CN103880024A - Preparation method of silica gel carrier with large pore volume - Google Patents
Preparation method of silica gel carrier with large pore volume Download PDFInfo
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- CN103880024A CN103880024A CN201210563343.XA CN201210563343A CN103880024A CN 103880024 A CN103880024 A CN 103880024A CN 201210563343 A CN201210563343 A CN 201210563343A CN 103880024 A CN103880024 A CN 103880024A
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Abstract
The invention provides a preparation method of a silica gel carrier with a large pore volume, and is used for solving problems of small pore volume and small pore size of existing silica gel carriers. The preparation method of a silica gel carrier with a large pore volume comprises the following steps: uniformly mixing a hydrolysis silicon source, an auxiliary agent and deionized water according to a preset ratio, performing precipitation and filtration to generate a silicon hydrolytic solution to keep in reserve; mixing inorganic acid diluted to a preset concentration with the silicon hydrolytic solution to generate silicic acid sol; adjusting the pH value of the silicic acid sol to generate silicic acid gel; aging the silicic acid gel with water under a preset condition to generate silicic acid gel particles, performing elution and filtration of the silicic acid gel particles to obtain the eluted and filtered silicic acid gel particles; drying and calcining the eluted and filtered silicic acid gel particles under a preset condition to obtain the silica gel carrier with a large pore volume. The silica gel carrier prepared by the preparation method of a silica gel carrier with a large pore volume of the invention has a pore volume of 2.0-3.5 ml/g or more, a bulk specific weight of less than 300 g/L, and a pore size of more than 40 nm.
Description
Technical field
The present invention relates to biological medicine and catalysis technical field, refer to especially a kind of preparation method of large pore volume silica-gel carrier.
Background technology
Silica gel has special pore structure, and large specific surface area and good thermostability are widely used in each industrial circles such as sorbent material, siccative, thickening material, matting agent, battery electron material and support of the catalyst.In recent years, polythene material has become the requisite part of national economy, and obtains swift and violent development, and poly production method has vapor phase process, slurry process and three kinds of production technique of solution method
In gas phase polymerization polyethylene catalysts preparation process, silica gel is widely used as a kind of carrier at present.The catalyzer that utilizes this carrier to make is mainly used in LLDPE(Linear Low-DensityPolyethy – lene, LLDPE) production.The silica-gel carrier using at present, its pore property is: pore volume 1.6ml/g, specific surface area 300 ~ 350m
2/ g, mean particle size 40 ~ 50 μ m.Utilize catalyst activity prepared by this carrier can only reach 3000 ~ 4000gPE/gcat, make so poly production cost high, external current research shows, the catalyst activity that utilizes large pore volume, bigger serface special silica-gel carrier to prepare can reach 6000 ~ 7000gPE/gcat, can make like this production equipment constant in the situation that, make production efficiency increase substantially, production cost is further reduced, the pore property of this carrier is: pore volume 2.4 ~ 2.8ml/g, specific surface area 500 ~ 600m
2/ g, mean particle size 50 ~ 150 μ m.But, this carrier still exists pore volume, aperture less than normal, macromole is difficult for being adsorbed or separating, the shortcoming that specific surface area is less than normal, thereby substituted by macroporous resin product in fields such as part industry, medicine purification and chromatograms, because it has the irreplaceable physical properties of macroporous resin, make its exploitation in some Application Areas and new technologies and materials be subject to certain attention, therefore product of the present invention has special meaning to the development of novel material new technology.
Summary of the invention
The present invention proposes a kind of preparation method of large pore volume silica-gel carrier, has solved silica-gel carrier in prior art and has had pore volume, aperture problem less than normal.
