CN111167473A - Copromoted cobaltosic oxide/silicon dioxide catalyst with Mn and Co, and preparation method and application thereof - Google Patents
Copromoted cobaltosic oxide/silicon dioxide catalyst with Mn and Co, and preparation method and application thereof Download PDFInfo
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- CN111167473A CN111167473A CN202010191487.1A CN202010191487A CN111167473A CN 111167473 A CN111167473 A CN 111167473A CN 202010191487 A CN202010191487 A CN 202010191487A CN 111167473 A CN111167473 A CN 111167473A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 48
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 33
- 238000011068 loading method Methods 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 20
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 20
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims description 49
- 239000002244 precipitate Substances 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000005303 weighing Methods 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000969 carrier Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910002521 CoMn Inorganic materials 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000001294 propane Substances 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 238000007084 catalytic combustion reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
Abstract
The invention discloses a Mn and Co Co-promoted cobaltosic oxide/silicon dioxide catalyst for removing non-methane total hydrocarbons in total hydrocarbons, and a preparation method and application thereof3O4And Co-modified SiO carrier2Wherein the loading amount of the active component is 20-30%, and the molar ratio of Mn to Co is n (Mn) = n (Co) = 1: 10-1: 20; co-modified SiO2Molar ratio of Co to Si in the carrier n (Co) = 1: 20-1: 30. the catalyst is synthesized by two steps by combining a hydrolysis method and a coprecipitation method. Modified Co-promoted SiO2The carrier has stronger bonding force with the active component, and Mn is introduced into Co3O4Further increasing catalyst activity and stability. The catalyst has the advantages of simple preparation method, low temperature of an operation window and high practical application value for removing non-methane total hydrocarbons in the total hydrocarbons.
Description
Technical Field
The invention belongs to the technical field of catalytic environmental protection, and particularly relates to a cobaltosic oxide/silicon dioxide catalyst promoted by Mn and Co together, and a preparation method and application thereof.
Background
Non-methane total hydrocarbons (NMHC) refers to the generic term for all hydrocarbons with volatility other than methane, such as alkanes, alkenes, aromatics, and oxygenated hydrocarbon components. When the NMHC in the environment exceeds a certain concentration, direct harm can be generated to human health, and a plurality of volatile organic compounds have carcinogenic effect on human bodies. When non-methane total hydrocarbon generates photochemical smog and ozone through chemical reaction under the condition of illumination, immeasurable damage is caused to the human environment. Therefore, in recent years, countries have increased the force of monitoring NMHC in the environment.
The detection methods currently used for non-methane total hydrocarbons (NMHC) mainly include catalytic oxidation and chromatography. The method for detecting the content of NMHC by gas chromatography specified in the HJ38-2017 standard is to directly inject a gas sample into a gas chromatograph with a hydrogen flame ionization detector, measure the content of total hydrocarbon and methane on a total hydrocarbon column and a methane column respectively, and obtain the difference between the total hydrocarbon and the methane as the content of the NMHC. The main difference between catalytic oxidation and chromatography is that catalytic methods analyze methane by catalytically oxidizing organic species other than methane. The catalytic oxidation method has the advantages of simplified equipment structure and simple method. At the same time, higher requirements are placed on the efficiency and temperature window of the catalyst for catalytically oxidizing non-methane total hydrocarbons in the total hydrocarbons.
Based on the characteristics that most of the current catalytic combustion catalysts for non-methane total hydrocarbons in the total hydrocarbons have narrow temperature windows and are difficult to control working windows. There is a need to further improve the efficiency of catalysts used in non-methane total hydrocarbon detection equipment, reduce energy consumption, and widen the operable temperature window.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a Mn and Co-promoted tricobalt tetroxide/silica catalyst useful for the removal of non-methane total hydrocarbons from the total hydrocarbons.
Yet another object of the present invention is to: provides a preparation method of the Mn and Co Co-promoted cobaltosic oxide/silicon dioxide catalyst product.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: mn and Co Co-promoted cobaltosic oxide/silica catalyst, the cobaltosic oxide/silica catalyst (Co)3O4/SiO2) Comprises active component Mn modified Co3O4And Co-modified SiO carrier2Wherein the loading amount of the active component is 20-30%, the molar ratio of Mn to Co in the active component is n (Mn) = n (Co) = 1: 10-1: 20; molar ratio of Co to Si in the carrier n (Co) = 1: 20-1: 30.
the invention provides a preparation method of Mn and Co Co-promoted cobaltosic oxide/silicon dioxide catalyst, which comprises the following steps:
step one, preparing SiO promoted by Co2Carrier:
(1) the molar ratio n (Co): n (Si) = 1: 20-1: 30 dissolving ethyl orthosilicate and cobalt chloride hexahydrate in V respectively1Dispersing in ethanol with volume for 30min by ultrasonic to obtain mixed solution;
(2) continuously dropwise adding the volume V into the mixed solution under the ultrasonic condition2Deionized water of (2) to (V)1：V2= 25: 1, continuing ultrasonic treatment for 2 h; then, the user can use the device to perform the operation,
(3) volume V of dropwise addition3Ammonia water of (2) to a volume ratio of V2:V3= 1: 2, continuing to perform ultrasonic treatment for 5 hours to obtain a precipitate;
(4) filtering the obtained precipitate, washing the precipitate for 3-5 times by using ethanol, and washing the precipitate for 3 times by using deionized water to obtain washed precipitate;
(5) drying the washed precipitate at 60 ℃ for 12h, and roasting at 500 ℃ in air for 3h to obtain Co-promoted SiO2A carrier;
step two, preparing Co Co-promoted by Mn and Co3O4/SiO2Catalyst:
(1) weighing a certain mass of Co-promoted SiO prepared in the first step2A carrier;
(2) weighing cobalt nitrate hexahydrate and 50% manganese nitrate solution according to the active component loading amount of 20% -30%, and preparing mixed metal salt solution with the molar concentration of 0.05mol/L, wherein the molar ratio is n (Mn) = n (Co) = 1: 1-1: 20, ultrasonically dispersing the weighed carrier prepared in the step one into the carrier to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is about =9 to obtain a precipitate;
(4) and ageing the obtained precipitate overnight for 12h, filtering, washing with deionized water, drying at 60 ℃ for 12h, and roasting at 500 ℃ in air for 3h to obtain the cobaltosic oxide/silicon dioxide catalyst promoted by Mn and Co together.
Furthermore, in the first step,
(1) the molar ratio n (Co): n (Si) = 1: 20 or 25 or 30, measuring tetraethoxysilane and cobalt chloride hexahydrate, dissolving in 100ml ethanol, and ultrasonically dispersing for 30min to obtain mixed solution, wherein the volume of the mixed solution is marked as V1；
(2) Continuously dropwise adding 4ml of deionized water into the mixed solution under the ultrasonic condition, wherein the volume is marked as V2Let V be1：V2= 25: 1, continuing ultrasonic treatment for 2 h;
(3) 8ml of ammonia water are added dropwise, the volume is recorded as V3Ammonia water of (2) to a volume ratio of V2:V3= 1: 2, continuing to perform ultrasonic treatment for 5 hours to obtain a precipitate;
(4) filtering the obtained precipitate, washing with ethanol for 5 times, and washing with deionized water for 3 times to obtain washed precipitate;
(5) drying the washed precipitate at 60 ℃ for 12h, and roasting at 500 ℃ in air for 3h to obtain Co-promoted SiO2And carriers, namely Si20Co1 carriers/or Si25Co1 carriers/or Si30Co1 carriers.
The invention also provides the application of the cobaltosic oxide/silicon dioxide catalyst promoted by Mn and Co together, which is used for detecting non-methane total hydrocarbons in detection equipment for detecting the non-methane total hydrocarbons by a catalytic oxidation method.
And (3) testing the activity of the catalyst:
the methane/propane mixed gas is used for simulating methane and non-methane total hydrocarbon pollution gas, the catalyst is used for catalytic combustion of methane and non-methane total hydrocarbon, and the activity evaluation of the catalyst used for catalytic combustion is carried out in a fixed bed microreactor (a quartz tube with the inner diameter of 3 mm). The catalyst amount is 100mg, and the temperature is automatically controlled by a K-type thermocouple. The methane/propane standard mixed gas is mixed with air and fed into the reactor to make combustion. The total flow is controlled by a mass flow meter, the concentration of methane and propane is 100ppm, air is used as carrier gas, the concentration of oxygen is 10 percent, the reaction temperature is 50-350 ℃, and the reaction is carried out under the normal pressure environment.
The invention has the advantages that: modified Co-promoted SiO2The carrier has stronger bonding force with the active component, and Mn is introduced into Co3O4Further increasing catalyst activity and stability. The catalyst has the advantages of simple preparation method, low temperature of an operation window and high practical application value for removing non-methane total hydrocarbons in the total hydrocarbons. The catalytic reaction temperature is reduced on the basis of the existing research, and the temperature window in the non-methane total hydrocarbon detection process is further expanded; the catalyst is used for detecting non-methane total hydrocarbons in the total hydrocarbons, so that the existing detection equipment can be simplified.
Detailed Description
Example 1
SiO promoted by Co2The carrier is prepared by the following steps:
(1) the molar ratio n (Co): n (Si) = 1: 20, weighing 5ml of ethyl orthosilicate, weighing 0.24g of cobalt chloride hexahydrate and dissolving in V1=100ml ethanol, and ultrasonic dispersion is carried out for 30min, so as to obtain mixed solution;
(2) continuously dropwise adding the volume V into the mixed solution under the ultrasonic condition2=4ml of deionized water, let V1：V2= 25: 1, continuing ultrasonic treatment for 2 h;
(3) volume V of dropwise addition38ml of ammonia water in a volume ratio of V2:V3= 1: 2, continuing to perform ultrasonic treatment for 5 hours to obtain a precipitate;
(4) filtering the obtained precipitate, washing with ethanol for 5 times, and washing with deionized water for 3 times to obtain washed precipitate;
(5) the washed precipitate was dried at 60 ℃ for 12h and then dried at 5Roasting for 3 hours at the temperature of 00 ℃ in the air to obtain SiO promoted by Co2Support, denoted as Si20Co1 support.
Example 2
SiO promoted by Co2The support was prepared in the same manner as in example 1 except that the molar ratio of n (Co): n (Si) = 1: 25 weighing ethyl orthosilicate and cobalt chloride hexahydrate, and preparing the material by the following steps:
6ml of ethyl orthosilicate was weighed, 0.24g of cobalt dichloride hexahydrate was weighed, and the rest of the experimental procedures were the same as in example 1 to obtain Co-promoted SiO2Support, denoted Si25Co1 support.
Example 3
SiO promoted by Co2The support was prepared in the same manner as in example 1 except that the molar ratio of n (Co): n (Si) = 1: 30, weighing ethyl orthosilicate and cobalt chloride hexahydrate, and preparing the material by the following steps:
weighing 7ml of ethyl orthosilicate, weighing 0.24g of cobalt dichloride hexahydrate and the rest of the experimental steps are the same as those in example 1 to obtain Co-promoted SiO2Support, denoted Si30Co1 support.
Example 4
A CoMn and Co Co-promoted cobaltosic oxide/silica catalyst is prepared according to the active component loading of 20 percent and comprises the following steps:
(1) weighing 2g of the Si20Co1 carrier prepared in example 1;
(2) according to the active component loading amount of 20%, the molar ratio of n (Mn): n (Co) = 1: weighing 0.48g of cobalt nitrate hexahydrate and 0.08g of 50% manganese nitrate solution, dissolving in 35ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and ultrasonically dispersing the weighed Si20Co1 carrier in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is about =9 to obtain a precipitate;
(4) the precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a CoO/Si catalyst Co-promoted with Mn and Co, designated 20% Co10Mn1-Si20Co 1.
The temperature range of the 20% Co10Mn1-Si20Co1 catalyst is shown in Table 1, and the temperature range of the methane and propane reaction is 310-325 ℃.
Example 5
Co Co-promoted by Mn and Co3O4/SiO2The catalyst is prepared according to the active component loading of 30 percent and comprises the following steps:
(1) weighing 2g of the Si20Co1 carrier of example 1;
(2) according to the active component loading amount of 30%, the molar ratio of n (Mn): n (Co) = 1: 10 weighing 0.70g of cobalt nitrate hexahydrate and 0.12g of 50% manganese nitrate solution, dissolving in 52ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and ultrasonically dispersing the weighed 2gSi20Co1 carrier in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is about =9 to obtain a precipitate;
(4) the resulting precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a Mn and Co Co-promoted cobaltosic oxide/silica catalyst, designated 30% Co10Mn1-Si20Co 1.
The temperature range of the 30% Co10Mn1-Si20Co1 catalyst is shown in Table 1, and the temperature range of the methane and propane reaction is 260-290 ℃.
Example 6
Co Co-promoted by Mn and Co3O4/SiO2The catalyst is prepared according to the active component loading of 30 percent and comprises the following steps:
(1) weighing 2g of the Si30Co1 carrier prepared in example 3;
(2) according to the active component loading amount of 30%, the molar ratio of n (Mn): n (Co) = 1: weighing 0.70g of cobalt nitrate hexahydrate and 0.12g of 50% manganese nitrate solution, dissolving in 52ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and ultrasonically dispersing the weighed 2gSi30Co1 carrier in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is about =9 to obtain a precipitate;
(4) the resulting precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a Mn and Co Co-promoted cobaltosic oxide/silica catalyst, designated 30% Co10Mn1-Si30Co 1.
The temperature range of the 30% Co10Mn1-Si30Co1 catalyst is shown in Table 1, and the temperature range of the methane and propane reaction is 245-290 ℃.
Example 7
Co Co-promoted by Mn and Co3O4/SiO2The catalyst is prepared according to the active component loading of 30 percent and comprises the following steps:
(1) weighing 2g of the Si30Co1 carrier prepared in example 3;
(2) according to the active component loading amount of 30%, the molar ratio of n (Mn): n (Co) = 1: 20, 0.71g of cobalt nitrate hexahydrate and 0.06g of 50% manganese nitrate solution are weighed and dissolved in 52ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and the weighed 2gSi30Co1 carrier is ultrasonically dispersed in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is about =9 to obtain a precipitate;
(4) the resulting precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a Mn and Co Co-promoted cobaltosic oxide/silica catalyst, designated 30% Co20Mn1-Si30Co 1.
The temperature range of the 30% Co20Mn1-Si30Co1 catalyst is shown in Table 1, and the temperature range of the methane and propane reaction is 295-320 ℃.
And (3) testing the activity of the catalyst:
the catalysts of examples 1 to 4 were used for catalytic combustion of methane and non-methane total hydrocarbons, and the activity evaluation of the catalyst used for catalytic combustion was carried out in a fixed-bed microreactor (quartz tube 3mm in inner diameter) using a methane/propane gas mixture to simulate methane and non-methane total hydrocarbon contaminant gases. The catalyst amount is 100mg, and the temperature is automatically controlled by a K-type thermocouple. The methane/propane standard mixed gas is mixed with air and fed into the reactor to make combustion. The total flow is controlled by a mass flow meter, the concentration of methane and propane is 100ppm, air is used as carrier gas, the concentration of oxygen is 10 percent, the reaction temperature is 50-350 ℃, and the reaction is carried out under the normal pressure environment. Examples 4 to 7 the temperature intervals for the reaction of methane and propane (temperature range for complete conversion of propane and methane conversion below 5%) are shown in the following table.
As can be seen from the above table, the catalysts of examples 4-7 showed better catalytic oxidation activity for non-methane total hydrocarbons in the total hydrocarbons, especially the catalysts obtained in example 6, which can achieve methane conversion less than 5% and complete catalytic oxidation of propane at 245-290 ℃ in a lower temperature and wider temperature range.
Claims (8)
1. A CoMn and Co Co-promoted cobaltosic oxide/silica catalyst, characterized in that the cobaltosic oxide/silica catalyst (Co)3O4/SiO2) Comprises active component Mn modified Co3O4And Co-modified SiO carrier2Wherein the loading amount of the active component is 20-30%, the molar ratio of Mn to Co in the active component is n (Mn) = n (Co) = 1: 10-1: 20; molar ratio of Co to Si in the carrier n (Co) = 1: 20-1: 30.
2. a method of preparing a Mn and Co promoted cobaltosic oxide/silica catalyst according to claim 1, comprising the steps of:
step one, preparing SiO promoted by Co2Carrier:
(1) the molar ratio n (Co): n (Si) = 1: 20-1: 30 dissolving ethyl orthosilicate and cobalt chloride hexahydrate in volume V1And ultrasonically dispersing for 30min to obtain a mixed solution;
(2) continuously dropwise adding the volume V into the mixed solution under the ultrasonic condition2Deionized water of (2) to (V)1：V2= 25: 1, continuing ultrasonic treatment for 2 h; then, the user can use the device to perform the operation,
(3) volume V of dropwise addition3Ammonia water of (2) to a volume ratio of V2:V3= 1: 2, continuing to perform ultrasonic treatment for 5 hours to obtain a precipitate;
(4) filtering the obtained precipitate, washing the precipitate for 3-5 times by using ethanol, and washing the precipitate for 3 times by using deionized water to obtain washed precipitate;
(5) drying the washed precipitate at 60 ℃ for 12h, and roasting at 500 ℃ in air for 3h to obtain Co-promoted SiO2A carrier;
step two, preparing Co Co-promoted by Mn and Co3O4/SiO2Catalyst:
(1) weighing the Co-promoted SiO prepared in the step one2A carrier;
(2) weighing cobalt nitrate hexahydrate and 50% manganese nitrate solution according to the active component loading amount of 20% -30%, preparing mixed metal salt solution with the molar concentration of 0.05mol/L, and ultrasonically dispersing the carrier weighed in the step one, wherein the molar ratio is n (Mn) = n (Co) = 1: 1-1: 20, obtaining a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is =9 to obtain a precipitate;
(4) and ageing the obtained precipitate overnight for 12h, filtering, washing with deionized water, drying at 60 ℃ for 12h, and roasting at 500 ℃ in air for 3h to obtain the cobaltosic oxide/silicon dioxide catalyst promoted by Mn and Co together.
3. The method of preparing a Mn and Co Co-promoted cobaltosic oxide/silica catalyst as claimed in claim 2, wherein, in the first step,
(1) the molar ratio n (Co): n (Si) = 1: 20 or 25 or 30, measuring tetraethoxysilane and cobalt chloride hexahydrate, dissolving in 100ml ethanol, and ultrasonically dispersing for 30min to obtain mixed solution, wherein the volume of the mixed solution is marked as V1；
(2) Continuously dropwise adding 4ml of deionized water into the mixed solution under the ultrasonic condition, wherein the volume is marked as V2Let V be1：V2=25: 1, continuing ultrasonic treatment for 2 h;
(3) 8ml of ammonia water are added dropwise, the volume is recorded as V3Ammonia water of (2) to a volume ratio of V2:V3= 1: 2, continuing to perform ultrasonic treatment for 5 hours to obtain a precipitate;
(4) filtering the obtained precipitate, washing with ethanol for 5 times, and washing with deionized water for 3 times to obtain washed precipitate;
(5) drying the washed precipitate at 60 ℃ for 12h, and roasting at 500 ℃ in air for 3h to obtain Co-promoted SiO2And carriers, namely Si20Co1 carriers/or Si25Co1 carriers/or Si30Co1 carriers.
4. The method of preparing a Mn and Co Co-promoted cobaltosic oxide/silica catalyst according to claim 2 or 3, wherein the Mn and Co Co-promoted Co is prepared at an active component loading of 20%3O4/SiO2The catalyst comprises the following steps:
(1) weighing 2g of the Si20Co1 carrier prepared in the step one;
(2) according to the active component loading amount of 20%, the molar ratio of n (Mn): n (Co) = 1: weighing 0.08g of 50% manganese nitrate solution and 0.48g of cobalt nitrate hexahydrate, dissolving in 35ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and ultrasonically dispersing the weighed Si20Co1 carrier in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is =9 to obtain a precipitate;
(4) the precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a CoO/Si catalyst Co-promoted with Mn and Co, designated 20% Co10Mn1-Si20Co 1.
5. The method of preparing a Mn and Co Co-promoted cobaltosic oxide/silica catalyst according to claim 2 or 3, wherein the Mn and Co Co-promoted Co is prepared at an active component loading of 30%3O4/SiO2The catalyst comprises the following steps:
(1) weighing 2g of Si20Co1 carrier;
(2) according to the active component loading amount of 30%, the molar ratio of n (Mn): n (Co) = 1: 10 weighing 0.70g of cobalt nitrate hexahydrate and 0.12g of 50% manganese nitrate solution, dissolving in 52ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and ultrasonically dispersing the weighed 2gSi20Co1 carrier in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is =9 to obtain a precipitate;
(4) the resulting precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a Mn and Co Co-promoted cobaltosic oxide/silica catalyst, designated 30% Co10Mn1-Si20Co 1.
6. The method of preparing a Mn and Co Co-promoted cobaltosic oxide/silica catalyst according to claim 2 or 3, wherein the Mn and Co Co-promoted Co is prepared at an active component loading of 30%3O4/SiO2The catalyst comprises the following steps:
(1) weighing 2g of Si30Co1 carrier;
(2) according to the active component loading amount of 30%, the molar ratio of n (Mn): n (Co) = 1: 10 weighing 0.70g of cobalt nitrate hexahydrate and 0.12g of 50% manganese nitrate solution, dissolving in 52ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and ultrasonically dispersing the weighed 2gSi30Co1 carrier in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is =9 to obtain a precipitate;
(4) the resulting precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a Mn and Co Co-promoted cobaltosic oxide/silica catalyst, designated 30% Co10Mn1-Si30Co 1.
7. Mn and Co Co-promoted tetraoxidation according to claim 2 or 3The preparation method of the cobaltosic/silicon dioxide catalyst is characterized in that Co Co-promoted by Mn and Co is prepared according to the active component loading of 30 percent3O4/SiO2The catalyst comprises the following steps:
(1) weighing 2g of Si30Co1 carrier;
(2) according to the active component loading amount of 30%, the molar ratio of n (Mn): n (Co) = 1: 20, 0.71g of cobalt nitrate hexahydrate and 0.06g of 50% manganese nitrate solution are weighed and dissolved in 52ml of deionized water to prepare a mixed metal salt solution with the molar concentration of 0.05mol/L, and the weighed 2gSi30Co1 carrier is ultrasonically dispersed in the mixed metal salt solution to obtain a mixed solution;
(3) dropwise adding 0.20mol/L sodium carbonate solution into the mixed solution until the pH value is =9 to obtain a precipitate;
(4) the resulting precipitate was aged overnight for 12h, filtered, washed with deionized water, dried at 60 ℃ for 12h and then calcined at 500 ℃ for 3h in air to give a Mn and Co Co-promoted cobaltosic oxide/silica catalyst, designated 30% Co20Mn1-Si30Co 1.
8. Use of a Mn and Co promoted cobaltosic oxide/silica catalyst according to claim 1 in a detection apparatus for detecting non-methane total hydrocarbons by catalytic oxidation.
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| CN114029059A (en) * | 2021-11-16 | 2022-02-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Catalyst suitable for portable sustainable detection of non-methane total hydrocarbons and preparation method and application thereof |
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