CN109126830B - Preparation method of titanium dioxide-based sulfur recovery catalyst - Google Patents

Preparation method of titanium dioxide-based sulfur recovery catalyst Download PDF

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CN109126830B
CN109126830B CN201810881090.8A CN201810881090A CN109126830B CN 109126830 B CN109126830 B CN 109126830B CN 201810881090 A CN201810881090 A CN 201810881090A CN 109126830 B CN109126830 B CN 109126830B
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catalyst
titanium dioxide
calcium
material block
sulfur recovery
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CN109126830A (en
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崔国栋
崔旭浩
胡文宾
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Shandong Xunda Chemical Industrial Group Co ltd
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/30—
    • B01J35/58—
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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

Abstract

The invention provides a preparation method of a titanium dioxide-based sulfur recovery catalyst, which comprises the following steps: adding calcium oxide and calcium hydroxide powder or slurry with required amount into metatitanic acid powder or wet material, mixing, adding ammonium sulfate solution, and kneading into uniform material block; curing the material block under the conditions of 120-; cooling the material block, extruding into strips, drying, and roasting at 500 deg.C for 2-4hr to obtain catalyst containing calcium sulfate 10-15m%, calcium oxide 0-0.5m%, and anatase titanium dioxide in balance, wherein part of calcium sulfate has fiber shape structure. The titanium dioxide-based sulfur recovery catalyst prepared by the invention has the advantages of easy standard reaching of mechanical strength, small discreteness, no nitric acid gas and nitrogen oxide yellow smoke generated by volatilization and decomposition when calcium nitrate is added, no sulfuric acid is used, the difficulties in purchase, storage and use are avoided, and the activity of the catalyst is reduced.

Description

Preparation method of titanium dioxide-based sulfur recovery catalyst
Technical Field
The invention belongs to the field of industrial catalysts, and particularly relates to a preparation method of a titanium dioxide-based sulfur recovery catalyst.
Prior Art
The existing titanium oxide-based sulfur recovery catalyst generally contains 80-90m percent of anatase titanium dioxide and 10-20m percent of calcium sulfate, and is usually prepared by sequentially adding sulfuric acid solution and calcium nitrate solution into metatitanic acid powder, kneading, extruding, drying and roasting, wherein calcium sulfate plays a role of a binder. The titanium dioxide-based sulfur recovery catalyst which is properly prepared has the following characteristics:
(1) for organic sulfur COS and CS2The hydrolysis reaction has high activity, and the conversion rate of the Claus reaction almost reaches the thermodynamic equilibrium conversion rate level; under the required temperature condition, can be 1200 hr-1The high space velocity of the reactor greatly reduces the volume of the reactor, and can greatly improve the gas handling capacity under the same contact time; can be used in the first Claus reactor to promote COS and CS2And used in the second and third claus reactors to increase the claus conversion;
(2) for trace O in the process gas2No sensitivity and no generation of sulfuric acidSalinization and poisoning;
(3) can be used for treating the lean acid gas and the Claus tail gas;
(4) the performance is stable in the application of sulfur recovery, and the service life can reach 5-10 years.
The existing titanium dioxide-based sulfur recovery catalyst has good performance, but is difficult to prepare, and mainly comprises the following problems:
(1) mechanical strength is not up to standard or discreteness is too large
(2) The added calcium nitrate or intermediate products volatilize and decompose to release nitric acid gas and nitric oxide yellow smoke which are difficult to treat, and have serious corrosion or higher corrosion resistance requirement on a kiln and a pipeline;
(3) there are various difficulties in purchasing, storing and using the added sulfuric acid.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a titanium oxide-based sulfur recovery catalyst, which comprises the following steps:
A. adding calcium oxide powder or calcium hydroxide powder or slurry containing 4.2-8.4 parts of calcium oxide or calcium hydroxide into metatitanic acid powder or aqueous metatitanic acid material containing 85-90 parts of titanium dioxide in parts by mass, uniformly mixing, adding ammonium sulfate solution, and kneading into uniform blocks;
B. placing the wet material block in a pressure-resistant tank, maintaining at 120-; part of the calcium sulfate is generated into fiber shape;
C. cooling the wet material block, extruding into strips, drying the extruded strips, roasting the dried strips at the temperature of 400-500 ℃ for 2-4hr to obtain a catalyst, wherein the catalyst contains 10-15m percent of calcium sulfate, 0-0.6m percent of calcium oxide and the balance of anatase titanium dioxide, and part of calcium sulfate has a fiber-shaped structure;
in the step A, the ratio of the sum of the amount of substances of ammonium sulfate contained in the ammonium sulfate solution and substances of sulfur contained in metatitanic acid which is converted into sulfuric acid to the amount of the added substances of calcium oxide or calcium hydroxide is 1: (1-1.1).
In step A, the moisture content in the wet material block is properly controlled, and the content of the moisture in the wet material block is preferably 70-90m%, preferably 80m%, of the total mass of the prepared catalyst, namely titanium dioxide and calcium sulfate. The water in the wet material block mainly comprises free water contained in the metatitanic acid wet material and water contained in an ammonium sulfate solution. The moisture content of the wet mass is controlled to ensure that the desired fiber shape is formed from the calcium sulfate in the 120-130 ℃ saturated steam curing process of step B, and to provide the extruded strands of step C with a sufficiently high hardness, with the former having a suitably high amount of water and the latter having a suitably low amount of water. Of course, the water content of the materials in the preparation process is always increased or decreased due to volatilization or condensation.
In the step B, in the curing treatment process under the condition of saturated steam at the temperature of 120-; the curing treatment is preferably carried out under the conditions of 120-130 ℃ saturated steam for 2hr, wherein 120 ℃ is preferred.
In the step C, the roasting temperature of the drying strip is preferably 420 ℃ and 450 ℃; when the roasting temperature is low, the metatitanic acid is not completely decomposed, and the calcium sulfate fiber or whisker is not stable enough; at higher firing temperatures, the surface area of the titanium dioxide produced is reduced.
The preparation method of the titanium dioxide based sulfur recovery catalyst has the following advantages:
(1) the mechanical strength of the catalyst is easy to reach the standard, and the discreteness is small;
(2) nitric acid gas and nitric oxide yellow smoke generated by volatilization and decomposition during the addition of calcium nitrate do not exist, the corrosion of a kiln and a pipeline is relatively clear or the requirement on corrosion resistance is relatively low, and equipment for specially absorbing and treating the nitric acid gas and the nitric oxide yellow smoke is not needed;
(3) sulfuric acid is not used, so that the difficulties in purchasing, storing and using the sulfuric acid are avoided;
(4) the catalyst activity did not decrease.
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.
Example 1
Preparing a titanium dioxide based sulphur recovery catalyst by:
A. 5.375kg of metatitanic acid powder L (with the average particle size of 0.72 mu m, 4.0m percent of sulfuric acid with sulfur broken out at 1150 ℃ and 80m percent of titanium dioxide), 0.295kg of calcium oxide powder N (-600 meshes, the purity of 99.4m percent and the magnesium oxide of 0.3m percent) are added and mixed evenly, 4.4kg of aqueous solution containing 0.412kg of ammonium sulfate is added and kneaded into a uniform wet block;
B. putting 9.63kg of wet material blocks into a polypropylene plastic bag (the mass of the plastic bag is 65 g), compacting into a thin layer, tying a port but ventilating a small amount, putting the thin layer into a middle bracket of a 30L autoclave, injecting 3000ml of pure water below the bracket, electrically heating the bottom of the autoclave, inserting a thermocouple into the center part of the wet material blocks of the plastic bag to detect the temperature, and preserving the heat outside the autoclave; closing the autoclave, starting and controlling external electric heating at the bottom of the autoclave, discharging air in the autoclave for 5min through a pressure release valve after pure water in the autoclave boils, closing the pressure release valve, raising the central temperature of a wet material block to 90 ℃, then preserving heat for 0.5hr at 90-100 ℃, opening the pressure release valve to discharge air in the autoclave for 5min, then closing the pressure release valve, raising the temperature to 120 ℃, then keeping the temperature for 2hr, keeping the pressure in the autoclave at 200 and 205kPa (absolute pressure) in the process of keeping the temperature at 120 ℃, and keeping the pressure in the autoclave at 120 ℃ to be higher than 200kPa before keeping the temperature; cutting off power after constant temperature is over, and cooling to below 100 deg.C for 0.5 hr;
C. opening the kettle, taking out the wet material block plastic bag, weighing 9.65kg, cooling to about 50 deg.C within 0.3hr, immediately extruding through a phi 3.5mm orifice plate to obtain relatively hard and straight strips, drying at 120 deg.C in a hot air mesh belt furnace for 0.3hr, and calcining 600g of dried strips in a muffle furnace at 450 deg.C for 3hr to obtain the catalyst.
60 measured catalysts are taken, the side pressure strength mean value is 112N/cm, and the standard deviation is 10N/cm. The pore volume of the catalyst was measured and taken to be 0.25ml/g, and the surface area was 116 m2(ii) in terms of/g. For the cylindrical product catalyst with phi of 3-4mm, the lateral pressure strength at least reaches 80N/cm, and preferably higher than 90N/cm.
If the volatilization loss is not counted, the free water amount in the wet material block in the step A accounts for about 80 percent of the mass of the catalyst which is obtained by feeding.
The feeding proportion of the catalyst is 85.8m percent of titanium dioxide and 14.2m percent of calcium sulfate; the ratio of the sum of the amounts of substances of ammonium sulfate contained in the ammonium sulfate solution and substances of sulfuric acid formed by the reduction of sulfur contained in metatitanic acid to the amount of the added calcium oxide is 1:1.
the surface and the section of the wet material block and the catalyst before the extrusion are observed by an optical microscope, and short fibrous materials are mixed among the catalyst micro-particles and are basically distributed isotropically, and the short fibrous materials are calcium sulfate fibers or crystal whiskers.
Example 2
The procedure of example 1 was substantially repeated to produce a titanium dioxide based sulphur recovery catalyst, except that the amount of calcium oxide powder N in step A was 0.313kg and the extruded strands in step C were also harder and straighter.
60 measured catalysts are taken, the side pressure strength mean value is 115N/cm, and the standard deviation is 10N/cm. Taking the pore volume of the catalyst to be measured, which is 0.26ml/g, and the surface area is 113 m2/g。
The feeding proportion of the catalyst is 85.5m percent of titanium dioxide, 14.1m percent of calcium sulfate and 0.35m percent of calcium oxide. The ratio of the sum of the amounts of substances of ammonium sulfate contained in the ammonium sulfate solution and substances of sulfuric acid formed by the reduction of sulfur contained in metatitanic acid to the amount of the added calcium oxide is 1: 1.06.
the surface and the section of the wet material block and the catalyst before extruding are observed by an optical microscope, and short fibrous materials are also seen to be mingled among catalyst micro-particles, are basically in isotropic distribution and are calcium sulfate fibers or crystal whiskers.
Example 3
The method of example 2 is basically repeated to prepare the titanium dioxide based sulfur recovery catalyst, the sum of the amount of substances of ammonium sulfate contained in the ammonium sulfate solution and sulfur contained in metatitanic acid which are converted into sulfuric acid and the amount of the added calcium oxide substance are 1:1.06, and the difference is that the feeding ratio of the catalyst is 89.6m percent of titanium dioxide, 10m percent of calcium sulfate and 0.35m percent of calcium carbonate; in the step A, 0.22kg of calcium oxide powder N is added into 0. 5.594kg of metatitanic acid powder, the mixture is mixed evenly, 4.3kg of aqueous solution containing 0.183kg of ammonium sulfate is added, and the strip extruded in the step C is also harder and straighter.
60 measured catalysts are taken, the average value of the lateral pressure intensity is 100N/cm, and the standard deviation is 9.4N/cm. The pore volume of the catalyst was measured and taken to be 0.29ml/g, and the surface area was 126 m2/g。
The surface and the section of the wet material block and the catalyst before extruding are observed by an optical microscope, and short fibrous materials are also seen to be mingled among catalyst micro-particles, are basically in isotropic distribution and are calcium sulfate fibers or crystal whiskers.
Example 4
Basically repeating the method of example 1 to prepare the titanium dioxide based sulfur recovery catalyst, except that the temperature of curing treatment of the wet material block kneaded in the step B under the saturated steam condition of a pressure resistant tank is changed from 120 ℃ to 130 ℃; the pressure in the kettle is 270-275kPa (absolute pressure) in the constant temperature process at 130 ℃, and the pressure in the kettle does not exceed 270kPa before the constant temperature at 130 ℃.
60 measured catalysts are taken, the side pressure strength mean value is 120N/cm, and the standard deviation is 10N/cm. The pore volume of the catalyst was measured and taken to be 0.25ml/g, and the surface area was 104 m2/g。
The feeding proportion of the catalyst is 85.8m percent of titanium dioxide and 14.2m percent of calcium sulfate; the mass ratio of the total amount of sulfuric acid to calcium carbonate was 1:1.
The surface and the section of the wet material block and the catalyst before the extrusion are observed by an optical microscope, and short fibrous materials are mixed among the catalyst micro-particles and are basically distributed isotropically, and the short fibrous materials are calcium sulfate fibers or crystal whiskers.
Comparative example 1
The feeding proportion is the same as that of the embodiment 1, but the maintenance treatment of the kneaded wet material block is not carried out under the condition of 120 ℃ and 130 ℃ saturated steam in the pressure-resistant tank, and the method mainly comprises the following steps:
A. adding 0.295kg of calcium oxide powder N into L5.375 kg of metatitanic acid powder, uniformly mixing, adding 4.4kg of aqueous solution of 0.412kg of ammonium sulfate, and kneading into a uniform wet material block;
C. extruding the wet material block through a phi 3.5mm pore plate to obtain relatively hard and straight strips, drying at 120 deg.C in a hot air mesh belt furnace for 0.3hr, and calcining at 450 deg.C for 3hr to obtain the catalyst.
60 measured catalysts are taken, the side pressure intensity mean value is 73N/cm, and the standard deviation is 12N/cm. The pore volume of the catalyst was measured and found to be 0.28ml/g, the surface area was 133 m2/g。
The feeding proportion of the catalyst is 85.8m percent of titanium dioxide and 14.2m percent of calcium sulfate.
The surface and cross section of the wet mass and the catalyst before extrusion were observed by an optical microscope, and short fibrous materials included between the catalyst fine particles in examples 1 to 4 were not observed, that is, calcium sulfate fibers or whiskers were not formed.
Comparative example 2
The feeding proportion is the same as that of the example 1, but the temperature of curing treatment of the wet material block kneaded in the step B under the saturated steam condition of a pressure-resistant tank is changed from 120 ℃ to 110 ℃, and the method mainly comprises the following steps:
A. adding 0.295kg of calcium oxide powder N into L5.375 kg of metatitanic acid powder, uniformly mixing, adding 4.4kg of aqueous solution of 0.412kg of ammonium sulfate, and kneading into a uniform wet material block;
B. putting the wet material block into a polypropylene plastic bag, tying the opening but ventilating a small amount, putting the bag into a middle bracket of a 30L high-pressure kettle, injecting 3000ml of pure water below the bracket, electrically heating the kettle bottom, inserting a thermocouple into the center of the wet material block of the plastic bag to detect the temperature, and preserving the heat outside the kettle; closing the autoclave, starting and controlling external electric heating at the bottom of the autoclave, discharging air in the autoclave for 5min through a pressure release valve after pure water in the autoclave boils, closing the pressure release valve, raising the central temperature of a wet material block to 90 ℃, then preserving heat for 0.5hr at 90-100 ℃, opening the pressure release valve to discharge air in the autoclave for 5min, then closing the pressure release valve, raising the temperature to 110 ℃, then keeping the temperature for 2hr, wherein the pressure in the autoclave is 140 plus 150kPa (absolute pressure) in the constant temperature process at 110 ℃, and the pressure in the autoclave does not exceed 140kPa before the temperature of 110 ℃ is kept constant; cutting off power after constant temperature is over, and cooling to below 100 deg.C for 0.3 hr;
C. extruding the wet material block through a phi 3.5mm pore plate to obtain relatively hard and straight strips, drying at 120 deg.C in a hot air mesh belt furnace for 0.3hr, and calcining at 450 deg.C for 3hr to obtain the catalyst.
60 measured catalysts are taken, the average value of the lateral pressure intensity is 90N/cm, and the standard deviation is 12N/cm. The pore volume of the catalyst was measured and taken to be 0.26ml/g, and the surface area was 118 m2/g。
The surface and cross section of the wet mass and the catalyst before extrusion were observed by an optical microscope, and short fibrous materials included between the catalyst fine particles in examples 1 to 4 were not observed, that is, calcium sulfate fibers or whiskers were not formed.
Comparative example 3
The titanium dioxide-based sulfur recovery catalyst is prepared by adopting metatitanic acid L according to the method of the prior art through the following steps:
A. adding 1.3kg of aqueous solution containing 0.30kg of sulfuric acid into L5.375 kg of metatitanic acid powder, uniformly mixing, adding 3.5kg of aqueous solution containing 0.968kg of calcium nitrate (calculated by anhydrous substances), uniformly mixing, and kneading into uniform wet blocks;
C. extruding the wet material block through a phi 3.5mm pore plate to obtain relatively hard and straight strips, drying at 120 deg.C in a hot air mesh belt furnace for 0.3hr, and calcining at 450 deg.C for 3hr to obtain the catalyst.
60 measured catalysts are taken, the side pressure strength mean value is 86N/cm, the standard deviation is 16N/cm, and the strength is general. The pore volume of the catalyst was measured and taken to be 0.25ml/g, and the surface area was 126 m2/g。
The feeding proportion of the catalyst is 85.8m percent of titanium dioxide and 14.2m percent of calcium sulfate; the mass ratio of the total amount of sulfuric acid to calcium nitrate was 1:1.
The surface and cross section of the wet mass and the catalyst before extrusion were observed by an optical microscope, and short fibrous materials included between the catalyst fine particles in examples 1 to 4 were not observed, that is, calcium sulfate fibers or whiskers were not formed.
The material kneading in the step A and the strip extruding in the step C have obvious sour taste, the generated nitric acid is volatilized, and more yellow smoke is emitted in the roasting process of the dried strip in the step C and is nitrogen dioxide.
Comparative example 4
In the preparation method of comparative example 3, a step of saturated steam treatment at 120 ℃ as in step B of example 1 was added to prepare a titania-based sulfur recovery catalyst:
A. adding 1.3kg of aqueous solution containing 0.30kg of sulfuric acid into L5.375 kg of metatitanic acid powder, uniformly mixing, adding 3.5kg of aqueous solution containing 0.968kg of calcium nitrate (calculated by anhydrous substances), uniformly mixing, and kneading into uniform wet blocks;
B. putting 9.50kg of wet material blocks into a polypropylene plastic bag (the mass of the plastic bag is 65 g), tying but ventilating a small amount, placing the plastic bag in a middle bracket of a 30L high-pressure kettle, injecting 3000ml of pure water below the bracket, inserting a thermocouple into the center of the wet material blocks of the plastic bag to detect the temperature, and preserving the heat outside the kettle; closing the autoclave, starting and controlling external electric heating at the bottom of the autoclave, discharging air in the autoclave for 5min through a pressure release valve after pure water in the autoclave boils, closing the pressure release valve, raising the central temperature of a wet material block to 90 ℃, then preserving heat for 0.5hr at 90-100 ℃, opening the pressure release valve to discharge air in the autoclave for 5min, then closing the pressure release valve, raising the temperature to 120 ℃, then keeping the temperature for 2hr, keeping the pressure in the autoclave at 200 and 205kPa (absolute pressure) in the process of keeping the temperature at 120 ℃, and keeping the pressure in the autoclave at 120 ℃ to be higher than 200kPa before keeping the temperature; cutting off power after constant temperature is over, and cooling to below 100 deg.C for 0.5 hr;
C. opening the kettle, taking out the wet material block plastic bag, weighing 9.53kg, cooling to about 50 deg.C within 0.3hr, immediately extruding through a phi 3.5mm orifice plate to obtain relatively hard and straight strips, drying at 120 deg.C in a hot air mesh belt furnace for 0.3hr, and calcining at 450 deg.C for 3hr to obtain the catalyst.
60 measured catalysts are taken, the side pressure strength mean value is 88N/cm, and the standard deviation is 14N/cm. Taking and measuring the pore volume of the catalyst, which is 0.24ml/g and the surface area is 110 m2/g。
The surface and cross section of the wet mass and the catalyst before extrusion were observed by an optical microscope, and short fibrous materials included between the catalyst fine particles in examples 1 to 4 were not observed, that is, calcium sulfate fibers or whiskers were not formed.
In the comparative example, the reason why the wet mass after kneading was treated with 120 ℃ saturated steam but calcium sulfate fibers were produced at the end was probably that the wet mass contained much nitric acid and was too acidic.
Evaluation examples
The catalyst samples of examples 1, 2, 3 and comparative example 3 were cut short, and the catalyst samples were taken at a length of 4 to 6mm, and the initial activity and the activity after aging of the catalyst were evaluated in a sulfur recovery evaluation apparatus, respectively. The inner diameter of the stainless steel tube reactor is 42mm, and a brass soaking sleeve with the wall thickness of 10mm is embedded outside the steel tube. The reaction furnace adopts electric heating, the length of a heating section is 600mm, and the reaction furnace is similar to an isothermal furnace body. The catalyst loading was 50ml each and diluted with 50ml of phi 3mm inert ceramic balls. The raw material gas is mixed and preheated and then enters a reactor for reaction, and the tail gas is discharged into a chimney for emptying after cooling and separating sulfur. Gas composition before and after the reaction was analyzed by gas chromatograph, and O was analyzed by using 5A molecular sieve packed column2The content of sulfide was analyzed by GDX-301 carrier-packed column.
Catalyst evaluation conditions: the composition (volume) of the reaction gas is H2S 6％，SO24％，CS21％，O20.2％，H2O30%, the balance beingN2(ii) a Gas volume space velocity of 2000hr-1The bed temperature was 320 ℃.
Each catalyst was evaluated by first evaluating the initial activity of the reaction gas of the above composition at the space velocity and temperature for 10hr under the above evaluation conditions, and then evaluating the CS at 8-10hr2The hydrolysis rate and the Claus conversion are shown in Table 1, respectively; then the volume ratio SO is changed2Aging gas 40% -60% of air, and rapidly heating to 450 deg.C for 700 hr-1Operating at space velocity for 2hr for sulfation poisoning aging treatment, cooling, and evaluating activity stability at the same temperature and reaction gas composition and space velocity as the initial activity for 10hr and CS at 8-10hr2The hydrolysis rate and the Claus conversion are shown in Table 1, respectively; the Claus conversion being contained H2S、SO2、CS2Total sulfur conversion.
Table 1 evaluation results of catalyst activity in%
Figure 352117DEST_PATH_IMAGE001
。
As can be seen from the results in Table 1, the titanium dioxide-based sulfur recovery catalyst prepared by the method of the invention has better reaction performance and stability, and is equivalent to the catalyst prepared by the existing method.

Claims (6)

1. A preparation method of a titanium dioxide based sulfur recovery catalyst comprises the following steps:
A. adding calcium oxide powder or calcium hydroxide powder or slurry containing 4.2-8.4 parts of calcium oxide or calcium hydroxide into metatitanic acid powder or aqueous metatitanic acid material containing 85-90 parts of titanium dioxide in parts by mass, uniformly mixing, adding ammonium sulfate solution, and kneading into uniform wet blocks;
B. placing the wet material block in a pressure-resistant tank, and curing at 120-;
C. cooling the wet material block, extruding into strips, drying the extruded strips, roasting the dried strips at the temperature of 400-500 ℃ for 2-4hr to prepare a catalyst, wherein the catalyst contains 10-15m% of calcium sulfate and the balance of anatase titanium dioxide, and part of calcium sulfate has a fiber-shaped structure;
in the step A, the ratio of the sum of the amount of substances of ammonium sulfate contained in the ammonium sulfate solution and substances of sulfur contained in metatitanic acid which is converted into sulfuric acid to the amount of the added substances of calcium oxide or calcium hydroxide is 1:1.
2. the method of claim 1, wherein the moisture content of the wet mass in step a is 70-90% of the mass of the catalyst produced.
3. The method of claim 2, wherein the moisture content of the wet cake in step a is 80% of the mass of the catalyst produced.
4. The method for preparing the titanium dioxide-based sulfur recovery catalyst as claimed in claim 1, wherein in step B, the curing treatment is carried out for 2hr under the saturated steam condition of 120 ℃ and 130 ℃.
5. The process for producing a titanium dioxide-based sulfur recovery catalyst according to claim 4, wherein in the step B, the temperature of the curing treatment under saturated steam conditions is 120 ℃.
6. The method of claim 1, wherein in step C, the calcination temperature of the dried strip is 420-450 ℃.
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CN111203203B (en) * 2020-02-16 2022-05-27 山东迅达化工集团有限公司 Calcium sulfate fiber reinforced titanium oxide carrier or catalyst and preparation method thereof
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