CN1203828A - Catalyst for vecovering elemental sulphur selective oxidation of hydrogen sulfide and its preparing method - Google Patents
Catalyst for vecovering elemental sulphur selective oxidation of hydrogen sulfide and its preparing method Download PDFInfo
- Publication number
- CN1203828A CN1203828A CN 97105940 CN97105940A CN1203828A CN 1203828 A CN1203828 A CN 1203828A CN 97105940 CN97105940 CN 97105940 CN 97105940 A CN97105940 A CN 97105940A CN 1203828 A CN1203828 A CN 1203828A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sulfur
- phosphate
- reaction
- selective oxidation
- 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.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for treating sulfur-bearing discharged gas. It can implement the selective oxidation of H2S to obtain element sulfur. Said invention is characterized by that in the course of preparation of the catalyst it uses inorganic acid, for example, phosphoric acid to make modification so as to make its surface do not produce activity on Claus reaction, and adopts the phosphate substances, such as ferric phosphate and chrome phosphate, etc. as catalytic activative substance to raise the activity and selectivity of sulfur production reaction.
Description
The invention relates to a sulfur-containing exhaust gas treatment catalyst and its preparation method, in particular, the present
Invention relates to a method for selectively oxidizing hydrogen sulfide to elemental sulfur catalyst and catalyst
Methods.
In the oil and gas processing, produce large amounts of hydrogen sulfide (H2S) gases. In order to protect the ring
Habitat and recovery of elemental sulfur, Claus process commonly used in industry deal with acid gas containing hydrogen sulfide.
Conventional Claus process sour gas feed to a third of H2S In the high temperature combustion of oxygen furnace
Of a SO2,SO
2And then with the remaining H2S reaction of elemental sulfur: To maximize the recovery of elemental sulfur, must be maintained H2S∶SO
2= 2:1. Moreover, since the reaction temperature is
Degree of restriction of chemical equilibrium, even when the device is in good condition and operating conditions, the use of good activity
Catalysts and three conversion processes, Claus sulfur recovery can only reach up to about 97%,
The remaining H2S, gaseous sulfur and sulfur which is equivalent to the amount of processing apparatus 3-4% sulfur, and finally to
SO2Form into the atmosphere, which seriously pollutes the environment.
H
2S to elemental sulfur in direct oxidation reactions with H2S and SO2Phase Claus reaction carried out
Instead, the following formula may be speaking from a thermodynamic reaction: In the absence of catalyst, the reaction (1) very slowly, and only at a temperature close to 300 ℃,
Reaction is rather obvious, but when the reaction temperature exceeds 300 ℃, but also accelerated the generation SO2Side effects: If the reaction temperature exceeds 400 ℃, generate SO may also occur3Side effects:These side effects will reduce H2S direct oxidation of sulfur levels. H in industrial installations2S Selective Catalytic
Oxidation process conditions, mainly primary reaction (1) and the side reaction (2) to (4), can be expressed by the following formula:
H
2Oxidation of S can be considered as two parallel reactions (1) and (2), and the reaction (1) of the two subsequent reaction (3) and
(4). The main reaction (1) to generate elemental sulfur is H2S partial oxidation results, side reaction (2) to (4) to generate SO2Is H2S further oxidation results. In order to limit SO2Generation, H2S oxidation must be less than
300 ℃ the process conditions, and the reaction temperature should be higher than 180 ~ 190 ℃, in order to avoid the gaseous sulfur
Condensation in the catalyst pores, so the development of a need to develop a high activity and selectivity of the catalyst, to promote
Into the temperature range of 190 ~ 300 ℃ the H2S selective oxidation reactions. Reaction (1) and (2) for the degree of
The chemical composition depends on the catalyst, and the reaction (3) and (4) for the degree, in addition to the catalyst used
The chemical composition, but also the pore structure of the catalyst, a large pore structure (low specific surface area) can Sulfur
Once generated molecules will quickly leave the pores, avoid sulfur vapor according to the reaction (3) and (4) further oxidized
SO2。
According to U.S. Patent 4311683, BSR-Selectox process uses a carrier for non-alkali
Porous refractory oxide of vanadium oxides and vanadium sulfide catalysts, and British Patent 2,122,597 intermediary
Shao can be used Modop process uses a TiO2Based catalysts. Lack of these two catalysts
The process gas is to the high concentration of water content in certain limits, because Klaus paragraph
Exhaust emissions after the hydrogenated with 25% to 30% water, a high partial pressure of water will drive the Claus reaction
Balance in favor of generating H2S and SO2The direction, so the gas to the selective oxidation reaction
The reactor is required before the contact condenser or quench water content in the gas stream is reduced to 5% (V) or so. Tail
The water content in the gas is lower, H2S conversion rate.
