CN114920632A - Method for preparing p-tolualdehyde by using wood chips - Google Patents
Method for preparing p-tolualdehyde by using wood chips Download PDFInfo
- Publication number
- CN114920632A CN114920632A CN202210568041.5A CN202210568041A CN114920632A CN 114920632 A CN114920632 A CN 114920632A CN 202210568041 A CN202210568041 A CN 202210568041A CN 114920632 A CN114920632 A CN 114920632A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tolualdehyde
- xylene
- reaction
- wood chips
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002023 wood Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 54
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 176
- 239000003054 catalyst Substances 0.000 claims abstract description 165
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 76
- 230000003197 catalytic effect Effects 0.000 claims abstract description 71
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 27
- -1 ferroferric oxide modified chromium hydroxide Chemical class 0.000 claims abstract description 16
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 35
- 239000002808 molecular sieve Substances 0.000 claims description 34
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 18
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000001844 chromium Chemical class 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 22
- 239000000126 substance Substances 0.000 abstract description 20
- 239000002028 Biomass Substances 0.000 abstract description 14
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 121
- 238000004523 catalytic cracking Methods 0.000 description 58
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 57
- 230000003647 oxidation Effects 0.000 description 43
- 125000003118 aryl group Chemical group 0.000 description 31
- 239000007791 liquid phase Substances 0.000 description 26
- 239000000376 reactant Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000011651 chromium Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000001913 cellulose Substances 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 12
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 229920005610 lignin Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 4
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 239000002029 lignocellulosic biomass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229940040102 levulinic acid Drugs 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- LXMQZGGLHVSEBA-UHFFFAOYSA-N chromium;trihydrate Chemical compound O.O.O.[Cr] LXMQZGGLHVSEBA-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 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
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/76—Iron group metals or copper
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- 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
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a method for preparing p-tolualdehyde by using wood chips, which comprises the following steps: s1) carrying out catalytic pyrolysis reaction on wood chips serving as a raw material in a protective atmosphere to obtain an intermediate rich in p-xylene; s2) carrying out catalytic oxidation reaction on the intermediate rich in p-xylene in the presence of a ferroferric oxide modified chromium hydroxide magnetic catalyst in a hydrogen peroxide atmosphere to obtain p-tolualdehyde. The invention improves the yield and selectivity of p-tolualdehyde by innovating designs of catalysts and the like, and effectively realizes the aim of directionally synthesizing p-tolualdehyde by wood chip biomass. The adopted heterogeneous catalyst is prepared by magnetic design, so that the difficulty in separating the catalyst from a reaction product is solved. The invention converts the sawdust raw material which is rich in resources, low in price and renewable into chemicals with high added value, thereby realizing high-valued comprehensive utilization of biomass resources, and the method is simple and convenient, the product is easy to separate, and the economic and environmental benefits are good.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing p-tolualdehyde by using wood chips.
Background
P-tolualdehyde is an important high value-added fine chemical, and is mainly used for the production of polyesters, plasticizers, medicines and perfumes. In the industry, p-tolualdehyde is generally prepared by catalytic Oxidation of p-xylene using a homogeneous catalyst (Co/Mn/Br catalyst), but this method has disadvantages of complicated process, large amount of discharged contaminants and difficulty in product separation (documents: Wanna WH, Janmanchi D, Thiyagarajan N, Ramu R, Tsai YF, Yu SSF, Selective Oxidation of Simple aromatic catalysis by Nano-biomimetric methods Catalysts: A Mini review. front chem.,2020,8, 589178). The preparation of aldehyde chemicals by selective oxidation of hydrocarbons has important application values in the chemical industry. Currently, several suitable alkylaromatic Oxidation Catalysts, such as Metal Oxide Catalysts or Metal complex Catalysts, have been studied (literature: Wanna WH, Janmanchi D, Thiyagarajan N, Ramu R, Tsai YF, Yu SSF, Selective Oxidation of Simple aromatic Catalysts by Nano-biological Metal oxides Catalysts: A Mini review. front chem.,2020,8, 589178); in comparison to homogeneous catalytic oxidation processes, catalysts are easily separated from the product in heterogeneous catalytic processes.
In view of the requirements of carbon emission reduction and sustainable development, the preparation of bio-based chemicals by using renewable biomass resources has important development prospect. Lignocellulosic biomass is the most abundant renewable resource, consisting mainly of cellulose, lignin and hemicellulose. In order to effectively utilize lignocellulose, development of relevant bio-based chemicals is required depending on the composition and structure of lignocellulose.
Cellulose is the most abundant component of lignocellulose, which is a polymer composed mainly of glucose units and linked by β -1, 4-glycosidic bonds. Currently, the development of cellulose-based chemicals, such as cellulose-based synthetic aromatics, furan, furfural, 5-hydroxymethylfurfural, valerolactone, levulinic acid, polyols and lactic acid, has been reported (documents: Ma J, Shi S, Jia X, Xia F, Ma H, Gao J, Xu J, Advances in catalytic conversion of lignocellulose to chemicals and liquid fuels, J.energy Chem.,2019,36, 74-86). Among them, catalytic cellulose cleavage is an effective method for producing aromatic chemicals (literature: Bayu A, Abudula A, Guan G, Reaction pathways and selectivity in chemical-catalytic conversion of biological-derived carbon substrates to high-value chemicals: A review. Fuel Process technology, 2019,196,106162). In addition, cellulose can be used for preparing high-value-added chemicals such as valerolactone and levulinic acid (documents: MaJ, Shi S, Jia X, Xia F, Ma H, Gao J, Xu J, Advances in catalytic conversion of lignocellulose to chemicals and liquid fuels, J.energy chem.,2019,36, 74-86); cellulose can be catalytically converted to sorbitol using noble metal catalysts (literature: Wang D, Niu W, Tan M, Wu M, Zheng X, Li Y, Tsubaki, NPtnocatalyss supported on reduced graphene oxide for selective conversion of cellulose or cellulose to sorbitol 2014, Chemschem, 7, 1398-.
Lignin is the second major component of lignocellulosic biomass, accounting for about 20-30% of lignocellulose (Ma J, Shi S, Jia X, Xia F, Ma H, Gao J, Xu J, Advances in catalytic conversion of lignocellulose to chemicals and liquid fuels, J. energy Chem.,2019,36, 74-86). Lignin is an aromatic polymer with a three-dimensional network structure, and mainly consists of three phenylpropane units and is linked through carbon-carbon bonds and ether bonds. Unlike cellulose, lignin has an aromatic ring structure and is rich in methoxy and other reactive groups. In view of the structural characteristics of lignin, the use of lignin for the preparation of phenolic compounds or aromatic chemicals is a promising transformation route (documents: Liu Y, Nie Y, Lu X, Zhang X, He H, Pan F, Zhou L, Liu X, Ji X, Zhang S, Cascade utilization of lignocellulosic biological to high-value products, Green chem.,2019, 20121, 3499) 3535).
However, the reaction paths and intermediates in the catalytic conversion of lignocellulose are often complex; to date, the directed production of aromatic aldehyde chemicals using lignocellulose remains a challenging technological challenge. To the best of our knowledge, no process for selectively producing p-tolualdehyde from lignocellulosic biomass has been reported.
Disclosure of Invention
The invention aims to provide a method for preparing p-tolualdehyde by using wood chips, which can realize oriented synthesis of p-tolualdehyde by using wood chip biomass, has high yield and selectivity, is simple in process, is easy to separate products, and can realize high-valued comprehensive utilization of biomass resources.
The invention provides a method for preparing p-tolualdehyde by using wood chips, which comprises the following steps:
s1) carrying out catalytic pyrolysis reaction on wood chips serving as a raw material in a protective atmosphere to obtain an intermediate rich in p-xylene;
s2) carrying out catalytic oxidation reaction on the intermediate rich in p-xylene in the presence of a heterogeneous catalyst in the hydrogen peroxide atmosphere to obtain p-tolualdehyde;
the heterogeneous catalyst is a ferroferric oxide modified chromium hydroxide magnetic catalyst.
Preferably, the heterogeneous catalyst contains 40-50 wt% of chromium hydroxide and 50-60 wt% of ferroferric oxide
Preferably, the heterogeneous catalyst is a ferroferric oxide modified chromium hydroxide magnetic catalyst obtained by ferroferric oxide and chromium salt in a hydrothermal synthesis mode.
Preferably, the mass ratio of the heterogeneous catalyst to the paraxylene-rich intermediate is 1: 9-10; the concentration of the paraxylene in the paraxylene-rich intermediate is more than 30 wt%.
Preferably, the mass ratio of the hydrogen peroxide to the intermediate rich in p-xylene is 4-6: 1, the temperature of the catalytic oxidation reaction is 70-85 ℃.
Preferably, the concentration of the paraxylene in the paraxylene-rich intermediate is 30.5-60.5 wt%.
Preferably, the catalyst used in the catalytic pyrolysis reaction in step S1) is one or more of a HMOR molecular sieve catalyst and an oxide-modified HMOR molecular sieve magnetic catalyst; further preferably an HMOR molecular sieve magnetic catalyst modified by both yttrium oxide and ferroferric oxide.
Preferably, in the step S1), the particle size of the raw material wood chips is 0.2-1 mm; the protective atmosphere comprises a nitrogen atmosphere and/or a noble gas atmosphere.
Preferably, in the step S1), the temperature of the catalytic cracking reaction is 450 to 480 ℃, and the time is 25 to 35 minutes.
Preferably, in step S2), the yield of p-tolualdehyde is 50.7% and the selectivity of p-tolualdehyde is 68.3%.
Compared with the prior art, the invention provides a novel method for directionally preparing p-tolualdehyde by using wood chips (a typical lignocellulose raw material): the method can use a molecular sieve magnetic catalyst modified by both yttrium oxide and ferroferric oxide to selectively catalyze and crack sawdust into an intermediate rich in p-xylene, and the intermediate rich in p-xylene is selectively oxidized into p-tolualdehyde under the action of the ferroferric oxide modified chromium hydroxide magnetic catalyst. The invention improves the yield and selectivity of p-tolualdehyde by the innovative design of catalysts and the like, and effectively realizes the aim of directionally synthesizing p-tolualdehyde by wood chip biomass. Experiments show that the yield of the p-tolualdehyde can reach 50.7 percent, and the selectivity of the p-tolualdehyde reaches 68.3 percent. In addition, the adopted heterogeneous catalyst is designed and prepared in a magnetic manner, so that the difficulty in separating the catalyst from a reaction product is solved. The method provided by the invention converts the sawdust raw material which is rich in resources, low in price and renewable into the chemical p-tolualdehyde with high added value, thereby realizing high-valued comprehensive utilization of biomass resources, and the method is simple and convenient, the product is easy to separate, and the method has good economic and environmental benefits.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a method for preparing p-tolualdehyde by using wood chips, which comprises the following steps:
s1) carrying out catalytic pyrolysis reaction on sawdust serving as a raw material in a protective atmosphere to obtain an intermediate rich in p-xylene;
s2) carrying out catalytic oxidation reaction on the intermediate rich in p-xylene in hydrogen peroxide atmosphere under the action of a magnetic heterogeneous catalyst to obtain p-tolualdehyde.
The method for selectively synthesizing p-tolualdehyde by using wood chip biomass has the characteristics of higher yield and selectivity, simple and convenient process, easy product separation and the like.
In the method provided in the embodiment of the present invention, step S1) is specifically: carrying out catalytic pyrolysis reaction on raw material wood chips in the presence of a catalyst in a protective atmosphere to obtain an intermediate rich in p-xylene. In the step S1), wood chips are used as raw materials, which belong to lignocellulose raw materials and mainly comprise cellulose (more than 40%), lignin (20-30%) and hemicellulose; the biomass raw material has wide source and low cost. The sawdust raw material is usually in the form of particle powder, and the particle size is preferably 0.2-1 mm, and more preferably 0.2-0.4 mm.
In the method provided in the embodiment of the present invention, the catalyst used in step S1) is denoted as a first catalyst (wood chip catalytic cracking catalyst), which may be an HMOR molecular sieve catalyst and an oxide-modified HMOR molecular sieve magnetic catalytic catalystOne or more molecular sieve catalysts in the catalyst are preferably molecular sieve magnetic catalysts modified by yttrium oxide and ferroferric oxide together. In some preferred embodiments, the first catalyst is Fe 3 O 4 @Y 2 O 3 @ HMOR, the specific surface area may be 199- 2 Per g, pore volume 0.12cm 3 Per gram, the average particle diameter is 25-30 nm.
The first catalyst of the embodiment of the invention uses the amount of the catalytic reaction system to perform pyrolysis reaction on the raw material system. For the preferred first catalyst (Fe) 3 O 4 @Y 2 O 3 @ HMOR), yttrium oxide (Y) 2 O 3 ) The content in the first catalyst is preferably 15-18 wt%, and specifically can be 15.0 wt%, 15.5 wt%, 16.0 wt%, 16.5 wt%, 17.0 wt%, 17.5 wt% or 18.0 wt%; ferroferric oxide (Fe) 3 O 4 ) The content in the first catalyst is preferably 5 to 8 wt%, and specifically can be 5.0 wt%, 5.5 wt%, 6.0 wt%, 6.5 wt%, 7.0 wt%, 7.5 wt%, or 8.0 wt%; the content of the HMOR molecular sieve in the first catalyst is preferably 74-80 wt%, and specifically may be 74.0 wt%, 74.5 wt%, 75.0 wt%, 75.5 wt%, 76.0 wt%, 76.5 wt%, 77.0 wt%, 77.5 wt%, or 80.0 wt%.
In the method provided by the embodiment of the present invention, the first catalyst used in step S1) is preferably obtained by modifying a molecular sieve with a rare earth salt and an iron source by using a hydrothermal synthesis method; the preparation method specifically comprises the following steps:
a) adding the HMOR molecular sieve to an aqueous solution containing yttrium chloride, and stirring at room temperature for 1-2 hours; b) sintering the obtained precipitate at 400-500 ℃ for 4-6 hours to obtain an yttrium oxide modified HMOR molecular sieve precursor; c) adding the yttria-modified HMOR molecular sieve precursor into an aqueous solution containing ferric chloride, adding ammonia water into the mixed solution, adjusting the pH value to 9-11, and stirring at room temperature for 1-2 hours; the usage proportion of the HMOR molecular sieve, the yttrium chloride and the ferric chloride is determined according to the content of the HMOR molecular sieve, the yttrium oxide and the ferroferric oxide in the first catalyst to be finally prepared, and is not limited independently; d) mixing the above mixed solutionReacting in a stainless steel autoclave at about 100 ℃ for 10-12 hours, respectively washing the reacted precipitate with water and ethanol for 3 times, and drying at 110 ℃ for 10-12 hours; e) sintering the dried precipitate at the temperature of 300-400 ℃ for 10-12 hours to obtain a molecular sieve magnetic catalyst jointly modified by yttrium oxide and ferroferric oxide; the specific surface area of the catalyst may be 199.8m 2 Per g, pore volume 0.12cm 3 (iv)/g, average particle diameter 25.8 nm.
In the method provided by the embodiment of the invention, preferably, the mass ratio of the first catalyst to the wood chips is 2:1, the temperature of the catalytic cracking reaction is preferably 450-480 ℃, and more preferably 470 ℃; the time of the catalytic cracking reaction can be 25-35 minutes, and preferably 30 minutes. The protective atmosphere can comprise nitrogen atmosphere and/or rare gas atmosphere, and the pressure of the reaction system is normal pressure.
The catalytic cracking of the wood chip raw material in the embodiment of the invention can be carried out in a fixed bed reactor, and the specific operation steps are as follows: introducing inert gas nitrogen into the fixed bed reactor, heating the fixed bed reactor to a reaction temperature by an external heating mode, mixing the first catalyst and the wood chips, injecting the mixture into a central constant temperature area of the catalytic reactor for catalytic cracking reaction, obtaining a liquid product which is an intermediate rich in paraxylene, and collecting the liquid product in a condensing tank through condensation.
In the embodiment of the invention, the main component of the intermediate rich in para-xylene is para-xylene, and aromatic substances such as benzene, toluene and the like are generally contained; the concentration of the paraxylene in the invention is preferably more than 30 wt%, more preferably 30.5-60.5 wt%, and even more preferably 58.5-60.5 wt%.
After the intermediate rich in p-xylene is obtained, the intermediate is subjected to selective catalytic oxidation in a liquid phase reaction kettle. That is, step S2) is specifically: and carrying out catalytic oxidation reaction on the intermediate rich in the p-xylene in the hydrogen peroxide atmosphere under the action of a second catalyst (a heterogeneous catalyst, a ferroferric oxide modified chromium hydroxide magnetic catalyst) to obtain p-tolualdehyde.
In the method provided by the embodiment of the present invention, in step S2), the second catalyst is a ferroferric oxide modified chromium hydroxide magnetic catalyst (cr (oh) 3 @Fe 3 O 4 ) (ii) a Chromium hydroxide (Cr (OH) 3 ) The content in the second catalyst is preferably 40 to 50 wt%, and specifically may be 40.0 wt%, 42.0 wt%, 44.0 wt%, 46.0 wt%, 48.0 wt%, or 50.0 wt%. The content of the ferroferric oxide in the second catalyst is preferably 50-60 wt%, and specifically may be 50.0 wt%, 52.0 wt%, 54.0 wt%, 56.0 wt%, 58.0 wt% or 60.0 wt%. In some specific examples, the specific surface area of the second catalyst may be 310m 2 More than/g, such as 310- 2 (iv) g; pore volume of 0.45cm 3 In terms of a/g, the average particle diameter is from 15 to 20nm, for example from 18 to 19 nm.
In the method provided by the present invention, the second catalyst used in step S2) is preferably obtained from ferroferric oxide and chromium salt by a hydrothermal synthesis method; the preparation method specifically comprises the following steps:
a) adding ferroferric oxide into an aqueous solution containing chromium nitrate, and stirring at room temperature for 1-2 hours; b) adding ammonia water into the mixed solution, adjusting the pH value to 9-11, and stirring at room temperature for 1-2 hours; the dosage proportion of the ferroferric oxide and the chromium nitrate is determined according to the content of the ferroferric oxide and the chromium hydroxide in the second catalyst to be prepared, and is not limited independently; c) reacting the mixed solution in a stainless steel autoclave for at least 24 hours at the temperature of 170-190 ℃; d) washing the reacted precipitate with water and ethanol for 3 times respectively, and drying at 100-110 ℃ for 10-12 hours; e) sintering the dried precipitate at the temperature of 300-400 ℃ for 10 hours to obtain a ferroferric oxide modified chromium hydroxide magnetic catalyst; the specific surface area of the material can be 310.4m 2 Per g, pore volume 0.45cm 3 (iv)/g, average particle diameter 18.7 nm.
In the method provided by the embodiment of the present invention, in the step S2), the mass ratio of the second catalyst to the intermediate rich in paraxylene is preferably 1: 9-10, and more preferably 1: 10.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared heterogeneous catalyst and an intermediate rich in p-xylene into a liquid phase reaction kettle, heating the reaction kettle under a protective atmosphere, adding hydrogen peroxide into the reaction kettle by using an injection pump, preferably under a stirring condition, further carrying out selective oxidation reaction on an aromatic hydrocarbon intermediate obtained by catalytic cracking of wood chips under the action of the specific heterogeneous catalyst, and reacting for a certain time to obtain a product, namely p-tolualdehyde.
In the embodiment of the invention, the mass ratio of the hydrogen peroxide to the intermediate rich in p-xylene is preferably 4-6: 1, more preferably 5: 1; the temperature of the catalytic oxidation reaction is preferably 70-85 ℃, and more preferably 80 ℃; the time of the catalytic oxidation reaction is preferably 5 to 8 hours, and more preferably 6 hours. According to the embodiment of the invention, a selective catalytic oxidation reaction is carried out, so that a chemical with p-tolualdehyde as a main component can be obtained, and the selectivity can reach 68.3%.
According to the method provided by the invention, the wood chip biomass raw material is firstly catalytically cracked into an intermediate rich in p-xylene, and then p-tolualdehyde is synthesized through catalytic oxidation. The method provided by the invention at least has the following advantages and beneficial technical effects:
according to the invention, a molecular sieve magnetic catalyst modified by ferroferric oxide and yttrium oxide together is preferentially used as a catalyst for catalytic cracking reaction, so that the sawdust can be selectively used for preparing an intermediate rich in p-xylene, the p-xylene selectivity is 60.3%, and the p-xylene yield reaches 21.3%. Then, the invention uses ferroferric oxide modified chromium hydroxide magnetic catalyst as the catalyst of selective oxidation reaction, and converts the midbody which is prepared by catalytic cracking of wood chips and is rich in p-xylene selectively into biomass-based high-value chemical products which take p-tolualdehyde as the main component, wherein the selectivity of p-tolualdehyde reaches 68.3 percent, and the yield of p-tolualdehyde reaches 50.7 percent.
In addition, the magnetic catalyst is used in the catalytic reaction process, so that the separation of the catalyst and a reaction product after the reaction is facilitated. The raw material used in the invention is wood chip biomass, the raw material has the advantages of rich resources, low price, renewability and the like, and the terminal product is a bio-based high-added-value chemical mainly containing p-tolualdehyde, thereby being beneficial to high-value comprehensive utilization of biomass resources.
For the sake of clarity, the following examples are given in detail. The wood chips used in the examples were from a wood processing plant in the city of Hefei province, Anhui province, and consisted of 41.9 wt% cellulose, 29.6 wt% lignin, and 19.3 wt% hemicellulose; the elemental composition included 46.2 wt% C, 6.0 wt% H, and 44.2 wt% O; the particle size of the ground sawdust is 0.2-0.4 mm.
Example 1
In this example, a molecular sieve magnetic catalyst (Y) modified by both yttria and ferroferric oxide was first examined 2 O 3 @Fe 3 O 4 @ HMOR) as the first catalyst, catalytic cracking of the wood chip feedstock results in an effect of enriched p-xylene aromatics intermediate.
Using Y 2 O 3 @Fe 3 O 4 The @ HMOR catalyst is prepared by adopting a conventional hydrothermal synthesis method and according to the following steps: a) 10g of HMOR molecular sieve was added to an aqueous solution containing yttrium chloride (4.0g) and deionized water (100g) and stirred at 25 ℃ for 2 hours at room temperature; b) sintering the precipitate at 450 ℃ for 5 hours to obtain an yttria-modified HMOR molecular sieve precursor; c) adding an yttrium oxide modified HMOR molecular sieve precursor into an aqueous solution containing 1.6g of ferric trichloride and 50g of deionized water, adding ammonia water into the mixed solution, adjusting the pH value to 10, and stirring at 25 ℃ and room temperature for 2 hours; d) reacting the mixed solution in a stainless steel high-pressure kettle at 100 ℃ for 10 hours, respectively washing the reacted precipitate with deionized water and ethanol for 3 times, and drying at 110 ℃ for 12 hours; e) and sintering the dried precipitate at 350 ℃ for 10 hours to obtain the molecular sieve magnetic catalyst jointly modified by the yttrium oxide and the ferroferric oxide. In the obtained catalyst, the content of yttrium oxide is 17.5 wt%, the content of ferroferric oxide is 5.5 wt%, and the content of HMOR molecular sieve is 77.0 wt%; the specific surface area of the catalyst was 199.8m 2 Per g, pore volume 0.12cm 3 (iv)/g, average particle diameter 25.8 nm.
In this example, the catalytic cracking of wood chips was carried out in a fixed bed reactor under the following reaction conditions: the weight ratio of the catalyst to the wood chip raw material is 2:1, the carrier gas is nitrogen, the pressure is normal pressure, and the temperature is 470 ℃; the time for the catalytic cracking reaction was 30 minutes.
The wood chip catalytic cracking comprises the following specific operation steps: introducing inert gas nitrogen (the flow rate is 100mL/min) into the fixed bed reactor; heating the fixed bed reactor to 470 ℃ by using an external heating mode; mixing the above Fe 3 O 4 @Y 2 O 3 Mixing a @ HMOR magnetic catalyst and sawdust (with the particle size range of 0.2-0.4 mm) according to the mass ratio of 2:1, and then injecting the mixture into a central constant-temperature area of a catalytic reactor for catalytic cracking reaction; and collecting a liquid product obtained by catalytic cracking of the sawdust in a condensing tank through condensation, reacting for 30 minutes, and carrying out quantitative analysis on the collected product components by using gas chromatography-mass spectrometry.
In this example, a molecular sieve magnetic catalyst (Fe) modified by both yttrium oxide and ferroferric oxide is used 3 O 4 @Y 2 O 3 @ HMOR) was used for catalytic cracking of wood chips, the p-xylene selectivity was 60.3% and the p-xylene yield reached 21.3%, with specific results detailed in table 1.
In this example, the use of a ferroferric oxide-modified chromium hydroxide catalyst (Cr (OH)) 3 @Fe 3 O 4 ) When the aromatic hydrocarbon obtained by catalytic cracking of the wood chips is used as a raw material, the selective catalytic oxidation of an aromatic hydrocarbon intermediate is carried out to prepare the p-tolualdehyde.
Cr (OH) used 3 @Fe 3 O 4 The catalyst is prepared by adopting a conventional hydrothermal reaction method and comprises the following specific steps: a) adding 10g of ferroferric oxide magnetic carrier into an aqueous solution containing 16.5g of chromium nitrate and 200g of deionized water, and stirring at 25 ℃ for 2 hours at room temperature; b) adding ammonia water into the mixed solution, adjusting the pH value to 10, and stirring at 25 ℃ for 2 hours at room temperature; c) reacting the mixed solution in a stainless steel autoclave at 180 ℃ for 24 hours; d) will be provided withWashing the reacted precipitate for 3 times by using deionized water and ethanol respectively, drying for 12 hours at 110 ℃, and e) sintering the dried precipitate for 10 hours at 350 ℃ to obtain the ferroferric oxide modified chromium hydroxide magnetic catalyst. Of the obtained catalyst, ferroferric oxide (Fe) 3 O 4 ) Is 55.5 wt%, a chromium hydroxide component (Cr (OH)) 3 ) Is 44.5 wt%; the specific surface area of the catalyst was 310.4m 2 Per g, pore volume 0.45cm 3 (iv)/g, average particle diameter 18.7 nm.
The intermediate selective catalytic oxidation reaction conditions adopted in this example were: ferroferric oxide modified Cr (OH) 3 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1: 10; the mass ratio of the hydrogen peroxide oxidant to the intermediate rich in p-xylene is 5: 1, the temperature of catalytic oxidation reaction is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In this example, when p-tolualdehyde was produced by selective catalytic oxidation of an aromatic hydrocarbon intermediate using a ferroferric oxide-modified chromium hydroxide catalyst, the selectivity for p-tolualdehyde was 68.3%, and the yield of p-tolualdehyde was 50.7%. The specific results are detailed in table 2.
Example 2
In this example, a molecular sieve catalyst (Y) modified with yttrium oxide was first examined 2 O 3 @ HMOR) as a catalyst, catalytic cracking of the wood chip feedstock to yield an intermediate rich in p-xylene.
Using Y 2 O 3 @ HMOR catalyst, by conventional hydrothermal synthesisThe method comprises the following steps: a) 10g of HMOR molecular sieve was added to an aqueous solution containing yttrium chloride (3.9g) and deionized water (100g) and stirred at 25 ℃ for 2 hours at room temperature; b) reacting the mixed solution in a stainless steel autoclave at 180 ℃ for 10 hours, respectively washing the reacted precipitate with deionized water and ethanol for 3 times, and drying at 110 ℃ for 12 hours; c) and sintering the precipitate at 450 ℃ for 5 hours to obtain the yttria-modified HMOR molecular sieve. The obtained catalyst had an yttrium oxide content of 17.8 wt% and an HMOR molecular sieve content of 82.0 wt%.
In this example, the catalytic cracking of wood chips was carried out in a fixed bed reactor under the following reaction conditions: the weight ratio of the catalyst to the wood chip raw material is 2:1, the carrier gas is nitrogen, the pressure is normal pressure, and the temperature is 470 ℃; the time for the catalytic cracking reaction was 30 minutes.
The wood chip catalytic cracking method comprises the following specific operation steps: introducing inert gas nitrogen (the flow rate is 100mL/min) into the fixed bed reactor; heating the fixed bed reactor to 470 ℃ by using an external heating mode; subjecting the above Y to 2 O 3 Mixing a @ HMOR catalyst and sawdust (with the particle size range of 0.2-0.4 mm) according to the mass ratio of 2:1, and then injecting the mixture into a central constant-temperature area of a catalytic reactor for catalytic cracking reaction; and collecting a liquid product obtained by catalytic cracking of the sawdust in a condensing tank through condensation, reacting for 30 minutes, and carrying out quantitative analysis on the collected product components by using gas chromatography-mass spectrometry.
In this example, a yttria-modified molecular sieve catalyst (Y) was used 2 O 3 @ HMOR) was used for catalytic cracking of wood chips, the p-xylene selectivity was 58.2%, the p-xylene yield reached 18.9%, and the specific results are detailed in table 1.
The use of a ferroferric oxide modified chromium hydroxide catalyst (Cr (OH)) 3 @Fe 3 O 4 ) The method has the effect of preparing p-tolualdehyde by selective catalytic oxidation of an aromatic hydrocarbon intermediate by taking aromatic hydrocarbon obtained by catalytic cracking of wood chips as a raw material.
In this example, a ferroferric oxide-modified chromium hydroxide catalyst (Cr (OH)) was used 3 @Fe 3 O 4 ) The preparation method and the composition thereof are the same as those of example 1.
The reaction conditions of the selective catalytic oxidation of the intermediate used in this example were: ferroferric oxide modified Cr (OH) 3 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1: 10; the mass ratio of the hydrogen peroxide oxidant to the intermediate rich in p-xylene is 5: 1, the temperature of catalytic oxidation reaction is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In this example, when p-tolualdehyde was produced by selective catalytic oxidation of an aromatic hydrocarbon intermediate using a ferroferric oxide-modified chromium hydroxide catalyst, the selectivity for p-tolualdehyde was 61.9%, and the yield of p-tolualdehyde was 43.6%. The specific results are detailed in table 2.
Example 3
In this example, the effect of catalytic cracking of wood chip feedstock to obtain a para-xylene-rich aromatic intermediate using HMOR molecular sieves as the catalyst was first examined.
In this example, the HMOR catalyst used was from the catalyst plant at the university of tianjin nan. The wood chip 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 wood chip raw material is 2:1, the carrier gas is nitrogen, the pressure is normal pressure, and the temperature is 470 ℃; the time for the catalytic cracking reaction was 30 minutes.
The wood chip catalytic cracking comprises the following specific operation steps: introducing inert gas nitrogen (the flow rate is 100mL/min) into the fixed bed reactor; heating the fixed bed reactor to 470 ℃ by using an external heating mode; mixing the HMOR catalyst and sawdust (with the particle size range of 0.2-0.4 mm) according to a mass ratio of 2:1, and then injecting the mixture into a central constant-temperature area of a catalytic reactor for catalytic cracking reaction; and collecting a liquid product obtained by catalytic cracking of the sawdust in a condensing tank through condensation, reacting for 30 minutes, and carrying out quantitative analysis on the collected product components by using gas chromatography-mass spectrometry.
In this example, when the HMOR molecular sieve catalyst is used for catalytic cracking of wood chips, the selectivity to p-xylene is 30.9%, and the yield of p-xylene is 11.3%, and the specific results are detailed in table 1.
The use of a ferroferric oxide modified chromium hydroxide catalyst (Cr (OH)) 3 @Fe 3 O 4 ) The method has the effect of preparing p-tolualdehyde by selective catalytic oxidation of an aromatic hydrocarbon intermediate by taking aromatic hydrocarbon obtained by catalytic cracking of wood chips as a raw material.
In this example, a ferroferric oxide-modified chromium hydroxide catalyst (Cr (OH)) was used 3 @Fe 3 O 4 ) The preparation method and the composition thereof are the same as those of example 1.
The reaction conditions of the selective catalytic oxidation of the intermediate used in this example were: ferroferric oxide modified Cr (OH) 3 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1: 10; the mass ratio of the hydrogen peroxide oxidant to the intermediate rich in p-xylene is 5: 1, the temperature of catalytic oxidation reaction is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In this example, when p-tolualdehyde was produced by selective catalytic oxidation of an aromatic hydrocarbon intermediate using a ferroferric oxide-modified chromium hydroxide catalyst, the selectivity for p-tolualdehyde was 45.6%, and the yield of p-tolualdehyde was 31.0%. The specific results are detailed in table 2.
TABLE 1 results of catalytic cracking of wood chips to obtain p-xylene rich intermediates
As can be seen from table 1, the wood chip biomass is subjected to catalytic cracking, deoxygenation, aromatization, isomerization and other reactions under the action of the catalyst to obtain an intermediate mainly containing p-xylene. Among all the first catalysts (sawdust catalytic cracking catalysts) examined, the molecular sieve magnetic catalyst modified by both yttrium oxide and ferroferric oxide gives the maximum yield of paraxylene.
In addition, the use of a catalyst with magnetic properties facilitates the separation of the catalyst from the reaction product after the reaction.
Example 4
In this example, a magnetic chromium hydroxide catalyst (Cr (OH)) modified with ferroferric oxide was examined 3 @Fe 3 O 4 -I) effect of selective catalytic oxidation of an aromatic intermediate rich in p-xylene to p-tolualdehyde using as a raw material an intermediate rich in p-xylene obtained from catalytic cracking of wood chips in example 1.
In this example, Cr (OH) was used 3 @Fe 3 O 4 The catalyst is prepared by adopting a conventional hydrothermal reaction method and comprises the following specific steps: a) 10g of ferroferric oxide magnetic carrier was added to an aqueous solution containing chromium nitrate (14.5g) and deionized water (200g), and stirred at 25 ℃ at room temperature for 2 hours; b) adding ammonia water into the mixed solution, adjusting the pH value to 10, and stirring at 25 ℃ for 2 hours at room temperature; c) reacting the mixed solution in a stainless steel autoclave at 180 ℃ for 24 hours; d) washing the reacted precipitate with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours, e) sintering the dried precipitate at 350 ℃ for 10 hours to obtain the ferroferric oxide modified chromium hydroxide magnetic catalyst. Among the catalysts obtained, the catalysts obtained were,ferroferric oxide (Fe) 3 O 4 ) 59.9 wt%, chromium hydroxide component (Cr (OH)) 3 ) Is 40.1 wt%.
In this example, the selective catalytic oxidation of the para-xylene enriched aromatic intermediate was carried out in a liquid phase reactor, and the reactant for the selective catalytic oxidation of aromatic hydrocarbon was derived from the para-xylene enriched intermediate obtained by catalytic cracking of wood chips in example 1 (see table 1).
The aromatic hydrocarbon intermediate selective catalytic oxidation reaction conditions adopted in the embodiment are as follows: cr (OH) 3 @Fe 3 O 4 -the mass ratio of catalyst to intermediate enriched in para-xylene is 1: 10; the mass ratio of the oxidant hydrogen peroxide to the aromatic hydrocarbon intermediate rich in p-xylene is 5: 1, the catalytic reaction temperature is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In this example, Cr (OH) was used 3 @Fe 3 O 4 When the magnetic catalyst I is used for preparing p-tolualdehyde by selective catalytic oxidation of aromatic hydrocarbon intermediates, the selectivity of the p-tolualdehyde reaches 65.7%, the yield of the p-tolualdehyde reaches 46.8%, and specific results are shown in Table 2.
Example 5
In this example, a magnetic chromium hydroxide catalyst (Cr (OH)) modified with ferroferric oxide was examined 3 @Fe 3 O 4 -II) effect of selective catalytic oxidation of an aromatic intermediate rich in para-xylene to p-tolualdehyde using as a starting material an intermediate rich in para-xylene obtained from catalytic cracking of wood chips in example 1.
In this example, Cr (OH) was used 3 @Fe 3 O 4 The catalyst II is prepared by adopting a conventional hydrothermal reaction method and comprises the following specific steps: a) 10g of ferroferric oxide magnetic carrier was added to an aqueous solution containing chromium nitrate (18.0g) and deionized water (200g), and stirred at 25 ℃ at room temperature for 2 hours; b) adding ammonia water into the mixed solution, adjusting the pH value to 10, and stirring at 25 ℃ for 2 hours at room temperature; c) reacting the mixed solution in a stainless steel autoclave at 180 ℃ for 24 hours; d) washing the reacted precipitate with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours, e) sintering the dried precipitate at 350 ℃ for 10 hours to obtain the ferroferric oxide modified chromium hydroxide magnetic catalyst. Of the obtained catalyst, ferroferric oxide (Fe) 3 O 4 ) Is 50.7 wt%, a chromium hydroxide component (Cr (OH)) 3 ) Is 49.3 wt%.
In this example, the selective catalytic oxidation of an aromatic intermediate rich in p-xylene was carried out in a liquid phase reactor, and the aromatic selective catalytic oxidation reactant was derived from the intermediate rich in p-xylene obtained by catalytic cracking of wood chips in example 1 (see table 1).
The aromatic hydrocarbon intermediate selective catalytic oxidation reaction conditions adopted in the embodiment are as follows: cr (OH) 3 @Fe 3 O 4 -the mass ratio of catalyst II to intermediate enriched in para-xylene is 1: 10; the mass ratio of the oxidant hydrogen peroxide to the aromatic hydrocarbon intermediate rich in p-xylene is 5: 1, the catalytic reaction temperature is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In bookIn the examples, Cr (OH) was used 3 @Fe 3 O 4 When the-II magnetic catalyst is used for selectively catalyzing and oxidizing aromatic hydrocarbon intermediates to prepare the p-tolualdehyde, the selectivity of the p-tolualdehyde reaches 68.0 percent, and the yield of the p-tolualdehyde reaches 50.3 percent. The specific results are detailed in table 2.
Comparative example 1
In this comparative example, the use of a chromium hydroxide catalyst (Cr (OH) 3 ) The effect of selective catalytic oxidation of an aromatic intermediate rich in p-xylene to p-tolualdehyde using an intermediate rich in p-xylene obtained by catalytic cracking of wood chips from example 1 as a starting material.
Cr (OH) used 3 The catalyst is prepared by a conventional hydrothermal reaction method, and comprises the following specific steps: a) 40g of chromium nitrate was added to deionized water (200g) and stirred at 25 ℃ for 2 hours at room temperature; b) adding ammonia water into the solution, adjusting the pH value to 10, and stirring at 25 ℃ for 2 hours at room temperature; c) reacting the mixed solution in a stainless steel autoclave at 180 ℃ for 24 hours; d) and washing the precipitate after the reaction with deionized water and ethanol for 3 times respectively, and drying at 110 ℃ for 12 hours to obtain a chromium hydroxide catalyst sample.
In this comparative example, the selective catalytic oxidation of an aromatic intermediate rich in p-xylene was carried out in a liquid phase reactor, and the aromatic selective catalytic oxidation reactant was derived from the aromatic intermediate obtained by catalytic cracking of wood chips in example 1 (see table 1).
The aromatic hydrocarbon intermediate selective catalytic oxidation reaction conditions adopted in the comparative example are as follows: cr (OH) 3 The mass ratio of the catalyst to the intermediate rich in p-xylene is 1: 10; the mass ratio of the hydrogen peroxide oxidant to the aromatic hydrocarbon intermediate rich in p-xylene is 5: 1, the temperature of catalytic oxidation reaction is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In the present comparative example, when p-tolualdehyde was produced by selective catalytic oxidation of an aromatic hydrocarbon intermediate using a chromium hydroxide catalyst, the selectivity for p-tolualdehyde was 61.9%, and the yield of p-tolualdehyde was 42.7%. The specific results are detailed in table 2.
Comparative example 2
In this comparative example, the use of a ferroferric oxide catalyst (Fe) was examined 3 O 4 ) The effect of selective catalytic oxidation of an aromatic intermediate rich in p-xylene to p-tolualdehyde using an intermediate rich in p-xylene obtained by catalytic cracking of wood chips from example 1 as a starting material.
The ferroferric oxide catalyst is prepared by a conventional hydrothermal reaction method, and the method comprises the following specific steps: a) adding 40g of ferric trichloride into 200g of deionized water, and stirring at 25 ℃ for 2 hours at room temperature; b) adding ammonia water into the mixed solution, adjusting the pH value to 10, and stirring at 25 ℃ for 2 hours at room temperature; c) reacting the mixed solution in a stainless steel autoclave at 100 ℃ for 24 hours; d) and washing the precipitate after the reaction by using deionized water and ethanol respectively for 3 times, and drying at 110 ℃ for 12 hours to obtain a ferroferric oxide catalyst sample.
In this comparative example, the selective catalytic oxidation of an aromatic intermediate rich in p-xylene was carried out in a liquid phase reactor, and the aromatic selective catalytic oxidation reactant was derived from the aromatic intermediate obtained by catalytic cracking of wood chips in example 1 (see table 1).
The aromatic hydrocarbon intermediate selective catalytic oxidation reaction conditions adopted in the comparative example are as follows: the mass ratio of the ferroferric oxide catalyst to the intermediate rich in p-xylene is 1: 10; the mass ratio of the hydrogen peroxide oxidant to the aromatic hydrocarbon intermediate rich in p-xylene is 5: 1, the catalytic reaction temperature is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In the present comparative example, when p-tolualdehyde was produced by selective catalytic oxidation of an aromatic hydrocarbon intermediate using a ferroferric oxide catalyst, the selectivity for p-tolualdehyde was 48.2%, and the yield of p-tolualdehyde was 9.7%, and the specific results are shown in table 2.
Comparative example 3
In this comparative example, the use of a nickel hydroxide catalyst (Ni (OH)) 2 ) The effect of selective catalytic oxidation of an aromatic intermediate rich in p-xylene to p-tolualdehyde using an intermediate rich in p-xylene obtained by catalytic cracking of wood chips in example 1 as a raw material.
Ni (OH) used 2 The catalyst is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: a) 40g of nickel nitrate was added to deionized water (200g) and stirred at 25 ℃ for 2 hours at room temperature; b) adding ammonia water into the solution, adjusting the pH value to 10, and stirring at 25 ℃ for 2 hours at room temperature; c) reacting the mixed solution in a stainless steel autoclave at 180 ℃ for 24 hours; d) and washing the precipitate after the reaction respectively by using deionized water and ethanol for 3 times, and drying at 110 ℃ for 12 hours to obtain a nickel hydroxide catalyst sample.
In this comparative example, the selective catalytic oxidation of an aromatic intermediate rich in p-xylene was carried out in a liquid phase reactor, and the aromatic selective catalytic oxidation reactant was derived from the aromatic intermediate obtained by catalytic cracking of wood chips in example 1 (see table 1).
The reaction conditions for the selective catalytic oxidation of the aromatic hydrocarbon intermediate adopted in the comparative example are as follows: ni (OH) 2 The mass ratio of the catalyst to the intermediate rich in paraxylene is 1: 10; preparation of hydrogen peroxide oxidant and aromatic hydrocarbon intermediate rich in p-xyleneThe mass ratio is 5: 1, the temperature of catalytic oxidation reaction is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In the present comparative example, when p-tolualdehyde was produced by selective catalytic oxidation of an aromatic hydrocarbon intermediate using a nickel hydroxide catalyst, the selectivity for p-tolualdehyde was 41.9%, and the yield for p-tolualdehyde was 23.3%. The specific results are detailed in table 2.
Comparative example 4
In this comparative example, the use of the iron hydroxide catalyst Fe (OH) 3 The effect of selective catalytic oxidation of an aromatic intermediate rich in p-xylene to p-tolualdehyde using an intermediate rich in p-xylene obtained by catalytic cracking of wood chips in example 1 as a raw material.
Fe (OH) used 3 The catalyst is prepared by adopting a conventional hydrothermal reaction method, and comprises the following specific steps: a) 40g of ferric nitrate was added to deionized water (200g) and stirred at 25 ℃ for 2 hours at room temperature; b) adding ammonia water into the solution, adjusting the pH value to 10, and stirring at 25 ℃ for 2 hours at room temperature; c) reacting the mixed solution in a stainless steel autoclave at 180 ℃ for 24 hours; d) and washing the precipitate after the reaction respectively by using deionized water and ethanol for 3 times, and drying at 110 ℃ for 12 hours to obtain an iron hydroxide catalyst sample.
In this comparative example, the selective catalytic oxidation of an aromatic intermediate rich in p-xylene was carried out in a liquid phase reactor, and the aromatic selective catalytic oxidation reactant was derived from the aromatic intermediate obtained by catalytic cracking of wood chips in example 1 (see table 1).
Aromatic hydrocarbons used in this comparative exampleThe reaction conditions of the selective catalytic oxidation of the intermediate are as follows: ni (OH) 2 The mass ratio of the catalyst to the intermediate rich in p-xylene is 1: 10; the mass ratio of the hydrogen peroxide oxidant to the aromatic hydrocarbon intermediate rich in p-xylene is 5: 1, the temperature of catalytic oxidation reaction is 80 ℃; the time for the catalytic cracking reaction was 6 hours.
The catalytic reaction operation steps of the aromatic hydrocarbon intermediate are as follows: firstly, respectively adding the prepared catalyst and the aromatic hydrocarbon intermediate into a liquid phase reaction kettle, wherein the dosage of the catalyst is 10g, and the dosage of the aromatic hydrocarbon intermediate reactant is 100 g; heating the reactor to 80 ℃ under an inert gas nitrogen atmosphere; slowly adding hydrogen peroxide (500g) into a liquid phase reaction kettle by using an injection pump; opening a stirrer in the reaction kettle to stir the reactant, and carrying out selective oxidation reaction; after 6 hours of reaction, the product was quantitatively analyzed by a chromatograph-mass spectrometer.
In the present comparative example, when p-tolualdehyde was produced by selective catalytic oxidation of an aromatic hydrocarbon intermediate using an iron hydroxide catalyst, the selectivity for p-tolualdehyde was 46.8%, and the yield of p-tolualdehyde was 15.2%. The specific results are detailed in table 2.
TABLE 2 results of catalytic oxidation of aromatic hydrocarbon intermediates for preparing p-tolualdehyde
As can be seen from Table 2, the intermediate rich in p-xylene obtained by catalytic cracking of wood chips is further subjected to catalytic oxidation reaction under the action of a catalyst, so that a chemical mainly comprising p-tolualdehyde can be obtained; of all the second catalysts examined (aromatic hydrocarbon oxidation catalysts), the ferroferric oxide-modified chromium hydroxide magnetic catalyst had the best selectivity and yield for p-tolualdehyde, 50.7% for p-tolualdehyde and 68.3% for p-tolualdehyde.
In addition, the catalyst with magnetism is used for facilitating the separation of the catalyst and reaction products after reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (9)
1. A method for preparing p-tolualdehyde by using wood chips is characterized by comprising the following steps:
s1) carrying out catalytic pyrolysis reaction on sawdust serving as a raw material in a protective atmosphere to obtain an intermediate rich in p-xylene;
s2) carrying out catalytic oxidation reaction on the intermediate rich in p-xylene in the presence of a heterogeneous catalyst in the hydrogen peroxide atmosphere to obtain p-tolualdehyde;
the heterogeneous catalyst is a ferroferric oxide modified chromium hydroxide magnetic catalyst.
2. The method for preparing p-tolualdehyde from wood chips as defined in claim 1, wherein the heterogeneous catalyst contains 40-50 wt% of chromium hydroxide and 50-60 wt% of ferroferric oxide.
3. The method for preparing p-methylbenzaldehyde from wood chips according to claim 2, wherein the heterogeneous catalyst is a ferroferric oxide modified chromium hydroxide magnetic catalyst obtained by ferroferric oxide and chromium salt through a hydrothermal synthesis mode.
4. The method for producing p-tolualdehyde using wood chips according to claim 1, wherein the mass ratio of the heterogeneous catalyst to the intermediate rich in p-xylene is 1: 9-10; the concentration of the paraxylene in the paraxylene-rich intermediate is more than 30 wt%.
5. The method for preparing p-tolualdehyde from wood chips as claimed in claim 4, wherein the mass ratio of hydrogen peroxide to the intermediate rich in p-xylene is 4-6: 1, the temperature of the catalytic oxidation reaction is 70-85 ℃.
6. The method for producing p-tolualdehyde from wood chips according to any one of claims 1 to 5, wherein the concentration of p-xylene in the intermediate rich in p-xylene is 30.5 to 60.5 wt%.
7. The method for preparing p-tolualdehyde using wood chips as claimed in claim 6, wherein the catalytic pyrolysis reaction of step S1) is carried out using one or more of HMOR molecular sieve catalyst and oxide-modified HMOR molecular sieve magnetic catalyst.
8. The method for preparing p-tolualdehyde from wood chips according to claim 7, wherein the catalyst used in the catalytic pyrolysis reaction in step S1) is a magnetic HMOR molecular sieve catalyst modified by yttrium oxide and ferroferric oxide.
9. The method for producing p-tolualdehyde from wood chips according to any of claims 1 to 5, wherein the yield of p-tolualdehyde in step S2) is 50.7%, and the selectivity to p-tolualdehyde is 68.3%.
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