CN109107555A - The preparation method of titania support - Google Patents
The preparation method of titania support Download PDFInfo
- Publication number
- CN109107555A CN109107555A CN201810881108.4A CN201810881108A CN109107555A CN 109107555 A CN109107555 A CN 109107555A CN 201810881108 A CN201810881108 A CN 201810881108A CN 109107555 A CN109107555 A CN 109107555A
- Authority
- CN
- China
- Prior art keywords
- filter cake
- titania support
- titanium tetrachloride
- carrier gas
- reaction
- 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.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 63
- 239000012065 filter cake Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 239000012159 carrier gas Substances 0.000 claims abstract description 30
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 25
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 25
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
- 230000032683 aging Effects 0.000 claims abstract description 16
- 238000004898 kneading Methods 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005587 bubbling Effects 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005457 optimization Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 22
- 238000001125 extrusion Methods 0.000 abstract description 14
- 239000000243 solution Substances 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000010410 dusting Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 210000000952 spleen Anatomy 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003020 moisturizing effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000005239 tubule Anatomy 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrogen ammonium salt Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/615—
-
- B01J35/633—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Abstract
The present invention provides a kind of preparation method of titania support, comprising the following steps: (1) using nitrogen or dry air as carrier gas, prepares the titanium tetrachloride carrier gas of 1-8% volume content；(2) ammonium hydrogen carbonate of compound concentration 1-4mol/L or sodium bicarbonate solution or slurries, continuous bubbling are passed through titanium tetrachloride carrier gas, control 10-40 DEG C of slurry temperature；(3) reaction rear slurry places aging 5-20hr, filters, and washing blows moisture, obtains half-dried filter cake；The 250-300 DEG C of hot wind rapid draing of the half-dried filter cake in part is taken, fast dry powder is obtained；(4) it takes half-dried filter cake to add nitric acid solution mixed processing, fast dry powder, kneading, extrusion, rapid draing, roasting, obtained titania support is added.Prepared titania support, pore volume, surface area, mechanical strength, thermal stability are all higher, and cost is relatively low.
Description
Technical field
The invention belongs to industrial catalyst fields, and in particular to a kind of preparation method of titania support.
The prior art
Carrier or catalyst of the cause with special surface nature, titania support or containing titanium dioxide component are very much
Reaction can play unique effect as in.
For example titania-based catalyst for recovering sulfur is to organic sulfur COS and CS2Hydrolysis has high activity, Crouse
Reaction nearly reaches the permitted conversion ratio of thermodynamical equilibrium can be with 1200 h under the conditions of required temperature-1High-speed make
With and do not generate Sulphated Poisoning, performance is stablized in sulphur recovery application, and the service life is up to 5-10.It is described titania-based
Sulfuric acid solution, calcium nitrate solution is successively added usually by metatitanic acid powder in catalyst for recovering sulfur, through kneading, extrusion, drying,
Roasting is made, and general 85-90m% containing anatase titanium dioxide, sulfur acid calcium 10-15m%, wherein calcium sulfate plays the work of binder
With.In recent years, due to oil refining, the development of coal chemical industry, which has been widely used.Because of hole
For the too small inconvenience of volume using the catalyst as carrier, catalyst is made in further load active component.
For another example the hydrogenation catalyst prepared by titania support Supported Co active component of cobalt, carrier surface and metal active
The interaction of component, catalyst have titanium dioxide that is very high desulphurizing activated, but needing pore volume, surface area all suitably big
The somewhat larger molding titania support of pore volume is preferably first made in carrier, in order to pass through infusion process supported active group
Divide and prepares catalyst.
The all biggish molding titania support of pore volume, surface area prepared by the prior art, in addition to there are processing costs
Problem, mechanical strength are usually relatively inaccessible to require, i.e., in limited cost-range, how to prepare pore volume, surface area, machinery
The all higher molding titania support of intensity, thermal stability is a technical problem.
Summary of the invention
In order to solve the above technical problems, the present invention provide a kind of pore volume, surface area, mechanical strength, thermal stability all compared with
The preparation method of high molding titania support, comprising the following steps:
(1) using titanium tetrachloride and carrier gas as raw material, by way of temperature control bubbling or spray, four chlorinations of 1-8% volume content are prepared
Titanium carrier gas；The carrier gas is nitrogen or dry air；
(2) ammonium hydrogen carbonate of compound concentration 1-4mol/L or sodium bicarbonate solution or slurries, continuous bubbling are passed through four chlorination
Titanium carrier gas controls 10-40 DEG C of slurry temperature；Reaction time 0.5-2hr, until slurries pH4.5-5.0 stops into the titanium tetrachloride
Carrier gas completes reaction；
(3) reaction rear slurry places aging 5-20hr, filtering, and 10-30 DEG C of water washing of filter cake blows away part with room temperature dry air
Water, obtains half-dried filter cake, and folding contains TiO215-25m%；It takes the half-dried filter cake in part to carry out rapid draing with 350-400 DEG C of hot wind, is made
Fast dry powder, folding contain TiO270-90m%；
(4) half-dried filter cake 60-90 mass parts in terms of titanium dioxide described in step 3 are taken, nitric acid solution 10-20 matter in terms of pure nitric acid is added
Part is measured, mixed processing 1-3hr is added fast dry powder 10-40 mass parts in terms of titanium dioxide, kneading 0.5-1hr described in step 3 and squeezes
Item, rapid draing, dried strip are roasted at 400-500 DEG C, and titania support is made.
