CN104445223B - Preparation method of large-aperture carrier silica gel - Google Patents
Preparation method of large-aperture carrier silica gel Download PDFInfo
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- CN104445223B CN104445223B CN201310416376.6A CN201310416376A CN104445223B CN 104445223 B CN104445223 B CN 104445223B CN 201310416376 A CN201310416376 A CN 201310416376A CN 104445223 B CN104445223 B CN 104445223B
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- silica gel
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- organic acid
- acid anhydride
- carrier silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000000741 silica gel Substances 0.000 title claims abstract description 54
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000007524 organic acids Chemical class 0.000 claims abstract description 23
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- -1 organic acids acid anhydride Chemical class 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 235000005985 organic acids Nutrition 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229960001866 silicon dioxide Drugs 0.000 description 42
- 239000000243 solution Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 11
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 235000019795 sodium metasilicate Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 229940093915 gynecological organic acid Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000937378 Everettia interior Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- PKHMTIRCAFTBDS-UHFFFAOYSA-N hexanoyl hexanoate Chemical compound CCCCCC(=O)OC(=O)CCCCC PKHMTIRCAFTBDS-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method of large-aperture carrier silica gel. Silicate and organic acid anhydride are used as reaction raw materials, the organic acid anhydride is micromolecule liquid organic acid anhydride formed by intermolecular dehydration of organic acid with carboxyl, and the preferable carbon number is C2‑C6The liquid organic acid anhydride is hydrolyzed to obtain the corresponding organic acid which has water solubility. The organic acid anhydride not only provides electrolyte for reaction after hydrolysis, but also can accelerate the dehydration condensation effect among molecules of orthosilicic acid under the water absorption effect in the hydrolysis process, promote the colloidal particle growth, enlarge the aperture of the carrier silica gel, and directly obtain the large-aperture silica gel for the polyolefin carrier.
Description
Technical field
The present invention relates to the preparation method of a kind of large aperture silica gel, be specifically related to sol-gal process large aperture carrier silicon
The preparation method of glue, product is particularly suitable for doing the carrier of polyolefin catalyst.
Background technology
Silica gel is particularly suitable for doing the carrier of various catalyst because having higher specific surface area.Polyolefin catalyst
Require that there is big aperture, high pore volume and specific surface area, preferable mechanical strength by carrier silica gel, exist
Ziegler-Natta catalyst, Cr series catalysts and metallocene catalyst obtain extensively application.In prior art,
Carrier silica gel many employings sol-gel process, prepares for raw material reaction with silicate, inorganic acid, passes through feed postition
Selection or the control of reaction condition, it is also possible to obtain particular characteristic silica gel.
It is known that the pore-size distribution of carrier can directly affect reactant and the product mass transfer at catalyst particles intragranular, i.e.
Interior diffusion.Large aperture silica gel not only contributes to the more uniform load in activated centre in aperture, Er Qie
Polymerization process is conducive to alkene carry out polymerisation in silica gel duct.Thus, prior art discloses many
Plant the method obtaining macropore carrier silica gel.ZL01100425.8 proposes with sodium metasilicate and dilute sulfuric acid as raw material, is passing
Increase steam on the basis of system silica gel preparation method to process, soak salt treatment operation, i.e. can get macro porous silica gel.Institute
The silica gel average pore size 10～60nm stated, average specific surface area 250～350m2/g, average pore volume 1.00～
2.00ml/g.ZL02159355.8 discloses and particle silica gel less for the aperture produced by sol method is placed in alkali
Property solution in, be heat-treated 1 hour～5 days at 50～200 DEG C, then drying, roasting prepare macro porous silica gel.Institute
Its BET average pore size of the macro porous silica gel stated is 10～30nm, BET specific surface area is 150～350m2/g, pore volume
It is 0.9～1.1ml/g.ZL200510002090.9 discloses the manufacture method of a kind of macro porous silica gel, by sodium metasilicate
Solution and dilute sulfuric acid are through gradual reaction and polycondensation generates gel particles, this gel particles warp again through the injection of this prilling granulator
Acid bubble, washing, aging, quadratic acid bubble, it is dried and processes, obtain large pore spherical silica gel product.ZL96122871.7
Propose alkaline silicate solution and inorganic acid are made instantaneous mixing so that it is form colloidal sol, then the colloidal sol spray that will be formed
Mist, in atmosphere, forms colloid, is consequently formed spherical silica-gel.It is characterized in that in preparation method, add
Water-fast, average grain diameter is consolidated at aluminum oxide, silica, titanium oxide or the zirconium oxide etc. of 0.1～15 μm
Body particle is as macropore accelerator, among at least one solution being scattered in silicate solutions or inorganic acid.
