CN114602487B - Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof - Google Patents
Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114602487B CN114602487B CN202210385919.1A CN202210385919A CN114602487B CN 114602487 B CN114602487 B CN 114602487B CN 202210385919 A CN202210385919 A CN 202210385919A CN 114602487 B CN114602487 B CN 114602487B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- catalyst
- tolerant
- solution
- resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a sulfur-resistant deoxidation catalyst and a preparation method and application thereof, wherein the structural formula of the sulfur-resistant deoxidation catalyst is aA x1 O y1 ·bB x2 O y2 ·nC x3 O y3 . When the catalyst is used, the catalyst reacts with hydrogen sulfide to generate a sulfide catalyst, and sulfides of transition metals of cobalt, nickel and iron and sulfides of molybdenum and tungsten easily generate special sulfide structures and new phases to generate good synergistic effect, so that the sulfide has good high-sulfur resistance and good deoxidation performance at lower temperature and under low hydrogen condition. The catalyst has good sulfur resistance, high deoxidation activity under the condition of low hydrogen, and the deoxidation rate is more than 90 percent; the sulfur-resistant deoxidation catalyst has the organic sulfur conversion rate of more than 90 percent; the sulfur-tolerant deoxygenation catalyst has low methanation side reaction and wide application range, and can be used at the temperature of 100-350 ℃ and the airspeed of 500-6000 h ‑1 Used under the conditions.
Description
Technical Field
The invention relates to the technical field of catalysts for industrial tail gas, in particular to a sulfur-resistant deoxidation catalyst and a preparation method and application thereof.
Background
With the improvement of environmental protection requirements and the requirement of enterprises for improving economic benefits, the production of products with high market demand and good economic benefits by utilizing various industrial tail gases is the target pursued by enterprises with industrial tail gas emission at present. To achieve the aim, various harmful components in the industrial tail gas need to be purified, wherein the purification and removal of oxygen is one of key contents. The traditional method for deoxidation is to desulfurize first and then deoxidize, and some industrial tail gases have various organic sulfur types and complex structures, so that the aim of desulfurization is fulfilled, the desulfurization cost is high, and the subsequent deoxidation catalyst is poisoned and inactivated quickly due to slight careless operation in actual production, so that the safety production is influenced, and the production cost of an enterprise is obviously increased. Some products are not economical after desulfurization, for example, the subsequent production has no requirement on sulfur, and the desulfurization procedure is added, so that the production cost is greatly increased. The currently used platinum and palladium noble metal deoxidation catalysts are too high in cost, are not sulfur-resistant, are easy to be poisoned, need to be desulfurized when in use, and are not applicable to high-CO process gas. Although the non-noble metal deoxidation catalyst solves the cost problem compared with the noble metal deoxidation catalyst, the non-noble metal deoxidation catalyst still has the problem of easy poisoning.
In summary, the existing deoxygenation catalysts cannot meet the requirement of removing oxygen from industrial tail gas because the industrial tail gas has low hydrogen content in most cases, contains various sulfides with complex structures and various poisons with lone electron pairs.
Disclosure of Invention
In view of the above, the invention provides a sulfur-tolerant deoxygenation catalyst, and a preparation method and an application thereof, so as to solve technical problems in the prior art.
In a first aspect, the invention provides a sulfur tolerant deoxygenation catalyst having a structural formula of aA x1 O y1 ·bB x2 O y2 ·nC x3 O y3 Wherein A is any one of cobalt, nickel and iron, B is molybdenum or tungsten, C x3 O y3 Is aluminum magnesium oxide or aluminum cerium oxide or a mixture thereof; wherein a, b and n respectively represent an oxide A x1 O y1 、B x2 O y2 、C x3 O y3 X1 and y1, and x2 and y2 are relatively prime integers respectively, and x3 and y3 are integers.
Preferably, the sulfur-tolerant deoxygenation catalyst is such that a is selected from the group consisting of x1 O y1 Accounting for 2-15% of the mass of the deoxidation catalyst, and the value of B is that B x2 O y2 Accounting for 5-20% of the mass of the sulfur-resistant deoxidation catalyst.
Preferably, the bulk density of the sulfur-tolerant deoxygenation catalyst is 0.60-0.85 g/cm 3 The specific surface area is 50 to 120m 2 /g。
In a second aspect, the present invention also provides a preparation method of the sulfur-tolerant deoxygenation catalyst, which comprises the following steps:
dissolving corresponding salt of cobalt, nickel or iron in water to obtain a first solution;
adding molybdenum salt or tungsten salt into ammonia water or water to obtain a second solution;
pulping and acidifying pseudo-boehmite and cerium oxide or magnesium oxide, adding a gelling agent, stirring, adding aluminum sol, forming by rolling balls, drying and roasting to obtain a carrier;
and (3) sequentially soaking the carrier in the first solution and the second solution, reacting and drying to obtain the sulfur-resistant deoxidation catalyst.
Preferably, in the method for preparing the sulfur-tolerant deoxygenation catalyst, the mass concentration of the ammonia water is 5-25%.
Preferably, the preparation method of the sulfur-resistant deoxygenation catalyst comprises the steps of sequentially soaking the carrier in the first solution and the second solution, reacting, and drying to obtain the sulfur-resistant deoxygenation catalyst, wherein the drying temperature is 110-130 ℃, and the drying time is 8-15 hours.
Preferably, in the preparation method of the sulfur-tolerant deoxidation catalyst, the corresponding salt of cobalt or nickel or iron comprises at least one of nitrate, oxalate and sulfate;
the molybdenum salt comprises at least one of molybdenum oxide and molybdenum salt;
the tungsten salt comprises at least one of tungstic acid, sodium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate and zinc tungstate.
In a third aspect, the invention also provides an application of the sulfur-resistant deoxygenation catalyst or the sulfur-resistant deoxygenation catalyst prepared by the preparation method in removal of oxygen in industrial tail gas.
Preferably, the application temperature is 100-350 ℃, and the space velocity is 500-6000 h -1 Under the condition, more than 90% of oxygen in the industrial tail gas can be removed.
Compared with the prior art, the sulfur-resistant deoxidation catalyst has the following beneficial effects:
when the sulfur-resistant deoxidation catalyst is used, the sulfur-resistant deoxidation catalyst reacts with hydrogen sulfide to generate a sulfide catalyst, and sulfides of transition metals of cobalt, nickel and iron, molybdenum and tungsten easily generate special sulfide structures and new phases to generate good synergistic effect, so that the sulfide has good high-sulfur resistance, and has good high-sulfur resistance under the conditions of low temperature and low hydrogenAnd (4) deoxidation performance. The sulfur-resistant deoxidation catalyst is a sulfide catalyst, has good sulfur resistance, and has no upper limit on sulfur resistance; the sulfur-tolerant deoxygenation catalyst has high deoxygenation activity under the condition of low hydrogen, and the deoxygenation rate is more than 90 percent; the sulfur-resistant deoxidation catalyst has high organic sulfur conversion rate, and the organic sulfur conversion rate is more than 90 percent; the sulfur-tolerant deoxygenation catalyst has low methanation side reaction, wide application range and high air speed of 500-6000 hr at 100-350 deg.c -1 Used under the conditions.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
The embodiment of the application provides a sulfur-resistant deoxidation catalyst, and the structural formula of the sulfur-resistant deoxidation catalyst is aA x1 O y1 ·bB x2 O y2 ·nC x3 O y3 Wherein A is any one of cobalt, nickel and iron, B is molybdenum or tungsten, C x3 O y3 Is aluminum magnesium oxide or aluminum cerium oxide or a mixture thereof; wherein a, b and n respectively represent oxide A x1 O y1 、B x2 O y2 、C x3 O y3 X1 and y1, and x2 and y2 are relatively prime integers respectively, and x3 and y3 are integers.
In the sulfur-tolerant deoxygenation catalyst of the present invention, a represents any one of cobalt, nickel, and iron, B represents molybdenum or tungsten, and C represents x3 O y3 Is aluminum magnesium oxide or aluminum cerium oxide or a mixture thereof (i.e., a mixture of aluminum magnesium and aluminum cerium); a. b and n are oxides A x1 O y1 、B x2 O y2 、C x3 O y3 Wherein x1 and y1, and x2 and y2 are prime integers respectively, x3 and y3 are integers, in particular, if A is cobalt, x1 is 1, y1 is 1, or x1 is 2, y1 is 3,or x1 is 3 and y1 is 4; if A is nickel, x1 is 1, y1 is 1, or x1 is 2, y1 is 3; if A is iron, then x1 is 2, y1 is 3, or x1 is 3, y1 is 4; x2 is 1, y2 is 2, or x1 is 1, y1 is 3; if C x3 O y3 Is an aluminum magnesium oxide, then x3: y3 is 2:5; if C x3 O y3 For aluminum cerium oxide, x3: y3 is 2:7. Specifically, A x1 O y1 Specifically CoO and Co 2 O 3 、Co 3 O 4 、NiO、Ni 2 O 3 、Fe 3 O 4 、Fe 2 O 3 Any one of (a); b is x2 O y2 Specifically MoO 2 、MoO 3 、WO 2 、WO 3 Any one of (a); c x3 O y3 Is an aluminum magnesium oxide, and specifically comprises the following components: al (Al) 2 O 3 ·MgO；C x3 O y3 Is an aluminum cerium oxide, and specifically comprises the following components: al (Al) 2 O 3 ·CeO 2 。
In some embodiments, a is chosen such that A x1 O y1 2-15% of the mass of the deoxidation catalyst, and the value of B is that B x2 O y2 5-20% of the sulfur-resistant deoxidation catalyst, and the rest is C x3 O y3 It is obvious that the mass fractions of different oxides can be adjusted by adjusting the values of a, b, n.
In some embodiments, the sulfur tolerant deoxygenation catalyst has a bulk density of 0.60 to 0.85g/cm 3 The specific surface area is 50 to 120m 2 /g。
When the sulfur-resistant deoxidation catalyst is used, the sulfur-resistant deoxidation catalyst reacts with hydrogen sulfide to generate a sulfide catalyst, and sulfides of transition metals of cobalt, nickel and iron, and sulfides of molybdenum and tungsten easily generate special sulfide structures and new phases to generate a good synergistic effect, so that the sulfides have good high-sulfur resistance, and have good deoxidation performance at a lower temperature and under a low-hydrogen condition. The sulfur-resistant deoxidation catalyst is a sulfide catalyst, has good sulfur resistance, and has no upper limit on sulfur resistance; the sulfur-tolerant deoxygenation catalyst has high deoxygenation activity under the condition of low hydrogen, and the deoxygenation rate is more than 90 percent; the sulfur tolerant deoxygenation catalyst of the present application hasThe conversion rate of organic sulfur is high, and the conversion rate of organic sulfur is more than 90 percent; the sulfur-tolerant deoxygenation catalyst has low methanation side reaction and wide application range, and can be used at the temperature of 100-350 ℃ and the airspeed of 500-6000 h -1 Used under the conditions.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the sulfur-tolerant deoxygenation catalyst, which comprises the following steps:
s1, dissolving corresponding salt of cobalt, nickel or iron in water to obtain a first solution;
s2, adding molybdenum salt or tungsten salt into ammonia water or water to obtain a second solution;
s3, pulping and acidifying pseudo-boehmite and cerium oxide or magnesium oxide, adding a gelling agent, stirring, adding aluminum sol, rolling ball forming, drying and roasting to obtain a carrier;
and S4, sequentially soaking the carrier in the first solution and the second solution, reacting, and drying to obtain the sulfur-resistant deoxygenation catalyst.
In some embodiments, the ammonia is used at a mass concentration of 5 to 25%.
In some embodiments, the sulfur-tolerant deoxygenation catalyst is obtained by sequentially soaking the carrier in the first solution and the second solution, reacting and drying, wherein the drying temperature is 110-130 ℃ and the drying time is 8-15 h.
Step S4 specifically includes: soaking the carrier in the first solution, soaking the carrier in the second solution after the carrier is absorbed completely, standing for 2-3 hr, and drying to obtain the sulfur-tolerant deoxidizing catalyst. Generally, the absorption of the carrier and the like can be completed within several minutes, and specifically, the carrier is firstly soaked in the first solution for 3-30 min, and the absorption of the carrier and the like can be completed.
In some embodiments, the corresponding salt of cobalt or nickel or iron comprises at least one of nitrate, oxalate, sulfate;
the molybdenum salt comprises at least one of molybdenum oxide and molybdenum salt;
the tungsten salt comprises at least one of tungstic acid, sodium tungstate, calcium tungstate, cobalt tungstate, cadmium tungstate, ferrous tungstate, ammonium tungstate and zinc tungstate.
Based on the same inventive concept, the invention also provides an application of the sulfur-resistant deoxidation catalyst or the sulfur-resistant deoxidation catalyst prepared by the preparation method in removal of oxygen in industrial tail gas.
Specifically, the application comprises the steps of placing the sulfur-resistant deoxidation catalyst in a reactor, heating to 100-350 ℃ in a nitrogen atmosphere, introducing hydrogen sulfide to convert the sulfur-resistant deoxidation catalyst into a sulfide catalyst, and introducing the sulfur-resistant deoxidation catalyst at an airspeed of 500-6000 h -1 The oxygen in the industrial tail gas can be removed. Under the conditions, more than 90% of oxygen in industrial tail gas such as converter tail gas, blast furnace tail gas and the like can be removed.
The following further describes the preparation method of the sulfur tolerant deoxygenation catalyst of the present application with specific examples.
Example 1
This example provides a method for preparing a carrier, including the following steps:
1000g of pseudo-boehmite and 50g of cerium oxide are pulped and acidized, then gelling agent is added, the mixture is stirred uniformly, alumina sol is added, the mixture is shaped by rolling balls, and then the mixture is immediately sent to a drying tower for quick drying and is roasted to obtain a carrier A.
Example 2
This example provides a method for preparing a carrier, including the following steps:
1000g of pseudo-boehmite and 70g of cerium oxide are pulped and acidified, then gelling agent is added and stirred uniformly, aluminum sol is added, the mixture is shaped by rolling balls and then immediately sent to a drying tower for quick drying, and the carrier B is obtained by roasting.
Example 3
The embodiment of the application provides a preparation method of a sulfur-resistant deoxidation catalyst, which comprises the following steps:
s1, dissolving 10.6g of cobalt nitrate hexahydrate in 20ml of deionized water, and heating to 40 ℃ to completely dissolve the cobalt nitrate hexahydrate to obtain a first solution;
s2, dissolving 12.96g of molybdenum oxide in 25ml of ammonia water with the mass concentration of 8% to obtain a second solution;
and S3, soaking 100g of the carrier A prepared in the embodiment 1 in the first solution, soaking the carrier A in the second solution after the carrier A and the like are completely absorbed, standing for 2-3 h, and drying at 120 ℃ for 4 h to obtain the sulfur-resistant deoxygenation catalyst.
Example 4
The embodiment of the application provides a preparation method of a sulfur-resistant deoxidation catalyst, which comprises the following steps:
s1, dissolving 10.6g of cobalt nitrate hexahydrate in 20ml of deionized water, and heating to 40 ℃ to completely dissolve the cobalt nitrate hexahydrate to obtain a first solution;
s2, dissolving 12.96g of molybdenum oxide in 25ml of ammonia water with the mass concentration of 8% to obtain a second solution;
and S3, soaking 100g of the carrier B prepared in the embodiment 2 in the first solution, soaking the carrier B in the second solution after the carrier B and the like are completely absorbed, standing for 2-3 h, and drying at 120 ℃ for 4 h to obtain the sulfur-resistant deoxygenation catalyst.
Example 5
The embodiment of the application provides a preparation method of a sulfur-resistant deoxidation catalyst, which comprises the following steps:
s1, dissolving 31.5g of nickel nitrate hexahydrate in 20ml of deionized water, and heating to 40 ℃ to completely dissolve the nickel nitrate hexahydrate to obtain a first solution;
s2, dissolving 11.34g of molybdenum oxide in 25ml of ammonia water with the mass concentration of 8% to obtain a second solution;
and S3, soaking 100g of the carrier A prepared in the embodiment 1 in the first solution, soaking the carrier B in the second solution after the carrier A and the like are completely absorbed, standing for 2-3 h, and drying at 120 ℃ for 4 h to obtain the sulfur-resistant deoxygenation catalyst.
Example 6
The embodiment of the application provides a preparation method of a sulfur-tolerant deoxygenation catalyst, which comprises the following steps:
s1, dissolving 42g of nickel nitrate hexahydrate in 20ml of deionized water, and heating to 40 ℃ to completely dissolve the nickel nitrate hexahydrate to obtain a first solution;
s2, dissolving 16.2g of molybdenum oxide in 25ml of ammonia water with the mass concentration of 8% to obtain a second solution;
and S3, soaking 100g of the carrier B prepared in the embodiment 1 in the first solution, soaking the carrier B in the second solution after the carrier B and the like completely absorb the carrier B, standing for 2-3 h, and drying at 120 ℃ for 4 h to obtain the sulfur-tolerant deoxygenation catalyst.
Example 7
The embodiment of the application provides a preparation method of a sulfur-resistant deoxidation catalyst, which comprises the following steps:
s1, dissolving 83.25g of ferrous sulfate heptahydrate in 25ml of deionized water, and heating to 40 ℃ to completely dissolve the ferrous sulfate heptahydrate to obtain a first solution;
s2, dissolving 24.3g of molybdenum oxide in 25ml of ammonia water with the mass concentration of 8% to obtain a second solution;
and S3, soaking 100g of the carrier A prepared in the embodiment 1 in the first solution, soaking the carrier A in the second solution after the carrier A and the like are completely absorbed, standing for 2-3 h, and drying at 120 ℃ for 4 h to obtain the sulfur-resistant deoxygenation catalyst.
Example 8
The embodiment of the application provides a preparation method of a sulfur-resistant deoxidation catalyst, which comprises the following steps:
s1, dissolving 21g of nickel nitrate hexahydrate in 20ml of deionized water, and heating to 40 ℃ to completely dissolve the nickel nitrate hexahydrate to obtain a first solution;
s2, dissolving 14.6g of tungstic acid in 20ml of ammonia water with the mass concentration of 8% to obtain a second solution;
and S3, soaking 100g of the carrier A prepared in the embodiment 1 in the first solution, soaking the carrier A in the second solution after the carrier A and the like are completely absorbed, standing for 2-3 h, and drying at 120 ℃ for 4 h to obtain the sulfur-resistant deoxygenation catalyst.
Example 9
The embodiment of the application provides a preparation method of a sulfur-resistant deoxidation catalyst, which comprises the following steps:
s1, dissolving 21g of nickel nitrate hexahydrate in 20ml of deionized water, and heating to 40 ℃ to completely dissolve the nickel nitrate hexahydrate to obtain a first solution;
s2, dissolving 29.2g of tungstic acid in 20ml of deionized water to obtain a second solution;
and S3, soaking 100g of the carrier A prepared in the embodiment 1 in the first solution, soaking the carrier A in the second solution after the carrier A and the like are completely absorbed, standing for 2-3 h, and drying at 120 ℃ for 4 h to obtain the sulfur-resistant deoxygenation catalyst.
The performance of the sulfur-tolerant deoxygenation catalyst obtained in the above examples was further evaluated as follows. The method specifically comprises the following steps:
adding the sulfur-tolerant deoxygenation catalyst prepared in examples 3-9 into a reactor, wherein the loading amount is 33mL, and the height-diameter ratio of a bed layer is 1.5; in the nitrogen atmosphere, the reactor is heated to the test temperature (namely the temperature in the table 1), then hydrogen sulfide is introduced into the reactor to convert the sulfur-resistant deoxidation catalyst into a sulfide catalyst, simulated industrial tail gas is introduced into the reactor through the reactor inlet (the space velocity of the industrial tail gas is shown in the table 1 below), the industrial tail gas after catalytic reaction is discharged from the reactor outlet, the industrial tail gas discharged from the outlet is compared with the industrial tail gas introduced from the inlet, and then O can be calculated 2 Conversion (%), COS conversion (%); wherein the simulated industrial tail gas introduced into the reactor through the inlet of the reactor comprises the following components: CO 55% and H 2 2％、CO 2 26％、O 2 1.0％、N 2 16％、COS 500mg/m 3 Wherein, CO, H 2 、CO 2 、O 2 、N 2 Are volume fractions. O at different temperatures and space velocities for different catalysts 2 The conversion (%) and the COS conversion (%) are shown in table 1 below.
TABLE 1 deoxygenation and COS conversions of sulfur tolerant deoxygenation catalysts prepared in various examples
As can be seen from Table 1, the sulfur-tolerant deoxygenation catalyst prepared by the method has good deoxygenation activity and COS conversion capability under low hydrogen conditions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. The application of the sulfur-resistant deoxidation catalyst in removing oxygen in industrial tail gas is characterized in that the application temperature is 100 to 350 ℃, and the airspeed is 500 to 6000 hours -1 Under the condition, more than 90 percent of oxygen in the industrial tail gas can be removed; wherein the industrial tail gas comprises the following components: CO 55% and H 2 2%、CO 2 26%、O 2 1.0%、N 2 16%、COS 500mg/m 3 Wherein, CO, H 2 、CO 2 、O 2 、N 2 Are all volume fractions; the structural formula of the sulfur-resistant deoxidation catalyst is aA x1 O y1 ·bB x2 O y2 ·nC x3 O y3 Wherein A is any one of cobalt, nickel and iron, B is molybdenum or tungsten, C x3 O y3 Is aluminum cerium oxide; wherein a, b and n respectively represent oxide A x1 O y1 、B x2 O y2 、C x3 O y3 X1 and y1, and x2 and y2 are relatively prime integers respectively, and x3 and y3 are integers;
the preparation method of the sulfur-tolerant deoxygenation catalyst comprises the following steps:
dissolving corresponding salt of cobalt, nickel or iron in water to obtain a first solution;
adding molybdenum oxide or tungstic acid into ammonia water or water to obtain a second solution;
pulping and acidifying pseudo-boehmite and cerium oxide, adding a gelling agent, stirring, adding aluminum sol, forming by rolling balls, drying and roasting to obtain a carrier;
and sequentially soaking the carrier in the first solution and the second solution, reacting and drying to obtain the sulfur-resistant deoxygenation catalyst.
2. The use of a sulfur tolerant deoxygenation catalyst of claim 1 to remove oxygen from industrial tail gas wherein a is selected such that a is x1 O y1 2 to 15% by mass of the deoxygenating catalyst, bIs valued such that B x2 O y2 Accounting for 5 to 20 percent of the mass of the sulfur-resistant deoxidation catalyst.
3. The application of the sulfur-tolerant deoxygenation catalyst of claim 1 in removing oxygen in industrial exhaust gas, wherein the bulk density of the sulfur-tolerant deoxygenation catalyst is 0.60 to 0.85g/cm 3 Specific surface area of 50 to 120m 2 /g。
4. The application of the sulfur-tolerant deoxygenation catalyst of claim 1 in removing oxygen in industrial exhaust gas, wherein the mass concentration of ammonia water is 5-25%.
5. The application of the sulfur-tolerant deoxygenation catalyst in removing oxygen in industrial tail gas according to claim 1, which is characterized in that a carrier is sequentially soaked in a first solution and a second solution, and the sulfur-tolerant deoxygenation catalyst is obtained by reaction and drying, wherein the drying temperature is 110-130 ℃ and the drying time is 8-15h.
6. Use of a sulfur tolerant deoxygenation catalyst according to claim 1 for the removal of oxygen from industrial tail gases wherein the corresponding salts of cobalt or nickel or iron comprise at least one of nitrate, oxalate, sulphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210385919.1A CN114602487B (en) | 2022-04-13 | 2022-04-13 | Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210385919.1A CN114602487B (en) | 2022-04-13 | 2022-04-13 | Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114602487A CN114602487A (en) | 2022-06-10 |
| CN114602487B true CN114602487B (en) | 2022-11-15 |
Family
ID=81869223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210385919.1A Active CN114602487B (en) | 2022-04-13 | 2022-04-13 | Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114602487B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463801A (en) * | 2002-06-12 | 2003-12-31 | 中国石化集团齐鲁石油化工公司 | Low cost sulfur transformation resistant deoxidizing agent |
| CN1464037A (en) * | 2002-06-12 | 2003-12-31 | 中国石化集团齐鲁石油化工公司 | Low cost sulfur transformation resistant deoxidizing agent and process for preparing the same |
| CN1899682A (en) * | 2006-07-11 | 2007-01-24 | 湖北省化学研究院 | Sulfur-proof deoxidizing agent and its preparing and use |
| CN101301611A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Sulfur-tolerance deoxidation catalyst and preparation and use thereof |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN107486214A (en) * | 2017-08-17 | 2017-12-19 | 江苏天东新材料科技有限公司 | A kind of preparation method and application for synthesis gas sulfur-tolerance deoxidation catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8519203B2 (en) * | 2010-02-17 | 2013-08-27 | Uop Llc | Low oxygen biomass-derived pyrolysis oils and methods for producing the same |
-
2022
- 2022-04-13 CN CN202210385919.1A patent/CN114602487B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463801A (en) * | 2002-06-12 | 2003-12-31 | 中国石化集团齐鲁石油化工公司 | Low cost sulfur transformation resistant deoxidizing agent |
| CN1464037A (en) * | 2002-06-12 | 2003-12-31 | 中国石化集团齐鲁石油化工公司 | Low cost sulfur transformation resistant deoxidizing agent and process for preparing the same |
| CN1899682A (en) * | 2006-07-11 | 2007-01-24 | 湖北省化学研究院 | Sulfur-proof deoxidizing agent and its preparing and use |
| CN101301611A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Sulfur-tolerance deoxidation catalyst and preparation and use thereof |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN107486214A (en) * | 2017-08-17 | 2017-12-19 | 江苏天东新材料科技有限公司 | A kind of preparation method and application for synthesis gas sulfur-tolerance deoxidation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114602487A (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101284238B (en) | Catalysts for stationary source ammine selective catalytic reduction for nitrous oxides | |
| CN103183346B (en) | Method of reverse water gas shift reaction for reverse water gas shift catalyst | |
| CN101322915A (en) | Composite adsorption desulfurizing agent and preparation method thereof | |
| CN107486223B (en) | Preparation method and application of high-efficiency organic sulfur hydroconversion catalyst | |
| CN106732581A (en) | A kind of Ru/CeTiO for low-temperature SCR reactionXThe preparation method of catalyst | |
| CN106732505A (en) | Denitrating catalyst and its preparation method and application | |
| CN107497432A (en) | Efficient cryogenic desulphurization denitration catalyst in coal tar kiln gas | |
| CN105562030A (en) | Aluminum trioxide sulfur recovery catalyst resistant to sulfation and preparation method thereof | |
| CN114602487B (en) | Sulfur-tolerant deoxygenation catalyst and preparation method and application thereof | |
| CN114505069A (en) | Hydrolysis catalyst for removing carbonyl sulfide in coal gas at low temperature and preparation method thereof | |
| CN106925355A (en) | A kind of maceration extract and the method that sulfur-resistant transformation catalyst is prepared using the maceration extract | |
| CN109894118B (en) | Nickel-based hydrogenation catalyst and application thereof | |
| CN107983354B (en) | Preparation method of alkali poisoning resistant copper-based spinel low-temperature denitration catalyst | |
| CN113600198A (en) | Biomass tar reforming catalyst and preparation method thereof | |
| CN112742414B (en) | Water-resistant and sulfur-resistant low-temperature SCR denitration catalyst and preparation method and application thereof | |
| CN108620085A (en) | Modified aluminium oxide supports and preparation method thereof and load hydrogenation catalyst for refining | |
| CN114558622B (en) | Desulfurization catalyst for cooperatively removing hydrogen sulfide and carbonyl sulfide and preparation method thereof | |
| CN114713243A (en) | Low-temperature efficient high-sulfur-resistance long-time stable SCR denitration catalyst and preparation method thereof | |
| CN105038863B (en) | Fine desulfurizer and preparation method thereof | |
| CN102773109B (en) | Catalyst for preparing hydrogen from hydrogen sulfide and preparation method thereof | |
| CN109745988A (en) | The preparation method of Cu based water gas converting catalysts | |
| CN102921289B (en) | Method for preparation of catalytic cracking flue gas sulfur transfer agent active constituent element | |
| CN106582638A (en) | Preparation method of (Au,Rh)-Cex/Al2O3 applied to NO+CO reaction | |
| CN109261159B (en) | Organic sulfur conversion type sulfur-tolerant shift catalyst and preparation method thereof | |
| CN109364941B (en) | High-temperature and high-pressure resistant copper-based transformation catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |