CN114773164B - Method for preparing 2, 5-dimethylphenol by using cellulose - Google Patents
Method for preparing 2, 5-dimethylphenol by using cellulose Download PDFInfo
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- CN114773164B CN114773164B CN202210568685.4A CN202210568685A CN114773164B CN 114773164 B CN114773164 B CN 114773164B CN 202210568685 A CN202210568685 A CN 202210568685A CN 114773164 B CN114773164 B CN 114773164B
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- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000001913 cellulose Substances 0.000 title claims abstract description 97
- 229920002678 cellulose Polymers 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 193
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 171
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 135
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 117
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- 230000003197 catalytic effect Effects 0.000 claims abstract description 89
- 239000013084 copper-based metal-organic framework Substances 0.000 claims abstract description 73
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 52
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002808 molecular sieve Substances 0.000 claims description 30
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000013110 organic ligand Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 239000002028 Biomass Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 142
- 230000033444 hydroxylation Effects 0.000 description 68
- 239000007791 liquid phase Substances 0.000 description 31
- 239000000376 reactant Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 125000003118 aryl group Chemical group 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 21
- 239000003153 chemical reaction reagent Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 238000007233 catalytic pyrolysis Methods 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 13
- 230000009471 action Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- -1 furfurals Chemical class 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000000640 hydroxylating effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Chemical group 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000013130 vanadium-based metal-organic framework Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000002029 lignocellulosic biomass Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical class OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The application provides a method for preparing 2, 5-dimethylphenol by using cellulose, which comprises the following steps: s1, carrying out catalytic cracking reaction on cellulose in a protective atmosphere to obtain an aromatic hydrocarbon intermediate rich in paraxylene; s2, carrying out catalytic hydroxylation reaction on the aromatic hydrocarbon intermediate rich in paraxylene in a hydrogen peroxide atmosphere in the presence of a magnetic catalyst to obtain 2, 5-dimethylphenol; the magnetic catalyst is a copper-based metal organic framework magnetic catalyst modified by ferroferric oxide. The invention realizes the goal of directionally synthesizing the 2, 5-dimethylphenol by the cellulose through technological innovation of catalysts and the like, and has higher yield and selectivity of the 2, 5-dimethylphenol. The method provided by the invention has simple process, converts the cellulose which is rich in resources and renewable into the chemical 2, 5-dimethylphenol with high added value, realizes the high-value comprehensive utilization of biomass resources, and has good economic and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing p-methylbenzaldehyde by using cellulose.
Background
As an important high value added fine chemical, 2, 5-dimethylphenol is widely used for preparing perfumes, medicines, pesticides, resins, dyes and antioxidants. At present, a sulfonation-alkali fusion method is widely adopted in industry to produce 2, 5-dimethylphenol. However, the method has the defects of complex process, serious pollutant emission, difficult product separation and the like, and is disclosed in the literature: synthesis and characterization of bio-inspired diiron complexes and their catalytic activity for direct hydroxylation of aromatic compounds.Wang, X., zhang, T., yang, Q., jiang, S., li, B., eur.J., inorg.chem.5,2015, 817-825).
In order to simplify the process and the like, the research and development of directly hydroxylating paraxylene to prepare the dimethylphenol have important application values. For the hydroxylation of alkylaromatic hydrocarbons, the catalyst used is generally chosen from metal oxide catalysts, zeolite catalysts or metal complex catalysts. However, the selective hydroxylation of alkylaromatic hydrocarbons to produce a single target phenolic chemical is still a challenging task for reasons which may include: the alkyl arene methyl oxidation and the hydroxylation reaction of the aromatic reactant form strong competition, and the selectivity of the target product is reduced. Therefore, although direct hydroxylation of xylene to 2, 5-dimethylphenol has good environmental benefits, improving the yield and selectivity of the target product remains a core problem to be solved.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing 2, 5-dimethylphenol by using cellulose, which can realize the selective synthesis of 2, 5-dimethylphenol by using cellulose, and has the advantages of high yield and selectivity of 2, 5-dimethylphenol, simple process and environmental protection.
The invention provides a method for preparing 2, 5-dimethylphenol by using cellulose, which comprises the following steps:
s1, carrying out catalytic cracking reaction on cellulose in a protective atmosphere to obtain an aromatic hydrocarbon intermediate rich in paraxylene;
s2, carrying out catalytic hydroxylation reaction on the aromatic hydrocarbon intermediate rich in paraxylene in a hydrogen peroxide atmosphere in the presence of a magnetic catalyst to obtain 2, 5-dimethylphenol;
the magnetic catalyst is a copper-based metal organic framework magnetic catalyst modified by ferroferric oxide.
Preferably, in step S1, the para-xylene concentration of the para-xylene enriched aromatic hydrocarbon intermediate is greater than 28 weight percent.
Preferably, in step S1, the catalyst in the catalytic cracking reaction process is an oxide modified molecular sieve.
Preferably, in step S1, the catalyst in the catalytic cracking reaction process is an H-Beta magnetic molecular sieve modified by ferroferric oxide and silicon oxide together.
Preferably, in the step S2, the content of the ferroferric oxide in the magnetic catalyst is 60-80 wt%, and the content of the copper-based metal organic framework material is 20-40 wt%.
Preferably, in step S2, the magnetic catalyst is prepared from ferroferric oxide, a copper source and an organic ligand by a hydrothermal synthesis method.
Preferably, in step S2, the mass ratio of the magnetic catalyst to the aromatic hydrocarbon intermediate rich in para-xylene is 1:9 to 11.
Preferably, in step S2, the mass ratio of the hydrogen peroxide to the aromatic hydrocarbon intermediate rich in para-xylene is 2.5-3.5: 1, wherein the temperature of the catalytic hydroxylation reaction is 75-85 ℃.
In the step S2, the yield of the 2, 5-dimethylphenol reaches 72.5%, and the selectivity of the 2, 5-dimethylphenol reaches 80.2%.
Biomass can be used as the only renewable resource in nature to produce bio-based chemicals, fuels and other materials. Lignocellulosic biomass is the most abundant type of biomass resources with annual output of about 1700 million tons, while cellulose is the most abundant component of lignocellulose, accounting for about 40-60wt% of lignocellulosic biomass (1) . Up to now, efforts have been made to prepare various high value-added chemicals such as aromatic hydrocarbons, furans, furfurals, 5-hydroxymethylfurals, valerolactone, levulinic acid, polyols and lactic acid by conversion of cellulose (2) . Cellulose can be pyrolyzed to form complex oxygenates such as dehydrated monosaccharides, furans, and acids. Further, intermediates produced by pyrolysis of cellulose can be formed into various aromatic compounds on a catalyst by aromatization, deoxygenation and isomerization catalytic cracking, which provides a valuable process for the preparation of aromatic compounds (3) . In addition to aroma compounds, cellulose can also be used to prepare other unique high value chemicals. In addition, the cellulose can be combined with metal, metal oxide or carbon nano material to synthesize a unique functional composite material, and can be used for preparing catalysts, antibacterial materials and energy storage materials (4) 。
The references are in turn: (1) Ma, j, shi, s, jia, x, xia, f, ma, h, gao, j, xu, j, advances in catalytic conversion oflignocellulose to chemicals and liquid fuels.j.energy chem.36,2019,74-86; (2) Liu, y, nie, y, lu, x, zhang, x, he, h, pan, f, zhou, l, liu, x, ji, x, zhang, s, cascade utilization of lignocellulosic biomass to high-value products.green chem.21,2019,3499-3535; (3) Bayu, a., abudula, a., guan, g., reaction pathways and selectivity in chemo-catalytic conversion of biomass-derived carbohydrates to high-value chemicals: a review process. Technology. 196,2019,106162 (4) Liu, y, nie, y, lu, x, zhang, x, he, h, pan, f, zhou, l, liu, x, ji, x, zhang, s, cascade utilization of lignocellulosic biomass to high-value products. Green chem.21,2019,3499-3535.
However, since the reaction path of catalytic conversion of cellulose is difficult to control, the directional preparation of 2, 5-dimethylphenol from cellulose is a great challenge, and the process for selectively preparing 2, 5-dimethylphenol from cellulose has not been reported.
The invention provides a new strategy for directionally preparing 2, 5-dimethylphenol: using cellulose as a starting material, and preferably using a magnetic zeolite catalyst to selectively catalyze and crack the cellulose to obtain an aromatic hydrocarbon intermediate rich in paraxylene; and then selectively hydroxylating the aromatic hydrocarbon intermediate rich in the paraxylene into 2, 5-dimethylphenol under the action of a copper-based metal-organic framework magnetic catalyst. The invention realizes the goal of directionally synthesizing 2, 5-dimethylphenol by cellulose through technological innovation of raw materials, catalysts and the like, and has higher yield and selectivity of the 2, 5-dimethylphenol. The method provided by the invention has simple process, converts the cellulose which is rich in resources and renewable into the chemical 2, 5-dimethylphenol with high added value, realizes the high-value comprehensive utilization of biomass resources, and has good economic and environmental benefits.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for preparing 2, 5-dimethylphenol by using cellulose, which comprises the following steps: s1, carrying out catalytic cracking reaction on cellulose in a protective atmosphere to obtain an aromatic hydrocarbon intermediate rich in paraxylene; s2, carrying out catalytic hydroxylation reaction on the aromatic hydrocarbon intermediate rich in paraxylene in a hydrogen peroxide atmosphere in the presence of a copper-based metal-organic framework magnetic catalyst to obtain 2, 5-dimethylphenol.
The method provided by the invention converts the renewable cellulose with abundant resources into chemicals with high added value, has higher yield and selectivity of 2, 5-dimethylphenol, is simple and easy to implement, effectively realizes the high-valued comprehensive utilization of biomass resources, and has good economic and environmental benefits.
The step S1 of the embodiment of the invention specifically comprises the following steps: in the presence of a catalyst, cellulose is subjected to catalytic cracking reaction in a protective atmosphere to obtain an aromatic hydrocarbon intermediate rich in paraxylene.
The invention takes cellulose as raw material, the cellulose is macromolecular polysaccharide composed of glucose, is a natural macromolecular compound with wide sources, and the production raw material is derived from cheap lignocellulose renewable resources such as wood chips, straws and the like. In the method provided by the embodiment of the present invention, in step S1, the particle size of the cellulose raw material is preferably 0.1 to 1mm, and more preferably 0.2 to 0.5mm. And the protective atmosphere comprises a nitrogen atmosphere and/or a rare gas atmosphere.
In the method provided by the embodiment of the present invention, the catalyst used in the step S1 is denoted as a first catalyst (i.e., a catalytic cracking catalyst) for catalyzing a catalytic cracking reaction of cellulose. The first catalyst can be one or more of oxide modified molecular sieves, the molecular sieve catalyst is specifically an H-Beta molecular sieve, and the modified material of the modified molecular sieve is one or more of silicon oxide and ferroferric oxide.
In some embodiments of the invention, the catalyst during the catalytic cracking reaction is a molecular sieve co-modified with ferric oxide and silica, and in other embodiments is a molecular sieve separately modified with ferric oxide or silica. Preferably, the first catalyst is a molecular sieve magnetic catalyst jointly modified by ferroferric oxide and silicon oxide.
The first catalyst of the embodiment of the invention enables cellulose to carry out cracking reaction by using the catalytic reaction system. For the preferred first catalyst (Fe 3 O 4 /SiO 2 H-Beta), in the H-Beta molecular sieve magnetic catalyst co-modified by ferroferric oxide and silicon oxide, ferroferric oxide (Fe 3 O 4 ) The content of (2) is preferably 4 to 5wt%, and may be specifically 4.0wt%, 4.2wt%, 4.4wt%, 4.6wt%, 4.8wt% or 5.0wt%; silicon oxide (SiO) 2 ) The content of (2) is preferably 20 to 22wt%, and may be specifically 20.0wt%, 20.2wt%, 20.4wt%, 20.6wt%, 20.8wt%, 21.0wt%, 21.2wt%, 21.4wt%, 21.6wt%, 21.8wt% or 22.0wt%; the H-Beta molecular sieve is preferably 73-76 wt%, and may be 73.0wt%, 73.2wt%, 73.4wt%, 73.6wt%, 73.8wt%, 74.0wt%, 74.2wt%, 74.4wt%, 74.6wt%, 74.8wt%, 75.0wt%, 75.2wt%, 75.4wt%, 75.6wt%, 75.8wt% or 76.0wt%.
In the method provided by the embodiment of the present invention, the first catalyst used in the step S1 may be commercially available, and is preferably prepared by using a hydrothermal synthesis method according to the following steps: a) Adding the H-Beta molecular sieve into a solution containing tetraethoxysilane and normal hexane, and stirring at room temperature; b) Sintering the obtained precipitate at 500-600 ℃ to obtain a silicon oxide modified H-Beta molecular sieve precursor; c) Adding a silicon oxide modified H-Beta molecular sieve precursor into an aqueous solution containing ferric chloride, adding ammonia water into the mixed solution, adjusting the pH value to be 10, and stirring at room temperature; the dosage proportion of the H-Beta molecular sieve, the ferric chloride and the tetraethoxysilane is determined according to the content of the H-Beta molecular sieve, the ferroferric oxide and the silicon oxide in the first catalyst to be finally prepared, and the dosage proportion is not limited independently; d) The mixed solution is reacted for 10 to 12 hours at the temperature of about 100 ℃, the precipitate after the reaction is respectively washed by water and ethanol for 3 times, and is dried for 10 to 12 hours at the temperature of 100 to 110 ℃; e) Sintering the dried precipitate at 300-400 ℃ for at least 10 hours to obtain the H-Beta molecular sieve magnetic catalyst jointly modified by ferroferric oxide and silicon oxide.
The modified molecular sieve magnetic catalyst used in some embodiments of the invention may have a specific surface area of 356.8m 2 Per gram, pore volume of 0.25cm 3 And/g, the average particle diameter is 23.7nm.
In the method provided by the embodiment of the present invention, in step S1, the mass ratio of the first catalyst to lignocellulose is preferably 3:1, a step of; the temperature of the catalytic cracking reaction is preferably 450-500 ℃, more preferably 450 ℃; the time for the catalytic cracking reaction is preferably 30 minutes. In certain embodiments, the catalytic cracking of cellulose is performed in a fixed bed reactor under the following reaction conditions: the weight ratio of the catalyst to the cellulose raw material is 3:1, the carrier gas is nitrogen, the pressure is normal pressure, and the temperature is 450 ℃.
The cellulose catalytic cracking specific operation steps of the embodiment of the invention are as follows: introducing a protective atmosphere into the fixed bed reactor; heating the fixed bed reactor to a reaction temperature by using an external heating mode; preferably, the molecular sieve magnetic catalyst (Fe) jointly modified by the ferroferric oxide and the silicon oxide is adopted 3 O 4 /SiO 2 Hbeta) and cellulose in a mass ratio of 3:1, and then injecting the mixture into a central constant temperature zone of a catalytic reactor for reaction; the liquid product obtained by catalytic cracking of cellulose is an aromatic hydrocarbon intermediate rich in paraxylene, and can be collected in a condensing tank through condensation.
In the embodiment of the invention, the main component of the aromatic hydrocarbon intermediate rich in paraxylene is paraxylene, and generally contains aromatic hydrocarbon substances such as benzene, toluene and the like; the concentration of paraxylene in the present invention is preferably more than 28wt%, and specifically may be 29.7wt%,30.5wt%,50.8wt%,59.2wt%,61.5wt%, etc.
According to the embodiment of the invention, the aromatic hydrocarbon intermediate rich in paraxylene is placed in a liquid phase reaction kettle, a magnetic catalyst is added, a reactor is heated to a certain temperature under the protection of protective atmosphere, and a hydrogen peroxide hydroxylation reagent is injected for selective hydroxylation reaction. The aromatic hydrocarbon intermediate rich in paraxylene is subjected to catalytic hydroxylation reaction under the action of a catalyst, and the obtained product is a product mainly containing 2, 5-dimethylphenol.
In the embodiment of the present invention, the magnetic catalyst in the step S2 may be referred to as a second catalyst (i.e. an aromatic hydrocarbon hydroxylation catalyst), and in the presence of the second catalyst, the aromatic hydrocarbon intermediate rich in para-xylene undergoes catalytic hydroxylation reaction in a hydrogen peroxide atmosphere, so that the obtained product is a product mainly comprising 2, 5-dimethylphenol.
In the method provided by the embodiment of the invention, in the step S2, the second catalyst is a ferroferric oxide modified copper-based metal-organic framework magnetic catalyst, which is denoted as Cu-mof@fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably from ferroferric oxide, a copper source and an organic ligand by hydrothermal synthesis. For example, the specific surface area of the second catalyst may be 317.1m 2 Per gram, pore volume of 0.23cm 3 And/g, the average particle diameter is 16.9nm.
The ferroferric oxide modified copper-based metal organic framework magnetic catalyst has magnetism, and the content of the ferroferric oxide in the catalyst is preferably 60-80 wt%, and can be 60.0wt%, 62.5wt%, 65.0wt%, 67.5wt%, 70.0wt%, 72.5wt%, 75.0wt%, 77.5wt% or 80.0wt%; the content of the copper-based metal-organic framework in the magnetic catalyst is preferably 20 to 40wt%, and may be specifically 20.0wt%, 22.5wt%, 25.0wt%, 27.5wt%, 30.0wt%, 32.5wt%, 37.5wt%32.5wt% or 40.0wt%.
In the method provided by the embodiment of the invention, the second catalyst used in the step S2 is preferably prepared by a hydrothermal synthesis method according to the following steps: a) Adding a ferroferric oxide magnetic carrier into an aqueous solution containing copper nitrate and dimethylformamide, and stirring at room temperature; b) Further adding an aqueous solution of a benzene organic ligand of 1,3, 5-tricarboxylic acid, and stirring at room temperature; the dosage proportion of the ferroferric oxide, the dimethylformamide and the 1,3, 5-tricarboxylic acid benzene is determined according to the content of the ferroferric oxide and the copper-based metal organic framework in the second catalyst to be finally prepared, and is not limited independently; c) Reacting the mixed solution in a stainless steel autoclave at 110-120 ℃ for 24 hours; d) And (3) washing the precipitate after the reaction with water and ethanol for 3 times respectively, and drying at 100-110 ℃ for 12 hours to obtain the ferroferric oxide modified copper-based metal-organic framework magnetic catalyst.
In the method provided by the embodiment of the invention, in step S2, the mass ratio of the second catalyst to the aromatic hydrocarbon intermediate rich in paraxylene is 1:9 to 11, preferably 1:10. The mass ratio of the hydrogen peroxide to the aromatic hydrocarbon intermediate rich in paraxylene is preferably 2.5-3.5: 1, more preferably 3:1. The catalytic hydroxylation oxidation reaction temperature is preferably 75-85 ℃, more preferably 80 ℃; the time for the catalytic hydroxylation reaction is preferably 4 hours.
According to the method provided by the invention, cellulose is firstly catalytically cracked into aromatic hydrocarbon intermediates rich in paraxylene, and then 2, 5-dimethylphenol is synthesized through catalytic hydroxylation. Compared with the prior art, the method provided by the invention has at least the following advantages and beneficial technical effects:
the invention takes cellulose as raw material, and uses ferroferric oxide and silicon oxide jointly modified molecular sieve magnetic catalyst and the like as catalyst of catalytic cracking reaction, thereby realizing selective preparation of aromatic hydrocarbon intermediate rich in paraxylene by lignocellulose, wherein the paraxylene selectivity reaches 62.3%, and the yield of paraxylene reaches 27.8%.
In the invention, the ferroferric oxide modified copper-based metal organic framework magnetic catalyst is used as a catalyst for selective hydroxylation reaction, so that the aromatic hydrocarbon intermediate rich in paraxylene prepared by catalytic pyrolysis of cellulose can be selectively converted into biomass-based high-value chemicals mainly containing 2, 5-dimethylphenol, specifically, the yield of 2, 5-dimethylphenol can reach 72.5 percent, and the selectivity of 2, 5-dimethylphenol can reach 80.2 percent.
The catalyst with magnetism is utilized in the catalytic reaction process of the embodiment of the invention, which is beneficial to separating the catalyst from reaction products after the reaction.
In addition, the raw material used in the invention is cellulose, and the raw material has the advantages of abundant resources, environmental protection, regeneration and the like, and the end product is a bio-based high-added value chemical product mainly comprising 2, 5-dimethylphenol, thereby being beneficial to the high-value comprehensive utilization of biomass resources.
For clarity, the following examples are provided in detail. The cellulose used in the examples was derived from Shijia Xinyuan cellulose limited, jinzhou, shijia, hebei province, and the elemental composition included 45.0wt% C, 6.2wt% H, and 48.8wt% O.
Example 1
In this example, a molecular sieve magnetic catalyst co-modified with ferroferric oxide and silica (Fe 3 O 4 /SiO 2 H-Beta) and the effect of catalytic cracking of the cellulosic feedstock.
Fe used 3 O 4 /SiO 2 The H-Beta catalyst is prepared by adopting a conventional hydrothermal synthesis method and comprises the following steps of:
a) 10g H-Beta molecular sieve was added to a solution containing ethyl orthosilicate (9.3 g) and n-hexane (30 g) and stirred at room temperature for 2 hours at 25 ℃; b) Sintering the precipitate at 550 ℃ for 10 hours to obtain a silicon oxide modified H-Beta molecular sieve precursor; c) Adding a silicon oxide modified H-Beta molecular sieve precursor into a water (20 g) solution containing ferric chloride (1.5 g), adding 30wt% ammonia water into the mixed solution, adjusting the pH value to 10, and stirring for 2 hours at the room temperature of 25 ℃; d) Reacting the mixed solution in a stainless steel autoclave for 10 hours at 100 ℃, respectively washing the precipitate after the reaction with deionized water and ethanol for 3 times, and drying for 12 hours at 110 ℃; e) And sintering the dried precipitate for 10 hours at 350 ℃ to obtain the H-Beta molecular sieve magnetic catalyst jointly modified by ferroferric oxide and silicon oxide. In the obtained catalyst, the content of ferroferric oxide is 4.9 weight percent, the content of silicon oxide is 20.1 weight percent, and the content of H-Beta molecular sieve is 75.0 weight percent.
In this example, the catalytic cracking of cellulose is carried out in a fixed bed reactor under the following reaction conditions: the weight ratio of the catalyst to the cellulose raw material is 3:1, the carrier gas is nitrogen, the pressure is normal pressure, and the temperature is 450 ℃.
The cellulose catalytic cracking comprises the following specific operation steps: introducing inert gas nitrogen (the flow rate is 100 mL/min) into the fixed bed reactor; heating the fixed bed reactor to 450 ℃ by using an external heating mode; the molecular sieve magnetic catalyst (Fe 3 O 4 /SiO 2 Mixing the catalyst with cellulose (with the particle size range of 0.2-0.5 mm) according to the mass ratio of 3:1, and then injecting the mixture into a central constant temperature area of a catalytic reactor for catalytic cracking reaction; liquid products obtained by catalytic pyrolysis of cellulose are collected in a condensing tank through condensation, and after 30 minutes of reaction, the collected product components are quantitatively analyzed by using gas chromatography-mass spectrometry.
In this example, a magnetic molecular sieve catalyst co-modified with ferric oxide and silica (Fe 3 O 4 /SiO 2 H-Beta) for catalytic cracking of cellulose, the selectivity of paraxylene is 62.3%, the yield of paraxylene is 27.8%, and the specific results are shown in Table 1.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 ) When the arene obtained by the catalytic pyrolysis of the cellulose is used as a raw material, the arene intermediate rich in paraxylene has the effect of preparing 2, 5-dimethylphenol through selective catalytic hydroxylation.
Cu-MOF@Fe used 3 O 4 The catalyst is prepared by adopting a conventional hydrothermal reaction method and comprises the following specific steps:
a) A ferroferric oxide carrier (9.5 g) was added to a solution of copper nitrate (2.2 g) and dimethylformamide (50 g) in water (50 g), and stirred at room temperature at 25 ℃ for 2 hours;
b) Further, a solution of 1,3, 5-tricarboxylic acid benzene (4 g) in water (50 g) as an organic ligand was added thereto, and stirred at room temperature at 25℃for 5 hours;
c) Reacting the mixed solution in a stainless steel autoclave at 120 ℃ for 24 hours;
d) And (3) washing the precipitate after the reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours to obtain the ferroferric oxide modified copper-based metal-organic framework magnetic catalyst.
In the catalyst obtained, ferroferric oxide (Fe 3 O 4 ) The mass fraction of the copper-based metal organic framework component (Cu-MOF) was 60 wt.%, and the mass fraction of the copper-based metal organic framework component (Cu-MOF) was 40 wt.%. The specific surface area of the catalyst is 317.1m 2 Per gram, pore volume of 0.23cm 3 And/g, the average particle diameter is 16.9nm.
In this example, the selective catalytic hydroxylation of para-xylene-rich aromatic intermediates was carried out in a liquid phase reaction vessel, and the aromatic selective catalytic hydroxylation reactants were derived from the aromatic intermediates obtained by catalytic cracking of cellulose in example 1 (see Table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this example are: cu-MOF@Fe 3 O 4 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1:10; the mass ratio of the hydroxylating reagent hydrogen peroxide to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle to ensure that an aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is prepared in a Cu-MOF@Fe way 3 O 4 Further carrying out selective hydroxylation reaction under the action of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 ) When the aromatic hydrocarbon intermediate is subjected to selective catalytic hydroxylation to prepare 2, 5-dimethylphenol, the yield of the 2, 5-dimethylphenol reaches 72.5%, and the selectivity of the 2, 5-dimethylphenol reaches 80.2%. The specific results are shown in Table 2.
Example 2
In this example, a molecular sieve modified with silica (SiO 2 and/H-Beta) is used as a catalyst, and the cellulose raw material is subjected to catalytic pyrolysis to obtain the effect of the para-xylene aromatic hydrocarbon-rich intermediate.
SiO used 2 The H-Beta catalyst is prepared by adopting a conventional hydrothermal synthesis method and comprises the following steps of: a) 10g H-Beta molecular sieve was added to a solution containing ethyl orthosilicate (8.6 g) and n-hexane (30 g) and stirred at room temperature for 2 hours at 25 ℃; b) Sintering the precipitate at 550 ℃ for 10 hours to obtain a silicon oxide modified H-Beta molecular sieve catalyst; the catalyst obtained had a silica content of 19.8% by weight and an H-Beta molecular sieve content of 80.2% by weight.
In this example, the catalytic cracking of cellulose is carried out in a fixed bed reactor under the following reaction conditions: the weight ratio of the catalyst to the cellulose raw material is 3:1, the carrier gas is nitrogen, the pressure is normal pressure, and the temperature is 450 ℃.
The cellulose catalytic cracking comprises the following specific operation steps: introducing inert gas nitrogen (the flow rate is 100 mL/min) into the fixed bed reactor; heating the fixed bed reactor to 450 ℃ by using an external heating mode; the above silica-modified molecular sieve catalyst (SiO 2 mixing/H-Beta) and cellulose (with the particle size range of 0.2-0.5 mm) according to the mass ratio of 3:1, and then injecting the mixture into a central constant temperature area of a catalytic reactor for catalytic cracking reaction; liquid products obtained by catalytic pyrolysis of cellulose are collected in a condensing tank through condensation, and after 30 minutes of reaction, the collected product components are quantitatively analyzed by using gas chromatography-mass spectrometry.
In this example, when the catalytic cracking of cellulose was carried out using a silica-modified molecular sieve catalyst, the selectivity for paraxylene was 59.2%, and the yield of paraxylene was 24.2%, and the specific results are shown in Table 1.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 ) When the aromatic hydrocarbon obtained by the catalytic pyrolysis of the cellulose is used as a raw material, the aromatic hydrocarbon rich in paraxyleneThe effect of preparing 2, 5-dimethylphenol by selectively catalyzing hydroxylation of the intermediate.
In this example, cu-MOF@Fe was used 3 O 4 The catalyst preparation method and its composition were the same as in example 1.
In this example, the selective catalytic hydroxylation of para-xylene-rich aromatic intermediates was carried out in a liquid phase reaction vessel, and the aromatic selective catalytic hydroxylation reactants were derived from the aromatic intermediates obtained by catalytic cracking of cellulose in this example (see Table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this example are: cu-MOF@Fe 3 O 4 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1:10; the mass ratio of the hydroxylating reagent hydrogen peroxide to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle to ensure that an aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is prepared in a Cu-MOF@Fe way 3 O 4 Further carrying out selective hydroxylation reaction under the action of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 ) When the aromatic hydrocarbon intermediate is subjected to selective catalytic hydroxylation to prepare 2, 5-dimethylphenol, the yield of the 2, 5-dimethylphenol reaches 67.0%, the selectivity of the 2, 5-dimethylphenol reaches 76.0%, and specific results are shown in Table 2.
Example 3
In this example, the effect of catalytic cracking using a molecular sieve catalyst (H-Beta) and a cellulosic feedstock was first examined.
In this example, the HBeta catalyst used was from the catalyst plant of the university of se, south opening. The cellulose catalytic cracking is carried out in a fixed bed reactor, and the reaction conditions are as follows: the weight ratio of the catalyst to the cellulose raw material is 3:1, the carrier gas is nitrogen, the pressure is normal pressure, and the temperature is 450 ℃.
The cellulose catalytic cracking comprises the following specific operation steps: introducing inert gas nitrogen (the flow rate is 100 mL/min) into the fixed bed reactor; heating the fixed bed reactor to 450 ℃ by using an external heating mode; mixing the Hbeta catalyst and cellulose (the particle size range is 0.2-0.5 mm) according to the mass ratio of 3:1, and then injecting the mixture into a central constant temperature area of a catalytic reactor for catalytic cracking reaction; liquid products obtained by catalytic pyrolysis of cellulose are collected in a condensing tank through condensation, and after 30 minutes of reaction, the collected product components are quantitatively analyzed by using gas chromatography-mass spectrometry.
In this example, when the H-Beta catalyst was used for catalytic cracking of cellulose, the selectivity for paraxylene was 29.7%, and the yield of paraxylene was 12.5%, and the specific results are shown in Table 1.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 ) When the arene obtained by the catalytic pyrolysis of the cellulose is used as a raw material, the arene intermediate rich in paraxylene has the effect of preparing 2, 5-dimethylphenol through selective catalytic hydroxylation.
In this example, cu-MOF@Fe was used 3 O 4 The catalyst preparation method and its composition were the same as in example 1.
In this example, the selective catalytic hydroxylation of para-xylene-rich aromatic intermediates was carried out in a liquid phase reaction vessel, and the aromatic selective catalytic hydroxylation reactants were derived from the aromatic intermediates obtained by catalytic cracking of cellulose in this example (see Table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this example are: cu-MOF@Fe 3 O 4 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1:10; hydroxylation reagent hydrogen peroxide and rich p-dimethylThe mass ratio of the aromatic hydrocarbon intermediate of benzene is 3:1, the catalytic hydroxylation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle to ensure that an aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is prepared in a Cu-MOF@Fe way 3 O 4 Further carrying out selective hydroxylation reaction under the action of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 ) When the aromatic hydrocarbon intermediate is subjected to selective catalytic hydroxylation to prepare 2, 5-dimethylphenol, the yield of 2, 5-dimethylphenol is 38.5%, the selectivity of 2, 5-dimethylphenol is 45.9%, and specific results are shown in Table 2.
In this example, the effect of preparing para-xylene-rich aromatic intermediates by catalytic cracking of cellulose using H-Beta molecular sieves as catalysts was also examined. The results are summarized in Table 1.
TABLE 1 results of catalytic cracking of cellulose to aromatic intermediates
As can be seen from table 1, the cellulose is subjected to catalytic cracking, deoxidizing, aromatizing, isomerizing and other reactions under the action of the first catalyst (catalytic cracking catalyst) to obtain an aromatic hydrocarbon intermediate mainly comprising para-xylene. In all catalysts examined, the ferroferric oxide and the silicon oxide were modified togetherMolecular sieve magnetic catalyst (Fe) 3 O 4 /SiO 2 H-Beta) gives the greatest para-xylene selectivity and yield, with a para-xylene selectivity of 62.3% and a para-xylene yield of 27.8%.
In addition, the use of a catalyst having magnetic properties facilitates separation of the catalyst from the reaction products after the reaction.
Example 4
In this example, an aromatic hydrocarbon intermediate obtained by catalytic cracking of cellulose in example 1 was examined as a raw material, and a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 -a) the effect of selective catalytic hydroxylation of aromatic intermediates enriched in para-xylene to produce 2, 5-dimethylphenol.
In this example, cu-MOF@Fe was used 3 O 4 The catalyst A is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: a) A ferroferric oxide carrier (9.5 g) was added to a solution of copper nitrate (2.0 g) and dimethylformamide (50 g) in water (50 g), and stirred at room temperature at 25 ℃ for 2 hours; b) Further, a solution of 1,3, 5-tricarboxylic acid benzene (4 g) in water (50 g) as an organic ligand was added thereto, and stirred at room temperature at 25℃for 5 hours; c) Reacting the mixed solution in a stainless steel autoclave at 120 ℃ for 24 hours; d) And (3) washing the precipitate after the reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours to obtain the ferroferric oxide modified copper-based metal-organic framework magnetic catalyst. In the catalyst obtained, ferroferric oxide (Fe 3 O 4 ) The mass fraction of the copper-based metal organic framework component (Cu-MOF) was 65.1wt%, and the mass fraction was 34.9wt%.
In this example, the selective catalytic hydroxylation of para-xylene-rich aromatic intermediates was carried out in a liquid phase reaction vessel, and the aromatic selective catalytic hydroxylation reactants were derived from the aromatic intermediates obtained by catalytic cracking of cellulose in example 1 (see Table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this example are: cu-MOF@Fe 3 O 4 The mass ratio of catalyst a to para-xylene-rich intermediate is 1:10; hydroxylation testThe mass ratio of the hydrogen peroxide to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle to ensure that an aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is prepared in a Cu-MOF@Fe way 3 O 4 -a further selective hydroxylation reaction under the action of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 -A) when the aromatic hydrocarbon intermediate is subjected to selective catalytic hydroxylation to prepare 2, 5-dimethylphenol, the yield of 2, 5-dimethylphenol reaches 71.9%, the selectivity of 2, 5-dimethylphenol reaches 80.3%, and the specific results are shown in Table 2.
Example 5
In this example, an aromatic hydrocarbon intermediate obtained by catalytic cracking of cellulose in example 1 was examined as a raw material, and a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 -B) effect of selective catalytic hydroxylation of aromatic hydrocarbon intermediates enriched in para-xylene to produce 2, 5-dimethylphenol.
In this example, cu-MOF@Fe was used 3 O 4 The catalyst B is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: a) A ferroferric oxide carrier (9.5 g) was added to a solution of copper nitrate (1.7 g) and dimethylformamide (50 g) in water (50 g), and stirred at room temperature at 25 ℃ for 2 hours; b) Further, a solution of 1,3, 5-tricarboxylic acid benzene (4 g) in water (50 g) as an organic ligand was added thereto, and stirred at room temperature at 25℃for 5 hours; c) Reacting the mixed solution in a stainless steel autoclave at 120 ℃ for 24 hours; d) Respectively utilizing deionized water to the precipitate after reaction Washing with ethanol for 3 times, and drying at 110 ℃ for 12 hours to obtain the ferroferric oxide modified copper-based metal-organic framework magnetic catalyst. In the catalyst obtained, ferroferric oxide (Fe 3 O 4 ) The mass fraction of the copper-based metal organic framework component (Cu-MOF) was 70.2wt%, and the mass fraction of the copper-based metal organic framework component (Cu-MOF) was 29.8wt%.
In this example, the selective catalytic hydroxylation of para-xylene-rich aromatic intermediates was carried out in a liquid phase reaction vessel, and the aromatic selective catalytic hydroxylation reactants were derived from the aromatic intermediates obtained by catalytic cracking of cellulose in example 1 (see Table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this example are: cu-MOF@Fe 3 O 4 The mass ratio of catalyst B to p-xylene-rich intermediate is 1:10; the mass ratio of the hydroxylating reagent hydrogen peroxide to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle to ensure that an aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is prepared in a Cu-MOF@Fe way 3 O 4 -B further carrying out a selective hydroxylation reaction in the presence of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 -B) when the aromatic hydrocarbon intermediate is subjected to selective catalytic hydroxylation to prepare 2, 5-dimethylphenol, the yield of 2, 5-dimethylphenol reaches 68.1%, the selectivity of 2, 5-dimethylphenol reaches 78.0%, and the specific results are shown in Table 2.
Example 6
In this example, the catalytic cracking of cellulose obtained in example 1 was examinedUses a copper-based metal-organic framework magnetic catalyst (Cu-MOF@Fe) modified by ferroferric oxide as a raw material 3 O 4 -C) effect of selective catalytic hydroxylation of aromatic hydrocarbon intermediates enriched in para-xylene to produce 2, 5-dimethylphenol.
In this example, cu-MOF@Fe was used 3 O 4 The catalyst C is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: a) A ferroferric oxide carrier (9.5 g) was added to a solution of copper nitrate (1.2 g) and dimethylformamide (50 g) in water (50 g), and stirred at room temperature at 25 ℃ for 2 hours; b) Further, a solution of 1,3, 5-tricarboxylic acid benzene (4 g) in water (50 g) as an organic ligand was added thereto, and stirred at room temperature at 25℃for 5 hours; c) Reacting the mixed solution in a stainless steel autoclave at 120 ℃ for 24 hours; d) And (3) washing the precipitate after the reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours to obtain the ferroferric oxide modified copper-based metal-organic framework magnetic catalyst. In the catalyst obtained, ferroferric oxide (Fe 3 O 4 ) Is 79.7wt% and the mass fraction of the copper-based metal organic framework component (Cu-MOF) is 20.3wt%.
In this example, the selective catalytic hydroxylation of para-xylene-rich aromatic intermediates was carried out in a liquid phase reaction vessel, and the aromatic selective catalytic hydroxylation reactants were derived from the aromatic intermediates obtained by catalytic cracking of cellulose in example 1 (see Table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this example are: cu-MOF@Fe 3 O 4 The mass ratio of catalyst C to para-xylene-rich intermediate is 1:10; the mass ratio of the hydroxylating reagent hydrogen peroxide to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase by using a syringe pumpThe reaction kettle is arranged; stirring reactants by opening a stirrer in a reaction kettle to ensure that an aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is prepared in a Cu-MOF@Fe way 3 O 4 -C further carrying out a selective hydroxylation reaction in the presence of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this example, a copper-based metal-organic framework magnetic catalyst modified with ferroferric oxide (Cu-MOF@Fe 3 O 4 When the aromatic hydrocarbon intermediate is subjected to selective catalytic hydroxylation to prepare 2, 5-dimethylphenol, the yield of the 2, 5-dimethylphenol reaches 50.1%, the selectivity of the 2, 5-dimethylphenol reaches 72.8%, and the specific results are shown in Table 2.
Comparative example 1
In this comparative example, the effect of selective catalytic hydroxylation of an aromatic hydrocarbon intermediate rich in para-xylene to produce 2, 5-dimethylphenol using a copper-based metal organic framework catalyst (Cu-MOF) as a raw material was examined using the aromatic hydrocarbon intermediate obtained by catalytic cracking of cellulose in example 1.
The Cu-MOF catalyst is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: a) Copper nitrate (2.2 g) was added to a water (50 g) solution of dimethylformamide (50 g), and stirred at room temperature at 25℃for 2 hours; b) Further, a solution of 1,3, 5-benzenetricarboxylic acid (4 g) in water (100 g) as an organic ligand was added thereto, and stirred at room temperature at 25℃for 5 hours; c) Reacting the mixed solution in a stainless steel autoclave at 120 ℃ for 24 hours; d) And (3) washing the precipitate after the reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours to obtain the copper-based metal-organic framework magnetic catalyst. Among the catalysts obtained, copper-based metal organic framework Cu-MOF catalysts were obtained. The copper-based metal organic framework catalyst contained 38.7wt% of copper.
In this comparative example, the selective catalytic hydroxylation of para-xylene-rich aromatic hydrocarbon intermediates was carried out in a liquid phase reaction vessel, and the aromatic hydrocarbon selective catalytic hydroxylation reactants were derived from the aromatic hydrocarbon intermediates obtained by catalytic cracking of cellulose in example 1 (see table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this comparative example are: the mass ratio of the Cu-MOF catalyst to the intermediate rich in paraxylene is 1:10; the mass ratio of the hydrogen peroxide (hydroxylating reagent) to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation oxidation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; the reactor was heated to 80 ℃ under an inert gas nitrogen atmosphere. Slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle, and further carrying out arene selective hydroxylation reaction on an arene intermediate obtained by catalytic pyrolysis of cellulose under the action of a Cu-MOF catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this comparative example, when 2, 5-dimethylphenol was prepared by selective catalytic hydroxylation of an aromatic hydrocarbon intermediate using a copper-based metal-organic framework catalyst (Cu-MOF), the yield of 2, 5-dimethylphenol was 70.2% and the selectivity of 2, 5-dimethylphenol was 81.6%, with specific results shown in Table 2.
Comparative example 2
In this comparative example, an aromatic hydrocarbon intermediate obtained by catalytic cracking of cellulose in example 1 was examined as a raw material, and a ferroferric oxide catalyst (Fe 3 O 4 ) During the process, the aromatic hydrocarbon intermediate rich in paraxylene has the effect of preparing 2, 5-dimethylphenol through selective catalytic hydroxylation.
Fe used 3 O 4 The catalyst is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: feCl is added 3 (20g) Adding into 100g deionized water, and stirring at 25deg.C for 2 hr at room temperature; b) Adding ammonia water into the mixed solution, adjusting the pH value to 10, and stirring for 2 hours; c) Reacting the mixed solution in a stainless steel autoclave at 100 ℃ for 10 hours; d) Washing the precipitate after reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours; e) Sintering the precipitate at 350 ℃ for 10 hours to obtain Fe 3 O 4 A catalyst.
In this comparative example, the selective catalytic hydroxylation of para-xylene-rich aromatic hydrocarbon intermediates was carried out in a liquid phase reaction vessel, and the aromatic hydrocarbon selective catalytic hydroxylation reactants were derived from the aromatic hydrocarbon intermediates obtained by catalytic cracking of cellulose in example 1 (see table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this comparative example are: fe (Fe) 3 O 4 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1:10; the mass ratio of the hydrogen peroxide hydroxylation reagent to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation oxidation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle to ensure that an aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is in Fe 3 O 4 Further carrying out aromatic hydrocarbon selective hydroxylation reaction under the action of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this comparative example, fe is used 3 O 4 When the catalyst is used for preparing 2, 5-dimethylphenol by carrying out selective catalytic hydroxylation on an aromatic hydrocarbon intermediate, the yield of the 2, 5-dimethylphenol is 6.5%, the selectivity of the 2, 5-dimethylphenol is 28.3%, and specific results are shown in Table 2.
Comparative example 3
In this comparative example, the effect of selective catalytic hydroxylation of an aromatic hydrocarbon intermediate rich in para-xylene to produce 2, 5-dimethylphenol using a vanadium-based metal organic framework catalyst (V-MOF) using the aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose in example 1 as a raw material was examined.
The V-MOF catalyst is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: a) Vanadium chloride (2.6 g) was added to a solution of dimethylformamide (50 g) in water (50 g), and stirred at room temperature at 25℃for 2 hours; b) Further, a solution of 1,3, 5-benzenetricarboxylic acid (4 g) in water (100 g) as an organic ligand was added thereto, and stirred at room temperature at 25℃for 5 hours; c) Reacting the mixed solution in a stainless steel autoclave at 120 ℃ for 24 hours; d) And (3) washing the precipitate after the reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours to obtain the vanadium-based metal-organic framework magnetic catalyst. Among the catalysts obtained, vanadium-based metal organic framework V-MOF catalysts were obtained. The vanadium content in the vanadium-based metal organic framework catalyst was 39.3wt%.
In this comparative example, the selective catalytic hydroxylation of para-xylene-rich aromatic hydrocarbon intermediates was carried out in a liquid phase reaction vessel, and the aromatic hydrocarbon selective catalytic hydroxylation reactants were derived from the aromatic hydrocarbon intermediates obtained by catalytic cracking of cellulose in example 1 (see table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this comparative example are: the mass ratio of the V-MOF catalyst to the p-xylene-rich intermediate is 1:10; the mass ratio of the hydrogen peroxide (hydroxylating reagent) to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation oxidation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; the reactor was heated to 80 ℃ under an inert gas nitrogen atmosphere. Slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring reactants by opening a stirrer in a reaction kettle, and further carrying out arene selective hydroxylation reaction on an arene intermediate obtained by catalytic pyrolysis of cellulose under the action of a V-MOF catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this comparative example, the 2, 5-dimethylphenol was produced by selective catalytic hydroxylation of an aromatic hydrocarbon intermediate using a vanadium-based metal organic framework catalyst (V-MOF) in a yield of 30.4% and a selectivity of 66.0% for 2, 5-dimethylphenol, with the specific results shown in Table 2.
Comparative example 4
In this comparative example, the test was conductedThe use of a vanadium pentoxide catalyst (V) 2 O 5 ) During the process, the aromatic hydrocarbon intermediate rich in paraxylene has the effect of preparing 2, 5-dimethylphenol through selective catalytic hydroxylation.
V used 2 O 5 The catalyst is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: vanadium chloride (20 g) was added to 100g deionized water and stirred at 25 ℃ for 2 hours at room temperature; b) Adding ammonia water into the mixed solution, adjusting the pH value to 10, and stirring for 2 hours; c) Reacting the mixed solution in a stainless steel autoclave at 100 ℃ for 10 hours; d) Washing the precipitate after reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours; e) Sintering the precipitate at 350deg.C for 10 hr to obtain V 2 O 5 A catalyst.
In this comparative example, the selective catalytic hydroxylation of para-xylene-rich aromatic hydrocarbon intermediates was carried out in a liquid phase reaction vessel, and the aromatic hydrocarbon selective catalytic hydroxylation reactants were derived from the aromatic hydrocarbon intermediates obtained by catalytic cracking of cellulose in example 1 (see table 1).
The conditions for the selective catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate employed in this comparative example are: v (V) 2 O 5 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1:10; the mass ratio of the hydrogen peroxide hydroxylation reagent to the aromatic hydrocarbon intermediate rich in paraxylene is 3:1, the catalytic hydroxylation oxidation reaction temperature is 80 ℃.
The operation steps of the catalytic hydroxylation reaction of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of an aromatic hydrocarbon intermediate reactant is 100g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding a hydrogen peroxide hydroxylation reagent (300 g) into the liquid phase reaction kettle by using a syringe pump; stirring the reactant by opening a stirrer in the reaction kettle to ensure that the aromatic hydrocarbon intermediate obtained by catalytic pyrolysis of cellulose is in V 2 O 5 Further carrying out aromatic hydrocarbon selective hydroxylation reaction under the action of a catalyst; after 4 hours of reaction, the product was quantitatively analyzed by chromatography-mass spectrometer.
In this comparative example, V was used 2 O 5 When the catalyst is used for preparing 2, 5-dimethylphenol by carrying out selective catalytic hydroxylation on an aromatic hydrocarbon intermediate, the yield of the 2, 5-dimethylphenol is 12.5%, the selectivity of the 2, 5-dimethylphenol is 36.8%, and specific results are shown in Table 2.
TABLE 2 results of catalytic hydroxylation of aromatic intermediates to 2, 5-dimethylphenol
As can be seen from Table 2, the aromatic hydrocarbon intermediate rich in paraxylene is subjected to catalytic hydroxylation reaction under the action of a catalyst, and the obtained product is a product mainly comprising 2, 5-dimethylphenol; of all catalysts examined, the ferroferric oxide modified copper-based metal-organic framework magnetic catalyst (Cu-MOF@Fe 3 O 4 ) The method has the best p-xylene hydroxylation activity and 2, 5-dimethylphenol selectivity, the yield of the 2, 5-dimethylphenol reaches 72.5 percent, and the selectivity of the 2, 5-dimethylphenol reaches 80.2 percent.
In addition, the use of a catalyst having magnetic properties facilitates separation of the catalyst from the reaction products after the reaction.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. A method for preparing 2, 5-dimethylphenol by using cellulose, which is characterized by comprising the following steps:
s1, carrying out catalytic cracking reaction on cellulose in a protective atmosphere to obtain an aromatic hydrocarbon intermediate rich in paraxylene; the para-xylene concentration of the para-xylene-enriched aromatic hydrocarbon intermediate is greater than 28wt%; the catalyst in the catalytic cracking reaction process is an oxide modified molecular sieve;
s2, carrying out catalytic hydroxylation reaction on the aromatic hydrocarbon intermediate rich in paraxylene in a hydrogen peroxide atmosphere in the presence of a magnetic catalyst to obtain 2, 5-dimethylphenol;
The magnetic catalyst is a copper-based metal organic framework magnetic catalyst modified by ferroferric oxide; the content of the ferroferric oxide in the magnetic catalyst is 60-80 wt%, and the content of the copper-based metal organic framework material is 20-40 wt%; the magnetic catalyst is prepared from ferroferric oxide, a copper source and an organic ligand through a hydrothermal synthesis mode.
2. The method according to claim 1, wherein in the step S1, the catalyst in the catalytic cracking reaction is H-Beta magnetic molecular sieve co-modified by ferroferric oxide and silicon oxide.
3. The method according to claim 1, wherein in step S2, the mass ratio of the magnetic catalyst to the para-xylene-rich aromatic hydrocarbon intermediate is 1:9 to 11.
4. The method according to claim 1, wherein in the step S2, the mass ratio of the hydrogen peroxide to the aromatic hydrocarbon intermediate rich in para-xylene is 2.5-3.5: 1, wherein the temperature of the catalytic hydroxylation reaction is 75-85 ℃.
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