CN113351196A - Ceria-supported magnesium aluminum hydrotalcite material in H2Application in S selective oxidation reaction - Google Patents
Ceria-supported magnesium aluminum hydrotalcite material in H2Application in S selective oxidation reaction Download PDFInfo
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- CN113351196A CN113351196A CN202010141687.6A CN202010141687A CN113351196A CN 113351196 A CN113351196 A CN 113351196A CN 202010141687 A CN202010141687 A CN 202010141687A CN 113351196 A CN113351196 A CN 113351196A
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- magnesium aluminum
- aluminum hydrotalcite
- selective oxidation
- cerium dioxide
- composite oxide
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 25
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 25
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 25
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 28
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 22
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract 2
- 238000005516 engineering process Methods 0.000 claims description 3
- 229910001051 Magnalium Inorganic materials 0.000 claims 1
- 229940044927 ceric oxide Drugs 0.000 claims 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- 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
- B01D53/8612—Hydrogen sulfide
-
- 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
- B01J23/007—Mixed salts
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0456—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process the hydrogen sulfide-containing gas being a Claus process tail gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2047—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
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- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Health & Medical Sciences (AREA)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention belongs to the technical field of sulfur recovery, and particularly relates to a cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide catalytic material in H2S is applied in the selective oxidation process. Mainly used for H in acid gas in chemical industry2S, selectively oxidizing and recovering elemental sulfur. The loaded cerium dioxide has different shapes of octahedron, rod, cube and block, is prepared by the chemical reaction of cerium nitrate and different reactants, and is loaded on the magnesium aluminum hydrotalcite through a solid phase method. The catalyst has the advantages of cheap and easily available materials and simple preparation processThe method is easy to realize industrialization, shows higher selectivity and conversion rate in the selective oxidation reaction of the hydrogen sulfide, and has wider application prospect.
Description
Technical Field
The invention relates to a cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide catalytic material in H2The application of S selective oxidation in recovering elemental sulfur belongs to the field of sulfur recovering technology.
Background
Hydrogen sulfide is one of the common industrial waste gases in the chemical industry, is a toxic and corrosive gas, and is considered from the aspects of environment, public health and economyThe emission reduction and the recovery of sulfur resources are all of great importance. Now, H2The most widely used technique for S elimination and sulfur resource recovery is the Claus process. However, due to thermodynamic limitations, 3% to 5% of the hydrogen sulfide in the Claus tail gas cannot be eliminated. With the increasing strictness of the environmental protection requirements of our country, the subsequent treatment of the Claus tail gas becomes more and more important.
In the Claus tail gas treatment technology, the selective oxidation of hydrogen sulfide has the advantages of low investment cost, no limitation of thermodynamic equilibrium and the like. The reaction process of the hydrogen sulfide selective oxidation is as follows:
H2S+1/2O2→1/nSn+H2O
however, side reactions such as oxidation of elemental sulfur as a product or over-oxidation of hydrogen sulfide to sulfur dioxide are always inevitable during the reaction, thereby reducing the conversion and selectivity of the reaction. Therefore, it is important to prepare and screen a catalyst having high conversion and selectivity by controlling the catalyst.
The hydrotalcite material is a layered anionic clay material, has the characteristics of high specific surface area and acid-base dual-function, is an ideal catalyst carrier, can promote the dispersion of active components, has catalytic performance, and can show acid-base synergistic effect, oxidation-reduction synergistic effect and the like in reaction after being mixed with other components. Ceria is a catalytic material with excellent redox properties and high oxygen storage capacity, and is widely used for the control of pollutants. Meanwhile, the cerium dioxide also has good catalytic effect in the selective oxidation reaction of hydrogen sulfide. Therefore, cerium dioxide is loaded on the magnesium-aluminum hydrotalcite through a solid phase grinding method, and the two components generate synergistic effect, so that the catalyst with good selectivity and sulfur yield can be obtained.
Disclosure of Invention
The invention aims to load cerium dioxide with a magnesium aluminum hydrotalcite composite oxide material (CeO)2/Mg2Al-NO3LDO) in chemical industry H2S selective oxidation process for recovering elemental sulfur, and provides a process with high activity and high sulfur recovery rateA catalytic material.
H according to the invention2The S selective oxidation catalyst is prepared from a magnesium-aluminum hydrotalcite carrier and cerium dioxide by a solvent-free solid phase grinding method.
Wherein, the magnesium-aluminum hydrotalcite carrier is synthesized by magnesium nitrate and aluminum nitrate through a one-step method; the cerium dioxide is prepared by the chemical reaction of cerium nitrate and different reactants.
Furthermore, the morphology of the cerium dioxide is octahedral (CeO)2-O), rod-like (CeO)2-R), cubic (CeO)2-C) and bulk (CeO)2-B), accounting for 1-20% of the mass of the carrier.
The hydrogen sulfide selective oxidation reaction conditions of the invention are as follows: h2The concentration of S is 20-50000 ppm; the airspeed is 1000-30000 h-1(ii) a The reaction temperature is 160-260 ℃; o is2At a concentration of H21/2 for S concentration, and nitrogen as balance gas.
The invention has the following beneficial effects:
1) the cerium dioxide loaded magnesium aluminum hydrotalcite catalytic material has the synergistic effect of double active components, and can keep higher selectivity and conversion rate in a wider temperature range (160-260 ℃).
2) The catalyst of the present invention has hydrogen sulfide converting rate up to 90%, 96%, simple substance sulfur generating selectivity up to 100%, sulfur yield up to 96%, high practical value and high economic benefit.
Drawings
FIG. 1: x-ray diffraction spectra of 10% loading cerium dioxide loading magnesium aluminum hydrotalcite composite oxides with different morphologies.
FIG. 2: projection electron micrographs of ceria in different morphologies.
FIG. 3: 10 percent loading cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide with different morphologies as H2S selects the conversion curve for the oxidation catalyst.
FIG. 4: 10 percent loading cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide with different morphologies as H2S selectionSulfur yield curve for selective oxidation catalyst.
Detailed Description
Example 1: octahedral cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide (10% CeO)2-O/Mg2Al-NO3LDO) preparation
The first step is as follows: magnesium aluminum hydrotalcite precursor (Mg)2Al-NO3Preparation of-LDH)
0.12mol of Mg (NO)3)2·6H2O and 0.04mol Al (NO)3)3·9H2Dissolving O in 400ml of deionized water with carbon dioxide removed by nitrogen in advance, rapidly pouring into 1600ml of 0.15mol/L NaOH solution, stirring for 15min under nitrogen atmosphere, centrifuging the obtained precipitate, washing for 3 times by using the deionized water with carbon removed, drying at 70 ℃ for 12h, and drying at 120 ℃ for 12h to obtain Mg2Al-NO3-LDH materials.
The second step is that: preparation of octahedral cerium oxide (CeO)2-O)
6mmol Ce (NO3)3·6H2O and 0.06mmol Na3PO4·12H2O was dissolved in 240ml of deionized water, stirred at room temperature for 1 hour, transferred to a hydrothermal reactor, and heated at 170 ℃ for 10 hours. Centrifuging the obtained precipitate, washing with deionized water and ethanol for 3 times, and drying at 60 deg.C to obtain CeO2-O。
The third step: loading of octahedral cerium dioxide in different proportions
2.5g of Mg are weighed2Al-NO3LDH and 0.25g CeO2Grinding the solid with agate mortar for 30min until the two phases are fully mixed, dispersing the mixture into 5ml of deionized water, ultrasonically treating for 2h, drying for 12h at 80 ℃, and roasting for 2h at 500 ℃ to obtain 10% CeO2-O/Mg2Al-NO3-LDO。
Example 2: rod-shaped cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide (10% CeO)2-R/Mg2Al-NO3LDO) preparation
In comparison with example 1, the difference is the preparation of the second rod-shaped ceria (CeO)2-R). Is 6mmol Ce (NO3)3·6H2Dissolving O and 720mmol of NaOH in 15ml and 105ml of deionized water respectively, mixing the two solutions, stirring for 30min, transferring the mixed solution into a hydrothermal kettle, and carrying out hydrothermal reaction at 100 ℃ for 24 h. Centrifuging the obtained precipitate, washing with deionized water and ethanol for 3 times, and drying at 60 deg.C to obtain CeO2-R. The other materials and operating conditions were the same as in example 1. Example 3: cubic ceria-supported magnesium aluminum hydrotalcite composite oxide (10% CeO)2-C/Mg2Al-NO3LDO) preparation
Example 2 was compared, except that the hydrothermal temperature of the second step was 180 ℃ and the hydrothermal time was 24 hours, and other materials and operating conditions were the same as in example 2.
Example 4: bulk ceria-supported magnesium aluminum hydrotalcite composite oxide (10% CeO)2-B/Mg2Al-NO3LDO) preparation
Example 1 comparison, except for the second step bulk ceria preparation (CeO)2-B). Is 20mmol Ce (NO)3)3·6H2O is dissolved in 100ml of deionized water, and ammonia water with the concentration of 25% is added dropwise to adjust the pH to 11 and stirred for 1 hour. Centrifuging the obtained precipitate, washing with deionized water and ethanol for 3 times, and drying at 60 deg.C to obtain CeO2-B. The other materials and operating conditions were the same as in example 1.
Example 5: ceria-loaded magnesium aluminum hydrotalcite composite oxide catalytic material in H2Catalytic activity test in S-selective oxidation reaction
H Using fixed bed reaction apparatus in laboratory2And S, selecting an activity test of an oxidation reaction, and putting 0.5ml of the cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide catalyst with the particle size of 20-40 meshes into a fixed bed reaction tube. Controlling the flow of gas using a mass flow meter, H2The concentration of S is 20-50000 ppm; the airspeed is 1000-30000 h-1；O2Concentration and H2The concentration ratio of S is 1/2, nitrogen is used as equilibrium gas, and the reaction temperature is 160-260 ℃. Concentration of gas Components after reaction gas phase with Flame Photometric Detector (FPD) was usedDetecting by chromatography. In this reaction the catalyst activity is determined by H2S conversion and sulfur yield, wherein:
H2conversion of S (H in inlet gas)2Concentration of S gas-residual H in off gas2Concentration of S gas)/H in Inlet gas2Concentration of S gas 100%
Sulfur yield (in inlet gas H)2Concentration of S gas-residual H in off gas2Concentration of S gas-SO in off gas2Concentration of gas)/H in inlet gas2Concentration of S gas 100%.
Claims (4)
1. The invention relates to a cerium dioxide loaded magnesium aluminum hydrotalcite composite oxide catalytic material in H2The application of S selective oxidation in recovering elemental sulfur belongs to the field of sulfur recovering technology.
2. The ceria supported magnesium aluminum hydrotalcite composite oxide catalytic material according to the present invention, as set forth in claim 1, is characterized in that: the shape of the cerium dioxide is octahedron, rod, cube or block.
3. The ceria supported magnesium aluminum hydrotalcite catalytic material as described in claim 1 is characterized by: the ceric oxide accounts for 1 to 20 percent of the mass fraction of the magnalium hydrotalcite.
4. The invention as claimed in claim 1, wherein the cerium-zirconium composite oxide catalytic material is mainly used for H in acid gas in chemical industry2The selective oxidation process of S is applicable to the airspeed of 1000-30000 h-1The concentration of hydrogen sulfide is 20-50000 ppm.
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- 2020-03-04 CN CN202010141687.6A patent/CN113351196A/en active Pending
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| Title |
|---|
| BINBO JIANG等: ""Ce/MgAl mixed oxides derived from hydrotalcite LDH precursors as highly efficient catalysts for ketonization of carboxylic acid"" * |
| 刘冰等: ""程序升温表面反应技术研究氧化铈上H2S的吸附和转化"" * |
| 朱益洋等: ""LDO/CeO2纳米复合材料的合成及性能研究"" * |
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