CN105363428A - Preparing method for wear-resisting micro spherical silicon dioxide carriers - Google Patents
Preparing method for wear-resisting micro spherical silicon dioxide carriers Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 44
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 4
- 239000000969 carrier Substances 0.000 title abstract 4
- 239000011148 porous material Substances 0.000 claims abstract description 44
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003595 mist Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 23
- 239000004005 microsphere Substances 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000011859 microparticle Substances 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005453 pelletization Methods 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 210000002966 serum Anatomy 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 50
- 238000005469 granulation Methods 0.000 abstract description 25
- 230000003179 granulation Effects 0.000 abstract description 25
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000006229 carbon black Substances 0.000 abstract 3
- 238000001556 precipitation Methods 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 26
- 229910003902 SiCl 4 Inorganic materials 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 235000013312 flour Nutrition 0.000 description 11
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 239000012530 fluid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 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 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000005049 silicon tetrachloride Substances 0.000 description 6
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 6
- 239000005052 trichlorosilane Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 208000020442 loss of weight Diseases 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 210000000952 spleen Anatomy 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005995 Aluminium silicate 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001354 calcination Methods 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 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
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity 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
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product 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
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparing method for wear-resisting micro spherical silicon dioxide carriers. The preparing method comprises the steps that silicon dioxide powder or white carbon black obtained through a precipitation method is roasted at 730-760 DEG C, so that the specific surface area of the silicon dioxide powder or white carbon black is reduced to 100-220 m<2>/g from 250-600 m<2>/g; the silicon dioxide powder or white carbon black obtained through the precipitation method is added with water, added with acid to adjust the PH to 2-3 and then ground and dispersed to be micro granules with the diameter all being 1 micrometer or smaller; the roasted silicon dioxide powder is added, the mixture is ground into micro granules with the average diameter ranging from 2 micrometers to 5 micrometers and sprayed for granulation, the granules are roasted at 650-720 DEG C, and the micro spherical carriers are prepared, wherein the average diameter ranges from 50 micrometers to 250 micrometers, the specific surface area ranges from 80 m<2>/g to 200 m<2>/g, the pore volume ranges from 0.5 ml/g to 0.7 ml/g, and the average pore diameter ranges from 15 nm to 25 nm. The micro spherical silicon dioxide carriers have a proper pore structure and high mechanical strength, wearing resistance and impact resistance, and are suitable for preparing a catalyst of a fluidized bed.
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 microspheroidal silica supports of ー kind wear and shock-resistant.
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 wear-resistance microspheres shape silica supports preparation method, prepared microspheroidal silica supports, not only there is suitable pore structure, 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 kind of wear-resistance microspheres shape silica supports preparation method, comprises the following steps successively:
A, by specific area 250-600m
2the precipitated silica powder of/g or white carbon are with SiO
2count 100 mass parts, 730-760 DEG C of roasting, make its specific area be reduced to 100-220m
2/ g, obtained roasting silicon dioxide powder;
B, by specific area 400-600m
2the precipitated silica powder of/g or white carbon are with SiO
2meter 10-20 mass parts, add water 350-500 mass parts, stirs evenly, and adds appropriate amount of acid and adjust PH2-3, process further, make silica or white carbon microparticle all refine to below diameter 1um with grinding distribution equipment, obtained emulsus glue;
C, by roasting silicon dioxide powder obtained by steps A, add emulsus glue obtained by step B, mixing, processes mixed serum further with grinding distribution equipment, makes the volume mean diameter of silica micro-particle be reduced to 2-5um, obtained silica dispersions;
D, by silica dispersions obtained by step C at 180-250 DEG C of mist projection granulating, pelletizing 680-720 DEG C of roasting 2-4hr, the microspheroidal silica supports of obtained average diameter 50-250um of the present invention, specific area 80-200m
2/ g, pore volume 0.5-0.7ml/g, average pore diameter 15-25nm.
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 C is relatively high, thus makes obtained silica supports have better intensity, wearability, resistance to impact.
