CN115970703A - WFe with photo-thermal catalytic activity m La n O x Catalyst, preparation method and application thereof - Google Patents
WFe with photo-thermal catalytic activity m La n O x Catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN115970703A CN115970703A CN202211575245.8A CN202211575245A CN115970703A CN 115970703 A CN115970703 A CN 115970703A CN 202211575245 A CN202211575245 A CN 202211575245A CN 115970703 A CN115970703 A CN 115970703A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- wfe
- catalytic activity
- preparation
- photo
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001361 adipic acid Substances 0.000 claims abstract description 29
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 73
- 238000001816 cooling Methods 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 32
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 20
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 19
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 19
- 150000003657 tungsten Chemical class 0.000 claims description 19
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 18
- 150000002603 lanthanum Chemical class 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 229910052724 xenon Inorganic materials 0.000 claims description 16
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000003349 gelling agent Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000002153 concerted effect Effects 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical group Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 3
- SRHILFZTCUSLKY-UHFFFAOYSA-N lanthanum hexahydrate Chemical compound O.O.O.O.O.O.[La] SRHILFZTCUSLKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 39
- 239000007787 solid Substances 0.000 description 38
- 239000000843 powder Substances 0.000 description 36
- 239000012298 atmosphere Substances 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000007710 freezing Methods 0.000 description 12
- 230000008014 freezing Effects 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- 229910002521 CoMn Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical group O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a WFe with photo-thermal catalytic activity m La n O x A catalyst, a preparation method and application thereof, belonging to the technical field of catalyst preparation and application. The method uses the condensed gel-roasting method to prepare WFe m La n O x Trimetallic oxide catalystThe preparation method comprises the steps of carrying out photo-thermal catalytic oxidation on cyclohexane by a catalyst to prepare adipic acid in one step, wherein a method of condensing gel can effectively prevent metal salt from being hydrolyzed, uniformly dispersing inorganic salt in a solvent to keep an amorphous structure, then effectively regulating and controlling a crystal phase in the catalyst by controlling a calcination temperature, and simultaneously effectively controlling the crystal phase by regulating the ratio of iron and lanthanum metal components in the catalyst, so that the reaction shows good catalytic activity and adipic acid selectivity under the condition of no solvent. The method has the advantages of simple operation, cheap and easily obtained raw materials and catalyst, small catalyst consumption, easy separation, excellent cyclicity, repeated use for many times and suitability for large-scale production.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and particularly relates to a WFe with photo-thermal catalytic activity m La n O x A catalyst, a preparation method and application thereof.
Background
Adipic acid (Adipic acid) and derivatives thereof are very important commercial aliphatic dibasic organic acids, can be condensed and polymerized into high molecular compounds, and are mainly used for preparing polyamide, polyester, polyurethane resin, nylon-66 fibers and the like. In addition, adipic acid can be used as an additive in the production of products such as lubricants, cosmetics, fertilizers, gelatin, paper, wax and the like, and is widely applied to the industries such as medicines, chemistry, foods and the like. Further, adipic acid is also useful as a base material for the synthesis of hexamethylenediamine, adipate and adiponitrile in organic synthesis, and thus its importance in the field of fine chemical engineering is self-evident. At present, the main method for industrially synthesizing adipic acid is to use cyclohexane as a raw material, oxidize molecular oxygen to generate K/A oil (cyclohexanone and cyclohexanol), and oxidize the K/A oil by using 50-60% concentrated nitric acid to obtain a target product. 1.3t of nitric acid with the concentration of 68 percent is consumed for producing 1t of adipic acid product, and 0.25t of N is generated 2 The steam of O and nitric acid and the waste acid liquor cause great pollution to the environment and high denitration energy consumption, which always troubles the development of the adipic acid generation process technology. The chemical process for directly producing adipic acid by using cyclohexane as a raw material and performing one-step oxidation by using molecular oxygen or hydrogen peroxide has the characteristics of economy, greenness, sustainability and the like, but the process has the selective activation and inhibition of a plurality of different C-H bonds of serial reaction. Thus, the C-H bond of cyclohexane which is relatively inert to oxidation and the deep oxidation of adipic acid with higher inhibition activity to CO are selected 2 And H 2 O is one of the most difficult and challenging research topics in heterogeneous catalytic technology research.
Iwahama et al (Iwahama T, syojyo K, sakaguchi S, et al&Development,1998,2 (4), 255-260.) reported a free radical catalyst, N-hydroxyphthalimide, which explored the use of molecular oxygen to oxidize cyclohexane in the presence of small amounts of the transition metal salts manganese acetylacetonate and cobalt acetate directly to adipic acid. Researches show that in the presence of manganese acetylacetonate, the conversion rate of cyclohexane and the selectivity of adipic acid are both as high as 73%, and excellent catalytic activity is shown. However, this method is limited because it uses an expensive radical catalyst and two promoters and requires acetic acid as a solvent, and it is difficult to apply this technique to industrial production. Chavan et al (Chavan S A, srinivas D, ratnasamy P. Journal of Catalysis,2002,212 (1), 39-45.) reported a new non-HNO 3 Route by using mu 3 Oxo-bridged Co/Mn cluster complex CoMn 2 (0) As a catalyst, the mixture of cyclohexane, cyclohexanol and cyclohexanone is oxidized in an acetic acid medium to prepare adipic acid, and high conversion rate and selectivity of a target product are obtained, but the catalyst can be seriously leached in a reaction system.
Lin et al (Lin S, weng H S. Applied Catalysis A-General,1993,105 (2), 289.) selected a Fe (III) doped molecular sieve catalyst FeAlPO-31 with appropriate pore size and high oxidizability as the metal ions in the molecular sieve structure to catalyze the oxidation of cyclohexane to prepare adipic acid. Reacting for 24 hours at 100 ℃ under the air of 1.5MPa without any initiator and solvent, and obtaining cyclohexaneThe conversion rate of the catalyst is 6.6 percent, and the selectivity of the adipic acid can reach 65 percent. In 2015, zou et al (Zou G, zong W, xu Q, et al catalysis Communication 2015,58, 46-52.) synthesized Mn, co, fe, cr doped titanium-silicon molecular sieve materials (HTS) with hollow structure, wherein Mn-HTS has better catalytic effect on cyclohexane. At 140 ℃ and 1.0MPa O 2 And the reaction is carried out for 6 hours without any initiator and solvent, the conversion rate of cyclohexane is 13.4 percent, and the selectivity of adipic acid is 57.5 percent. Although the molecular sieve material catalyst has the advantages of controllable pore structure, stable catalytic activity, easy recovery, no need of a solvent or an initiator in the catalytic process, repeated reuse and the like, the adipic acid yield is generally low, the preparation process of the molecular sieve is complex, the preparation cost is high, and the molecular sieve catalyst has no great development in the recent years in catalyzing one-step preparation of adipic acid from cyclohexane. Therefore, the development of a catalyst which is more effective, high in selectivity, easy to separate, low in cost and reusable in cyclohexane catalytic oxidation is of great significance.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the present invention aims to provide a WFe having photothermal catalytic activity m La n O x The catalyst, the preparation method and the application thereof are used for solving the technical problems of low efficiency, poor selectivity, difficult separation, high cost and the like in the existing method for preparing adipic acid.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in ethanol, and mixing to obtain a mixed solution;
s2: adding a gelling agent into the mixed solution, and cooling to obtain gel;
s3: drying and grinding the gel to obtain a precursor sample; calcining the precursor sample to obtain the WFe with photo-thermal catalytic activity m La n O x A catalyst.
Further, in S1, the dosage ratio of the tungsten salt, the iron salt, the lanthanum salt hexahydrate and ethanol is (9-45) mmol: (9 to 81) mmol: (9 to 63) mmol: (260-1750) mmol:2mL; the tungsten salt is tungsten hexachloride, the ferric salt is ferric chloride hexahydrate, and the lanthanum salt is lanthanum nitrate hexahydrate.
Further, in S1, the temperature of the ethanol is-5 to 5 ℃; the mixing is carried out in an ultrasonic mixing mode; the temperature during ultrasonic mixing is-5 to 5 ℃.
Further, in S2, a gelling agent is added into the mixed solution at the temperature of-5 ℃, and the mixed solution is cooled at the temperature of 0-5 ℃ to obtain gel.
In S2, the molar ratio of the tungsten chloride to the gelling agent is (9-45): (260-1300).
Further, in S2, the gelling agent is epichlorohydrin or propylene oxide; the cooling time is 2-3 days.
Further, in S3, the drying temperature is 70-80 ℃, and the drying time is 12-24 h.
Further, in S3, the calcination process parameters are as follows: heating to 350-850 ℃ at the heating rate of 5-8 ℃/min, and roasting at constant temperature for 5-7 h.
The invention also discloses a WFe with photo-thermal catalytic activity prepared by the method m La n O x A catalyst, wherein m: n = (3.
The invention also discloses the WFe with the photo-thermal catalytic activity m La n O x Application of catalyst, WFe with photo-thermal catalytic activity m La n O x The catalyst is used for preparing adipic acid by one-step catalysis of cyclohexane under the photo-thermal concerted catalysis under the solvent-free condition, and the reaction conditions are as follows: adding WFe with photo-thermal catalytic activity into a photo-thermal reaction kettle m La n O x Under the illumination of a xenon lamp, the reaction temperature of the catalyst and cyclohexane is 130 ℃, the reaction time is 4-8h 2 The pressure of (A) is 1-2 MPa; the WFe with photothermal catalytic activity m La n O x CatalysisThe dosage ratio of the agent to cyclohexane is (50-60) mg: (7-8) g.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the steps of uniformly distributing tungsten salt, iron salt and lanthanum salt in cooling ethanol through cooling ultrasound, activating the surface of an oxide through a special metal amorphous appearance, having rich oxygen vacancies and excellent physical oxygen adsorption capacity, being beneficial to improving electron transfer and photo-generated electron migration, further improving the selection of adipic acid, and enabling the adipic acid to be a main product and to have excellent stability, so that the catalyst can be recycled for multiple times. The method uses the condensed gel-roasting method to prepare WFe m La n O x The three-metal oxide catalyst is used for preparing adipic acid by one-step photo-thermal catalytic oxidation of cyclohexane, wherein a method of a cold gel can effectively prevent metal salt from being hydrolyzed, inorganic salt is uniformly dispersed in a solvent to keep an amorphous structure, a crystalline phase in the catalyst can be effectively regulated and controlled by controlling a calcination temperature, and meanwhile, a crystalline phase can be effectively controlled by regulating the ratio of iron to lanthanum metal components in the catalyst, so that the reaction shows good catalytic activity and adipic acid selectivity under the condition of no solvent. The preparation method disclosed by the invention is simple to operate, the raw materials and the catalyst are cheap and easy to obtain, the catalyst is low in dosage and easy to separate, the cyclicity is excellent, the catalyst can be repeatedly used for many times, and the preparation method is suitable for large-scale production.
The invention also discloses WFe with photo-thermal catalytic activity prepared by the preparation method m La n O x The catalyst, because of adopting the preparation method, realizes the close contact among the tungsten salt, the ferric salt, the lanthanum salt and the like, provides precondition for the high-efficiency electron transfer, and the catalyst contains a small amount of ferric salt and lanthanum salt to further improve the thermal activity of the reaction; due to the introduction of the gel, a large specific surface area is provided in the calcining process, the generation of active species and the adsorption and desorption of a substrate and a product are facilitated, and the catalyst has good catalytic activity.
The invention also discloses the WFe with the photo-thermal catalytic activity m La n O x The application of the catalyst in one-step preparation of adipic acid by photo-thermal concerted catalysis of cyclohexane under the solvent-free condition is proved by experiments, and when the calcination temperature is 450 ℃, the weight ratio of W: fe: la =1:5: WFe at 5 hours 5 La 5 O x The 450 catalyst shows the optimal activity and selectivity for preparing adipic acid by one-step oxidation of cyclohexane in the presence of solvent-free catalyst, which shows that the three-way metal oxide catalyst prepared by the method has excellent activity and selectivity for preparing adipic acid by one-step oxidation of cyclohexane in the presence of solvent-free catalyst.
Drawings
FIG. 1 is a view showing a WFe having photothermal catalytic activity prepared according to the present invention m La n O x XRD pattern of the catalyst;
wherein: a-is obtained through different calcining temperatures; b-is obtained by calcining at 450-750 ℃; c-obtained in different metal proportions; d-different metal ratio 6:4 to 9:1, obtaining;
FIG. 2 shows WFe 5 La 5 O x Catalytic performance results of 5 cycles of the catalyst test 450.
Detailed Description
To make the features and effects of the invention comprehensible to those skilled in the art, general description and definitions shall be provided below with respect to terms and words mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," "including," "having," or similar terms, shall mean "consisting of ..., composition" and "consisting essentially of ..., composition" such as "A comprises a" shall mean "A comprises a and the other" and "A comprises a only".
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention provides a WFe with photo-thermal catalytic activity m La n O x The catalyst is prepared by taking tungsten chloride, ferric chloride hexahydrate and lanthanum nitrate hexahydrate as raw materials, and amorphous WFe is prepared by a special cold gel-roasting method 5 La 5 O x The preparation process of the metal oxide comprises the following steps:
dropwise adding low-temperature epichlorohydrin into a dispersion (adopting low-temperature absolute ethyl alcohol as a solvent) containing tungsten chloride, ferric chloride hexahydrate and lanthanum nitrate hexahydrate, placing the dispersion into a refrigerator for gelling for 3 days, and then drying the gel for 24 hours at 80 ℃; grinding the solid till the powder is placed in a muffle furnace, and calcining for 5 hours at 350-850 ℃ in air atmosphere to obtain WFe m La n O x A catalyst.
Preferably, the molar ratio between the tungsten chloride, ferric chloride hexahydrate, lanthanum nitrate hexahydrate, absolute ethyl alcohol and epichlorohydrin is 9:9:9:347:256, the resulting mixed solution was put into a refrigerator to gel for 3 days.
Preferably, the gel is put into an oven at 80 ℃ for drying for 24 hours to obtain a bulk solid for grinding; transferring the ground solid into a crucible, putting the crucible into a muffle furnace, and respectively heating to 350 ℃,450 ℃, 550 ℃, 650 ℃ at the speed of 5 ℃/min in the air atmosphere,Keeping the temperature at 750 ℃ and 850 ℃ for 5h, and naturally cooling to obtain WFe m La n O x -Y catalyst (Y stands for calcination temperature).
For the WFe prepared m La n O x -Y catalyst is subjected to photothermal oxidation experiment, and the catalyst is used in a one-step adipic acid preparation process by solvent-free photothermal catalytic oxidation of cyclohexane, the process comprising the following steps:
50mgWFe is added into the photo-thermal reaction kettle m La n O x X catalyst, 7.6g cyclohexane;
b. filling 1.0MPa of oxygen into the reaction kettle;
c. the reactor is stirred for 5 hours at 130 ℃, and under the illumination of a xenon lamp (lambda is more than or equal to 400) as a light source, the stirring speed is 90rpm, and then the product adipic acid and the byproduct KA oil (K represents cyclohexanone, A represents cyclohexanol in fact) can be obtained.
The following detailed description is illustrative of the embodiments and is intended to provide further detailed description of the invention, but the scope of the invention is not limited to these embodiments.
Tungsten chloride (chemical formula, WCl) 6 ) CAS number: 13283-01-7.
Ferric chloride hexahydrate (chemical formula, feCl) 3 ·H 2 O), CAS number: 10025-77-1.
Lanthanum nitrate hexahydrate (chemical formula, la (NO) 3 ) 3 ·6H 2 O), CAS number: 100587-94-8.
Absolute ethanol (chemical formula, C) 2 H 5 OH), CAS number: 64-17-5.
Epichlorohydrin (chemical formula, C) 3 H 5 ClO), CAS number: 106-89-8.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten chloride, ferric chloride hexahydrate and lanthanum nitrate hexahydrate in absolute ethyl alcohol at the temperature of-5 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-5 ℃, and cooling the gel for 3 days under the freezing condition of 0 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 9:9:9:350:260, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving heat for 5h, and naturally cooling to obtain WFe 5 La 5 O x -450 catalysts.
Example 2
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-5 ℃, and mixing to obtain a mixed solution;
s2: then adding propylene oxide into the mixed solution under the cooling condition of-3 ℃, and gelling for 3 days under the freezing condition of 1 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 45:72:18:1750:1300, (2 mL of both propylene oxide and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving the temperature for 5h, and naturally cooling to obtain WFe 8 La 2 O x -450 catalysts.
Example 3
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-4 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-4 ℃, and cooling the gel for 3 days under the freezing condition of 5 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 45:63:27:1750, (2 mL of epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving the temperature for 5h, and naturally cooling to obtain WFe 7 La 3 O x -450 catalysts.
Example 4
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at 5 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of 5 ℃, and gelling for 3 days under the freezing condition of 0 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 45:54:36:1750:1300, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 deg.C for 24h to form a solid powder, grinding the solid powder and transferring to a muffle furnace,heating to 450 deg.C at 5 deg.C/min in air atmosphere, maintaining for 5h, and naturally cooling to obtain WFe 6 La 4 O x -450 catalysts.
Example 5
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of 3 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of 3 ℃, and cooling the gel for 3 days under the freezing condition of 0 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 45:81:9:1750:1300 (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving the temperature for 5h, and naturally cooling to obtain WFe 9 La 4 O 1 -450 catalysts.
Example 6
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-1 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-1 ℃, and gelling for 3 days under the freezing condition of 0 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate to the epichlorohydrin to the ethanol is 45:36:54:1750:1300, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving the temperature for 5h, and naturally cooling to obtain WFe 4 La 6 O X -450 catalysisAnd (3) preparing.
Example 7
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-1 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-1 ℃, and gelling for 3 days under the freezing condition of 1 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 45:27:63:1750:1300, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving heat for 5h, and naturally cooling to obtain WFe 3 La 7 O X -450 catalysts.
Example 8
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-5 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-5 ℃, and gelling for 3 days under the freezing condition of 2 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 9:9:9:350:260, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 350 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving heat for 5h, and naturally cooling to obtain WFe 5 La 5 O X -350 catalyst.
Example 9
WFe with photo-thermal catalytic activity m La n O x Preparation of the catalystThe method comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-5 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-5 ℃, and cooling the gel for 3 days under the freezing condition of 3 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 9:9:9:350:260, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving the heat for 5h, and naturally cooling to obtain WFe 5 La 5 O X -550 catalyst.
Example 10
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-4 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-4 ℃, and cooling the gel for 3 days under the freezing condition of 0 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 9:9:9:350:260. (2 mL of epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 650 ℃ at 5 ℃/min in the air atmosphere, preserving the heat for 5h, and naturally cooling to obtain WFe 5 La 5 O X -650 catalyst.
Example 11
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-5 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-5 ℃, and cooling the gel for 3 days under the freezing condition of 0 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 9:9:9:350:260, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 750 ℃ at the speed of 5 ℃/min under the air atmosphere, preserving the heat for 5h, and naturally cooling to obtain WFe 5 La 5 O X -750 catalyst.
Example 12
WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst comprises the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in absolute ethyl alcohol at the temperature of-5 ℃, and mixing to obtain a mixed solution;
s2: then adding epoxy chloropropane into the mixed solution under the cooling condition of-5 ℃, and cooling the gel for 3 days under the freezing condition of 0 ℃ to obtain gel; wherein the molar ratio of the tungsten chloride to the ferric chloride hexahydrate to the lanthanum nitrate hexahydrate is 9:9:9:350:260, (2 mL of both epichlorohydrin and ethanol);
s3: drying the gel in a drying oven at 80 ℃ for 24h to form solid powder, grinding the solid powder, transferring the solid powder into a muffle furnace, heating to 850 ℃ at 5 ℃/min under the air atmosphere, preserving the heat for 5h, and naturally cooling to obtain WFe 5 La 5 O X -850 catalyst.
Example 13
Except for the difference from example 1, in this example, the temperature rising rate of calcination was 8 ℃/min, the constant-temperature calcination time was 7 hours, and the remaining parameters and steps were the same as those of example 1.
Application example 1
To a 100mL photothermal reactor equipped with a polytetrafluoroethylene liner was added 7.6g of cyclohexane and 50mg of WFe 5 La 5 O x 450, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 In the atmosphere, 1The reaction is carried out for 5h at 30 ℃, and the reaction result is shown in Table 1.
Application example 2
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 8 La 2 O x 450, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 3
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 7 La 3 O x 450, under xenon lamp (. Lamda.gtoreq.400) and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 4
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 6 La 4 O x 450, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 5
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 9 La 1 O x 450, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 Reacting for 5 hours at 130 ℃ under the atmosphere, wherein the reaction results are shown in Table 1
Application example 6
To a 100mL photothermal reactor equipped with a polytetrafluoroethylene liner was added 7.6g of cyclohexane and 50mg of WFe 4 La 6 O x 450, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 7
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 3 La 7 O x 450, under xenon lamp (. Lamda.gtoreq.400) and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 8
To a 100mL photothermal reactor equipped with a polytetrafluoroethylene liner was added 7.6g of cyclohexane and 50mg of WFe 5 La 5 O x 350, under xenon lamp (. Lamda.gtoreq.400) and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 9
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 5 La 5 O x 550, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 10
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 5 La 5 O x 650, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 11
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 5 La 5 O x 750, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
Application example 12
A100 mL photothermal reactor with a polytetrafluoroethylene liner was charged with 7.6g of cyclohexane and 50mg of WFe 5 La 5 O x 850, under xenon lamp (lambda.gtoreq.400) irradiation and 1MPa of O 2 The reaction is carried out for 5h at 130 ℃ under the atmosphere, and the reaction result is shown in Table 1.
The rest proportion and WO (OH), feO (OH) and LaO (OH) can not be prepared due to the particularity of the preparation method.
Application example 13
In contrast to application example 1, the reaction time was 4h 2 At a pressure of 2MPa, the WFe having photothermal catalytic activity m La n O x The dosage ratio of the catalyst to the cyclohexane is 60mg:8g, the remaining parameters being the same as in application example 1.
For WFe with photothermal catalytic activity m La n O x XRD analysis is carried out on the catalyst, from the temperature, the catalyst presents an amorphous structure marked by WFeLaO (OH) when not calcined, no obvious crystal face peak is generated on XRD, along with the increase of the calcination temperature (less than or equal to 450 ℃), the appearance of crystal face and a small amount of La are obviously found in the XRD pattern between 20 and 30 DEG 2 (WO 4 ) 3 The crystal planes of (see in detail figure 1 a). However, when the temperature is higher than 450 ℃, WO is apparently found 3 、Fe 2 O 3 、La 2 (WO 4 ) 3 、FeWO 4 The crystal face exposure gradually increases and as the temperature continues to increase, the exposed La 2 (WO 4 ) 3 Crystal planes gradually increased and the crystal bread at 20 deg. -30 deg. also gradually disappeared, indicating that the catalyst crystal planes were gradually stabilized (see figure 1b for details). From the ratio, it is clear that with increasing Fe ratio in the system, more W tends to expose WO 3 Crystal face and Fe is exposed to more Fe 2 O 3 Crystal planes (see figure 1c for details). And La 2 (WO 4 ) 3 The exposed crystal face is relatively stable, and La does not occur 2 (WO 4 ) 3 Excessive exposure of the crystal planes (see FIG. 1d for details). WFe calcined at 450 deg.C 5 La 5 O x -450 has a certain amorphous structure, but in contrast to WFeLaO (OH), WFe 5 La 5 O x 350 and WFe 3 La 7 O x -450，WFe 5 La 5 O x The distinct presence of a portion of the crystalline phase at-450 indicates that at this temperature and metal ratio, a crystalline phase transition has begun to occur.
Table 1 shows WFemLanO with photothermal catalytic activity prepared in the above examples x The catalytic activity of the catalyst. Cyclohexane conversion of pure WFeLaO (OH) was only 4.4% and AA selectivity was 34.77%. After calcination, the reaction mixture was calcined by adjusting the Fe: the La ratio can be found in Fe: la =6:4 highest conversion and relatively low AA selectivity (43.15%); when the ratio of Fe: la =5:5 hour, WFe 5 La 5 O X Conversion of the-450 catalytic system is only slight compared to the formerDecreased, but AA selectivity increased to 61.19%, thus Fe: la =5:5 is a proper proportion. The catalyst calcination temperature was also optimized, and Table 1 shows that WFe prepared at a calcination temperature of 450 deg.C 5 La 5 O X The-450 catalyst has high cyclohexane conversion rate and AA selectivity at the same time. Therefore, fe: la =5: 5. WFe with calcination temperature of 450 DEG C 5 La 5 O X -450 is the optimal catalyst.
Table 1 catalyst activity table a
a The reaction conditions are as follows: reacting for 5 hours at 130 ℃ with a catalyst of 50mg and a xenon lamp (lambda is more than or equal to 400); wherein TC represents a purely thermal reaction and PTC represents a photothermal reaction.
FIG. 2 shows WFe 5 La 5 O x The results of catalytic performance of the catalyst 450 in 5 cycles of the test show that the performance of the catalyst is stable after 5 cycles, the conversion rate of cyclohexane is kept at about 12%, the yield of AA is kept above 7%, and the selectivity of AA is kept above 60%. The results show that WFe 5 La 5 O x The-450 catalyst has excellent cyclicity, can be repeatedly recycled for many times, and is suitable for large-scale production.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. WFe with photo-thermal catalytic activity m La n O x The preparation method of the catalyst is characterized by comprising the following steps:
s1: dissolving tungsten salt, ferric salt and lanthanum salt in ethanol to obtain a mixed solution;
s2: adding a gelling agent into the mixed solution, and cooling to obtain gel;
s3: drying and grinding the gel to obtain a precursor sample; calcining the precursor sample to obtain the WFe with photo-thermal catalytic activity m La n O x A catalyst.
2. The WFe having photothermal catalytic activity of claim 1 m La n O x The preparation method of the catalyst is characterized in that in S1, the using amount ratio of the tungsten salt, the ferric salt, the lanthanum salt hexahydrate and the ethanol is (9-45) mmol: (9 to 81) mmol: (9 to 63) mmol: (260-1750) mmol:2mL; the tungsten salt is tungsten hexachloride, the ferric salt is ferric chloride hexahydrate, and the lanthanum salt is lanthanum nitrate hexahydrate.
3. The WFe having photothermal catalytic activity of claim 1 m La n O x The preparation method of the catalyst is characterized in that in S1, the temperature of the ethanol is-5 ℃; the mixing is carried out in an ultrasonic mixing mode; the temperature during ultrasonic mixing is-5 to 5 ℃.
4. The WFe having photothermal catalytic activity of claim 1 m La n O x The preparation method of the catalyst is characterized in that in S2, the gel is added into the mixed solution at the temperature of-5 ℃, and the mixed solution is cooled at the temperature of 0-5 ℃ to obtain the gel.
5. The WFe with photothermal catalytic activity according to claim 1 m La n O x The preparation method of the catalyst is characterized in that in S2, the molar ratio of the tungsten chloride to the gelling agent is (9-45): (260-1300).
6. The WFe having photothermal catalytic activity of claim 1 m La n O x The preparation method of the catalyst is characterized in that in S2, the gelling agent is epichlorohydrin or epoxypropane; the cooling isThe cooling time is 2 to 3 days.
7. The WFe with photothermal catalytic activity according to claim 1 m La n O x The preparation method of the catalyst is characterized in that in S3, the drying temperature is 70-80 ℃, and the drying time is 12-24 h.
8. The WFe having photothermal catalytic activity of claim 1 m La n O x The preparation method of the catalyst is characterized in that in S3, the calcination process parameters are as follows: heating to 350-850 ℃ at the heating rate of 5-8 ℃/min, and roasting at constant temperature for 5-7 h.
9. WFe with photo-thermal catalytic activity m La n O x The catalyst is characterized in that the WFe with the photo-thermal catalytic activity m La n O x The catalyst adopts WFe with photothermal catalytic activity as defined in any one of claims 1 to 8 m La n O x The catalyst is prepared by a preparation method, wherein m: n = (3.
10. A WFe with photothermal catalytic activity according to claim 9 m La n O x Use of a catalyst, characterized in that the WFe having photothermal catalytic activity m La n O x The catalyst is used for preparing adipic acid by one-step catalysis of cyclohexane under the photo-thermal concerted catalysis under the solvent-free condition, and the reaction conditions are as follows: adding WFe with photo-thermal catalytic activity into a photo-thermal reaction kettle m La n O x Under the illumination of a xenon lamp, the reaction temperature of the catalyst and cyclohexane is 130 ℃, the reaction time is 4-8h 2 The pressure of (A) is 1-2 MPa; the WFe having photothermal catalytic activity m La n O x The dosage ratio of the catalyst to the cyclohexane is (50-60) mg: (7-8) g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211575245.8A CN115970703B (en) | 2022-12-08 | 2022-12-08 | WFe with photo-thermal catalytic activitymLanOxCatalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211575245.8A CN115970703B (en) | 2022-12-08 | 2022-12-08 | WFe with photo-thermal catalytic activitymLanOxCatalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115970703A true CN115970703A (en) | 2023-04-18 |
| CN115970703B CN115970703B (en) | 2024-07-12 |
Family
ID=85960332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211575245.8A Active CN115970703B (en) | 2022-12-08 | 2022-12-08 | WFe with photo-thermal catalytic activitymLanOxCatalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115970703B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1953954A (en) * | 2004-05-18 | 2007-04-25 | 住友化学株式会社 | Process for producing adipic acid |
| CN102040504A (en) * | 2010-10-29 | 2011-05-04 | 华南理工大学 | Method for preparing adipic acid by taking carbon nanotube filled with magnetic iron particles as catalyst |
| CN107999072A (en) * | 2017-12-05 | 2018-05-08 | 广东工业大学 | A kind of photo-thermal catalyst, its preparation method and the method for being catalyzed cyclohexane oxidation |
| WO2018163198A1 (en) * | 2017-03-07 | 2018-09-13 | Council Of Scientific & Industrial Research | A single step process for the oxidation of cyclohexane |
| KR20220072027A (en) * | 2020-11-23 | 2022-06-02 | 한국생산기술연구원 | Spinel structure catalyst for preparing adipic acid and method of preparing adipic acid using same |
| CN117299111A (en) * | 2023-09-25 | 2023-12-29 | 陕西科技大学 | Ternary H x V 2 O 5 /LaVO 4 /WO 3 Catalyst, preparation method and application thereof |
-
2022
- 2022-12-08 CN CN202211575245.8A patent/CN115970703B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1953954A (en) * | 2004-05-18 | 2007-04-25 | 住友化学株式会社 | Process for producing adipic acid |
| CN102040504A (en) * | 2010-10-29 | 2011-05-04 | 华南理工大学 | Method for preparing adipic acid by taking carbon nanotube filled with magnetic iron particles as catalyst |
| WO2018163198A1 (en) * | 2017-03-07 | 2018-09-13 | Council Of Scientific & Industrial Research | A single step process for the oxidation of cyclohexane |
| CN107999072A (en) * | 2017-12-05 | 2018-05-08 | 广东工业大学 | A kind of photo-thermal catalyst, its preparation method and the method for being catalyzed cyclohexane oxidation |
| KR20220072027A (en) * | 2020-11-23 | 2022-06-02 | 한국생산기술연구원 | Spinel structure catalyst for preparing adipic acid and method of preparing adipic acid using same |
| CN117299111A (en) * | 2023-09-25 | 2023-12-29 | 陕西科技大学 | Ternary H x V 2 O 5 /LaVO 4 /WO 3 Catalyst, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| SIVA PRASAD MEKALA ET AL.: ""Green synthesis of cyclohexanone to adipic acid over Fe-W oxides incorporated mesoporous carbon support"", 《CATALYSIS COMMUNICATIONS》, vol. 168, 30 May 2022 (2022-05-30), pages 106466, XP087103518, DOI: 10.1016/j.catcom.2022.106466 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115970703B (en) | 2024-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2010537798A (en) | A method for producing a multicomponent bismuth molybdate catalyst with pH adjustment and a method for producing 1,3-butadiene using the same. | |
| CN108821306B (en) | Preparation method of metal modified hierarchical pore HZSM-5 molecular sieve | |
| CN104549373B (en) | Low-carbon alkanes ammoxidation catalyst | |
| CN111167460A (en) | Preparation of H by direct cracking of natural gas2Catalyst with CNTs (carbon nanotubes), and preparation method and application thereof | |
| CN103418405B (en) | Replenishment catalyst for maintaining stabilization production of acrylonitrile device | |
| CN114105818A (en) | Catalyst for catalyzing butyrolactone to obtain succinonitrile and synthesis method | |
| CN101147867B (en) | Fluidized bed catalyst for oxidation of propene ammonia | |
| CN115970703B (en) | WFe with photo-thermal catalytic activitymLanOxCatalyst, preparation method and application thereof | |
| CN117299111A (en) | Ternary H x V 2 O 5 /LaVO 4 /WO 3 Catalyst, preparation method and application thereof | |
| CN102744090B (en) | Catalyst for ammoxidation preparation of 2,4-dichlorobenzonitrile | |
| CN110801828A (en) | Catalyst for preparing olefin by oxidative dehydrogenation of ethane chemical chain and application of catalyst in oxidative dehydrogenation reaction of ethane | |
| CN107282036A (en) | Low-carbon alkanes ammoxidation catalyst | |
| CN104549224B (en) | Unsaturated nitrile catalyst and preparation method thereof | |
| CN102814193B (en) | Copper-composite molecular sieve catalyst used for synthesis of diethyl carbonate through gas-phase oxidative carbonylation and its preparation method | |
| CN112387272B (en) | Titanium-manganese-cerium co-oxide catalytic material, preparation method thereof and application thereof in synthesis of methacrylonitrile | |
| CN116135308A (en) | Cobalt-doped manganese-based catalyst and preparation and application thereof | |
| CN108671935A (en) | A kind of preparation method and application of the carried copper-base catalyst of surface acidity enhancing | |
| CN100384531C (en) | Fluid-bed catalyst for ammoxidation to prepare acrylonitrile | |
| CN100408172C (en) | Acrylonitrile fluid bed catalyst | |
| CN113976151A (en) | Catalyst and method for synthesizing succinonitrile by tetrahydrofuran | |
| CN112390291A (en) | Preparation method of vanadate cocatalyst material | |
| CN112642418A (en) | CO2Catalyst for preparing ethylene by selective oxidation ethane dehydrogenation and preparation method thereof | |
| CN101306372B (en) | Fluid bed catalyst for acrylonitrile production | |
| CN100566828C (en) | The fluid catalyst of preparation acrylonitrile | |
| CN111229201B (en) | Mo-based catalyst taking scheelite oxide as precursor, and 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 |