CN111151235A - Titanium-based shift catalyst and preparation method and application thereof - Google Patents

Titanium-based shift catalyst and preparation method and application thereof Download PDF

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CN111151235A
CN111151235A CN202010041531.0A CN202010041531A CN111151235A CN 111151235 A CN111151235 A CN 111151235A CN 202010041531 A CN202010041531 A CN 202010041531A CN 111151235 A CN111151235 A CN 111151235A
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titanium
tio
sio
shift catalyst
catalyst
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沈炳龙
沈雁军
沈雁鸣
沈雁来
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Sanlong Catalyst Co ltd
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
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    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
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Abstract

The invention discloses a titanium-based shift catalyst, a preparation method and application thereof, wherein the catalyst comprises 0.8-1.5% of CoO and MoO36～8％、K2O 5～8％、CeO20-7% and the balance of TiO2/SiO2. The new titanium-based conversion catalyst system provided by the invention has high activity at low temperature (180-250 ℃) and high temperature (250 ℃)Still has high activity and stability at 450 ℃. The invention adopts TiO2/SiO2The catalyst can be used as a carrier of a titanium-based shift catalyst, and can keep the self-sulfuration state to avoid the occurrence of reverse sulfuration; for poisons HCN, COS and CS2Has higher hydrolysis function; the structural stability of the catalyst is improved, and the catalyst is favorable for long-life operation.

Description

Titanium-based shift catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of carbon monoxide catalysts, in particular to a titanium-based shift catalyst and a preparation method and application thereof.
Background
The carbon monoxide shift reaction refers to the reaction of carbon monoxide and water vapor under the action of a catalyst to generate hydrogen and carbon dioxide. The catalyst is suitable for a transformation process of gas production by a heavy oil and residual oil partial oxidation method or a coal gasification method, promotes the transformation reaction of CO in sulfur-containing gas, and is a CO sulfur-tolerant transformation catalyst which is suitable for wide temperature range (200-500 ℃), wide sulfur range (the sulfur content of process gas is more than or equal to 0.1% (v/v)) and high water-gas ratio (0.3-1.6).
At present, carbon monoxide shift catalysts can be divided into three major classes (1) Cu-Zn class, and the catalysts have high activity at low temperature (180-250 ℃), but easily lose activity at high temperature; and is easy to be poisoned by sulfide in raw gas, and the service cycle is short. (2) Fe-Cr, the sulfur poisoning resistance of the catalyst is better than that of Cu-Zn; but has considerable activity only at higher temperature (300-450 ℃). (3) Co-Mo catalysts have high manufacturing cost, but have the advantages of high activity in a wide temperature range (170-450 ℃) and low possibility of being poisoned by sulfide. Therefore, in recent years, the third type of catalyst has been widely used, gradually replacing the first two types of catalysts.
The prior art discloses the use of r-Al2O3Co-Mo system conversion catalyst as carrier; in addition, the addition of alkali metal (such as K, Na) elements has been found to improve the activity of the catalyst, and the corresponding patent is CN 87107892, which discloses that the alkali metal-containing catalyst is suitable for the operation conditions of low reaction pressure (0.3-3.0 Mpa) and low steam-gas ratio. However, the problems of potassium loss, reverse vulcanization, poor thermal stability, carrier phase change, short service life of the catalyst and the like exist in the use of the supported potassium-containing catalyst.
Disclosure of Invention
In view of the above-mentioned drawbacks and deficiencies of the prior art, the present invention provides a novel CO-Mo-K/TiO catalyst system2/SiO2、Co-Mo-Ni-K/TiO2/SiO2Co-Mo-K/r-Al as conversion catalyst2O3Co-Mo-K/Mg-Al spinel systems are completely different. The new CO transformation catalyst system has high activity at low temperature (180-250 ℃), high activity and stability at high temperature (250-450 ℃) and high activity under pressure (normal pressure-6.0 Mpa).
In order to achieve the above object, the present invention provides a method for preparing a titanium-based shift catalyst, comprising:
(1) preparation of TiO2/SiO2A carrier;
(2) preparing a steeping fluid;
(3) active component supported on TiO2/SiO2On a carrier;
(4) drying and activating to prepare the titanium-based shift catalyst.
Preferably, the raw materials adopted in the step (1) are a titanium iron-removing solution of a titanium dioxide factory and an acidic commercial silica sol according to TiO2/SiO2Uniformly mixing the components in a molar ratio of 3: 1; then coprecipitating with ammonia water or urea solution at 80-85 ℃, controlling the PH at 8.0-9.0, aging the obtained precipitate, washing with water, and filter-pressing with a filter to obtain a titanium-silicon filter cake; and (4) putting the filter cake into an oven for drying and crushing to obtain the titanium silicon powder.
Preferably, the raw material adopted in the step (1) contains TiO in the iron-removed titanium solution2300g/l, acidic commercial silica sol containing SiO2200g/l。
Preferably, titanium silicon powder is weighed and put into a kneader, and auxiliary materials and deionized water are added and kneaded in the kneader; and putting the kneaded material into a strip extruding machine for extruding strips to obtain strips.
Preferably, the noodles are placed in an oven for drying; breaking and sieving the dried strip-shaped objects, and feeding the strip-shaped objects into a muffle furnace for roasting for 1-4 hours to prepare the TiO2/SiO2And (3) a carrier.
Preferably, said TiO is2/SiO2The specific surface of the carrier is 300-350m2/g。
Preferably, said TiO is2/SiO2The pore volume of the carrier is 0.65-0.75 ml/g.
Preferably, said TiO is2/SiO2Surface acid of carrierThe sex can be adjusted.
Preferably, the auxiliary materials comprise aluminum hydroxide, sesbania powder, hydroxypropyl methyl cellulose, polyethylene oxide and glycerol.
Preferably, the raw materials for preparing the impregnation liquid in the step (2) comprise: cobalt nitrate, ammonium tetramolybdate, nickel nitrate hexahydrate and potassium carbonate.
Preferably, the step (2): weighing quantitative cobalt nitrate, nickel nitrate and ammonium molybdate, putting the cobalt nitrate, the nickel nitrate and the ammonium molybdate into a beaker, adding deionized water, concentrated ammonia water and a stabilizer ethylenediamine, and then supplementing the deionized water to prepare the impregnation liquid.
Preferably, the step (3) uses an equal volume impregnation method.
The invention also aims to provide a titanium-based shift catalyst which comprises the following components in percentage by mass: 0.8-1.5% of CoO and MoO36～8％、K2O 5～8％、CeO20-7% and the balance of TiO2/SiO2。
Preferably, said TiO is2/SiO2The preparation raw materials are a deferrization titanium solution and an acid silica sol, and TiO is added according to the molar ratio of 3:12/SiO2Mixing uniformly; then coprecipitating with ammonia water or urea solution, aging the obtained precipitate, washing with water, and filter-pressing with a filter to obtain a titanium-silicon filter cake; and (4) putting the filter cake into an oven for drying and crushing to obtain the titanium silicon powder.
Preferably, said TiO is2/SiO2The de-iron titanium liquid in the preparation raw material contains TiO2300g/l。
Preferably, said TiO is2/SiO2The acidic commercial silica sol in the raw material contains SiO2200g/l。
Preferably, said TiO is2/SiO2The preparation raw materials are the iron-removed titanium liquid of titanium dioxide factory and acidic commercial silica sol according to TiO2/SiO2Uniformly mixing the components in a molar ratio of 3: 1; then coprecipitating with ammonia water or urea solution at 80-85 ℃, controlling the PH at 8.0-9.0, aging the obtained precipitate, washing with water, and filter-pressing with a filter to obtain a titanium-silicon filter cake; drying the filter cake in oven, and pulverizingAnd obtaining the titanium-silicon powder.
In another preferred embodiment, the invention provides a titanium-based shift catalyst, which comprises the following components in percentage by mass: 1.0-1.2% of CoO and MoO36～8％、K2O 5～8％、CeO22-4%, NiO 0-5%, and TiO in balance2/SiO2。
Preferably, said TiO is2/SiO2The preparation raw materials are a deferrization titanium solution and an acid silica sol, and TiO is added according to the molar ratio of 3:12/SiO2Mixing uniformly; then coprecipitating with ammonia water or urea solution, aging the obtained precipitate, washing with water, and filter-pressing with a filter to obtain a titanium-silicon filter cake; and (4) putting the filter cake into an oven for drying and crushing to obtain the titanium silicon powder.
Preferably, said TiO is2/SiO2The de-iron titanium liquid in the preparation raw material contains TiO2300g/l。
Preferably, said TiO is2/SiO2The acidic commercial silica sol in the raw material contains SiO2200g/l。
Preferably, said TiO is2/SiO2The preparation raw material is the iron-removed titanium liquid of titanium dioxide factory according to TiO2/SiO2Uniformly mixing the components in a molar ratio of 3: 1; then coprecipitating with ammonia water or urea solution at 80-85 ℃, controlling the PH at 8.0-9.0, aging the obtained precipitate, washing with water, and filter-pressing with a filter to obtain a titanium-silicon filter cake; and (4) putting the filter cake into an oven for drying and crushing to obtain the titanium-silicon-carried powder.
The invention also aims to provide the application of the titanium-based shift catalyst in treating the carbon monoxide in the flue gas.
Preferably, the titanium-based shift catalyst can treat CO removal in the presence of harmful substances such as sulfur dioxide, water and the like in flue gas.
Compared with the prior art, the invention has the technical effects that:
the titanium-based shift catalyst protected by the present invention uses TiO as the catalyst2/SiO2As a carrier, has the following advantages:
(1)TiO2、TiO2/SiO2has strong affinity to sulfide, and can keep the sulfuration state of the raw material gas to avoid the occurrence of counter sulfuration under the condition of low hydrogen sulfide content.
(2)TiO2、TiO2/SiO2Has strong hydrolysis capability to poisons HCN, COS and CS2Has a high content of>More than 95%) hydrolysis function.
(3) The active alumina is used as carrier, and has hydration reaction and phase change under the conditions of high temperature and high water-vapor ratio. However, use of TiO2、TiO2/SiO2The catalyst is not hydrated and does not change phase when used as a carrier, so that the structural stability of the catalyst is improved, and the catalyst is favorable for long-life operation.
(4) The titanium-based shift catalyst does not generate methanation reaction at the high water-vapor ratio of more than 350 ℃.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
The raw materials used in the examples of the present invention and the comparative examples are commercially available or synthesized.
The titanium-based shift catalyst comprises the following components in percentage by weight: 0.8-1.5% of CoO and MoO36～8％、K2O 5～8％、CeO20-7% and the balance of TiO2/SiO2. The most preferable range is 1.0-1.2% of CoO and 1.2% of MoO36～8％、K2O 5～8％、CeO22-4% of TiO2/SiO2。
Preparation of TiO2/SiO2The adopted raw material is the iron-removed titanium liquid (containing TiO) of a titanium dioxide factory2300g/l) and acidic commercial silica sol (containing SiO)2200g/l) according to TiO2/SiO2＝31 mol of is mixed evenly. Then coprecipitating with ammonia water or urea solution at the temperature of 80-85 ℃, controlling the PH to be 8.0-9.0, and aging, washing with water and filter-pressing the obtained precipitate by a filter to obtain a titanium-silicon filter cake; and (4) putting the filter cake into an oven for drying and crushing to obtain the titanium silicon powder.
The reaction mechanism of the carbon monoxide shift reaction is:
CO+H2O＝H2+CO2△H＝-41.19kj/mol
because the support is TiO2Can occur along with the organic sulfur hydrolysis reaction:
CS2+2H2O＝H2S+CO2
COS+H2O＝H2S+CO2
by utilizing the reaction mechanism, the inventor utilizes the carbon monoxide titanium-based shift catalyst to treat the phenomenon that the CO in the flue gas generated in biomass power generation and waste incineration exceeds the standard. The inventors carried out a series of experiments and evaluation studies. The evaluation results indicated that: the CO conversion catalyst can treat the over-standard emission of CO in the flue gas, and the catalyst can treat SO in the flue gas2、H2And removing CO when harmful substances such as O and the like exist.
The preparation method of the carbon monoxide titanium-based shift catalyst comprises the following steps:
mono, TiO2/SiO2Preparation of the support
The adopted raw material is the iron-removed titanium liquid (containing TiO) of a titanium dioxide factory2300g/l) and acidic commercial silica sol (containing SiO)2200g/l) according to TiO2/SiO2The mixture is mixed evenly according to the molar ratio of 3: 1. Then coprecipitating with ammonia water or urea solution at the temperature of 80-85 ℃, controlling the PH to be 8.0-9.0, and aging, washing with water and filter-pressing the obtained precipitate by a filter to obtain a titanium-silicon filter cake; and (3) drying the filter cake in an oven at 100-120 ℃, and crushing to 200 meshes for later use.
Weighing titanium silicon powder crushed to 200 meshes, putting the titanium silicon powder into a kneader, and adding auxiliary materials such as aluminum hydroxide, sesbania powder, hydroxypropyl methyl cellulose, polyethylene oxide, glycerol and the like; adding a proper amount of deionized water into the mixture to knead the mixture for about 40 minutes in a kneader; putting the kneaded material into a strip extruding machine for extruding strips to obtain strips; drying the strips in an electric muffle head oven at the temperature of 80-120 ℃; and breaking the dried strips, sieving, and roasting in a muffle furnace at the roasting temperature of 450-550 ℃ for 1-4 hours to obtain the titanium-silicon carrier.
Secondly, preparing an impregnation liquid:
1. specification of raw materials
Figure BDA0002367917020000061
2. Preparation of impregnation liquid
The active component is loaded on the titanium carrier, and proper impregnation liquid is prepared according to the moisture absorption of the titanium carrier. If the titanium carrier is less hygroscopic and more active ingredient is impregnated, a part of the active ingredient may be added at the time of kneading of the titanium-silicon carrier.
The preparation of the impregnation liquid is as follows: weighing a certain amount of cobalt nitrate, nickel nitrate and ammonium molybdate, putting the cobalt nitrate, nickel nitrate and ammonium molybdate into a beaker, adding a certain amount of deionized water, concentrated ammonia water and a stabilizing agent ethylenediamine, and then supplementing the deionized water, thereby preparing the impregnation liquid. The impregnation liquid contains active components which can be carried on a titanium silicon carrier.
3. Supporting of active ingredients
And heating the impregnation liquid to 45-65 ℃, and slowly putting the prepared titanium-silicon carrier into the impregnation liquid to ensure that the titanium-silicon carrier is fully adsorbed in the impregnation liquid. The impregnation solution can also be sprayed onto the support by spraying.
4. Drying and activating:
the wet catalyst precursor was fed to a heated oven for drying. The drying temperature is 80-120 ℃, and the drying time is about 4-8 hours. And (4) feeding the dried catalyst into a muffle furnace for roasting. The roasting condition is slightly lower than that of the titanium-silicon carrier, and the roasting time is about 450-500 ℃ and 2-4 hours. And the temperature rise speed is controlled to prevent the cracking.
The sulfur-tolerant shift catalyst is used as a standard sample, which is a CO activity evaluation method commonly adopted in China. The evaluation method adopts a national standard HG/T4553-2013 'evaluation method for high-pressure activity in a carbon monoxide sulfur-tolerant shift catalyst'.
Example 1
102.44g of titanium silicon powder (TiO) is weighed2/SiO2Putting 3:1 with the solid content of 82 percent), 1g of hydroxypropyl methylcellulose (CMC) and 2.5g of cyanine powder into a kneader, starting the kneader and adding a certain amount of deionized water to knead the materials until the materials can be extruded and molded on a bar extruder. Putting the kneaded material into a strip extruding machine for extruding strips to obtain strips; drying the strips in an electric oven at 80-120 deg.C; and (3) breaking and sieving the dried strips, and feeding the strips into a muffle furnace for co-roasting at the roasting temperature of 500 ℃ for 2 hours to obtain the titanium-silicon carrier. The titanium silicalite support had a 34% hygroscopicity.
Weighing 3.88g of cobalt nitrate, 60.08g of ammonium molybdate and 11.74g of potassium carbonate, putting the cobalt nitrate, the ammonium molybdate and the potassium carbonate into a 250ml beaker, adding deionized water to the scale of 100ml, slightly heating the mixture on an electric furnace to 45-55 ℃ to completely dissolve the added substances, and preparing the impregnation liquid.
The active component is loaded on the titanium carrier by the method of equal volume impregnation. The wet catalyst precursor was fed to a heated oven for drying. The drying temperature is 80-120 ℃, and the drying time is about 8 hours. And (4) feeding the dried catalyst into a muffle furnace for roasting. The roasting condition is slightly lower than that of the titanium carrier, and the roasting time is about 480 ℃ and 2 hours. And the temperature rise speed is controlled to be a certain speed (30 ℃/0.5 hour) so as to prevent the cracking.
The prepared titanium-based shift catalyst group comprises the following components in percentage by weight: CoO 1%, MoO37％、K2O8 percent and the balance of TiO2/SiO2。
The conversion rate of CO in the titanium-based shift catalyst and a standard sample in the embodiment is detected by adopting a test method for testing the high-pressure activity in the carbon monoxide sulfur-resistant shift catalyst. Through detection, the CO conversion rate of the standard sample reaches 90 percent; the evaluation is carried out under the same condition, the CO conversion rate of the titanium-based shift catalyst reaches 92 percent, and the CO conversion rate is 2 percent; under the action of the catalyst, the conversion rate of CO is difficult to improve, and the conversion rate of CO of the titanium-based transformation catalyst of the embodiment is remarkably improved although 2 percent is provided.
Example 2
Weighing and crushing titanium silicon powder (TiO) for later use2/SiO23:1 solid content 82%) 105.12g, hydroxypropyl methylcellulose (CMC)1g, methyl cyanine powder 2.5g, and polyethylene oxide (PEO)0.5g were put into a kneader, and the kneader was started and a certain amount of deionized water was added to knead the materials to be extrusion-moldable on a bar extruder. Putting the kneaded material into a strip extruding machine for extruding strips to obtain strips; drying the strips in an electric oven at the temperature of 80-120 ℃; and (3) breaking and sieving the dried strips, and feeding the strips into a muffle furnace for co-roasting at the roasting temperature of 500 ℃ for 2 hours to obtain the titanium-silicon carrier. The titanium silicalite support had a hygroscopicity of 30%.
Weighing 3.11g of cobalt nitrate, 51.49g of ammonium molybdate, 4.89g of nickel nitrate and 7.34g of potassium carbonate, putting the weighed materials into a 250ml beaker, adding deionized water to 100ml of scales, slightly heating the mixture on an electric furnace to 45-55 ℃, completely dissolving the added materials, and preparing the impregnation solution.
The active component is loaded on the titanium silicon carrier by the method of equal volume impregnation. The wet catalyst precursor was fed to a heated oven for drying. The drying temperature is 80-120 ℃, and the drying time is about 8 hours. And (4) feeding the dried catalyst into a muffle furnace for roasting. The roasting condition is slightly lower than that of the titanium-silicon carrier, and the roasting time is about 480 ℃ and 2 hours. And the temperature rise speed is controlled to be a certain speed (30 ℃/0.5 hour) so as to prevent the cracking.
The prepared titanium-based converter catalyst component is as follows: CoO 0.8%, MoO36％、NiO 2％、K2O5% and the balance TiO2/SiO2。
The conversion rate of CO in the titanium-based shift catalyst and a standard sample in the embodiment is detected by adopting a test method for testing the high-pressure activity in the carbon monoxide sulfur-resistant shift catalyst. Through detection, the CO conversion rate of the standard sample reaches 90 percent; the evaluation is carried out under the same condition, the CO conversion rate of the titanium-based shift catalyst reaches 93 percent, and the CO conversion rate is 3 percent; under the action of the catalyst, the conversion rate of CO is difficult to improve, and the conversion rate of CO of the titanium-based transformation catalyst of the embodiment is remarkably improved although 3 percent is provided.
The titanium-based shift catalyst has the CO conversion rate of 92.4 percent at the temperature of 240 ℃ under normal pressure; under the same conditions, the CO conversion rate of the Co-Mo-K/Mg-Al spinel conversion catalyst is only 31.2 percent, and almost only 1/3 percent.
Example 3
Weighing titanium silicon powder (TiO)2/SiO23:1 solid content 82%) 103.41g, hydroxypropyl methylcellulose (CMC)1g, methyl cyanine powder 2.5g and glycerol 0.5g are put into a kneader, and the kneader is started and a certain amount of deionized water is added to knead the materials to be extruded and molded on a bar extruder. Putting the kneaded material into a strip extruding machine for extruding strips to obtain strips; drying the strips in an electric oven at the temperature of 80-120 ℃; and (3) breaking and sieving the dried strips, and feeding the strips into a muffle furnace for co-roasting at the roasting temperature of 500 ℃ for 2 hours to obtain the titanium-silicon carrier. The titanium silicalite support had 42% hygroscopicity.
Weighing 4.66g of cobalt nitrate, 68.66g of ammonium molybdate and 8.80g of potassium carbonate, putting the cobalt nitrate, the ammonium molybdate and the potassium carbonate into a 250ml beaker, adding deionized water to 100ml of scales, slightly heating the mixture on an electric furnace to 45-55 ℃ to completely dissolve the added substances, and preparing the impregnation liquid.
The active component is loaded on the titanium silicon carrier by the method of equal volume impregnation. The wet catalyst precursor was fed to a heated oven for drying. The drying temperature is 80-120 ℃, and the drying time is about 8 hours. And (4) feeding the dried catalyst into a muffle furnace for roasting. The roasting condition is slightly lower than that of the titanium-silicon carrier, and the roasting time is about 480 ℃ and 2 hours. And the temperature rise speed is controlled to be a certain speed (30 ℃/0.5 hour) so as to prevent the cracking.
The prepared titanium-based converter catalyst component is as follows: CoO 1.2%, MoO38％、K2O6 percent and the balance of TiO2/SiO2。
The conversion rate of CO in the titanium-based shift catalyst and a standard sample in the embodiment is detected by adopting a test method for testing the high-pressure activity in the carbon monoxide sulfur-resistant shift catalyst. Through detection, the CO conversion rate of the standard sample reaches 90 percent; the evaluation is carried out under the same condition, the CO conversion rate of the titanium-based shift catalyst reaches 94 percent, and the CO conversion rate is 4 percent; under the action of the catalyst, the conversion rate of CO is difficult to improve, and the conversion rate of CO of the titanium-based transformation catalyst of the embodiment is remarkably improved although 4 percent is provided.
Example 4
94.51g (TiO) of titanium silicon powder is weighed2/SiO2The solid content is 82 percent), hydroxypropyl methyl cellulose (CMC)1g and the cyanine powder 2.5g are put into a kneader, the kneader is started and a certain amount of deionized water is added, so that the materials are kneaded to be extruded and molded on a bar extruder. Putting the kneaded material into a strip extruding machine for extruding strips to obtain strips; drying the strips in an electric oven at the temperature of 80-120 ℃; and (3) breaking and sieving the dried strips, and feeding the strips into a muffle furnace for co-roasting at the roasting temperature of 500 ℃ for 2 hours to obtain the titanium carrier. The titanium silicalite support had 42% hygroscopicity.
Weighing 5.83g of cobalt nitrate, 60.08g of ammonium molybdate, 10.27g of potassium carbonate and 7g of cerium oxide, putting the weighed materials into a 250ml beaker, adding deionized water to 100ml of scales, slightly heating the materials on an electric furnace to 45-55 ℃, completely dissolving the added materials, and preparing the impregnation solution.
The active component is loaded on the titanium silicon carrier by the method of equal volume impregnation. The wet catalyst precursor was fed to a heated oven for drying. The drying temperature is 80-120 ℃, and the drying time is about 8 hours. And (4) feeding the dried catalyst into a muffle furnace for roasting. The roasting condition is slightly lower than that of the titanium-silicon carrier, and the roasting time is about 480 ℃ and 2 hours. And the temperature rise speed is controlled to be a certain speed (30 ℃/0.5 hour) so as to prevent the cracking.
The prepared titanium-based converter catalyst component is as follows: CoO 1.5%, MoO37％、K2O 6％、CeO27 percent of TiO for the rest2/SiO2。
The conversion rate of CO in the titanium-based shift catalyst and a standard sample in the embodiment is detected by adopting a test method for testing the high-pressure activity in the carbon monoxide sulfur-resistant shift catalyst. Through detection, the CO conversion rate of the standard sample reaches 90 percent; the evaluation is carried out under the same condition, the CO conversion rate of the titanium-based shift catalyst reaches 94 percent, and the CO conversion rate is 4 percent; under the action of the catalyst, the conversion rate of CO is difficult to improve, and the conversion rate of CO of the titanium-based transformation catalyst of the embodiment is remarkably improved although 4 percent is provided.
Example 5
Weighing and crushing titanium silicon powder (TiO) for later use2/SiO2Solid content 82%) 100g, aluminum hydroxide (Al)2O3Content 62%) 30g, hydroxypropyl methylcellulose (CMC)1g and methyl cyanine powder 2.5g are put into a kneader, the kneader is started and a certain amount of deionized water is added, so that the materials are kneaded to be extruded and molded on a bar extruder. Putting the kneaded material into a strip extruding machine for extruding strips to obtain strips; drying the strips in an electric oven at 80-120 deg.C; and (3) breaking and sieving the dried strips, and feeding the strips into a muffle furnace for co-roasting at the roasting temperature of 500 ℃ for 2 hours to obtain the titanium carrier. The titanium silicalite support had 53% hygroscopicity.
Weighing 3.88g of nitric acid, 60.08g of ammonium molybdate, 8.80g of potassium carbonate and 3g of cerium oxide, putting the nitric acid, the ammonium molybdate, the potassium carbonate and the cerium oxide into a 250ml beaker, adding deionized water to the scale of 100ml, slightly heating the mixture on an electric furnace to 45-55 ℃ to completely dissolve the added substances, and preparing the impregnation solution.
The active component is loaded on the titanium silicon carrier by the method of equal volume impregnation. The wet catalyst precursor was fed to a heated oven for drying. The drying temperature is 80-120 ℃, and the drying time is about 8 hours. And (4) feeding the dried catalyst into a muffle furnace for roasting. The roasting condition is slightly lower than that of the titanium-silicon carrier, and the roasting time is about 480 ℃ and 2 hours. And the temperature rise speed is controlled to be a certain speed (30 ℃/0.5 hour) so as to prevent the cracking.
The prepared titanium-based converter catalyst component is as follows: CoO 1%, MoO37％、K2O 6％、CeO23% and the balance TiO2/SiO2。Al2O3The specific surface of the carrier is increased, which is beneficial to improving the catalytic action of the titanium-based catalyst.
The conversion rate of CO in the titanium-based shift catalyst and a standard sample in the embodiment is detected by adopting a test method for testing the high-pressure activity in the carbon monoxide sulfur-resistant shift catalyst. Through detection, the CO conversion rate of the standard sample reaches 90 percent; the evaluation is carried out under the same condition, the CO conversion rate of the titanium-based shift catalyst reaches 93 percent, and the CO conversion rate is 3 percent; under the action of the catalyst, the conversion rate of CO is difficult to improve, and the conversion rate of CO of the titanium-based transformation catalyst of the embodiment is remarkably improved although 3 percent is provided.
Example 6 comparison of the Effect of catalysis on titanium silicon Supports with pure titanium Supports
1. Titanium-based shift catalyst for preparing pure titanium
1000g (TiO) of commercially available metatitanic acid was weighed282 percent of sulfate ions are washed by deionized water to remove sulfate ions (SO) carried in metatitanic acid4 2-) Washing until the mass percentage of the metatitanic acid powder is 2-3%; then filtering by using a vacuum filter to obtain a clean metatitanic acid filter cake; the metatitanic acid filter cake is put into an oven to be dried for 8 hours at the temperature of 100-120 ℃ and is crushed to 200 meshes for standby.
Weighing and crushing metatitanic acid (TiO) for later use2Content 82%) 103.41g, hydroxypropyl methyl cellulose (CMC)1g, cyanine powder 2.5g and glycerol 0.5g were put into a kneader, and the kneader was started and a certain amount of deionized water was added to knead the materials to be extrusion-molded on a plodder. Putting the kneaded material into a strip extruding machine for extruding strips to obtain strips; drying the strips in an electric oven at 80-120 deg.C; and (3) breaking and sieving the dried strips, and feeding the strips into a muffle furnace for co-roasting at the roasting temperature of 500 ℃ for 2 hours to obtain the titanium carrier. The titanium carrier had a 42% hygroscopicity.
Weighing 4.66g of cobalt nitrate, 68.66g of ammonium molybdate and 8.80g of potassium carbonate, putting the cobalt nitrate, the ammonium molybdate and the potassium carbonate into a 250ml beaker, adding deionized water to 100ml of scales, slightly heating the mixture on an electric furnace to 45-55 ℃ to completely dissolve the added substances, and preparing the impregnation liquid.
The active component is loaded on the titanium carrier by the method of equal volume impregnation. The wet catalyst precursor was fed to a heated oven for drying. The drying temperature is 80-120 ℃, and the drying time is about 8 hours. And (4) feeding the dried catalyst into a muffle furnace for roasting. The roasting condition is slightly lower than that of the titanium carrier, and the roasting time is about 480 ℃ and 2 hours. And the temperature rise speed is controlled to be a certain speed (30 ℃/0.5 hour) so as to prevent the cracking.
The prepared pure titanium-based heat-exchange catalyst comprises the following components: CoO 1.2%, MoO38％、K2O6 percent and the balance of TiO2。
The conversion rate of CO in the titanium-based shift catalyst and a standard sample in the embodiment is detected by adopting a test method for testing the high-pressure activity in the carbon monoxide sulfur-resistant shift catalyst. The detection shows that the CO conversion rate of the standard sample reaches 90 percent.
The evaluation is carried out under the same condition, and the CO conversion rate of the titanium-based transformation catalyst of pure titanium reaches 90 percent.
This example is identical to example 3 in terms of active ingredient, but with a different support, example 3 using TiO2/SiO2Support, and TiO is used in this example2And (3) a carrier. Therefore, the CO conversion rate was reduced by 4%, and the titanium silicon support had a greater influence on the catalyst activity than the pure titanium support.
Example 7
This example demonstrates essentially the supported TiO of a titanium-based shift catalyst2/SiO2Can occur along with the organic sulfur hydrolysis reaction:
CS2+2H2O＝H2S+CO2
COS+H2O＝H2S+CO2
the titanium-based shift catalyst prepared in example 5 was evaluated, and the titanium-based shift catalyst prepared in example 5 had the following components in percentage by mass: CoO 1%, MoO37％、K2O 6％、CeO23% and the balance TiO2/SiO2。
The conversion rate of CO in the titanium-based shift catalyst and a standard sample in the embodiment is detected by adopting a test method for testing the high-pressure activity in the carbon monoxide sulfur-resistant shift catalyst. Through detection, the CO conversion rate of the standard sample reaches 90 percent; the CO conversion rate of the titanium-based shift catalyst is up to 93 percent when the evaluation is carried out under the same condition. Evaluation Process feed gas introduced CS2300mg/m3、COS 200mg/m3。
The hydrolysis results are shown in the following table:
Figure BDA0002367917020000131
EXAMPLE 8 use of titanium-based shift catalysts to command carbon monoxide in exhaust gases
The reaction mechanism of the carbon monoxide shift reaction is:
CO+H2O＝H2+CO2△H＝-41.19kj/mol
because the support is TiO2Can occur along with the organic sulfur hydrolysis reaction:
CS2+2H2O＝H2S+CO2
COS+H2O＝H2S+CO2
by utilizing the reaction mechanism, the inventor utilizes the carbon monoxide titanium-based shift catalyst to treat the phenomenon that the CO in the flue gas generated in biomass power generation and waste incineration exceeds the standard. The inventors carried out a series of experiments and evaluation studies. The evaluation results indicated that: the CO conversion catalyst can treat the over-standard emission of CO in the flue gas, and the catalyst can treat SO in the flue gas2、H2And O and other harmful substances.
CO in flue gas generated in the process of combustion power generation by taking biomass as a raw material is often discharged out of standard. CO is a flammable and easily poisoned gas. In practice, it was found that 2CO + O2＝2CO2The process can remove CO by △ H-41.19 kj/mol.
Evaluation device, catalytic loading 100ml, nitrogen as carrier gas, CO content 300mg/m3、O2The content is 500mg/m3The airspeed surveys: 2000- -5000/h CO removal efficiency, the results are given in the following table:
Figure BDA0002367917020000141
the above description is only for the purpose of illustrating preferred embodiments of the present invention and is not intended to limit the scope of the present invention, so that all variations of the features, characteristics, steps and formula equivalent to the scope of the present invention are included in the claims of the present invention.

Claims (11)

1. A preparation method of a titanium-based shift catalyst is characterized by comprising the following steps:
(1) preparation of TiO2/SiO2A carrier;
(2) preparing a steeping fluid;
(3) active component supported on TiO2/SiO2A carrier;
(4) drying and activating to prepare the titanium-based shift catalyst.
2. The method for preparing titanium-based shift catalyst according to claim 1, wherein the raw materials used in step (1) are iron-removed titanium solution and acidic silica sol, and TiO is added according to a molar ratio of 3:12/SiO2Mixing uniformly; then coprecipitating with ammonia water or urea solution, aging the obtained precipitate, washing with water, and filter-pressing with a filter to obtain a titanium-silicon filter cake; and (4) putting the filter cake into an oven for drying and crushing to obtain the titanium silicon powder.
3. The method for preparing the titanium-based shift catalyst according to claim 2, wherein the titanium silicon powder is weighed and put into a kneader, and the auxiliary material and deionized water are added and kneaded in the kneader; and putting the kneaded material into a strip extruding machine for extruding strips to obtain strips.
4. The method for preparing a titanium-based shift catalyst according to claim 3, wherein the strip is dried in an oven; breaking and sieving the dried strip-shaped objects, and feeding the strip-shaped objects into a muffle furnace for roasting for 1-4 hours to prepare the TiO2/SiO2And (3) a carrier.
5. The method of claim 1, wherein the TiO is selected from the group consisting of2/SiO2The specific surface of the carrier is 300-350m2/g。
6. The method for preparing a titanium-based shift catalyst according to claim 3, wherein the auxiliary materials comprise aluminum hydroxide, sesbania powder, hydroxypropyl methylcellulose, polyethylene oxide and glycerol.
7. The method of claim 1, wherein the step (2) of preparing the impregnation solution comprises: cobalt nitrate, ammonium tetramolybdate, nickel nitrate hexahydrate and potassium carbonate.
8. The titanium-based shift catalyst is characterized by comprising the following components in percentage by mass: 0.8-1.5% of CoO and MoO36～8％、K2O 5～8％、CeO20-7% and the balance of TiO2/SiO2。
9. The titanium-based shift catalyst of claim 8 wherein said TiO is selected from the group consisting of2/SiO2The preparation raw materials are a deferrization titanium solution and an acid silica sol, and TiO is added according to the molar ratio of 3:12/SiO2Mixing uniformly; then coprecipitating with ammonia water or urea solution, aging the obtained precipitate, washing with water, and filter-pressing with a filter to obtain a titanium-silicon filter cake; and (4) putting the filter cake into an oven for drying and crushing to obtain the titanium silicon powder.
10. The titanium-based shift catalyst of claim 8, further comprising NiO 0-5%.
11. The use of the titanium-based shift catalyst of claim 8 in the remediation of carbon monoxide in flue gases.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115569664A (en) * 2021-06-21 2023-01-06 中国石油化工股份有限公司 Preparation method of SBA-15 supported sulfur-tolerant shift catalyst
CN116273022A (en) * 2023-03-21 2023-06-23 昆明理工大学 Catalytic material with hollow core-shell structure and preparation method and application thereof
CN116273022B (en) * 2023-03-21 2024-06-07 昆明理工大学 Catalytic material with hollow core-shell structure and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115569664A (en) * 2021-06-21 2023-01-06 中国石油化工股份有限公司 Preparation method of SBA-15 supported sulfur-tolerant shift catalyst
CN115569664B (en) * 2021-06-21 2023-10-20 中国石油化工股份有限公司 Preparation method of SBA-15 supported sulfur-tolerant shift catalyst
CN116273022A (en) * 2023-03-21 2023-06-23 昆明理工大学 Catalytic material with hollow core-shell structure and preparation method and application thereof
CN116273022B (en) * 2023-03-21 2024-06-07 昆明理工大学 Catalytic material with hollow core-shell structure and preparation method and application thereof

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Application publication date: 20200515