Wherein, in step B, precipitated silica powder or the white carbon of or calcination process dry through less than 450 DEG C temperature can be adopted, the preferably precipitated silica through less than 250 DEG C temperature drying process of more easy grinding dispersion, especially preferably grinding distribution better effects if through 180-250 DEG C of spray-dired precipitated silica, to obtain, dispersion is better, the better emulsus glue of sintering character.
Wherein, in step B, C, the grinding distribution method of silica in described emulsus glue, dispersion liquid, be colloid milling or homogenizer method, wherein the grinding distribution effect of homogenizer method is best, fastest.
Wherein, in step B, described acid can be nitric acid, also can be the weak acid such as acetic acid, citric acid, optimization citric acid; When adding acetic acid, citric acid, the preferred 3-10 part of addition.The shortcoming of nitric acid produces NO in the roasting process of step D
2tobacco, acetic acid can produce tart flavour in the spray-drying process of step D, if with hydrochloric acid, oxalic acid, can in grinding distribution, spray-drying process contact stainless steel component and cause corrosion and finally cause pollution to carrier of the present invention, sulfuric acid then can volatilize and cause more serious equipment corrosion in the roasting process of step D, adopts citric acid then can avoid these problems.Acid adding adjusts PH2-3 can accelerate the speed of grinding distribution, and makes emulsus glue keep stablizing more than one day.
Wherein, in step C, preferably that silica dioxide granule is levigate, to the average diameter 3um of silica micro-particle.
Wherein, in step D, the preferred 700-720 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, B, preferably Na is adopted
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 silica dispersions in step D, 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.
Wear-resistance microspheres shape 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 C, the micelle in emulsus glue is further refinement in grinding distribution process, and colloid size should be tens to nm up to a hundred, but retains largely because the duct in micelle still has, and thus activity is higher, has good sintering character;
In c, step C, 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;
D, in step C gained dispersion liquid, because the internal pore volume of silica micro-particle is less much than the volume of an intergranular water or slurries, so after the further refinement of emulsus glue introduced by step B, the overwhelming majority is dispersed between silica micro-particle, in the pelletizing microballoon that the mist projection granulating of step D is prepared fast, silica particle in the glue still overwhelming majority is dispersed between silica micro-particle, thus serve good bonding effect after baking, 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,
In e, carrier 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;
F, carrier of the present invention, be provided with more suitable pore structure 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) add water 1070g precipitated silica A 19930g, stirs evenly, and adds appropriate nitric acid and adjust PH2.5, use homogenizer process, make below the diameter 1um that white carbon microparticle all refine to, obtained emulsus glue A, its SiO
2mass concentration 5%;
(5) add water 1100g precipitated silica C 23900g, stirs evenly, and adds 60g citric acid and adjust PH2.5, use homogenizer process, make below the diameter 1um that white carbon microparticle all refine to, obtained emulsus glue C, its SiO
2mass concentration 4%.
Embodiment 1
Get 1000g roasting silicon dioxide powder A, add in agitator tank, add 4000g emulsus glue A (containing SiO
2200g), open stirring to pulp, after being uniformly dispersed, with homogenizer grinding distribution to average diameter of particles 5um, 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, makes 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 wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 220um, sphericity is better, and intensity is better; Specific area 170m
2/ g, pore volume 0.61ml/g, average pore diameter 15nm; 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 wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 213um, sphericity is better, and intensity is better; Specific area 175m
2/ g, pore volume 0.60ml/g, average pore diameter 15nm; 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 3500g emulsus glue A (containing SiO
2175g), open stirring to pulp, after being uniformly dispersed, with homogenizer grinding distribution to average diameter of particles 5um, 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, makes 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 wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 215um, sphericity is better, and intensity is better; Specific area 153m
2/ g, pore volume 0.70ml/g, average pore diameter 19nm; 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 wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 210um, sphericity is better, and intensity is better; Specific area 146m
2/ g, pore volume 0.68ml/g, average pore diameter 18nm; 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 4000g emulsus glue C (containing SiO
2160g), open stirring to pulp, after being uniformly dispersed, with homogenizer grinding distribution to average diameter of particles 5um, 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, makes 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 wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 218um, sphericity is better, and intensity is better; Specific area 110m
2/ g, pore volume 0.55ml/g, average pore diameter 22nm; 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 106m
2/ g, pore volume 0.55ml/g, average pore diameter 21nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 7
Basic with embodiment 5, difference is to add 3200g emulsus glue C (containing SiO
2128g), obtained wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 218um, sphericity is better, and intensity is better; Specific area 105m
2/ g, pore volume 0.56ml/g, average pore diameter 23nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 8
Basic with embodiment 3, difference is with homogenizer grinding distribution liquid to average diameter of particles 3um, obtained wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 208um, sphericity is better, and intensity is better; Specific area 150m
2/ g, pore volume 0.68ml/g, average pore diameter 16nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 9
Basic with embodiment 5, difference is with homogenizer grinding distribution liquid to average diameter of particles 3um, obtained wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 212um, sphericity is better, and intensity is better; Specific area 115m
2/ g, pore volume 0.57ml/g, average pore diameter 19nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 10
Basic with embodiment 3, 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 700 DEG C of roasting 3hr, obtains wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 70um, sphericity is better, and intensity is better; Specific area 110m
2/ g, pore volume 0.55ml/g, average pore diameter 18nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Embodiment 11
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 700 DEG C of roasting 3hr, obtains wear-resistance microspheres shape silica supports of the present invention.Survey carrier average diameter 72um, sphericity is better, and intensity is better; Specific area 110m
2/ g, pore volume 0.55ml/g, average pore diameter 22nm; Survey wear rate, cracked rate is lower, specifically see the following form institute's column data.
Comparative example 1
Get 1000g roasting silicon dioxide powder A, by method substantially identical in embodiment 1, prepare silica supports, difference is the step not using homogenizer grinding distribution, carrier ball-type degree after gained granulation micro mist and roasting is bad, intensity is general, and survey wear rate, cracked rate is higher, specifically see the following form institute's column data.
Comparative example 2
Get 1000g roasting silicon dioxide powder A, by method substantially identical in embodiment 1, prepare silica supports, difference is not add emulsus glue, and the carrier sphericity after result granulation micro mist and roasting is weaker, and intensity is poor; Survey wear rate, cracked rate is very high, specifically see the following form institute's column data.
Comparative example 3
Get silica supports 400g prepared in comparative example 1, 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.
Comparative example 4
Get silica supports 400g prepared in comparative example 2, 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 10hr, 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 %)
In above embodiment, comparative example, the pore structure of carrier, mechanical strength, wear rate, cracked rate Data Comparison illustrate, the dispersion grinding of silicon dioxide powder, add intensity and wearability, resistance to impact that white carbon emulsion significantly improves 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.
The pore structure of carrier, mechanical strength, wear rate, the explanation of cracked rate Data Comparison in above embodiment, comparative example, the roasting of spray-dired precipitated silica, the dispersion grinding of silicon dioxide powder, add the Combination of Methods of Ludox, significantly improve intensity and wearability, the resistance to impact 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.
Get the microspheroidal silica supports of the embodiment of the present invention and comparative example, spray cobalt nitrate solution, 120 DEG C of dry 3hr after placement homogenizing, then 500 DEG C of roastings 2 hours, obtain wear-resisting microspheroidal CoO/SiO2 catalyst.
The wear rate of table 2 catalyst, cracked rate test result (unit %)
Application examples 1
By microspheroidal CoO/SiO obtained by embodiment 1-10
2catalyst, in fixed bed reactors, for being reacted by preparing trichlorosilane from silicon tetrachloride through hydrogenation, carry out initial activity evaluation respectively, evaluation result lists in table 3.Appreciation condition: take glass lining steel pipe as reaction tube, internal diameter 10mm, loaded catalyst 3.0ml (about 2g), reaction pressure 1.8MPa, H
2/ SiCl
4ratio (mol) 2, gas space velocity 36000hr
-1, reaction temperature 400/450 DEG C, gas passes through beds.Catalyst first uses H
2carry out temperature programmed reduction, be heated to first in atmospheric conditions by the speed heating reduction to 450 DEG C of 1 DEG C/min after 150 DEG C, H
20.10SLM, air speed 2000hr
-1, then improve H
2to 1.20SLM air speed 24000hr
-1, improve system pressure to 1.8MPa simultaneously, after reduction 30min, cut SiCl
4, constant-flux pump flow 2.94ml/min, in beds, gas raw material is relative to the air speed 36000hr of catalyst
-1, maintain system pressure 1.8MPa, after question response stablizes 30min, sampling detects the composition of implication and content (on-line period, probe temperature 70-90 DEG C, higher than SiCl
4boiling point 58 DEG C, trichlorosilane boiling point 33 DEG C, identical below), calculate SiCl
4conversion ratio and HSiCl
3selective, get survey once totally 5 times, using mean value as initial activity evaluation result every 30min.
By embodiment 1,4 catalyst, after completing initial activity evaluation, proceed the long period activity rating of 250hr, evaluation result lists in table 4.Every 2hr sampling once, detect composition and the content of implication, calculate SiCl respectively
4conversion ratio and HSiCl
3selective, calculate every daily mean, the results are shown in table 5.
Application examples 2
By microspheroidal CoO/SiO obtained by embodiment 1
2catalyst, 200ml fluid bed micro anti-evaluation device carries out fluidized-bed reaction test, for H
2, SiCl
4trichlorosilane reaction is prepared in hydrogenation, and carry out the investigation of 250hr, result of the test lists in table 5.Experimental condition: reactor wall and connecting line inwall enamel, loaded catalyst 8.0ml (5.5g), first uses H
2temperature programmed reduction is carried out to catalyst, is heated to first in atmospheric conditions by the speed heating reduction to 450 DEG C of 2 DEG C/min after 150 DEG C, H
20.40SLM, from bottom to top, air speed 3000hr
-1, then improve H
2to 3.20SLM air speed 24000hr
-1, improve system pressure to 1.8MPa simultaneously, after reduction 30min, cut SiCl
4, constant-flux pump flow 7.84ml/min, H
2/ SiCl
4ratio (mol) 2, maintain system pressure 1.8MPa, in fluidized-bed layer, gas raw material is relative to the air speed 36000hr of catalyst
-1, gas, from bottom to top by catalyst and silica flour fluidisation, controls reaction temperature 450 DEG C, often according to H in operation process
2the Pressure Drop low velocity of steel cylinder, SiCl
4the loss of weight speed of stock bottle, to H
2flowmeter and SiCl
4the traffic timing of constant-flux pump is carried out contrast and is demarcated and adjustment; Question response starts to sample the composition and content that detect implication after stablizing 2hr, every 2hr gets survey once, calculates every daily mean.
Catalyst in bed is all collected after having tested by the investigation of 250hr, surveys gross mass, compared with the initial input (5.5g) of catalyst, extrapolates the wear extent of catalyst.
In process of the test, the size of microparticle in condensate liquid of working off one's feeling vent one's spleen collected by regular check, does not find the particle of more than diameter 20um.
Application examples 3
By microspheroidal CoO/SiO obtained by embodiment 4
2catalyst, 500ml fluid bed micro anti-evaluation device carries out fluidized-bed reaction test, for silica flour, H
2, SiCl
4trichlorosilane reaction is prepared in hydrogenation, and carry out the investigation of 250hr, result of the test lists in table 6.Experimental condition: reactor wall and connecting line inwall enamel, loaded catalyst 8.0ml (5.5g), allocates purity 99.9%, granularity 80-100 object silica flour 20g into; First use H
2temperature programmed reduction is carried out to catalyst, is heated to first in atmospheric conditions by the speed heating reduction to 450 DEG C of 2 DEG C/min after 150 DEG C, H
20.40SLM, from bottom to top, air speed 3000hr
-1, then improve H
2to 3.20SLM air speed 24000hr
-1, improve system pressure to 1.8MPa simultaneously, after reduction 30min, cut SiCl
4, constant-flux pump flow 7.84ml/min, H
2/ SiCl
4ratio (mol) 2, maintain system pressure 1.8MPa, in fluidized-bed layer, gas raw material is relative to the air speed 36000hr of catalyst
-1, gas, from bottom to top by catalyst and silica flour fluidisation, controls reaction temperature 450 DEG C, often according to H in operation process
2the Pressure Drop low velocity of steel cylinder, SiCl
4the loss of weight speed of stock bottle, to H
2flowmeter and SiCl
4the traffic timing of constant-flux pump is carried out contrast and is demarcated and adjustment); Question response starts to sample the composition and content that detect implication after stablizing 2hr, every 2hr gets survey once, calculates SiCl respectively
4conversion ratio, silica flour conversion ratio and HSiCl
3selective, calculate every daily mean, and fill into a silica flour according to the every 2hr of silica flour conversion results situation calculated, make silica flour conversion ratio maintain substantially identical level.
After the investigation of 250hr has been tested, catalyst in bed and silica flour are all collected, survey gross mass, survey CoO total amount (conversion of Co total amount) wherein, according to surveyed CoO total amount compared with the initial input (5.5gx10.0%) of catalyst, extrapolate the wear extent of catalyst.
In process of the test, the size of microparticle in condensate liquid of working off one's feeling vent one's spleen collected by regular check, does not find the particle of more than diameter 20um.
Can infer from the data of table 3-6, the microspheroidal CoO/SiO prepared by carrier of the present invention
2catalyst, through H
2higher SiCl can be reached after reduction
4conversion ratio and HSiCl
3yield, can steady in a long-term operate, catalyst expends lower; Allocate appropriate metallic silicon power continuously in fluid bed, also can reach good reaction effect, the stable performance of catalyst, catalyst granules is slowly cracked, and efflorescence is slow, and wear extent, consumption are not high yet, can obtain good effect and efficiency-cost ratio for industrial process.
The initial activity that table 3 catalyst reacts at preparing trichlorosilane from silicon tetrachloride through hydrogenation
10 days Activity evaluation that table 4 embodiment 1,4 catalyst reacts at hydrogenation of silicon tetrachloride
The evaluation result that table 5 embodiment 1 catalyst reacts at 250hr hydrogenation of silicon tetrachloride
| 1st day | SiCl 4Conversion ratio 38.2%, HSiCl 3Selective 98.6% |
| 6th day | SiCl 4Conversion ratio 37.0%, HSiCl 3Selective 98.4% |
| 10th day | SiCl 4Conversion ratio 35.7%, HSiCl 3Selective 98.5% |
| Catalyst abrasion amount, % | 8 |
The evaluation result that table 6 embodiment 4 catalyst reacts at 250hr hydrogenation of silicon tetrachloride
| 1st day | SiCl 4Conversion ratio 38.8%, HSiCl 3Selective 98.2% |
| 6th day | SiCl 4Conversion ratio 36.5%, HSiCl 3Selective 98.4% |
| 10th day | SiCl 4Conversion ratio 34.4%, HSiCl 3Selective 98.3% |
| Silica flour inversion quantity, g/ days | 65 |
| Silica flour fills into total amount, g | 650 |
| Catalyst abrasion amount, % | 13 |
Investigate through Henan producer device, under similarity condition, the catalyst that inventive silica carrier is prepared than device silica supports used, can cost-saving 30-50%.
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 white carbon, water content, average diameter and Na
2o content is provided by manufacturer, in emulsus glue, dispersion liquid, the average diameter of silica dioxide granule, silica particles is recorded by laser particle analyzer, is volume mean diameter, specific area is recorded by nitrogen adsorption method, and pore volume is recorded by Ethanol Adsorption 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.The wear rate of catalyst, cracked rate method of testing and carrier are similar.
Claims (7)
1. a wear-resistance microspheres shape silica supports preparation method, comprises the following steps:
A, by specific area 250-600m
2the precipitated silica powder of/g or white carbon are with SiO
2count 100 mass parts, 730-760 DEG C of roasting, make its specific area be reduced to 100-220m
2/ g, obtained roasting silicon dioxide powder;
B, by specific area 400-600m
2the precipitated silica powder of/g or white carbon are with SiO
2meter 10-20 mass parts, add water 350-500 mass parts, stirs evenly, and adds appropriate amount of acid and adjust PH2-3, process further, make silica or white carbon microparticle all refine to below diameter 1um with grinding distribution equipment, obtained emulsus glue;
C, by roasting silicon dioxide powder obtained by steps A, add emulsus glue obtained by step B, mixing, processes mixed serum further with grinding distribution equipment, makes the volume mean diameter of silica micro-particle be reduced to 2-5um, obtained silica dispersions;
D, by silica dispersions obtained by step C at 180-250 DEG C of mist projection granulating, pelletizing 680-720 DEG C of roasting 2-4hr, the microspheroidal silica supports of obtained average diameter 50-250um of the present invention, specific area 80-200m
2/ g, pore volume 0.5-0.7ml/g, average pore diameter 15-25nm.
2. wear-resistance microspheres shape silica supports preparation method as claimed in claim 1, it is characterized in that, in steps A, described white carbon is through 150-250 DEG C of spray-dired precipitated silica.
3. wear-resistance microspheres shape silica supports preparation method as claimed in claim 1, it is characterized in that, in step B, in described dispersion liquid, silica dioxide granule is ground to average diameter 3um.
4. wear-resistance microspheres shape silica supports preparation method as claimed in claim 1, it is characterized in that, in step B, the grinding distribution method of silica in described dispersion liquid is colloid milling.
5. wear-resistance microspheres shape silica supports preparation method as claimed in claim 1, it is characterized in that, in step B, the grinding distribution method of silica in described dispersion liquid is homogenizer method.
6. wear-resistance microspheres shape silica supports preparation method method as claimed in claim 1, it is characterized in that, in step D, the temperature of pelletizing roasting is 700-720 DEG C.
7. wear-resistance microspheres shape silica supports preparation method as claimed in claim 1, is characterized in that, described precipitated silica powder or white carbon Na
2o≤0.30%.
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|---|---|---|---|---|
| CN1097351A (en) * | 1993-07-16 | 1995-01-18 | 中国石油化工总公司 | The preparation method of microspheroidal gama-alumina |
| US5925592A (en) * | 1995-10-04 | 1999-07-20 | Katoh; Akira | Process for preparing alumina carrier |
| CN1491132A (en) * | 2001-02-28 | 2004-04-21 | Attrition resistant inorganic microspheroidal particles | |
| CN1657571A (en) * | 2004-02-17 | 2005-08-24 | 吉林市吉清科技开发有限公司 | Preparation method of microspherical silica used as alkene polymerization catalyst carrier |
| CN1942242B (en) * | 2004-03-12 | 2011-07-27 | 圣戈本陶瓷及塑料股份有限公司 | Spray dried alumina for catalyst carrier |
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2015
- 2015-12-16 CN CN201510943282.3A patent/CN105363428A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097351A (en) * | 1993-07-16 | 1995-01-18 | 中国石油化工总公司 | The preparation method of microspheroidal gama-alumina |
| US5925592A (en) * | 1995-10-04 | 1999-07-20 | Katoh; Akira | Process for preparing alumina carrier |
| CN1491132A (en) * | 2001-02-28 | 2004-04-21 | Attrition resistant inorganic microspheroidal particles | |
| CN1657571A (en) * | 2004-02-17 | 2005-08-24 | 吉林市吉清科技开发有限公司 | Preparation method of microspherical silica used as alkene polymerization catalyst carrier |
| CN1942242B (en) * | 2004-03-12 | 2011-07-27 | 圣戈本陶瓷及塑料股份有限公司 | Spray dried alumina for catalyst carrier |
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