ZL02127599.8 be silica gel is placed in alkaline solution carry out being heat-treated at 50～200 DEG C 1 hour to 5 days, obtain
Obtain macro porous silica gel.CN200610129489.8 discloses by the strict material concentration controlled in acidization and joins
Ratio, is 2～the method producing gas phase ethene polymerization catalyst macro porous silica gel carrier 4 times at pH.Additionally,
CN102794202A discloses the preparation method of the catalyst carrier silicone of a kind of aperture controllable, at sodium metasilicate and
Sulfuric acid solution is separately added into PDDA as chemical additives, through synthetic reaction granulation
Become gel particles.Similarly, ZL96117058.1 uses and prepared water-setting silica gel is placed in aqueous surfactant solution
In, soaking 4～48 hours, surfactant as aging medium, obtains adjustable after aging, dry, roasting
The silica gel of knothole structure.Document " the reaming progress of catalyst carrier silicone " (Wang Hai etc., " Gansu chemical industry ",
1st phase in 2006, P18-21,27) in, the expanding method to silica gel has been also carried out more comprehensive summary.
In a word, in prior art, various expanding methods still suffer from some problems.As hydro-thermal reaming method makes silica gel machinery strong
Degree susceptible, produces Fragmentation Phenomena；The alkaline solution reamings such as ammoniacal liquor, mainly regulate gel by pH value
Aperture, but the expanded scope in aperture is very limited, and along with being continuously added of ammonia, the physicochemical property of silica gel there will be fall
Low, aperture can diminish on the contrary.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of large aperture carrier silica gel.
Technical solutions according to the invention are the methods preparing silica gel for raw material with silicate and organic acid anhydride.Invention
People is found by research, is not merely provided for the electrolyte of reaction, in its hydrolytic process after organic acid anhydride hydrolysis
Water sorption can also accelerate the intermolecular dehydrating condensation effect of orthosilicic acid, promote growth of colloidal particles, expand and carry
The aperture of body silica gel.
Specifically, the preparation method of large aperture of the present invention carrier silica gel includes:
1) at a temperature of 20～50 DEG C, the silicate solutions that concentration is 0.1～2.0mol/L is more than 97% with concentration
Organic acid anhydride hybrid reaction, until system is instantaneous be completely converted into gel time, add deionized water, constant temperature 20～
60 minutes；
2) be warming up to 50～80 DEG C aging 5～10 hours, add acid or acid anhydrides adjust system pH 2.0～
4.0, by filtering, wash, be dried, roasting obtains product.
Organic acid anhydride of the present invention is the little molecule that the organic acid with a carboxyl is formed through intermolecular dehydration
Liquid organic acids acid anhydride, preferably carbon number is at C2-C6Liquid organic acids acid anhydride, hydrolysis obtains corresponding organic acid and should have
Water-soluble.It is chosen in particular from acetic anhydride, propionic andydride or butyric anhydride one therein, preferably acetic anhydride.
The described cation in silicate is selected from alkali metal ion, preferably sodium ion.
Described acid is selected from dilute sulfuric acid or watery hydrochloric acid, and acid anhydrides is the carbon number liquid organic acids acid anhydride at C2-C6.
The inorganic acid that the present invention uses organic acid anhydride to substitute prior art is raw material, and acid anhydrides is held concurrently and played the work of expanding agent
With, wide-aperture carrier silica gel can be directly obtained, and preparation method is simply easy to promote.
Detailed description of the invention
Test condition
Aperture, pore volume, specific surface: use GB/T19587-2004 test, Kang Ta company of U.S. NOVA2000e ratio
Surface void instrument is analyzed.
Embodiment 1
Adding 300ml concentration in reactor is the sodium silicate solution of 0.5mol/L, starts stirring, is warming up to 40 DEG C and delays
The slow addition concentration acetic anhydride more than 97%, stops when mother liquor sodium metasilicate is completely converted into gel adding acid anhydrides,
Add 200ml deionized water constant temperature 20min；It is warming up to 70 DEG C of aging 6h, adds the concentration acetic acid more than 97%
Acid anhydride adjusts pH value and is down to 3.5；After being washed with distilled water to neutrality, dry 7 hours at 120 DEG C, in Muffle furnace
According to 200 DEG C-1 hour, 400 DEG C-1 hour, 600 DEG C of gradient roasting conditions of-2 hours finally obtain the present invention's
Large aperture carrier silica gel, silica gel test result is shown in Table 1.
Embodiment 2
Adding 300ml concentration in reactor is the sodium silicate solution of 1mol/L, and other prepares the step of silica gel with real
Executing example 1, silica gel test result is shown in Table 1.
Embodiment 3
Acetic anhydride is changed into propionic andydride, and other preparation conditions are shown in Table 1 with embodiment 1, silica gel test result.
Embodiment 4
Acetic anhydride is changed into butyric anhydride, and other preparation conditions are shown in Table 1 with embodiment 1, silica gel test result.
Embodiment 5
Acetic anhydride is changed into caproic anhydride, and other preparation conditions are shown in Table 1 with embodiment 1, silica gel test result.
Embodiment 6
Adding 300ml concentration in reactor is the sodium silicate solution of 0.5mol/L, starts stirring, is warming up to 40 DEG C,
It is slowly added to the concentration acetic anhydride more than 97%, stops when mother liquor sodium metasilicate is completely converted into gel adding acid anhydrides,
Add 200ml deionized water constant temperature 20min；Being warming up to 70 DEG C of aging 6h, adding concentration is the dilute of 0.5mol/L
Sulfuric acid solution is until pH value is down to 3.5, and subsequent step is shown in Table 1 with embodiment 1, silica gel test result.
Comparative example 1
Acetic anhydride is changed into the dilute sulfuric acid that concentration is 0.5mol/L, the other the same as in Example 1, and silica gel test result is shown in
Table 1.
Comparative example 2:
Acetic anhydride is changed into glacial acetic acid, the other the same as in Example 1, and silica gel test result is shown in Table 1.
The physical property of table 1 embodiment/comparative example silica gel product
As can be seen from the above results, the pore substantially ratio using organic acid anhydride to prepare uses traditional inorganic acid
The pore prepared is big, and pore size is the most adjustable.Meanwhile, pore volume and specific surface are complete
Disclosure satisfy that the requirement preparing polyolefin catalyst as carrier.
Claims (8)
1. the preparation method of a large aperture carrier silica gel, it is characterised in that with silicate and organic acid anhydride as raw material,
Concrete preparation method includes:
1) at a temperature of 20～50 DEG C, the silicate solutions that concentration is 0.1～2.0mol/L is more than 97% with concentration
Organic acid anhydride hybrid reaction, until system is instantaneous be completely converted into gel time, add deionized water, constant temperature 20～
60 minutes；
2) be warming up to 50～80 DEG C aging 5～10 hours, add acid or acid anhydrides adjust system pH 2.0～
4.0, by filtering, wash, being dried to obtain product.
The preparation method of carrier silica gel the most according to claim 1, it is characterised in that described organic acid anhydride choosing
Carry the little molecule liquid organic acids acid anhydride that the organic acid of a carboxyl is formed through intermolecular dehydration.
The preparation method of carrier silica gel the most according to claim 2, it is characterised in that organic acid anhydride is that carbon number exists
C2-C6Liquid organic acids acid anhydride, hydrolysis obtains corresponding organic acid and has water solubility.
The preparation method of carrier silica gel the most according to claim 3, it is characterised in that organic acid anhydride be acetic anhydride,
Propionic andydride or butyric anhydride one therein.
The preparation method of carrier silica gel the most according to claim 4, it is characterised in that organic acid anhydride is acetic anhydride.
The preparation method of carrier silica gel the most according to claim 1, it is characterised in that in described silicate
Cation is alkali metal ion.
The preparation method of carrier silica gel the most according to claim 6, it is characterised in that in described silicate
Cation is sodium ion.
8. according to the preparation method of the described carrier silica gel of one of claim 1 to 7, it is characterised in that described acid is
Dilute sulfuric acid or watery hydrochloric acid, acid anhydrides is that carbon number is at C2-C6Liquid organic acids acid anhydride.
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| CN201310416376.6A CN104445223B (en) | 2013-09-13 | 2013-09-13 | Preparation method of large-aperture carrier silica gel |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079526A (en) * | 2009-12-01 | 2011-06-01 | 中国石油天然气股份有限公司 | Preparation process of high-purity macroporous silica gel |
| CN102515172A (en) * | 2011-11-28 | 2012-06-27 | 上海交通大学 | Preparation method of macroporous silica material |
| 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 |
| CN103159220A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of macroporous silica gel |
-
2013
- 2013-09-13 CN CN201310416376.6A patent/CN104445223B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079526A (en) * | 2009-12-01 | 2011-06-01 | 中国石油天然气股份有限公司 | Preparation process of high-purity macroporous 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 |
| CN102515172A (en) * | 2011-11-28 | 2012-06-27 | 上海交通大学 | Preparation method of macroporous silica material |
| CN103159220A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of macroporous silica gel |
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