CN106187956B - A kind of method that furfural prepares 2- methylfuran through add in-place hydrogen - Google Patents
A kind of method that furfural prepares 2- methylfuran through add in-place hydrogen Download PDFInfo
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- CN106187956B CN106187956B CN201610510424.1A CN201610510424A CN106187956B CN 106187956 B CN106187956 B CN 106187956B CN 201610510424 A CN201610510424 A CN 201610510424A CN 106187956 B CN106187956 B CN 106187956B
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- furfural
- hydrogen
- methylfuran
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 74
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 230000035484 reaction time Effects 0.000 claims abstract description 18
- 229910002482 Cu–Ni Inorganic materials 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 84
- 229910052759 nickel Inorganic materials 0.000 claims description 63
- 239000010949 copper Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 238000003756 stirring Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 41
- 229910002651 NO3 Inorganic materials 0.000 description 14
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 10
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000008892 Helianthus tuberosus Species 0.000 description 1
- 235000003230 Helianthus tuberosus Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019897 RuOx Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method that furfural prepares 2- methylfuran through add in-place hydrogen, include the following steps: to react after 1) mixing furfural, catalyst with hydrogen supply agent, is heated to 190~250 DEG C, the reaction time is 0.5~9h；The catalyst is Cu-Ni/Al2O3Catalyst, active component Cu, Ni alloy, carrier Al2O3；2) reaction product is cooling, and organic solvent dissolution obtains 2- methylfuran after filtering.The preparation method is easy to operate, not the addition of hydrogen, greatly reduces hydrogen consumption and reduces production equipment cost；Secondly, catalyst is the non-precious metal catalyst without Cr element, reduce the pollution to environment and the harm of human body.
Description
Technical field
The present invention relates to the preparation fields of 2- methylfuran, and in particular to a kind of furfural prepares 2- methyl furan through add in-place hydrogen
The method muttered.
Background technique
2- methylfuran (2-MF) is a kind of important biomass platform chemicals, and organic solvent and basic chemical industry are former
Material, there is critically important application in pesticide, medicine, the field of polymers.2-MF can be by the non-cereal crops system such as jerusalem artichoke, corn stover
Take, raw material sources are abundant, and due to 2-MF octane number with higher, quality is low, calorific value with respect to ethyl alcohol improves about 16% and
The advantages such as water are slightly soluble in, are considered as one of substitute Fuel of Internal Combustion Engine [Feng Dengquan, internal combustion engine journal, (2014) 340].
The method of industrial production 2-MF is mainly made by furfural (furfuryl alcohol) catalytic hydrogenation at present, and this method needs to consume
A large amount of hydrogen, higher requirements are also raised for reaction unit for the hydrogen of high pressure at the same time.And H2There are biggish
Safety and storage and transportation problem, and China has that energy consumption is high, dirty mainly with the fossil energies hydrogen manufacturing such as coal, natural gas, in hydrogen production process
The problems such as dye is serious and CO2 emission intensity is big.Furthermore industrially production 2-MF master's catalyst to be used is Cu-Cr body
Series catalysts, it is expensive, but also cause serious environmental pollution.Therefore replace hydrogen as hydrogen source using hydrogen supply agent,
Become the target of more and more researcher researchs using more cheap, environmental protection catalyst.
The related work for having there are some document reports to prepare 2-MF about furfural add in-place hydrogen at present, and obtain
Good achievement.Vlachos etc. (Applied Catalysis A:General, 2014,480,17-24) is reported with Ru/C
As catalyst, under conditions of isopropanol is as hydrogen supply agent, the 2-MF that yield is 61% can be obtained.Subsequent Vlachos etc.
(ACS Catalysis,2015,5,3988-3994)(Journal of Molecular Catalysis A:Chemical,
2014,392,223-228) a kind of difunctional Ru/RuOx/C catalyst is reported again, in 2- butanol and 2- amylalcohol as hydrogen source
When, furfural add in-place hydrogen can be catalyzed and obtain yield as 76% 2-MF, and give certain explanation in mechanism.
Hermans etc. (Chemsuschem, 2014,7,268-275) uses Pd/Fe2O3Catalyst, furfural add in-place hydrogen have obtained 2-MF
With 2- methyltetrahydrofuran (2-MTHF), gross production rate 62%.But it is main during furfural add in-place hydrogen prepares 2-MF
The catalyst to be used is still to concentrate on noble metal, and expensive price is that it is hindered to industrialize maximum obstacle.
Chinese invention patent (CN 104549319A), (CN 105498787A), (CN 101422731A), (CN
104368346A) and (CN 104383929A) discloses preparation by furfural gas phase hydrogenation for some techniques and catalyst preparation of 2-MF,
And some catalyst also use cheap non-precious metal catalyst, but these patents still need to disappear without exception
Consume the hydrogen of high pressure.
Summary of the invention
2- methyl furan is prepared through add in-place hydrogen in view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of furfural
The method muttered.Entire reaction process is easy to operate, the not addition of hydrogen, greatly reduces hydrogen consumption and reduces cost；Its
Secondary, catalyst is non-precious metal catalyst, reduces the pollution to environment and the harm of human body.
Technical solution provided by the present invention are as follows:
A kind of method that furfural prepares 2- methylfuran through add in-place hydrogen, includes the following steps:
1) furfural, catalyst and hydrogen supply agent are reacted after mixing, is heated to 190~250 DEG C, the reaction time is
0.5~9h；The catalyst is Cu-Ni/Al2O3Catalyst, active component Cu, Ni alloy, carrier Al2O3；
2) reaction product is cooling, and organic solvent dissolution obtains 2- methylfuran after filtering.
In above-mentioned preparation method, with non-precious metal catalyst Cu-Ni/Al2O3It is catalyzed furfural add in-place hydrogen and prepares 2-MF, phase
Have process simple than prior art, zero hydrogen consumption, the advantages that catalyst is at low cost, improve furfural conversion ratio and 2-MF it is total
Molar yield.
Preferably, hydrogen supply agent is in methanol, ethyl alcohol, isopropanol, n-butyl alcohol, glycerol or glucose in the step 1)
One kind.
Preferably, organic solvent is methanol in the step 2).
Preferably, the mass ratio of furfural and catalyst is 1~20:1 in the step 1).
Preferably, the Cu-Ni/Al2O3The mass percentage of Cu, Ni are 0.1~60% in catalyst, surplus
For Al2O3.Further preferably, the Cu-Ni/Al2O3The mass percentage of Cu, Ni are 20~40% in catalyst, surplus
For Al2O3。
Preferably, the mass ratio of furfural and catalyst is 4~8:1 in the step 1)；Hydrogen supply agent is isopropanol；Instead
Answering temperature is 225~235 DEG C；The mass fraction of Cu is 18~22% in catalyst, the mass fraction of Ni is 38~42%, surplus
For Al2O3.The total moles yield that the conversion ratio of furfural reaches 100%, 2-MF in the technical solution can reach 75% or more.
Preferably, Cu-Ni/Al in the step 1)2O3Catalyst the preparation method comprises the following steps: I) according to each in catalyst
Ratio shared by component prepares the mixed solution of copper, nickel and aluminium salt, is denoted as solvent A；Alkaline solution is configured, solution B is denoted as；Ⅱ)
Solution A and B are add to deionized water, pH=8~11 are stirred and control, generates sediment；III) by sediment be aged 3~
7h；It is then centrifuged for cleaning at 100~130 DEG C of temperature, dry 10~15h；IV) continue to roast 3~8h at 500~800 DEG C；Most
Afterwards at 350~700 DEG C, 1~2h of hydrogen reducing obtains Cu-Ni/Al2O3Catalyst.
Preferably, controlling pH=9.3~9.7 in the step II).Further preferably pH=9.5.
Preferably, maturing temperature is 600~700 DEG C in the step IV).
Preferably, the copper, nickel and aluminium salt are respectively copper nitrate, nickel nitrate and aluminum nitrate；The alkali is hydrogen-oxygen
Change the mixture of sodium and sodium carbonate.
Preferably, the mass ratio of the sodium hydroxide and sodium carbonate is 3.2~1:1.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) the catalyst raw material in the present invention is cheap and preparation method is simple；
(2) catalyst in the present invention is free of toxic metals Cr, reduces environmental pollution and human body harm, and have higher
Activity, selectivity and repeat performance；
(3) present invention prepares 2-MF with non-precious metal catalyst catalysis furfural add in-place hydrogen, has compared to prior art
Journey is simple, zero hydrogen consumption, catalyst advantage at low cost；
(4) the total moles yield that the conversion ratio of furfural reaches 100%, 2-MF in the present invention can reach 75% or more.
Detailed description of the invention
Fig. 1 is 20%Cu-40%Ni/Al in the present invention2O3The experimental result of the STEM-EDS partial face surface sweeping of catalyst
Figure；
Fig. 2 is 20%Cu-40%Ni/Al in the present invention2O3The experimental result of the STEM-EDS local line surface sweeping of catalyst
Figure；
Fig. 3 is the XRD spectrum of the catalyst fines of difference Cu, Ni load capacity in the present invention, wherein a) 60%Cu/Al2O3；
B) 50%Cu-10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30%Cu-30%Ni/Al2O3；E) 20%Cu-40%
Ni/Al2O3；F) 10%Cu-50%Ni/Al2O3；G) 60%Ni/Al2O3；
Fig. 4 is the H of the catalyst fines of difference Cu, Ni load capacity in the present invention2- TPR map, wherein a) 60%Cu/
Al2O3；B) 50%Cu-10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30%Cu-30%Ni/Al2O3；E) 20%
Cu-40%Ni/Al2O3；F) 10%Cu-50%Ni/Al2O3；G) 60%Ni/Al2O3。
Specific embodiment
All raw materials involved in following embodiment are commercially available or simple process is passed through with regard to getable in laboratory.
The recycling of catalyst is by simply filtering and drying steps in following embodiment.
Pass through GC-FID quantitative analysis furfural and 2-MTHF in following embodiment.Concrete analysis condition is as follows: chromatographic column is
Agilent HP-5 capillary column (30m × 0.32mm × 0.25 μm), injector temperature: 300 DEG C；Sample volume: 1 μ L；Split ratio:
10:1；FID detection temperature: 320 DEG C；Temperature programming: 30 DEG C are kept for 4 minutes, are warming up to 140 later with 10 DEG C of speed per minute
DEG C, then 300 DEG C are raised to 20 DEG C per minute.
2-MF carries out quantitative analysis by high performance liquid chromatography, and specific analytical method is as follows: chromatographic column Phenomenex
Gemini 5u C18 110A (250 × 4.60mm, 5 μm), detector are UV detector, and eluant, eluent is 60% water and 40% second
Nitrile mixed liquor, eluant, eluent flow velocity are 0.6mL/min, and column temperature is 30 DEG C, and sample injection volume is 1 μ L.
The calculation method of relevant parameter is as follows:
Embodiment 1:
Weigh copper nitrate (Cu (NO3)2·3H2O) 9.664g, aluminum nitrate (Al (NO3)3·9H2O) 12.47g dissolves in 400mL
In deionized water, 6g NaOH and 5.299g Na are weighed2CO3It is dissolved in 400mL deionized water, is added in conical flask first
100mL deionized water, and be stirred continuously.Two solution are added dropwise in conical flask respectively, and are stirred continuously, control reaction pH
9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C value, after solution drips, is continued to stir 3h, is then stood aging 4h,
Filtering, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, finally in tube furnace 650 DEG C of reductase 12 h to get arriving
Catalyst 60%Cu/Al2O3。
By 0.1g furfural, 0.025g catalyst 60%Cu/Al2O314mL high temperature high pressure reverse is added after mixing with 7mL isopropanol
It answers in kettle, is heated to 230 DEG C, reaction time 4h, reaction product is cooling, carries out GC-FID respectively after organic solvent dissolution
And efficient liquid phase chromatographic analysis, reaction result such as table 1:
Table 1, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 24 |
| 2 | 92 | 37 |
| 4 | 100 | 43 |
| 8 | 100 | 41 |
Embodiment 2:
Weigh copper nitrate (Cu (NO3)2·3H2O) 9.664g, nickel nitrate (Ni (NO3)2·6H2O) 2.508g and aluminum nitrate
(Al(NO3)3·9H2O) 15g dissolves in 400mL deionized water, weighs 8g NaOH and 3.180g Na2CO3Be dissolved in 400mL go from
In sub- water, 100mL deionized water is added first in conical flask, and be stirred continuously.Triangle is added dropwise in two solution respectively
It in flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C control pH value in reaction, is dripped to solution
Afterwards, continue to stir 3h, then stand aging 4h, filter, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, finally
In tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 50%Cu-10%Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 50%Cu-10%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 2:
Table 2, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 21 |
| 2 | 92 | 35 |
| 4 | 100 | 41 |
| 8 | 100 | 39 |
Embodiment 3:
Weigh copper nitrate (Cu (NO3)2·3H2O) 9.664g, nickel nitrate (Ni (NO3)2·6H2O) 6.281g and aluminum nitrate
(Al(NO3)3·9H2O) 18.756g dissolves in 400mL deionized water, weighs 9.2g NaOH and 5.299g Na2CO3It is dissolved in
In 400mL deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.Respectively dropwise by two solution
It is added in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C, to solution control pH value in reaction
After dripping, continue to stir 3h, then stands aging 4h, filtering, 110 DEG C of dry 12h, then 600 DEG C of roastings in Muffle furnace
4h, finally in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 40%Cu-20%Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 40%Cu-20%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 3:
Table 3, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 25 |
| 2 | 92 | 39 |
| 4 | 100 | 45 |
| 8 | 100 | 41 |
Embodiment 4:
Weigh copper nitrate (Cu (NO3)2·3H2O) 4.832g, nickel nitrate (Ni (NO3)2·6H2O) 6.281g and aluminum nitrate
(Al(NO3)3·9H2O) 12.470g dissolves in 400mL deionized water, weighs 6.4g NaOH and 3.18g Na2CO3It is dissolved in 400mL
In deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.Two solution are added dropwise respectively
It in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C control pH value in reaction, is added dropwise to solution
After complete, continue to stir 3h, then stand aging 4h, filter, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, most
Afterwards in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 30%Cu-30%Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 30%Cu-30%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 4:
Table 4, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 36 |
| 2 | 92 | 48 |
| 4 | 100 | 55 |
| 8 | 100 | 50 |
Embodiment 5:
Weigh copper nitrate (Cu (NO3)2·3H2O) 4.832g, nickel nitrate (Ni (NO3)2·6H2O) 12.533g and aluminum nitrate
(Al(NO3)3·9H2O) 18.756g dissolves in 400mL deionized water, weighs 10g NaOH and 3.18g Na2CO3It is dissolved in 400mL
In deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.Two solution are added dropwise respectively
It in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C control pH value in reaction, is added dropwise to solution
After complete, continue to stir 3h, then stand aging 4h, filter, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, most
Afterwards in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 20%Cu-40%Ni/Al2O3。
By 0.1g furfural, a certain amount of catalyst 20%Cu-40%Ni/Al2O314mL is added after mixing with 7mL isopropanol
In high-temperature high-pressure reaction kettle, it is heated to 190-250 DEG C, the reaction time is 1~8h, and reaction product is cooling, and organic solvent is molten
GC-FID and efficient liquid phase chromatographic analysis are carried out after solution respectively.Reaction result such as table 5:
Furfural conversion ratio and 2-MF yield under table 5, differential responses temperature, reaction time and catalyst dosage
| Reaction temperature/DEG C | Catalyst dosage/g | Reaction time/h | Furfural conversion ratio/% | 2-MF yield/% |
| 190 | 0.025 | 2 | 88 | 11 |
| 190 | 0.025 | 9 | 100 | 59 |
| 230 | 0.025 | 4 | 100 | 67 |
| 210 | 0.025 | 1 | 91 | 18 |
| 210 | 0.025 | 6 | 100 | 61 |
| 230 | 0.025 | 9 | 100 | 52 |
| 230 | 0.025 | 0.5 | 81 | 19 |
| 250 | 0.025 | 2 | 100 | 41 |
| 250 | 0.025 | 6 | 100 | 1 |
| 230 | 0.017 | 4 | 100 | 75 |
| 230 | 0.1 | 4 | 100 | 0 |
| 230 | 0.005 | 4 | 60 | 19 |
| 230 | 0.05 | 4 | 100 | 4 |
| 210 | 0.017 | 9 | 100 | 68 |
Embodiment 6:
Weigh copper nitrate (Cu (NO3)2·3H2O) 2.416g, nickel nitrate (Ni (NO3)2·6H2O) 15.674g and aluminum nitrate
(Al(NO3)3·9H2O) 18.721g dissolves in 400mL deionized water, weighs 10g NaOH and 5.299g Na2CO3It is dissolved in 400mL
In deionized water, 100mL deionized water is added first in conical flask, and be stirred continuously.Two solution are added dropwise respectively
It in conical flask, and is stirred continuously, 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C control pH value in reaction, is added dropwise to solution
After complete, continue to stir 3h, then stand aging 4h, filter, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, most
Afterwards in tube furnace 650 DEG C of reductase 12 h to get arrive catalyst 10%Cu-50%Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 10%Cu-50%Ni/Al2O314mL high is added after mixing with 7mL isopropanol
In warm autoclave, be heated to 230 DEG C, reaction time 4h, reaction product is cooling, after organic solvent dissolution respectively into
Row GC-FID and efficient liquid phase chromatographic analysis.Reaction result such as table 6:
Table 6, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 14 |
| 2 | 92 | 17 |
| 4 | 100 | 20 |
| 8 | 100 | 18 |
Embodiment 7:
Weigh nickel nitrate (Ni (NO3)2·6H2O) 11.632g and aluminum nitrate (Al (NO3)3·9H2O) 11.569g dissolves in
In 400mL deionized water, 6g NaOH and 5.299g Na are weighed2CO3It is dissolved in 400mL deionized water, first in conical flask
100mL deionized water is added, and is stirred continuously.Two solution are added dropwise in conical flask respectively, and are stirred continuously, control is anti-
Answer pH value 9.5, the temperature of simultaneous reactions liquid is controlled at 30 DEG C, after solution drips, is continued to stir 3h, is then stood aging
4h, filtering, 110 DEG C of dry 12h, then 600 DEG C of roasting 4h in Muffle furnace, finally in tube furnace 650 DEG C of reductase 12 h to get
To catalyst 60%Ni/Al2O3。
By 0.1g furfural, 0.025g catalyst 60%Ni/Al2O314mL high temperature high pressure reverse is added after mixing with 7mL isopropanol
It answers in kettle, is heated to 230 DEG C, reaction time 4h, reaction product is cooling, carries out GC-FID respectively after organic solvent dissolution
And efficient liquid phase chromatographic analysis.Reaction result such as table 7:
Table 7, furfural conversion ratio and 2-MF yield under the differential responses time
| Reaction time/h | Furfural conversion ratio (%) | 2-MF yield (%) |
| 1 | 60 | 15 |
| 2 | 92 | 19 |
| 4 | 100 | 22 |
| 8 | 100 | 19 |
Catalyst characterization
It is as shown in Figure 1 catalyst 20%Cu-40%Ni/Al2O3STEM-EDS figure, Cu, Ni element in derived sample
It is evenly distributed on same specific position in figure, and Al, O element are generally evenly distributed in the entire Electronic Speculum visual field.
And obtained from the line total number evidence of Fig. 2 individual particle and EDS quantitative analysis results (Cu:Ni=1:2.3), each
The content of Ni is similar to 2 times of Cu on grain, i.e., the catalyst that this method prepares is the mass ratio of a kind of Cu, Ni close to 1:2
CuNi2Alloy catalyst, i.e. 20%Cu-40%Ni/Al2O3.The analysis method of the catalyst of other load capacity and the catalyst
Analysis method it is consistent.
Table 8 is different catalysts { a) 60%Cu/Al2O3；B) 50%Cu-10%Ni/Al2O3；C) 40%Cu-20%Ni/
Al2O3；D) 30%Cu-30%Ni/Al2O3；E) 20%Cu-40%Ni/Al2O3；F) 10%Cu-50%Ni/Al2O3；G) 60%
Ni/Al2O3ICP-OES characterization result, it can be deduced that catalyst 20%Cu-40%Ni/Al2O3Actual Cu, Ni mass is
1:1.73, the result gap obtained with EDS is little, and possible one of the reason of error therein is because EDS determines element
Amount analysis has only taken a panel region of wherein very little, may and actual result somewhat deviation；In addition may be by
It is inconsistent in the settling rate of different metal in the solution, and without 100% completely precipitating, result in actually obtained Cu with
The content of Ni is more slightly lower than theoretical value.
The ICP-OES characterization result of 8. different catalysts of table
aContent < 0.1% shared by metal
The characterize data of XRD shown in Fig. 3, a, b, c, d, e, f, g respectively indicate a) 60%Cu/Al2O3；B) 50%Cu-
10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30%Cu-30%Ni/Al2O3；E) 20%Cu-40%Ni/Al2O3；
F) 10%Cu-50%Ni/Al2O3；G) 60%Ni/Al2O3。
Wherein in catalyst a three main peaks be belonging respectively to Ni (JCPDS 04-0850) (111), (200) and (220) it is brilliant
Face, and Cu (the JCPDS 65-9743) of (111), (200) and (220) be respectively belonging to to(for) three main peaks of catalyst g are brilliant
Face.And the 2 θ values of Ni are greater than Cu, from Fig. 3 it can be seen that as the 2 θ values that are gradually increased of the content of Ni become larger, more
Carry out the 2 θ values closer to Ni, also demonstrates a kind of presence of the Cu-Ni alloy of different ratio.
Fig. 4 is the H of different catalysts2- TPR, wherein a, b, c, d, e, f, g respectively indicate a) 60%Cu/Al2O3；B) 50%
Cu-10%Ni/Al2O3；C) 40%Cu-20%Ni/Al2O3；D) 30%Cu-30%Ni/Al2O3；E) 20%Cu-40%Ni/
Al2O3；F) 10%Cu-50%Ni/Al2O3；G) 60%Ni/Al2O3。
By scheming it can be concluded that 60%Ni/Al2O3The precursor reduction temperature of catalyst is very high, illustrates may there is Ni/ at this time
Al2O4Presence, and 60%Cu/Al2O3The precursor reduction temperature of catalyst is lower.But for Cu-Ni/Al2O3Catalyst,
In addition to 10%Cu-50%Ni/Al2O3Catalyst substantially only one corresponding reduction of outer others Cu, Ni ratio of catalyst
Peak also further illustrates the presence of Cu-Ni alloy.As for 10%Cu-50%Ni/Al2O3The corresponding high temperature of catalyst and low temperature
The reduction peak of the reduction peak in stage, hot stage can be construed to Ni/Al caused by excessive Ni2O3There are the reason of, low temperature rank
Section is the corresponding Cu-Ni alloy of a certain ratio.The explanation of other comparison catalysts and 20%Cu-40%Ni/Al2O3It is similar.
Claims (3)
1. a kind of method that furfural prepares 2- methylfuran through add in-place hydrogen, which comprises the steps of:
1) furfural, catalyst and hydrogen supply agent be reacted after mixing, and will be heated to 225~235 DEG C, the reaction time is 4~
9h；The catalyst is Cu-Ni/Al2O3Catalyst, active component Cu, Ni alloy, carrier Al2O3；Cu in catalyst
Mass fraction be 18~22%, the mass fraction of Ni is 38~42%, surplus Al2O3；The hydrogen supply agent is isopropanol；Institute
The mass ratio for stating furfural and catalyst is 4~8:1；
The Cu-Ni/Al2O3Catalyst the preparation method comprises the following steps:
I) ratio according to shared by each component in catalyst prepares the mixed solution of copper, nickel and aluminium salt, is denoted as solution A；Configure alkali
Property solution, is denoted as solution B；
II) solution A is add to deionized water with B, stirs and control pH=8~11, generate sediment；
III) sediment is aged 3~7h；It is then centrifuged for cleaning at 100~130 DEG C of temperature, dry 10~15h；
IV) continue to roast 3~8h at 500~800 DEG C；Finally at 350~700 DEG C, 1~2h of hydrogen reducing obtains Cu-Ni/
Al2O3Catalyst；
2) reaction product is cooling, and organic solvent dissolution obtains 2- methylfuran after filtering；The organic solvent is methanol.
2. the method that furfural according to claim 1 prepares 2- methylfuran through add in-place hydrogen, which is characterized in that described
Copper, nickel and aluminium salt are respectively copper nitrate, nickel nitrate and aluminum nitrate；The alkali is the mixture of sodium hydroxide and sodium carbonate.
3. the method that furfural according to claim 2 prepares 2- methylfuran through add in-place hydrogen, which is characterized in that described
The mass ratio of sodium hydroxide and sodium carbonate is 3.2~1:1.
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| CN110180553A (en) * | 2019-04-04 | 2019-08-30 | 沈阳化工大学 | A kind of high-efficiency furfural gas phase conversion is the method for 2- methylfuran catalyst |
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