CN106423203A - Method for non-hydrogen decarboxylation of fatty acid - Google Patents
Method for non-hydrogen decarboxylation of fatty acid Download PDFInfo
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- CN106423203A CN106423203A CN201610850213.2A CN201610850213A CN106423203A CN 106423203 A CN106423203 A CN 106423203A CN 201610850213 A CN201610850213 A CN 201610850213A CN 106423203 A CN106423203 A CN 106423203A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for non-hydrogen decarboxylation of fatty acid. The method comprises the following steps: 1) adding a catalyst carrier into an organic solvent, ultrasonically dispersing, then heating for removing the organic solvent, and adopting an atomic layer deposition method for depositing a platinum source and a nickel source onto the catalyst carrier, thereby acquiring a platinum nickel alloy loaded catalyst; and 2) dispersing the platinum nickel alloy loaded catalyst acquired in the step 1) into the fatty acid, heating to 330-370 DEG C, and reacting for 100-140min. According to the method, the platinum nickel alloy loaded catalyst is prepared by doping nickel into the metal platinum, so that the cost of the catalyst is lowered while the conversion rate of non-hydrogen decarboxylation of the fatty acid and the C17 yield are increased.
Description
Technical field
The present invention relates to decarboxylation of fatty acids field is and in particular to a kind of method of aliphatic acid non-hydrogen decarboxylation.
Background technology
Precious metals pt supported catalyst is studied to prove a kind of good aliphatic acid non-hydrogen decarboxylation catalyst.But
In terms of economics point, high cost is still its topmost shortcoming, and the purpose substituting fossil energy with script runs in the opposite direction.
In consideration of it, Ni supported catalyst enters the visual field of people, and the hydrodeoxygenation being used for aliphatic acid by numerous studies is ground
In studying carefully.Crocker (document 1：Morgan,T.；Grubb,D.；Santillan-Jimenez,E.；Crocker,M.,
Conversion of Triglycerides to Hydrocarbons Over Supported Metal
Catalysts.Top Catal 2010,53 (11-12), 820-829.) seminar compares carbon load Ni, tri- kinds of Pd and Pt urge
The deoxy performance to triglycerides for the agent, research finds, the hydrodeoxygenation deoxy activity of 20wt%Ni/C catalyst compares 5wt%
The deoxy activity of Pd/C and 1wt%Pt/C is high, illustrate when Ni in Ni supported catalyst load capacity increase to a certain extent after, Ni
The catalysis activity of catalyst is to reach the catalytic performance of Pd and Pt supported catalyst phase same level.
With the bimetallic catalyst of W metal doping Pt preparation, the cost of precious metals pt catalyst not only can be reduced, with
When can also improve the catalysis activity of catalyst, have become as one of focus of current research, and have a lot of research reports with regard to Pt-
M especially Pt-Ni bimetallic catalyst is applied in hydrogenation reaction, dehydrogenation reaction, oxygen reformation, CO oxidation, water gas shift and oxygen
In reduction reaction, but the research in vegetable oil decarboxylation is also little, has very big research space.
Content of the invention
Present invention aims to the deficiencies in the prior art, provide a kind of method of aliphatic acid non-hydrogen decarboxylation, with
Platinum adulterated by nickel prepares platinum-nickel alloy supported catalyst, not only reduces the cost of catalyst, improves that aliphatic acid is non-to be faced simultaneously
The conversion ratio of hydrogen decarboxylation and C17 yield.
Technical scheme provided by the present invention is：
A kind of method of aliphatic acid non-hydrogen decarboxylation, comprises the steps：
1) catalyst carrier is added to organic solvent for ultrasonic dispersion, then heating removes organic solvent, using atom
Layer sedimentation deposits to platinum source and nickel source in catalyst carrier, obtains platinum-nickel alloy supported catalyst；
2) by step 1) obtain platinum-nickel alloy supported catalyst and be scattered in aliphatic acid, it is heated to 330～370 DEG C of reactions 40
～140min.
Atomic layer deposition method (ALD) deposits the platinum-nickel alloy of Nano grade, precise control platinum nickel in catalyst support surface
The particle size of alloy and make its big low height homogeneous.Atomic layer deposition method can be carried out in ald instrument,
Platinum-nickel alloy is loaded in catalyst carrier, not only increases decentralization, platinum-nickel alloy and the catalyst carrier of platinum-nickel alloy
Between active force, and with platinum adulterated by nickel prepare bimetallic catalyst reduce catalyst cost, improve fat simultaneously
The conversion ratio of sour non-hydrogen decarboxylation and C17 yield.
Described step 1) in organic solvent can be the volatile organic solvent such as ethanol, methyl alcohol, acetone.
Preferably, after catalyst carrier is added to organic solvent for ultrasonic dispersion, being added drop-wise on quartz wafer, using red
Outer lamp heating removes organic solvent.
Preferably, described step 1) in atomic layer deposition method first platinum source or nickel source one of which are deposited to catalyst and carry
On body, then another kind is deposited on the metal that catalyst carrier has loaded.Preferentially one of which metal deposit is existed
In catalyst carrier, then deposit another kind of metal, gained platinum-nickel alloy supported catalyst is for aliphatic acid non-hydrogen decarboxylation
When its conversion ratio and C17 yield be further enhanced, the catalyst that effect obtains better than two kinds of metal alternating deposits.Mainly former
Because being：The introducing of nickel can improve the catalysis activity of platinum, essentially consists in the electronics d- rail that nickel can change platinum outermost bed boundary
Road and lattice surface, change its absorption property.So on a catalyst support and then depositing another for a kind of metal deposit
Plant metallic catalyst, the interface electron orbit of platinum and lattice surface are affected by nickel metal, improve interfacial activity Pt for reactant
The adsorbing and rupture of carbon-carbon bond (C-C), and improve the desorption of platinum surface oxidation material (CO or OH) to avoid covering its activity
Position is so that reaction transformation frequency is accelerated.And the catalyst that two kinds of metal alternating deposits are obtained, the two-layer up and down of each layer of platinum
All affected by nickel, this may will affect the disorder of its metal electron track, lead to its activity to reduce.
Preferably, described step 1) in atomic layer deposition method the deposition number of turns in platinum source be 0～30 circle, the deposition of nickel source
The number of turns is 0～30 circle.Further preferably, the deposition number of turns in platinum source is 15～20 circles, and the deposition number of turns of nickel source is 15～20 circles.
Preferably, described step 1) in the reaction temperature of atomic layer deposition method be 260～300 DEG C.Further preferably, instead
Temperature is answered to be 280 DEG C.
Preferably, described step 1) in catalyst carrier be SiO2、ZrO2、Al2O3, MgO, CNT or molecular sieve
One of.
Preferably, described step 1) in platinum source be trimethyl methyl cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.
Preferably, described step 1) in platinum source and nickel source when depositing in catalyst carrier, the particle diameter of platinum and nickel is 1.0
～4.0nm, average grain diameter is 2.4～2.6nm.More preferably 2.5-3.0nm.
Preferably, described step 2) in aliphatic acid be oleic acid, tetradecenoic acid, gaidic acid, eicosenoic acid, mustard
One of acid, linoleic acid, stearic acid.
Preferably, described step 2) in platinum-nickel alloy supported catalyst be 1 with the mass ratio of aliphatic acid:3～7.Enter one
Step is preferably 1:5.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
The present invention adopts atomic layer deposition method to deposit the platinum-nickel alloy of Nano grade, preparation technology in catalyst support surface
Flow process is simple, takes short, its metallic particles size is homogeneous, and the Nano grade platinum-nickel alloy supported catalyst of synthesis is used for aliphatic acid
Its conversion ratio of non-hydrogen decarboxylation and C17 yield are more superior than business Pt/C catalyst performance, and the load capacity of Pt is lower, reduces
Catalyst cost.
Brief description
Fig. 1 is Pt15Ni15-ALD/Al in embodiment 12O3TEM figure；
Fig. 2 is Pt15Ni15-ALD/Al in embodiment 12O3Grain size distribution.
Specific embodiment
In the embodiment of the present invention, the content of metal of catalyst is detected by inductively coupled plasma (ICP).
In embodiment, the qualitative and quantitative analysis of decarboxylation of fatty acids product are unified uses Agilent gas-chromatography (Agilent
7890B)-mass spectrum (Agilent 5977A MSD) combined instrument, chromatographic column HP-5MS (30m × 0.25mm × 0.25 μm) capillary
Tubing string, is furnished with hydrogen ion flame detector (FID) and thermal conductivity detector (TCD) (TCD).
Ald instrument in the embodiment of the present invention：A hot-wall closed chamber-type ALD, purchase
Buy from Shanxi coalification institute.Miniature batch reactor：It is made up of one 3/8 inch of stainless steel tube and two 3/8 inch of nuts,
Volume is 1.67cm3, purchased from Swagelok company of the U.S..
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
Alumina powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 15 circle Ni after deposition 15 circle Pt, catalyst is named as Pt15Ni15-ALD/
Al2O3, it is 1.83wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 1.11wt%.
By Pt15Ni15-ALD/Al2O3Carry out transmission electron microscope analysis, result is as shown in figure 1, particle diameter is 1.0～4.0nm.With
Shi Jinhang granularmetric analysis, the result of particle size obtains the checking as Fig. 2, and average grain diameter is 2.46nm.
In miniature batch reactor (1.67cm3) in add the oleic acid of 75mg and the catalyst Pt 15Ni15- of 15mg
ALD/Al2O3, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, instead
Cooling is taken out after answering 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Reaction is produced
After thing analysis, conversion ratio is 95.94%, and yield is 85.97%.
Embodiment 2
Alumina powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 15 circle Pt after deposition 15 circle Ni, catalyst is named as Ni15Pt15-ALD/
Al2O3, it is 2.31wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 1.00wt%.
In miniature batch reactor (1.67cm3) in add the oleic acid of 75mg and the catalyst n i15Pt15- of 15mg
ALD/Al2O3, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, instead
Cooling is taken out after answering 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Reaction is produced
After thing analysis, conversion ratio is 87.36%, and yield is 84.68%.
Embodiment 3
Carbon nanotube powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartz
On disk, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl
Methyl cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 10 circle Ni after deposition 25 circle Pt, catalyst is named as Pt25Ni10-
ALD/C, is 2.79wt% through the load capacity that ICP detects Pt, and the load capacity of Ni is 0.67wt%.
In miniature batch reactor (1.67cm3) in add the eicosenoic acid of 75mg and the catalyst of 15mg
Pt25Ni10-ALD/C, after sand-bath is heated to reaction temperature (350 DEG C), puts into sand-bath after reactor two nut is tightened
In, take out cooling after reaction 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.
After product analysis, conversion ratio is 90.13%, and yield is 83.62%.
Embodiment 4
Carbon nanotube powder (15ml) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartz
On disk, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl
Methyl cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 15 circle Pt after deposition 20 circle Ni, catalyst is named as Ni20Pt15-
ALD/C, is 2.03wt% through the load capacity that ICP detects Pt, and the load capacity of Ni is 1.38wt%.
In miniature batch reactor (1.67cm3) in add the stearic acid of 75mg and the catalyst n i20Pt15- of 15mg
ALD/C, after sand-bath is heated to reaction temperature (350 DEG C), puts in sand-bath after reactor two nut is tightened, reaction
Cooling is taken out after 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Product
After analysis, conversion ratio is 94.22%, and yield is 84.13%.
Embodiment 5
Zirconium oxide powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 25Ni circle after deposition 18 circle Pt, catalyst is named as Pt18Ni25-ALD/
ZrO2, it is 2.51wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 1.41wt%.
In miniature batch reactor (1.67cm3) in add the gaidic acid of 75mg and the catalyst of 15mg
Pt18Ni25-ALD/ZrO2, after sand-bath is heated to reaction temperature (350 DEG C), put into after reactor two nut is tightened
In sand-bath, after reaction 120min, take out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to
15ml.After product analysis, conversion ratio is 96.03%, and yield is 86.64%.
Embodiment 6
Zirconium oxide powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 20 circle Pt after deposition 15 circle Ni, catalyst is named as Ni15Pt20-ALD/
ZrO2, it is 2.71wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 0.88wt%.
In miniature batch reactor (1.67cm3) in add the linoleic acid of 75mg and the catalyst n i15Pt20- of 15mg
ALD/ZrO2, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, instead
Cooling is taken out after answering 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Reaction is produced
After thing analysis, conversion ratio is 91.42%, and yield is 84.64%.
Embodiment 7
Silicon oxide powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 10 circle Ni after deposition 15 circle Pt, catalyst is named as Pt15Ni10-ALD/
SiO2, it is 1.98wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 0.74wt%.
In miniature batch reactor (1.67cm3) in add the erucic acid of 75mg and the catalyst Pt 15Ni10- of 15mg
ALD/SiO2, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, instead
120min is answered to take out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Product
After analysis, conversion ratio is 92.43%, and yield is 80.11%.
Embodiment 8
Silicon oxide powder (15ml) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 10 circle Ni after deposition 20 circle Pt, catalyst is named as Pt20Ni10-ALD/
SiO2, it is 2.81wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 0.66wt%.
In miniature batch reactor (1.67cm3) in add the tetradecenoic acid of 75mg and the catalyst of 15mg
Pt15Ni10-ALD/SiO2, after sand-bath is heated to reaction temperature (350 DEG C), put into after reactor two nut is tightened
In sand-bath, after reaction 120min, take out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to
15ml.After product analysis, conversion ratio is 92.45%, and yield is 82.98%.
Embodiment 9
ZSM-5 powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartz wafer
On, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl methyl
Cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 15 circle Ni after deposition 15 circle Pt, catalyst is named as Pt15Ni15-ALD/
ZSM-5, is 1.75wt% through the load capacity that ICP detects Pt, and the load capacity of Ni is 1.18wt%.
In miniature batch reactor (1.67cm3) in add the tetradecenoic acid of 75mg and the catalyst of 15mg
Pt15Ni15-ALD/ZSM-5, after sand-bath is heated to reaction temperature (350 DEG C), puts into after reactor two nut is tightened
In sand-bath, after reaction 120min, take out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to
15ml.After product analysis, conversion ratio is 95.34%, and yield is 84.64%.
Embodiment 10
ZSM-5 powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartz wafer
On, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl methyl
Cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.First deposition 20 circle Pt after deposition 20 circle Ni, catalyst is named as Ni20Pt20-ALD/
ZSM-5, is 2.98wt% through the load capacity that ICP detects Pt, and the load capacity of Ni is 1.21wt%.
In miniature batch reactor (1.67cm3) in add the linoleic acid of 75mg and the catalyst n i20Pt20- of 15mg
ALD/ZSM-5, after sand-bath is heated to reaction temperature (350 DEG C), puts in sand-bath after reactor two nut is tightened, instead
Cooling is taken out after answering 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Reaction is produced
After thing analysis, conversion ratio is 87.64%, and yield is 89.13%.
Comparative example 1
Alumina powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.Deposition 30 circle Pt, catalyst is named as Pt30-ALD/Al2O3, detect Pt's through ICP
Load capacity is 3.61wt%.
In miniature batch reactor (1.67cm3) in add the linoleic acid of 75mg and the catalyst Pt 30-ALD/ of 15mg
Al2O3, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, reaction
120min takes out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Product is divided
After analysis, conversion ratio is 95.58%, and yield is 86.95%.
Comparative example 2
Alumina powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.Deposition 30 circle Ni, catalyst is named as Ni30-ALD/Al2O3, detect Ni's through ICP
Load capacity is 1.78wt%.
In miniature batch reactor (1.67cm3) in add the erucic acid of 75mg and the catalyst n i30-ALD/ of 15mg
Al2O3, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, reaction
Cooling is taken out after 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Product
After analysis, conversion ratio is 89.1%, and yield is 13.6%.
Comparative example 3
ZSM-5 powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartz wafer
On, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl methyl
Cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.Deposition 30 circle Ni, catalyst is named as Ni30-ALD/ZSM-5, detects that Ni's is negative through ICP
Carrying capacity is 1.69wt%.
In miniature batch reactor (1.67cm3) in add the stearic acid of 75mg and the catalyst n i30-ALD/ of 15mg
ZSM-5, after sand-bath is heated to reaction temperature (350 DEG C), puts in sand-bath after reactor two nut is tightened, reaction
Cooling is taken out after 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Product
After analysis, conversion ratio is 85.37%, and yield is 20.12%.
Comparative example 4
ZSM-5 powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartz wafer
On, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl methyl
Cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.Deposition 15 circle Pt, catalyst is named as Pt15-ALD/ZSM-5, detects that Pt's is negative through ICP
Carrying capacity is 2.01wt%.
In miniature batch reactor (1.67cm3) in add the eicosenoic acid of 75mg and the catalyst Pt 15- of 15mg
ALD/ZSM-5, after sand-bath is heated to reaction temperature (350 DEG C), puts in sand-bath after reactor two nut is tightened, instead
Cooling is taken out after answering 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Reaction is produced
After thing analysis, conversion ratio is 85.32%, and yield is 80.31%.
Interpretation of result according to comparative example 1～4 and embodiment 1～10：Load platinum-nickel alloy after catalyst with
When aliphatic acid non-hydrogen decarboxylation, its comparative conversions and C17 yield under the level of identical active metal load capacity will be better than
Single Supported Pt Nanoparticles or the catalyst of nickel, illustrate that its transformation frequency is high, reduce catalyst cost.
Comparative example 5
In miniature batch reactor (1.67cm3) in add the oleic acid of 75mg and the business Pt/C catalyst of 15mg, Pt
Load capacity is 5wt%, after sand-bath is heated to reaction temperature (350 DEG C), puts into sand-bath after reactor two nut is tightened
In, take out cooling after reaction 120min.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.
After product analysis, conversion ratio is 99%, and yield is 78.2%.
Comparative example 6
In miniature batch reactor (1.67cm3) in add the business Pt/C catalysis of the tetradecenoic acid of 75mg and 15mg
Agent, Pt load capacity is 5wt%, after sand-bath is heated to reaction temperature (350 DEG C), puts into after reactor two nut is tightened
In sand-bath, after reaction 120min, take out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to
15ml.After product analysis, conversion ratio is 97.13%, and yield is 79.66%.
Comparative example 5～6 is understood with the interpretation of result of embodiment 1～10：Catalyst after load platinum-nickel alloy is for fat
During fat acid non-hydrogen decarboxylation, its C17 yield will be better than business Pt/C catalyst, and conversion ratio business Pt/C catalyst is more preferably, main
Reason is wanted to be：The catalyst activity metal particle diameter of ALD preparation is little, and decentralization is high, higher with carrier function power.In addition platinum mixes
The catalysis activity of active metal can be improved after nickel, strengthen active metal for the adsorption capacity of reactant group, be conducive to carboxylic
The decarboxylation of acid.
Comparative example 7
Alumina powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartzy circle
On piece, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl first
Butylcyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.Deposition 1 circle Ni after deposition 1 circle Pt, so repeatedly 15 times, catalyst is named as
(PtNi)15-ALD/Al2O3, it is 2.27wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 1.05wt%.
In miniature batch reactor (1.67cm3) in add the linoleic acid of 75mg and catalyst (PtNi) 15- of 15mg
ALD/Al2O3, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, instead
120min is answered to take out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Product
After analysis, conversion ratio is 92.58%, and yield is 23.95%.
Comparative example 8
ZSM-5 powder (0.1g) is added after ethanol (15ml) dissolving, ultrasonic with Ultrasound Instrument, then it is added drop-wise to quartz wafer
On, infrared lamps remove ethanol, are then placed in deposition in ALD instrument, and reaction temperature is 280 DEG C, and platinum source is trimethyl methyl
Cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.Deposition 1 circle Ni after deposition 1 circle Pt, so repeatedly 15 times, catalyst is named as (PtNi)
15-ALD/Al2O3, it is 2.17wt% through the load capacity that ICP detects Pt, the load capacity of Ni is 1.12wt%.
In miniature batch reactor (1.67cm3) in add the linoleic acid of 75mg and catalyst (PtNi) 15- of 15mg
ALD/Al2O3, after sand-bath is heated to reaction temperature (350 DEG C), put in sand-bath after reactor two nut is tightened, instead
120min is answered to take out cooling.Then on one side ultrasonic while product is come out with acetone, be then diluted to 15ml.Product
After analysis, conversion ratio is 91.88%, and yield is 24.32%.
So comparative example 5～8 is understood with the interpretation of result of embodiment 1～10, a kind of metal deposit is carried in catalyst
On body, then deposit another kind of metallic catalyst, the interface electron orbit of platinum and lattice surface are affected by nickel metal, improve activity
Metal adsorbs and ruptures for reactant carbon-carbon bond (C-C), and improves the desorption of platinum surface oxidation material (CO or OH) and lead
Cause avoids covering metal active position so that reaction transformation frequency is accelerated.And the catalyst that two kinds of metal alternating deposits are obtained,
The two-layer up and down of each layer of platinum is all affected by nickel, and this may will affect the disorder of its metal electron track, leads to its activity to reduce.
Claims (9)
1. a kind of method of aliphatic acid non-hydrogen decarboxylation is it is characterised in that comprise the steps：
1) catalyst carrier is added to organic solvent for ultrasonic dispersion, then heating removes organic solvent, using atomic layer deposition
Area method deposits to platinum source and nickel source in catalyst carrier, obtains platinum-nickel alloy supported catalyst；
2) by step 1) obtain platinum-nickel alloy supported catalyst and be scattered in aliphatic acid, be heated to 330～370 DEG C of reactions 40～
140min.
2. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 1) in atomic layer
Platinum source or nickel source one of which are first deposited in catalyst carrier by sedimentation, then another kind have been deposited to catalyst carrier
On metal through having loaded.
3. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 1) in atomic layer
In sedimentation, the deposition number of turns in platinum source is 0～30 circle, and the deposition number of turns of nickel source is 0～30 circle.
4. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 1) in atomic layer
The reaction temperature of sedimentation is 260～300 DEG C.
5. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 1) in catalyst
Carrier is SiO2、ZrO2、Al2O3, MgO, one of CNT or molecular sieve.
6. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 1) in platinum source be
Trimethyl methyl cyclopentadiene platinum, nickel source is dicyclopentadienyl nickel.
7. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 1) in platinum source and
When nickel source deposits in catalyst carrier, the particle diameter of platinum and nickel is 1.0～4.0nm, and average grain diameter is 2.4～2.6nm.
8. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 2) in aliphatic acid
For one of oleic acid, tetradecenoic acid, gaidic acid, eicosenoic acid, erucic acid, linoleic acid, stearic acid.
9. the method for aliphatic acid non-hydrogen decarboxylation according to claim 1 is it is characterised in that described step 2) in platinum nickel close
Golden supported catalyst is 1 with the mass ratio of aliphatic acid:3～7.
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| CN107118793A (en) * | 2017-06-26 | 2017-09-01 | 浙江大学 | A kind of application of metal carrying catalyst in grease and biomass copyrolysis prepare aromatic hydrocarbons |
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