The titania support of the method for the present invention preparation, pore volume, surface area, mechanical strength are all higher, carrier specific surface
Product 120-160m2The cylindrical product of/g, pore volume 0.3-0.4ml/g, Φ 3-4mm, side pressure strength can reach 90N/cm, or even
100 N/cm or more；Primary raw material is the lower titanium tetrachloride of price and ammonium hydrogen carbonate or sodium bicarbonate, and preparation process is conventional
Technique, thus cost is relatively low.
In TiO 2 carrying preparation of the invention, the volume content of step (1) titanium tetrachloride carrier gas is preferably
3-8%, when titanium tetrachloride content is lower, carrier gas consumption is larger, when titanium tetrachloride content is higher local reaction excessively acutely and
Absorption is not easy i.e. discharge gas completely easily with smog；Tetrachloro according to the saturated vapour pressure data of titanium tetrachloride, at 30 DEG C of carrier gas
Changing titanium highest volume content is 2.1%, is 3.4% at 40 DEG C, and 50 DEG C of whens are 5.3%, and 60 DEG C of whens are 8.1%, and 70 DEG C of whens are 12%；When
Titanium tetrachloride easily in the carrier gas distributor for being dipped in slurries bottom and sprays when carrier gas temperature is too many higher than reacting slurry temperature
It is condensed at mouthful, hydrolysis accumulation be easy to cause spout to block.
In TiO 2 carrying preparation of the invention, step (3) reaction rear slurry first pass through change water reduce mother liquor it is dense
Degree places aging again, to obtain better aging and impurity-eliminating effect, half-dried filter cake is made to be easier to washing to required Cl-Content is wanted
It asks.
In TiO 2 carrying preparation of the invention, the ammonium hydrogen carbonate or sodium bicarbonate solution that step (2) uses, just
Beginning pH value be no greater than 8.5 and titanium tetrachloride carrier gas reaction it is more gentle.The benefit of ammonium hydrogen carbonate is that prepared carrier is free of
Sodium, can the higher solution of compound concentration, but initial reaction stage can blow out ammonia by carrier gas and produced carbon dioxide when concentration is higher
Gas, in addition to causing significant loss, the smell of ammonia is also larger, can configure low concentration solution before the reaction and more during the reaction
It is secondary to fill into, to improve concentration of slurry and production efficiency；Sodium bicarbonate solubility is lower but benefit is not generate ammonia odor.Carbonic acid
Hydrogen sodium is 10.3-12.7g/100ml water in 25-40 DEG C of solubility, can be made into the solution of 1.2-1.4mol/L, but can match and be slurried
Liquid uses, and only needs to can guarantee the suspension of sodium bicarbonate in reaction process.
In TiO 2 carrying preparation of the invention, the main component of half-dried filter cake obtained by step (3) is positive metatitanic acid,
Due to being to be generated in low-temp reaction, and end is dry through the long-time such as 100 DEG C of temperatures above, there is certain reactivity,
The colloid of cementation can have been generated in step (4) with nitric acid reaction, has assigned and squeezes out item, dried strip with intensity, and in 400-
Intensity needed for obtaining titania support after 450 DEG C of roastings.Rapid draing institute is carried out with 250-300 DEG C of hot wind by half-dried filter cake
Fast dry powder is made, use is the humidity that kneading material is adjusted, controlled in the kneading process of step (4), to guarantee to squeeze out item
With hardness appropriate, prevent from squeezing out item in the dry and cracked line of rapid draing rear surface appearance, while reducing and containing to the half-dried filter cake
The requirement of water.The rapid draing of half-dried filter cake is carried out preferably by pneumatic conveying dryer；In Optimization of Gas Flow Drying, half-dried filter cake
It can be extruded into slice by screw auger and enter velocity heated gas, can be further crushed through high speed blade after charging, surface layer material is rapid
Dehydration dusting, which is detached from, enters air-flow, blows away with air-flow and rapid draing and partially dehydrated, it is dry after powder through cyclone separator and
Bag filter is collected, and wherein the slice dusting time is the only several seconds drying time after dusting, de- in filter cake within a few minutes
Positive metatitanic acid structure change is little during water, also has largely in the structure of the partially dehydrated metatitanic acid positive in the process of positive metatitanic acid
Retain；Although residence time of the powder in cyclone separator and bag filter may be more slightly longer after dry, to quick-drying
The influence of mealiness matter may less, if the every 10min discharging of cyclone separator is primary, the every 30min rapping discharging one of bag filter
Secondary, cyclone separator and the material in bag filter, air temperature control are 150-200 DEG C in the embodiment of the present invention, and powder has been done
It is dry removed completely to free water, the degree of water of constitution partial removal.Half-dried filter cake contained humidity is more, in pinching close to room temperature
It has during conjunction and greatly volatilizees, to make to expect that block moisture content is moderate after mediating, harder item can be squeezed out.
In TiO 2 carrying preparation of the invention, the rapid draing that step (4) squeezes out item is also very crucial, embodiment
In 130 DEG C of hot blast temperature, time 0.4hr, that is, suitable；By the positive metatitanic acid of the half-dried filter cake introducing, by described fast during this
The structure for the titanic acid-like substance that dry powder introduces, is still largely retained, otherwise finally prepares pore volume, the table of carrier
Area can decrease.
The thermal stability of titania support prepared by the method for the present invention is also preferable, 420 DEG C, 450 DEG C, 500 DEG C of roasting institutes
The side pressure strength of titania support, specific surface area, pore volume difference are little.
Specific embodiment
Technical solution of the present invention is specifically described and is illustrated below with reference to embodiment, but is not constituted to of the invention
Limitation.
In the preparation process of titania support of the present invention, the positive half-dried filter cake preparation of metatitanic acid and the preparation of fast dry powder are main works
Make.
The positive half-dried filter cake preparation of metatitanic acid, device therefor mainly include positive metatitanic acid precipitation reactor and attached gas dosing,
Titanium tetrachloride saturator.Wherein gas dosing and control pass through a nitrogen range 5-50Nm3The mass flowmenter of/hr carries out,
Coefficient conversion adjusts when blowing air, and accurate filter is arranged before flowmeter；Titanium tetrachloride saturation after being located at mass flowmenter
Device is a 50L stainless cylinder of steel, bottom setting stainless steel rounding dish type gas distributor and 6kw electrically heated rod group, disk in tank
Shape gas distributor has about 500 Φ 1mm spray orifices, and pitch of holes about 15mm, electrically heated rod group is located on gas distributor,
In titanium tetrachloride saturator and temperature of working off one's feeling vent one's spleen is controlled by electrically heated rod group temperature controller, and glass-tube liquid level meter is housed outside tank；Titanic
Sour precipitation reactor main body is a stainless steel cylinder barrel reactor, internal diameter Φ 400, high 2000mm, upper opening, in reactor
Stainless steel rounding dish type gas distributor (about 500 Φ 1mm spray orifices of band, pitch of holes about 15mm) is arranged in bottom, gas distributor
It connects titanium tetrachloride saturator and exports gas pipeline, reactor middle and lower part sets Φ 15x1.5 spiral shape stainless steel water cooling tube close to inner wall
About 20m long, the tap water of interior 20 DEG C of logical inlet temperature, which rises, moves hot temperature control function；Titanium tetrachloride saturator and later with step (2)
Insulating layer is designed with outside the connecting tube of stainless steel cylindrical drum bottom；It is equipped with by the gas around titanium tetrachloride saturator after mass flowmenter
Road, in precipitation reactor, gas can be passed through through the gas distributor of bottom in bypass, reacted device with liquid and after the reaction was completed
Reactor plays stirring and keeps gas reactor distributor internally dry and the unobstructed effect of spray orifice.Mass flowmenter, tetrachloro
Change between titanium saturator, precipitation reactor gas distributor in pipeline, and around the gas bypassing of titanium tetrachloride saturator, all sets
Valve controls on-off.
The rapid draing of half-dried filter cake is carried out in the engineer testing device of pneumatic conveying dryer producer；Half-dried filter cake passes through spiral shell
Rotation auger is extruded into slice and enters high speed hot-air flow, and slice through set high speed blade into being also further crushed after such as hot-air flow
With quickening dusting, 350-400 DEG C of hot-wind inlet temperature regulating range；Powder is through a cyclone separator and a pocket type after drying
Filter is collected；Cyclone separator discharging speed, bag filter rapping frequency and discharging speed are adjustable；Control cyclone separator
And material, the air temperature in bag filter are 150-200 DEG C.
Other equipment used include conventional small-sized flame filter press, kneader, banded extruder, the baking oven recycled in hot wind,
And Muffle furnace.
Embodiment 1
(1) mass flowmenter control dry air 5Nm is opened3/ hr, purge empty titanium tetrachloride saturator, in reactor bottom gas
Body distributor cuts out titanium tetrachloride saturator after 0.2hr, injects titanium tetrachloride about 50kg, and starting electric heating temperature control is to being saturated
Temperature 50 C in device；Dry air continues to be blown into the gas of bottom in reactor by the gas bypassing around titanium tetrachloride saturator
Distributor；
(2) in reactor plus water (deionized water, the same below) is to depth 1200mm, add ammonium hydrogen carbonate 32kg, dissolve, moisturizing is to molten
Liquid depth 1600mm, volume 200L or so, ammonium bicarbonate concentration 2mol/L, 20 DEG C of temperature, pH8.2；Dry air is cut from bypass
Titanium tetrachloride saturator is returned, the gas distributor continuous bubbling for generating bottom in the reacted device of titanium tetrachloride carrier gas is passed through carbonic acid
In hydrogen ammonium salt solution, dry air tolerance is gradually adjusted to 30Nm in 0.2hr3/ hr, and control titanium tetrachloride saturator and work off one's feeling vent one's spleen temperature
50 DEG C, until slurries pH5.0 stops into the titanium tetrachloride carrier gas, i.e., dry air is passed through into the gas around titanium tetrachloride saturator
Bypass is blown into the gas distributor of bottom in reactor and is reduced to 5Nm3/ hr, amount to reaction 1.9hr, reaction rear slurry temperature by
It edges up up to 40 DEG C；
(3-1) is continuously repeated step (2) 3 times totally in 6.5hr, every time all to titanium tetrachloride saturator charging about 20kg before operation
Titanium tetrachloride is maintained into initial liquid level, each reaction rear slurry all squeezes into 1000L agitator tank, total 600L after mixing, carries out old
Change processing, timing aging squeezing into completion since the 3rd slurries, the every 1hr of aging period open stirring 3min；Aging 10hr rear slurry
It 26 DEG C of temperature, is filtered in sheet frame filter, playing 20 DEG C of water washing filter cakes to silver nitrate solution is passed through can't detect Cl-, with room temperature
0.5MPa dry air blows away part water, draws off filter and obtains half-dried filter cake, there are half-dried filter cake about 100kg, and sampling is surveyed more than 500 DEG C of bakings
Amount is TiO2Content average value 23m%；Moisture is kept to be sent immediately to pneumatic conveying dryer factory prepared half-dried filter cake pack sealing
The engineer testing device progress rapid draing of family, 280 DEG C of hot-wind inlet temperature, drying capacity 40kg water/hr；Half-dried filter cake passes through
Screw auger is extruded into diameter 3mm slice and enters high speed hot-air flow, and powder is further crushed and accelerated through 2600rpm high speed blade
Change, half-dried filter cake slice whole dusting is detached from the executeaaafunction for entering thermal current no more than 1min, and the drying time after dusting is not
More than 3sec, powder is collected through a cyclone separator and a bag filter after drying；90 DEG C of cyclone separator wind-warm syndrome and
Every 10min discharging is primary, 87 DEG C of bag filter wind-warm syndrome and every 30min rapping discharging is primary；Cyclonic separation is obtained after the completion of dry
Device fast dry powder 25.1kg, 500 DEG C of baking surplus, that is, TiO2Content 74m%, the fast dry powder 2.8kg of bag filter, 500 DEG C of baking surpluses are
TiO2Content 80m%, two kinds of gained fast dry powder are all very thin, all can all pass through 325 meshes.
(3-2) is repeated step (2) 1 times after the fast dry powder of step (3-1) is fetched, and reaction rear slurry stops cooling water, is continued
Logical dry air 5Nm3/ hr aging 10hr, aging period maintain dry air 5Nm3/ hr is constant, until slurries are closed after getting completely；Slurry
Liquid is filtered in sheet frame filter, and logical 20 DEG C of water washing filter cakes can't detect Cl to silver nitrate solution is passed through-, dry with the 0.5MPa of room temperature
Air blows away part water, draws off filter and obtains half-dried filter cake, surveys 500 DEG C of baking surplus i.e. TiO220m%；
(4) half-dried filter cake 15kg(folding TiO is taken immediately2It 3kg) smashes and is placed on kneader, 40m% nitric acid 1.5kg(is added to contain
HNO30.60kg), starting is shut down after mediating 10min to basic mix, and is switched on every 25min mediates 5min, total co-blended later
React 2hr10min, back mediate side and be spilled into the fast dry powder of cyclone separator obtained by step (3-1) in 20min or so time
1.35kg(rolling over TiO21kg), in banded extruder by Φ 3.5mm orifice plate extrusion, extrusion item is harder relatively straight, and part is taken to squeeze out item not
Rust steel mesh discharge straticulation, which is placed in, to be preheated to 130 DEG C of baking oven and carries out rapid draing, and circulation in hot wind is opened, and 0.4hr is dried,
Dried strip roasts 3hr in 420 DEG C of Muffle furnaces, and titania support is made；Carrier appearance is bright and clean, 108 N/cm of side pressure strength, carries
Surface area per unit volume accumulates 139m2/ g, pore volume 0.36ml/g.
During made above, the ammonium hydrogen carbonate of step (2) feeds intake, dissolves and cuts the first of titanium tetrachloride carrier gas
Phase, reactor slightly ammonia odor suitable for reading is not very big, but does not have smog.Step (4) half-dried filter cake close to room temperature kneading,
Most of moisture is volatilized in placement process, and block small volume is expected after kneading.
Embodiment 2
The basic method for repeating embodiment 1 prepares titania support, and the main distinction is that step (2) reactor adds bicarbonate
Ammonium 64kg, step and situation are as follows:
(1) the titanium tetrachloride saturator cut out reinjects about 20kg for titanium tetrachloride on the basis of former remaining titanium tetrachloride
Initial liquid level is maintained, temperature 50 C in electric heating temperature control to saturator is started；
(2) mass flowmenter control dry air 5Nm is opened3/ hr, by being blown into reaction around the gas bypassing of titanium tetrachloride saturator
The gas distributor of bottom in device；Depth 1200mm is added water in reactor, adds ammonium hydrogen carbonate 64kg, moisturizing to solution deep
1600mm, volume 200L or so, ammonium hydrogen carbonate largely dissolve, and nominal concentration 4mol/L, temperature is down to 10 DEG C, pH8.3；It will do
For air from bypass switchback titanium tetrachloride saturator, the gas distributor for generating bottom in the reacted device of titanium tetrachloride carrier gas is continuous
It is bubbled into ammonium bicarbonate soln, dry air tolerance is gradually adjusted to 30Nm in 0.2hr3/ hr, and control titanium tetrachloride saturation
Device is worked off one's feeling vent one's spleen temperature 50 C, intermediate to inject about 20kg to titanium tetrachloride saturator titanium tetrachloride is maintained initial liquid level；Reaction
Stop to slurries pH5.0 into the titanium tetrachloride carrier gas, by dry air by being blown around the gas bypassing of titanium tetrachloride saturator
Enter the gas distributor of bottom in reactor and is reduced to 5Nm3/ hr amounts to reaction 3.6hr, controls the spiral in reaction process
Slurry temperature after being gradually increasing is maintained 40 DEG C by the originally water flow of shape stainless steel water cooling tube；
(3) reaction rear slurry stops cooling water, continues logical dry air 5Nm3/ hr aging 15hr is filtered in sheet frame filter, with 20 DEG C of water
Washing extremely can't detect Cl by silver nitrate solution-, part water is blown away with room temperature dry air, obtains half-dried filter cake, is surveyed more than 500 DEG C of bakings
Amount is TiO225m%；
(4) half-dried filter cake 12kg(folding TiO is taken2It 3kg) smashes and is placed on kneader, 40m% nitric acid 1.06kg(is added to contain
HNO30.43kg), starting is shut down after mediating 10min to basic mix, and is switched on every 25min mediates 5min, total co-blended later
React 2hr10min, back mediate side in 20min or so time to be spilled into bag filter obtained by 1 step of embodiment (3-1) fast
Dry powder 0.66kg(rolls over TiO20.53kg), it takes part to squeeze out item by Φ 3.5mm orifice plate extrusion in banded extruder and is arranged in stainless (steel) wire
It puts straticulation and is placed in and be preheated to 130 DEG C of baking oven and carry out rapid draing, open circulation in hot wind, 0.4hr is dried, dried strip
3hr is roasted in 420 DEG C of Muffle furnaces, titania support is made；Carrier appearance is bright and clean, and 117 N/cm of side pressure strength, carrier compares table
Area 141m2/ g, pore volume 0.34ml/g.
During made above, the ammonium hydrogen carbonate of step (2) feeds intake, dissolves and cuts the first of titanium tetrachloride carrier gas
Phase, reactor is suitable for reading larger ammonia odor, without smog.Step (4) half-dried filter cake is in the kneading close to room temperature, placement process
Middle most of moisture volatilization, expects block small volume after kneading.
Embodiment 3
The basic method for repeating embodiment 3 prepares titania support, and it is to add carbonic acid that difference, which is that step (2) changes ammonium hydrogen carbonate,
Hydrogen sodium 67kg, step and situation are as follows:
(1) the titanium tetrachloride saturator cut out reinjects about 20kg on the basis of former remaining titanium tetrachloride, starts electric heating
Temperature 60 C in temperature control to saturator；
(2) mass flowmenter control dry air 5Nm is opened3/ hr, by being blown into reaction around the gas bypassing of titanium tetrachloride saturator
The gas distributor of bottom in device；Depth 1200mm is added water in reactor, adds sodium bicarbonate 67kg, moisturizing to solution deep
1600mm, volume 200L or so, the dissolution of sodium bicarbonate a part, slurries nominal concentration 4mol/L, 25 DEG C of temperature, pH8.3；It will do
For air from bypass switchback titanium tetrachloride saturator, the gas distributor for generating bottom in the reacted device of titanium tetrachloride carrier gas is continuous
It is bubbled into ammonium bicarbonate soln, dry air tolerance is gradually adjusted to 30Nm in 0.2hr3/ hr, and control titanium tetrachloride saturation
Device is worked off one's feeling vent one's spleen temperature 60 C, until slurries pH5.0 stops into the titanium tetrachloride carrier gas, it is intermediate to the injection of titanium tetrachloride saturator about
20kg amounts to reaction 2.4hr, the originally water flow of the spiral shape stainless steel water cooling tube is controlled in reaction process, will gradually on
Slurry temperature after rising maintains 35 DEG C；
(3) reaction rear slurry stops cooling water, continues logical dry air 5Nm3/ hr aging 15hr is filtered in sheet frame filter, with 20 DEG C of water
Washing extremely can't detect Cl by silver nitrate solution-, part water is blown away with room temperature dry air, obtains half-dried filter cake, is surveyed more than 500 DEG C of bakings
Amount is TiO215m%；
(4) half-dried filter cake 20kg(folding TiO is taken2It 3kg) smashes and is placed on kneader, 40m% nitric acid 2.0kg(is added to contain
HNO30.80kg), starting is shut down after mediating 10min to basic mix, and is switched on every 25min mediates 5min, total co-blended later
React 2hr10min, back mediate side and be spilled into the fast dry powder of cyclone separator obtained by step (3-1) in 30min or so time
2.7kg(rolls over TiO22kg), in banded extruder by Φ 3.5mm orifice plate extrusion, extrusion item is harder relatively straight, and part is taken to squeeze out item not
Rust steel mesh discharge straticulation, which is placed in, to be preheated to 130 DEG C of baking oven and carries out rapid draing, and circulation in hot wind is opened, and 0.4hr is dried,
Dried strip roasts 3hr in 420 DEG C of Muffle furnaces, and titania support is made；Carrier appearance is bright and clean, 108 N/cm of side pressure strength, carries
Surface area per unit volume accumulates 133m2/ g, pore volume 0.36ml/g.
During made above, step (2) feeds intake, dissolves and cuts the first of titanium tetrachloride carrier gas in sodium bicarbonate
Phase, the reactor ammonia odor suitable for reading all without embodiment 1 do not have smog substantially yet.Step (4) half-dried filter cake is close to room temperature
Kneading, most of moisture volatilization in placement process, block small volume is expected after kneading.
Embodiment 4
The dried strip of 3 step of Example (4) roasts 4hr in 400 DEG C of Muffle furnaces, and titania support is made；The outer mass color of carrier
It is clean, side pressure strength 102N/cm, carrier specific surface area 149m2/ g, pore volume 0.36ml/g.
Embodiment 5
The dried strip of 3 step of Example (4) roasts 3hr in 450 DEG C of Muffle furnaces, and titania support is made；The outer mass color of carrier
It is clean, 113 N/cm of side pressure strength, carrier specific surface area 130m2/ g, pore volume 0.35ml/g.
Embodiment 6
By the dried strip of embodiment 1-3 step (4), it is respectively placed in 500 DEG C of Muffle furnace roasting 2hr.Gained titania support, with
Corresponding 420 DEG C of roastings 3hr resulting vehicle is compared, and side pressure strength all slightly improves, and the decline of specific surface area, pore volume all exists
Within 10%, illustrate the better heat stability of titania support of the present invention.
Comparative example 1
The half-dried filter cake 15kg(of 1 step of Example (3-2) rolls over TiO2It 3kg) smashes and is placed on kneader, add 40m% nitric acid
1.14kg(containing HNO30.45kg), kneading 2hr, in banded extruder by Φ 3.5mm orifice plate extrusion, extrusion item is slightly soft compared with embodiment 1,
Take part squeeze out item stainless (steel) wire discharge straticulation be placed in be preheated to 130 DEG C baking oven carry out rapid draing, open in hot wind
Circulation, 0.4hr is dried, and dried strip roasts 3hr in 420 DEG C of Muffle furnaces, and titania support is made；Carrier appearance is bright and clean, side
98 N/cm of Compressive Strength, carrier specific surface area 142m2/ g, pore volume 0.35ml/g.
This comparative example explanation, the addition of fast dry powder make to squeeze out a hardness raising, and the intensity of prepared carrier improves.
Comparative example 2
The part extrusion item of Example 1,4 steps (4), is separately filled in enamel tray, covers, be placed in and be preheated to 130 DEG C
Baking oven is dried, and discovery all ends parch when 2hr, 4hr, and when 6hr is just dried, and dried strip is roasted in 420 DEG C of Muffle furnaces respectively
3hr, the specific surface area of obtained titania support, pore volume all reduce by 20% or more.
Comparative example 3
The half-dried filter cake 25kg of 1 step of Example (3-2) is filled and is placed in the baking oven for being preheated to 130 DEG C in enamel tray, capping
It is dried, discovery all ends parch when 2hr, 4hr, and when 6hr is just dried, after quick ultra-fine grinding, dry powder 5.3kg(are taken to roll over
TiO2It 4kg) is placed in kneader, adds nitric acid solution 6.4kg(containing HNO30.45kg), kneading 2hr passes through the hole Φ 3.5mm in banded extruder
Plate extrusion, extrusion item is relatively straight hard, and surface shows slightly coarse；It takes part extrusion item to be placed in stainless (steel) wire discharge straticulation to be preheated to
130 DEG C of baking oven carries out rapid draing, opens circulation in hot wind, and 0.4hr is dried, and dried strip roasts 3hr in 420 DEG C of Muffle furnaces,
Titania support is made；Carrier appearance is bright and clean, 93 N/cm of side pressure strength, carrier specific surface area 116m2/ g, pore volume
0.35ml/g。
Comparative example 4
According to known methods, it is prepared with titanium tetrachloride and ammonium hydrogen carbonate raw material:
(1) add water about 10L in 200L gravity tank, add trash ice about 30kg, be inserted to liquid level with tubule and be pushed down into titanium tetrachloride 20kg, stir
It is even, 30 DEG C of temperature or so, it is made into titanium tetrachloride solution；50 water of heating degree about 150L, adds bicarbonate in another 200L gravity tank
Ammonium 32kg stirring and dissolving, is made into ammonium bicarbonate soln；
(2) add water 40L that can extremely stir in 250L reaction kettle, reacting kettle jacketing leads to 25 DEG C of tap water；By titanium tetrachloride solution and
Ammonium bicarbonate soln is controlled through valve and flowmeter respectively, and cocurrent is put into reaction kettle and is stirred to react, and controls slurries pH4.5-
5.0, until ammonium bicarbonate soln is finished, titanium tetrachloride solution shows a small surplus；Amount to reaction 1.6hr, slurry temperature in reaction process
No more than 35 DEG C；
(3) reaction rear slurry stands aging 10hr, and every 1hr opens stirring 2 minutes；Aging rear slurry is filtered in sheet frame filter, is led to
20 DEG C of water washing filter cakes can't detect Cl to silver nitrate solution is passed through-, discovery is washed much than embodiment 1-5 step (3) difficulty, with normal
Warm dry air blows moisture, and discovery is blown much than embodiment 1-5 step (3) difficulty, long-time air blow draw off after water filter obtain it is half-dried
Filter cake surveys 500 DEG C of baking surplus i.e. TiO220m%；
(4) half-dried filter cake 15kg(folding TiO is taken2It 3kg) smashes and is placed on kneader, 40m% nitric acid 0.9kg(is added to contain
HNO30.36kg), kneading 2hr, in banded extruder by Φ 3.5mm orifice plate extrusion, take part squeeze out item stainless (steel) wire discharge at
Thin layer, which is placed in, to be preheated to 130 DEG C of baking oven and carries out rapid draing, opens circulation in hot wind, 0.4hr is dried, and dried strip is 420
DEG C Muffle furnace roasts 3hr, and titania support is made；Carrier appearance is bright and clean, 118 N/cm of side pressure strength, carrier specific surface area
115m2/ g, pore volume 0.29ml/g.
