CN109107555B - Preparation method of titanium dioxide carrier - Google Patents
Preparation method of titanium dioxide carrier Download PDFInfo
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- CN109107555B CN109107555B CN201810881108.4A CN201810881108A CN109107555B CN 109107555 B CN109107555 B CN 109107555B CN 201810881108 A CN201810881108 A CN 201810881108A CN 109107555 B CN109107555 B CN 109107555B
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- titanium tetrachloride
- filter cake
- titanium dioxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 19
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 73
- 239000007789 gas Substances 0.000 claims abstract description 57
- 238000001035 drying Methods 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000012065 filter cake Substances 0.000 claims abstract description 51
- 239000002002 slurry Substances 0.000 claims abstract description 37
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 30
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 30
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 27
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- 238000004898 kneading Methods 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 13
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007664 blowing Methods 0.000 claims abstract description 8
- 239000012159 carrier gas Substances 0.000 claims abstract description 7
- 230000005587 bubbling Effects 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 26
- 239000000243 solution Substances 0.000 description 31
- 239000012043 crude product Substances 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005485 electric heating Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001502 supplementing effect Effects 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
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000003916 acid precipitation Methods 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
- 238000005520 cutting process Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 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 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 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
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012066 reaction slurry Substances 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
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of a titanium dioxide carrier, which comprises the following steps: (1) preparing titanium tetrachloride diluent gas with the volume content of 1-8% by taking nitrogen or dry air as carrier gas; (2) preparing ammonium bicarbonate or sodium bicarbonate solution or slurry with the concentration of 1-4mol/L, continuously bubbling and introducing titanium tetrachloride diluent gas, and controlling the temperature of the slurry to be 10-40 ℃; (3) aging the slurry for 5-20hr, filtering, washing with water, and blowing water to obtain semi-dry filter cake; taking part of the half-dried filter cake, and quickly drying the half-dried filter cake by using hot air at the temperature of 250-300 ℃ to obtain quick-drying powder; (4) and (3) adding a nitric acid solution into the semi-dry filter cake, mixing, adding the quick-drying powder, kneading, extruding, quickly drying and roasting to obtain the titanium dioxide carrier. The prepared titanium dioxide carrier has high pore volume, surface area, mechanical strength and thermal stability and low cost.
Description
Technical Field
The invention belongs to the field of industrial catalysts, and particularly relates to a preparation method of a titanium dioxide carrier.
Prior Art
Because of their particular surface properties, titania supports or catalysts containing titania components can play a unique role in many reactions such as the polymerization of olefins.
For example, titanium dioxide-based sulfur recovery catalyst for organic sulfur COS and CS2The hydrolysis reaction has high activity, the conversion rate allowed by thermodynamic equilibrium of the Claus reaction is almost achieved, and 1200 h can be realized under the required temperature condition-1The catalyst is used at high airspeed, does not produce sulfation poisoning, has stable performance in sulfur recovery application, and has a service life of 5-10 years. The titanium dioxide-based sulfur recovery catalyst is generally prepared by sequentially adding a sulfuric acid solution and a calcium nitrate solution into metatitanic acid powder, kneading, extruding, drying and roasting, wherein the anatase titanium dioxide content is 85-90m%, the calcium sulfate content is 10-15m%, and calcium sulfate plays a role of a binder. In recent years, due to the development of oil refining and coal chemical industry, the titanium dioxide-based sulfur recovery catalyst has been widely used. The pore volume is too small, so that the catalyst is inconvenient to be used as a carrier and an active component is further loaded to prepare the catalyst.
In addition, as hydrogenation catalysts prepared by loading cobalt molybdenum active components on titanium dioxide carriers, the interaction between the surfaces of the carriers and the metal active components, the catalysts have high desulfurization activity, but the titanium dioxide carriers with appropriate pore volume and surface area are needed, and preferably, the titanium dioxide carriers are formed with slightly larger pore volume so as to be convenient for loading the active components by an impregnation method to prepare the catalysts.
Except for the problem of processing cost, the formed titanium dioxide carrier with larger pore volume and surface area prepared by the prior art is difficult to meet the requirement on mechanical strength, namely, the technical problem of how to prepare the formed titanium dioxide carrier with higher pore volume, surface area, mechanical strength and thermal stability in a limited cost range is solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a formed titanium dioxide carrier with higher pore volume, surface area, mechanical strength and thermal stability, which comprises the following steps:
(1) preparing titanium tetrachloride diluent gas with the volume content of 1-8% by taking titanium tetrachloride and carrier gas as raw materials in a temperature-controlled bubbling or spraying mode; the carrier gas is nitrogen or dry air;
(2) preparing ammonium bicarbonate or sodium bicarbonate solution or slurry with the concentration of 1-4mol/L, continuously bubbling and introducing the titanium tetrachloride diluent gas, and controlling the temperature of the slurry to be 10-40 ℃; reacting for 0.5-2hr until pH of the slurry is 4.5-5.0, and stopping feeding the titanium tetrachloride diluent gas to complete the reaction;
(3) aging the slurry for 5-20hr, filtering, washing the filter cake with 10-30 deg.C water, blowing off part of water with normal temperature dry air to obtain semi-dry filter cake, and removing TiO215-25 m%; taking part of the half-dry filter cake, and quickly drying the half-dry filter cake by using 350-400 ℃ hot air to prepare quick-drying powder containing TiO2 70-90m%；
(4) And (3) taking 60-90 parts by mass of the semi-dry filter cake in the step (3) calculated by titanium dioxide, adding 10-20 parts by mass of nitric acid solution calculated by pure nitric acid, mixing for 1-3 hours, adding 10-40 parts by mass of the quick-drying powder in the step (3) calculated by titanium dioxide, kneading for 0.5-1 hour, extruding strips, quickly drying, and roasting the dried strips at the temperature of 400-500 ℃ to obtain the titanium dioxide carrier.
The titanium dioxide carrier prepared by the method has higher pore volume, surface area and mechanical strength, and the specific surface area of the carrier is 120-2The volume of the product per gram, and the diameter of the product are 0.3-0.4ml/g, and the lateral pressure strength of the product is 3-4mm, and can reach 90N/cm, even more than 100N/cm; the main raw material is four with lower priceTitanium chloride and ammonium bicarbonate or sodium bicarbonate, and the preparation process is a conventional process, so the cost is low.
In the preparation method of the titanium dioxide carrier, the volume content of the titanium tetrachloride diluent gas in the step (1) is preferably 3-8%, when the content of titanium tetrachloride is lower, the consumption of the carrier gas is larger, when the content of titanium tetrachloride is higher, the partial reaction is too violent, and the absorption is not complete, namely the exhaust gas is easy to carry smoke; according to the saturated vapor pressure data of titanium tetrachloride, the highest volume content of titanium tetrachloride at 30 ℃ of the diluent gas is 2.1%, 3.4% at 40 ℃, 5.3% at 50 ℃, 8.1% at 60 ℃ and 12% at 70 ℃; when the temperature of the diluent gas is too high than that of the reaction slurry, titanium tetrachloride is easy to condense in a diluent gas distributor immersed at the bottom of the slurry and at a nozzle, and hydrolysis accumulation of the titanium tetrachloride easily causes nozzle blockage.
In the preparation method of the titanium dioxide carrier, after the reaction in the step (3), the slurry is firstly changed with water to reduce the concentration of the mother liquor and then is placed for aging, so that better aging and impurity removal effects are obtained, and the semi-dry filter cake is easier to wash to the required Cl-The content requirement.
In the preparation method of the titanium dioxide carrier, the ammonium bicarbonate or sodium bicarbonate solution adopted in the step (2) has the initial pH value not higher than 8.5, and the reaction with the titanium tetrachloride diluent gas is relatively mild. The ammonium bicarbonate has the advantages that the prepared carrier does not contain sodium, a solution with higher concentration can be prepared, but ammonia gas can be blown out by carrier gas and generated carbon dioxide at the initial stage of reaction when the concentration is higher, so that raw material loss is caused, the smell of the ammonia gas is also larger, and a low-concentration solution can be prepared before the reaction and can be supplemented for many times in the reaction process, so that the slurry concentration and the production efficiency are improved; sodium bicarbonate has a somewhat lower solubility but the benefit is that it does not produce an ammonia odor. The solubility of sodium bicarbonate at 25-40 ℃ is 10.3-12.7g/100ml water, 1.2-1.4mol/L solution can be prepared, but the sodium bicarbonate can be prepared into slurry for use, and only the suspension of the sodium bicarbonate can be ensured in the reaction process.
In the preparation method of the titanium dioxide carrier, the main component of the semi-dry filter cake obtained in the step (3) is orthotitanic acid which is generated in a low-temperature reaction and has certain reaction activity because the semi-dry filter cake is not dried for a long time at the temperature of more than 100 ℃, the semi-dry filter cake can react with nitric acid in the step (4) to generate a colloidal body with a bonding effect, the extruded strip and the dried strip are endowed with strength, and the titanium dioxide carrier obtains the required strength after being roasted at the temperature of 400-450 ℃. And (3) rapidly drying the semi-dry filter cake by using hot air at the temperature of 250-300 ℃ to obtain the rapid dry powder, wherein the purpose is to adjust and control the dryness and humidity of the kneaded materials in the kneading process in the step (4) so as to ensure that the extruded strip has proper hardness, prevent the surface of the extruded strip from having dry cracks after rapid drying, and simultaneously reduce the requirement on the water content of the semi-dry filter cake. The rapid drying of the semi-dry filter cake is preferably carried out using an air-flow drying apparatus; in the air flow drying process, the semi-dry filter cake can be extruded into thin strips by a spiral auger to enter high-speed hot air, the thin strips can be further crushed by a high-speed blade after being fed, the surface layer material is quickly dehydrated, pulverized and separated from the air flow, the surface layer material is blown away along with the air flow and is quickly dried and partially dehydrated, the dried powder is collected by a cyclone separator and a bag filter, the pulverizing time of the thin strips is within a few minutes, the drying time after pulverization is only a few seconds, the structure of orthotitanic acid is not greatly changed in the filter cake dehydration process, and the structure of the orthotitanic acid is also greatly preserved in the partial dehydration process of the orthotitanic acid; although the residence time of the dried powder in the cyclone separator and the bag filter may be slightly longer, the influence on the properties of the fast dry powder may not be great, for example, the cyclone separator discharges the powder once every 10min, and the bag filter discharges the powder once every 30min by rapping, in the embodiment of the invention, the temperature of the material and the air in the cyclone separator and the bag filter is controlled to be 200 ℃ at 150 ℃, and the powder is dried to the extent that the free water is completely removed and the combined water is partially removed. The semi-dry filter cake contains more water, and a large part of the semi-dry filter cake volatilizes in the kneading process close to the normal temperature, so that the water content of the kneaded material block is moderate, and harder strips can be extruded.
In the preparation method of the titanium dioxide carrier, the rapid drying of the extruded strips in the step (4) is also critical, and the temperature of hot air in the embodiment is 130 ℃, and the time is suitable to be 0.4 hr; the structure of orthotitanic acid introduced from the semi-dried filter cake and orthotitanic acid analogue introduced from the quick-dried powder in the process is still retained to a large extent, otherwise the pore volume and the surface area of the finally prepared carrier are reduced.
The titanium dioxide carrier prepared by the method has good thermal stability, and the lateral pressure strength, the specific surface area and the pore volume of the titanium dioxide carrier obtained by roasting at 420 ℃, 450 ℃ and 500 ℃ are not greatly different.
Detailed description of the preferred embodiments
The technical solution of the present invention will be specifically described and illustrated with reference to the following examples, but the present invention is not limited thereto.
In the preparation process of the titanium dioxide carrier, the preparation of the titanic acid semi-dry filter cake and the preparation of the quick-drying powder are main works.
The equipment for preparing the semi-dry filter cake of orthotitanic acid mainly comprises an orthotitanic acid precipitation reactor, an attached gas metering device and a titanium tetrachloride saturator. Wherein the gas metering and control is through a nitrogen range of 5-50Nm3Performing mass flow meter per hr, adjusting by coefficient conversion when introducing air, and arranging a precision filter in front of the flow meter; the titanium tetrachloride saturator arranged behind the mass flow meter is a 50L stainless steel tank, the bottom in the tank is provided with a stainless steel disc-shaped gas distributor and a 6kw electric heating rod group, the disc-shaped gas distributor is provided with about 500 phi 1mm spray holes, the hole distance is about 15mm, the electric heating rod group is arranged above the gas distributor, the temperature of the gas in the titanium tetrachloride saturator and the temperature of the gas at the outlet are controlled by temperature controllers of the electric heating rod group, and a glass tube liquid level meter is arranged outside the tank; the main body of the orthotitanic acid precipitation reactor is a stainless steel cylindrical reactor, the inner diameter is phi 400, the height is 2000mm, the upper part is open, a stainless steel disc-shaped gas distributor (with about 500 phi 1mm spray holes and the hole spacing is about 15 mm) is arranged at the bottom in the reactor, the gas distributor is connected with an outlet gas pipeline of a titanium tetrachloride saturator, a phi 15x1.5 spiral stainless steel water cooling pipe which is about 20m long is arranged at the middle lower part of the reactor close to the inner wall, and tap water with the inner inlet temperature of 20 ℃ plays a role in heat transfer and temperature control; insulating layers are arranged outside the titanium tetrachloride saturator and the stainless steel cylindrical barrel bottom connecting pipe in the step (2); a gas bypass bypassing the titanium tetrachloride saturator is arranged behind the mass flow meter, and after the liquid preparation of the precipitation reactor and the reaction are finished, the gas can be introduced into the reactor through the bypass and a gas distributor at the bottom in the reactor to stir and keep the gas in the reactorDrying the inside of the distributor and opening the orifices. The mass flowmeter, the titanium tetrachloride saturator, the pipeline among the gas distributors of the precipitation reactor and the gas bypass bypassing the titanium tetrachloride saturator are all provided with valves for controlling the on-off.
The quick drying of the semi-dry filter cake is carried out in a process test device of an airflow drying equipment manufacturer; extruding the semi-dry filter cake into thin strips by a spiral auger, feeding the thin strips into high-speed hot air flow, further crushing and accelerating pulverization by a high-speed blade after the thin strips enter the hot air flow, wherein the temperature regulation range of a hot air inlet is 350-; collecting the dried powder through a cyclone separator and a bag filter; the discharging speed of the cyclone separator, the vibration frequency of the bag filter and the discharging speed are adjustable; the temperature of the materials and the air in the cyclone separator and the bag filter is controlled to be 150-200 ℃.
Other equipment used included conventional small plate and frame filters, kneaders, plotters, ovens with internal circulation of hot air, and muffle furnaces.
Example 1
(1) Open mass flow meter for controlling dry air 5Nm3Purging empty titanium tetrachloride saturator and a gas distributor at the bottom in the reactor, cutting out the titanium tetrachloride saturator after 0.2hr, injecting about 50kg of titanium tetrachloride, and starting electric heating to control the temperature to 50 ℃ in the saturator; the dry air is continuously blown into a gas distributor at the bottom in the reactor through a gas bypass bypassing the titanium tetrachloride saturator;
(2) adding water (deionized water, the same below) into the reactor to the depth of 1200mm, adding 32kg of ammonium bicarbonate, dissolving, and supplementing water to the depth of 1600mm, the volume of 200L, the concentration of ammonium bicarbonate of 2mol/L, the temperature of 20 ℃, and the pH value of 8.2; the dry air is returned to the titanium tetrachloride saturator from the bypass, the generated titanium tetrachloride diluent gas is continuously bubbled into the ammonium bicarbonate solution through a gas distributor at the bottom in the reactor, and the amount of the dry air is gradually adjusted to 30Nm within 0.2hr3The temperature of the outlet gas of the titanium tetrachloride saturator is controlled to be 50 ℃ and the titanium tetrachloride diluent gas is stopped from entering until the pH of the slurry is 5.0, namely dry air is blown into a gas distributor at the bottom in the reactor through a gas bypass bypassing the titanium tetrachloride saturator and is reduced to 5Nm3The total reaction time is 1.9hr, and the slurry temperature is gradually increased to 40 ℃ after the reaction;
(3-1) continuously repeating the step (2) for 3 times within 6.5hr, adding about 20kg of titanium tetrachloride to a titanium tetrachloride saturator before each operation to maintain the initial liquid level of titanium tetrachloride, adding the slurry into a 1000L stirring tank after each reaction, mixing for 600L, aging, timing aging from the completion of the slurry injection for 3 rd time, and stirring for 3min every 1hr during aging; aging for 10hr, filtering at 26 deg.C, filtering with plate-and-frame filter, washing filter cake with water at 20 deg.C until no Cl is detected by silver nitrate solution-Blowing off part of water by using normal-temperature 0.5MPa dry air, discharging out of filter to obtain semi-dry filter cake, and sampling to measure TiO residue at 500 deg.C2The average content value is 23 m%; bagging the prepared semi-dry filter cake, sealing, keeping water separate, and sending to a process test device of an airflow drying equipment manufacturer for rapid drying, wherein the inlet temperature of hot air is 280 ℃, and the drying capacity is 40kg of water/hr; extruding the semi-dry filter cake into thin strips with the diameter of 3mm by a spiral auger, entering high-speed hot air flow, further crushing and accelerating pulverization by a 2600rpm high-speed blade, wherein the experience time of all pulverization of the semi-dry filter cake strips separated from entering hot air flow is not more than 1min, the drying time after pulverization is not more than 3sec, and collecting the dried powder by a cyclone separator and a bag filter; discharging once every 10min when the air temperature of the cyclone separator is 90 ℃, and discharging once every 30min when the air temperature of the bag filter is 87 ℃; 25.1kg of quick-drying powder of the cyclone separator is obtained after drying, and TiO is obtained after the drying residue is dried at 500 DEG C274m percent of the rapid dry powder of the bag filter is 2.8kg, and the rest is TiO after being dried at 500 DEG C2The content is 80m%, and the two obtained quick-drying powders are both fine and can pass through a 325-mesh sieve.
(3-2) after the quick-drying powder in the step (3-1) is taken back, the step (2) is repeated for 1 time, cooling water is stopped for the slurry after the reaction, and dry air is continuously introduced for 5Nm3Aging for 10hr with dry air of 5Nm3The/hr is not changed, and the slurry is closed after being completely pumped out; filtering the slurry in a plate-and-frame filter, and washing the filter cake by water at 20 ℃ until no Cl is detected by a silver nitrate solution-Blowing off part of water by using normal-temperature 0.5MPa dry air, discharging the water out of a filter to obtain a semi-dry filter cake,measuring the baking allowance at 500 ℃ to obtain TiO2 20m%；
(4) Immediately taking 15kg of semi-dry filter cake (folded TiO)23 kg) of the crude product, crushing the crude product, placing the crushed crude product in a kneader, and adding 1.5kg of 40m% nitric acid (containing HNO)30.60 kg), starting kneading for 10min till basically mixing uniformly, stopping the machine, starting kneading for 5min every 25min, mixing and reacting for 2hr10min totally, then spraying 1.35kg (folded TiO) of quick-drying powder of the cyclone separator obtained in the step (3-1) for about 20min while kneading21 kg) of the titanium dioxide carrier, extruding the strips through a phi 3.5mm pore plate in a strip extruding machine, enabling the extruded strips to be harder and straighter, taking part of the extruded strips to be discharged into a thin layer in a stainless steel net, placing the thin layer in an oven preheated to 130 ℃ for quick drying, starting hot air internal circulation, drying the strips after 0.4hr, and roasting the dried strips in a muffle furnace at 420 ℃ for 3hr to obtain the titanium dioxide carrier; the carrier has smooth surface, lateral pressure strength of 108N/cm and specific surface area of 139m2Pore volume 0.36 ml/g.
In the preparation process, the ammonium bicarbonate in the step (2) is fed, dissolved and cut into the initial stage of the titanium tetrachloride diluent gas, the upper opening of the reactor has slight ammonia smell, is not large, and has no smoke. Most of water in the semi-dry filter cake in the step (4) is volatilized in the kneading and placing processes close to the normal temperature, and the volume of the kneaded material block is small.
Example 2
The method of example 1 is basically repeated to prepare the titanium dioxide carrier, and the main difference is that in the step (2), 64kg of ammonium bicarbonate is added into the reactor, and the steps and conditions are as follows:
(1) injecting about 20kg of titanium tetrachloride saturator into the cut titanium tetrachloride saturator based on the original residual titanium tetrachloride to maintain the initial liquid level of the titanium tetrachloride, and starting electric heating to control the temperature to be 50 ℃ in the saturator;
(2) open mass flow meter for controlling dry air 5Nm3A gas distributor which is blown into the bottom in the reactor through a gas bypass which bypasses the titanium tetrachloride saturator; adding water into the reactor to the depth of 1200mm, adding 64kg of ammonium bicarbonate, supplementing water to the solution depth of 1600mm and the volume of about 200L, dissolving most of the ammonium bicarbonate, wherein the nominal concentration is 4mol/L, reducing the temperature to 10 ℃, and adjusting the pH to 8.3; dry air is diverted from the bypass back to the titanium tetrachloride saturator to produce tetrachloro compoundsContinuously bubbling titanium diluent gas into ammonium bicarbonate solution via gas distributor at bottom of reactor, and gradually regulating dry air flow to 30Nm within 0.2hr3Controlling the temperature of outlet gas of the titanium tetrachloride saturator to be 50 ℃, and injecting about 20kg of titanium tetrachloride into the titanium tetrachloride saturator to maintain the initial liquid level of the titanium tetrachloride; the titanium tetrachloride dilution gas was stopped until the slurry pH was 5.0, and dry air was blown into the gas distributor at the bottom in the reactor through a gas bypass bypassing the titanium tetrachloride saturator and was reduced to 5Nm3The total reaction time is 3.6 hours, the tap water flow of the spiral stainless steel water cooling pipe is controlled in the reaction process, and the temperature of the slurry after gradual rising is maintained at 40 ℃;
(3) after the reaction, cooling water is stopped for the slurry, and dry air is continuously introduced for 5Nm3Aging for 15hr, filtering with plate-frame filter, washing with water at 20 deg.C until no Cl is detected by silver nitrate solution-Blowing off part of water with normal temperature dry air to obtain semi-dry filter cake, and measuring the baking allowance at 500 deg.C to obtain TiO2 25m%；
(4) Taking 12kg of semi-dry filter cake (folded TiO)23 kg) of the crude product, crushing the crude product, placing the crushed crude product in a kneader, and adding 1.06kg of 40m% nitric acid (containing HNO)30.43 kg), starting kneading for 10min until the mixture is basically mixed, stopping the mixing, starting kneading every 25min for 5min, mixing and reacting for 2hr10min totally, then spraying 0.66kg (folded TiO) of bag filter quick-drying powder obtained in the step (3-1) of example 1 for about 20min while kneading20.53 kg), extruding the strips through a phi 3.5mm pore plate in a strip extruder, taking part of the extruded strips to be arranged into a thin layer in a stainless steel net, placing the thin layer in an oven preheated to 130 ℃ for quick drying, starting hot air internal circulation, drying the strips after 0.4hr, and roasting the dried strips in a muffle furnace at 420 ℃ for 3hr to obtain a titanium dioxide carrier; the carrier has smooth surface, lateral pressure strength of 117N/cm and specific surface area of 141m2Pore volume 0.34 ml/g.
In the preparation process, the ammonium bicarbonate in the step (2) is fed, dissolved and cut into the initial stage of the titanium tetrachloride diluent gas, and the upper opening of the reactor has large ammonia smell and no smoke. Most of water in the semi-dry filter cake in the step (4) is volatilized in the kneading and placing processes close to the normal temperature, and the volume of the kneaded material block is small.
Example 3
The process of example 3 was substantially repeated to prepare a titania carrier, except that in step (2), 67kg of sodium bicarbonate was added instead of ammonium bicarbonate, and the steps and conditions were as follows:
(1) injecting about 20kg of cut titanium tetrachloride saturator on the basis of the original residual titanium tetrachloride, and starting electric heating to control the temperature in the saturator to be 60 ℃;
(2) open mass flow meter for controlling dry air 5Nm3A gas distributor which is blown into the bottom in the reactor through a gas bypass which bypasses the titanium tetrachloride saturator; adding water into a reactor to the depth of 1200mm, adding 67kg of sodium bicarbonate, supplementing water to the solution depth of 1600mm and the volume of about 200L, dissolving part of sodium bicarbonate, and making the slurry have the nominal concentration of 4mol/L, the temperature of 25 ℃ and the pH value of 8.3; the dry air is returned to the titanium tetrachloride saturator from the bypass, the generated titanium tetrachloride diluent gas is continuously bubbled into the ammonium bicarbonate solution through a gas distributor at the bottom in the reactor, and the amount of the dry air is gradually adjusted to 30Nm within 0.2hr3Controlling the temperature of outlet gas of a titanium tetrachloride saturator to be 60 ℃, stopping feeding titanium tetrachloride diluent gas until the pH value of slurry is 5.0, injecting about 20kg of titanium tetrachloride saturator in the middle, and reacting for 2.4 hours, wherein the flow of tap water of the spiral stainless steel water cooling pipe is controlled during the reaction process, and the temperature of the slurry after gradual rising is maintained at 35 ℃;
(3) after the reaction, cooling water is stopped for the slurry, and dry air is continuously introduced for 5Nm3Aging for 15hr, filtering with plate-frame filter, washing with water at 20 deg.C until no Cl is detected by silver nitrate solution-Blowing off part of water with normal temperature dry air to obtain semi-dry filter cake, and measuring the baking allowance at 500 deg.C to obtain TiO2 15m%；
(4) Taking 20kg of semi-dry filter cake (folded TiO)23 kg) of the crude product, crushing the crude product, placing the crushed crude product in a kneader, and adding 2.0kg of 40m% nitric acid (containing HNO)30.80 kg), starting kneading for 10min till basically mixing uniformly, stopping the machine, starting kneading for 5min every 25min, mixing and reacting for 2hr10min totally, then spraying 2.7kg (folded TiO) of quick-drying powder of the cyclone separator obtained in the step (3-1) for about 30min while kneading22 kg) of the waste water, extruding the waste water into strips by a strip extruding machine through a phi 3.5mm orifice plate, and extruding the stripsHardening, placing part of the extruded strips in stainless steel mesh to form thin layer, rapidly drying in oven preheated to 130 deg.C, circulating with hot air for 0.4hr, and roasting at 420 deg.C in muffle furnace for 3hr to obtain titanium dioxide carrier; the carrier has smooth surface, lateral pressure strength of 108N/cm and specific surface area of 133m2Pore volume 0.36 ml/g.
In the above preparation process, in the initial stage of the sodium bicarbonate feeding, dissolution and cutting into the titanium tetrachloride diluent gas in the step (2), the upper mouth of the reactor is free from the ammonia odor of example 1 and is also substantially free from the smoke. Most of water in the semi-dry filter cake in the step (4) is volatilized in the kneading and placing processes close to the normal temperature, and the volume of the kneaded material block is small.
Example 4
Roasting the dried strip obtained in the step (4) in the example 3 in a muffle furnace at 400 ℃ for 4 hours to obtain a titanium dioxide carrier; the carrier has smooth surface, side pressure strength of 102N/cm and specific surface area of 149m2Pore volume 0.36 ml/g.
Example 5
Roasting the dried strip obtained in the step (4) in the embodiment 3 in a muffle furnace at 450 ℃ for 3 hours to obtain a titanium dioxide carrier; the carrier has smooth surface, side pressure strength of 113N/cm and specific surface area of 130m2G, pore volume 0.35 ml/g.
Example 6
The dried strands obtained in step (4) of examples 1 to 3 were each calcined in a muffle furnace at 500 ℃ for 2 hr. Compared with the corresponding carrier obtained by roasting at 420 ℃ for 3 hours, the side pressure strength of the obtained titanium dioxide carrier is slightly improved, and the reduction of the specific surface area and the pore volume is within 10 percent, which shows that the titanium dioxide carrier has better thermal stability.
Comparative example 1
15kg of the semi-dried cake obtained in the step (3-2) of example 1 (TIO broken)23 kg) was broken, and then placed in a kneader, to which 1.14kg of 40m% nitric acid (containing HNO) was added30.45 kg), kneading for 2hr, extruding into strips with a pore plate of phi 3.5mm in a strip extruder, slightly softening the extruded strips compared with example 1, placing part of the extruded strips in a stainless steel net to form a thin layer, placing in an oven preheated to 130 deg.C for quick drying, circulating with hot air, and drying for 0.4hrDrying, and roasting the dried strip in a muffle furnace at 420 deg.C for 3hr to obtain titanium dioxide carrier; the carrier has smooth surface, lateral pressure strength of 98N/cm and specific surface area of 142m2G, pore volume 0.35 ml/g.
This comparative example demonstrates that the addition of a fast drying powder increases the hardness of the extruded strands and the strength of the prepared carrier.
Comparative example 2
And (3) taking the partial extruded strips obtained in the step (4) of the examples 1 and 4, respectively filling the partial extruded strips in an enamel plate, covering the enamel plate, placing the enamel plate in an oven preheated to 130 ℃ for drying, wherein the partial extruded strips are completely dried after 2 hours and 4 hours, the partial extruded strips are dried after 6 hours, and the dried strips are respectively roasted in a muffle furnace at 420 ℃ for 3 hours, so that the specific surface area and the pore volume of the prepared titanium dioxide carrier are reduced by more than 20 percent.
Comparative example 3
Taking 25kg of the semi-dried filter cake obtained in step (3-2) of example 1, filling into an enamel tray, covering, drying in an oven preheated to 130 deg.C for 2hr and 4hr, drying after 6hr, rapidly micronizing to obtain 5.3kg of dry powder (TiO-24 kg) in a kneader, 6.4kg of nitric acid solution (containing HNO) is added30.45 kg), kneading for 2hr, extruding into strips through a phi 3.5mm orifice plate in a strip extruder, wherein the extruded strips are straight and hard, and the surface is slightly rough; placing part of the extruded strips in stainless steel mesh, placing into oven preheated to 130 deg.C, quickly drying, circulating with hot air for 0.4hr, and roasting at 420 deg.C in muffle furnace for 3hr to obtain titanium dioxide carrier; the carrier has smooth surface, lateral pressure strength of 93N/cm and specific surface area of 116m2G, pore volume 0.35 ml/g.
Comparative example 4
The preparation is carried out in a known manner using titanium tetrachloride and ammonium bicarbonate as starting materials:
(1) adding water of about 10L into a 200L high-level tank, adding crushed ice of about 30kg, inserting a thin tube to the liquid level, pressing titanium tetrachloride of 20kg, stirring uniformly at the temperature of about 30 ℃ to prepare titanium tetrachloride solution; adding 50-liter water into another 200-liter high-level tank at a temperature of about 150 liters, adding 32kg of ammonium bicarbonate, stirring and dissolving to prepare an ammonium bicarbonate solution;
(2) adding 40L of water into a 250L reaction kettle until stirring is realized, and introducing 25 ℃ tap water into a jacket of the reaction kettle; controlling a titanium tetrachloride solution and an ammonium bicarbonate solution through a valve and a flowmeter respectively, and putting the titanium tetrachloride solution and the ammonium bicarbonate solution into a reaction kettle in a parallel flow manner for stirring reaction, wherein the pH value of slurry is controlled to be 4.5-5.0, and the titanium tetrachloride solution is slightly remained until the ammonium bicarbonate solution is used up; the total reaction time is 1.6hr, and the slurry temperature in the reaction process is not more than 35 ℃;
(3) standing and aging the slurry after reaction for 10hr, and stirring for 2 min every 1 hr; filtering the aged slurry in a plate-and-frame filter, and washing the filter cake by water at 20 ℃ until no Cl is detected by a silver nitrate solution-The washing is much more difficult than the step (3) of the examples 1 to 5, the water is blown by the normal temperature dry air, the washing is much more difficult than the step (3) of the examples 1 to 5, the semi-dry filter cake is obtained by discharging the filter after the water is blown by the air for a long time, and the TiO is measured when the drying allowance at 500℃ is measured2 20m%；
(4) Taking 15kg of semi-dry filter cake (folded TiO)23 kg) of the crude product, crushing the crude product, placing the crushed crude product in a kneader, and adding 0.9kg of 40m% nitric acid (containing HNO)30.36 kg), kneading for 2hr, extruding with a phi 3.5mm pore plate in a strip extruder, collecting part of the extruded strip, placing in a stainless steel net to form a thin layer, placing in an oven preheated to 130 deg.C, rapidly drying, circulating with hot air, drying for 0.4hr, and roasting the dried strip in a muffle furnace at 420 deg.C for 3hr to obtain titanium dioxide carrier; the carrier has smooth surface, lateral pressure strength of 118N/cm and specific surface area of 115m2Pore volume 0.29 ml/g.
Comparative example 5
Basically the same as the comparative example 2, but the reaction temperature is about 80 ℃, which is as follows:
(1) adding about 30L of water into a 200L high-level tank, adding about 10kg of crushed ice, inserting a thin tube to the liquid level, pressing 20kg of titanium tetrachloride, stirring uniformly at the temperature of about 80 ℃ to prepare a titanium tetrachloride solution; adding water of about 150L into another 200L high-level tank, adding 32kg ammonium bicarbonate, stirring and dissolving to prepare ammonium bicarbonate solution;
(2) 40L of water is added into a 250L reaction kettle to be stirred, and large-flow 85 ℃ hot water is led into a reaction kettle jacket; controlling a titanium tetrachloride solution and an ammonium bicarbonate solution through a valve and a flowmeter respectively, and putting the titanium tetrachloride solution and the ammonium bicarbonate solution into a reaction kettle in a parallel flow manner for stirring reaction, wherein the temperature of slurry is controlled to be 80-85 ℃, the pH value is controlled to be 4.5-5.0, and the titanium tetrachloride solution is remained until the ammonium bicarbonate solution is used up; the total reaction time is 1.6 hr;
(3) after the reaction, the slurry is aged for 2hr at the temperature of 85 ℃, then filtered in a plate-and-frame filter, and the filter cake is washed by water at the temperature of 20 ℃ until no Cl is detected by a silver nitrate solution-Blowing water with normal temperature dry air, discharging from the filter to obtain semi-dry filter cake, and measuring the baking allowance at 500 deg.C to obtain TiO2 35m%；
(4) 8.6kg of semi-dry filter cake (TiO 2)23 kg) of the crude product, crushing the crude product, placing the crushed crude product in a kneader, and adding 0.9kg of 40m% nitric acid (containing HNO)30.36 kg), kneading for 2hr, finding that the intensity of the kneaded material is low, the intensity of the strip extruded by a strip extruder through a phi 3.5mm orifice plate is also low, taking part of the extruded strip to be discharged into a thin layer in a stainless steel net and placing the thin layer in an oven preheated to 130 ℃ for quick drying, easily breaking the extruded strip, roasting the dried strip in a muffle furnace at 420 ℃ for 3hr, obtaining a carrier with low lateral pressure intensity of only 43N/cm, continuously roasting in the muffle furnace at 500 ℃ for 2hr, obtaining the carrier with lateral pressure intensity of 60N/cm and the specific surface area of 86m2Pore volume 0.22 ml/g.
The main component of the semi-dried cake in step (3) of this comparative example 5 should be metatitanic acid, and the strength of the prepared carrier is low because the activity of the prepared metatitanic acid is low, the gelling reaction with nitric acid is not easy or less, and the pore volume of the carrier is also small.
Claims (7)
1. A method for preparing a titanium dioxide carrier comprises the following steps:
(1) preparing titanium tetrachloride diluent gas with the volume content of 1-8% by taking titanium tetrachloride and carrier gas as raw materials in a temperature-controlled bubbling or spraying mode; the carrier gas is nitrogen or dry air;
(2) preparing ammonium bicarbonate or sodium bicarbonate solution or slurry with the concentration of 1-4mol/L, continuously bubbling and introducing the titanium tetrachloride diluent gas, and controlling the temperature of the slurry to be 10-40 ℃; reacting for 0.5-2hr until pH of the slurry is 4.5-5.0, and stopping feeding the titanium tetrachloride diluent gas to complete the reaction;
(3) aging the slurry for 5-20hr, filtering, washing the filter cake with 10-30 deg.C water, blowing off part of water with normal temperature dry air to obtain semi-dry filter cake, and removing TiO215-25 m%; taking part of the semi-dry filterThe cake is rapidly dried by 350-plus 400 ℃ hot air to prepare fast dry powder containing TiO2 70-90m%；
(4) Taking 60-90 parts by mass of the semi-dry filter cake in the step (3) calculated by titanium dioxide, adding 10-20 parts by mass of nitric acid solution calculated by pure nitric acid, mixing and processing for 1-3hr, adding 10-40 parts by mass of the quick-drying powder in the step (3) calculated by titanium dioxide, kneading for 0.5-1hr, extruding strips, quickly drying, and roasting the dried strips at the temperature of 400-500 ℃ to obtain the titanium dioxide carrier.
2. The process for producing a titania carrier according to claim 1, wherein the volume content of the titanium tetrachloride diluent gas in the step (1) is 3 to 8%.
3. The method for producing a titania carrier according to claim 2, wherein a sodium hydrogencarbonate solution or slurry is prepared in the step (2).
4. The method for preparing the titania carrier according to claim 1, wherein a low-concentration ammonium bicarbonate or sodium bicarbonate solution is prepared before the reaction in the step (2), and the ammonium bicarbonate or sodium bicarbonate raw material is replenished several times during the reaction.
5. The process for producing a titania carrier according to claim 1, wherein the slurry after the reaction in the step (3) is aged after the mother liquor concentration is lowered by changing water.
6. The method for preparing a titania carrier according to claim 1, wherein the rapid drying of the semi-dried cake in the step (3) is carried out by using an air-flow drying apparatus; in the air flow drying process, the semi-dry filter cake is extruded into thin strips by a spiral auger, enters high-speed hot air flow and is further crushed by a high-speed blade.
7. The method for preparing the titania support according to claim 1, wherein the conditions for the rapid drying of the extruded strip in the step (4) are a hot air temperature of 130 ℃ and a time of 0.4 hr.
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