CN112808229A - Preparation method and application of copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant - Google Patents
Preparation method and application of copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant Download PDFInfo
- Publication number
- CN112808229A CN112808229A CN202011525903.3A CN202011525903A CN112808229A CN 112808229 A CN112808229 A CN 112808229A CN 202011525903 A CN202011525903 A CN 202011525903A CN 112808229 A CN112808229 A CN 112808229A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- beta molecular
- beta
- copper
- 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
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000010949 copper Substances 0.000 title claims abstract description 22
- 239000011572 manganese Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000001294 propane Substances 0.000 claims abstract description 36
- 239000002912 waste gas Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 13
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 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 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000035859 Drug effect increased Diseases 0.000 description 1
- 101000713575 Homo sapiens Tubulin beta-3 chain Proteins 0.000 description 1
- 101000713585 Homo sapiens Tubulin beta-4A chain Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 102100036790 Tubulin beta-3 chain Human genes 0.000 description 1
- 102100036788 Tubulin beta-4A chain Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VGQXTTSVLMQFHM-UHFFFAOYSA-N peroxyacetyl nitrate Chemical compound CC(=O)OO[N+]([O-])=O VGQXTTSVLMQFHM-UHFFFAOYSA-N 0.000 description 1
- XDTRNDKYILNOAP-UHFFFAOYSA-N phenol;propan-2-one Chemical compound CC(C)=O.OC1=CC=CC=C1 XDTRNDKYILNOAP-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
Abstract
The invention provides a preparation method and application of a copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant, belonging to the technical field of catalytic environmental protection. Using Beta molecular sieve and copper nitrate (Cu (NO)3)2·3H2O) and manganese nitrate (Mn (NO)3)2·4H2O) is taken as a raw material to prepare the composite Beta molecular sieve catalyst. The Beta molecular sieve has a particle size of 30-50 um and a silicon-aluminum ratio (n (SiO)2)/n(Al2O3) Is less than or equal to 40: 1; the atomic number ratio of Cu to Mn to Al in the catalyst is (0.05-0.20): (0.10-0.25): (0.75 to 1.25). According to the preparation method of the catalyst, materials are mixed according to the proportion by adopting an impregnation-roasting method, the mixture is stirred for 6-24 hours, the mixture is placed in a drying box to be dried for 12 hours at the temperature of 80 ℃, the temperature is raised to 300-600 ℃ at the microwave roasting temperature rise rate of 25-35 ℃/min, and the required catalyst is prepared by reaction under the heat preservation time of 10-60 min. The invention uses microwave to assist in preparing the composite Beta molecular sieve catalyst, which can efficiently degrade propane waste gas.
Description
Technical Field
The invention relates to a preparation method and application of a copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant, belonging to the technical field of catalytic environmental protection.
Background
"volatile organic compounds" (VOCs) generally refer to organic compounds having a boiling point below 250 ℃ at standard atmospheric pressure (101.325 kPa). The majority of emitted VOCs contribute to the formation of secondary pollutants such as tropospheric ozone, peroxyacetyl nitrate, etc., the toxicity and carcinogenic effects of which have been widely documented on human health. The rapid urbanization and industrialization are closely related to the increase of the discharge amount of VOCs.
Alkanes are the simplest organic compounds containing hydrogen and carbon, and they account for a large proportion of the VOC emitted annually. Wherein the concentration of propane or butane in the organic waste gas of the sewage treatment plant of the refinery enterprise can reach 100mg/m3The concentration of propane in the waste gas produced by the epoxypropane/styrene (PO/SM) is 60-100 mg/m3The concentration of propane in the tail gas of the phenol-acetone device is 50-90 mg/m3The refining of acrylonitrile, acrylic acid and other chemical products, and the production, transportation, loading and unloading of liquefied petroleum gas have a large amount of propane-containing waste gas. Compared with aromatic hydrocarbon, oxygen-containing organic matter and macromolecular alkane, the low-carbon hydrocarbon is difficult to decompose.
Regarding the treatment of propane waste gas, adsorption enrichment is mainly adopted. The method for recovering the propane waste gas by the adsorption method is one of the widely adopted methods at present, and the aim of purifying the gas is achieved by physically adsorbing VOCs in the waste gas by an adsorbent. However, the adsorption method has the problems of saturated adsorption, easy secondary pollution, difficult regeneration of the adsorption material and the like. The catalytic oxidation method can treat the low-concentration VOCs gas at a temperature far lower than the direct combustion temperature (most hydrocarbons can be oxidized at the temperature of 200-600 ℃), and has the characteristics of high purification efficiency, no secondary pollution, low energy consumption and the like, but the catalytic oxidation method usually uses noble metal catalysts such as platinum, palladium and the like, and has high cost, so that the catalytic oxidation method is difficult to be practically applied.
The invention discloses a honeycomb ceramic carrier catalyst suitable for VOCs catalytic combustion and a preparation method thereof, which are disclosed by Chinese patent with the publication number of CN 108043473A. The catalyst is prepared from the following raw materials: the catalyst layer comprises a catalytic inner layer and a catalytic outer layer, wherein the catalytic inner layer and the catalytic outer layer comprise rare earth oxides (cerium nitrate, lanthanum nitrate and zirconyl nitrate), modified alumina, a binder, active components (one or more mixed materials of Pt, Pd, Cu, Fe, Mn and Co), a molecular sieve and a pH regulator. The preparation method coats the prepared catalytic inner layer and the catalytic outer layer on the honeycomb ceramic carrier to achieve the effective preparation of the catalyst. The invention has the advantages of high coating consistency, high stability and the like, but the catalyst in the invention has the problem of poor catalytic use effect.
Disclosure of Invention
In order to overcome the defects of the prior art, the adsorption-catalytic oxidant is prepared by combining Beta molecular sieve, copper nitrate and manganese nitrate. The following is a technical solution of the present invention.
The preparation method of the copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant comprises the following steps:
step 1, preparing a composite Beta molecular sieve catalyst by using a Beta molecular sieve, copper nitrate and manganese nitrate as raw materials;
the Beta molecular sieve silicon-aluminum ratio (n (SiO)2)/n(Al2O3))≤40:1；
The atomic number ratio of Cu, Mn and Al in the catalyst is (0.05-0.20), (0.10-0.25) and (0.75-1.25).
And 2, mixing the materials according to the proportion in the step 1, stirring for 6-24 hours, placing the mixture in a drying oven, drying for 12 hours at the temperature of 80 ℃, carrying out microwave roasting, raising the temperature to 300-600 ℃ at the rate of temperature rise of 25-35 ℃/min, and carrying out reaction for 10-60 minutes to obtain the required catalyst.
In the step 1, the Beta molecular sieve has a grain diameter of 30-50 um and a silicon-aluminum ratio (n (SiO)2)/n(Al2O3) Is less than or equal to 40:1, preferably (10-30): 1.
The application of the copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant according to any one of claims 1-2 is as follows: and (3) degrading the propane waste gas.
The invention has the advantages that:
(1) the Beta molecular sieve with the silicon-aluminum ratio of less than or equal to 40:1 is used as a carrier, so that the dispersity of active sites is improved, the reactant adsorption is facilitated, and the manufacturing cost of the catalyst is reduced. The catalyst prepared by the invention realizes obvious effect of degrading propane waste gas under the condition of low silicon-aluminum ratio, shows good catalytic activity and is beneficial to realizing industrial production.
(2) Copper nitrate and manganese nitrate are used as modification materials, and on one hand, the double metals are used together to prevent the active metal from migrating and agglomerating after aging, so that the stability of the catalyst is improved; on the other hand, the transition metal oxide is loaded to replace the noble metal, so that the required noble metal loading is reduced, and the method has economic advantages.
(3) The preparation method is simple in preparation process, the active metals mixed in different proportions are uniformly loaded on the surface of the Beta molecular sieve carrier by an impregnation method, the dispersion degree of the active metals on the surface of the Beta molecular sieve carrier is improved by changing the impregnation time, and the preparation method is low in energy consumption and easy to operate.
(4) The catalyst is prepared by microwave roasting assistance, the wave absorbing performance of the catalyst is good, the temperature rise rate is high during microwave-assisted heating, active metal is favorably dispersed on the surface of the molecular sieve, and the catalytic performance is improved.
(5) The adsorption-catalytic oxidant prepared by the invention has no secondary pollution to the degradation reaction process of the propane waste gas and low energy consumption; and the catalyst can be recycled for many times, the degradation rate of the propane waste gas is kept above 80%, and the catalyst is energy-saving and environment-friendly.
Drawings
FIG. 1 is an SEM and EDS image of a Beta molecular sieve catalyst prepared in example 4 of the present invention;
FIG. 2 shows the effect of Beta molecular sieve catalyst prepared in example 4 of the present invention on the degradation of propane waste gas by catalytic oxidation;
detailed description of the preferred embodiment
The invention is described in detail by the figures and the detailed implementation steps.
Example 1
Blank experiment, selecting a certain amount of Beta molecular sieve with the particle size of 35um and the silicon-aluminum ratio (n (SiO)2)/n(Al2O3) 15); heating the mixture to 400 ℃ at the heating rate of 25 ℃/min by microwave roasting, and reacting the mixture for 20min to obtain a catalyst which is recorded as Beta-1;
the application of the compound Beta molecular sieve catalyst is to adsorb and degrade propane waste gas by catalytic oxidation.
Beta-1 molecular sieve catalyst prepared in example 1 at reaction conditions: the gas component is air, the propane content is 1%, the gas flow is 100mL/min, and the propane degradation rate reaches 39.6% at the reaction temperature of 500 ℃.
Example 2
The following are the specific steps of the preparation method of the supported Beta molecular sieve catalyst:
step 1, preparing a composite Beta molecular sieve catalyst by using a Beta molecular sieve and copper nitrate as raw materials;
the Beta molecular sieve has a particle size of 35um and a silicon-aluminum ratio (n (SiO)2)/n(Al2O3))＝15；
The atomic number ratio of Cu to Al in the catalyst is 0.10: 1.
Step 2, mixing the materials according to the proportion in the step 1, stirring for 12h, placing the mixture in a drying oven to dry for 12h at the temperature of 80 ℃, carrying out microwave roasting, heating to 400 ℃ at the heating rate of 25 ℃/min, and reacting for 20min to obtain a catalyst which is recorded as Beta-2;
the application of the compound Beta molecular sieve catalyst is to adsorb and degrade propane waste gas by catalytic oxidation.
Beta-2 molecular sieve catalyst prepared in example 2 at reaction conditions: the gas component is air, the propane content is 1%, the gas flow is 100mL/min, and the propane degradation rate reaches 51.8% at the reaction temperature of 500 ℃.
Example 3
The following are the specific steps of the preparation method of the supported Beta molecular sieve catalyst:
step 1, preparing a composite Beta molecular sieve catalyst by using a Beta molecular sieve, copper nitrate and manganese nitrate as raw materials;
the Beta molecular sieve has a particle size of 35um and a silicon-aluminum ratio (n (SiO)2)/n(Al2O3))＝15；
The atomic number ratio of Cu to Mn to Al in the catalyst is 0.05:0.10: 1.
Step 2, mixing the materials according to the proportion in the step 1, stirring for 12h, placing the mixture in a drying oven to dry for 12h at the temperature of 80 ℃, carrying out microwave roasting, heating to 400 ℃ at the heating rate of 25 ℃/min, and reacting for 20min to obtain a catalyst which is recorded as Beta-3;
the application of the compound Beta molecular sieve catalyst is to adsorb and degrade propane waste gas by catalytic oxidation.
Beta-3 molecular sieve catalyst prepared in example 3 at reaction conditions: the gas component is air, the propane content is 1%, the gas flow is 100mL/min, and the propane degradation rate reaches 74.5% at the reaction temperature of 500 ℃.
Beta-3 in example 3 showed an increase in catalytic efficiency of 34.9% and 22.7% compared to the catalysts of examples 1 and 2, respectively. The Beta-3 catalyst utilizes the combination of copper and manganese double metals to prevent the migration and agglomeration of active metals after aging and improve the catalytic activity of the catalyst.
Example 4
The following are the specific steps of the preparation method of the supported Beta molecular sieve catalyst:
step 1, preparing a composite Beta molecular sieve catalyst by using a Beta molecular sieve, copper nitrate and manganese nitrate as raw materials;
the Beta molecular sieve has the grain diameter of 38um and the silicon-aluminum ratio (n (SiO)2)/n(Al2O3))＝20；
The atomic number ratio of Cu to Mn to Al in the catalyst is 0.10:0.10:1, 0.10:0.15:1, 0.10:0.20:1, 0.15:0.15:1, 0.15:0.20:1 and 0.20:0.25: 1.
Step 2, mixing the materials according to the proportion in the step 1, stirring for 18h, placing the mixture in a drying box, drying for 12h at the temperature of 80 ℃, carrying out microwave roasting, heating to 500 ℃ at the heating rate of 35 ℃/min, and reacting for 40min to prepare the catalysts which are respectively marked as Beta-4, Beta-5, Beta-6, Beta-7, Beta-8 and Beta-9;
the application of the compound Beta molecular sieve catalyst is to adsorb and degrade propane waste gas by catalytic oxidation.
The composite molecular sieve catalyst prepared in example 5 was prepared under the following reaction conditions: the gas component is air, the content of propane is 1%, the gas flow is 100mL/min, and the degradation rates of propane respectively reach 78.8%, 79.5%, 81.6%, 83.8%, 89.5% and 85.6% at the reaction temperature of 500 ℃. Wherein the best effect of Beta-8 on the degradation of propane is 89.5 percent, and the atomic number ratio of Cu to Mn to Al in the catalyst is 0.15:0.20: 1.
The SEM and EDS of the compound Beta-8 molecular sieve prepared by the embodiment are shown in figure 1. As shown in the figure, the catalyst mainly comprises Si, Al, O, Cu and Mn elements.
The degradation effect of the composite Beta-8 molecular sieve prepared by the embodiment on the propane waste gas is shown in figure 2, and the degradation effect of the composite Beta-8 molecular sieve on the propane waste gas after recycling is shown in table 1. After the catalyst is recycled, the degradation rate of the Beta-8 molecular sieve catalyst on the propane waste gas is kept above 80%, which shows that the prepared catalyst has good recyclable performance, and is energy-saving and environment-friendly.
TABLE 1 degradation rate of waste gas from catalytic oxidation of propane by circulation of composite Beta molecular sieve
| Catalyst and process for preparing same | 1 | 2 | 3 | 4 |
| Beta-8 | 89.5％ | 86.5％ | 83.1％ | 80.4％ |
Example 5
The lower is loaded gamma-Al2O3The preparation method of the catalyst comprises the following specific steps:
step 1, selecting upsilon-Al2O3Preparation of composite Al by using copper nitrate and manganese nitrate as raw materials2O3A catalyst;
the atomic number ratio of Cu to Mn to Al in the catalyst is 0.15:0.20: 1.
Step 2, mixing the materials according to the proportion in the step 1, stirring for 18h, placing the mixture in a drying oven to dry for 12h at the temperature of 80 ℃, carrying out microwave roasting, heating to 500 ℃ at the heating rate of 35 ℃/min, and reacting for 40min to obtain a catalyst which is recorded as Beta-10;
compound upsilon-Al2O3The application of the catalyst is to absorb and catalyze, oxidize and degrade propane waste gas.
Beta-10 catalyst prepared in example 5 at reaction conditions: the gas component is air, the propane content is 1%, the gas flow is 100mL/min, and the propane degradation rate reaches 57.3% at the reaction temperature of 500 ℃;
the catalytic effect of the catalyst Beta-8 in example 4 is compared with that of Beta-10 in this example, Beta molecular sieve is used as carrier ratio and gamma-Al is used2O3The catalytic effect of the carrier is increased by 32.2%. In contrast, the Beta molecular sieve has good hydrothermal stability, is easy to increase the dispersibility of active sites and help the absorption of reactants, and is used as a carrier to ensure better degradation performance.
Example 6
The following are the specific steps of the preparation method of the supported Beta molecular sieve catalyst:
step 1, preparing a composite Beta molecular sieve catalyst by using a Beta molecular sieve, copper nitrate and manganese nitrate as raw materials;
the Beta molecular sieve has the grain diameter of 38um and the silicon-aluminum ratio (n (SiO)2)/n(Al2O3))＝20；
The atomic number ratio of Cu to Mn to Al in the catalyst is 0.15:0.20: 1.
And 2, mixing the materials according to the proportion in the step 1, stirring for 18h, placing the mixture in a drying box, drying for 12h at the temperature of 80 ℃, conventionally roasting, heating to 500 ℃ at the heating rate of 25 ℃/min, and reacting for 40min to obtain the catalyst, namely Beta-11.
The application of the compound Beta molecular sieve catalyst is to adsorb and degrade propane waste gas by catalytic oxidation.
Beta-11 molecular sieve catalyst prepared in example 6 at reaction conditions: the gas component is air, the propane content is 1%, the gas flow is 100mL/min, and the propane degradation rate reaches 72.7% at the reaction temperature of 500 ℃.
Compared with the Beta-11 catalyst in the embodiment, the Beta-8 catalyst in the embodiment 4 has the catalytic effect increased by 16.8% compared with the catalyst prepared by the conventional roasting assistance. Microwave roasting belongs to an internal heating mode, utilizes electromagnetic energy to directly act on materials to convert the materials into heat, and has the transmission performance to simultaneously heat the materials inside and outside without heat conduction. The catalyst has good wave absorbing performance, and the temperature rise rate is higher during microwave-assisted heating, so that the active metal can be favorably dispersed on the surface of the molecular sieve, and the catalytic performance is improved.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (3)
1. The preparation method of the copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant comprises the following steps:
step 1, selecting Beta molecular sieve and copper nitrate (Cu (NO)3)2·3H2O) and manganese nitrate (Mn (NO)3)2·4H2O) is taken as a raw material to prepare a composite Beta molecular sieve catalyst;
the Beta molecular sieve silicon-aluminum ratio (n (SiO)2)/n(Al2O3))≤40:1；
The atomic number ratio of Cu, Mn and Al in the catalyst is (0.05-0.20), (0.10-0.25) and (0.75-1.25).
And 2, mixing the materials according to the proportion in the step 1, stirring for 6-24 hours, placing the mixture in a drying oven, drying for 12 hours at the temperature of 80 ℃, carrying out microwave roasting, raising the temperature to 300-600 ℃ at the rate of temperature rise of 25-35 ℃/min, and carrying out reaction for 10-60 minutes to obtain the required catalyst.
2. In the step 1, the Beta molecular sieve has a grain diameter of 30-50 um and a silicon-aluminum ratio (n (SiO)2)/n(Al2O3) Is less than or equal to 40:1, preferably (10-30): 1.
3. The application of the copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant according to any one of claims 1-2 is as follows: and (3) degrading the propane waste gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011525903.3A CN112808229B (en) | 2020-12-22 | 2020-12-22 | Preparation method and application of copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011525903.3A CN112808229B (en) | 2020-12-22 | 2020-12-22 | Preparation method and application of copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112808229A true CN112808229A (en) | 2021-05-18 |
| CN112808229B CN112808229B (en) | 2022-05-27 |
Family
ID=75853615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011525903.3A Active CN112808229B (en) | 2020-12-22 | 2020-12-22 | Preparation method and application of copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112808229B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713849A (en) * | 2021-09-15 | 2021-11-30 | 美埃(中国)环境科技股份有限公司 | Adsorption catalysis material and preparation method thereof |
| CN115487776A (en) * | 2021-11-26 | 2022-12-20 | 北京科技大学 | Ketone VOCs adsorbent and its preparation method and use |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905145A (en) * | 2010-09-15 | 2010-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN104383962A (en) * | 2014-12-01 | 2015-03-04 | 中国科学院上海硅酸盐研究所 | Base metal load type multistage pore zeolite molecular sieve catalyst of efficient catalytic combustion soot particles and preparation and application of catalyst |
| CN104785099A (en) * | 2015-03-25 | 2015-07-22 | 中国石油天然气股份有限公司 | Method for purifying acrylonitrile device absorber off-gas by using CeMn/Me-beta molecular sieve |
| CN106540739A (en) * | 2015-09-16 | 2017-03-29 | 中国石化扬子石油化工有限公司 | A kind of preparation method of supported catalyst burning catalyst |
| CN106732755A (en) * | 2016-12-23 | 2017-05-31 | 中节能万润股份有限公司 | A kind of preparation method of the compound integral extruding type denitrating catalyst of molecular sieve multivariant oxide |
| CN110876944A (en) * | 2019-12-09 | 2020-03-13 | 大连瑞克科技有限公司 | Catalyst for catalytic combustion and preparation method thereof |
| CN111135816A (en) * | 2019-12-25 | 2020-05-12 | 宁波鸿朗环保科技有限公司 | Catalyst for catalytic combustion of chlorine-containing volatile organic gas and preparation method thereof |
| CN112169827A (en) * | 2020-08-20 | 2021-01-05 | 浙江天蓝环保技术股份有限公司 | Monolithic catalyst with selective adsorption-catalytic oxidation organic waste gas function and preparation method and application thereof |
-
2020
- 2020-12-22 CN CN202011525903.3A patent/CN112808229B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905145A (en) * | 2010-09-15 | 2010-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Molecular sieve cellular material and preparation method thereof |
| CN104383962A (en) * | 2014-12-01 | 2015-03-04 | 中国科学院上海硅酸盐研究所 | Base metal load type multistage pore zeolite molecular sieve catalyst of efficient catalytic combustion soot particles and preparation and application of catalyst |
| CN104785099A (en) * | 2015-03-25 | 2015-07-22 | 中国石油天然气股份有限公司 | Method for purifying acrylonitrile device absorber off-gas by using CeMn/Me-beta molecular sieve |
| CN106540739A (en) * | 2015-09-16 | 2017-03-29 | 中国石化扬子石油化工有限公司 | A kind of preparation method of supported catalyst burning catalyst |
| CN106732755A (en) * | 2016-12-23 | 2017-05-31 | 中节能万润股份有限公司 | A kind of preparation method of the compound integral extruding type denitrating catalyst of molecular sieve multivariant oxide |
| CN110876944A (en) * | 2019-12-09 | 2020-03-13 | 大连瑞克科技有限公司 | Catalyst for catalytic combustion and preparation method thereof |
| CN111135816A (en) * | 2019-12-25 | 2020-05-12 | 宁波鸿朗环保科技有限公司 | Catalyst for catalytic combustion of chlorine-containing volatile organic gas and preparation method thereof |
| CN112169827A (en) * | 2020-08-20 | 2021-01-05 | 浙江天蓝环保技术股份有限公司 | Monolithic catalyst with selective adsorption-catalytic oxidation organic waste gas function and preparation method and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| PETR SAZAMA ET AL.: ""Effect of the Nuclearity and Coordination of Cu and Fe Sites in β Zeolites on the Oxidation of Hydrocarbons"", 《ACS CATALYSI》 * |
| PETR SAZAMA ET AL.: ""Effect of the Nuclearity and Coordination of Cu and Fe Sites in β Zeolites on the Oxidation of Hydrocarbons"", 《ACS CATALYSI》, vol. 10, 24 February 2020 (2020-02-24), pages 3984 - 4002 * |
| W. B. LI ET AL.: ""MCM-41 Supported Cu-Mn Catalysts for Catalytic Oxidation of Toluene at Low Temperatures"", 《J. PHYS. CHEM. B》 * |
| W. B. LI ET AL.: ""MCM-41 Supported Cu-Mn Catalysts for Catalytic Oxidation of Toluene at Low Temperatures"", 《J. PHYS. CHEM. B》, vol. 110, 6 October 2006 (2006-10-06), pages 21568 - 21571 * |
| 杨鑫: ""分子筛结构及化学改性对VOCs吸附影响的分子模拟及实验研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 杨鑫: ""分子筛结构及化学改性对VOCs吸附影响的分子模拟及实验研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》, no. 4, 15 April 2019 (2019-04-15), pages 016 - 315 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713849A (en) * | 2021-09-15 | 2021-11-30 | 美埃(中国)环境科技股份有限公司 | Adsorption catalysis material and preparation method thereof |
| CN115487776A (en) * | 2021-11-26 | 2022-12-20 | 北京科技大学 | Ketone VOCs adsorbent and its preparation method and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112808229B (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Catalytic ozonation of toluene using Mn–M bimetallic HZSM-5 (M: Fe, Cu, Ru, Ag) catalysts at room temperature | |
| CN112808229B (en) | Preparation method and application of copper and manganese modified Beta molecular sieve adsorption-catalytic oxidant | |
| CN109248679B (en) | VOCs normal-temperature degradation efficient catalyst and preparation and application thereof | |
| CN111359650B (en) | Preparation method, product and application of iron, nickel and palladium co-doped graphite-phase carbon nitride composite catalyst | |
| CN112844459B (en) | VOCs catalytic oxidation catalyst and preparation method and application thereof | |
| CN113181956A (en) | Combined catalyst and method for treating nitrogen-containing volatile organic compound pollutants | |
| CN114259978A (en) | Preparation process of efficient coal-fired flue gas demercuration adsorbent and product thereof | |
| CN113546632A (en) | Catalyst for treating phenolic wastewater by wet oxidation method and preparation method thereof | |
| CN112827505A (en) | Integral catalyst for catalyzing ozone to degrade VOCs (volatile organic compounds), and preparation and application thereof | |
| CN112058216B (en) | Modified silicon-based adsorption material and low-temperature in-situ degradation method for organic pollutants | |
| CN111203179A (en) | Preparation method and application of renewable phenol-containing organic wastewater catalytic adsorption material | |
| Soltan et al. | Bimetallic Fe-Mn loaded H-ZSM-5 zeolites for excellent VOCs catalytic oxidation at low-temperatures: Synergistic effects and catalytic mechanisms | |
| CN101264996B (en) | Method for treating aniline waste water by absorption-low temperature dry method | |
| CN112058217A (en) | Silicon-based adsorption material capable of being rapidly regenerated and method for microwave in-situ degradation of organic pollutants | |
| CN110302819B (en) | MOFs-derived bimetallic magnetic nanoporous carbon ozone catalyst and application thereof | |
| CN114471695B (en) | Catalyst capable of efficiently degrading cyanide-containing waste gas and preparation method and application thereof | |
| CN113522354A (en) | Preparation and application of molecular sieve supported composite metal oxide catalyst | |
| Zhu et al. | Variation of catalyst structure and catalytic activity during catalyst preparation for catalytic ozonation of heavy oil produced water | |
| CN112044468A (en) | Ozone catalyst for treating reactive dye waste gas, preparation method and application thereof | |
| CN112588298A (en) | Composite catalyst for air purification and preparation method and application thereof | |
| KR100622993B1 (en) | Dual Functional Catalyst System Performing Reaction of Adsorbent and Catalyst of VOC | |
| CN114749178B (en) | Method for preparing catering oil smoke purifying catalyst by using crab shells and application of catalyst | |
| CN113231073B (en) | Nano CuO-MnO 2 Glass fiber composite material, and preparation method and application thereof | |
| CN114100650B (en) | Ozone-hydrogen peroxide catalytic oxidation catalyst and method for treating biochemical wastewater by using same | |
| CN115608411B (en) | Catalyst, preparation method and application 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 |