CN114700092B - Nickel phosphide catalyst for hydrodeoxygenation of phenolic compound and preparation method thereof - Google Patents
Nickel phosphide catalyst for hydrodeoxygenation of phenolic compound and preparation method thereof Download PDFInfo
- Publication number
- CN114700092B CN114700092B CN202210218968.6A CN202210218968A CN114700092B CN 114700092 B CN114700092 B CN 114700092B CN 202210218968 A CN202210218968 A CN 202210218968A CN 114700092 B CN114700092 B CN 114700092B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sio
- hydrodeoxygenation
- carrier
- preparing
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000002989 phenols Chemical class 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 239000011734 sodium Substances 0.000 claims abstract description 145
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 126
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- -1 phenol compound Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 55
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 14
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 14
- 229940094933 n-dodecane Drugs 0.000 claims description 14
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 7
- 238000004817 gas chromatography Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 14
- 230000035484 reaction time Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 37
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 20
- 239000011148 porous material Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000007605 air drying Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or 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
- B01J35/20—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
-
- 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
- B01J35/617—500-1000 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
- B01J35/635—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
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A nickel phosphide catalyst for hydrodeoxygenation of phenol compound is prepared from nano sodium carbonate modified silicon dioxide Na 2 CO 3 ‑SiO 2 As a carrier and Ni on the carrier 2 The P active phase. The catalyst of the invention adopts cheap Ni 2 P is the active phase and Ni 2 P/Na 2 CO 3 ‑SiO 2 The preparation method of the catalyst precursor is simple, and has the advantages of low preparation cost, short preparation time and the like of the catalyst; the method for preparing cycloalkane by hydrodeoxygenation of the nickel phosphide catalyst phenol compound has the advantages of short hydrodeoxygenation reaction time and high hydrogenation activity, and achieves the excellent effect of preparing cycloalkane by efficiently hydrodeoxygenation of the phenol compound by perfect combination of catalytic activity, selectivity and mass transfer.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds and a preparation method thereof.
Background
With the increasing shortage of energy and pollution, the search for sustainable green energy is currently the primary topic. Lignin is the second largest biomass resource in nature, except cellulose, and is the only clean non-petroleum resource in nature that can provide renewable aromatic compounds. The biomass oil obtained by pyrolysis of lignin has more benzene ring structural units, is a cheap and clean resource capable of being converted into high-energy aromatic hydrocarbon and naphthenic hydrocarbon, and is one of the most potential petroleum supplementary energy sources. Lignin has been successfully depolymerized into crude biomass oil by a variety of advanced conversion techniques such as pyrolysis, liquefaction, and the like. However, crude biomass oil has high oxygen content, and contains oxygen-containing compounds such as phenol, ketone, aldehyde, furan, alcohol, ether and ester, so that the combustion heat value is low, the stability and the oil solubility are poor, the corrosiveness is strong, and the practical application is greatly limited. Therefore, the upgrading modification of the crude biomass oil to achieve high-grade utilization thereof is of great significance.
Hydrodeoxygenation (HDO) is an efficient way to convert oxygen-containing derivatives in poor crude biomass oil to clean oxygen-free naphthene products. There are two main approaches to hydrodeoxygenation of typical biomass oil model compounds: (1) Direct Deoxygenation (DDO), the deoxygenation product being an aromatic hydrocarbon; (2) Hydro-deoxygenation (HYD), deoxygenation product is cycloalkane (fig. 1). The cycloparaffin obtained by the HYD reaction path has high heat quantity and low solidifying point, is not only an important component of transportation fuels such as gasoline, diesel oil and aviation kerosene, but also an important chemical raw material, and has higher added value of products. Therefore, the selective HDO of crude biomass oil to produce naphthenes is of interest.
The content of phenolic compounds in the oxygenated compounds in the crude biomass oil is the highest. Because the oxygen in the phenolic hydroxyl groups is directly connected with the benzene rings in the phenolic oxygen-containing compounds, the oxygen-containing functional groups are stable, and the activation energy required for breaking the C-O bonds is high. Therefore, the HDO has high difficulty, harsh reaction conditions and long reaction time. At present, there are many articles and patents reporting methods for preparing hydrocarbon fuels using the oxygen-containing organic compound HDO. However, in the existing hydrodeoxygenation catalytic technology, the noble metal catalyst has high reaction activity, but the catalyst has poor stability, high cost and limited industrial application. Non-noble metal sulphide catalysts require the introduction of sulphide compounds to maintain their activity, which lead to contamination of the product. Table 1 summarizes the literature reported p-cresol HDO performance of the different catalysts. As can be seen from the table, the p-cresol HDO of different catalysts has long reaction time (> 240 min) and low conversion rate of partial catalyst raw materials, and in order to achieve high methyl cyclohexane selectivity, severe reaction conditions such as high temperature or high pressure are required. Therefore, developing a high-efficiency HDO catalyst, shortening the reaction time and realizing the selective hydrogenation of phenolic compounds to prepare naphthenes with high added value is important.
Studies have shown that the hydrogenation activity of phenolic compounds can be realized by regulating the morphology of Pt nanocrystals, such as the hydrogenation activity of a Pt concave cube with a high index surface, which is 6.3 times and 1.3 times higher than that of the Pt cube and octahedron respectively. The structural characteristics, morphology and crystal face of the carrier also have a significant effect on the catalytic activity of the catalyst. As HDO catalyst support, (1) has a specific surface area large enough to facilitate the dispersion of the hydrogenation-active component; (2) Suitable pore volume and pore structure are required to facilitate mass transfer of reactants and products; (3) Suitable acid sites or defect sites are provided to enhance the activity of the catalyst. However, so far, there have been few reports on researches on the preparation of cycloalkanes from phenolic compounds HDO with respect to carriers having a specific pore structure.
Disclosure of Invention
The invention aims to provide a nickel phosphide catalyst for hydrodeoxygenation of a phenolic compound, which solves the problems of high cost of a noble metal catalyst and long reaction time of a non-noble metal catalyst when a prior HDO catalyst is adopted to prepare cycloalkane from a phenolic oxygen-containing compound HDO, and realizes efficient hydrodeoxygenation of the phenolic oxygen-containing compound to prepare the cycloalkane.
The second object of the invention is to provide a preparation method of the nickel phosphide catalyst for hydrodeoxygenation of the phenolic compound.
It is a third object of the present invention to provide a process for preparing cycloalkanes by catalysis with the above catalyst.
The invention is realized by the following technical scheme:
1. a nickel phosphide catalyst for hydrodeoxygenation of phenol compound is prepared from sodium carbonate modified nano silicon dioxide Na 2 CO 3 -SiO 2 Support and Ni on the support 2 P active phase.
2. According to the preparation method of the phenol compound hydrodeoxygenation nickel phosphide catalyst, tetraethyl orthosilicate is used as a silicon source, cetyl ammonium bromide is used as a surfactant, sodium benzoate ortho-hydroxy is used as a structure guiding agent, triethanolamine is used as a chelating agent, the hydrolysis speed is regulated and controlled by controlling the pH value of the solution, and sodium carbonate is added for modification and synthesis of Na 2 CO 3 -SiO 2 The carrier is loaded with a nickel source and a phosphorus source, and Ni is obtained through reduction 2 P/Na 2 CO 3 -SiO 2 A catalyst.
Further, the molar ratio of silicon to sodium carbonate=5 to 20:1.
Further, the specific steps are as follows:
(1) Dissolving 1.4 mmol of triethanolamine and 3.7 mmol of sodium o-hydroxy benzoate in 75mL of water, adding cetyl ammonium bromide, and stirring at 80deg.C for 30min under ultrasound, wherein the molar ratio of cetyl ammonium bromide to sodium o-hydroxy benzoate is 0.2-0.6:1;
(2) Adding 12 mL silicon source, ultrasonic stirring for 60min, adding sodium carbonate, regulating pH to 9 with ethanolamine, ultrasonic stirring for 15 min, placing in 80 deg.C oven at constant temperature of 2-3 h, cooling to room temperature, filtering, washing, drying, and calcining the obtained white powder in muffle furnace at 600 deg.C for 4 h to obtain Na 2 CO 3 -SiO 2 A carrier; the silicon source is tetraethyl orthosilicate, si/Na 2 CO 3 The molar ratio is 5-20:1;
(3) A nickel source, a phosphorus source and (2) Na 2 CO 3 -SiO 2 Adding the carrier into water, continuously stirring for 2 h, standing for 12 h at room temperature, then placing in a 90 ℃ air blast drying oven 12 h to obtain a catalyst precursor, and performing temperature programming reduction to obtain Ni 2 P/Na 2 CO 3 -SiO 2 Catalytic reactionAn agent; the concentration of Ni is 0.1-0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9.
Further, the nickel source is any one of nickel chloride, nickel nitrate and nickel acetate.
Further, the phosphorus source is any one of ammonium hypophosphite and sodium hypophosphite.
Further, the washing in the step (2) is to alternately wash with ethanol and water for 3-6 times, and the drying is to dry in vacuum for 8-24 hours at 50-100 ℃.
Further, the temperature-programmed reduction method in the step (3) is specifically to put the catalyst precursor into a tube furnace, and take 3 in a hydrogen atmosphere of 150 mL/min o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
3. The method for preparing cycloalkane by catalyzing nickel phosphide catalyst of hydrodeoxygenation of phenolic compound takes mixture of straight-chain alkane and naphthalene as solvent, phenolic compound as raw material, and the reaction is stopped at the reaction temperature of 200-275 ℃ and the hydrogen partial pressure of 2-4 MPa for 0.5-2 hours, and the supernatant is taken to analyze the product composition by gas chromatography; the mass percentage of the phenolic compound in the reaction system is 2-5%, ni 2 P/Na 2 CO 3 -SiO 2 The mass ratio of the catalyst to the phenol is 0.002-0.008:1.
Further, the phenolic compound is one of phenol, o-cresol, m-cresol and p-cresol, the mixed solvent of straight-chain alkane and naphthalene is a mixed solvent of n-dodecane with stable property and any one of decalin and tetrahydronaphthalene, wherein the mass percentage of the n-dodecane is 80%.
The technical scheme has the advantages that:
(1) The catalyst of the invention adopts cheap Ni 2 P is an active phase, and a simple one-step method is adopted to synthesize Ni 2 P/ Na 2 CO 3 -SiO 2 The catalyst precursor has the advantages of low catalyst preparation cost, short preparation time and the like;
(2) The method for preparing cycloalkane by selective hydrogenation of phenolic compounds has the advantage of short HDO reaction time, and is mainly because: (a) The micelle formed by the surfactant cetyl ammonium bromide in the aqueous solution forms a straight-through special pore structure which expands outwards from the center, and the catalyst has a large pore diameter (14.1 nm) while the large pore volume which cannot be realized by other conventional methods is obtained; this greatly increases the mass transfer rate of the reactants to the active sites on the catalyst surface; (b) The addition of ethanolamine can further control the hydrolysis speed of tetraethyl orthosilicate by adjusting the pH value of the solution, thereby ensuring that the obtained carrier has a radial pore structure with regular and uniform size (200 nm) and promoting the mass transfer speed of reactants; (c) Na added in the carrier preparation process 2 CO 3 And (3) hydrolyzing in the aqueous solution to obtain bicarbonate and hydroxide, wherein the generated hydroxide can influence the hydrolysis speed of tetraethyl orthosilicate, further regulate and control the pore structure of the carrier and promote the mass transfer speed of reactants. Thus, the Ni obtained 2 P/Na 2 CO 3 -SiO 2 The reaction time for preparing cycloalkane by phenol hydrogenation of the catalyst is greatly shortened;
(3) The method for preparing cycloalkane by selectively hydrogenating the phenolic compound provided by the invention has high hydrogenation activity, mainly because: (a) Ni (Ni) 2 P/Na 2 CO 3 -SiO 2 The through special pore structure of the catalyst which is expanded outwards from the center is beneficial to fully utilizing each active site in the catalyst, and the large specific surface area is beneficial to highly dispersing the active phase, so that the activity of the catalyst is improved; (b) Na added in the carrier preparation process 2 CO 3 Generating bicarbonate and hydroxyl by hydrolysis, decomposing the bicarbonate to release gas at high temperature, and forming defect sites on the surface of the carrier, wherein the defect sites can regulate and control the coordination environment of Ni, so that the hydrogenation activity of the catalyst is improved;
(4) Through perfect combination of catalytic activity, selectivity and mass transfer, the excellent effect of preparing cycloalkane from phenol compounds by high-efficiency HDO is realized.
Drawings
FIG. 1 is a chemical reaction equation for hydrodeoxygenation to produce cycloalkanes;
FIG. 2 is Ni 2 P/Na 2 CO 3 -SiO 2 XRD pattern of the catalyst;
FIG. 3 is Ni 2 P/Na 2 CO 3 -SiO 2 A TEM (a) and a comparative supported activity (b) graph of the catalyst;
FIG. 4 shows the reaction time vs. Ni 2 P/Na 2 CO 3 -SiO 2 Influence of catalyst HDO performance;
FIG. 5 shows the reaction temperature vs. Ni 2 P/Na 2 CO 3 -SiO 2 Influence of catalyst HDO performance;
FIG. 6 shows reaction pressure vs. Ni 2 P/Na 2 CO 3 -SiO 2 Influence of catalyst HDO performance;
description of the embodiments
The technical scheme of the present invention is further described below with reference to specific examples, but should not be construed as limiting the present invention:
examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst and XRD and FTIR characterization.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 0.8 mmol of cetylammonium bromide are weighed, dissolved in 75mL water and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of Na 2 CO 3 (Si/Na 2 CO 3 The molar ratio is 5:1), after the pH value of the solution is regulated to 9 by ethanolamine, the ultrasonic stirring is continued for 15 min, and the solution is placed in an 80 ℃ oven for constant temperature 2 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 3 times, and vacuum drying at 80 ℃ for 12 hours. The white powder obtained is placed in a muffle furnace to be roasted at 600 DEG C4 h to obtain Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 The carrier, nickel chloride and ammonium hypophosphite are dissolved in water. Wherein the concentration of Ni in water is 0.1 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
Ni obtained in this example 2 P/Na 2 CO 3 -SiO 2 Catalyst XRD and FTIR characterization:
ni obtained in the step (2) 2 P/Na 2 CO 3 -SiO 2 XRD characterization of the catalyst, analysis of the active phase in the tested catalyst, showed (see FIG. 2) that an amorphous-characterized peak appears near 2θ=23° belonging to SiO 2 Is a characteristic peak of (2). Characteristic peaks at 2θ=40.8°,44.6 °,47.3 ° and 54.2 ° are attributed to Ni 2 P phases of Ni 2 The P (111), (201), (210) and (300) planes (PDF#03-0953) indicate Ni 2 P/Na 2 CO 3 -SiO 2 The active phase of the catalyst is Ni 2 P nanoparticle form. No diffraction peak of other Ni phases is seen in the spectrogram, which shows that only single Ni exists in the catalyst 2 P nano particles, and no other impurity phase.
Ni obtained in the step (2) 2 P/Na 2 CO 3 -SiO 2 Carrying out FTIR characterization on the catalyst, wherein 1050-1300 cm is obtained in an FTIR spectrum -1 A stretching vibration peak of Si-O-Si appears at 471 and 471 cm -1 The Si-O-Si bending vibration peak appears at the position and is attributed to SiO 2 . At Na (Na) 2 CO 3 -SiO 2 During the carrier synthesis, it is extremely important that the ethanolamine regulates the pH of the solution. The pH control can control the hydrolysis speed of tetraethyl orthosilicate, and plays a role in promoting the formation of Si-O-Si structures and controlling the particle size of the carrier (see TEM characterization).
Examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 The preparation of the catalyst and the TEM characterization were compared with the loading activity.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 1.0 mmol of cetylammonium bromide were weighed out, dissolved in 75mL and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of Na 2 CO 3 (Si/Na 2 CO 3 The molar ratio is 10:1), after the pH value of the solution is regulated to 9 by ethanolamine, the ultrasonic stirring is continued for 15 min, and the solution is placed in an 80 ℃ oven for constant temperature 3 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 5 times, and vacuum drying at 80 ℃ for 12 hours. The obtained white powder was calcined at 600℃in a muffle furnace for 4 h to give Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/ Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 The carrier, nickel acetate and ammonium hypophosphite are dissolved in water. Wherein the concentration of Ni in water is 0.1 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
Ni obtained in this example 2 P/Na 2 CO 3 -SiO 2 Catalyst TEM characterization:
ni obtained in the step (2) 2 P/Na 2 CO 3 -SiO 2 The catalyst was subjected to TEM characterization and the results are shown in FIG. 3. Active phase Ni in catalyst 2 P is uniformly dispersed, no obvious aggregation phenomenon exists, and the hydrolysis speed of tetraethyl orthosilicate is controlled by adjusting the pH value of the solution, thus obtaining Ni with the particle size of about 200nm 2 P/Na 2 CO 3 -SiO 2 A catalyst; ni (Ni) 2 P/Na 2 CO 3 -SiO 2 The catalyst has a straight-through cell structure that expands outwardly from the center (see fig. 3 (a)). The special structure carrier prepared by the invention is beneficial to fully utilizing the catalytic active site, the reaction raw material can quickly reach the active site of the catalyst surface, and the reaction product can be promoted to quickly leave the catalyst surface (see figure 3 (b)). This is a key point that the catalyst has high hydrogenation activity of phenols and converts its phenol compounds into cycloalkanes in a short period of time.
Examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst and BET characterization.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 1.8 mmol of cetylammonium bromide were weighed out, dissolved in 75mL and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of Na 2 CO 3 (Si/Na 2 CO 3 Molar ratio of 10:1), with ethanolamineAfter the pH value of the solution reaches 9, ultrasonic stirring is continued for 15 min, and the solution is placed in an 80 ℃ oven for constant temperature 2 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 3 times, and vacuum drying at 80 ℃ for 24 hours. The obtained white powder was calcined at 600℃in a muffle furnace for 4 h to give Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 The carrier, nickel nitrate and sodium hypophosphite are dissolved in water. Wherein the concentration of Ni in water is 0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
Na obtained in this example 2 CO 3 -SiO 2 Support and Ni 2 P/Na 2 CO 3 -SiO 2 Catalyst BET characterization:
for comparison purposes, siO 2 Ordinary, siO 2 The invention does not add Na 2 CO 3 (using the process of the invention, but without addition of Na) 2 CO 3 ) Na (sodium carbonate) 2 CO 3 -SiO 2 The BET data for the support and the corresponding catalyst are shown in Table 2.
As can be seen from Table 2, na 2 CO 3 -SiO 2 The specific surface area of the carrier is as high as 587 m 2 Per g, pore volume and pore diameter are respectively2.10 cm 3 And/g and 14.3. 14.3 nm, not only has a large specific surface area, but also has a large pore volume and a large pore diameter. And not adding Na 2 CO 3 The resulting vector was compared to (474 m) 2 Per g), the specific surface area is increased by 114 and 114 m 2 And/g. This is due to the Na added during the preparation of the support 2 CO 3 The hydrogen carbonate and the hydroxyl are obtained by hydrolysis in the aqueous solution, and the generated hydroxyl can influence the hydrolysis speed of tetraethyl orthosilicate and further regulate and control the pore structure of the carrier. With Ni 2 P/SiO 2 (Na is not added in the invention) 2 CO 3 ) Catalyst phase (302 m) 2 /g),Ni 2 P/Na 2 CO 3 -SiO 2 Specific surface area of catalyst (525 m) 2 /g) is greatly improved.
With SiO 2 (conventional method) compared with Na obtained by the present invention 2 CO 3 -SiO 2 The carrier has larger specific surface area and pore volume, which indicates that the preparation method of the invention can obtain larger specific surface area. The large specific surface area is beneficial to the high dispersion of the active phase, thereby improving the activity of the catalyst. With Ni 2 P/SiO 2 (general method) and Ni 2 P/SiO 2 (Na is not added in the invention) 2 CO 3 ) Compared with the catalyst, ni 2 P/Na 2 CO 3 -SiO 2 The specific surface area of the catalyst is greatly improved.
Examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of catalyst and Na 2 CO 3 Modification of the influence on the catalytic hydrogenation performance of m-cresol.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 1.7 mmol of cetylammonium bromide were weighed out, dissolved in 75mL and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of Na 2 CO 3 (Si/Na 2 CO 3 The molar ratio is 20:1), after the pH value of the solution is regulated to 9 by ethanolamine, the ultrasonic stirring is continued for 15 min, and the solution is placed in an 80 ℃ oven for constant temperature 2 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 6 times, and vacuum drying at 50 ℃ for 24 hours. The obtained white powder was calcined at 600℃in a muffle furnace for 4 h to give Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 The carrier, nickel chloride and ammonium hypophosphite are dissolved in water. Wherein, the concentration of Ni in water is 0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
For comparison, na was not added 2 CO 3 SiO obtained by the process according to the invention 2 As a carrier, a catalyst was prepared by the same method and designated Ni 2 P/SiO 2 Unmodified catalysts according to the invention.
The Ni is 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the reaction of preparing methylcyclohexane by hydrogenating m-cresol:
ni is added with 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the experiment of preparing methylcyclohexane by the selective hydrogenation of m-cresol. The method comprises the steps of taking a mixture of decalin and n-dodecane as a solvent, wherein the mass fraction of n-dodecane is 80%, and preparing a reaction solution system with the mass fraction of phenol being 5%. Adding Ni 2 P/Na 2 CO 3 -SiO 2 Catalytic reactionThe catalyst and the phenol solution have the mass ratio of 0.002:1, the reaction kettle is sealed, the nitrogen leakage detection is carried out, the hydrogen is introduced after the hydrogen is replaced for three times, and the reaction is stopped after stirring and reacting for 1 hour at the temperature of 250 ℃ and the pressure of 3 MPa; the reaction vessel was cooled to room temperature, hydrogen was purged, the reaction mixture was decanted, and the supernatant was analyzed for product composition by gas chromatography. Experimental results show that Ni 2 P/Na 2 CO 3 -SiO 2 Catalyst meta-cresol conversion>99.9% methylcyclohexane selectivity was 99.9%. Under the same conditions, ni 2 P/SiO 2 The conversion of m-cresol without Al catalyst is only 64.7%, and the selectivity of methylcyclohexane is 91.0%, which shows that Na is added 2 CO 3 The effect of (3) is obvious. This is mainly due to the Na added during the preparation of the support 2 CO 3 The hydrogen carbonate and the hydroxyl are generated by hydrolysis, and when the hydrogen carbonate is decomposed to release gas at high temperature, defect positions are formed on the surface of the carrier, and the defect positions can regulate and control the coordination environment of Ni, so that the hydrogenation activity of the catalyst is improved.
Examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst and m-cresol catalytic hydrogenation experiments.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 1.7 mmol of cetylammonium bromide were weighed out, dissolved in 75mL and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of Na 2 CO 3 (Si/Na 2 CO 3 The molar ratio is 20:1), after the pH value of the solution is regulated to 9 by ethanolamine, the ultrasonic stirring is continued for 15 min, and the solution is placed in an 80 ℃ oven for constant temperature 2 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 6 times, and vacuum drying at 50 ℃ for 24 hours. The obtained white powder was calcined at 600℃in a muffle furnace for 4 h to give Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 The carrier, nickel chloride and ammonium hypophosphite are dissolved in water. Wherein, the concentration of Ni in water is 0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
The Ni is 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the reaction of preparing methylcyclohexane by hydrogenating m-cresol:
ni is added with 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the experiment of preparing methylcyclohexane by the selective hydrogenation of m-cresol. The method comprises the steps of taking a mixture of decalin and n-dodecane as a solvent, wherein the mass fraction of n-dodecane is 80%, and preparing a reaction solution system with the mass fraction of phenol being 5%. Adding Ni 2 P/Na 2 CO 3 -SiO 2 The catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, the reaction kettle is sealed, the leakage detection is carried out by nitrogen, the hydrogen is introduced after the hydrogen is replaced for three times, and the reaction is stopped after stirring and reacting for a certain time at 250 ℃ and 3 MPa; the reaction vessel was cooled to room temperature, hydrogen was purged, the reaction mixture was decanted, and the supernatant was analyzed for product composition by gas chromatography. The experimental results are shown in FIG. 4, wherein the reaction time is 30min, the conversion rate of m-cresol is 74.8%, the selectivity of methylcyclohexane is 95.7%, and the conversion rate of m-cresol is increased after the reaction time is prolonged to 60min>99.9% methylcyclohexane selectivity was 99.9%.
Examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst and m-cresol catalytic hydrogenation experiments.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 0.9 mmol of cetylammonium bromide were weighed out, dissolved in 75mL and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of NaAlO 2 (Si/Al molar ratio is 5:1), regulating the pH value of the solution to 9 by using ethanolamine, continuing ultrasonic stirring for 15 min, and placing the solution in an 80 ℃ oven at constant temperature of 2 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 6 times, and vacuum drying at 100 ℃ for 18 hours. The obtained white powder was calcined at 600℃in a muffle furnace for 4 h to give Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/ Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 The carrier, nickel nitrate and sodium hypophosphite are dissolved in water. Wherein the concentration of Ni in water is 0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
The Ni is 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the reaction of preparing methylcyclohexane by hydrogenating m-cresol:
ni is added with 2 P/Na 2 CO 3 -SiO 2 Catalyst for preparing methyl by m-cresol selective hydrogenationCyclohexane experiment. The method comprises the steps of taking a mixture of decalin and n-dodecane as a solvent, wherein the mass fraction of the n-dodecane is 80%, and preparing a reaction solution system with the mass fraction of p-cresol being 2%. Adding Ni 2 P/Na 2 CO 3 -SiO 2 The catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.008:1, the reaction kettle is sealed, the leakage detection is carried out by nitrogen, the hydrogen is introduced after the hydrogen is replaced for three times, and the reaction is stopped after stirring and reacting for 60min at 200-275 ℃ and 3 MPa; the reaction vessel was cooled to room temperature, hydrogen was discharged, the reaction mixture was poured out, the supernatant was analyzed for the composition of the product by gas chromatography, the experimental result was shown in FIG. 5, the conversion of m-cresol was 65.4% and the selectivity of methylcyclohexane was 91.37% at a reaction temperature of 200℃and the conversion of m-cresol was observed after the reaction temperature was raised to 250 ℃>99.9% methylcyclohexane selectivity was 99.9%.
Examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst and m-cresol catalytic hydrogenation experiments.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 0.9 mmol of cetylammonium bromide were weighed out, dissolved in 75mL and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of Na 2 CO 3 (Si/Na 2 CO 3 The molar ratio is 10:1), after the pH value of the solution is regulated to 9 by ethanolamine, the ultrasonic stirring is continued for 15 min, and the solution is placed in an 80 ℃ oven for constant temperature 2 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 6 times, and vacuum drying at 80 ℃ for 24 hours. The obtained white powder was calcined at 600℃in a muffle furnace for 4 h to give Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 Support, nickel acetate and hypophosphiteAmmonium acid, dissolved in water. Wherein the concentration of Ni in water is 0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
The Ni is 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the reaction of preparing methylcyclohexane by hydrogenating m-cresol:
ni is added with 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the experiment of preparing methylcyclohexane by the selective hydrogenation of m-cresol. The method comprises the steps of taking a mixture of decalin and n-dodecane as a solvent, wherein the mass fraction of n-dodecane is 80%, and preparing a reaction solution system with the mass fraction of m-cresol being 3%. Adding Ni 2 P/Na 2 CO 3 -SiO 2 The catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.005:1, the reaction kettle is sealed, the leakage detection is carried out by nitrogen, the hydrogen is introduced after the hydrogen is replaced for three times, and the reaction is stopped after stirring and reacting for 60min at 250 ℃ and 2-4 MPa; the reaction vessel was cooled to room temperature, hydrogen was discharged, the reaction mixture was poured out, the supernatant was analyzed for the composition of the product by gas chromatography, the experimental result was shown in FIG. 6, the conversion of m-cresol was 76.4% and the methylcyclohexane selectivity was 95.2% when the reaction pressure was 2 MPa, and the conversion of m-cresol was found when the reaction pressure was raised to 3MPa>99.9% methylcyclohexane selectivity was 99.9%.
Examples
This example illustrates Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst and catalytic experiments of different phenolic compounds.
(1) Na 2 CO 3 -SiO 2 Preparation of the carrier:
(a) 1.4 mmol of triethanolamine, 3.7 mmol of sodium o-hydroxy benzoate and 0.9 mmol of cetylammonium bromide were weighed out, dissolved in 75mL and stirred ultrasonically at 80℃for 30 min.
(b) Adding 12 mL tetraethyl orthosilicate into the solution obtained in the step (a), stirring for 60min by ultrasonic, and adding a certain amount of Na 2 CO 3 (Si/ Na 2 CO 3 The molar ratio is 10:1), after the pH value of the solution is regulated to 9 by ethanolamine, the ultrasonic stirring is continued for 15 min, and the solution is placed in an 80 ℃ oven for constant temperature 2 h. After cooling to room temperature, filtration, washing with ethanol and water alternately 3 times, and vacuum drying at 80 ℃ for 24 hours. The obtained white powder was calcined at 600℃in a muffle furnace for 4 h to give Na 2 CO 3 -SiO 2 A carrier.
(2) Ni 2 P/Na 2 CO 3 -SiO 2 Preparation of the catalyst:
(a) Na obtained in the above (1) 2 CO 3 -SiO 2 The carrier, nickel acetate and ammonium hypophosphite are dissolved in water. Wherein the concentration of Ni in water is 0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9. Stirring was continued for 2 h, left to stand at room temperature for 12 h, then placed in a 90 ℃ forced air drying oven 12 h to give a catalyst precursor.
(b) The catalyst precursor obtained in the step (a) is put into a tube furnace and is put into a hydrogen atmosphere of 150 mL/min for 3 percent o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, switching air treatment for 1h, and cooling to room temperature to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
The Ni is 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for the reaction of preparing methylcyclohexane by hydrogenating different phenolic compounds:
ni is added with 2 P/Na 2 CO 3 -SiO 2 The catalyst is used for experiments of preparing methylcyclohexane by selective hydrogenation of phenol, lin Jiafen and o-cresol respectively. The mixture of decalin and n-dodecane is used as a solvent, wherein the mass fraction of the n-dodecane is 80 percent, and the mixture is respectively preparedAnd the mass fraction of the phenol, o-cresol and p-cresol solution is 3 percent. Ni was added to each of the three systems 2 P/Na 2 CO 3 -SiO 2 The catalyst, wherein the mass ratio of the catalyst to the phenolic compound is 0.008:1, the reaction kettle is sealed, the nitrogen leakage detection is carried out, the hydrogen is introduced after the hydrogen is replaced for three times, the reaction is stopped after the hydrogen is introduced, and the reaction is carried out for 90 min under the condition of 250 ℃ and 3 MPa; the reaction vessel was cooled to room temperature, hydrogen was purged, the reaction mixture was decanted, and the supernatant was analyzed for product composition by gas chromatography. The results show that the conversion rate of phenol and p-cresol reaches 99.9%, and the selectivity of methylcyclohexane also reaches 99.9%. The conversion of the o-cresol is 95.9%, and the selectivity of the methylcyclohexane is 98.4%.
Claims (10)
1. A nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds, which is characterized in that: the catalyst is prepared from nano sodium carbonate modified silicon dioxide Na with radial center 2 CO 3 -SiO 2 As a carrier, ni on the carrier 2 P active phase constitution; the catalyst is prepared by the following steps: tetraethyl orthosilicate is used as a silicon source, cetyl ammonium bromide is used as a surfactant, sodium benzoate ortho-hydroxy is used as a structure guiding agent, triethanolamine is used as a chelating agent, the pH of the solution is controlled by the ethanolamine, the hydrolysis speed is regulated and controlled, and sodium carbonate is added for modifying and synthesizing Na 2 CO 3 -SiO 2 The carrier is loaded with a nickel source and a phosphorus source, and Ni is obtained through reduction 2 P/Na 2 CO 3 -SiO 2 A catalyst.
2. The method for preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 1, which is characterized in that: the method takes tetraethyl orthosilicate as a silicon source, cetyl ammonium bromide as a surfactant, sodium benzoate ortho-hydroxy as a structure guiding agent and triethanolamine as a chelating agent, controls the pH of the solution through ethanolamine, regulates and controls the hydrolysis speed, and adds sodium carbonate to modify and synthesize Na 2 CO 3 -SiO 2 The carrier is loaded with a nickel source and a phosphorus source, and Ni is obtained through reduction 2 P/Na 2 CO 3 -SiO 2 A catalyst.
3. The method for preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 2, which is characterized in that: the molar ratio of silicon to sodium carbonate=5-20:1.
4. The method for preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 2, which is characterized in that: the method comprises the following specific steps:
(1) Dissolving 1.4 mmol of triethanolamine and 3.7 mmol of sodium o-hydroxy benzoate in 75mL water, adding cetyl ammonium bromide, and stirring at 80deg.C for 30min under ultrasonic wave, wherein the molar ratio of cetyl ammonium bromide to sodium o-hydroxy benzoate is 0.2-0.6:1;
(2) Adding 12 mL silicon source, ultrasonic stirring for 60min, adding sodium carbonate, regulating pH to 9 with ethanolamine, ultrasonic stirring for 15 min, standing in 80 deg.C oven at constant temperature of 2-3 h, cooling to room temperature, filtering, washing, drying to obtain white powder, and calcining in muffle furnace at 600 deg.C for 4 h to obtain Na 2 CO 3 -SiO 2 A carrier; the silicon source is tetraethyl orthosilicate, si/Na 2 CO 3 The molar ratio is 5-20:1;
(3) Nickel source, phosphorus source and Na 2 CO 3 -SiO 2 Adding the carrier into water, continuously stirring for 2 h, standing for 12 h at room temperature, then placing in a 90 ℃ air blast drying oven for 12 h to obtain a catalyst precursor, and performing temperature programming reduction to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst; the concentration of Ni is 0.1-0.5 mol/L, the molar ratio of Ni to P is 1:2, and the ratio of Ni to Na is 1:2 2 CO 3 -SiO 2 The mass ratio of the carrier is 1:9.
5. The method for preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 4, which is characterized in that: the nickel source is any one of nickel chloride, nickel nitrate and nickel acetate.
6. The method for preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 4, which is characterized in that: the phosphorus source is any one of ammonium hypophosphite and sodium hypophosphite.
7. The method for preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 4, which is characterized in that: the washing in the step (2) is to alternately wash 3-6 times by ethanol and water, and the drying is to be carried out for 8-24 hours at 50-100 ℃.
8. The method for preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 4, which is characterized in that: the temperature programming reduction method in the step (3) is to put the catalyst precursor into a tube furnace, and the catalyst precursor is mixed with 3 in a hydrogen atmosphere of 150 mL/min o C/min, from room temperature to 400 o C and hold 2 h down to 50 o After C, air treatment is switched for 1h, and then the mixture is reduced to obtain Ni 2 P/Na 2 CO 3 -SiO 2 A catalyst.
9. The method for preparing cycloalkane by catalyzing and preparing nickel phosphide catalyst by hydrodeoxygenation of phenolic compound according to claim 1, which is characterized in that: taking a mixture of linear alkane and naphthalene as a solvent, taking a phenolic compound as a raw material, stopping the reaction at the reaction temperature of 200-275 ℃ and the hydrogen partial pressure of 2-4 MPa for 0.5-2 hours, and taking a supernatant liquid to analyze the product composition by using gas chromatography; the mass percentage of the phenolic compound in the reaction system is 2-5%, ni 2 P/Na 2 CO 3 -SiO 2 The mass ratio of the catalyst to the phenol is 0.002-0.008:1.
10. The method for preparing cycloalkane by catalyzing and preparing the nickel phosphide catalyst for hydrodeoxygenation of phenolic compounds according to claim 9, which is characterized in that: the phenolic compound is one of phenol, o-cresol, m-cresol and p-cresol, the mixed solvent of straight-chain alkane and naphthalene is a mixed solvent of n-dodecane with stable property and any one of decalin and tetrahydronaphthalene, wherein the mass percentage of the n-dodecane is 80%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210218968.6A CN114700092B (en) | 2022-03-08 | 2022-03-08 | Nickel phosphide catalyst for hydrodeoxygenation of phenolic compound and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210218968.6A CN114700092B (en) | 2022-03-08 | 2022-03-08 | Nickel phosphide catalyst for hydrodeoxygenation of phenolic compound and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114700092A CN114700092A (en) | 2022-07-05 |
CN114700092B true CN114700092B (en) | 2023-04-25 |
Family
ID=82168033
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210218968.6A Active CN114700092B (en) | 2022-03-08 | 2022-03-08 | Nickel phosphide catalyst for hydrodeoxygenation of phenolic compound and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114700092B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1101530A1 (en) * | 1999-11-19 | 2001-05-23 | Engelhard Corporation | Nickel-iron containing hydrogenation catalyst |
CN110935473A (en) * | 2019-12-09 | 2020-03-31 | 山东理工大学 | Hydrodeoxygenation catalyst and preparation method and application thereof |
-
2022
- 2022-03-08 CN CN202210218968.6A patent/CN114700092B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1101530A1 (en) * | 1999-11-19 | 2001-05-23 | Engelhard Corporation | Nickel-iron containing hydrogenation catalyst |
CN110935473A (en) * | 2019-12-09 | 2020-03-31 | 山东理工大学 | Hydrodeoxygenation catalyst and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114700092A (en) | 2022-07-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
RU2430780C2 (en) | Transition metal-based nanocatalyst, preparation method thereof and use in fischer-tropsch synthesis reactions | |
CN113145155B (en) | Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof | |
CN114405505B (en) | Platinum modified indium-based oxide catalyst and preparation method and application thereof | |
CN114029070A (en) | In-situ hydrogenolysis aryl ether bond catalyst and preparation method and application thereof | |
CN102125847A (en) | Copper nickel silicon catalyst for preparing ethylene glycol and preparation method thereof | |
CN111468121A (en) | Preparation and application of MXene modified biomass carbon nano metal catalyst | |
CN107500296A (en) | A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation | |
CN101428229B (en) | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof | |
Guo et al. | Selective hydrogenation of diphenyl ethers over NiCo bimetallic catalyst | |
CN111644169B (en) | Metal composite modified nano zirconium oxide catalyst and preparation method and application thereof | |
CN108970637B (en) | Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas | |
CN114700092B (en) | Nickel phosphide catalyst for hydrodeoxygenation of phenolic compound and preparation method thereof | |
CN108970635B (en) | Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas | |
CN114832844B (en) | Catalyst for preparing cycloalkane by selective hydrodeoxygenation of phenolic compound and preparation method thereof | |
CN110560137A (en) | Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof | |
CN104128186B (en) | For being prepared the Catalysts and its preparation method of low-carbon alcohols by synthesis gas | |
CN113457724B (en) | Dual-functional catalyst for preparing toluene and co-producing diphenylmethane through direct conversion of synthesis gas and benzene, and preparation method and application thereof | |
CN107537475B (en) | Composite catalyst, preparation method and application thereof | |
CN107537489B (en) | Porous composite catalyst, preparation method and application thereof | |
CN111715252B (en) | Method for catalytically synthesizing organic compound, catalyst and application thereof | |
Li et al. | A catalyst with high activity and selectivity for the synthesis of C2+-OH: ADM catalyst modified by nickel | |
CN114570374A (en) | Cobalt-based catalyst, preparation method and application | |
CN111068662B (en) | Metal nano catalyst and preparation method and application thereof | |
CN117797842B (en) | Catalyst applied to high-carbon alkane preparation by hydrogenolysis of high-carbon alcohol and preparation method thereof | |
CN114984952B (en) | Carbon-coated copper material and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |