manufacture method main technique condition embodiment of large pore spherical silica gel and pore structure thereof
Annotate: ASAP2000 type and Tristar3000 type analysis instrument that the pore structure data system that above-mentioned table 1,2 is measured adopts U.S. Mai Ke instrument company to produce are measured.
Claims (9)
1, a kind of manufacture method of large pore spherical silica gel, its by sodium silicate solution and dilute sulphuric acid in DL formula prilling granulator, carry out gradual reaction and through the nozzle ejection of this prilling granulator to air, and then polycondensation generates the gel grain, this gel grain is warp again: aging-→ the acid bubble-→ washing-→ the exsiccant art breading, thereby obtain the large pore spherical silica gel product, it is characterized in that: described aging technique is handled, and is to place 70-200 ℃ hot water to handle this gel grain that granulation generates; Described drying process is handled, and is this gel grain of washing that warm water is handled is pulled out, and drying equipment is under 160-950 ℃ of high temperature, and oven dry is handled.
2, according to the manufacture method of the described large pore spherical silica gel of claim 1, it is characterized in that: described aging technique is handled, and is this gel grain that granulation generates was handled 0.5-48 hour through hot water thermal insulating.
3, according to the manufacture method of the described large pore spherical silica gel of claim 1, it is characterized in that: described drying process is handled, and is that this gel grain hyperthermia drying of washing after warm water is handled was handled 1 second-4 hours.
4, a kind of another kind of manufacture method of large pore spherical silica gel, its by sodium silicate solution and dilute sulphuric acid in DL formula prilling granulator, carry out gradual reaction and through the nozzle ejection of this prilling granulator to air, and then polycondensation generates the gel grain, this gel grain is warp again: the acid bubble-→ washing-→ aging-→ the quadratic acid bubble-→ the exsiccant art breading, thereby obtain the large pore spherical silica gel product, it is characterized in that: described aging technique is handled, and is to place 120-200 ℃ hot water to handle again this gel grain of washing that warm water is handled; Described quadratic acid bubble art breading is that this gel grain after the burin-in process is immersed in the 0.01-1.0% lower concentration acid solution; Described drying process is handled, and is this gel grain that the quadratic acid bubble is handled is pulled out, and drying equipment is under 160-950 ℃ of high temperature, and oven dry is handled.
5, according to the manufacture method of the described large pore spherical silica gel of claim 4, it is characterized in that: described aging technique is handled, and is this gel grain of washing that warm water is handled was handled 0.5-48 hour through hot water thermal insulating again.
6, according to the manufacture method of the described large pore spherical silica gel of claim 4, it is characterized in that: described quadratic acid bubble art breading is that this gel grain after the burin-in process was soaked 2-16 hour in the lower concentration acid solution.
7, according to the manufacture method of the described large pore spherical silica gel of claim 4, it is characterized in that: described drying process is handled, and is that this gel grain hyperthermia drying after the quadratic acid bubble is handled was handled 1 second-4 hours.
8, according to the manufacture method of the described large pore spherical silica gel of claim 4, it is characterized in that: described drying process is handled, be this gel grain after the quadratic acid bubble is handled under 500-850 ℃ of high temperature, oven dry was handled 1 second-4 hours.
9, according to the manufacture method of the described large pore spherical silica gel of claim 4, it is characterized in that: described quadratic acid bubble art breading, selected acid is: sulfuric acid, nitric acid, hydrochloric acid, formic acid, a kind of in the acetic acid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100020909A CN100376480C (en) | 2003-02-21 | 2003-02-21 | Production of macroporous silica gel |
| CN 03111888 CN1207193C (en) | 2003-02-21 | 2003-02-21 | Process for manufacturing macroreticular spherical silica gel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111888 CN1207193C (en) | 2003-02-21 | 2003-02-21 | Process for manufacturing macroreticular spherical silica gel |
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| CNB2005100020909A Division CN100376480C (en) | 2003-02-21 | 2003-02-21 | Production of macroporous silica gel |
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| CN1522958A true CN1522958A (en) | 2004-08-25 |
| CN1207193C CN1207193C (en) | 2005-06-22 |
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| CN 03111888 Expired - Fee Related CN1207193C (en) | 2003-02-21 | 2003-02-21 | Process for manufacturing macroreticular spherical silica gel |
| CNB2005100020909A Expired - Fee Related CN100376480C (en) | 2003-02-21 | 2003-02-21 | Production of macroporous silica gel |
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Cited By (10)
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| CN100337912C (en) * | 2005-12-23 | 2007-09-19 | 李永兆 | Process for mfg. water resisting type large pore spherical silica gel |
| CN102190306A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Silica microspheres and its preparation method |
| CN102260359A (en) * | 2011-01-06 | 2011-11-30 | 上海海源化工科技有限公司 | Method for preparing chromium silica gel catalyst carrier with high specific surface area and large pore volume |
| CN102649090A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Preparing method of catalyst carrier for preparation of ethylene glycol by oxalate through hydrogenation |
| CN102757058A (en) * | 2012-06-12 | 2012-10-31 | 山东辛化硅胶有限公司 | Novel B type large-pore volume silica gel and manufacture method thereof |
| CN103880024A (en) * | 2012-12-21 | 2014-06-25 | 青岛美格斯科技有限公司 | Preparation method of silica gel carrier with large pore volume |
| CN105195087A (en) * | 2015-10-26 | 2015-12-30 | 王立卓 | Extra-large-aperture silicon dioxide new material and preparation method thereof |
| CN105819884A (en) * | 2016-03-10 | 2016-08-03 | 青岛海洋化工有限公司 | Waterproof alumina-silica gel particle product and production method thereof |
| CN106241820A (en) * | 2016-08-12 | 2016-12-21 | 乳山市大洋硅胶厂 | A kind of aeroge raw material and preparation method thereof |
| CN109287685A (en) * | 2018-09-21 | 2019-02-01 | 郑州格美家生物技术有限公司 | Anti-mite silica gel and preparation method thereof |
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| CN101205066B (en) * | 2007-12-17 | 2010-06-02 | 李永兆 | Macroporous microsphere silica gel preparation thereof |
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| CN106044787B (en) * | 2016-08-12 | 2018-06-12 | 乳山市大洋硅胶厂 | A kind of preparation method of aeroge |
| CN110918048A (en) * | 2019-12-19 | 2020-03-27 | 乳山市大洋硅胶厂 | Preparation method of hydrogen-absorbing pressure swing adsorption silica gel |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5401596A (en) * | 1991-10-14 | 1995-03-28 | Stoilov; Georgi T. | Hermetically sealed dry accumulator |
| CN1081608C (en) * | 1996-08-13 | 2002-03-27 | 中国石化金陵石油化工公司 | Silica gel prepn. method capable of regulating its pore structure |
| US6838068B2 (en) * | 2000-06-30 | 2005-01-04 | Mitsubishi Chemical Corporation | Silica gel |
| CN1186254C (en) * | 2001-01-11 | 2005-01-26 | 青岛美高集团有限公司 | macroreticular silica gel and its preparing process |
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2003
- 2003-02-21 CN CN 03111888 patent/CN1207193C/en not_active Expired - Fee Related
- 2003-02-21 CN CNB2005100020909A patent/CN100376480C/en not_active Expired - Fee Related
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| CN100337912C (en) * | 2005-12-23 | 2007-09-19 | 李永兆 | Process for mfg. water resisting type large pore spherical silica gel |
| CN102190306A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Silica microspheres and its preparation method |
| CN102190306B (en) * | 2010-03-03 | 2012-11-14 | 中国石油化工股份有限公司 | Silica microspheres and its preparation method |
| CN102260359A (en) * | 2011-01-06 | 2011-11-30 | 上海海源化工科技有限公司 | Method for preparing chromium silica gel catalyst carrier with high specific surface area and large pore volume |
| CN102260359B (en) * | 2011-01-06 | 2013-09-04 | 上海海源化工科技有限公司 | Method for preparing chromium silica gel catalyst carrier with high specific surface area and large pore volume |
| CN102649090B (en) * | 2011-02-25 | 2014-03-26 | 中国石油化工股份有限公司 | Preparing method of catalyst carrier for preparation of ethylene glycol by oxalate through hydrogenation |
| CN102649090A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Preparing method of catalyst carrier for preparation of ethylene glycol by oxalate through hydrogenation |
| CN102757058B (en) * | 2012-06-12 | 2016-08-17 | 山东辛化硅胶有限公司 | A kind of Type B big pore volume silica gel and preparation method thereof |
| CN102757058A (en) * | 2012-06-12 | 2012-10-31 | 山东辛化硅胶有限公司 | Novel B type large-pore volume silica gel and manufacture method thereof |
| CN103880024A (en) * | 2012-12-21 | 2014-06-25 | 青岛美格斯科技有限公司 | Preparation method of silica gel carrier with large pore volume |
| CN103880024B (en) * | 2012-12-21 | 2015-11-18 | 青岛美格斯科技有限公司 | A kind of preparation method of large pore volume silica-gel carrier |
| CN105195087A (en) * | 2015-10-26 | 2015-12-30 | 王立卓 | Extra-large-aperture silicon dioxide new material and preparation method thereof |
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| CN105819884B (en) * | 2016-03-10 | 2018-10-23 | 青岛海湾集团有限公司 | Water-fast Guanulated gelatinized silica-alumina product and its production method |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1896000A (en) | 2007-01-17 |
| CN100376480C (en) | 2008-03-26 |
| CN1207193C (en) | 2005-06-22 |
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