Technical scheme of the present invention is achieved in that
A preparation method for large pore volume silica-gel carrier, comprises the following steps:
Hydrolysis silicon source, auxiliary agent and deionized water are mixed and sedimentation and filtration according to preset ratio, generate silicon hydrating solution for subsequent use;
The mineral acid that is diluted to preset concentration is mixed with described silicon hydrating solution and generates silicic acid sol;
Regulate the pH value of described silicic acid sol to producing silicic acid gel;
Lower to described silicic acid gel, the ageing that adds water generates silicic acid gel grain pre-conditioned, and described silicic acid gel grain is carried out to wash-out filtration, obtains the silicic acid gel grain after wash-out filters;
Under pre-conditioned, the silicic acid gel grain after described wash-out is filtered is dried calcination, obtains large pore volume silica-gel carrier.
Further, described hydrolysis silicon source, auxiliary agent and deionized water are mixed and sedimentation and filtration according to preset ratio, generate silicon hydrating solution step for subsequent use and be specially:
By even according to the mixed in molar ratio of 45～80:0.05～2:20～50 to hydrolysis silicon source, auxiliary agent and deionized water, at 15 DEG C～35 DEG C temperature, be mixed with the solution of 12 ~ 30 degree Beaume, after sedimentation and filtration, generate silicon hydrating solution for subsequent use.
Preferably, described hydrolysis silicon source be in water glass, tetraethoxy, TMOS any one or multiple.
Further, describedly the mineral acid that is diluted to preset concentration mixed to the step that generates silicic acid sol be specially with described silicon hydrating solution:
It is 3.02mol/L ~ 21.38mol/L that mineral acid is diluted to concentration;
It is in the mineral acid of 3.02mol/L ~ 21.38mol/L, to mix to generate silicic acid sol that described silicon hydrating solution is added to described concentration.
Further, described lower to described silicic acid gel, the ageing that adds water generates silicic acid gel grain pre-conditioned, and described silicic acid gel grain is carried out to wash-out filtration, and the step that obtains the silicic acid gel grain after wash-out filters is specially:
At 20 DEG C ~ 90 DEG C temperature to the ageing 2 ~ 48 hours that adds water of described silicic acid gel, adding massfraction is 0.04 ~ 0.23% mineral acid, adding add water described in the regulating pH value of silicic acid gel of ageing of described auxiliary agent is 7 again, continues reaction 8 ~ 24 hours, generates silicic acid gel grain;
Be that under 6.5 ~ 8.0 conditions, wash-out filters by described silicic acid gel grain at pH value, and control that foreign matter content is less than 10ppm, specific conductivity is less than or equal to 50 μ S/cm, obtain the silicic acid gel grain after wash-out filters.
Preferably, described mineral acid be in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, chloric acid any one or multiple.
Preferably, described auxiliary agent be in amino dodecane, urea, ammoniacal liquor, sequestrant, tensio-active agent any one or multiple.
Preferably, the massfraction of the auxiliary agent of the pH value of the described silicic acid gel for the ageing that adds water described in regulating is 0.01 ~ 0.25%.
Further, described under pre-conditioned, the silicic acid gel grain after described wash-out is filtered is dried calcination, and the step that obtains large pore volume silica-gel carrier is specially:
At 100 DEG C ~ 500 DEG C temperature, the silicic acid gel grain after described wash-out is filtered is dried calcination 3 ~ 18 hours, obtains large pore volume silica-gel carrier.
Beneficial effect of the present invention is:
1, the silica-gel carrier that the preparation method of large pore volume silica-gel carrier of the present invention makes, its pore volume can be at 2.0 ~ 3.5ml/g, or larger, and bulk specific gravity is less than 300g/L, and aperture is greater than 40nm.
2, the preparation method of large pore volume silica-gel carrier of the present invention, its raw material is easy to get, with low cost, simple to operate, does not need complicated technique and facility, does not increase extras and drops into, and is easy to quantize to produce.
3, the silica-gel carrier that the preparation method of large pore volume silica-gel carrier of the present invention makes; compared with existing silica-gel carrier; Application Areas is expanded; can replace part macroporous resin, application and the new product development in the fields such as high-end electronics, pottery, high-grade paint, food sanitation, rubber, biological medicine, household chemicals, environment protection, petrochemical complex, new forms of energy battery material, aerospace and military technique are played to the effect can not be substituted.
4, the silica-gel carrier that the preparation method of large pore volume silica-gel carrier of the present invention makes, exceed or identical with the performance of world-class product, can replace the expensive goods of most of dependence on import, and can realize foreign exchange earning, market outlook are wide, can realize higher economic benefit.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the preparation method's of a kind of large pore volume silica-gel carrier of the present invention flow chart of steps.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
As shown in Figure 1, the preparation method of a kind of large pore volume silica-gel carrier of the present invention, comprises the following steps:
Hydrolysis silicon source, auxiliary agent and deionized water are mixed and sedimentation and filtration according to preset ratio, generate silicon hydrating solution for subsequent use;
The mineral acid that is diluted to preset concentration is mixed with described silicon hydrating solution and generates silicic acid sol;
Regulate the pH value of described silicic acid sol to producing silicic acid gel;
Lower to described silicic acid gel, the ageing that adds water generates silicic acid gel grain pre-conditioned, and described silicic acid gel grain is carried out to wash-out filtration, obtains the silicic acid gel grain after wash-out filters;
Under pre-conditioned, the silicic acid gel grain after described wash-out is filtered is dried calcination, obtains large pore volume silica-gel carrier.
The preparation method's of a kind of large pore volume silica-gel carrier of the present invention embodiment is provided below, further to describe:
1, by even according to the mixed in molar ratio of 45～80:0.05～2:20～50 to hydrolysis silicon source, auxiliary agent and deionized water, at 15 DEG C～35 DEG C temperature, be mixed with the solution of 12 ~ 30 degree Beaume, after sedimentation and filtration, generate silicon hydrating solution for subsequent use.Wherein, the mol ratio of described hydrolysis silicon source, auxiliary agent and deionized water can be selected according to actual needs, for example, be hydrolyzed silicon source, auxiliary agent and deionized water according to the mixed in molar ratio of 65:1.05:35; Described temperature can be according to practical situation, and for example difference of four seasons temperature, selects different temperature, as long as in temperature range, for example spring, summer, autumn, winter are selected respectively 18 DEG C, 32 DEG C, 20 DEG C, 15 DEG C; The degree Beaume of described solution can be according to the actual temp of selecting, and means obtain by experiment, and this common practise that is those skilled in the art, no longer repeats at this.
Wherein, preferably, described hydrolysis silicon source be in water glass, tetraethoxy, TMOS any one or multiple, certainly, can select other to can be used as the material in hydrolysis silicon source, the present invention does not limit this.
2, mineral acid being diluted to concentration is 3.02mol/L ~ 21.38mol/L;
It is in the mineral acid of 3.02mol/L ~ 21.38mol/L, to mix to generate silicic acid sol that described silicon hydrating solution is added to described concentration
3, regulate the pH value of described silicic acid sol to producing silicic acid gel.
4, at 20 DEG C ~ 90 DEG C temperature to the ageing 2 ~ 48 hours that adds water of described silicic acid gel, adding massfraction is 0.04 ~ 0.23% mineral acid, adding add water described in the regulating pH value of silicic acid gel of ageing of described auxiliary agent is 7 again, continues reaction 8 ~ 24 hours, generates silicic acid gel grain;
Be that under 6.5 ~ 8.0 conditions, wash-out filters by described silicic acid gel grain at pH value, and control that foreign matter content is less than 10ppm, specific conductivity is less than or equal to 50 μ S/cm, obtain the silicic acid gel grain after wash-out filters.
Wherein, preferably, the massfraction of auxiliary agent of pH value for the silicic acid gel that regulates the ageing that adds water described in this step is 0.01 ~ 0.25%.
Wherein, described impurity is specially metal-salt or other material.
5,, at 100 DEG C ~ 500 DEG C temperature, the silicic acid gel grain after described wash-out is filtered is dried calcination 3 ~ 18 hours, obtains large pore volume silica-gel carrier.
Wherein, preferably, described mineral acid be in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, chloric acid any one or multiple, certainly, can select other mineral acid, the present invention does not limit this.
Wherein, preferably, described auxiliary agent be in amino dodecane, urea, ammoniacal liquor, sequestrant, tensio-active agent any one or multiple, certainly, can select other similar auxiliary agent, the present invention does not limit this.Wherein, sequestrant can be Acetyl Acetone, dithizone etc., and tensio-active agent can be non-ionic type alkenyl sulphonate etc.
The preparation method of large pore volume silica-gel carrier of the present invention, advantage is:
1, the silica-gel carrier that the preparation method of large pore volume silica-gel carrier of the present invention makes, its pore volume can be at 2.0 ~ 3.5ml/g, or larger, and bulk specific gravity is less than 300g/L, and aperture is greater than 40nm.
2, the preparation method of large pore volume silica-gel carrier of the present invention, its raw material is easy to get, with low cost, simple to operate, does not need complicated technique and facility, does not increase extras and drops into, and is easy to quantize to produce.
3, the silica-gel carrier that the preparation method of large pore volume silica-gel carrier of the present invention makes; compared with existing silica-gel carrier; Application Areas is expanded; can replace part macroporous resin, application and the new product development in the fields such as high-end electronics, pottery, high-grade paint, food sanitation, rubber, biological medicine, household chemicals, environment protection, petrochemical complex, new forms of energy battery material, aerospace and military technique are played to the effect can not be substituted.
4, the silica-gel carrier that the preparation method of large pore volume silica-gel carrier of the present invention makes, exceed or identical with the performance of world-class product, can replace the expensive goods of most of dependence on import, and can realize foreign exchange earning, market outlook are wide, can realize higher economic benefit.
5, the silica-gel carrier that the preparation method of large pore volume silica-gel carrier of the present invention makes, the easier washing and filtering in wide aperture, saves the energy, and protection of the environment, has further reduced cost.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a preparation method for large pore volume silica-gel carrier, is characterized in that, comprises the following steps:
Hydrolysis silicon source, auxiliary agent and deionized water are mixed and sedimentation and filtration according to preset ratio, generate silicon hydrating solution for subsequent use;
The mineral acid that is diluted to preset concentration is mixed with described silicon hydrating solution and generates silicic acid sol;
Regulate the pH value of described silicic acid sol to producing silicic acid gel;
Lower to described silicic acid gel, the ageing that adds water generates silicic acid gel grain pre-conditioned, and described silicic acid gel grain is carried out to wash-out filtration, obtains the silicic acid gel grain after wash-out filters;
Under pre-conditioned, the silicic acid gel grain after described wash-out is filtered is dried calcination, obtains large pore volume silica-gel carrier.
2. preparation method according to claim 1, is characterized in that, described hydrolysis silicon source, auxiliary agent and deionized water is mixed and sedimentation and filtration according to preset ratio, generates silicon hydrating solution step for subsequent use and is specially:
By even according to the mixed in molar ratio of 45～80:0.05～2:20～50 to hydrolysis silicon source, auxiliary agent and deionized water, at 15 DEG C～35 DEG C temperature, be mixed with the solution of 12 ~ 30 degree Beaume, after sedimentation and filtration, generate silicon hydrating solution for subsequent use.
3. preparation method according to claim 2, is characterized in that, described hydrolysis silicon source be in water glass, tetraethoxy, TMOS any one or multiple.
4. preparation method according to claim 3, is characterized in that, describedly the mineral acid that is diluted to preset concentration is mixed to the step that generates silicic acid sol is specially with described silicon hydrating solution:
It is 3.02mol/L ~ 21.38mol/L that mineral acid is diluted to concentration;
It is in the mineral acid of 3.02mol/L ~ 21.38mol/L, to mix to generate silicic acid sol that described silicon hydrating solution is added to described concentration.
5. preparation method according to claim 4, it is characterized in that, described lower to described silicic acid gel, the ageing that adds water generates silicic acid gel grain pre-conditioned, and described silicic acid gel grain is carried out to wash-out filtration, and the step that obtains the silicic acid gel grain after wash-out filters is specially:
At 20 DEG C ~ 90 DEG C temperature to the ageing 2 ~ 48 hours that adds water of described silicic acid gel, adding massfraction is 0.04 ~ 0.23% mineral acid, adding add water described in the regulating pH value of silicic acid gel of ageing of described auxiliary agent is 7 again, continues reaction 8 ~ 24 hours, generates silicic acid gel grain;
Be that under 6.5 ~ 8.0 conditions, wash-out filters by described silicic acid gel grain at pH value, and control that foreign matter content is less than 10ppm, specific conductivity is less than or equal to 50 μ S/cm, obtain the silicic acid gel grain after wash-out filters.
6. preparation method according to claim 5, is characterized in that, described mineral acid be in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, chloric acid any one or multiple.
7. preparation method according to claim 6, is characterized in that, described auxiliary agent be in amino dodecane, urea, ammoniacal liquor, sequestrant, tensio-active agent any one or multiple.
8. preparation method according to claim 7, is characterized in that, the massfraction of the auxiliary agent of the pH value of the described silicic acid gel for the ageing that adds water described in regulating is 0.01 ~ 0.25%.
9. preparation method according to claim 8, is characterized in that, described under pre-conditioned, and the silicic acid gel grain after described wash-out is filtered is dried calcination, and the step that obtains large pore volume silica-gel carrier is specially:
At 100 DEG C ~ 500 DEG C temperature, the silicic acid gel grain after described wash-out is filtered is dried calcination 3 ~ 18 hours, obtains large pore volume silica-gel carrier.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044787A (en) * | 2016-08-12 | 2016-10-26 | 乳山市大洋硅胶厂 | Preparation method for aerogel |
| CN110540210A (en) * | 2019-09-12 | 2019-12-06 | 青岛美高集团有限公司 | Low-energy-consumption large-pore-volume silica gel and production method thereof |
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| US5231066A (en) * | 1991-09-11 | 1993-07-27 | Quantum Chemical Corporation | Bimodal silica gel, its preparation and use as a catalyst support |
| GB2269377A (en) * | 1992-08-07 | 1994-02-09 | British Petroleum Co Plc | Silica gel and process for making it from polysilicic acid |
| 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 |
| CN1522958A (en) * | 2003-02-21 | 2004-08-25 | 青岛海洋化工有限公司 | Process for manufacturing macroreticular spherical silica gel |
| CN102745698A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
-
2012
- 2012-12-21 CN CN201210563343.XA patent/CN103880024B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231066A (en) * | 1991-09-11 | 1993-07-27 | Quantum Chemical Corporation | Bimodal silica gel, its preparation and use as a catalyst support |
| GB2269377A (en) * | 1992-08-07 | 1994-02-09 | British Petroleum Co Plc | Silica gel and process for making it from polysilicic acid |
| 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 |
| CN1522958A (en) * | 2003-02-21 | 2004-08-25 | 青岛海洋化工有限公司 | Process for manufacturing macroreticular spherical silica gel |
| CN102745698A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044787A (en) * | 2016-08-12 | 2016-10-26 | 乳山市大洋硅胶厂 | Preparation method for aerogel |
| CN110540210A (en) * | 2019-09-12 | 2019-12-06 | 青岛美高集团有限公司 | Low-energy-consumption large-pore-volume silica gel and production method thereof |
| CN110540210B (en) * | 2019-09-12 | 2022-12-27 | 青岛美高集团有限公司 | Low-energy-consumption large-pore-volume silica gel and production method thereof |
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