WO2020010749A1 - 一种改性氮化碳光催化剂及其制备与光催化氧化木糖合成木糖酸的方法 - Google Patents
一种改性氮化碳光催化剂及其制备与光催化氧化木糖合成木糖酸的方法 Download PDFInfo
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- WO2020010749A1 WO2020010749A1 PCT/CN2018/111942 CN2018111942W WO2020010749A1 WO 2020010749 A1 WO2020010749 A1 WO 2020010749A1 CN 2018111942 W CN2018111942 W CN 2018111942W WO 2020010749 A1 WO2020010749 A1 WO 2020010749A1
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- Prior art keywords
- photocatalyst
- xylose
- acid
- modified
- photocatalytic oxidation
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- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 title claims abstract description 146
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 88
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 title claims abstract description 73
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000003647 oxidation Effects 0.000 title claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 28
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 8
- -1 salt compound Chemical class 0.000 claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 10
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000811 xylitol Substances 0.000 claims description 10
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 10
- 229960002675 xylitol Drugs 0.000 claims description 10
- 235000010447 xylitol Nutrition 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 150000001804 chlorine Chemical class 0.000 claims description 3
- 239000003637 basic solution Substances 0.000 claims description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- QXKAIJAYHKCRRA-UHFFFAOYSA-N D-lyxonic acid Natural products OCC(O)C(O)C(O)C(O)=O QXKAIJAYHKCRRA-UHFFFAOYSA-N 0.000 claims 1
- QXKAIJAYHKCRRA-FLRLBIABSA-N D-xylonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C(O)=O QXKAIJAYHKCRRA-FLRLBIABSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- ACXCKRZOISAYHH-UHFFFAOYSA-N molecular chlorine hydrate Chemical compound O.ClCl ACXCKRZOISAYHH-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000001228 spectrum Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000002186 photoelectron spectrum Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000003247 decreasing effect Effects 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- VQUZNVATTCZTQO-NUNKFHFFSA-N D-xyluronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)C(O)=O VQUZNVATTCZTQO-NUNKFHFFSA-N 0.000 description 5
- VQUZNVATTCZTQO-UHFFFAOYSA-N D-xyluronic acid Natural products O=CC(O)C(O)C(O)C(O)=O VQUZNVATTCZTQO-UHFFFAOYSA-N 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 235000000346 sugar Nutrition 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- MUQYPLLTMWVNSU-UHFFFAOYSA-N 1,6-dimethylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound CC1C=CC=CC1(C)C(O)=O MUQYPLLTMWVNSU-UHFFFAOYSA-N 0.000 description 2
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 2
- 230000036983 biotransformation Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 229960001040 ammonium chloride Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 229940032296 ferric chloride Drugs 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960002337 magnesium chloride Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
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- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
Definitions
- the invention relates to a modified carbonitride photocatalyst, a method for preparing the same and a photocatalytic oxidation of xylose to synthesize xylose, and belongs to the technical field of catalysts and xylose.
- lignocellulose is mainly composed of hemicellulose and cellulose. It can be used in biorefinery to prepare bio-liquid fuels (such as ethanol or butanol) and other bio-based chemicals.
- bio-liquid fuels such as ethanol or butanol
- lignocellulosic raw materials are of great significance to promote the world's low-carbon economy, maintain energy security, and promote ecological and socio-economic development.
- xylose group accounts for a large proportion of lignocellulosic raw materials.
- xylose group can reach 18% to 30%, which accounts for about 30% to 50%. Therefore, the efficient utilization and conversion of xylose are the key factors and prerequisites that affect the economic benefits and commercial production of the industrial production system for biorefining of wood fiber raw materials. At present, we still lack the technologies and methods for efficient biotransformation of xylose, and the use of xylose has become one of the key technical bottlenecks in this field.
- Xylose the most promising xylose biotransformation product, is one of the 30 target products or basic building blocks of chemical industry with the most development potential for biomass refining.
- xylose can be used as complexing agent, chelating agent, plasticizer, glass cleaning agent, metallurgical rust remover, textile bleaching aid, pesticide suspension agent, tanning agent, concrete Dispersant or high-efficiency cement binder, can be used as precursor of some mixtures such as polyamide, polyester, hydrogel, etc.
- xylitol is also an important energetic material, butanitol nitrate precursor 1, The intermediate of 2,4-butanetriol may also be used as a biocide.
- the biological oxidation method has mild production conditions and is environmentally friendly, but requires strict experimental conditions, long cycles, difficult to separate by-products, and affects product purity.
- the intermediate steps of the homogeneous catalytic oxidation process are complicated, there are many by-products, it is difficult to separate the products, it is difficult to recycle the catalyst, and the waste causes great harm to the environment.
- the electrolytic oxidation method solves the disadvantages of multiple by-products and complicated steps in the biological fermentation method and the homogeneous chemical oxidation method, but the energy consumption in industrial production is large and the conditions are not easy to control.
- Heterogeneous catalytic oxidation uses supported noble metal materials as a catalyst and oxygen (or air) as an oxidant. It catalyzes the oxidation of sugars to produce sugar acids and their derivatives under alkaline or neutral conditions, but there are also reaction conditions that require high temperature, high pressure, etc. problem. Therefore, it is of great significance to develop a new simple and efficient method for synthesizing xylitol.
- photocatalytic technology is widely used for carbon dioxide reduction, nitrogen reduction, photolysis of water, and degradation of organic matter due to its advantages such as non-toxicity, safety, good stability, high catalytic activity, fast effect, low energy consumption, and reusability. field.
- the application of photocatalytic technology to the synthesis of xylitol will open up a new way to synthesize xylitol.
- the purpose of the present invention is to provide a photocatalyst (modified carbon nitride photocatalyst) capable of catalyzing the synthesis of xylulic acid and a preparation method thereof in view of the deficiency of the existing xyluric acid synthesis.
- photocatalytic technology is used in the synthesis of xylitol to form a new way of synthesizing xylose.
- nitrogen-containing organic matter precursors urea, thiourea, dicyandiamine, melamine, etc.
- low-melting chlorine salts or chloride hydrates such as aluminum chloride hexahydrate, iron chloride hexahydrate, chloride Zinc, magnesium chloride, ammonium chloride, etc.
- a cyano group is selectively introduced by a certain method to obtain a modified carbon nitride (gC 3 N x ) photocatalytic material.
- the gC 3 N x photocatalytic material of the invention has the advantages of good thermal stability, high catalytic activity, reusability, etc .; its preparation method has good universality and can be produced on a large scale.
- Another object of the present invention is to provide a method for photocatalytic oxidation of xylose to synthesize xylitol using the above photocatalyst.
- gC 3 N x is used as a photocatalyst
- xylose which is the second largest sugar in nature, is oxidized into xyluronic acid through a light reaction.
- the synthesis method of the invention is simple and easy to control, has low cost, and is "green" without pollution.
- the photocatalytic oxidation of gC 3 N x photocatalytic material for the preparation of xylanoic acid has the advantages of non-toxicity, safety, quick response and low energy consumption. It solves the current problems of synthesizing xylic acid by microbial and chemical methods. Synthesis provides a new way.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- the chlorine-containing salt compound is a low-melting salt compound with a melting point ⁇ 550 ° C;
- the nitrogen-containing organic substance precursor in step (1) is one or more of urea, thiourea, dicyandiamine, or melamine;
- the chlorine-containing salt compounds are anhydrous chloride salts and / or chloride hydrates; preferably, aluminum chloride hexahydrate (AlCl 3 ⁇ 6H 2 O), iron chloride hexahydrate (FeCl 3 ⁇ 6H 2 O), aluminum chloride, ferric chloride, zinc chloride, magnesium chloride hexahydrate and ammonium chloride;
- the mass ratio of the nitrogen-containing organic substance precursor and the chlorine-containing salt compound in step (1) is 10: (0-10), preferably 10: (0.5-2);
- the solvent described in step (1) is preferably water
- step (1) The mixing in step (1) is until the nitrogen-containing organic precursor and the chlorine-containing salt compound are completely dissolved; the removal of the solvent refers to evaporation to dryness, and the temperature to dryness is 40 to 100 ° C, preferably 60 to 80 °C.
- the solid product in step (1) may be subjected to a grinding treatment before being calcined.
- the calcining temperature in step (2) is 400-600 ° C, preferably 500-600 ° C; the calcining time is 2-6h.
- the acid in step (2) is hydrochloric acid or hydrofluoric acid, the mass concentration of hydrochloric acid is ⁇ 20%, and the mass concentration of hydrofluoric acid is ⁇ 20%; the acid treatment time is 6-15 hours.
- step (2) The calcination in step (2) is performed in a nitrogen atmosphere.
- the washing in step (2) means washing with water.
- the modified carbonitride photocatalyst is prepared by the above method.
- a method for photocatalytic oxidation of xylose to xyluric acid by modified carbonitride photocatalyst includes the following steps:
- the modified carbonitride photocatalyst photocatalyzes the oxidation of xylose under the conditions of light to obtain xylose acid.
- the alkaline solution is a strong alkaline solution or a weak alkaline solution;
- the strong alkaline solution is one or more of a KOH solution and a NaOH solution, and the weak alkaline solution is a Na 2 CO 3 solution, a NaHCO 3 solution, and K 2
- the alkaline solution is preferably a KOH solution;
- the concentration of the alkaline solution is 0 to 0.1 mol / L, preferably 0.01 to 0.1 mol / L;
- the photocatalytic oxidation time is 15 to 120min; the photocatalytic oxidation temperature is 20 to 60 ° C;
- the mass ratio of the xylose to the modified carbonitride photocatalyst is 0.1 g: (10 to 70) mg;
- the mass-volume ratio of the xylose to the alkaline solution is 0.1 g: (5-20) mL.
- the present invention uses a photocatalyst to catalyze the oxidation of xylose to synthesize xyluronic acid under the conditions of light and alkaline.
- the synthetic route is:
- the photocatalyst gC 3 N x generates electrons and holes under light.
- the holes themselves are oxidizing. They can also react with hydroxide ions in alkaline solutions to generate hydroxide radicals, which also have oxidation. At this time, the oxidizing substances in the system oxidize xylose to xylose acid.
- the gC 3 N x catalyst for photocatalytic oxidation of xylolic acid can be used as a new energy and high-value chemical.
- the present invention has the following advantages and beneficial effects:
- the xylose synthesized by the present invention is a high-value chemical and an important chemical intermediate
- the raw materials for preparing the catalyst of the present invention are relatively inexpensive and readily available, and are suitable for industrial production;
- (4) gC 3 N x prepared by the present invention as a catalyst has the advantages of good thermal stability, high catalytic activity, and good recyclability;
- the present invention utilizes gC 3 N x photocatalyst to photocatalyze the oxidation of xylose to successfully synthesize xylose.
- the synthesis method is safe, non-toxic, quick-acting, and low energy consumption; mild reaction conditions during the synthesis process; the synthesis method of the present invention can Realize industrialized production;
- the present invention utilizes a gC 3 N x photocatalyst to photocatalyze the oxidation of xylose to synthesize xyluronic acid, which has a high yield; the product of the present invention provides an effective way to solve the energy crisis problem.
- Example 1 is an XRD spectrum of a gC 3 N x photocatalyst prepared in Example 1; a: gC 3 N 4 (ie, gC 3 N x -0), b: gC 3 N x -0.005, and c: gC 3 N x -0.05, d: gC 3 N x -0.1, e: gC 3 N x -0.5, f: gC 3 N x -1.0; gC 3 N x -0 means that the amount of the chloride-containing compound is 0, gC 3 N x -0.005 means that the added amount of the chloride-containing compound is 0.005g;
- Example 2 is a FT-IR spectrum of a gC 3 N x photocatalyst prepared in Example 1; a: gC 3 N 4 (ie, gC 3 N x -0), b: gC 3 N x -0.005, and c: gC 3 N x -0.05, d: gC 3 N x -0.1, e: gC 3 N x -0.5, f: gC 3 N x -1.0; gC 3 N x -0 means that the amount of the chloride-containing compound is 0, gC 3 N x -0.005 means that the added amount of the chloride-containing salt compound is 0.005g;
- Example 3 is a PL spectrum of a gC 3 N x photocatalyst prepared in Example 1; a: gC 3 N 4 , b: gC 3 N x -0.05, c: gC 3 N x -0.5, d: gC 3 N x -1.0;
- FIG 4 is a UV-vis-DRS spectra and XPS gC 3 N x prepared in Example photocatalyst; gC 3 N x A photocatalyst which is prepared in Example 1 (gC 3 N 4 (i.e.
- UV-vis-DRS spectrum is the UV-vis-DRS spectrum and photoelectron spectrum of the gC 3 N x photocatalyst prepared in Example 1;
- C is the UV-vis-DRS spectrum and photoelectron spectrum of the gC 3 N x photocatalyst prepared in Example 4 (corresponding to the small graph in the upper right corner);
- D is the UV-vis-DRS spectrum and photoelectron spectrum of the gC 3 N x photocatalyst prepared in Example 5 (corresponding to the small graph in the upper right corner);
- E is the gC 3 N x photocatalyst prepared in Example 7 and Example 8 UV-vis-DRS spectrum and photoelectron spectrum (corresponding to the small top right corner);
- F is the UV-vis-DRS spectrum and photoele
- FIG. 5 is an ESR spectrum of a gC 3 N x photocatalyst prepared in Example 1; where gC 3 N 4 (that is, gC 3 N x -0), and gC 3 N x -0 represents the addition amount of the chloride-containing compound as 0, gC 3 N x -0.5 indicates that the amount of the chloride-containing salt compound is 0.5 g; gC 3 N x -1.0 indicates that the amount of the chloride-containing salt compound is 1 g; control is that no light is applied;
- Example 6 is a SEM image of a gC 3 N x -1.0 photocatalyst prepared in Example 1; A and B are graphs at different magnifications;
- Example 7 is a TEM image of a gC 3 N x -1.0 photocatalyst prepared in Example 1; A, B, and C are diagrams at different magnifications;
- FIG. 8 is a spectrum of the effects of different KOH concentrations, catalyst dosage, light time, and reaction temperature on the photocatalytic oxidation of gC 3 N x to xylolic acid;
- FIG. 9 is a cycle performance chart of the gC 3 N x -1.0 photocatalyst prepared in Example 1.
- FIG. 9 is a cycle performance chart of the gC 3 N x -1.0 photocatalyst prepared in Example 1.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- step (1) (2) calcining the solid product of step (1) at 550 ° C for 4h to obtain a calcined product
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- step (1) The nitrogen-containing organic precursor of step (1) was replaced with thiourea, and the amount of AlCl 3 ⁇ 6H 2 O was changed to 1 g, and the remaining conditions were the same as those in Example 1.
- Step (2) and step (3) are the same as in Example 1.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- step (1) The nitrogen-containing organic precursor of step (1) was replaced with dicyandiamine, and the amount of AlCl 3 ⁇ 6H 2 O was changed to 1 g, and the remaining conditions were the same as in Example 1;
- Step (2) and step (3) are the same as in Example 1.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- step (1) The nitrogen-containing organic precursor of step (1) was changed to melamine, and the amount of AlCl 3 ⁇ 6H 2 O was changed to 1 g, and the remaining conditions were the same as those in Example 1;
- Step (2) and step (3) are the same as in Example 1.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- the chlorine-containing salt compound in step (1) was changed to FeCl 3 ⁇ 6H 2 O, and the amount was maintained at 1 g, and the remaining conditions were the same as in Example 1;
- Step (2) and step (3) are the same as in Example 1.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- the chlorine-containing salt compound in step (1) was changed to MgCl 2 ⁇ 6H 2 O, and the amount was maintained at 1 g, and the remaining conditions were the same as in Example 1;
- Step (2) and step (3) are the same as in Example 1.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- the chlorine-containing salt compound in step (1) was changed to ZnCl 2 , and the amount was maintained at 1 g, and the remaining conditions were the same as those in Example 1.
- Step (2) and step (3) are the same as in Example 1.
- a method for preparing a modified carbon nitride photocatalyst includes the following steps:
- the low-melting chlorine-containing salt compound of step (1) was changed to NH 4 Cl, and the amount was maintained at 1 g, and the remaining conditions were the same as in Example 1;
- Step (2) and step (3) are the same as in Example 1.
- a method for photocatalytic oxidation of xylose to xyluric acid by modified carbonitride photocatalyst includes the following steps:
- step (2) adding a magneton to the system of step (1), and sonicating for 5 min;
- step (3) The system of step (2) is reacted at 30 ° C for 60 min under a xenon lamp;
- step (3) The filtrate obtained in step (3) is subjected to high-performance liquid chromatography to determine the amount of xylose synthesis.
- a method for photocatalytic oxidation of xylose to xyluric acid by modified carbonitride photocatalyst includes the following steps:
- step (1) the concentration of the KOH solution was maintained at 0.05 mol / L, and the amount of the gC 3 N x photocatalyst was 10 mg, 20 mg, 30 mg, 40 mg, 50 mg, 60 mg, and 70 mg, and the others were the same as in Example 9;
- Step (2) and step (3) are the same as in Example 9;
- step (3) The filtrate obtained in step (3) is subjected to high-performance liquid chromatography to determine the amount of xylose synthesis.
- a method for photocatalytic oxidation of xylose to xyluric acid by modified carbonitride photocatalyst includes the following steps:
- step (1) the amount of gC 3 N x photocatalyst was maintained at 50 mg, and the others were the same as those in Example 10.
- Step (2) is the same as in Example 9;
- step (3) the xenon lamp is applied with different illumination times (15min, 30min, 45min, 60min, 90min, 120min);
- step (3) The filtrate obtained in step (3) is subjected to high-performance liquid chromatography to determine the amount of xylose synthesis.
- a method for photocatalytic oxidation of xylose to xyluric acid by modified carbonitride photocatalyst includes the following steps:
- step (1) the amount of gC 3 N x photocatalyst was maintained at 50 mg, and the others were the same as those in Example 10.
- Step (2) is the same as in Example 9;
- the illumination time applied by the xenon lamp in step (3) is 90 minutes, and the reaction temperatures are 20, 30, 40, 50, and 60 ° C, respectively;
- step (3) The filtrate obtained in step (3) is subjected to high-performance liquid chromatography to determine the amount of xylose synthesis.
- a method for photocatalytic oxidation of xylose to xyluric acid by a modified carbonitride photocatalyst includes the following steps:
- step (1) The illumination time in step (1) is maintained at 90 minutes, and the catalyst is changed to a recycled catalyst, and the others are the same as in Example 11;
- Step (2) and step (3) are the same as in Example 9;
- step (3) The filtrate obtained in step (3) is subjected to high-performance liquid chromatography to determine the amount of xylose synthesis.
- a method for photocatalytic oxidation of xylose to xyluric acid by modified carbonitride photocatalyst includes the following steps:
- step (3) The filtrate obtained in step (3) is subjected to high-performance liquid chromatography to determine the amount of xylose synthesis.
- Example 1 is an XRD spectrum of a gC 3 N x photocatalyst prepared in Example 1; a: gC 3 N 4 (ie, gC 3 N x -0), b: gC 3 N x -0.005, and c: gC 3 N x -0.05, d: gC 3 N x -0.1, e: gC 3 N x -0.5, f: gC 3 N x -1.0; gC 3 N x -0 means that the amount of the chloride-containing compound is 0, gC 3 N x -0.005 means that the added amount of the chloride-containing compound is 0.005 g.
- the spectrum of the gC 3 N x catalyst is very similar to the spectrum of the gC 3 N 4 catalyst.
- the basic skeleton of the gC 3 N x catalyst does not have changes happened.
- the gC 3 N 4 catalyst has obvious characteristic peaks at two positions of 13 ° and 27.4 °, and belongs to the (100) and (002) crystal planes of the gC 3 N 4 catalyst, which respectively represent gC In- plane and interfacial stacking of 3 N 4 catalysts.
- Example 2 is a FT-IR spectrum of a gC 3 N x photocatalyst prepared in Example 1; a: gC 3 N 4 (ie, gC 3 N x -0), b: gC 3 N x -0.005, and c: gC 3 N x -0.05, d: gC 3 N x -0.1, e: gC 3 N x -0.5, f: gC 3 N x -1.0; gC 3 N x -0 means that the amount of the chloride-containing compound is 0, gC 3 N x -0.005 means that the added amount of the chloride-containing salt compound is 0.005 g.
- the spectrum of the gC 3 N x catalyst is very similar to the spectrum of the gC 3 N 4 catalyst.
- the basic skeleton of the gC 3 N x catalyst does not have Significant changes have taken place.
- Example 3 is a PL spectrum of a gC 3 N x photocatalyst prepared in Example 1; a: gC 3 N 4 , b: gC 3 N x -0.05, c: gC 3 N x -0.5, d: gC 3 N x -1.0. It was found that with the increase of the amount of AlCl 3 ⁇ 6H 2 O, the PL intensity decreased sharply, which indicated that the recombination of photogenerated carriers in gC 3 N x was effectively suppressed.
- N defects can effectively improve the conductivity of the catalyst, which is conducive to the rapid migration and transport of photo-generated carriers; secondly, the introduction of N defects easily generates surface heterojunctions on the catalyst. , To promote the effective separation of photo-generated carriers, thereby inhibiting their recombination.
- FIG 4 is a UV-vis-DRS spectra and XPS gC 3 N x prepared in Example photocatalyst; gC 3 N x A photocatalyst which is prepared in Example 1 (gC 3 N 4 (i.e.
- UV-vis-DRS spectrum is the UV-vis-DRS spectrum and photoelectron spectrum of the gC 3 N x photocatalyst prepared in Example 1;
- C is the UV-vis-DRS spectrum and photoelectron spectrum of the gC 3 N x photocatalyst prepared in Example 4 (corresponding to the small graph in the upper right corner);
- D is the UV-vis-DRS spectrum and photoelectron spectrum of the gC 3 N x photocatalyst prepared in Example 5 (corresponding to the small graph in the upper right corner);
- E is the gC 3 N x photocatalyst prepared in Example 7 and Example 8 UV-vis-DRS spectrum and photoelectron spectrum (corresponding to the small top right corner);
- F is the UV-vis-DRS spectrum and photoele
- the band gap energy of gC 3 N x samples gradually decreased.
- the decrease of band gap energy can increase the absorption capacity of gC 3 N x samples to visible light, and then improve the photocatalytic performance.
- the band energy of gC 3 N x samples prepared with different nitrogen-containing compound precursors and different low-melting chlorine salts or chloride hydrates under the same conditions will also be significantly reduced, indicating the preparation method of the photocatalyst. It is universal, and can optionally introduce cyano.
- FIG. 5 is an ESR spectrum of a gC 3 N x photocatalyst prepared in Example 1; where gC 3 N 4 (that is, gC 3 N x -0), and gC 3 N x -0 represents the addition amount of the chloride-containing compound as 0, gC 3 N x -0.5 indicates that the added amount of the chloride-containing salt compound is 0.5g; gC 3 N x -1.0 indicates that the added amount of the chloride-containing salt compound is 1g; control is that no light is applied, and the other groups are illuminated for 10min . Found, e - the transfer has not occurred, the detected stronger e - peak signal.
- e - is transferred from the gC 3 N 4 or gC 3 N x TEMPO surface to form TEMPOH, e - signal is reduced.
- the e - signal of gC 3 N x samples weakened.
- FIG. 8 is a graph showing the effect of different KOH concentrations, catalyst dosage, light time, and reaction temperature on the photocatalytic oxidation of gC 3 N x (gC 3 N x -1.0 prepared in Example 1) to xyluronic acid. pH is an important parameter for carbohydrate conversion. The study found that only a trace amount of xylose was observed under neutral conditions. When the KOH concentration is 0.01mol / L, the yield of gC 3 N x to catalyze the oxidation of xyluronic acid to 25.4% under light conditions, but only traces are observed under the same reaction conditions when gC 3 N 4 is used as the photocatalyst.
- the amount of xylose showed that KOH concentration and gC 3 N x had a promoting effect on the conversion of xylose to xylose. Therefore, we studied different concentrations of KOH.
- the KOH concentration was increased to 0.05 mol / L
- the yield of xylose increased from 25.4% to 56.9%.
- the KOH concentration was further increased to 0.06 to 0.10 mol / L
- the yield of xylitol decreased to some extent, which can be attributed to the gradual increase of by-products. Therefore, the optimal KOH concentration in the reaction system is 0.05 mol / L.
- the amount of catalyst is also an important parameter affecting the conversion of xylose.
- the amount of gC 3 N x was more than 50 mg, the yield of xylose decreased to some extent. This may be because the reactants form intermediates on the catalyst surface, which reduces the activation energy of the reaction. Therefore, the amount of the catalyst is preferably 50 mg as the optimal condition for further research on the catalytic process.
- FIG. 9 is a cycle performance chart of the gC 3 N x -1.0 photocatalyst prepared in Example 1.
- FIG. The study found that after the catalyst was recycled 10 times, the conversion of xylose and the yield of xylose could still reach 99% and 97.2% of the initial reaction. This shows that the catalyst has good stability and recycling performance.
- Example 14 The product obtained in Example 14 was detected: the light source was sunlight, the reaction temperature was room temperature, and the sample was detected after 90 minutes of light irradiation. The yield of xylose was 64%. The process of photocatalytic oxidation to prepare xylic acid has certain industrial production potential.
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Abstract
Description
Claims (10)
- 一种改性氮化碳光催化剂的制备方法,其特征在于:包括以下步骤:(1)将含氮有机物前驱体与含氯的盐类化合物在溶剂中混匀,去除溶剂,获得固体产物;所述含氯的盐类化合物为低熔点盐类化合物,熔点≤550℃;(2)将固体产物进行煅烧,酸处理,洗涤,干燥,获得改性氮化碳光催化剂。
- 根据权利要求1所述改性氮化碳光催化剂的制备方法,其特征在于:步骤(1)中所述含氮有机物前驱体为尿素、硫脲、二氰二胺或三聚氰胺中一种以上;所述含氯的盐类化合物为无水的氯盐和/或氯盐水合物。
- 根据权利要求2所述改性氮化碳光催化剂的制备方法,其特征在于:所述含氯的盐类化合物为AlCl 3·6H 2O、FeCl 3·6H 2O、氯化铝、氯化铁、氯化锌、六水氯化镁及氯化铵中一种以上。
- 根据权利要求1所述改性氮化碳光催化剂的制备方法,其特征在于:步骤(1)中所述含氮有机物前驱体与含氯的盐类化合物的质量比为10:(0~10);步骤(2)中所述煅烧的温度为400~600℃。
- 根据权利要求4所述改性氮化碳光催化剂的制备方法,其特征在于:步骤(1)中所述含氮有机物前驱体与含氯的盐类化合物的质量比为10:(0.5~2);步骤(2)中所述煅烧的温度为500~600℃。
- 根据权利要求1所述改性氮化碳光催化剂的制备方法,其特征在于:步骤(1)中所述的溶剂为水;步骤(2)中所述煅烧的时间为2~6h;步骤(2)中所述酸为盐酸或氢氟酸。
- 一种由权利要求1~6任一项所述制备方法得到的改性氮化碳光催化剂。
- 根据权利要求7所述改性氮化碳光催化剂在木糖酸合成中的应用。
- 一种改性氮化碳光催化剂光催化氧化木糖合成木糖酸的方法,其特征在于:包括如下步骤:在碱性溶液中,改性氮化碳光催化剂在光照的条件下光催化氧化木糖,获得木糖酸;所述改性氮化碳光催化剂如权利要求7所定义。
- 根据权利要求9所述改性氮化碳光催化剂光催化氧化木糖合成木糖酸的方法,其特征在于:所述碱性溶液的浓度为0~0.1mol/L;所述光催化氧化的时间为15~120min;光催化氧化的温度为20~60℃;所述木糖与改性氮化碳光催化剂的质量比为0.1g:(10~70)mg。
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