U.S. Patent 4,818,740 discloses a process from the high concentration of the catalytic effect of water content
Agent, the catalyst can be used in Super Claus process, the carrier is α-Al2O
3, The active ingredient is
Fe2O
3-Cr
2O
3. The catalyst composition of the gas to H2S 1%(V)、O
2 0.6%(V)、H
2O 30%
(V), the balance helium and the reaction temperature 270 ℃, 1000h-1Gas space velocity under laboratory conditions, H2S conversion
Rate of 100%, the selectivity of up to 93%. But industrial installations operating data has indicated that the upstream mining
Claus catalytic conversion process with two selective oxidation reactor, the process gas at the inlet water content far
Reached 30% (V) of more moderate conditions of an industrial atmosphere, H2S is the actual conversion rate of 95 ~
96%, the selectivity was 80 to 82%, the yield of sulfur which is only 76 ~ 79%. The catalyst in industrial conditions
Selective is not high, indicating that it failed to maximize the suppression reaction (4), which may lead to the establishment failed to exclude
The equilibrium Claus catalyst surface of the solid base. Furthermore, the catalyst preparation method is not
Simple enough, the preparation of iron complexes of ammonia and ammonium chromium need to use a 25% solution of concentrated aqueous ammonia, the drying process will be
Release of ammonia; while, in order to completely cover the active ingredient with the carrier containing alkaline or insignificant portion
Position, the first active ingredient with a complex salt was impregnated α-Al2O
3Powder, dried, and then 160MPa
Pressure extrusion molding, preparation process is more complicated.
Disclosed in European Patent 409353A1 catalyst preparation procedures and methods for their U.S. Patent
4818740 substantially the same, except that the high surface area carrier is a SiO2Vector, not α-Al2O
3Load
Body. The high activity of the catalyst surface area as small α-Al2O
3Based catalyst, but its activity at low temperatures, but
Is obviously superior to α-Al2O
3Based catalysts. In industrial installations, the use of these two catalysts mixed square
Method, the inlet temperature can bed 255 ℃ reduced from the original 200 ℃, at the same time, the maximum temperature bed
Also dropped from the original 300 ℃ 260 ℃. Given the adiabatic condition, 1% (V), H2S selective oxidation
To elemental sulfur, the resulting reaction heat sufficient to reactor bed temperature 60 ℃, thus reducing bed
Layer relaxes the inlet temperature means that H2S concentration limits, H2The concentration of S from the original
0.55% (V) ~ 0.65% (V) widened to 0.9% (V) ~ 1.0% (V), thus increasing the operation of the apparatus
Be flexible and make the total sulfur recovery unit from 98.0% -98.3% to 98.7% ~ 98.9%.
But according to the above-mentioned technical ideas, want to need to improve the overall sulfur recovery unit, the need to further improve the catalyst
Activity levels.
The object of the present invention is to provide a preparation method is simple, the new high activity for H2S selective oxidation catalyst
Agent.
In preparing the present catalyst, in order to ensure that the reaction conditions in the gas phase catalyst exposed
Surface is not alkaline, improve H2S to elemental sulfur direct oxidation selectivity, the carrier used for preparing α-
Al2O
3Should no alkali, or the amount of alkali metal and alkaline earth metal hydroxides of less than 3% (m /
m), and the use of the acidic substance are inorganic acids such as phosphoric acid in particular to modulate the sub Claus reaction-inert non-
Carrier and an alkaline catalyst surface, inhibiting the occurrence of side reactions Claus while using substances such as phosphates
Phosphate, iron phosphate, chromium, supported on a carrier, as a catalyst active component.
As we all know, according to the Lewis acid-base theory proposed, Al2O
3Acid sites present on the surface and the base
Hydrates chiral centers are generated during the dewatering process, this process can be roughly expressed as follows:Wherein (a) said Lewis acid sites, electron-deficient central part, (b) said basic sites, is charged
Sub-center. The roasting process and the degree of dehydration of alumina and alumina crystal relevant. After
Above 1200 ℃ high temperature treated α-Al2O
3Generally regarded as chemically inert substances, in theory, should have
Not contain or contain basic sites obvious, but in fact even pure α-Al2O
3Also due to dehydration
Process will inevitably produce lattice defects, more or less always show some degree of acidity
Nature, especially industrial α-Al2O
3Also often contains impurities, further strengthened its base properties. Such as alkali metal
Or alkaline earth metal oxide impurities will increase the α-Al2O
3The alkaline nature of the halogen impurity ions are
Enhanced α-Al2O
3Acidic nature. Increasing Al2O
3Alkaline, helps the Al2O
3Based catalysts
Claus activity, but it is precisely the Claus reaction H2S is oxidized to elemental sulfur directly inverse reaction,
It should try to curb the Al2O
3Rendered alkaline; introducing F-、Cl
-Such as halogen ion, although increases Al2O
3Of
Acid, but the high temperature firing device be serious corrosion.
Thus, the effective modulation Al2O
3Alkaline-based catalyst surface is to improve the H2Direct oxidation of S
The key element sulfur selective. In the present invention, by introducing an inorganic acid such as phosphoric acid, not only effectively modulation
The α-Al2O
3Catalyst for the base, while the morphology of the active ingredient with the existing patent
CN87103687 the different.
The present invention uses a temperature-programmed reduction (TPR) techniques and CO2- Programmed desorption (TPD)
The catalysts were characterized by technical research. As can be seen from the TPR results (see Figure 1): In industrial α-
Al2O
3On, Cr2O
3Reduction of low chromium reduction peak temperature ratio Fe2O
3Reduced to cheap iron reduction peak temperature
Clearly in advance, indicating Cr2O
3Than Fe2O
3Easy to H2Reduced to low state; in FeCr / α-Al2O
3Appears on three samples of hydrogen consumption peaks, with Cr / α-Al2O
3And Fe / α-Al2O
3Compared to samples shows that the first consumption
Hydrogen peak of Cr2O
3Reduction of hydrogen consumption peaks, the second and third reduction peaks of Fe2O
3Reduction of hydrogen consumption peaks, while in
According to the present invention is prepared by adding phosphoric FeCrP / α-Al2O
3Sample, the TPR curve (Figure 1
a, b, c, d line) were significantly different from the FeCr / α-Al2O
3Sample, when the added amount of P is small, the consumption of chromium reduction
Little change in the hydrogen peak, but the peak temperature of the iron reduction was after the shift, and with the increase of phosphorus content, the reduction of chromium
Hydrogen consumption peaks gradually become obvious, while the iron was hot hydrogen consumption peaks gradually disappear, while the reduction of the sample peak shape
Has evolved into a broad reduction peaks, indicating that the introduction of phosphate only modulation of the active ingredient and a carrier
Interactions, but also changed the active ingredient is the chemical form of the carrier surface. The X-photoelectron
Spectroscopy, infrared spectroscopy and X-ray diffraction analysis confirmed that the Fe and Cr on the surface morphology of phosphorus chemical
Phosphoric acid, iron and chromium.
From the CO2-TPD results (see Figure 2) can be seen: pure Fe2O
3There are two CO2Take off
With peaks, respectively, at 79 ℃ and 326 ℃ at the office, indicating Fe2O
3There are two desorption centers and α-Al2O
3Only a low-temperature CO2Desorption peak; But according to the present invention is prepared, plus a sample of phosphoric acid has been mainly table
Now the high-temperature CO2Desorption (350 ℃ or so), which shows the introduction of phosphorus modulation, the surface characteristics of the catalyst
Resistance, adding a small amount of phosphorus desorption of CO can cause hypothermia2The surface of the basic sites disappear, and the high-temperature CO2Desorption
With the active phosphorus content increases, the desorption peak area gradually decreases as the phosphorus content of 1.27%,
Has largely undetectable CO2Desorption, indicating that the introduction of phosphorus modulation basicity of the catalyst, and
And with the increase of phosphorus content, the surface of the catalyst gradually decrease basic sites.
In the present invention, the use of the carrier shall be no significant activity for the Claus reaction inert carrier, for example,
To use an alkali or alkaline surface is not significant α-Al2O
3. If I choose to alkali-containing α-Al2O
3Its amount of alkali
Alkali metal and alkaline earth metal oxides, the percentage should be less than 3 mass%, preferably less than 0.3%, and
With an acidic substance such as phosphoric acid to be modulated, is not significant to the surface alkaline.
Modulation with phosphoric acid, the phosphoric acid is added in an amount of not only the nature of the carrier, but also with the use Activity
Components of the nature and volume. The content of phosphorus element phosphorus, was 0.01% (m / m) ~ 10% (m / m).
When preparing the catalyst of the invention, can be directly used iron, chromium nitrate and phosphate complexes formulated
Impregnating the α-Al2O
3The method is simple; addition, the introduction of not only changed phosphate of iron, chromium surface of the carrier
The traditional chemical form, but also effectively modulating the basicity of the catalyst, its activity and selection
Resistance than conventional catalysts are significantly improved, thereby further improving the overall sulfur recovery efficiency of the apparatus.
Figure 1 is a diagram of different samples TPR;
Figure 2 is a diagram of different samples TPD.
Example 1
The 12gFe (NO3)
3·9H
2O and 1.3gCr (NO3)
3·9H
2O was dissolved in a small amount of demineralized water
Then adding 4gH3P
O4, and then diluted with demineralized water to 60ml, formulated into a pale blue containing
[Fe (HPO4)]
4 +And Cr2H
2(HPO
4)
4The complex solution. The preparation of liquid impregnation 97.5gΦ3mm
α-Al2O
3Crowded bar (one kind of soda lime sintering industrial production of high alkali content α-Al2O
3, The specific surface area
To 2.99m2/ G), and then dried for 24 hours at room temperature, then at 120 ℃ and then dried for 4 hours, after
Calcination at 500 ℃ for 6 hours to obtain a pale yellow finished catalyst A, a specific surface area of 5.1m measured2/ G,
Iron phosphate 4.15% (m / m), chromium phosphate 0.47% (m / m).
Example 2
Preparation steps of Example 1, but the H3PO
4Join minus the 2g, the resulting complex solution
Slightly darker color, finished catalyst B was yellow rice.
Example 3
Preparation steps of Example 1, but the H3PO
4Join minus is 1.35g, the resulting complex is dissolved
Liquid darker finished catalyst C was khaki.
Example 4
Preparation steps of Example 1, but the H3PO
4Dosage further reduced to 0.35g, this time due to
Complexation is not complete, formulated liquid color was blue, the finished catalyst D was drab.
Example 5
The catalyst prepared in the above embodiment broken into 20 mesh to 40 mesh particle size, the sample 10ml
Φ18mm diameter into a stainless steel reactor, placed above a thick layer of quartz sand 4cm to
To ensure uniform mixing of the reactants, the reactor inlet gas comprising H2S 1%(V),O
2 0.6%(V),H
2O
30% (V), the other is N2. Small devices using a laboratory to evaluate the activity of the catalyst.
All tests are typically 270 ℃ and 2500h-1High space velocity conditions. H2S conversion rate
ηH2s%, selectivity Ss% S% and sulfur yield is calculated as follows:
The formula [H2S]
Entering,And [SO2]
Entering,Represents a reactive compound H artifacts2S% (V) and SO2% (V) concentration
Degrees. Activity evaluation results are shown in the following table.
Catalyst | H 2S conversion rate % | Selective % | Sulfur yield % |
| 100 | 96 | 96 |
| 100 | 94.8 | 94.8 |
C | 99 | 94.6 | 93.7 |
D | 83.6 | 92.3 | 77.2 |
CRS-31 | 78.2 | 80.2 | 62.7 |
As can be seen from the data in the table: The activity and selectivity of catalysts of the invention is obviously superior to industrial
CRS-31TiO2Catalyst, and accompanied by the increase of phosphoric acid, the final form of iron phosphate, phosphorus
Chromium catalyst has excellent activity and selectivity.
Claims (7)
- A method for the H2S to elemental sulfur in a selective oxidation catalyst, characterized in that the catalyst preparation Process, with a mineral acid to modulate the basicity of the catalyst, so that in the Claus reaction under the reaction conditions Inert to the catalyst and the catalytic active material is phosphate.
- 2, according to claim 1, wherein the catalyst is characterized in that the inorganic acid is phosphoric acid.
- 3, according to claim 1, wherein the catalyst, characterized in that the catalytically active material is iron phosphate and / or Chromic phosphate.
- 4, according to claim 3, wherein the catalyst characterized in that the iron phosphate, chromium phosphate content of 0.05% ~ 30% (m / m).
- 5, according to claim 1, wherein the catalyst, characterized in that the carrier is not used in the α-alkali Al2O 3。
- 6, according to claim 1, wherein the catalyst, characterized in that the alkali used in the carrier is α- Al2O 3。
- As claimed in any of claims 1 to 6 wherein the catalyst is one of the preceding claim, characterized in that the catalyst The content of phosphorus (as elemental phosphorus) is 0.01% ~ 10% (m / m).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN97105940A CN1088607C (en) | 1997-06-27 | 1997-06-27 | Catalyst for vecovering elemental sulphur selective oxidation of hydrogen sulfide and its preparing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN97105940A CN1088607C (en) | 1997-06-27 | 1997-06-27 | Catalyst for vecovering elemental sulphur selective oxidation of hydrogen sulfide and its preparing method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1203828A true CN1203828A (en) | 1999-01-06 |
CN1088607C CN1088607C (en) | 2002-08-07 |
Family
ID=5168227
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN97105940A Expired - Fee Related CN1088607C (en) | 1997-06-27 | 1997-06-27 | Catalyst for vecovering elemental sulphur selective oxidation of hydrogen sulfide and its preparing method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1088607C (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100346877C (en) * | 2005-12-30 | 2007-11-07 | 黑龙江大学 | Catalyst for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde, its prepn. method and application thereof |
CN103182316A (en) * | 2011-12-30 | 2013-07-03 | 北京北大先锋科技有限公司 | Catalyst for dephosphorizing yellow phosphorus tail gas and preparation method thereof |
CN104208992A (en) * | 2014-09-17 | 2014-12-17 | 宁波市化工研究设计院有限公司 | Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur |
CN104475104A (en) * | 2014-11-05 | 2015-04-01 | 杨楠 | Catalyst for selectively catalytically oxidizing hydrogen sulfide, tail-gas burning catalyst and technology for deeply catalytically oxidizing hydrogen sulfide for generating sulphur |
CN114471635A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalytic oxidation catalyst and preparation method and application thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311683A (en) * | 1976-06-28 | 1982-01-19 | Union Oil Company Of California | Process for removal of hydrogen sulfide from gas streams |
NL8600959A (en) * | 1986-04-16 | 1987-11-16 | Veg Gasinstituut Nv | CATALYST FOR THE SELECTIVE OXYDATION OF SULFUR-CONTAINING COMPOUNDS, IN PARTICULAR SULFUR HYDROGENIC TO ELEMENTAL SULFUR; METHOD FOR PREPARING THE CATALYST AND METHOD FOR SELECTIVE OXIDIZATION OF SULFUR CONTAINERS, IN THE PARTICULAR SULFUR HYDROGENIC SODIUM SULFUR. |
NL8901893A (en) * | 1989-07-21 | 1991-02-18 | Veg Gasinstituut Nv | Selective oxidn. catalyst - used to oxidise sulphur cpds. partic. hydrogen sulphide to elemental sulphur |
-
1997
- 1997-06-27 CN CN97105940A patent/CN1088607C/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100346877C (en) * | 2005-12-30 | 2007-11-07 | 黑龙江大学 | Catalyst for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde, its prepn. method and application thereof |
CN103182316A (en) * | 2011-12-30 | 2013-07-03 | 北京北大先锋科技有限公司 | Catalyst for dephosphorizing yellow phosphorus tail gas and preparation method thereof |
CN103182316B (en) * | 2011-12-30 | 2015-02-04 | 北京北大先锋科技有限公司 | Catalyst for dephosphorizing yellow phosphorus tail gas and preparation method thereof |
CN104208992A (en) * | 2014-09-17 | 2014-12-17 | 宁波市化工研究设计院有限公司 | Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur |
CN104208992B (en) * | 2014-09-17 | 2017-02-01 | 宁波市化工研究设计院有限公司 | Method for desulfurizing acid gas containing hydrogen sulfide and recycling sulfur |
CN104475104A (en) * | 2014-11-05 | 2015-04-01 | 杨楠 | Catalyst for selectively catalytically oxidizing hydrogen sulfide, tail-gas burning catalyst and technology for deeply catalytically oxidizing hydrogen sulfide for generating sulphur |
CN114471635A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalytic oxidation catalyst and preparation method and application thereof |
CN114471635B (en) * | 2020-10-27 | 2024-01-12 | 中国石油化工股份有限公司 | Catalytic oxidation catalyst and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN1088607C (en) | 2002-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4605546A (en) | Catalytic process for the production of sulfur from a gas containing H2 S | |
US4210628A (en) | Removal of nitrogen oxides | |
KR101594227B1 (en) | Composition based on oxides of cerium, of niobium and, optionally, of zirconium and use thereof in catalysis | |
CN106345523B (en) | A kind of low-temperature denitration catalyst and preparation method thereof based on carbonization MOFs | |
US4640908A (en) | Catalyst for the oxidation of hydrogen sulfide and process for the preparation of the catalyst | |
JP2000501061A (en) | Compositions based on cerium oxide and zirconium oxide with high specific surface area and high oxygen storage capacity, process for their preparation and use in catalytic reactions | |
CN109012144B (en) | Hexaaluminate composite oxide material in H2Application of S in catalytic decomposition reaction | |
CN112410037B (en) | Composite functional material for soil pollution treatment and preparation method thereof | |
KR20090007438A (en) | Composition based on alumina, cerium and barium and/or strontium, used especially for trapping nitrogen oxides (nox) | |
WO1999002258A1 (en) | Selective catalytic reduction for the removal of nitrogen oxides and catalyst body thereof | |
CN105107521A (en) | Mn-Fe double metal-doped active carbon-based desulfurization catalyst, and preparation method thereof | |
US7754650B2 (en) | Trifunctional catalyst for sulphur transfer, denitrogenation and combustion promoting and a method for preparing the same | |
JPS6128454A (en) | Catalyst for removing nitrogen oxide in exhaust gas | |
CN1203828A (en) | Catalyst for vecovering elemental sulphur selective oxidation of hydrogen sulfide and its preparing method | |
CN109250763B (en) | Method for preparing hydrogen by reforming hydrogen sulfide and methane | |
CN116216717A (en) | Preparation method of activated carbon and low-temperature SCR denitration catalyst and flue gas denitration method | |
CN113828311B (en) | High sulfur-resistant catalyst for removing CO and preparation method thereof | |
CN111545054B (en) | Application of spinel catalytic material | |
Hibbert et al. | The reduction of sulphur dioxide by carbon monoxide on a La0. 5Sr0. 5CoO3 catalyst | |
CN112892569B (en) | Silicon carbide loaded cerium oxide catalyst and method for preparing sulfur by hydrogen sulfide selective oxidation under medium-high temperature condition by adopting same | |
US3755550A (en) | Process for reduction of so2 | |
CN112642396B (en) | Modified activated carbon and composite material as well as preparation method and application thereof | |
CN112642397A (en) | Composite material and preparation method and application thereof | |
CN1265883C (en) | Catalyst for purifying cokery tail gas and recovering sulfur and preparing method thereof | |
SU825133A1 (en) | Catalyst for conversion of sulfur-containing gases to elemental sulfur |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |