CN105733646B - A kind of method of high-grade aliphatic ester Hydrogenation hydrocarbon - Google Patents
A kind of method of high-grade aliphatic ester Hydrogenation hydrocarbon Download PDFInfo
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Abstract
A kind of method of 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, the catalyst contains the sulfur-containing compound containing 50 10000wtppm in terms of sulphur in the phosphide of group VIII or group VIII vib metal, the raw material.Compared with prior art, the method provided by the present invention has preferably hydrogenation decarbonylation and hydrogenation decarboxylation selectivity.
Description
Technical field
The present invention relates to the method for high-grade aliphatic ester deoxidation hydrocarbon.
Background technology
Growing tension and increasingly serious, many countries of environmental pollution with fossil resources such as oil, natural gas and coals
The exploitation of renewable resource carried out, utilized.Biomass is can be uniquely converted into the regenerative resource of carbonaceous liquid fuel.
Wherein, the alkane for preparing similar petroleum based diesel component by vegetable fat deoxidation is closed by domestic and international industrial quarters and academia
Note.
Vegetable fat deoxidation can be carried out by hydrogenation deoxidation and hydrogenation decarbonylation/two kinds of hydrogenation decarboxylation approach.Wherein, through adding
Hydrogen deoxidation approach can obtain with corresponding aliphatic acid carbon number identical hydrocarbon, and hydrogenated decarbonylation/hydrogenation decarboxylic reaction obtain with it is right
Answer the hydrocarbon of the few carbon atom of aliphatic acid carbon number.The purpose product carbon yield of hydrogenation deoxidation approach is higher, but oxygen is in the form of water
Removing, hydrogen-consuming volume are higher；It is hydrogenated with decarbonylation/hydrogenation decarboxylation pathway oxygen main with CO/CO2Form is removed, although carbon yield has dropped
Low but hydrogen-consuming volume is reduced.Therefore, for hydrogen-consuming volume angle is reduced, fatty acid ester hydrogenation decarbonylation/hydrogenation decarboxylation pathway is more real
Border meaning.
In the prior art, metal and transient metal sulfide are used hydrogenation deoxidation catalyst more.Wherein, noble metal and Ni etc.
It is the higher metallic catalyst of activity, high-grade aliphatic ester deoxidation thereon is to be hydrogenated with based on decarbonylation/hydrogenation decarboxylation pathway.However,
MetalNicatalyst has stronger C-C key hydrogenolysis abilities simultaneously, pyrolysis product can be produced, so as to reduce the receipts of purpose product
Rate；Meanwhile, metalNicatalyst has very high methanation activity, deoxidation products CO/CO2Methanation causes hydrogen-consuming volume substantially to increase
Plus.In addition, noble metal catalyst has the problem of cost is high in actual application.Vulcanize Raney nickel on deoxidation approach with
It is hydrogenated with based on decarbonylation/hydrogenation decarboxylation, but its catalytic activity is relatively low.Transition metal for high-grade aliphatic ester deoxidation process vulcanizes
Bimetallic Ni (Co)-Mo (W) sulfide is used thing more, and the presence of Mo or W components may advantageously facilitate hydrogenation deoxidation approach.Most
Closely, as a kind of new material, transition metal phosphide also has been reported that for high-grade aliphatic ester deoxidation.
CN 102427880, which discloses a kind of catalyst comprising metal phosphide, to be used to prepare biodiesel；Also disclose
It is a kind of to carry out hydrotreating using the catalyst, so as to prepare the method for biodiesel by the raw material comprising vegetable oil.When making
During with the catalyst comprising metal phosphide as catalyst for preparing biodiesel, the biodiesel of hydrotreating
Preparation activity it is high, vulcanizing agent without interruption is not required to, and hydrotreating is carried out simultaneously with isomerization reaction, thus, it is possible to obtain
The low high-quality hydrotreating biodiesel of pour point.
CN 103962165 discloses a kind of transition metal phosphide hydrogenation catalyst and preparation method thereof.The catalyst
With inorganic porous material as carrier, load active component and metal promoters, active component is tungsten, nickel and phosphorus, tungsten and nickel
Oxide gross weight be the 1~60% of total catalyst weight, the ratio of the amount of the material of tungsten and nickel is 1：0~10:1, tungsten and nickel
Total material amount and phosphorus material amount ratio be 1:4~6:1, the metal promoters are selected from Ce elements and/or titanium member
Element；Inorganic porous material amorphous silicon aluminium content is the 3~75% of vehicle weight, and macroporous aluminium oxide content is the 10 of vector contg
~80%, mesopore molecular sieve is the 0~50% of vehicle weight, and binder content is the 0.1~30% of total weight of carrier, the catalysis
Agent can effectively remove sulfur-containing compound and nitrogen-containing compound in petroleum distillate, reach deep desulfuration, denitrogenation purpose.
CN 103756794 discloses a kind of method of gutter oil hydrogenation production second generation biodiesel.This method first will
The pretreatments such as the gutter oil of collection is filtered, is dehydrated, desalination, by hydrogenation in the presence of transition metal phosphide catalyst
Deoxidation, the reaction such as hydrogenation decarboxylation and hydrogenation decarbonylation obtains second generation biodiesel.The invention utilizes the class of transition metal phosphide
Metalline and excellent Hydrogenation, oxygen-free fat alkane is converted into by gutter oil, and the by-product of pollution environment is not produced
Thing, gained diesel cetane-number is high, condensation point is low.
CN 102585876 discloses a kind of method of metal phosphide catalyst by high-grade aliphatic ester deoxidation hydrocarbon.Should
Procedure is：Metal phosphide catalyst is housed in fixed bed reactors, is with high-grade aliphatic ester mol ratio by hydrogen
10~500:1 charging, 250~450 DEG C, 0.1~8.0MPa of Hydrogen Vapor Pressure and high-grade aliphatic ester weight space velocity 0.1~
15h-1Under conditions of generate hydrocarbon；Metal phosphide catalyst be with silica, aluminum oxide, HY molecular sieves, HZSM-5 molecular sieves,
Titania-alumina composite oxides or cerium oxide-alumina composite oxide are carrier, and its activity is mutually metallic element
Ni, Co, Fe, Mo, W, Ni-Co, Ni-Fe, Ni-Mo, Ni-W or Co-Mo phosphide, wherein metallic element and P elements quality
The 3~40% and 1~15% of catalyst quality are accounted for respectively.
Research shows that the effect of phosphorus causes it to be hydrogenated with decarbonylation/hydrogenation decarboxylation performance significantly lower than corresponding gold in phosphide
Category.For example, the hydrogenation decarbonylation activity of catalyst of phosphatizing nickel is significantly lower than metallic nickel, but the CO methanations of catalyst of phosphatizing nickel and C-
Extremely low (the Applied Catalysis B of C key hydrogenolysis lytic activities:Environmental, 2014,144：870-884).
The content of the invention
It is real by being hydrogenated with decarboxylation+hydrogenation decarbonylation approach the technical problem to be solved in the present invention is to provide a kind of high selectivity
The method of existing high-grade aliphatic ester deoxidation hydrocarbon.
The present invention relates to a kind of method of high-grade aliphatic ester Hydrogenation hydrocarbon, including in presence of hydrogen, senior fat will be contained
The raw material of fat acid esters and catalyst haptoreaction, it is characterised in that the catalyst is with group VIII or the VIB of group VIII-the
The phosphide of metal is the sulfur-containing compound containing the 50-10000wtppm in terms of sulphur in active component, the raw material.
Preferably, the sulfur-bearing chemical combination containing the 200-1000wtppm in terms of sulphur in the raw material containing high-grade aliphatic ester
Thing；The sulfur-containing compound is preferably H2S。
Preferably, the phosphide of group VIII or group VIII-the vib metal can be selected from nickel phosphide, cobalt phosphorus
One or more in compound, iron phosphide, palladium phosphide, cobalt-molybdenum phosphide, nickel-tungsten phosphide, more preferably nickel phosphorus
Compound, more preferably Ni2P。
Preferably, the catalyst contains carrier, and the carrier is selected from silica, aluminum oxide, HY molecular sieves, HZSM-5
One or more in molecular sieve, titanium dioxide, cerium oxide, titanium dioxide-aluminum oxide, cerium oxide-aluminum oxide, preferably wherein
CeO2.They can be commercially available commodity, it would however also be possible to employ arbitrary existing method is prepared.
Preferably, on the basis of catalyst, the content of carrier is that 60-97 weight % is more preferably in the catalyst
70-95 weight %, the weight by 3-40 of the content of the group VIII of elemental metal or the phosphide of the vib metal of group VIII-the
Measure %, more preferably 5-30 weight %.
Inventor has found under study for action, when using the phosphide of the group VIII or the vib metal of group VIII-the to urge
It is appropriate in the raw material to introduce sulfur-containing compound when agent carries out high-grade aliphatic ester hydrogenation reaction, it can be obviously improved and add
Hydrogen decarbonylation, the selectivity for being hydrogenated with decarboxylation.Particularly when the catalyst is with cerium oxide (CeO2) it is carrier loaded Ni2P catalyst
Effect is especially apparent.
In the present invention, can use arbitrary prior art prepare be suitable for the present invention with group VIII or VIII
The phosphide of the vib metal of race-the is the catalyst of active component.For example, being prepared using the method disclosed in CN102585876A
Catalyst, you can for the present invention.
In one preferred embodiment, the preparation method of the catalyst includes：
(1) solution of nickel compound containing and phosphorus-containing compound is prepared；
(2) solution impregnating carrier prepared using step (1), is dried, is calcined afterwards；
(3) product that phosphating step (2) roasting is obtained, obtains catalyst；
In the present invention, the nickel compound containing is selected from arbitrary water-soluble nickel compound containing, such as nickel nitrate；Institute
State phosphorus-containing compound and be selected from arbitrary water-soluble phosphorus-containing compound, such as ammonium dihydrogen phosphate.
The drying of the step (2) and the method for roasting are usual method, and drying can be in baking oven to example as mentioned
Carry out, the drying condition includes：80 DEG C -140 DEG C of temperature, preferably 100 DEG C -120 DEG C, the time is -24 hours 4 hours, excellent
Elect as -16 hours 10 hours；The roasting is carried out in tube furnace, and the condition of the roasting includes：300 DEG C -800 DEG C of temperature,
Preferably 400 DEG C -600 DEG C, the time is -12 hours 2 hours, preferably -8 hours 4 hours.
In the present invention, by before the raw material containing high-grade aliphatic ester and catalyst haptoreaction, including by catalyst
At room temperature with containing O2Nitrogen atmosphere under the step of be passivated.The nitrogen atmosphere is preferably to contain O2Stream of nitrogen gas, the gas
Flow is 50 milliliters/- 300 milliliters of (gram catalyst minute)/(gram catalyst minute), wherein, the oxygen content in nitrogen is
The volume % of 0.5 volume -1.0, passivation time is -10 hours 4 hours.
On the premise of being enough to make the raw material containing high-grade aliphatic ester and catalyst haptoreaction, the present invention is described to realizing
The reaction unit of reaction is not particularly limited, for example, can be carried out in fixed bed reactors, can also be in tank reactor
Carry out.Wherein, the introducing of the sulfur-containing compound can directly mix sulfur-containing compound with the high-grade aliphatic ester, it
After introduce reactor；Can also be that the high-grade aliphatic ester raw material, sulfur-containing compound are introduced into reactor respectively；Can also be by
Sulfur-containing compound is mixed with hydrogen, and reactor is introduced afterwards.
In the present invention, the catalytic condition is preferably included：0.1~8MPa of Hydrogen Vapor Pressure, 250~450 DEG C of temperature,
Hydrogen-oil ratio 10~500:1st, weight (hourly) space velocity (WHSV) (WHSV) 0.1~15h-1；Further preferably include：0.2~7MPa of Hydrogen Vapor Pressure, temperature
280~420 DEG C, hydrogen-oil ratio 15~400:1st, 0.3~12h of weight (hourly) space velocity (WHSV)-1。
In the present invention, the high-grade aliphatic ester be derived from animal and plant fat in one or more of mixtures, preferably its
In the fatty acid methyl ester containing 8~22 carbon atoms, ethyl ester or triglyceride.
Compared with prior art, the method provided by the present invention is when keeping higher higher fatty acids ester conversion rate, with 11
Alkane and the decarbonylation of dodecane molar ratio sign, decarboxylation are selectively significantly improved.
Embodiment
The present invention will now be further described by way of examples.
Agents useful for same in example, is chemically pure reagent except as expressly described.
Embodiment 1-5 illustrates catalyst and its preparation for being suitable for the present invention.
Embodiment 1
CeO2Carrier is prepared by template agent method, is specially：Prepare 0.1mol/L cetyl trimethylammonium bromide
(CTAB) solution, a certain amount of 0.1mol/L Ce (NO are prepared by n (CTAB)/n (Ce)=0.83)3·6H2O solution.In stirring
Under the conditions of CTAB solution is added rapidly to Ce (NO3)3·6H2In O solution, and quickly stir 20min.In slightly slow stirring speed
Under degree, 25% ammonia spirit is slowly dropped in above-mentioned mixed solution, when PH=11 untill, and continue stir 2h.
Obtained light yellow mixture is placed in round-bottomed flask, 90 DEG C of constant temperature water baths 4 days, thing to be mixed is cooled to suction filtration after room temperature, uses
Absolute ethyl alcohol and distilled water alternately wash suction filtration, until can't detect Cl in filtrate-And NO3 -Untill ion.By the sample after cleaning
120 DEG C of air atmospheres of product dry 12h.Then 500 DEG C of roasting 3h in moving air, that is, obtain cerium oxide carrier.
Take 4.008 grams of Fe (NO3)3·9H2O and 1.129 gram of NH4H2PO48 milliliters of the aqueous solution is made into, the solution is added drop-wise to 5
Gram CeO2On carrier impregnate, dipping thing with drying at room temperature, after 120 DEG C drying 12 hours, in air atmosphere in 500 DEG C
Roasting prepares catalyst precursor in 4 hours.1 gram of presoma is taken to be placed in quartz ampoule fixed bed reactors (internal diameter 12mm),
The hydrogen that flow is 300 ml/mins is passed through, with 1 DEG C/min of speed by room temperature to 650 DEG C and in 650 DEG C of constant temperature reduction
CeO is prepared after 3 hours2Load Fe2P catalyst C-1.Catalyst C-1 uses 0.5%O at room temperature2/N2(oxygen content is 0.5
Volume % nitrogen) air-flow (200 ml/min) be passivated 6 hours after it is standby.Fe content is 9.6 weight % in the catalyst.
Embodiment 2
Catalyst preparation process be the same as Example 1, is a difference in that 2.753 grams of Ni (NO of weighing3)2·6H2O and 1.089 gram
NH4H2PO4The aqueous solution is made into, prepared catalyst is CeO2Load Ni2P catalyst C-2.According to method same as Example 1
Catalyst C-2 is passivated, it is standby.The content of nickel is 9.6 weight % in catalyst C-2.
Embodiment 3
Catalyst preparation process be the same as Example 1, is a difference in that 2.753 grams of Co (NO of weighing3)2·6H2O and 1.634 gram
NH4H2PO4The aqueous solution is made into, prepared catalyst is CeO2Load C oP catalyst C-3.According to method same as Example 1
Catalyst C-3 is passivated, it is standby.The content of cobalt is 9.7 weight % in catalyst C-3.
Embodiment 4
Catalyst preparation process be the same as Example 1, is a difference in that 4.372 grams of Ni (NO of weighing3)2·6H2O and 1.729 gram
NH4H2PO4The aqueous solution is made into, prepared catalyst is CeO2Load Ni2P catalyst C-4.According to method same as Example 1
Catalyst C-4 is passivated, it is standby.The content of nickel is 14.8 weight % in catalyst C-4.
Embodiment 5
Catalyst preparation process be the same as Example 1, is a difference in that 6.25 grams of Ni (NO of weighing3)2·6H2O and 2.436 gram
NH4H2PO4The aqueous solution is made into, prepared catalyst is CeO2Load Ni2P catalyst C-5.According to method same as Example 1
Catalyst C-5 is passivated, it is standby.The content of nickel is 19.8 weight % in catalyst C-5.
Comparative example 1-4 illustrates non-invention method catalyst and its preparation.
Comparative example 1
Catalyst preparation process be the same as Example 1, is a difference in that 0.510 gram of Ni (NO of weighing3)2·6H2O and 0.198 gram
NH4H2PO4The aqueous solution is made into, prepared catalyst is CeO2Load Ni2P catalyst D-1.According to method same as Example 1
Catalyst D-1 is passivated, it is standby.The content of nickel is 1.8 weight % in catalyst D-1.
Comparative example 2
Take 4.372 grams of Ni (NO3)2·6H2O is made into 9 milliliters of the aqueous solution, and the solution is added drop-wise into 5 grams of SiO2Soaked on carrier
Stain, dip compound dries at room temperature, after 120 DEG C dry 12 hours, in air atmosphere in 500 DEG C roasting 4 hours make
It is standby to obtain catalyst precursor.Take 1 gram of presoma to be placed in quartz ampoule fixed bed reactors, be passed through flow for 300 ml/mins
Hydrogen, prepare SiO after room temperature to 450 DEG C of constant temperature reductase 12s hour with 10 DEG C/min of speed2Load Ni catalysis
Agent D-2.Ni contents are 14.8 weight % in catalyst D-2.
Comparative example 3
Preparation method is with comparative example 2, except that using CeO2Carrier, prepared catalyst is CeO2Load Ni catalysis
Agent D-3.
Comparative example 4
Take 4.372 grams of Ni (NO3)2·6H2O and 1.729 gram of NH4H2PO49 milliliters of the aqueous solution is made into, the solution is added drop-wise to 5
Gram SiO2Impregnated on carrier, dip compound dries at room temperature, 12 hours are dried after 120 DEG C, in air atmosphere in 500
DEG C roasting prepares catalyst precursor in 4 hours.Take 1 gram of presoma to be placed in quartz ampoule fixed bed reactors, be passed through flow
For the hydrogen of 300 ml/mins, with 1 DEG C/min of speed by room temperature to 650 DEG C and after 650 DEG C of constant temperature are reduced 3 hours
Prepare SiO2Load Ni2P catalyst D-4, the catalyst uses 0.5%O at room temperature2/N2Air-flow (200 ml/min) is blunt
It is standby after changing 6 hours.Nickel content is 14.8 weight % in catalyst D-4.
Embodiment 6-9 and comparative example 5-8 illustrates the application effect of method and comparative example method that the present invention is provided respectively.
Embodiment 6
Reactor：Length is used for the stainless steel fixed bed reactors that 800 millimeters, internal diameter are 12 millimeters, catalyst is to apply
CeO prepared by example 12Load Fe2P, 1 gram of consumption.
Raw material：Methyl laurate；Sulfide hydrogen 400ppm (quality) hydrogen.
1.0 grams of catalyst C-1 are fitted into reactor, and 4.0 grams of quartz sands are placed into beds top with pre-
Thermal response thing.Before reaction, in H2In (flow velocity is 100 ml/mins) 450 DEG C of constant temperature are risen to 10 DEG C/min of heating rates
Reducing catalyst 2 hours.After reduction is finished, by reaction temperature and H2Pressure is adjusted to 340 DEG C and 3.0MPa, then to anti-respectively
Answer in device while being passed through methyl laurate and the hydrogen containing 400ppm hydrogen sulfide, the weight (hourly) space velocity (WHSV) of methyl laurate is 5h-1, hydrogen
The volume ratio of gas and methyl laurate is 25.Using equipped with HP-5 capillary columns (30m × 0.33mm × 0.5 μm) and hydrogen flame from
The SP-3420 gas chromatographs of sub- detector (FID) carry out quantitative analysis to product liquid, and naphthane is used as internal standard.As a result it is：
Methyl laurate conversion ratio is 67%, total choosing of hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane
Selecting property is 85%, and wherein hendecane and dodecane mol ratio are 31.In addition, oxygen-containing midbody product is selectively 14.1%, split
It is selectively 0.9% to solve product (C6~C10 hydrocarbon).
Embodiment 7
According to the same procedure of be the same as Example 6 evaluate catalyst C-2, as a result for：Methyl laurate conversion ratio is 92%, hydrogenation
The overall selectivity of decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 95%, wherein hendecane and 12
Alkane mol ratio is 60.In addition, oxygen-containing midbody product is selectively 4.4%, pyrolysis product (C6~C10 hydrocarbon) is selectively
0.6%.
Embodiment 8
According to the same procedure of be the same as Example 6 evaluate catalyst C-3, as a result for：Methyl laurate conversion ratio is 85%, hydrogenation
The overall selectivity of decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 91%, wherein hendecane and 12
Alkane mol ratio is 45.In addition, oxygen-containing midbody product is selectively 8.4%, pyrolysis product (C6~C10 hydrocarbon) is selectively
0.6%.
Embodiment 9
According to the same procedure of be the same as Example 6 evaluate catalyst C-4, as a result for：Methyl laurate conversion ratio is 100%, plus
The overall selectivity of hydrogen decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane be 99.3%, wherein hendecane and
Dodecane mol ratio is 86.In addition, pyrolysis product (C6~C10 hydrocarbon) is selectively 0.7%.
Comparative example 5
According to the same procedure of be the same as Example 6 evaluate catalyst D-3, as a result for：Methyl laurate conversion ratio is 46%, hydrogenation
The overall selectivity of decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 69%, wherein hendecane and 12
Alkane mol ratio is 45.In addition, oxygen-containing midbody product is selectively 29.7%, pyrolysis product (C6~C10 hydrocarbon) is selectively
1.3%.
Comparative example 6
Catalyst C-4 is evaluated according to the same procedure of be the same as Example 6, the difference is that using not hydrogen sulfide containing in course of reaction
Hydrogen, as a result for：Methyl laurate conversion ratio is 100%, hydrogenation decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product
The overall selectivity of dodecane is 98.5%, and wherein hendecane and dodecane mol ratio are 6.5.In addition, pyrolysis product (C6~C10
Hydrocarbon) it is selective for 1.5%.
Comparative example 7
According to the same procedure of comparative example 6 evaluate catalyst D-4, as a result for：Methyl laurate conversion ratio is 100%, hydrogenation
The overall selectivity of decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 58.5%, wherein hendecane and ten
Dioxane mol ratio is 40.In addition, pyrolysis product (C6~C10 hydrocarbon) is selectively 41.5%.
Comparative example 8
According to method same as Example 6 evaluate catalyst D-1, as a result for：Methyl laurate conversion ratio is 35%, hydrogenation
The overall selectivity of decarbonylation/hydrogenation decarboxylate hendecane and hydrogenation deoxidation product dodecane is 55%, wherein hendecane and 12
Alkane mol ratio is 15.In addition, oxygen-containing midbody product is selectively 44.4%, pyrolysis product (C6~C10 hydrocarbon) is selectively
0.6%.
Claims (11)
1. a kind of method of high-grade aliphatic ester Hydrogenation hydrocarbon, including in presence of hydrogen, by the raw material containing high-grade aliphatic ester
With catalyst haptoreaction, it is characterised in that the catalyst is with group VIII or the phosphide of the vib metal of group VIII-the
For active metal component, the sulfur-containing compound containing the 50-10000wtppm in terms of sulphur in the raw material；The catalyst contains
Carrier, one or more of the carrier in cerium oxide, cerium oxide-aluminum oxide.
2. according to the method described in claim 1, it is characterised in that contain the 200-1000wtppm in terms of sulphur in the raw material
Sulfur-containing compound.
3. method according to claim 1 or 2, it is characterised in that the sulfur-containing compound is H2S。
4. according to the method described in claim 1, it is characterised in that the phosphorus of group VIII or group VIII-the vib metal
One kind in nickel phosphide, cobalt phosphide, iron phosphide, palladium phosphide, cobalt-molybdenum phosphide, nickel-tungsten phosphide of compound or
It is several.
5. according to the method described in claim 1, it is characterised in that on the basis of catalyst, carrier contains in the catalyst
Measure as 60-97 weight %, using the content of the group VIII of elemental metal or the phosphide of the vib metal of group VIII-the as 3-40
Weight %.
6. method according to claim 5, it is characterised in that the carrier is CeO2, the hydrogenation active metal component is
Nickel phosphide, on the basis of catalyst, the content of carrier is 70-95 weight % in the catalyst, with the of elemental metal
The content of the phosphide of VIII or the vib metal of group VIII-the is 5-30 weight %.
7. method according to claim 6, it is characterised in that the nickel phosphide is Ni2P。
8. according to the method described in claim 1, it is characterised in that the catalytic condition includes：Hydrogen Vapor Pressure 0.1~
8MPa, 250~450 DEG C of temperature, hydrogen-oil ratio 10~500:1st, 0.1~15h of weight (hourly) space velocity (WHSV)-1。
9. method according to claim 8, it is characterised in that the catalytic condition includes：Hydrogen Vapor Pressure 0.2~
7MPa, 280~420 DEG C of temperature, hydrogen-oil ratio 15~400:1st, 0.3~12h of weight (hourly) space velocity (WHSV)-1。
10. according to the method described in claim 1, it is characterised in that the high-grade aliphatic ester is derived from animal and plant fat
One or more of mixtures.
11. according to the method described in claim 1 or 10, it is characterised in that the high-grade aliphatic ester is to contain 8~22 carbon originals
Fatty acid methyl ester, ethyl ester or the triglyceride of son.
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| CN111036206B (en) * | 2018-10-15 | 2023-02-21 | 中国石油化工股份有限公司 | Glycerol hydrogenolysis catalyst, preparation method and application thereof, and glycerol hydrogenolysis method |
| CN110756194A (en) * | 2019-09-03 | 2020-02-07 | 湘潭大学 | Sulfur-free nickel-based hydrodeoxygenation catalyst and application thereof |
| CN110586112B (en) * | 2019-09-17 | 2022-04-01 | 湘潭大学 | Hydrodeoxygenation solid acid catalyst Ni/CeO2-Al2O3 |
| CN110904468B (en) * | 2019-12-05 | 2021-07-13 | 河北大学 | Cerium-doped tungsten phosphide submicron sphere composite material and preparation method and application thereof |
| CN112604699B (en) * | 2020-12-11 | 2023-03-17 | 浙江海洋大学 | Ni for improving reaction selectivity of reverse water gas 2 P/CeO 2 Catalyst and preparation method thereof |
| CN113600142B (en) * | 2021-08-19 | 2023-08-01 | 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 derivative thereof |
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| CN102585876A (en) * | 2012-03-07 | 2012-07-18 | 天津大学 | Method for preparing hydrocarbon from higher aliphatic ester by metal phosphide catalyst |
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