CN111282561A - Titanium dioxide catalyst with high strength and large specific surface area for sulfur recovery and preparation method thereof - Google Patents
Titanium dioxide catalyst with high strength and large specific surface area for sulfur recovery and preparation method thereof Download PDFInfo
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- CN111282561A CN111282561A CN202010240062.5A CN202010240062A CN111282561A CN 111282561 A CN111282561 A CN 111282561A CN 202010240062 A CN202010240062 A CN 202010240062A CN 111282561 A CN111282561 A CN 111282561A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 34
- 239000011593 sulfur Substances 0.000 title claims abstract description 34
- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 241000219793 Trifolium Species 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000005096 rolling process Methods 0.000 claims abstract description 22
- 230000032683 aging Effects 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 230000003020 moisturizing effect Effects 0.000 claims abstract description 6
- 241000219782 Sesbania Species 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 244000275012 Sesbania cannabina Species 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000004876 x-ray fluorescence 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a titanium dioxide catalyst with high strength and large specific surface area for sulfur recovery and a preparation method thereof, belonging to the technical field of catalysts and preparation thereof. The preparation method comprises the following steps: firstly, mixing wet metatitanic acid as a raw material with dry alumina rubber powder and sesbania powder in proportion, rolling for a period of time, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling, and preserving moisture and aging; and adding the material obtained by moisturizing and aging into an automatic pressing and strip extruding machine, selecting a clover template/clover template for extruding strips, drying the extruded material by a drying box to remove moisture, and roasting by a muffle furnace to obtain the finished product. The catalyst of the invention adopts wet metatitanic acid as a raw material, and compared with a dry raw material, the wet metatitanic acid is stable in chemical property and has a large number of active centers; the catalyst of the invention is in the shape of clover/clover, and compared with the cylindrical catalyst in the prior art, the crushing strength and the specific surface area of the catalyst are improved.
Description
Technical Field
The invention belongs to the technical field of catalysts and preparation thereof, and particularly relates to a titanium dioxide catalyst for sulfur recovery and a preparation method thereof.
Background
A large amount of H-containing gas is produced during petroleum refining, natural gas processing and coal chemical industry2Acid gas of S. In order to protect the environment and recover elemental sulphur, it is common in the industry to treat such acid gases using the claus sulphur recovery process. In the sulfur recovery process, 65-70% of H is generated in the high-temperature thermal reaction stage in the combustion furnace2S is converted into elemental sulfur, and the rest part is converted into elemental sulfur as far as possible under the action of a catalyst in the low-temperature catalytic reactor. In the early Claus sulfur recovery device, natural bauxite is used as a catalyst, the sulfur yield is only 80-85%, the active alumina-based catalyst is developed later, the sulfur yield reaches 94-96%, and the rest part of H2S、SO2And organic sulfide, and the organic sulfide is discharged after reaching the standard after being treated by tail gas. Due to the limitation of operation conditions and reaction balance, all the alumina-based sulfur recovery catalysts have the problems of easy sulfation poisoning, activity reduction, low equilibrium conversion rate and low organic sulfur hydrolysis rate, and especially in the final stage of device operation, the standard-reaching emission of sulfur smoke is difficult.
Titanium dioxide catalyst vs. H compared to alumina-based sulfur recovery catalysts2S and SO2The Claus reaction of (1) has higher catalytic activity, almost reaches thermodynamic equilibrium conversion rate, and allows shorter contact time for reaching the same conversion rate level; strong ability to hydrolyze organic sulfides, CS2The hydrolysis rate is almost more than 1 time of that of the active alumina-based catalyst; due to H2S、SO2In TiO2The surfaces of the titanium dioxide catalyst are easy to desorb, so the titanium dioxide catalyst is not easy to be sulfated and is not sensitive to oxygen leakage poisoning; even if poisoning is caused by "oxygen leakage", once normal operating conditions are restored, the activity is almost completely restored and a high catalytic activity can be maintained throughout the life cycle. Therefore, under the condition that the environmental protection pressure is gradually increased, the popularization and application speed of the sulfur recovery titanium dioxide catalyst is increased continuously, which represents the development trend of the future sulfur recovery catalyst.
Activity of titanium dioxide catalyst for sulfur recoveryMainly on the specific surface area of the catalyst and its lifetime mainly on the crush strength of the catalyst. At present, the existing titanium dioxide catalyst for recovering sulfur adopts dry titanium dioxide as a raw material, the appearance is cylindrical and strip-shaped, the crushing strength of the catalyst is about 120N/cm, and the specific surface area is 110m2About/g, the key indexes of the two catalysts are not high; during the drying process of the titanium dioxide raw material, the anatase type crystal lattice structure is partially converted, and the specific surface area is lost, thereby influencing the activity and the service life of the catalyst.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: solves the technical problems of small specific surface area and low crushing strength of the titanium dioxide catalyst for sulfur recovery.
In order to solve the above-mentioned problems, an object of the present invention is to provide a titanium dioxide catalyst for sulfur recovery, which has high crushing strength and a large specific surface area.
A titanium dioxide catalyst for recovering sulfur is in the shape of clover/clover, and is prepared from wet metatitanic acid, alumina dry glue powder and sesbania powder.
The beneficial technical effects directly brought by the technical scheme are as follows:
wet metatitanic acid is selected as a raw material, the wet metatitanic acid is undried and has no crystal form structure change, and compared with the dried raw material, the wet metatitanic acid is stable in chemical property and has a large number of active centers; the titanium dioxide catalyst is in the shape of clover/clover, and compared with the prior art, the titanium dioxide catalyst has improved crushing strength and specific surface area.
As a preferable embodiment of the present invention, the above-mentioned wet metatitanic acid is a dry TiO2The content is more than or equal to 90 wt%, and the water content<50wt％，SO4 2-Content (wt.)<2wt％。
In another preferred embodiment of the present invention, the dry alumina content of the alumina dry glue powder is not less than 68 wt%.
More preferably, the sesbania powder has the particle size of 120-150 meshes, the viscosity of more than or equal to 300mpa.s, the water content of less than or equal to 8wt percent and the residue of less than or equal to 1.5wt percent.
More preferably, the clover shape and the clover shape are extruded through a clover die plate and a clover die plate, respectively.
Another task of the present invention is to provide a method for preparing a titanium dioxide catalyst for sulfur recovery, which comprises the following steps:
a. mixing wet metatitanic acid as a raw material with dry alumina rubber powder and sesbania powder in proportion, rolling for a period of time, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling, and preserving moisture and aging;
b. adding the material obtained by moisturizing and aging into an automatic pressing and strip extruding machine, selecting a clover template/clover template for extruding strips, drying the extrudate through a drying box to remove moisture, and roasting through a muffle furnace to obtain the finished product.
Preferably, in the step a, the rolling time of the raw material wet metatitanic acid, the alumina dry glue powder and the sesbania powder after being mixed in proportion is 20-40 minutes, the rolling time after the mixed solution is added is 30-50 minutes, and the aging is kept for 20-40 minutes.
Further preferably, the temperature of the drying oven is 100-130 ℃, and the drying time is 2-4 hours.
Preferably, in the step b, the roasting temperature in the muffle furnace is 400-500 ℃, and the roasting time is 2-4 hours.
Compared with the prior art, the invention has the following beneficial technical effects:
the titanium dioxide catalyst for sulfur recovery provided by the invention selects wet metatitanic acid as a raw material, and the appearance of the titanium dioxide catalyst is clover or clover strip. The catalyst has the characteristics of high crushing strength and large specific surface area. Compared with the prior cylindrical catalyst taking dry titanium dioxide as a raw material, the catalyst has higher reaction activity and longer service life.
The advantages of the compressive strength and specific surface area of the titanium dioxide catalyst for sulfur recovery according to the present invention will be further illustrated by the following examples.
Detailed Description
The invention provides a titanium dioxide catalyst with high strength and large specific surface area for sulfur recovery and a preparation method thereof, and in order to make the advantages and technical scheme of the invention clearer and more clear, the invention is described in detail with reference to specific examples.
Firstly, the selected raw materials of the invention are mainly explained:
dry basis TiO of wet metatitanic acid2The content is more than or equal to 90 wt%, and the water content<50wt％，SO4 2-Content (wt.)<2wt％。
The dry alumina content of the alumina dry glue powder is more than or equal to 68wt percent.
The sesbania powder has the granularity of 120-150 meshes, the viscosity of more than or equal to 300mpa.s, the water content of less than or equal to 8wt percent and the residue of less than or equal to 1.5wt percent.
Next, the detection method used for the sample (product) of the present invention will be described below.
The composition of the sample is detected by a Bruker S2 PUMA X-ray fluorescence spectrometer;
the crushing strength is measured by a DL3 intelligent particle strength detector;
the specific surface area is determined by the ASAP2020PLUS Low temperature Nitrogen adsorption method (BET).
The present invention will be described in detail with reference to specific examples.
Example 1:
raw materials: wet metatitanic acid (dry TiO)2The content is more than or equal to 90 wt%, and the water content<50wt％,SO4 2-Content (wt.)<2wt percent), alumina dry glue powder and sesbania powder as raw materials.
The preparation method comprises the following steps:
mixing wet metatitanic acid as a raw material with alumina dry glue powder and sesbania powder in proportion, rolling for 20 minutes, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling for 30 minutes, and preserving moisture and aging for 20 minutes;
adding the material obtained by moisturizing and aging into an automatic pressing and strip extruding machine, selecting a clover template for extruding strips, drying the extrudate through a drying oven to remove water, wherein the temperature of the drying oven is 100 ℃, the drying time is 2 hours, then roasting through a muffle furnace, the roasting temperature is 400 ℃, and the roasting time is 4 hours to obtain the clover-shaped titanium dioxide catalyst，TiO2More than or equal to 85 wt% of Al2O3The content is more than or equal to 10 wt%.
Example 2:
raw materials: wet metatitanic acid (dry TiO)2The content is more than or equal to 90 wt%, and the water content<50wt％,SO4 2-Content (wt.)<2wt percent), alumina dry glue powder and sesbania powder as raw materials.
The preparation method comprises the following steps:
mixing wet metatitanic acid as a raw material with alumina dry glue powder and sesbania powder in proportion, rolling for 20 minutes, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling for 30 minutes, and preserving moisture and aging for 20 minutes;
adding the material obtained by moisture retention and aging into an automatic material pressing and strip extruding machine, selecting a clover template for strip extrusion, drying the extrudate through a drying oven to remove moisture, wherein the temperature of the drying oven is 100 ℃, the drying time is 2 hours, then roasting through a muffle furnace, the roasting temperature is 400 ℃, and the roasting time is 4 hours to obtain the clover-shaped titanium dioxide catalyst, TiO2More than or equal to 85 wt% of Al2O3The content is more than or equal to 10 wt%.
Comparative example 1:
raw materials: wet metatitanic acid (dry TiO)2The content is more than or equal to 90 wt%, and the water content<50wt％,SO4 2-Content (wt.)<2wt percent), alumina dry glue powder and sesbania powder as raw materials.
The preparation method comprises the following steps:
mixing wet metatitanic acid as a raw material with alumina dry glue powder and sesbania powder in proportion, rolling for 20 minutes, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling for 30 minutes, and preserving moisture and aging for 20 minutes;
adding the material obtained by moisturizing and aging into an automatic material pressing and strip extruding machine, selecting a cylindrical template for extruding strips, drying the extruded material by a drying oven to remove moisture, wherein the temperature of the drying oven is 100 ℃, the drying time is 2 hours, then roasting by a muffle furnace, the roasting temperature is 400 ℃, and the roasting time is 4 hours to obtain a cylindrical titanium dioxide catalyst, and TiO2More than or equal to 85 wt% of Al2O3The content is more than or equal to 10 wt%.
The crush strength and specific surface area of the catalysts obtained in examples 1 and 2 and comparative example 1 were measured, and the results are shown in table 1.
TABLE 1
As can be seen from the data in table 1, the crush strength and specific surface area of the cylindrical catalyst samples are less than the clover and clover shapes, with the clover shape being the most preferred.
The performance of this batch of cloverleaf catalyst (example 1) was evaluated using a laboratory fixed bed microreflection evaluation system.
The raw material gas composition is as follows: h2S is 6 (V)%, SO2Is 3 (V)%, CS2Is 1 (V)%, O23000ppm, H2O is 30 (V)%, and the rest is N2(ii) a Airspeed of 1800h-1(ii) a The reaction temperature is 320 ℃; the gas composition analysis was determined by a Furli GC9790 II TCD gas chromatograph. During 3000 hours of operation, the total sulfur conversion decreased from greater than 89% to 85%;
the performance of this batch of clover shaped catalyst (example 2) was evaluated without changing other conditions, and the total sulfur conversion decreased from greater than 89% to 85% over the course of 3500 hours of operation.
Comparative example 2:
raw materials: dry titanium dioxide (TiO)2Not less than 90 wt%, water content<3wt％，SO4 2-Content (wt.)<2wt percent), alumina dry glue powder (the content of dry alumina is more than or equal to 68wt percent), sesbania powder (the granularity is 120 meshes and 150 meshes, the viscosity is more than or equal to 300mpa.s, the water content is less than or equal to 8wt percent, and the residue is less than or equal to 1.5wt percent).
The preparation method comprises the following steps:
mixing the raw material dry titanium dioxide with alumina dry glue powder and sesbania powder in proportion, rolling for 40 minutes, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling for 50 minutes, and preserving moisture and aging for 40 minutes;
adding the material obtained by moisture retention and aging into an automatic material pressing and strip extruding machine, and selectingExtruding the clover template into strips, drying the extruded material in a drying oven at 130 deg.C for 4 hr, roasting in a muffle furnace at 500 deg.C for 2 hr to obtain clover-shaped titanium dioxide catalyst, TiO2More than or equal to 85 wt% of Al2O3The content is more than or equal to 10 wt%.
Comparative example 3:
raw materials: dry titanium dioxide (TiO)2Not less than 90 wt%, water content<3wt％，SO4 2-Content (wt.)<2wt percent), alumina dry glue powder (the content of dry alumina is more than or equal to 68wt percent), sesbania powder (the granularity is 120 meshes and 150 meshes, the viscosity is more than or equal to 300mpa.s, the water content is less than or equal to 8wt percent, and the residue is less than or equal to 1.5wt percent).
The preparation method comprises the following steps:
mixing the raw material dry titanium dioxide with alumina dry glue powder and sesbania powder in proportion, rolling for 40 minutes, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling for 50 minutes, and preserving moisture and aging for 40 minutes;
adding the material obtained by moisture retention and aging into an automatic material pressing and strip extruding machine, selecting a clover template for strip extrusion, drying the extrudate through a drying oven to remove moisture, wherein the temperature of the drying oven is 130 ℃, the drying time is 4 hours, then roasting through a muffle furnace, the roasting temperature is 500 ℃, and the roasting time is 2 hours to obtain the clover-shaped titanium dioxide catalyst, TiO2More than or equal to 85 wt% of Al2O3The content is more than or equal to 10 wt%.
Comparative example 4:
raw materials: dry titanium dioxide (TiO)2Not less than 90 wt%, water content<3wt％，SO4 2-Content (wt.)<2wt percent), alumina dry glue powder (the content of dry alumina is more than or equal to 68wt percent), sesbania powder (the granularity is 120 meshes and 150 meshes, the viscosity is more than or equal to 300mpa.s, the water content is less than or equal to 8wt percent, and the residue is less than or equal to 1.5wt percent).
The preparation method comprises the following steps:
mixing the raw material dry titanium dioxide with alumina dry glue powder and sesbania powder in proportion, rolling for 40 minutes, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling for 50 minutes, and preserving moisture and aging for 40 minutes;
adding the material obtained by moisturizing and aging into an automatic material pressing and strip extruding machine, selecting a cylindrical template for extruding strips, drying the extruded material by a drying oven to remove moisture, wherein the temperature of the drying oven is 130 ℃, the drying time is 4 hours, then roasting by a muffle furnace, the roasting temperature is 500 ℃, and the roasting time is 2 hours to obtain a cylindrical titanium dioxide catalyst, and TiO2More than or equal to 85 wt% of Al2O3The content is more than or equal to 10 wt%.
The crush strength and specific surface area of the catalysts obtained in comparative examples 2, 3 and 4 were measured, and the results are shown in Table 2.
TABLE 2
As can be seen from the data in table 2, the crush strength and specific surface area of the cylindrical catalyst samples are less than the clover and clover shapes, with the clover shape being the most preferred.
The batch of cylindrical catalyst (comparative example 4) was evaluated for performance using a laboratory fixed bed microreflection evaluation system.
The raw material gas composition is as follows: h2S is 6 (V)%, SO2Is 3 (V)%, CS2Is 1 (V)%, O23000ppm, H2O is 30 (V)%, and the rest is N2(ii) a Airspeed of 1800h-1(ii) a The reaction temperature is 320 ℃; the gas composition analysis was determined by a Furli GC9790 II TCD gas chromatograph. During 2000 hours of operation, the total sulfur conversion dropped from 87% to 81%.
From the above examples 1 and 2, and comparative examples 1 to 4, it can be seen that the titanium dioxide catalyst of the present invention (in the form of clover or clover) has higher crushing strength, larger specific surface area, higher reactivity and longer service life than the existing cylindrical catalyst using dry titanium dioxide as a raw material.
The parts which are not described in the invention can be realized by taking the prior art as reference.
It should be noted that: any equivalents or obvious modifications thereof which may occur to persons skilled in the art and which are given the benefit of this description are deemed to be within the scope of the invention.
Claims (9)
1. A titanium dioxide catalyst for sulfur recovery is characterized in that: the shape of the catalyst is clover/clover, and the titanium dioxide catalyst adopts wet metatitanic acid, alumina dry glue powder and sesbania powder as raw materials.
2. The titanium dioxide catalyst for sulfur recovery according to claim 1, wherein: the dry TiO of the wet metatitanic acid2The content is more than or equal to 90 wt%, and the water content<50wt％，SO4 2-Content (wt.)<2wt％。
3. The titanium dioxide catalyst for sulfur recovery according to claim 2, wherein: the dry alumina content of the alumina dry glue powder is more than or equal to 68wt percent.
4. The titanium dioxide catalyst for sulfur recovery according to claim 3, wherein: the sesbania powder has the granularity of 120-150 meshes, the viscosity of more than or equal to 300mpa.s, the water content of less than or equal to 8wt percent and the residue of less than or equal to 1.5wt percent.
5. The titanium dioxide catalyst for sulfur recovery according to claim 4, wherein: the clover shape and the clover shape are respectively extruded through a clover template and a clover template.
6. The preparation method of the titanium dioxide catalyst for sulfur recovery according to any one of claims 1 to 5, comprising the following steps in sequence:
a. mixing wet metatitanic acid as a raw material with dry alumina rubber powder and sesbania powder in proportion, rolling for a period of time, adding a certain amount of mixed solution of water, organic acid and nitric acid into the rolled material, continuing rolling, and preserving moisture and aging;
b. adding the material obtained by moisturizing and aging into an automatic pressing and strip extruding machine, selecting a clover template/clover template for extruding strips, drying the extrudate through a drying box to remove moisture, and roasting through a muffle furnace to obtain the finished product.
7. The method for preparing the titanium dioxide catalyst for sulfur recovery according to claim 6, wherein: in the step a, the rolling time of the raw material wet metatitanic acid, the alumina dry glue powder and the sesbania powder after being mixed in proportion is 20-40 minutes, the rolling time after the mixed liquid is added is 30-50 minutes, and the aging is kept for 20-40 minutes.
8. The method for preparing the titanium dioxide catalyst for sulfur recovery according to claim 6, wherein: in the step b, the temperature of the drying oven is 100-130 ℃, and the drying time is 2-4 hours.
9. The method for preparing the titanium dioxide catalyst for sulfur recovery according to claim 6, wherein: in the step b, the roasting temperature in the muffle furnace is 400-500 ℃, and the roasting time is 2-4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010240062.5A CN111282561A (en) | 2020-03-31 | 2020-03-31 | Titanium dioxide catalyst with high strength and large specific surface area for sulfur recovery and preparation method thereof |
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| CN114433049A (en) * | 2022-02-11 | 2022-05-06 | 射洪科瑞沃环保技术有限公司 | Titanium oxide sulfur recovery catalyst with high specific surface area and preparation method thereof |
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| CN114433049A (en) * | 2022-02-11 | 2022-05-06 | 射洪科瑞沃环保技术有限公司 | Titanium oxide sulfur recovery catalyst with high specific surface area and preparation method thereof |
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