CN113996334A - For N2Direct oxidation of CH by O4Preparation method of Cu-SSZ-13 molecular sieve catalyst for preparing methanol - Google Patents
For N2Direct oxidation of CH by O4Preparation method of Cu-SSZ-13 molecular sieve catalyst for preparing methanol Download PDFInfo
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- CN113996334A CN113996334A CN202111252552.8A CN202111252552A CN113996334A CN 113996334 A CN113996334 A CN 113996334A CN 202111252552 A CN202111252552 A CN 202111252552A CN 113996334 A CN113996334 A CN 113996334A
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- 238000000034 method Methods 0.000 title claims abstract description 101
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- 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 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 142
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 71
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 69
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 69
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 38
- 239000012298 atmosphere Substances 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 24
- 238000005342 ion exchange Methods 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 110
- 238000000227 grinding Methods 0.000 claims description 48
- 239000010453 quartz Substances 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 26
- 238000007873 sieving Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 17
- 230000005587 bubbling Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 235000013842 nitrous oxide Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 69
- 229910001868 water Inorganic materials 0.000 description 65
- 238000010926 purge Methods 0.000 description 34
- 238000012360 testing method Methods 0.000 description 32
- 238000011156 evaluation Methods 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 27
- 238000005303 weighing Methods 0.000 description 26
- 238000012216 screening Methods 0.000 description 25
- 238000003756 stirring Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 23
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 23
- 239000010431 corundum Substances 0.000 description 22
- 229910052593 corundum Inorganic materials 0.000 description 22
- 229910052573 porcelain Inorganic materials 0.000 description 22
- 230000000694 effects Effects 0.000 description 16
- 238000002390 rotary evaporation Methods 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OGNJZVNNKBZFRM-UHFFFAOYSA-N 1-(5-methoxy-1H-indol-3-yl)-2-propanamine Chemical group COC1=CC=C2NC=C(CC(C)N)C2=C1 OGNJZVNNKBZFRM-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- KCBWAFJCKVKYHO-UHFFFAOYSA-N 6-(4-cyclopropyl-6-methoxypyrimidin-5-yl)-1-[[4-[1-propan-2-yl-4-(trifluoromethyl)imidazol-2-yl]phenyl]methyl]pyrazolo[3,4-d]pyrimidine Chemical compound C1(CC1)C1=NC=NC(=C1C1=NC=C2C(=N1)N(N=C2)CC1=CC=C(C=C1)C=1N(C=C(N=1)C(F)(F)F)C(C)C)OC KCBWAFJCKVKYHO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 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
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Catalysts (AREA)
Abstract
For N2Direct oxidation of CH by O4A preparation method of a Cu-SSZ-13 molecular sieve catalyst for preparing methanol belongs to the fields of chemical engineering technology and catalysts. The invention is used for N2The O-DMTM catalyst takes H-SSZ-13 as a carrier and load Cu as an active component of the catalyst. In the invention, under the atmosphere of ammonia water or nitrogen, the copper is loaded on the H-SSZ-13 by adopting a solid ion exchange method, thereby not only improving the dispersibility of the copper on the catalyst, but also reducing the generation of CuO, and further improving the N2Activity of O-DMTM. The mass of Cu accounts for 0.1-5% of the total mass of the catalyst, CuCl is selected as a copper source precursor, and the molar concentration of ammonia water is 11.74-13.33 mol/L. The solid ion exchange method has simple process and low preparation cost, and the obtained molecular sieve catalystN of reagent2The O-DMTM has excellent performance.
Description
Technical Field
The invention belongs to the field of chemical technology and catalysts, and particularly relates to a solid-state ion exchange method for preparing an ammonia water atmosphere of a Cu-SSZ-13 catalyst, and a prepared catalystThe agent is mainly used for preparing methanol (N) by directly oxidizing methane with laughing gas2O-DMTM).
Background
Nitrous oxide (N)2O) is also called laughing gas, is a greenhouse gas and has greenhouse effect. The "United nations climate Change framework convention" held in Kyoto, Japan in 1997 at 12 months passed the Kyoto protocol which explicitly will be N2O、CO2、CH4Fall into a class of greenhouse gases, in which N2The latent heat of warming O is CO2310 times of methane and 28 times of methane. N is a radical of2O is mainly derived from the combustion of coal in a fluidized bed, the chemical production of adipic acid and nitric acid and the emission of tail gas of a motor vehicle, wherein the emission in the chemical production process of the adipic acid and the nitric acid is N2The main source of O, especially in the production of adipic acid, emits large amounts of off-gases during its production. N is a radical of2O is very stable in the atmosphere, the service life of the O is as long as 150 years, and ozone in the atmosphere is damaged to form acid rain, so that the O causes great harm to the living environment of human beings.
At present, N2The treatment method of O mainly includes direct catalytic decomposition method, selective catalytic reduction method, high-temperature thermal decomposition method, cyclohexanol absorption oxidation method, etc. For example, CN1980726 patent adopts ion exchange method to prepare bimetallic (platinum, gold and iron, cobalt and copper) supported catalyst, and directly catalyzes and decomposes N2O, which has high running cost and is susceptible to O in the reaction process2、H2O influence and the like. The CN103949264A patent uses a high temperature thermal decomposition method, which has good activity in high temperature region, but has high requirement for high temperature resistance of the equipment. The CN102482211A patent proposes the most preferable of the above methods is a selective catalytic reduction method, and the commonly used reducing agent is olefin, alcohol, etc. However, for technical and economic reasons, saturated hydrocarbons are added to N2Among O, most preferred is methane (CH)4) Liquefied petroleum gas (LPG: c3H8And C4H10Mixtures of (a) and the like. More CH is used than LPG4。
Methane is a main component of carbon-containing resources such as natural gas, pit gas, methane, combustible ice and the like, and is commonly called as gas. Phase (C)Compared with coal and petroleum, the high-carbon-hydrogen-ratio coal has a higher carbon-hydrogen ratio, can be used as fuel and raw materials for producing hydrogen, carbon black, carbon monoxide, acetylene, hydrocyanic acid, formaldehyde and the like, and is considered as a novel clean energy and high-quality chemical raw material with great development potential in the 21 st century. However, methane is an effective greenhouse gas, and 4 months and 2 days in 2018, researchers in lawrence berkeley national laboratories, the U.S. department of energy, directly prove for the first time that methane causes the greenhouse effect on the earth surface to be increased. Thus, the appropriate oxidant is selected to react CH4The conversion into high value-added products is very significant. Generally, N is utilized2O、O2And the methane is catalytically converted into a high value-added product by using an equal oxidant. The invention adopts N2O is used as oxidant, which can react with catalyst to generate alpha-O structure, namely pure O2The yield of the methanol obtained by using the oxidizing agent is higher. Thus, N2O-DMTM can not only realize N2O and CH4The method has high utilization efficiency, important academic value and profound environmental protection significance.
In recent years, a series of efficient catalysts for preparing methanol by directly oxidizing methane by laughing gas are proposed, wherein the Cu-SSZ-13 catalyst is widely concerned due to high catalytic activity and high hydrothermal stability. At present, the preparation method of Cu-SSZ-13 mainly comprises a one-pot method (EP2931406(A1), CN104812469A), an ion exchange method (CN107115888A), a rotary evaporation method (CN107519920A) and the like, but the methods have the problems that the metal loading of the catalyst is difficult to accurately control, a large amount of harmful waste liquid is generated in the post-treatment of the catalyst, the process is complicated, the time consumption is long and the like. Therefore, the invention adopts the solid ion exchange method of ammonia water atmosphere to apply the modified Cu-SSZ-13 molecular sieve to N2In O-DMTM, high activity and thermal stability are ensured, and the invention has the advantages of simple preparation process, strong controllability, low preparation cost and the like. Compared with the traditional rotary evaporation method and the solid ion exchange method under the inert atmosphere, the solid ion exchange method under the ammonia water atmosphere is adopted, and the prepared Cu-SSZ-13 has higher activity. Therefore, the Cu-SSZ-13 prepared by the solid-state ion exchange method in the ammonia water atmosphere is selected for N2The O-DMTM has wide industrial application prospect.
Disclosure of Invention
Aiming at the problems in the existing Cu-SSZ-13 preparation process, the invention aims to provide a solid ion exchange method for preparing the Cu-SSZ-13 catalyst in an ammonia water atmosphere, which can greatly shorten the preparation period of the catalyst, reduce the cost and reduce the emission of three wastes. Catalysts prepared by solid state ion exchange in an ammonia atmosphere are compared to rotary evaporation in N2The O-DMTM process has higher activity.
For N2The preparation method of the Cu-SSZ-13 molecular sieve catalyst of O-DMTM is characterized by comprising the following steps: CuCl is selected as a precursor, and Cu is loaded on an H-SSZ-13 molecular sieve.
Wherein, the prepared Cu-SSZ-13 catalyst can be prepared under the atmosphere of ammonia water and nitrogen and under the atmosphere of pure nitrogen.
Wherein the mass of Cu accounts for 0.1-5% of the total mass of the catalyst, namely
Wherein the molar concentration of the ammonia water is 11.74-13.33 mol/L.
Wherein the prepared catalyst is used for N2The reaction space velocity of O-DMTM is 12000h-1The reaction temperature is 320-480 ℃, the methane is 15%, the laughing gas is 30%, and the balance gas is helium.
The preparation method of the molecular sieve catalyst for N2O-DMTM is characterized by comprising the following steps:
the first step is as follows: mixing the H-SSZ-13 molecular sieve with a Cu salt precursor by using a mechanical mixing method;
the second step is that: roasting in ammonia water and nitrogen atmosphere or pure nitrogen atmosphere, wherein solid ion exchange occurs in the roasting process, and the activation of the catalyst is realized through the solid ion exchange.
And ammonia water with the roasting temperature of 450 ℃ and the molar concentration of 11.74-13.33 mol/L is introduced into the reaction system through nitrogen bubbling.
Further, the present invention was compared with Cu-SSZ-13 in a pure nitrogen atmosphere.
Furthermore, the Cu-SSZ-13 molecular sieve catalyst prepared by the rotary evaporation method is adopted for comparison.
In the method, the prepared Cu-SSZ-13 molecular sieve catalyst is filled in a constant temperature area of a fixed bed micro quartz tube reactor. Reaction space velocity 12000h-1The feed ratio is 30 percent N2O，15％CH4The balance gas is helium. The reacted gas enters a gas chromatograph for product analysis.
Compared with the prior art, the invention has the advantages that:
(1) the catalyst prepared by the solid-state ion exchange method has the advantages of simple technical process and strong controllability of the preparation process.
(2) NH is introduced when the solid ion exchange method is adopted to prepare Cu-SSZ-133·H2O, improves the dispersibility of Cu, and improves the N of the Cu-SSZ-13 catalyst compared with the traditional solid ion exchange method and rotary evaporation method2O-DMTM activity.
(3) The preparation process shortens the preparation period from several days of traditional ion exchange to one day.
(4) The preparation process generates almost no waste liquid, especially no waste liquid containing inorganic acid and ammonium nitrate.
(5) The Cu-SSZ-13 catalyst obtained by the process has N which can be compared with the Cu-SSZ-13 catalyst prepared by the traditional preparation method2O-DMTM activity.
Drawings
FIG. 1 shows 5% Cu-SSZ-13 (NH)3·H2O)、3％Cu-SSZ-13(NH3·H2O)、2％Cu-SSZ-13(NH3·H2O)、1.5％Cu-SSZ-13(NH3·H2O)、0.8％Cu-SSZ-13(NH3·H2O)、0.5％Cu-SSZ-13(NH3·H2O)、0.3％Cu-SSZ-13(NH3·H2O)、0.1％Cu-SSZ-13(NH3·H2O) catalyst, methanol yield profile when used in N2O-DMTM system.
FIG. 2 shows 5% Cu-SSZ-13, 3% Cu-SSZ-13, 2% Cu-SSZ-13, 1.5% Cu-SSZ-13, 0.8% Cu-SSZ-13, 0.5% Cu-SSZ-13, 0.3% Cu-SSZ-13. 0.1% Cu-SSZ-13 catalyst for N2The yield of methanol in the O-DMTM system is shown.
FIG. 3 is 0.3% Cu-SSZ-13 (NH)3·H2O)、0.5％Cu-SSZ-13(NH3·H2O)、0.8％Cu-SSZ-13(NH3·H2O) and 0.3% Cu-SSZ-13, 0.5% Cu-SSZ-13, 0.8% Cu-SSZ-13, catalyst for N2Comparison of methanol yields in the O-DMTM system.
FIG. 4 is 0.3% Cu-SSZ-13 (NH)3·H2O)、R-0.3％Cu-SSZ-13、2.5％Cu-SSZ-13(NH3·H2O)、R-2.5％Cu-SSZ-13、4％Cu-SSZ-13(NH3·H2O), R-4% Cu-SSZ-13, use of catalyst for N2Comparison of methanol yields in the O-DMTM system.
FIG. 5 is 0.3% Cu-SSZ-13 (NH)3·H2O) catalysts with N respectively2O and O2Oxidation of CH4The yield of methanol is shown by comparison.
Detailed Description
In order to explain the technical content, the achieved purpose and the effect of the invention in detail, the technical scheme of the invention is further explained by examples (examples and comparative examples). It should be understood by those skilled in the art that the examples are given only to assist understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 15% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the CuCl dosage of 5 percent of Cu-SSZ-13, weighing 0.0820g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 5% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 24% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the CuCl dosage of 4 percent of Cu-SSZ-13, weighing 0.0649g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 4% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 33% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the CuCl dosage of 3 percent of Cu-SSZ-13, weighing 0.0482g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a 40-60-mesh sample to obtain 3% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 42.5% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the CuCl dosage of 2.5 percent of Cu-SSZ-13, weighing 0.0399g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 2.5% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 52% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the CuCl dosage of 2 percent of Cu-SSZ-13, weighing 0.0318g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 2% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 61.5% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the CuCl dosage of 1.5 percent of Cu-SSZ-13, weighing 0.0237g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 1.5% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 71% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 1 percent of CuCl of the Cu-SSZ-13, weighing 0.0157g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 1% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 80.8% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.8 percent of CuCl of the Cu-SSZ-13, weighing 0.0126g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 0.8% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 90.5% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.5 percent of CuCl of the Cu-SSZ-13, weighing 0.0078g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 0.5% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 100.3% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.3 percent of CuCl of the Cu-SSZ-13, weighing 0.0047g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 0.3% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
Example 110.1% Cu-SSZ-13 (NH)3·H2O) preparation
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.1 percent of CuCl of the Cu-SSZ-13, weighing 0.0016g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing 12.5mol/L ammonia water into the quartz tube by nitrogen bubbling for 4 hours, wherein the nitrogen flow is 30 ml/min;
m4: after purging is finished, continuously introducing nitrogen and ammonia water, setting the initial temperature of the tube furnace to be 25 ℃, controlling the heating rate by using programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain 0.1% Cu-SSZ-13 (NH)3·H2O) samples for subsequent evaluation tests.
EXAMPLE 125% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of CuCl of 5 percent of Cu-SSZ-13, weighing 0.0820g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 5% Cu-SSZ-13 sample for subsequent evaluation and test.
EXAMPLE 134% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 4 percent of CuCl of the Cu-SSZ-13, weighing 0.0649g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 4% Cu-SSZ-13 sample for subsequent evaluation and test.
EXAMPLE 143% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of CuCl of 3 percent of Cu-SSZ-13, weighing 0.0482g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 3% Cu-SSZ-13 sample for subsequent evaluation and test.
Example 152.5% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 2.5 percent of CuCl of the Cu-SSZ-13, weighing 0.0399g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 2.5% Cu-SSZ-13 sample for subsequent evaluation and test.
EXAMPLE 162 preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the using amount of 2 percent of CuCl of the Cu-SSZ-13, weighing 0.0318g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 2% Cu-SSZ-13 sample for subsequent evaluation and test.
EXAMPLE 171.5% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 1.5 percent of CuCl of the Cu-SSZ-13, weighing 0.0237g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 1.5% Cu-SSZ-13 sample for subsequent evaluation and test.
EXAMPLE 181% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 1 percent of CuCl of the Cu-SSZ-13, weighing 0.0157g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 1% Cu-SSZ-13 sample for subsequent evaluation and test.
EXAMPLE 190.8% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.8 percent of CuCl of the Cu-SSZ-13, weighing 0.0126g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 0.8% Cu-SSZ-13 sample for subsequent evaluation and test.
Example 200.5% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.5 percent of CuCl of the Cu-SSZ-13, weighing 0.0078g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 0.5% Cu-SSZ-13 sample for subsequent evaluation and test.
Example 210.3% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.3 percent of CuCl of the Cu-SSZ-13, weighing 0.0047g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 0.3% Cu-SSZ-13 sample for subsequent evaluation and test.
Example 220.1% preparation of Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2, grinding the roasted H-SSZ-13, calculating the use amount of 0.1 percent of CuCl of the Cu-SSZ-13, weighing 0.0016g of CuCl and 1g H-SSZ-13 in a corundum porcelain boat, and stirring for 20min to fully and uniformly mix the CuCl and the H-SSZ-13;
m3, putting the uniformly mixed sample into a quartz tube of a tube furnace, and introducing nitrogen into the quartz tube, wherein the purging time is 4 hours, and the nitrogen flow is 30ml/min, so that the whole tube furnace is kept in an inert atmosphere;
m4: after purging is finished, continuously introducing nitrogen, setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min, reaching the set temperature of 450 ℃ after 42.5min, and keeping the temperature at 450 ℃ for 13 h;
m5: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain a 0.1% Cu-SSZ-13 sample for subsequent evaluation and test.
Comparative example 23R-preparation of 0.3% Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2 calculation of Cu (NO) in terms of Cu mass accounting for 0.3% of the total mass of the catalyst3)2·3H2O amount, 5g H-SSZ-13 was weighed into a round bottom flask, and 0.0572g of Cu (NO) was weighed by calculation3)2·3H2Adding O into a round-bottom flask, adding 200ml of deionized water and magnetons, and sealing the round-bottom flask with a preservative film to prevent evaporation of water in the heating process;
m3, heating and stirring the round-bottom flask in a constant-temperature water bath at the temperature of 90 ℃ for 4 hours;
m4, placing the mixed sample on a rotary evaporator, and performing vacuum rotary evaporation by adopting a constant-temperature water bath at 60 ℃ until the solution is evaporated to dryness, wherein the vacuum degree is 0.1 MPa;
m5, putting the obtained catalyst sample into a drying oven at 100 ℃ for drying for 12 hours;
m6: placing the dried sample in a muffle furnace, heating by using a programmed heating method at 5 ℃/min, reaching a termination temperature of 550 ℃ after 104min, and roasting at 550 ℃ for 6 h;
m7: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain the R-0.3% Cu-SSZ-13 molecular sieve catalyst for subsequent evaluation and test.
Comparative example 24R preparation of 2.5% Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2 calculation of Cu (NO) based on Cu mass 2.5% of the total mass of the catalyst3)2·3H2O amount, weighing 5g H-SSZ-13 in round bottom flask, and weighing 0.4874g Cu (NO) by calculation3)2·3H2Adding O into a round-bottom flask, adding 200ml of deionized water and magnetons, and sealing the round-bottom flask with a preservative film to prevent evaporation of water in the heating process;
m3, heating and stirring the round-bottom flask in a constant-temperature water bath at the temperature of 90 ℃ for 4 hours;
m4, placing the mixed sample on a rotary evaporator, and performing vacuum rotary evaporation by adopting a constant-temperature water bath at 60 ℃ until the solution is evaporated to dryness, wherein the vacuum degree is 0.1 MPa;
m5, putting the obtained catalyst sample into a drying oven at 100 ℃ for drying for 12 hours;
m6: placing the dried sample in a muffle furnace, heating by using a programmed heating method at 5 ℃/min, reaching a termination temperature of 550 ℃ after 104min, and roasting at 550 ℃ for 6 h;
m7: and tabletting, grinding and sieving the prepared sample, and screening out a sample of 40-60 meshes to obtain the R-2.5% Cu-SSZ-13 molecular sieve catalyst for subsequent evaluation and test.
Comparative example 25R-preparation of 4% Cu-SSZ-13
The method comprises the following steps:
m1, roasting H-SSZ-13 in a muffle furnace, setting the initial temperature to be 30 ℃, heating by using a programmed heating method with the temperature of 5 ℃/min, reaching the final temperature of 550 ℃ after 104min, and keeping the temperature at 550 ℃ for 6H;
m2 calculation of Cu (NO) based on Cu mass at 4% of the total mass of the catalyst3)2·3H2O amount, weighing 5g H-SSZ-13 in round bottom flask, weighing 0.7921g Cu (NO) according to calculated amount3)2·3H2Adding O into a round-bottom flask, adding 200ml of deionized water and magnetons, and sealing the round-bottom flask with a preservative film to prevent evaporation of water in the heating process;
m3, heating and stirring the round-bottom flask in a constant-temperature water bath at the temperature of 90 ℃ for 4 hours;
m4, placing the mixed sample on a rotary evaporator, and performing vacuum rotary evaporation by adopting a constant-temperature water bath at 60 ℃ until the solution is evaporated to dryness, wherein the vacuum degree is 0.1 MPa;
m5, putting the obtained catalyst sample into a drying oven at 100 ℃ for drying for 12 hours;
m6: placing the dried sample in a muffle furnace, heating by using a programmed heating method at 5 ℃/min, reaching a termination temperature of 550 ℃ after 104min, and roasting at 550 ℃ for 6 h;
m7: and tabletting, grinding and sieving the prepared sample, and screening out a 40-60-mesh sample to obtain the R-4% Cu-SSZ-13 molecular sieve catalyst for subsequent evaluation and test.
Molecular sieve catalyst activity evaluation test
The molecular sieve catalyst prepared by the method is used for N2O-DMTM, and the specific flow is as follows:
s1: filling a molecular sieve catalyst into a fixed bed reactor, opening a control panel of the fixed bed reactor, starting a hydrogen-air generator, and starting a gas chromatography GC;
s2: pretreating the catalyst with helium at 550 ℃, purging impurities for 90min, and then cooling to 320 ℃;
s3: will contain N2O、CH4Introducing mixed gas of helium and the gas into the fixed bed at the gas speed of 25ml/min for reactionIn a bed, the catalytic reaction is carried out at a reaction temperature of 320 to 480 ℃ and under normal pressure, wherein N2The content of O accounts for 30 percent of the total gas introduced, the content of CH4 accounts for 15 percent of the total gas introduced, and the balance gas is helium;
s4: the product was detected by gas chromatography and the measured concentration data was calculated to yield methanol.
Test example 1
At 5% Cu-SSZ-13 (NH)3·H2O)、3％Cu-SSZ-13(NH3·H2O)、2％Cu-SSZ-13(NH3·H2O)、1.5％Cu-SSZ-13(NH3·H2O)、0.8％Cu-SSZ-13(NH3·H2O)、0.5％Cu-SSZ-13(NH3·H2O)、0.3％Cu-SSZ-13(NH3·H2O)、0.1％Cu-SSZ-13(NH3·H2O) the above activity evaluation test was performed, and the yield of methanol in the temperature range of 320 to 480 ℃ was plotted in fig. 1.
As can be seen from fig. 1: compared with other samples, the Cu-SSZ-13 (NH) with the concentration of 0.3 percent is within 340-440 DEG C3·H2O) the yield of the obtained methanol is the highest and can reach 160 umol.g-1·h-1(ii) a 0.8% Cu-SSZ-13 (NH) at 440-520 DEG C3·H2O) the highest yield of methanol was obtained.
Test example 2
The above-described activity evaluation test was performed on 5% Cu-SSZ-13, 3% Cu-SSZ-13, 2% Cu-SSZ-13, 1.5% Cu-SSZ-13, 0.8% Cu-SSZ-13, 0.5% Cu-SSZ-13, 0.3% Cu-SSZ-13, 0.1% Cu-SSZ-13, and the yield of methanol in a temperature range of 320 to 480 ℃ was plotted in FIG. 2.
As can be seen from fig. 2: the yield of methanol was highest in the range of 0.5% Cu-SSZ-13 over the entire temperature range compared to several other samples within 320-460 ℃.
From a comparison of the methanol yields in FIG. 3, it can be seen that: introduction of NH3·H2The yield of the samples obtained by O is higher than that of the samples without introducing methanol, which also shows that the solid-state ion exchange method introducing ammonia water can improve the dispersity of the loaded metal more, thereby improving the activity of the molecular sieve catalystAnd (4) sex.
Comparative example 3
At R-0.3% Cu-SSZ-13, R-2.5% Cu-SSZ-13, R-4% Cu-SSZ-13, 0.3% Cu-SSZ-13 (NH)3·H2O)、2.5％Cu-SSZ-13(NH3·H2O)、4％Cu-SSZ-13(NH3·H2O) the above activity evaluation test was performed, and the yield of methanol in the temperature range of 320 to 480 ℃ was plotted in fig. 4.
As can be seen from fig. 4: 0.3% Cu-SSZ-13 (NH) prepared by solid-state ion exchange3·H2O)、2.5％Cu-SSZ-13(NH3·H2O)、4％Cu-SSZ-13(NH3·H2O) the obtained methanol yields are all higher than those of R-0.3 percent Cu-SSZ-13, R-2.5 percent Cu-SSZ-13 and R-4 percent Cu-SSZ-13, which shows that compared with the traditional rotary evaporation method, the solid ion exchange method under the ammonia atmosphere is used for the N2O-DMTM system, and higher activity is generated.
Comparative example 4
By the use of O2As an oxidizing agent, 0.3% Cu-SSZ-13 (NH)3·H2O) activity evaluation test was performed, and the yield of methanol in the temperature range of 320 to 480 ℃ was plotted in fig. 5.
As can be seen from fig. 5: by using O2Oxidation of CH4Manufacture of CH3The yield of OH is far less than with N2Oxidation of CH by O4Manufacture of CH3Yield of OH, which indicates N2O to O2More suitably as CH4Oxidation to CH3And (4) an OH system.
Claims (5)
1. For N2Direct oxidation of CH by O4The preparation method of the Cu-SSZ-13 molecular sieve catalyst for preparing the methanol is characterized by comprising the following steps of:
(1) roasting of the H-SSZ-13 molecular sieve: setting the initial temperature of the muffle furnace to be 30 ℃, heating by using a programmed heating method at 5 ℃/min to reach the termination temperature of 550 ℃, and keeping the temperature at 550 ℃ for 6 h;
(2) mixing and roasting: mixing an H-SSZ-13 molecular sieve with a Cu salt precursor, roasting in a tubular furnace in an ammonia water atmosphere, and introducing 11.74-13.33 mol/L ammonia water into a quartz tube through nitrogen bubbling;
or mixing the H-SSZ-13 molecular sieve with a Cu salt precursor, roasting in a tubular furnace in a nitrogen atmosphere,
setting the initial temperature of the tubular furnace to be 25 ℃, controlling the heating rate by using the programmed heating at 10 ℃/min to reach the set temperature of 450 ℃, and keeping the temperature at 450 ℃ for 13 h; the mass of Cu accounts for 0.1-5% of the total mass of the final Cu-SSZ-13 molecular sieve catalyst;
(3) and (3) post-treatment: and (3) tabletting, grinding and sieving the solid product obtained in the step (2) to obtain the Cu-SSZ-13 molecular sieve catalyst.
2. The method of claim 1, wherein: the molar concentration of the ammonia water is 12.5 mol/L.
3. The method for preparing Cu-SSZ-13 molecular sieve catalyst by loading copper in solid-state ion exchange method of ammonia water atmosphere as claimed in claim 1, which is characterized in that: CuCl is selected as a copper source precursor.
4. The Cu-SSZ-13 molecular sieve catalyst prepared by the method in claim 1 is used for a system for preparing methanol by directly oxidizing methane with laughing gas.
5. Use according to claim 4, characterized in that: will contain N2O、CH4Introducing the mixed gas into a reaction bed filled with a catalyst, wherein the temperature is 320-480 ℃, and the reaction space velocity is 12000h-1The reaction was carried out at a total gas flow rate of 25 ml/min.
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| CN110681414A (en) * | 2019-12-09 | 2020-01-14 | 山东国瓷功能材料股份有限公司 | Copper-containing loaded molecular sieve with high hydrothermal stability, and preparation method and application thereof |
| CN112619699A (en) * | 2020-12-21 | 2021-04-09 | 山东齐鲁华信高科有限公司 | Post-treatment method of SSZ-13 molecular sieve |
| CN113387369A (en) * | 2020-03-12 | 2021-09-14 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Preparation method of Cu-SSZ-13 molecular sieve |
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| CN107519920A (en) * | 2017-08-22 | 2017-12-29 | 无锡威孚环保催化剂有限公司 | The method that revolving method supported copper prepares the molecular sieve catalysts of Cu SSZ 13 |
| CN110681414A (en) * | 2019-12-09 | 2020-01-14 | 山东国瓷功能材料股份有限公司 | Copper-containing loaded molecular sieve with high hydrothermal stability, and preparation method and application thereof |
| CN113387369A (en) * | 2020-03-12 | 2021-09-14 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Preparation method of Cu-SSZ-13 molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115069285A (en) * | 2022-06-14 | 2022-09-20 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane, and preparation method and application thereof |
| CN115069285B (en) * | 2022-06-14 | 2024-01-16 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane and preparation method and application thereof |
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