CN105733646A - Method for hydrocarbon preparation through high-grade fatty acid ester hydrogenation - Google Patents
Method for hydrocarbon preparation through high-grade fatty acid ester hydrogenation Download PDFInfo
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Abstract
The invention discloses a method for hydrocarbon preparation through high-grade fatty acid ester hydrogenation. In the presence of hydrogen, a high-grade fatty acid ester-containing raw material contacts with a catalyst and undergoes a reaction. The method is characterized in that the catalyst contains a phosphide of VIII group metal or VIII group-VIB metal and the raw material contains 50-10000wtppm by sulfur weight of a sulfur-containing compound. Compared with the prior art, the method has better hydrogenation decarbonylation and hydrogenation decarboxylation selectivity.
Description
Technical field
The method that the present invention relates to high-grade aliphatic ester deoxidation hydrocarbon.
Background technology
Day by day serious along with the growing tension of the fossil resources such as oil, natural gas and coal and environmental pollution, a lot of countries have carried out the exploitation of Renewable resource, utilization.Biomass are the regenerative resources that uniquely can be converted into carbonaceous liquid fuel.Wherein, Vegetable oil lipoprotein deoxidation prepare the alkane of similar petroleum based diesel component to be paid close attention to by domestic and international industrial quarters and academia.
Vegetable oil lipoprotein deoxidation can be undertaken by hydrogenation deoxidation and hydrogenation decarbonylation/hydrogenation decarboxylation two kinds approach.Wherein, hydrogenated deoxidation approach can obtain the hydrocarbon identical with corresponding fatty acid carbon number, and hydrogenated decarbonylation/hydrogenation decarboxylic reaction obtains and the hydrocarbon of the few carbon atom of corresponding fatty acid carbon number.The purpose product carbon yield of hydrogenation deoxidation approach is higher, but oxygen removes with the form of water, hydrogen-consuming volume is higher；Hydrogenation decarbonylation/hydrogenation decarboxylation pathway oxygen is mainly with CO/CO2Form removes, although carbon yield decreases but hydrogen-consuming volume reduces.Therefore, from reducing hydrogen-consuming volume angle, fatty acid ester hydrogenation decarbonylation/hydrogenation decarboxylation pathway more practical significance.
In prior art, hydrogenation deoxidation catalyst many employings metal and transient metal sulfide.Wherein, noble metal and Ni etc. are the metallic catalysts that activity is higher, and on it, high-grade aliphatic ester deoxidation is to be hydrogenated with decarbonylation/hydrogenation decarboxylation pathway.But, metalNicatalyst has stronger C-C key hydrogenolysis ability simultaneously, can produce pyrolysis product, thus reducing the yield of purpose product；Meanwhile, metalNicatalyst has significantly high methanation activity, deoxidation products CO/CO2Methanation causes that hydrogen-consuming volume substantially increases.Additionally, noble metal catalyst has the problem that cost is high in actual application.On nickel sulfide catalyst, deoxidation approach is to be hydrogenated with decarbonylation/hydrogenation decarboxylation, but its catalysis activity is relatively low.For transient metal sulfide many employings bimetallic Ni (Co)-Mo (W) sulfide of high-grade aliphatic ester deoxidation process, and the existence of Mo or W component may advantageously facilitate hydrogenation deoxidation approach.Recently as a kind of new material, transition metal phosphide also has been reported that for high-grade aliphatic ester deoxidation.
CN102427880 discloses a kind of catalyst comprising metal phosphide for preparing biodiesel；Also disclosing one utilizes described catalyst to carry out hydrotreatment, thus the method being prepared biodiesel by the raw material comprising vegetable oil.When the catalyst comprising metal phosphide described in using is as during for preparing the catalyst of biodiesel, the preparation activity of the biodiesel of hydrotreatment is high, do not need vulcanizing agent without interruption, and hydrotreatment and isomerization reaction carry out simultaneously, it is possible to obtain the high-quality hydrotreatment biodiesel that pour point is low.
CN103962165 discloses a kind of transition metal phosphide hydrogenation catalyst and preparation method thereof.Described catalyst inorganic porous material is as carrier, load active component and metal promoters, active component is tungsten, nickel and phosphorus, tungsten and oxide gross weight is total catalyst weight the 1～60% of nickel, the ratio of tungsten and the amount of substance of nickel is 1:0～10:1, tungsten and total amount of substance of nickel are 1:4～6:1 with the ratio of the amount of substance of phosphorus, described metal promoters selected from cerium element and/or titanium elements；Inorganic porous material amorphous silicon aluminium content is the 3～75% of vehicle weight, macroporous aluminium oxide content is the 10～80% of vector contg, mesopore molecular sieve is the 0～50% of vehicle weight, binder content is the 0.1～30% of total weight of carrier, this catalyst can effectively remove the sulfur-containing compound in petroleum distillate and nitrogen-containing compound, reaches deep desulfuration, denitrogenation purpose.
CN103756794 discloses the method that a kind of waste oil hydrogenation produces second filial generation biodiesel.The pretreatment the such as first waste oil of collection is filtered by the method, dehydration, desalination, through hydrogenation deoxidation under the effect of transition metal phosphide catalyst, hydrogenation decarboxylation and hydrogenation decarbonylation etc. are obtained by reacting second filial generation biodiesel.This invention utilizes the metal-like properties of transition metal phosphide and excellent Hydrogenation, waste oil is converted into oxygen-free fat alkane, does not produce the by-product of contaminated environment, and gained diesel cetane-number is high, condensation point is low.
CN102585876 discloses a kind of metal phosphide catalyst method by high-grade aliphatic ester deoxidation hydrocarbon.The method process is: equipped with metal phosphide catalyst in fixed bed reactors, is 10～500:1 charging by hydrogen and high-grade aliphatic ester mol ratio, at 250～450 DEG C, Hydrogen Vapor Pressure 0.1～8.0MPa and high-grade aliphatic ester weight space velocity 0.1～15h-1When generate hydrocarbon；Metal phosphide catalyst is with silicon dioxide, aluminium oxide, HY molecular sieve, HZSM-5 molecular sieve, titania-alumina composite oxides or cerium oxide-alumina composite oxide for carrier, its activity is the phosphide of metallic element Ni, Co, Fe, Mo, W, Ni-Co, Ni-Fe, Ni-Mo, Ni-W or Co-Mo mutually, and wherein metallic element and P elements quality account for the 3～40% and 1～15% of catalyst quality respectively.
Research shows, in phosphide, the effect of phosphorus causes that its hydrogenation decarbonylation/hydrogenation decarboxylation performance is significantly lower than corresponding metal.Such as, the hydrogenation decarbonylation activity of catalyst of phosphatizing nickel is significantly lower than metallic nickel, but the CO methanation of catalyst of phosphatizing nickel and C-C key hydrogenolysis lytic activity extremely low (AppliedCatalysisB:Environmental, 2014,144:870-884).
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high selective by being hydrogenated with the method that decarboxylation+hydrogenation decarbonylation approach realizes high-grade aliphatic ester deoxidation hydrocarbon.
A kind of method that the present invention relates to high-grade aliphatic ester Hydrogenation hydrocarbon, including in presence of hydrogen, by the raw material containing high-grade aliphatic ester and catalyst haptoreaction, it is characterized in that, described catalyst with the phosphide of group VIII or group VIII-vib metal for active component, sulfur-containing compound containing the 50-10000wtppm in sulfur in described raw material.
Preferably, the described raw material containing high-grade aliphatic ester contains the sulfur-containing compound of the 200-1000wtppm in sulfur；Described sulfur-containing compound is preferably H2S。
Preferably, the phosphide of described group VIII or group VIII-vib metal can be selected from one or more in nickel phosphide, cobalt phosphide, ferrum phosphide, palladium phosphide, cobalt-molybdenum phosphide, nickel-tungsten phosphide, more preferably nickel phosphide, it is more preferable to for Ni2P。
Preferably, described catalyst contains carrier, one or more in described carriers selected from silica, aluminium oxide, HY molecular sieve, HZSM-5 molecular sieve, titanium dioxide, cerium oxide, titanium dioxide-aluminum oxide, cerium oxide-aluminium oxide, it is preferable that CeO therein2.They can be commercially available commodity, it would however also be possible to employ arbitrary existing method prepares.
Preferably, with catalyst for benchmark, in described catalyst, the content of carrier is 60-97 weight % more preferably 70-95 weight %, with the content of the group VIII of elemental metal or the phosphide of group VIII-vib metal for 3-40 weight %, more preferably 5-30 weight %.
Inventor finds under study for action, when the phosphide adopting described group VIII or group VIII-vib metal be catalyst carry out high-grade aliphatic ester hydrogenation reaction time, described raw material introduces sulfur-containing compound in right amount, it is possible to be obviously improved the selectivity of hydrogenation decarbonylation, hydrogenation decarboxylation.Particularly when described catalyst is with cerium oxide (CeO2) for carrier loaded Ni2The effect of P catalyst is especially apparent.
In the present invention, it is possible to adopt the catalyst that the phosphide with group VIII or group VIII-vib metal that the preparation of arbitrary prior art is suitable for the present invention is active component.Such as, adopt the method disclosed in CN102585876A to prepare catalyst, namely can be used for the present invention.
In one preferred embodiment, the preparation method of described catalyst includes:
(1) solution of preparation nickel compound containing and phosphorus-containing compound；
(2) adopt step (1) solution impregnating carrier prepared, be dried afterwards, roasting；
(3) product that phosphating step (2) roasting obtains, obtains catalyst；
In the present invention, described nickel compound containing is selected from arbitrary water-soluble nickel compound containing, for instance nickel nitrate etc.；Described phosphorus-containing compound is selected from arbitrary water-soluble phosphorus-containing compound, for instance ammonium dihydrogen phosphate etc..
Dry and roasting the method for described step (2) is usual method, example is dry as mentioned can be carry out at baking oven, and described drying condition includes: temperature 80 DEG C-140 DEG C, it is preferred to 100 DEG C-120 DEG C, time is 4 hours-24 hours, it is preferred to 10 hours-16 hours；Described roasting carries out in tube furnace, and the condition of described roasting includes: temperature 300 DEG C-800 DEG C, it is preferred to 400 DEG C-600 DEG C, and the time is 2 hours-12 hours, it is preferred to 4 hours-8 hours.
In the present invention, by before the described raw material containing high-grade aliphatic ester and catalyst haptoreaction, including by catalyst at room temperature with containing O2Nitrogen atmosphere under passivation step.Described nitrogen atmosphere is preferably containing O2Stream of nitrogen gas, described gas flow is 50 milliliters/(gram catalyst minute)-300 milliliters/(gram catalyst minute), and wherein, the oxygen content in nitrogen is 0.5 volume-1.0 volume %, and passivation time is 4 hours-10 hours.
Being enough to make the raw material containing high-grade aliphatic ester with under the catalytic premise of catalyst, the reaction unit realizing described reaction is not particularly limited by the present invention, for instance, it is possible to carry out in fixed bed reactors, it is also possible to carry out in tank reactor.Wherein, the introducing of described sulfur-containing compound can be directly mixed with described high-grade aliphatic ester by sulfur-containing compound, introduces reactor afterwards；Can also be that described high-grade aliphatic ester raw material, sulfur-containing compound are introduced reactor respectively；Sulfur-containing compound can also be mixed with hydrogen, introduce reactor afterwards.
In the present invention, described catalytic condition preferably includes: Hydrogen Vapor Pressure 0.1～8MPa, temperature 250～450 DEG C, hydrogen-oil ratio 10～500:1, weight (hourly) space velocity (WHSV) (WHSV) 0.1～15h-1；It is preferred that include: Hydrogen Vapor Pressure 0.2～7MPa, temperature 280～420 DEG C, hydrogen-oil ratio 15～400:1, weight (hourly) space velocity (WHSV) 0.3～12h-1。
In the present invention, the mixture of one or more that described high-grade aliphatic ester is derived from animal and plant fat, it is preferable that therein containing the fatty acid methyl ester of 8～22 carbon atoms, ethyl ester or triglyceride.
Compared with prior art, the present invention provides method when keeping higher higher fatty acids ester conversion rate, significantly improves with hendecane and the decarbonylation of dodecane molar ratio sign, decarboxylation selectivity.
Detailed description of the invention
The present invention is further illustrated following by embodiment.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
Embodiment 1-5 illustrates to be suitable for catalyst and the preparation thereof of the present invention.
Embodiment 1
CeO2Carrier is to be prepared by template agent method, particularly as follows: cetyl trimethylammonium bromide (CTAB) solution of preparation 0.1mol/L, prepares the Ce (NO of a certain amount of 0.1mol/L by n (CTAB)/n (Ce)=0.83)3·6H2O solution.When stirring, CTAB solution is added rapidly to Ce (NO3)3·6H2In O solution, and quickly stir 20min.Under slightly slow mixing speed, the ammonia spirit by 25% is slowly added dropwise in above-mentioned mixed solution, until during PH=11, and continue stirring 2h.The light yellow mixture obtained is placed in round-bottomed flask, and 90 DEG C of constant temperature water baths 4 days, thing to be mixed is cooled to sucking filtration after room temperature, alternately washs sucking filtration with dehydrated alcohol and distilled water, until can't detect Cl in filtrate-And NO3 -Till ion.120 DEG C of air atmosphere of sample after cleaning are dried 12h.Then 500 DEG C of roasting 3h in moving air, namely obtain cerium oxide carrier.
Take 4.008 grams of Fe (NO3)3·9H2O and 1.129 grams of NH4H2PO4It is made into aqueous solution 8 milliliters, this solution is added drop-wise to 5 grams of CeO2Carrier impregnates, dries under dipping thing and room temperature, afterwards in 120 DEG C dry 12 hours, in air atmosphere, within 4 hours, prepare catalyst precursor in 500 DEG C of roastings.Take 1 gram of presoma to be placed in quartz ampoule fixed bed reactors (internal diameter 12mm), pass into the hydrogen that flow is 300 ml/min, prepare CeO with 1 DEG C/min of speed by room temperature to 650 DEG C and after 650 DEG C of constant temperature reduce 3 hours2Load Fe2P catalyst C-1.Catalyst C-1 at room temperature uses 0.5%O2/N2The nitrogen of 0.5 volume % (oxygen content be) air-flow (200 ml/min) is standby after being passivated 6 hours.In this catalyst, the content of Fe is 9.6 weight %.
Embodiment 2
Catalyst preparation process, with embodiment 1, is a difference in that 2.753 grams of Ni (NO of weighing3)2·6H2O and 1.089 grams of NH4H2PO4Being made into aqueous solution, prepared catalyst is CeO2Load Ni2P catalyst C-2.According to embodiment 1 same procedure, catalyst C-2 is passivated, standby.In catalyst C-2, the content of nickel is 9.6 weight %.
Embodiment 3
Catalyst preparation process, with embodiment 1, is a difference in that 2.753 grams of Co (NO of weighing3)2·6H2O and 1.634 grams of NH4H2PO4Being made into aqueous solution, prepared catalyst is CeO2Load C oP catalyst C-3.According to embodiment 1 same procedure, catalyst C-3 is passivated, standby.In catalyst C-3, the content of cobalt is 9.7 weight %.
Embodiment 4
Catalyst preparation process, with embodiment 1, is a difference in that 4.372 grams of Ni (NO of weighing3)2·6H2O and 1.729 grams of NH4H2PO4Being made into aqueous solution, prepared catalyst is CeO2Load Ni2P catalyst C-4.According to embodiment 1 same procedure, catalyst C-4 is passivated, standby.In catalyst C-4, the content of nickel is 14.8 weight %.
Embodiment 5
Catalyst preparation process, with embodiment 1, is a difference in that 6.25 grams of Ni (NO of weighing3)2·6H2O and 2.436 grams of NH4H2PO4Being made into aqueous solution, prepared catalyst is CeO2Load Ni2P catalyst C-5.According to embodiment 1 same procedure, catalyst C-5 is passivated, standby.In catalyst C-5, the content of nickel is 19.8 weight %.
Comparative example 1-4 illustrates non-invention method catalyst and preparation thereof.
Comparative example 1
Catalyst preparation process, with embodiment 1, is a difference in that 0.510 gram of Ni (NO of weighing3)2·6H2O and 0.198 gram of NH4H2PO4Being made into aqueous solution, prepared catalyst is CeO2Load Ni2P catalyst D-1.According to embodiment 1 same procedure, catalyst D-1 is passivated, standby.In catalyst D-1, the content of nickel is 1.8 weight %.
Comparative example 2
Take 4.372 grams of Ni (NO3)2·6H2O is made into aqueous solution 9 milliliters, and this solution is added drop-wise to 5 grams of SiO2Carrier impregnates, dries under dip compound room temperature, afterwards in 120 DEG C dry 12 hours, in air atmosphere, within 4 hours, prepare catalyst precursor in 500 DEG C of roastings.Take 1 gram of presoma to be placed in quartz ampoule fixed bed reactors, pass into the hydrogen that flow is 300 ml/min, prepared SiO with 10 DEG C/min of speed by after room temperature to 450 DEG C constant temperature reductase 12 hour2Supported ni catalyst D-2.In catalyst D-2, Ni content is 14.8 weight %.
Comparative example 3
Preparation method is with comparative example 2, and institute is the difference is that adopting CeO2Carrier, prepared catalyst is CeO2Supported ni catalyst D-3.
Comparative example 4
Take 4.372 grams of Ni (NO3)2·6H2O and 1.729 grams of NH4H2PO4It is made into aqueous solution 9 milliliters, this solution is added drop-wise to 5 grams of SiO2Carrier impregnates, dries under dip compound room temperature, afterwards in 120 DEG C dry 12 hours, in air atmosphere, within 4 hours, prepare catalyst precursor in 500 DEG C of roastings.Take 1 gram of presoma to be placed in quartz ampoule fixed bed reactors, pass into the hydrogen that flow is 300 ml/min, prepare SiO with 1 DEG C/min of speed by room temperature to 650 DEG C and after 650 DEG C of constant temperature reduce 3 hours2Load Ni2P catalyst D-4,0.5%O at room temperature used by this catalyst2/N2Air-flow (200 ml/min) is standby after being passivated 6 hours.In catalyst D-4, nickel content is 14.8 weight %.
Embodiment 6-9 and comparative example 5-8 is described separately the application effect of method provided by the invention and comparative example method.
Embodiment 6
Reactor: the rustless steel fixed bed reactors that to adopt length be 800 millimeters, internal diameter is 12 millimeters, catalyst is execute the CeO prepared by example 12Load Fe2P, consumption 1 gram.
Raw material: methyl laurate；The hydrogen of sulfide hydrogen 400ppm (quality).
1.0 grams of catalyst C-1 are loaded in reactor, and 4.0 grams of quartz sands is placed into beds top to preheat reactant.Before reaction, at H2(flow velocity is 100 ml/min) rises to 450 DEG C of constant temperature reducing catalysts 2 hours with 10 DEG C/min of heating rates.After reduction, by reaction temperature and H2Pressure regulates respectively to 340 DEG C and 3.0MPa, then passes into methyl laurate and the hydrogen containing 400ppm hydrogen sulfide in reactor simultaneously, and the weight (hourly) space velocity (WHSV) of methyl laurate is 5h-1, the volume ratio of hydrogen and methyl laurate is 25.Adopting the SP-3420 gas chromatograph equipped with HP-5 capillary column (30m × 0.33mm × 0.5 μm) and hydrogen flame ionization detector (FID) that product liquid is carried out quantitative analysis, naphthane is as interior mark.Result is: methyl laurate conversion ratio is 67%, and the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 85%, and wherein hendecane and dodecane mol ratio are 31.Additionally, oxygen-containing midbody product selectivity is 14.1%, pyrolysis product (C6～C10 hydrocarbon) selectivity is 0.9%.
Embodiment 7
Evaluating catalyst C-2 according to same embodiment 6 same procedure, result is: methyl laurate conversion ratio is 92%, and the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 95%, and wherein hendecane and dodecane mol ratio are 60.Additionally, oxygen-containing midbody product selectivity is 4.4%, pyrolysis product (C6～C10 hydrocarbon) selectivity is 0.6%.
Embodiment 8
Evaluating catalyst C-3 according to same embodiment 6 same procedure, result is: methyl laurate conversion ratio is 85%, and the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 91%, and wherein hendecane and dodecane mol ratio are 45.Additionally, oxygen-containing midbody product selectivity is 8.4%, pyrolysis product (C6～C10 hydrocarbon) selectivity is 0.6%.
Embodiment 9
Catalyst C-4 is evaluated according to same embodiment 6 same procedure, result is: methyl laurate conversion ratio is 100%, the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 99.3%, and wherein hendecane and dodecane mol ratio are 86.Additionally, pyrolysis product (C6～C10 hydrocarbon) selectivity is 0.7%.
Comparative example 5
Evaluating catalyst D-3 according to same embodiment 6 same procedure, result is: methyl laurate conversion ratio is 46%, and the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 69%, and wherein hendecane and dodecane mol ratio are 45.Additionally, oxygen-containing midbody product selectivity is 29.7%, pyrolysis product (C6～C10 hydrocarbon) selectivity is 1.3%.
Comparative example 6
Catalyst C-4 is evaluated according to same embodiment 6 same procedure, the difference is that course of reaction adopts not hydrogen sulfide containing hydrogen, result is: methyl laurate conversion ratio is 100%, the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 98.5%, and wherein hendecane and dodecane mol ratio are 6.5.Additionally, pyrolysis product (C6～C10 hydrocarbon) selectivity is 1.5%.
Comparative example 7
Evaluating catalyst D-4 according to comparative example 6 same procedure, result is: methyl laurate conversion ratio is 100%, and the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 58.5%, and wherein hendecane and dodecane mol ratio are 40.Additionally, pyrolysis product (C6～C10 hydrocarbon) selectivity is 41.5%.
Comparative example 8
Evaluating catalyst D-1 according to embodiment 6 same procedure, result is: methyl laurate conversion ratio is 35%, and the overall selectivity of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 55%, and wherein hendecane and dodecane mol ratio are 15.Additionally, oxygen-containing midbody product selectivity is 44.4%, pyrolysis product (C6～C10 hydrocarbon) selectivity is 0.6%.
Claims (11)
1. the method for a high-grade aliphatic ester Hydrogenation hydrocarbon, including in presence of hydrogen, by the raw material containing high-grade aliphatic ester and catalyst haptoreaction, it is characterized in that, described catalyst with the phosphide of group VIII or group VIII-vib metal for active metal component, sulfur-containing compound containing the 50-10000wtppm in sulfur in described raw material.
2. method according to claim 1, it is characterised in that contain the sulfur-containing compound of the 200-1000wtppm in sulfur in described raw material.
3. method according to claim 1 and 2, it is characterised in that described sulfur-containing compound is H2S。
4. method according to claim 1, it is characterised in that one or more in nickel phosphide, cobalt phosphide, ferrum phosphide, palladium phosphide, cobalt-molybdenum phosphide, nickel-tungsten phosphide of the phosphide of described group VIII or group VIII-vib metal.
5. method according to claim 1, it is characterized in that, described catalyst contains carrier, one or more in described carriers selected from silica, aluminium oxide, HY molecular sieve, HZSM-5 molecular sieve, titanium dioxide, cerium oxide, titanium dioxide-aluminum oxide, cerium oxide-aluminium oxide, with catalyst for benchmark, in described catalyst, the content of carrier is 60-97 weight %, with the content of the group VIII of elemental metal or the phosphide of group VIII-vib metal for 3-40 weight %.
6. method according to claim 5, it is characterised in that described carrier is CeO2, described hydrogenation active metals component is nickel phosphide, and with catalyst for benchmark, in described catalyst, the content of carrier is 70-95 weight %, with the content of the group VIII of elemental metal or the phosphide of group VIII-vib metal for 5-30 weight %.
7. method according to claim 6, it is characterised in that described nickel phosphide is Ni2P。
8. method according to claim 1, it is characterised in that described catalytic condition includes: Hydrogen Vapor Pressure 0.1～8MPa, temperature 250～450 DEG C, hydrogen-oil ratio 10～500:1, weight (hourly) space velocity (WHSV) 0.1～15h-1。
9. method according to claim 8, it is characterised in that described catalytic condition includes: Hydrogen Vapor Pressure 0.2～7MPa, temperature 280～420 DEG C, hydrogen-oil ratio 15～400:1, weight (hourly) space velocity (WHSV) 0.3～12h-1。
10. method according to claim 1, it is characterised in that the mixture of one or more that described high-grade aliphatic ester is derived from animal and plant fat.
11. the method according to claim 1 or 10, it is characterised in that described high-grade aliphatic ester is containing the fatty acid methyl ester of 8～22 carbon atoms, ethyl ester or triglyceride.
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| CN110586112A (en) * | 2019-09-17 | 2019-12-20 | 湘潭大学 | Hydrodeoxygenation solid acid catalyst Ni/CeO2-Al2O3 |
| CN110756194A (en) * | 2019-09-03 | 2020-02-07 | 湘潭大学 | Sulfur-free nickel-based hydrodeoxygenation catalyst and application thereof |
| CN110904468A (en) * | 2019-12-05 | 2020-03-24 | 河北大学 | Cerium-doped tungsten phosphide submicron sphere composite material and preparation method and application thereof |
| CN111036206A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Glycerol hydrogenolysis catalyst, preparation method and application thereof, and glycerol hydrogenolysis method |
| CN112604699A (en) * | 2020-12-11 | 2021-04-06 | 浙江海洋大学 | Ni for improving reaction selectivity of reverse water gas2P/CeO2Catalyst and preparation method thereof |
| CN113600142A (en) * | 2021-08-19 | 2021-11-05 | 中国科学院青岛生物能源与过程研究所 | Preparation method and application of formed layered double hydroxide and derivatives thereof |
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