Comparative example 5
Substantially with comparative example 2, but reaction temperature is 80 DEG C or so, specific as follows:
(1) add water about 30L in 200L gravity tank, add trash ice about 10kg, be inserted to liquid level with tubule and be pushed down into titanium tetrachloride 20kg, stir
It is even, 80 DEG C of temperature or so, it is made into titanium tetrachloride solution；Add water about 150L in another 200L gravity tank, adds ammonium hydrogen carbonate 32kg
Stirring and dissolving is made into ammonium bicarbonate soln；
(2) add water 40L that can extremely stir in 250L reaction kettle, reacting kettle jacketing leads to 85 DEG C of hot water of big flow；Titanium tetrachloride is molten
Liquid and ammonium bicarbonate soln are controlled through valve and flowmeter respectively, and cocurrent is put into reaction kettle and is stirred to react, and control slurries temperature
80-85 DEG C, pH4.5-5.0 of degree, until ammonium bicarbonate soln is finished, titanium tetrachloride solution has residue；Amount to reaction 1.6hr；
(3) reaction rear slurry is filtered in sheet frame filter later in 85 DEG C of heat preservation aging 2hr, leads to 20 DEG C of water washing filter cakes to passing through
Silver nitrate solution can't detect Cl-, moisture is blown with room temperature dry air, filter is drawn off and obtains half-dried filter cake, surveys 500 DEG C of baking surpluses i.e.
TiO235m%；
(4) half-dried filter cake 8.6kg(folding TiO is taken2It 3kg) smashes and is placed on kneader, 40m% nitric acid 0.9kg(is added to contain
HNO30.36kg), kneading 2hr, discovery, which is mediated, expects that intensity is lower, passes through the intensity that Φ 3.5mm orifice plate squeezes out in banded extruder
It is lower, take part to squeeze out item easy when stainless (steel) wire discharge straticulation is placed in the baking oven progress rapid draing for being preheated to 130 DEG C
Fracture, dried strip roast 3hr in 420 DEG C of Muffle furnaces, and resulting vehicle side pressure strength is very low, only 43N/cm, continue in 500 DEG C of horses
Not furnace roasts 2hr, resulting vehicle side pressure strength 60N/cm, carrier specific surface area 86m2/ g, pore volume 0.22ml/g.
The main component of half-dried filter cake in 5 step of this comparative example (3) should be metatitanic acid, prepared support strength is low be because
It is very low for the activity of prepared metatitanic acid, it is not easy or gelatinization reaction occurs for less and nitric acid, the pore volume of carrier is also smaller.
Claims (7)
1. a kind of preparation method of titania support, comprising the following steps:
(1) using titanium tetrachloride and carrier gas as raw material, by way of temperature control bubbling or spray, four chlorinations of 1-8% volume content are prepared
Titanium carrier gas；The carrier gas is nitrogen or dry air；
(2) ammonium hydrogen carbonate of compound concentration 1-4mol/L or sodium bicarbonate solution or slurries, continuous bubbling are passed through four chlorination
Titanium carrier gas controls 10-40 DEG C of slurry temperature；Reaction time 0.5-2hr, until slurries pH4.5-5.0 stops into the titanium tetrachloride
Carrier gas completes reaction；
(3) reaction rear slurry places aging 5-20hr, filtering, and 10-30 DEG C of water washing of filter cake blows away part with room temperature dry air
Water, obtains half-dried filter cake, and folding contains TiO215-25m%；It takes the half-dried filter cake in part to carry out rapid draing with 350-400 DEG C of hot wind, is made
Fast dry powder, folding contain TiO270-90m%；
(4) half-dried filter cake 60-90 mass parts in terms of titanium dioxide described in step 3 are taken, nitric acid solution 10-20 matter in terms of pure nitric acid is added
Part is measured, mixed processing 1-3hr is added fast dry powder 10-40 mass parts in terms of titanium dioxide, kneading 0.5-1hr described in step 3 and squeezes
Item, rapid draing, dried strip are roasted at 400-500 DEG C, and titania support is made.
2. the preparation method of titania support as described in claim 1, which is characterized in that step (1) titanium tetrachloride carrier gas
Volume content be preferably 3-8%.
3. the preparation method of titania support as claimed in claim 2, which is characterized in that prepare sodium bicarbonate in step (2)
Solution or slurries.
4. the preparation method of titania support as claimed in claim 4, which is characterized in that match before reaction in step (2) and set low
The ammonium hydrogen carbonate or sodium bicarbonate solution of concentration and repeatedly fill into ammonium hydrogen carbonate or sodium bicarbonate raw material during the reaction.
5. the preparation method of titania support as described in claim 1, which is characterized in that starched after reaction in step step (3)
Liquid first pass through change water reduce mother liquid concentration place aging again.
6. the preparation method of titania support as described in claim 1, which is characterized in that half-dried filter cake in step step (3)
Rapid draing utilize pneumatic conveying dryer carry out；In Optimization of Gas Flow Drying, half-dried filter cake by screw auger be extruded into slice into
Enter velocity heated gas and is further crushed through high speed blade.
7. the preparation method of titania support as described in claim 1, which is characterized in that squeeze out the quick of item in step (4)
Drying condition is 130 DEG C of hot blast temperature, time 0.4hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810881108.4A CN109107555B (en) | 2018-08-04 | 2018-08-04 | Preparation method of titanium dioxide carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810881108.4A CN109107555B (en) | 2018-08-04 | 2018-08-04 | Preparation method of titanium dioxide carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109107555A true CN109107555A (en) | 2019-01-01 |
| CN109107555B CN109107555B (en) | 2021-07-23 |
Family
ID=64851836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810881108.4A Active CN109107555B (en) | 2018-08-04 | 2018-08-04 | Preparation method of titanium dioxide carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109107555B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080271642A1 (en) * | 2007-05-03 | 2008-11-06 | Tronox Llc | Making co-precipitated mixed oxide-treated titanium dioxide pigments |
| US20100121100A1 (en) * | 2008-11-12 | 2010-05-13 | Daniel Travis Shay | Supported palladium-gold catalysts and preparation of vinyl acetate therewith |
| CN102086046A (en) * | 2010-12-31 | 2011-06-08 | 东莞市明天纳米科技有限公司 | Preparation method of nano-TiO2 lyosol |
| CN102272050A (en) * | 2009-02-20 | 2011-12-07 | 克罗内斯国际公司 | Multistage method for producing titanium dioxide |
| CN107954472A (en) * | 2017-11-29 | 2018-04-24 | 广西雅照钛白有限公司 | A kind of titanium white production technique |
-
2018
- 2018-08-04 CN CN201810881108.4A patent/CN109107555B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080271642A1 (en) * | 2007-05-03 | 2008-11-06 | Tronox Llc | Making co-precipitated mixed oxide-treated titanium dioxide pigments |
| US20100121100A1 (en) * | 2008-11-12 | 2010-05-13 | Daniel Travis Shay | Supported palladium-gold catalysts and preparation of vinyl acetate therewith |
| CN102272050A (en) * | 2009-02-20 | 2011-12-07 | 克罗内斯国际公司 | Multistage method for producing titanium dioxide |
| CN102086046A (en) * | 2010-12-31 | 2011-06-08 | 东莞市明天纳米科技有限公司 | Preparation method of nano-TiO2 lyosol |
| CN107954472A (en) * | 2017-11-29 | 2018-04-24 | 广西雅照钛白有限公司 | A kind of titanium white production technique |
Non-Patent Citations (1)
| Title |
|---|
| SEMIN CHUN等: "Characteristics of Titanium Dioxide Synthesized by the Carbon Dioxide Microwave Plasma at Atmospheric Pressure", 《SCIENCE OF ADVANCED MATERIALS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109107555B (en) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105461572B (en) | A kind of cleaning procedure for being continuously synthesizing to the chloroaniline of 2,4 dinitro 6 | |
| CN109761209A (en) | A kind of production technology and its production equipment of ferric phosphate | |
| CN104495886A (en) | Device and method for producing magnesium sulfate | |
| CN106430787B (en) | A kind of APT production wastewater recycling method | |
| CN103991893A (en) | Preparing method of high-purity basic cupric carbonate | |
| CN105347703B (en) | A kind of decomposition method of calcium carbonate and magnesium carbonate ore deposit | |
| CN106518656B (en) | A kind of method for crystallising of adipic acid | |
| CN109107555A (en) | The preparation method of titania support | |
| CN102381722B (en) | Preparation method of activated aluminum oxide and product prepared by using same | |
| CN106800276A (en) | Using the industrialized preparing process of sterling sulfur trioxide vapor- phase synthesis chlorosulfonic acid | |
| CN205874265U (en) | Preparation facilities of biruea | |
| CN109126894A (en) | A kind of preparation method of titania support | |
| CN106220534B (en) | A kind of preparation facilities and preparation method of biruea | |
| CN109053610A (en) | A kind of good process for cleanly preparing of environment of high-purity cyanuric acid | |
| CN107233794A (en) | A kind of method of hydrogen sulfide in removal gas | |
| CN111874924A (en) | Process and system for producing molten salt-grade potassium nitrate by utilizing double decomposition method | |
| CA1123576A (en) | Alumina production by nitric acid extraction of clay | |
| CN106588797B (en) | The method that ball-milling method prepares melamine cyanurate flame retardant | |
| CN107750236A (en) | High-purity synthesis fluorite, prepare its method and apparatus | |
| CN207786614U (en) | The system for preparing magnetic bio carbon composite | |
| CN103274921B (en) | Device and method for preparing calcium formate by utilizing yellow phosphorus tail gas | |
| CN109956487A (en) | Circulating ammonia coupling reaction is filtered, washed, drying system and method | |
| CN207738468U (en) | A kind of thick VOCl3Prepare high-purity V2O5System | |
| CN104557613B (en) | Methyl isocyanate quantity-produced deslagging method | |
| CN1202463A (en) | Process for high-yield synthesis of high content vanadylic sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |