CN113145121B - Nickel-carbon catalyst with high specific surface area and preparation method and application thereof - Google Patents
Nickel-carbon catalyst with high specific surface area and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000002699 waste material Substances 0.000 claims description 38
- 230000003197 catalytic effect Effects 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims 1
- 229920005610 lignin Polymers 0.000 abstract description 14
- 238000001994 activation Methods 0.000 description 23
- 230000004913 activation Effects 0.000 description 22
- 230000000694 effects Effects 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- OCDXZFSOHJRGIL-UHFFFAOYSA-N cyclohexyloxycyclohexane Chemical compound C1CCCCC1OC1CCCCC1 OCDXZFSOHJRGIL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- ANKVSZOYVTWLQO-UHFFFAOYSA-N 1-methoxypropylbenzene Chemical group CCC(OC)C1=CC=CC=C1 ANKVSZOYVTWLQO-UHFFFAOYSA-N 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
-
- 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
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
-
- 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
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- 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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a nickel-carbon catalyst with high specific surface area and a preparation method and application thereof. The nickel-carbon catalyst can selectively hydrogenize the model compound diphenyl ether of the lignin under milder conditions (140 ℃, 0.5MPa) to promote the breaking of C-O bonds in the diphenyl ether.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a nickel-carbon catalyst with high specific surface area, and a preparation method and application thereof.
Background
The lignin is a potential renewable raw material, is a three-dimensional amorphous network consisting of methoxyphenyl propane units, contains a large amount of aromatic main chains and organic carbon, and has wide application prospect. By cleaving the C-O bonds in lignin, a number of valuable aromatics and liquid fuels can be obtained. The lignin contains a large amount of aryl ether C-O bonds, mainly alpha-O-4, beta-O-4 and 4-O-5 bonds, wherein the 4-O-5 bond is the strongest C-O bond in the lignin, so that the selective cracking of the C-O bond in the 4-O-5 bond has important significance for the depolymerization of the lignin. Catalytic hydrogenolysis is considered as one of the effective methods for lignin depolymerization, and due to the complexity of lignin structure, extensive studies on lignin model compounds (diphenyl ether) have been conducted to reveal the mechanism of lignin depolymerization into small molecules.
The preparation of the high-activity catalyst is the key point of catalytic hydrogenolysis of lignin and model compounds thereof. High-concentration waste sugar liquor (WSS) is generated in the production process of vitamin C, and contains various wastes such as waste acid, organic matters and the like, so that the direct discharge can pollute the environment and waste recyclable resources. CN107010625A discloses a method for preparing porous carbon balls from waste sugar liquid, and a method for preparing tremella-shaped porous carbon from CN109052395A waste sugar liquid, wherein the above technologies all realize the utilization of the waste sugar liquid with high added value, but the waste sugar liquid is only used as an electrode material of a capacitor and is not used in the reaction of catalytic hydrogenolysis lignin and model compounds thereof.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a nickel-carbon catalyst with high specific surface area, and broaden the utilization modes of waste sugar liquid.
One of the purposes of the invention is to provide the nickel-carbon catalyst with high specific surface area prepared by the preparation method.
The invention also aims to provide the application of the nickel-carbon catalyst with high specific surface area in catalytic hydrogenolysis.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect of the present invention, a method for preparing a nickel-carbon catalyst with a high specific surface area is provided, which comprises the following steps:
(1) selecting waste sugar liquid generated in the production process of vitamin C as a raw material, removing insoluble substances on the surface of the waste sugar liquid by vacuum filtration, drying the waste sugar liquid, and grinding the waste sugar liquid into powder to obtain solid raw material waste sugar residues; putting a proper amount of waste sugar residues into a tubular furnace to be carbonized for 2h at the temperature of 600-;
(2) adding the carrier AC prepared in the step (1) into a nickel salt aqueous solution under stirring to ensure high dispersity, and then soaking the mixed solution at room temperature for 24 hours; then drying the sample; placing the dried catalyst in a tubular furnace, and calcining for 2 hours at the temperature of 450 ℃ in an inert atmosphere; and finally, putting the calcined catalyst in a pyrolysis tube, and reducing for 2h at the temperature of 450 ℃ in a hydrogen atmosphere to obtain the Ni/AC catalyst.
Preferably, the nickel salt in step (2) is selected from one or more of nickel nitrate hexahydrate, nickel chloride hexahydrate, basic nickel carbonate or nickel acetate.
In another aspect of the invention, a nickel-carbon catalyst with high specific surface area is provided, which is prepared by the preparation method.
Preferably, the loading of nickel in the nickel carbon catalyst is 10 wt.%.
In another aspect of the invention, the application of the nickel-carbon catalyst with high specific surface area in the aspect of catalytic hydrogenolysis of diphenyl ether is provided.
The specific application steps comprise: putting substrate diphenyl ether, nickel-carbon catalyst and isopropanol into a reactor, sealing, and then removing residual air by introducing hydrogen; then, pressurizing the reactor to 0.1-0.5MPa by hydrogen at room temperature, setting the temperature to 140-160 ℃, and keeping the temperature for 30-60min at the rotation speed of 700-900 rpm; after the reaction is finished, naturally cooling the reactor to room temperature and relieving pressure; finally, the mixture in the reaction kettle was collected in a beaker and the compound was filtered and the liquid product was analyzed by gas chromatography-mass spectrometer (GC-MS) and Gas Chromatograph (GC).
Preferably, the reaction pressure is 0.5MPa, the reaction temperature is 140 ℃ and the reaction temperature is 60 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts high-concentration waste sugar liquid generated in the production process of vitamin C as raw material, the waste sugar liquid is dried to obtain waste sugar residues, and the specific surface area of the waste sugar residues is up to 3220m by carbonizing and activating the waste sugar residues and regulating and controlling the preparation conditions of the waste sugar residues2The porous AC of/g can uniformly disperse nickel on the AC with high specific surface area by loading metallic nickel through an impregnation method, and the obtained nickel-carbon catalyst can effectively promote the cracking of diphenyl ether, thereby realizing the high value-added utilization of wastes and reducing the pollution to the environment.
2. Compared with other nickel-based catalysts, the nickel-carbon catalyst prepared by the invention can selectively hydrogenolyze the lignin model compound diphenyl ether under milder conditions (140 ℃, 0.5MPa) to ensure that the diphenyl ether is completely converted.
Drawings
FIG. 1 is an XRD pattern of Ni/AC-600-700-2.5 catalyst prepared in example 1 of the present invention;
FIG. 2 is an SEM image of the catalyst Ni/AC-600-700-2.5 prepared in example 1 of the present invention;
FIG. 3 is a TEM image of the catalysts Ni/AC-600-700-2.5 prepared in example 1 of the present invention;
FIG. 4 is a distribution diagram of the metal nickel particle size in the catalyst Ni/AC-600-700-2.5 prepared in example 1 of the present invention;
FIG. 5 is a graph of the effect of reaction temperature on the catalytic hydrogenolysis of diphenyl ether;
FIG. 6 is a graph showing the effect of reaction time on the catalytic hydrogenolysis of diphenyl ether
Figure 7 is a graph of the effect of hydrogen pressure on the catalytic hydrogenolysis of diphenyl ether.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The ACs prepared in the following examples are named as follows: AC-X-Y-Z (X600, 650 for carbonization temperature; Y600, 700 for activation temperature; Z2, 2.5, 3 for activation time).
Example 1: preparation of catalyst Ni/AC-600-700-2.5
First, preparation of the vector AC-600-700-2.5
The waste sugar liquid generated in the production process of vitamin C is selected as a raw material, insoluble substances on the surface of the waste sugar liquid are removed through vacuum filtration, and then the waste sugar liquid is dried for a certain time in an oven at 105 ℃ and ground into powder to obtain solid raw material waste sugar residue. Selecting 5g of waste sugar residues, putting the waste sugar residues into a tubular furnace, carbonizing the waste sugar residues for 2h at 600 ℃, grinding and uniformly mixing coke obtained after carbonization and potassium hydroxide (the mass ratio of the potassium hydroxide to the coke is 3:1), then putting the mixture into the tubular furnace for activation for 2.5h at 700 ℃, washing an activated sample by using 2mol/L dilute hydrochloric acid and deionized water until a filtrate is neutral, and drying the washed sample for 4h in a drying oven at 105 ℃ to obtain a carrier AC-600-type 700-2.5.
Second, impregnation method for preparing nickel-carbon catalyst
0.55g of nickel nitrate hexahydrate (Ni (NO)3)2·6H2O) was placed in a beaker and 2mL of deionized water was added. After stirring until it was completely dissolved, the AC (1g) prepared above was added to the aqueous solution kept under stirring to ensure high dispersion. The mixed solution was then immersed at room temperature for 24h to ensure high dispersion of the metal precursor on the support. The sample was then dried in an oven at 110 ℃ for 6 h. The dried catalyst is placed in a tubular furnace, argon (Ar) is used as protective gas, the flow rate is 60mL/min, and the catalyst is calcined for 2h at the temperature of 450 ℃. Finally, the calcined catalystThe agent was placed in a pyrolysis tube and hydrogen (H) at a flow rate of 60mL/min2) Reducing for 2h under the condition of atmosphere and temperature of 450 ℃ to obtain the catalyst Ni/AC-600-700-2.5. The prepared catalyst was placed in a desiccator for replacement. The loading amount is 10% by weight.
Example 2: preparation of catalyst Ni/AC-600-700-2
The preparation process was substantially the same as that of example 1 except that the carbonization temperature was 600 ℃, the activation temperature was 700 ℃ and the activation time was 2 hours.
Example 3: preparation of catalyst Ni/AC-600-700-3
The preparation method was substantially the same as that of example 1, except that the carbonization temperature was 600 ℃, the activation temperature was 700 ℃ and the activation time was 3 hours.
Example 4: preparation of catalyst Ni/AC-600-2
The preparation method was substantially the same as that of example 1 except that the carbonization temperature was 600 ℃, the activation temperature was 600 ℃ and the activation time was 2 hours.
Example 5: preparation of catalyst Ni/AC-650-700-2
The preparation process was substantially the same as that of example 1 except that the carbonization temperature was 650 deg.C, the activation temperature was 700 deg.C, and the activation time was 2 hours.
TABLE 1 physical Properties of Nickel-carbon catalysts and Supports
aThe total specific surface area is calculated by the BET formula.
bAt a relative pressure P/P0Total pore volume was determined when 0.99.
cThe specific surface area and volume of the micropores were calculated by the t method.
dThe total specific surface area and the micropore surface area and the difference between the total pore volume and the micropore volume.
The physicochemical properties of the catalyst and the support are listed in table 1. AC-600-700-2.5-prepared by carbonizing and activating waste sugar residuesCan reach 3220m2The specific surface area of the prepared catalyst is reduced with the impregnation of nickel into the carrier, which shows that the nickel can be loaded into the pore channels of the AC, and the specific surface area of the Ni/AC-600-700-2.5 is reduced more than that of other catalysts, which shows that the nickel is more uniformly dispersed on the carrier.
FIG. 1 is an XRD pattern of the catalyst Ni/AC-600-700-2.5 prepared in example 1; as can be seen from FIG. 1, the spectral distribution of the nickel-carbon catalyst is substantially consistent with that of the AC carrier, and the characteristic peak of nickel is not observed very clearly, which indicates that nickel is distributed very uniformly on the AC-600-700-2.5 carrier, and the characteristic peak of nickel is not shown on the spectrum.
FIG. 2 is the SEM image of the carrier AC-600-700-2.5 and the catalyst Ni/AC-600-700-2.5 obtained in example 1; as can be seen from FIG. 2, the waste sugar residues generate more micropores and mesopores through the carbonization and activation process, which is beneficial to the distribution of metallic nickel; the metal nickel is uniformly distributed in the pore channels of the AC, thereby being beneficial to the catalytic process.
FIG. 3 is a TEM image of the catalysts Ni/AC-600-700-2.5 obtained in example 1; as shown in FIG. 3, the metal nickel is uniformly distributed in the Ni/AC-600-700-2.5 catalyst without agglomeration.
FIG. 4 is a distribution diagram of the metal nickel particle size in the catalyst Ni/AC-600-700-2.5 prepared in example 1; as can be seen from fig. 4, the average particle size of nickel in the catalyst is 4.4nm, which is smaller than the particle size of the metal on other catalysts, and the small particle size of the catalyst enables the catalytic reaction to proceed more easily, so that the C — O bond in DPE is more easily broken to obtain the target product.
Example 6: catalytic hydrogenolysis application of diphenyl ether
Diphenyl ether (DPE) was chosen as a model compound for the 4-O-5 bond to explore the catalytic process of C-O bond cleavage in lignin.
100mg of DPE, 50mg of catalyst and 20mL of isopropanol were placed in a 100mL stainless steel autoclave and sealed. Then, the reaction vessel was purged with hydrogen three times to remove excess air, and hydrogen (1MPa) was charged under a certain pressure. The temperature was set to the desired reaction temperature (140 ℃) and held at 800rpm for a certain time (120 min). After the reaction is finished, the reactor is naturally cooled to room temperature and decompressed. Finally, the mixture in the reaction kettle was collected in a beaker and the compound was filtered and the liquid product was analyzed by gas chromatography-mass spectrometer (GC-MS) and Gas Chromatograph (GC).
TABLE 2 Effect of different nickel-carbon catalysts on DPE catalytic hydrogenolysis
And (3) the DPE breaks C-O bonds under the action of a nickel-carbon catalyst and is hydrogenated to produce a target product: benzene, phenol, cyclohexane and cyclohexanol. A small portion of the DPE is also hydrogenated directly to by-products: cyclohexyl ether and dicyclohexyl ether. The formation of by-products is avoided during the reaction, because the stability of the by-products is very good and the cracking to the target product is difficult to occur. As shown in Table 2, the best catalytic hydrogenolysis effect of the DPE by the Ni/AC-600-700-2.5 is realized, the conversion rate of the DPE can reach 100 percent, and the AC carrier prepared by carbonizing the carrier waste sugar residues at 600 ℃, activating at 700 ℃ and keeping the activation time for 2 hours is used for loading the metallic nickel to prepare the catalyst with the best effect. The best effect is achieved when the carbonization temperature is 600 ℃, and the effect of the catalyst is remarkably reduced when the carbonization temperature is further increased to 650 ℃, which may be that the structure of the prepared coke is compact due to the overhigh carbonization temperature, which is not beneficial to KOH activation pore-forming, so that nickel cannot be well dispersed on the carrier. The activation temperature is the best at 700 ℃, the effect is poorer at 600 ℃, and the increase of the activation temperature is beneficial to the proceeding of the activation reaction, further promotes the increase of the specific surface area and is beneficial to the dispersion of the metal. By changing the carbonization temperature and the activation temperature, the optimal preparation conditions of the porous AC are preliminarily determined, and then the influence of the activation time is mainly researched, so that the catalytic effect of the supported nickel is better when the activation time is 2.5h, the catalytic effect is not better than 2.5h when the activation time is 2h, the hydrogenation effect of the Ni/AC-600-700-2.5 on DPE is better than that of the Ni/AC-600-700-2, and the benzene and the phenol are easier to hydrogenate to produce the cyclohexane and the cyclohexanol. When the activation time is further increased to 3h, the conversion of DPE drops from 100% to 61%, possibly resulting in collapse of AC pore structure due to too long activation time and thus affecting the loading of nickel.
Example 7: effect of reaction temperature on Diphenyl Ether conversion
The reaction procedure was as in example 6, except that the reaction conditions were: 100mg DPE, 50mg Ni/AC-600-700-2.5, 20mL isopropanol, 1MPa H2，2h。
The reaction temperature plays an important role in the catalytic hydrogenolysis process of DPE. Therefore, the best Ni/AC-600-700-2.5 was selected, and the influence of temperature on the catalytic hydrogenolysis of DPE was studied. As can be seen from fig. 5, at a reaction temperature of 120 ℃, the conversion of DPE reached 84%, and as the temperature was further increased to 140 ℃, DPE could be completely converted and the yield of benzene and phenol decreased, which was gradually hydrogenated to cyclohexane and cyclohexanol, the yield of phenol was 0, which was completely converted to cyclohexanol. It can be seen from the figure that the selectivity of C-O cracking of DPE is greater than that of direct hydrogenation with increasing reaction temperature, the formation of the target product is favored by increasing temperature, and the yield of the target product is basically unchanged with further increasing temperature to 160 ℃, so the optimal temperature for the hydrogenolysis of DPE is 140 ℃.
Example 8: effect of reaction time on Diphenyl Ether conversion
The reaction procedure was as in example 6, except that the reaction conditions were: 100mg DPE, 50mg Ni/AC-600-700-2.5, 20mL isopropanol, 1MPa H2，160℃。
Figure 6 shows the effect of reaction time on DPE catalytic hydrogenolysis. The reaction was stopped immediately when the reaction temperature rose to 160 ℃ and the product obtained was the result of a 0min reaction. It can be seen that at 0min, the conversion rate of DPE reaches 90%, and the excellent catalytic performance of the nickel-carbon catalyst is shown. With further increase in time, benzene and phenol were further reduced to cyclohexane and cyclohexanol, and at 30min the conversion of DPE reached 100% and phenol was completely converted to cyclohexanol. When the reaction time is 60min, the yield of the objective product is substantially constant with further increase of the reaction time, so that the optimum reaction time is 60 min.
Example 9: effect of Hydrogen pressure on Diphenyl Ether conversion
The reaction procedure was as in example 6, except that the reaction conditions were: 100mg diphenyl ether, 20mL isopropanol, 50mg Ni/AC-600-700-2.5, 160 ℃ for 2 h.
Figure 7 explores the effect of hydrogen pressure on DPE catalytic hydrogenolysis during the reaction. When the reaction pressure is 0.1MPa, the conversion rate of DPE reaches 100%, and the hydrogen pressure is low, so that a large amount of benzene and phenol exist in the product, the phenol gradually disappears and is converted into cyclohexanol with further increase of the reaction pressure, the selectivity of the target product reaches the maximum when the reaction pressure is 0.5MPa, and the by-product is increased with further increase of the reaction pressure, so that the most suitable hydrogen reaction pressure is 0.5 MPa.
Claims (5)
1. The application of the high-specific-surface-area nickel-carbon catalyst in the aspect of catalytic hydrogenolysis of diphenyl ether is characterized in that the preparation of the high-specific-surface-area nickel-carbon catalyst comprises the following steps:
(1) selecting waste sugar liquid generated in the production process of vitamin C as a raw material, removing insoluble substances on the surface of the waste sugar liquid by vacuum filtration, drying the waste sugar liquid, and grinding the waste sugar liquid into powder to obtain solid raw material waste sugar residues; a proper amount of waste sugar residues are placed in a tube furnace at 600-650oCarbonizing at the temperature of C for 2h, grinding and mixing the coke obtained after carbonization and potassium hydroxide according to the mass ratio of 1:3 uniformly, and then placing the mixture into a tubular furnace for 600-700 timesoActivating for 2-3h at the temperature of C, washing the activated sample by dilute hydrochloric acid and deionized water in sequence until the filtrate is neutral, and drying to obtain a carrier AC;
(2) adding the carrier AC prepared in the step (1) into a nickel salt aqueous solution under stirring to ensure high dispersity, and then soaking the mixed solution at room temperature for 24 hours; then drying the sample; the dried catalyst was placed in a tube furnace under inert atmosphere at 450 deg.foCalcining for 2 hours at the temperature of C; finally, the calcined catalyst is placed in a pyrolysis tube in a hydrogen atmosphere at 450 deg.CoAnd reducing for 2h at the temperature of C to obtain the Ni/AC catalyst.
2. Use according to claim 1, wherein the nickel salt in step (2) is selected from one or more of nickel nitrate hexahydrate, nickel chloride hexahydrate, nickel hydroxycarbonate or nickel acetate.
3. The use according to claim 1, wherein the nickel loading in the nickel carbon catalyst is 10 wt.%.
4. The use according to claim 1, characterized in that the specific application steps comprise: putting substrate diphenyl ether, nickel-carbon catalyst and isopropanol into a reactor, sealing, and then removing residual air by introducing hydrogen; subsequently, the reactor was pressurized to 0.1-0.5MPa with hydrogen at room temperature, and the temperature was set to 140-oC, keeping the rotation speed of 700-900rpm for 30-60 min; after the reaction is finished, naturally cooling the reactor to room temperature and relieving pressure; finally, the mixture in the reaction kettle was collected in a beaker and the compound was filtered and the liquid product was analyzed by gas chromatography-mass spectrometer and gas chromatograph.
5. Use according to claim 4, wherein the reaction pressure is 0.5MPa and the reaction temperature is 140 MPaoAnd C, the reaction time is 60 min.
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