CN105396569A - Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier - Google Patents
Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier Download PDFInfo
- Publication number
- CN105396569A CN105396569A CN201510943461.7A CN201510943461A CN105396569A CN 105396569 A CN105396569 A CN 105396569A CN 201510943461 A CN201510943461 A CN 201510943461A CN 105396569 A CN105396569 A CN 105396569A
- Authority
- CN
- China
- Prior art keywords
- silica
- average diameter
- roasting
- preparation
- pore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011148 porous material Substances 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 239000011859 microparticle Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000003595 mist Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 16
- 239000008187 granular material Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 abstract description 22
- 230000003179 granulation Effects 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000005507 spraying Methods 0.000 abstract description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 2
- 241000872198 Serjania polyphylla Species 0.000 abstract 1
- 239000006229 carbon black Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Silicon Compounds (AREA)
Abstract
A provided preparation method for an antiwear large-pore-volume microspherical silicon dioxide carrier comprises the following steps: roasting precipitation-process silicon dioxide power or white carbon black with the specific surface area of 250-600 m<2>/g at 730-760 DEG C, so as to reduce the specific surface area to 100-220 m<2>/g, adding water and uniformly mixing, performing grinding dispersing until the microparticle average diameter is 2-5 mu m, adding an active carbon emulsion and silica sol, uniformly mixing, performing spraying granulation, roasting at 650-720 DEG C, so as to prepare the microspherical silicon dioxide carrier with the average diameter of 50-250 mu m, the specific surface area of 80-200 m<2>/g, the pore volume of 0.7-1.1 mL/g and the average pore diameter of 20-40 nm. The microspherical silicon dioxide carrier possesses relatively large pore volume and appropriate pore structure, relatively high mechanical strength and wear resistance and impact resistance, and is applicable to further load an active composition for preparing a fluidized-bed catalyst.
Description
Technical field
The invention belongs to catalyst field, relate to a kind of preparation method of microspheroidal silica supports, its She of You is Ji the preparation method of the wear-resisting macropore volume microspheroidal silica supports of ー kind.
Background technology
Catalyst is except having suitable pore structure; also to have higher mechanical strength and wearability; especially in fluid bed; solid phase reaction raw material in catalyst particles intergranular, catalyst granules and reactor wall, catalyst granules and fluid bed or between product; can occur to rub frequently, collide; the broken particle formed can make fluidized-bed layer expand, and the trickleer powder formed such as the part of below 10-15um is very easily blown off fluid bed, has substantially scrapped.
First prepare carrier, more impregnated activated component, be the most frequently used method for preparing catalyst, the pore structure of catalyst obtained by this method, mechanical strength and wearability, give primarily of carrier.Wherein, the catalyst be made up of silica supports load active component, has and applies more widely, is particularly suited for the reaction under acid condition, such as prepares vinyl acetate by preparing trichlorosilane from silicon tetrachloride through hydrogenation, acetic acid and ethylene oxidation reactions.First prepare silica composition and active component mixture semi-finished product by coprecipitation, then through sintering, shaping prepared catalyst, its wearability is usually lower, is unsuitable for the micro-spherical catalyst making fluid bed.
But preparation has the microspheroidal silica supports of appropriate bore structure, mechanical strength and wearability, and be a technical barrier of this area, reason is that silica material is as precipitated silica, fumed silica, and usual sintering character is poor; Make binding agent with Ludox, mechanical strength and the wearability of silica supports can be improved, but limited use, even if process as hydrothermal treatment consists through recrystallization, the wearability of carrier still can not significantly improve again.Make binding agent with aluminium oxide, calcium oxide, kaolin etc., also can improve mechanical strength and wearability, but in acid condition, not acidproof one-tenth branch contained by binding agent suffers erosion, the mechanical strength of carrier and wearability can be reduced gradually.
Summary of the invention
For above technological deficiency, the invention provides a kind of preparation method of wear-resisting macropore volume microspheroidal silica supports, prepared microspheroidal silica supports, not only there is comparatively macropore volume, also there is higher mechanical strength and wearability, resistance to impact, be applicable to further load active component, for the preparation of the catalyst of fluid bed.
Technical scheme of the present invention is:
A preparation method for wear-resisting macropore volume microspheroidal silica supports, comprises the following steps:
A, by specific area 250-600m
2the precipitated silica powder of/g or white carbon, at 730-760 DEG C of roasting 2-4hr, make its specific area be reduced to 100-220m
2/ g, obtained roasting silicon dioxide powder;
B, in mass parts, water 300-500 part, roasting silicon dioxide powder 100 parts, mixing, is ground to average diameter 2-5um with grinding distribution equipment by silica micro-particle, obtained dispersion liquid;
C, by the powdered activated carbon 10-20 mass parts of ash content≤1.0%, add water 100-150 part, process with grinding distribution equipment, make the 0.3-0.5 of microparticle average diameter in the average diameter of active carbon microparticle silica dispersions obtained by step B doubly, obtained active carbon emulsion;
D, active carbon emulsion obtained by silica dispersions, step C obtained by step B to be mixed, add Ludox 50-150 part, mix, obtained mixed slurry; SiO introduced by Ludox
2amount be the total SiO of carrier
2the 15-25% of amount; The particle median diameter of Ludox is 10-20nm;
E, mixed slurry are at 180-250 DEG C of mist projection granulating, and pelletizing 650-720 DEG C of roasting 2-4hr, obtains the microspheroidal silica supports of average diameter 50-250um of the present invention, specific area 80-200m
2/ g, pore volume 0.7-1.1ml/g, average pore diameter 20-40nm.
Wherein, in steps A, preferably through 150-250 DEG C of spray-dired precipitated silica, its granule interior structure is relatively tight, the microparticle of obtained roasting silicon dioxide powder granule interior, namely the silica dioxide granule intensity in dispersion liquid obtained by step B is relatively high, thus makes obtained silica supports have better intensity, wearability, resistance to impact.
Wherein, in step B, preferably that silica dioxide granule is levigate, to the average diameter 3um of silica micro-particle.
Wherein, the grinding distribution method of silica in dispersion liquid in step B, the grinding distribution method of active carbon in step C emulsion, be colloid milling or homogenizer method, wherein the grinding distribution effect of homogenizer method is best, fastest.
Wherein, in step D, in wherein said Ludox, silica quality concentration is 20%-40%.
Wherein, in step C, described powdered activated carbon comprises coal mass active carbon through pressurization alkali treatment, pressurization pickling two step chemical deliming or wood activated charcoal, the 0.3-0.5 active carbon microparticle doubly of microparticle average diameter in average diameter silica dispersions obtained by step B, play pore-creating effect in the carrier, improve the pore volume of carrier, especially the volume of macropore.
Wherein, in step e, the preferred 690-720 DEG C of temperature of pelletizing roasting, higher intensity, wearability, the resistance to impact that reach to make gained silica supports.
Wherein, in steps A, preferably adopt Na
2the precipitated silica powder of O≤0.30% or white carbon, to reduce carrier erosion suffered under highly acid application conditions, and maintain its intensity, wearability, resistance to impact.
Spray drying temperature in the stock preparation process of precipitated silica described in steps A, the mist projection granulating temperature of mixed slurry in step e, for adopted representative temperature condition, because dehydration institute calorific requirement is provided by hot blast, there is the larger temperature difference in hot blast inlet/outlet and device interior.
Macropore volume microspheroidal silica supports prepared by the present invention, has the following advantages:
In a, steps A, precipitated silica powder or white carbon are at 730-760 DEG C of roasting 2-4hr, and its specific area is reduced to 100-200m
2/ g, illustrates that granule interior there occurs significant sintering process, and the intensity of particle, wearability, resistance to impact can be greatly increased, thus improves intensity and wearability, the resistance to impact of carrier;
In b, step B, dispersion grinding is 2-5um to the average diameter of silica micro-particle, this is the key improving carrier mechanical strength, wearability, resistance to impact, after experienced by violent process of lapping, obtain the intensity of particle, wearability, resistance to impact improve further than the larger particles before grinding, thus further increase intensity and wearability, the resistance to impact of carrier;
In c, step C, the content of ashes of described powdered activated carbon is lower, and mainly SiO
2, thus while playing pore-creating effect, improving pore volume, substantially can not reduce the acid-fast ability of carrier;
D, step D, in the mixed slurry of E, because the internal pore volume of silica micro-particle is less much than the volume of an intergranular water or slurries, so the micelle of Ludox, the overwhelming majority is dispersed in the water between silica micro-particle, in the pelletizing microballoon that the mist projection granulating of step D is prepared fast, the overwhelming majority is still dispersed between silica micro-particle, thus, good bonding effect is served in the roasting process of step e, carrier is made to reach higher mechanical strength and wearability, resistance to impact, spherical shape makes the wearability of carrier, resistance to impact is better,
E, Ludox used, its micelle composition is between silica and silicic acid, crystallization is insufficient, inner, surperficial defect is many, average diameter only 10 arrives 20nm, and active high, sintering character is good, the roasting of about 650-720 DEG C temperature conditions, makes carrier have higher mechanical strength and wearability, resistance to impact;
F, active carbon emulsion are introduced active carbon microparticle and are filled between silica micro-particle, burn completely after aerobic conditions roasting, play pore-creating effect, improve the pore volume of carrier, especially the volume of macropore; Then pore-creating effect is little lower than 0.3 times of microparticle average diameter in silica dispersions for the average diameter of active carbon microparticle, higher than 0.5 times then wearability reduce;
In g, carrier substantially containing the impurity beyond silica as aluminium oxide, acid and alkali material is as the erosion of HCl, and pore structure in acid condition can keep stable, and service life is longer;
H, carrier of the present invention, be provided with larger pore volume and higher mechanical strength, wearability, resistance to impact, acid resistance simultaneously; Obtained catalyst after impregnated activated component, for the fluidized-bed reaction under acid condition, catalytic perfomance is stablized, and catalyst granules is not easily broken, not easily efflorescence, and consumption is low.
Detailed description of the invention
First carry out following Feedstock treating:
(1) by 3500g precipitated silica A (250 DEG C of spraying dry, moisture 6%, specific area 370m
2/ g, average diameter of particles 40um, Na
2o0.20%) at 740 DEG C of roasting 3hr, its specific area is reduced to 195m
2/ g, is numbered roasting silicon dioxide powder A;
(2) by 2300g precipitated silica powder B (SiO
2content 99%, specific area 263m
2/ g, Na
2o0.26%) at 750 DEG C of roasting 3hr, its specific area is reduced to 162m
2/ g, is numbered roasting silicon dioxide powder B;
(3) by 3500g precipitated silica C (190 DEG C of spraying dry, moisture 8%, specific area 550m
2/ g, average diameter of particles 25um, Na
2o0.14%) at 760 DEG C of roasting 2hr, its specific area is reduced to 126m
2/ g, is numbered roasting silicon dioxide powder C;
(4) by the powdery coal mass active carbon through pressurization alkali treatment, pressurization pickling two step chemical deliming of 2000g ash content 0.8%, add water 18000g, process with grinding distribution equipment, make the average diameter 1.5um of active carbon microparticle, obtained active carbon emulsion M, its quality of activated carbon concentration 10%.
(5) by powdery coal mass active carbon 250g used in (4), add water 2250g, stirs evenly, and uses homogenizer process, makes the average diameter 5um of active carbon microparticle, obtained active carbon emulsion L, its quality of activated carbon concentration 10%.
(6) by powdery coal mass active carbon 250g used in (4), add water 2250g, stirs evenly, and uses homogenizer process, makes the average diameter 0.5um of active carbon microparticle, obtained active carbon emulsion N, its quality of activated carbon concentration 10%.
Embodiment 1
Get 1000g roasting silicon dioxide powder A, add in agitator tank, add 3000g deionized water, open stirring to pulp, after being uniformly dispersed, with homogenizer grinding distribution to average diameter of particles 5um, add 2000g active carbon emulsion M (containing active carbon 200g, the average diameter 1.5um of active carbon microparticle), stir after 10 minutes and mix, add 600g Ludox D (SiO mass concentration 30%, Na
2o0.06%, particle median diameter 10nm), stir after 10 minutes and mix, pump into the atomizer comminutor being preheating to 200 DEG C of operating temperatures and carry out granulation, the rotating speed of adjustment feed pump and centrifuge, make gained micro mist average diameter 230um and sphericity reaches better level, within 30 minutes, complete granulation, gained granulation micro mist intensity is better; Get half 680 DEG C of roasting 3hr under aerobic conditions of granulation micro mist, obtain macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 210um, sphericity is better, and intensity is better; Specific area 175m
2/ g, pore volume 0.93ml/g, average pore diameter 23nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 2
By second half of granulation micro mist in embodiment 1 at 720 DEG C of roasting 3hr, obtain macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 213um, sphericity is better, and intensity is better; Specific area 170m
2/ g, pore volume 0.90ml/g, average pore diameter 22nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 3
Get 1000g roasting silicon dioxide powder B, add in agitator tank, add 3000g deionized water, open stirring to pulp, after being uniformly dispersed, with homogenizer grinding distribution to average diameter of particles 5um, add 2500g active carbon emulsion M (containing active carbon 250g, the average diameter 1.5um of active carbon microparticle), stir after 10 minutes and mix, add 1200g Ludox E (silica quality concentration 20%, Na
2o0.10%, particle median diameter 20nm), stir after 10 minutes and mix, pump into the atomizer comminutor being preheating to 240 DEG C of operating temperatures and carry out granulation, the rotating speed of adjustment feed pump and centrifuge, make gained micro mist average diameter 230um and sphericity reaches better level, within 30 minutes, complete granulation, gained granulation micro mist intensity is better; Get half 680 DEG C of roasting 3hr under aerobic conditions of granulation micro mist, obtain macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 212um, sphericity is better, and intensity is better; Specific area 145m
2/ g, pore volume 1.09ml/g, average pore diameter 36nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 4
By second half of granulation micro mist in embodiment 3 at 710 DEG C of roasting 2hr, obtain macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 206um, sphericity is better, and intensity is better; Specific area 140m
2/ g, pore volume 1.05ml/g, average pore diameter 35nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 5
Get 1000g roasting silicon dioxide powder C, add in agitator tank, add 3000g deionized water, open stirring to pulp, after being uniformly dispersed, with homogenizer grinding distribution to average diameter of particles 5um, add 1500g active carbon emulsion M (containing active carbon 150g, the average diameter 1.5um of active carbon microparticle), stir after 10 minutes and mix, add 900g Ludox E (silica quality concentration 20%, Na
2o0.10%, particle median diameter 20nm), stir after 10 minutes and mix, pump into the atomizer comminutor being preheating to 200 DEG C of operating temperatures and carry out granulation, the rotating speed of adjustment feed pump and centrifuge, make gained micro mist average diameter 230um and sphericity reaches better level, within 30 minutes, complete granulation, gained granulation micro mist intensity is better; The half of getting granulation micro mist, at 680 DEG C of roasting 3hr, obtains macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 215um, sphericity is better, and intensity is better; Specific area 106m
2/ g, pore volume 0.73ml/g, average pore diameter 33nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 6
By second half of granulation micro mist in embodiment 5 at 720 DEG C of roasting 3hr.Gained carrier surveys average diameter 210um, and sphericity is better, and intensity is better; Specific area 100m
2/ g, pore volume 0.71ml/g, average pore diameter 32nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 7
Basic with embodiment 3, difference is with homogenizer grinding distribution liquid to average diameter of particles 3um, obtained macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 208um, sphericity is better, and intensity is better; Specific area 148m
2/ g, pore volume 1.10ml/g, average pore diameter 32nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 8
Basic with embodiment 5, difference is with homogenizer grinding distribution liquid to average diameter of particles 3um, obtained macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 212um, sphericity is better, and intensity is better; Specific area 112m
2/ g, pore volume 0.76ml/g, average pore diameter 30nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 9
Basic with embodiment 5, difference is the rotating speed adjusting feed pump and centrifuge, makes gained micro mist average diameter 80um and sphericity reaches better level, and within 40 minutes, complete granulation, gained granulation micro mist intensity is better; The half of getting granulation micro mist, at 680 DEG C of roasting 3hr, obtains macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 74um, sphericity is better, and intensity is better; Specific area 110m
2/ g, pore volume 0.75ml/g, average pore diameter 31nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Comparative example 1
Basic with embodiment 1, difference is not add active carbon emulsion M, replaces with the water of identical amount, obtained macropore volume microspheroidal silica supports of the present invention.Survey carrier average diameter 215um, sphericity is better, and intensity is better; Specific area 180m
2/ g, pore volume 0.81ml/g, average pore diameter 16nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Comparative example 2
Basic with embodiment 1, difference is the active carbon emulsion L by equal in quality, and replace active carbon emulsion M, prepare silica supports, result carrier wear rate, cracked rate are higher, and specifically see the following form institute's column data.
Comparative example 3
Basic with embodiment 1, difference is the active carbon emulsion N by equal in quality, replaces active carbon emulsion M, prepares silica supports, result pore volume 0.65ml/g, and the effect that raising pore volume plays in active carbon institute is less.
Comparative example 4
Basic with embodiment 1, difference is not to the step of the mixed serum homogenizer grinding distribution of roasting silicon dioxide powder A and water, and the carrier sphericity after result granulation micro mist and roasting is poor, and intensity is general, survey carrier wear rate, cracked rate is higher, specifically see the following form institute's column data.
Comparative example 5
Basic with embodiment 1, difference is not add active carbon emulsion M, do not add Ludox D, replaces with the water of identical amount, prepare silica supports, the carrier sphericity after result granulation micro mist and roasting is poor, and intensity is poor, survey carrier wear rate, cracked rate is very high, specifically see the following form institute's column data.
Comparative example 6
With precipitated silica A (250 DEG C of spraying dry, moisture 6%, specific area 370m
2/ g, average diameter of particles 40um, Na
2o0.20%) 1000g, by method substantially identical in embodiment 1, prepares silica supports, and difference is the Feedstock treating step not preparing roasting silicon dioxide powder at 740 DEG C of roasting 3hr.Survey carrier wear rate, cracked rate is very high, specifically in table 1 column data.
Comparative example 7
Get silica supports 400g prepared in comparative example 6, add 1000g deionized water, add 20g acetic acid, 20g ammonium acetate, stir evenly, in 2000ml autoclave, be heated to 160 DEG C of constant temperature process 20hr, process abundant after washing, 500 DEG C of roasting 2hr, gained carrier specific area 80m
2/ g, pore volume 0.60ml/g, average pore diameter 33nm; Survey wear rate, cracked rate is higher, specifically in table 1 column data.
The wear rate of table 1 carrier, cracked rate test result (unit %)
| Embodiment | 2hr | 10hr | 50hr | 250hr |
| 1 | 1.0/0.3 | 3.2/1.1 | 12.0/4.3 | |
| 2 | 0.9/0.3 | 2.7/0.9 | 10.8/3.5 | |
| 3 | 1.5/0.4 | 4.6/1.0 | 13.1/4.7 | |
| 4 | 1.3/0.4 | 4.1/0.9 | 13.0/4.3 | |
| 5 | 0.9/0.2 | 3.7/1.1 | 11.6/3.8 | |
| 6 | 0.7/0.3 | 2.8/1.1 | 9.1/3.5 | |
| 7 | 1.3/0.3 | 4.2/0.8 | 12.9/4.1 | |
| 8 | 0.6/0.1 | 2.1/0.9 | 9.4/3.2 | |
| 9 | 0.6/0.4 | 1.8/1.0 | 7.8/3.5 | |
| Comparative example 1 | 1.8/0.7 | 4.8/2.2 | 17.2/6.2 | |
| Comparative example 2 | 1.8/0.6 | 5.3/2.5 | ||
| Comparative example 4 | 1.5/0.8 | 5.2/4.3 | 13/10 | |
| Comparative example 5 | 10.7/8.5 | |||
| Comparative example 6 | 4.8/2.6 | 13/7 | ||
| Comparative example 7 | 2.0/3.1 | 6.2/5.0 |
The pore structure of carrier, mechanical strength, wear rate, the explanation of cracked rate Data Comparison in above embodiment, comparative example, the dispersion grinding of silicon dioxide powder, add intensity and wearability, resistance to impact that Ludox significantly improves carrier, the active carbon of microparticle moderate dimensions improves the pore volume of carrier.In general, microspheroidal silica supports of the present invention has suitable pore structure, and higher mechanical strength and wearability, resistance to impact, can reach gratifying result of use and service life in commercial Application.
Inventive silica carrier can be used for preparing microspheroidal CoO/SiO2 catalyst, for H
2, SiCl
4the reaction of trichlorosilane is prepared in hydrogenation, investigates through Henan producer device, and under similarity condition, the catalyst that inventive silica carrier is prepared than device silica supports used, can cost-saving 30-40%.
Inventive silica carrier also can be used for other Fluidized Multicomponent Metallic Oxides Catalysts carrier.
In above embodiment, comparative example, the spray drying temperature of precipitated silica, white carbon, water content, average diameter and Na
2o content is provided by manufacturer, the SiO of Ludox
2concentration, Na
2o content, particle median diameter are provided by manufacturer, in dispersion liquid, in the average diameter of silica dioxide granule, active carbon emulsion, the average diameter of microparticle is recorded by laser particle analyzer, is volume mean diameter, specific area is recorded by nitrogen adsorption method, and pore volume is recorded by mercury injection method, the average diameter of granulation micro mist and microspheroidal silica supports and sphericity are judged by light microscope and range estimation, intensity judges substantially by rolling between finger, wearability is recorded by straight tube method abrasion index determinator, loadings 30g (500 DEG C are dried 1hr), be source of the gas with the air of humidification, sequentially determining 2hr, 10hr, 50hr, the wear rate of 250hr and cracked rate, in test process, fluid height is controlled to about 5 times of static height, namely the fluidized state of each carrier is controlled to identical degree as far as possible, wear rate is the ratio of collected dust (below particle diameter 15um) quality and loadings 30g, first collected dust is placed in 500 DEG C, crucible together with filter paper before weighing and dries 1hr burning-off filter paper and moisture, cracked rate is by cracked number in latter about microballoon 500-5000 of light microscopy wearing and tearing.
Claims (8)
1. a preparation method for wear-resisting macropore volume microspheroidal silica supports, comprises the following steps:
A, by specific area 250-600m
2the precipitated silica powder of/g or white carbon, at 730-760 DEG C of roasting 2-4hr, make its specific area be reduced to 100-220m
2/ g, obtained roasting silicon dioxide powder;
B, in mass parts, water 300-500 part, roasting silicon dioxide powder 100 parts, mixing, is ground to average diameter 2-5um with grinding distribution equipment by silica micro-particle particle, obtained dispersion liquid;
C, by the powdered activated carbon 10-20 mass parts of ash content≤1.0%, add water 100-150 part, process with grinding distribution equipment, make the 0.3-0.5 of microparticle average diameter in the average diameter of active carbon microparticle silica dispersions obtained by step B doubly, obtained active carbon emulsion;
D, active carbon emulsion obtained by silica dispersions, step C obtained by step B to be mixed, add Ludox 50-150 part, mix, obtained mixed slurry; SiO introduced by Ludox
2amount be the total SiO of carrier
2the 15-25% of amount; The particle median diameter of Ludox is 10-20nm;
E, mixed slurry are at 180-250 DEG C of mist projection granulating, and pelletizing 650-720 DEG C of roasting 2-4hr, obtains the microspheroidal silica supports of average diameter 50-250um of the present invention, specific area 80-200m
2/ g, pore volume 0.7-1.1ml/g, average pore diameter 20-40nm.
2. the preparation method of macropore volume microspheroidal silica supports wear-resisting as claimed in claim 1, is characterized in that, in steps A, described white carbon is through 150-250 DEG C of spray-dired precipitated silica.
3. the preparation method of macropore volume microspheroidal silica supports wear-resisting as claimed in claim 1, is characterized in that, in step B, in described dispersion liquid, silica dioxide granule is ground to average diameter 3um.
4. the preparation method of macropore volume microspheroidal silica supports wear-resisting as claimed in claim 1, is characterized in that, in step B, the grinding distribution method of silica in described dispersion liquid is colloid milling.
5. the preparation method of macropore volume microspheroidal silica supports wear-resisting as claimed in claim 1, is characterized in that, in step B, the grinding distribution method of silica in described dispersion liquid is homogenizer method.
6. the preparation method of macropore volume microspheroidal silica supports wear-resisting as claimed in claim 1, is characterized in that, in step C, described powdered activated carbon comprises coal mass active carbon through pressurization alkali treatment, pressurization pickling two step chemical deliming or wood activated charcoal.
7. the preparation method of macropore volume microspheroidal silica supports wear-resisting as claimed in claim 1, is characterized in that, in step e, the temperature of pelletizing roasting is 690-720 DEG C.
8. the preparation method of macropore volume microspheroidal silica supports wear-resisting as claimed in claim 1, is characterized in that, described precipitated silica powder or white carbon Na
2o≤0.30%, described Ludox Na
2o≤0.20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943461.7A CN105396569A (en) | 2015-12-16 | 2015-12-16 | Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943461.7A CN105396569A (en) | 2015-12-16 | 2015-12-16 | Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105396569A true CN105396569A (en) | 2016-03-16 |
Family
ID=55462520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510943461.7A Pending CN105396569A (en) | 2015-12-16 | 2015-12-16 | Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105396569A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115448316A (en) * | 2022-09-21 | 2022-12-09 | 江西联锴科技有限公司 | Preparation method of large-aperture spherical silicon dioxide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491132A (en) * | 2001-02-28 | 2004-04-21 | Attrition resistant inorganic microspheroidal particles | |
| US20090075814A1 (en) * | 2007-09-14 | 2009-03-19 | Rentech, Inc. | Promoted, attrition resistant, silica supported precipitated iron catalyst |
| CN102091625A (en) * | 2010-12-24 | 2011-06-15 | 南京工业大学 | Nickel-based catalyst prepared by solid-phase thermal dispersion and preparation method thereof |
| CN102728379A (en) * | 2011-04-14 | 2012-10-17 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis catalyst, its preparation method and application thereof |
| US20140045952A1 (en) * | 2011-04-28 | 2014-02-13 | Basf Nederland B.V. | Catalysts |
| CN104667973A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Catalyst carrier material and preparation method thereof |
-
2015
- 2015-12-16 CN CN201510943461.7A patent/CN105396569A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491132A (en) * | 2001-02-28 | 2004-04-21 | Attrition resistant inorganic microspheroidal particles | |
| US20090075814A1 (en) * | 2007-09-14 | 2009-03-19 | Rentech, Inc. | Promoted, attrition resistant, silica supported precipitated iron catalyst |
| CN102091625A (en) * | 2010-12-24 | 2011-06-15 | 南京工业大学 | Nickel-based catalyst prepared by solid-phase thermal dispersion and preparation method thereof |
| CN102728379A (en) * | 2011-04-14 | 2012-10-17 | 中科合成油技术有限公司 | Fischer-Tropsch synthesis catalyst, its preparation method and application thereof |
| US20140045952A1 (en) * | 2011-04-28 | 2014-02-13 | Basf Nederland B.V. | Catalysts |
| CN104667973A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Catalyst carrier material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115448316A (en) * | 2022-09-21 | 2022-12-09 | 江西联锴科技有限公司 | Preparation method of large-aperture spherical silicon dioxide |
| CN115448316B (en) * | 2022-09-21 | 2024-02-27 | 江西联锴化学有限公司 | Preparation method of large-aperture spherical silicon dioxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3636758B2 (en) | Removal method of hydrogen sulfide | |
| CN103611495B (en) | A kind ofly remove adsorbent of organic chloride in hydrocarbonaceous stream and preparation method thereof | |
| WO2012024896A1 (en) | Non-adhesive molecular sieve catalyst and preparation method therefor | |
| CN105396588A (en) | Preparation method and application of antiwear microspherical CuO/SiO2 catalyst | |
| US20020018853A1 (en) | Sulfur sorbent composition and sorption process | |
| CN107837798A (en) | A kind of alumina globule carrier and preparation method thereof and catalytic reforming catalyst | |
| CN111151232A (en) | Preparation method of spherical alumina | |
| CN105396569A (en) | Preparation method for antiwear large-pore-volume microspherical silicon dioxide carrier | |
| CN103962169B (en) | It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed | |
| CN105435858A (en) | Preparation method of wear-resistant large-pore-volume microspherical silica carrier | |
| CN105498853A (en) | Method for preparing wear-resisting large-pore-volume micro-spherical silicon dioxide carrier | |
| CN105521829A (en) | Preparation method of wear-resistant large-pore-volume microspherical silica carrier | |
| US3344086A (en) | Method for removing ammonia from an ammonium zeolite | |
| CN105618156B (en) | A kind of alumina support and its roller forming methods and applications | |
| CN105562118A (en) | Preparation method of abrasion-resistant and impact-resistant microspherical silicon dioxide carrier | |
| JP3507567B2 (en) | Spherical alumina and its manufacturing method | |
| JP2011224458A (en) | Method of producing carbon monoxide reduction catalyst and carbon monoxide reduction catalyst | |
| CN103861660B (en) | A kind of rolling forming method of spherical titanium aluminium composite oxide | |
| US3793230A (en) | Catalyst for sulfuric acid contact process | |
| US3933991A (en) | Sulfuric acid contact process | |
| CN105536796A (en) | Wear-resistant microspheric Fe2O3/SiO2 catalyst preparation method | |
| US2966466A (en) | Production of attrition-resistant silica-alumina gels | |
| CN105363429A (en) | Preparing method for wear-resisting and impact-resisting micro spherical silicon dioxide carriers | |
| Fan et al. | Stable Pt catalysts anchored by Mn-SBA-15 support for propane dehydrogenation | |
| CN115364837A (en) | Macroporous spherical alumina and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160316 |