CN110862873A - Method for preparing hydrogenated biodiesel by catalyzing grease directional hydrodeoxygenation - Google Patents
Method for preparing hydrogenated biodiesel by catalyzing grease directional hydrodeoxygenation Download PDFInfo
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 56
- 239000004519 grease Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006606 decarbonylation reaction Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 230000006324 decarbonylation Effects 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- 239000003921 oil Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 30
- 230000003197 catalytic effect Effects 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 235000014123 Pistacia chinensis Nutrition 0.000 claims description 7
- 240000000432 Pistacia chinensis Species 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002161 passivation Methods 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 244000248162 Xanthoceras sorbifolium Species 0.000 claims description 3
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 claims description 3
- 239000001289 litsea cubeba fruit oil Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 241000221089 Jatropha Species 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000003925 fat Substances 0.000 description 8
- 238000006392 deoxygenation reaction Methods 0.000 description 7
- -1 alkane compound Chemical class 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 238000004868 gas analysis Methods 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001048891 Jatropha curcas Species 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 125000005457 triglyceride group Chemical group 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for preparing hydrogenated biodiesel by catalyzing grease directional hydrodeoxygenation, belonging to the technical field of hydrogenated biodiesel preparation. Catalyzing the hydrodeoxygenation reaction of the grease raw material by adopting a molecular sieve supported catalyst in a hydrodedecarboxylation/decarbonylation mode to obtain hydrogenated biodiesel, wherein the total content of pentadecane and heptadecane in the hydrogenated biodiesel is more than 85%; the active component of the catalyst is Ni2P, the dosage of the catalyst is 5-10% of the weight of the reaction grease raw material; the main components of the hydrogenated biodiesel are pentadecane and heptadecane, and the directional hydrogenation decarboxylation/decarbonylation selectivity of the invention is more than 80 percent, thereby reducing the generation of reaction water, avoiding the defect that the catalyst is easy to be activated when meeting water, and prolonging the service life of the catalyst; the reaction conversion rate of the hydrogenated biodiesel prepared by the method is more than 95 percent, the temperature and the time of the hydrodeoxygenation reaction of the grease are greatly reduced, the energy consumption of the reaction is remarkably reduced, andand (4) cost.
Description
Technical Field
The invention belongs to the technical field of preparation of hydrogenated biodiesel, and particularly relates to a method for preparing hydrogenated biodiesel by catalyzing oil and fat to perform directional hydrodeoxygenation.
Background
With the rapid development of the world economy, the energy supply required by the human society is rapidly increased, the normal survival and development of human beings are seriously threatened by the imminent exhaustion of the traditional fossil energy and the ecological environmental problem generated in the use process, and the urgent need of finding the alternative energy of the petrochemical energy is urgent. For a long time, research and use of biodiesel having green, low carbon, clean, renewable properties has been of great interest. The first generation biodiesel is fatty acid methyl ester, has mature process and application, has many advantages as a substitute fuel, but also has certain defects and limitations, high cold filter plugging point, high viscosity and poor oxidation stability, and limits the popularization and application of fatty acid methyl ester biodiesel.
As a new generation of biological liquid fuel capable of replacing petroleum diesel, hydrogenated biological diesel is proposed, which is directly converted into a C15-C18 alkane compound by grease (triglyceride) through catalytic hydrodeoxygenation reaction, has the same molecular structure as petroleum diesel, has good oxidation stability and higher cetane number, and can be mixed with the petroleum diesel for use. However, the process of converting the grease into the hydrogenated biodiesel through catalytic hydrogenation has high requirements on catalytic activity, and generally uses a noble metal catalyst, which is expensive and has high cost; the common transition metal sulfide catalyst has certain improved catalytic activity, is not environment-friendly, is easy to cause sulfur pollution to the prepared biodiesel, and simultaneously, sulfur in the catalyst is easy to lose, so that the active center structure of the catalyst is changed, and a sulfur source needs to be continuously supplemented in the reaction process. The catalytic hydrogenation reaction path in the preparation process of the hydrogenated biodiesel is undefined, so that the defects of more hydrogenated product components, lower alkane content in the product and the like are caused, the catalytic hydrogenation reaction of the oil mainly generates reactions such as double bond hydrogenation saturation, direct deoxidation by hydrogenation, hydrogenation decarboxylation, hydrogenation decarbonylation and the like, and the reaction process is as follows:
firstly, double bond hydrogenation saturation is generated, double bond functional groups in triglyceride side chains are eliminated, and the stability of the product is further improved; the direct deoxidation by hydrogenation is to make all oxygen atoms in the grease to generate H2Removing O in a form, and generating alkane compounds with hexadecane and octadecane as main components; the hydrodedecarboxylation is to convert oxygen atoms in the fats and oils to CO2Formally removed and produces alkane compounds with pentadecane and heptadecane as main components; the hydrogenation decarbonylation is to convert oxygen atoms in the grease into CO and H2The O form is removed, and alkane compounds with pentadecane and heptadecane as main components are produced. The direct hydrodeoxygenation consumes a large amount of hydrogen sources, and the hydrogen sources are completely converted into water, so that the catalyst is easy to deactivate along with the enrichment of the water; the hydrogenation decarboxylation and the hydrogenation decarbonylation consume less hydrogen, only generate trace moisture and even no moisture, and prolong the service life of the catalyst. The existing problems are how to improve the directional selectivity of catalytic hydrogenation decarboxylation and hydrogenation decarbonylation of the grease, so as to define the main path of catalytic hydrogenation reaction, improve the total content of pentadecane and heptadecane in the product, reduce the content of other alkane byproducts and obtain high-quality hydrogenated biodiesel with concentrated component content.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing hydrogenated biodiesel by catalyzing oil and fat directional hydrogenation and deoxidation, which catalyzes oil and fat directional hydrogenation and decarboxylation and hydrogenation and decarbonylation reactions, greatly reduces the generation of reaction water, prolongs the service life of a catalyst, greatly reduces the temperature and reaction time of the catalytic hydrogenation reaction, and reduces the reaction energy consumption.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for preparing hydrogenated biodiesel by catalyzing grease directional hydrodeoxygenation adopts a molecular sieve supported catalyst, the catalytic grease raw material hydrodeoxygenation reaction is carried out in a hydrodedecarboxylation/decarbonylation way, and the reaction is carried out for 2-4h at the temperature of 280-320 ℃ to obtain the hydrogenated biodiesel, wherein the total content of pentadecane and heptadecane in the hydrogenated biodiesel is more than 85%; the active component of the molecular sieve supported catalyst is Ni2The mass of the P and the Ni elements is 5-15 wt.% of the carrier; the dosage of the molecular sieve supported catalyst is 5-10% of the weight of the reaction grease raw material. The method specifically comprises the following steps:
(1) adding a grease raw material into a hydrocarbon solvent, and uniformly stirring to obtain a mixed solution; the hydrocarbon solvent is one or two of cyclohexane or normal hexane, and the grease raw material accounts for 15-30% of the mass of the solvent;
(2) transferring the mixed solution into a high-temperature high-pressure reaction kettle, adding a molecular sieve supported catalyst, replacing the internal air, introducing 2-4MPa of hydrogen from the outside, stirring, heating, and obtaining the hydrogenated biodiesel after the reaction is finished.
According to the method for preparing the hydrogenated biodiesel by the catalytic oil directional hydrodeoxygenation, the oil raw materials are waste oil, jatropha oil, xanthoceras sorbifolia bunge oil, litsea cubeba oil or pistacia chinensis oil.
According to the method for preparing the hydrogenated biodiesel by catalyzing the oil and fat to carry out directional hydrodeoxygenation, the hydrocarbon solvent is cyclohexane, and the oil and fat raw material accounts for 20% of the mass of the solvent.
The method for preparing the hydrogenated biodiesel by catalyzing the grease directional hydrodeoxygenation comprises the step of preparing the hydrogenated biodiesel by using Ni as the molecular sieve supported catalyst2P/SAPO-11, mass of Ni element 15 wt.% of support.
The method for preparing the hydrogenated biodiesel by the directional hydrodeoxygenation of the catalytic oil has the hydrodeoxygenation reaction temperature of 300 ℃ and the reaction time of 4 hours.
According to the method for preparing the hydrogenated biodiesel by catalyzing the oil and fat directional hydrodeoxygenation, the dosage of the molecular sieve supported catalyst is 6% of the weight of the oil and fat raw material.
The method for preparing hydrogenated biodiesel by catalyzing grease directional hydrodeoxygenation is characterized in that the catalyst Ni2The preparation method of the P/SAPO-11 comprises the following steps:
(1) adding SAPO-11 into an aqueous solution of a nickel source and a phosphorus source, and performing ultrasonic impregnation, drying and calcination to obtain a catalyst precursor; the phosphorus source is one or a mixture of ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the nickel source is nickel nitrate hexahydrate;
(2) adding a catalyst precursor into a tubular furnace, introducing hydrogen to carry out temperature programming reduction, and carrying out passivation treatment after the reduction is finished and the temperature is reduced to room temperature to obtain a catalyst Ni2P/SAPO-11；H2The flow rate is 100-150 mL/min; the temperature programming process comprises the following steps: heating to 250-300 ℃ at a speed of 10-12 ℃/min, heating to 350-400 ℃ at a speed of 5-7 ℃/min, heating to 600-650 ℃ at a speed of 1-2 ℃/min, maintaining the constant temperature of 600-650 ℃, and reducing for 2-3 h, wherein the temperature is 1% O at normal temperature2/N2Passivating for 0.5-1 h.
The method for preparing the hydrogenated biodiesel by catalyzing the directional hydrodeoxygenation of the grease specifically comprises the following steps:
(1) adding SAPO-11 into an aqueous solution of nickel nitrate hexahydrate and diammonium hydrogen phosphate, wherein the mass of a Ni element is 15 wt% of that of a carrier, ultrasonically dipping for 30min, drying for 12h at 80 ℃, transferring to a muffle furnace at 550 ℃ to calcine for 4h, and crushing and screening by using an 80-mesh screen to obtain a catalyst precursor; adding a catalyst precursor into a tubular furnace, introducing hydrogen to carry out temperature programming reduction, and carrying out passivation treatment after the reduction is finished and the temperature is reduced to room temperature to obtain a catalyst Ni2P/SAPO-11；H2The flow rate is 150 mL/min; the temperature programming process comprises the following steps: heating to 250 deg.C at 10 deg.C/min, heating to 350 deg.C at 5 deg.C/min, heating to 650 deg.C at 1 deg.C/min, and maintaining the constant temperature of 650 deg.C for reduction for 3 h; at room temperature at 1% O2/N2Passivating for 0.5 h;
(2) the catalyst Ni2Adding P/SAPO-11 and 20% pistacia chinensis bunge oil cyclohexane solution into a high-temperature high-pressure reaction kettle, displacing internal air, introducing 2.5MPa of hydrogen from the outside, stirring and heating, reacting for 4 hours at 320 ℃, and obtaining hydrogenated biodiesel after the reaction is finished; catalyst Ni2The dosage of the P/SAPO-11 is 6 percent of the weight of the Pistacia chinensis oil.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the invention adopts catalyst Ni2P/SAPO-11 catalyzed grease directional hydrodeoxygenation for preparing hydrogenated biodiesel, and active component Ni2P shows the catalytic activity of noble metal, the deoxidation conversion rate is more than 95%, the temperature and time of the grease hydrodeoxygenation reaction are greatly reduced, and the reaction energy consumption and cost are obviously reduced.
(2) The invention realizes the preparation of hydrogenated biodiesel by catalyzing the directional hydrodeoxygenation of grease, the catalytic hydrodecarbonylation/decarboxylation directional selectivity is more than 85 percent, the high-quality hydrogenated biodiesel taking pentadecane and heptadecane as main components is obtained, the effective substitution of petroleum diesel can be realized, and the upgrading and updating of biodiesel products are promoted.
(3) The invention prepares the hydrogenated biodiesel by catalyzing the grease directional hydrogenation decarboxylation/decarbonylation reaction path, reduces the generation of reaction moisture, avoids the defect that the catalyst is easy to be activated when meeting water, and prolongs the service life of the catalyst.
Drawings
FIG. 1 shows Ni of example 12XRD patterns of the P/SAPO-11 catalyst and the carrier SAPO-11;
FIG. 2 is a diagram showing a gas mass analysis of the reaction product of example 1.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
Catalyst Ni2The preparation method of the P/SAPO-11 comprises the following steps:
controlling the content of nickel element to be 15 wt.% of the mass of the carrier, wherein the nickel element is nickelDissolving nickel nitrate hexahydrate and diammonium hydrogen phosphate which are metered according to the molar ratio of 1: 1 to phosphorus in deionized water, transferring the mixture into a crucible after the mixture is uniformly dissolved, adding SAPO-11, ultrasonically dipping the mixture for 30min, transferring the dipping solution into an oven with the temperature of 80 ℃ for drying for 12h, finally transferring the dried product into a muffle furnace with the temperature of 550 ℃ for calcining for 4h, and crushing the calcined product through a screen with the size of 80 meshes to obtain a catalyst precursor; adding the catalyst precursor into a tubular furnace, introducing hydrogen for programmed temperature reduction, and H2The flow rate is 150mL/min, the temperature is raised to 250 ℃ at the speed of 10 ℃/min, then the temperature is raised to 350 ℃ at the speed of 5 ℃/min, finally the temperature is raised to 650 ℃ at the speed of 1 ℃/min, and the constant temperature is kept for reducing for 3h at 650 ℃; after the reduction is finished and the temperature is reduced to room temperature, 0.1 percent of O is introduced2/N2Passivating under atmosphere to obtain Ni catalyst2P/SAPO-11(Ni-15wt.％)。
FIG. 1 shows Ni in example 1 of the present invention2XRD patterns of the P/SAPO-11 catalyst and the carrier SAPO-11 can be known from figure 1 that the characteristic diffraction peaks of the carrier SAPO-11 are shown when the 2 theta is at 13.2 degrees, 15.9 degrees and 21.1-23.2 degrees; ni2Ni appears in the P/SAPO-11 catalyst at 2 theta of 40.5 degrees, 44.5 degrees, 47.9 degrees and 54.1 degrees2The characteristic diffraction peak of P shows that the catalyst prepared by the preparation method of the catalyst has pure active phases of Ni and P.
The method for preparing the hydrogenated biodiesel by the directional hydrodeoxygenation of the catalytic oil comprises the following steps:
ni prepared as above2Respectively adding a P/SAPO-11(Ni-15 wt.%) catalyst and a 15% jatropha curcas oil cyclohexane solution into a 100mL high-temperature high-pressure reaction kettle, wherein the addition amount of the catalyst is 10% of the weight of grease, displacing internal air, introducing 4MPa of hydrogen from the outside, stirring, heating, reacting for 2 hours at 300 ℃, after the reaction is finished, taking a liquid product, carrying out gas analysis, and calculating the deoxygenation conversion rate and the directional selectivity.
FIG. 1 is a gas mass analysis diagram of hydrogenated biodiesel as a reaction product of example 1, and it can be seen from FIG. 1 that pentadecane and heptadecane are mainly contained in the products, respectively accounting for 23.3% and 67.8% of the total product, indicating that the catalytic reaction mainly carries out the directional hydrodedecarboxylation/decarbonylation reaction.
Example 2
Catalyst Ni2The preparation method of the P/SAPO-11 comprises the following steps:
controlling the content of nickel element to be 10 wt% of the mass of the carrier, dissolving nickel nitrate hexahydrate and ammonium dihydrogen phosphate which are measured according to the molar ratio of nickel to phosphorus of 1: 1 in deionized water, transferring the mixture into a crucible after the nickel nitrate hexahydrate and the ammonium dihydrogen phosphate are uniformly dissolved, adding SAPO-11, ultrasonically dipping the mixture for 30min, transferring the dipping solution into an oven with the temperature of 80 ℃ for drying for 12h, finally transferring the dipping solution into a muffle furnace with the temperature of 550 ℃ for calcining for 4h, and crushing the product through a sieve with the size of 80 meshes to obtain a catalyst precursor; adding a catalyst precursor into a high-temperature tubular furnace, introducing hydrogen to carry out programmed heating reduction, heating the H2 flow rate to 250 ℃ at 10 ℃/min, heating to 350 ℃ at 5 ℃/min, heating to 650 ℃ at 1 ℃/min, and keeping the constant temperature of 650 ℃ for reduction for 3H; after the reduction is finished and the temperature is reduced to room temperature, 0.1 percent of O is introduced2/N2Passivating under atmosphere to obtain Ni catalyst2P/SAPO-11(Ni-10wt.％)。
The method for preparing the hydrogenated biodiesel by the directional hydrodeoxygenation of the catalytic oil comprises the following steps:
ni prepared as above2Respectively adding a P/SAPO-11(Ni-10 wt.%) catalyst and a 25% shinyleaf yellowhorn oil cyclohexane solution into a 100mL high-temperature high-pressure reaction kettle, wherein the addition amount of the catalyst is 5% of the weight of grease, replacing internal air, introducing 3MPa of hydrogen from the outside, stirring, heating, reacting for 4 hours at 320 ℃, taking a liquid product after the reaction is finished, performing gas analysis, and calculating the deoxygenation conversion rate and the directional selectivity.
Example 3
Catalyst Ni2The preparation method of the P/SAPO-11 comprises the following steps:
controlling the content of nickel element to be 5 wt% of the mass of the carrier, dissolving nickel nitrate hexahydrate and diammonium hydrogen phosphate which are measured according to the molar ratio of nickel to phosphorus of 1: 1 in deionized water, transferring the mixture into a crucible after the nickel nitrate hexahydrate and the diammonium hydrogen phosphate are uniformly dissolved, adding SAPO-11, ultrasonically dipping the mixture for 30min, transferring the dipping solution into an oven at 80 ℃ for drying for 12h, finally transferring the drying solution into a muffle furnace at 550 ℃ for calcining for 4h, and crushing the calcined solution through an 80-mesh screen to obtain a catalyst precursor; adding a catalyst precursor into a high-temperature tubular furnace, introducing hydrogen to carry out programmed heating reduction, heating the H2 flow rate to 250 ℃ at 10 ℃/min, heating to 350 ℃ at 5 ℃/min, heating to 650 ℃ at 1 ℃/min, and keeping the constant temperature of 650 ℃ for reduction for 3H;after the reduction is finished and the temperature is reduced to the room temperature, the passivation treatment is carried out in the atmosphere of 0.1 percent O2/N2 to obtain the catalyst Ni2P/SAPO-11(Ni-5wt.％)。
The method for preparing the hydrogenated biodiesel by the directional hydrodeoxygenation of the catalytic oil comprises the following steps:
ni prepared as above2Respectively adding a P/SAPO-11(Ni-5 wt.%) catalyst and a 30% waste grease cyclohexane solution into a 100mL high-temperature high-pressure reaction kettle, wherein the addition amount of the catalyst is 8% of the weight of grease, replacing internal air, introducing 2MPa of hydrogen from the outside, stirring, heating, reacting for 4 hours at 320 ℃, taking a liquid product after the reaction is finished, carrying out gas analysis, and calculating the deoxygenation conversion rate and the directional selectivity.
Example 4
The method for preparing the hydrogenated biodiesel by the directional hydrodeoxygenation of the catalytic oil comprises the following steps:
ni prepared in example 12Respectively adding a P/SAPO-11(Ni-15 wt.%) catalyst and a 20% Pistacia chinensis oil n-hexane solution into a 100mL high-temperature high-pressure reaction kettle, wherein the addition amount of the catalyst is 6% of the weight of the grease, replacing internal air, introducing 2.5MPa of hydrogen from the outside, stirring, heating, reacting for 4 hours at 300 ℃, after the reaction is finished, taking a liquid product, performing gas analysis, and calculating the deoxygenation conversion rate and the directional selectivity.
Example 5
The method for preparing the hydrogenated biodiesel by the directional hydrodeoxygenation of the catalytic oil comprises the following steps:
ni prepared in example 22Respectively adding a P/SAPO-11(Ni-10 wt.%) catalyst and a 26% waste grease n-hexane solution into a 100mL high-temperature high-pressure reaction kettle, wherein the addition amount of the catalyst is 10% of the weight of grease, displacing internal air, introducing 2MPa of hydrogen from the outside, stirring, heating, reacting for 4 hours at 320 ℃, taking a liquid product after the reaction is finished, carrying out gas analysis, and calculating the deoxygenation conversion rate and the directional selectivity.
Example 6
The method for preparing the hydrogenated biodiesel by the directional hydrodeoxygenation of the catalytic oil comprises the following steps:
ni prepared in example 32P/SAPO-11(Ni-5 wt.%) catalyst and 18% litsea cubeba oil in n-hexane solution, respectivelyAdding the mixture into a 100mL high-temperature high-pressure reaction kettle, wherein the addition amount of a catalyst is 9% of the weight of the grease, replacing internal air, introducing 3.5MPa of hydrogen from the outside, stirring and heating, reacting for 4 hours at 290 ℃, after the reaction is finished, taking a liquid product for gas analysis, and calculating the deoxygenation conversion rate and the directional selectivity.
Note: hydrodeoxygenation conversion ═ relative content of hydrocarbons in product/relative total content of compounds in product
Hydrodecarbonylation/decarboxylation directional selectivity (the relative content of (C15+ C17) in the product/the relative total content of hydrocarbons in the product).
TABLE 1 results of catalytic reactions in examples 1 to 6
| Catalyst Performance | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Hydrogenation to deoxygenation conversion | 99.7％ | 98％ | 95.2％ | 100％ | 96.3％ | 95.5％ |
| Directed selectivity | 91.1％ | 81.7％ | 80.3％ | 85.2％ | 85.7％ | 82.2％ |
Claims (9)
1. A method for preparing hydrogenated biodiesel by catalyzing oil and fat directional hydrodeoxygenation is characterized in that a molecular sieve supported catalyst is adopted, the hydrodeoxygenation reaction of a catalytic oil and fat raw material is carried out in a hydrodedecarboxylation/decarbonylation mode, and the reaction is carried out for 2-4h at the temperature of 280-320 ℃ to obtain the hydrogenated biodiesel, wherein the total content of pentadecane and heptadecane in the hydrogenated biodiesel is more than 85%; the active component of the molecular sieve supported catalyst is Ni2The mass of the P and the Ni elements is 5-15 wt.% of the carrier; the dosage of the molecular sieve supported catalyst is 5-10% of the mass of the grease raw material.
2. The method for preparing hydrogenated biodiesel by catalytic grease directional hydrodeoxygenation according to claim 1, characterized by comprising the following steps:
(1) adding a grease raw material into a hydrocarbon solvent, and uniformly stirring to obtain a mixed solution; the hydrocarbon solvent is one or two of cyclohexane or normal hexane, and the grease raw material accounts for 15-30% of the mass of the solvent;
(2) transferring the mixed solution into a high-temperature high-pressure reaction kettle, adding a molecular sieve supported catalyst, replacing the internal air, introducing 2-4MPa of hydrogen from the outside, stirring, heating for reaction, and obtaining the hydrogenated biodiesel after the reaction is finished.
3. The method for preparing hydrogenated biodiesel by catalytic directional hydrodeoxygenation of grease according to claim 1 or 2, wherein the grease raw material is waste grease, jatropha oil, xanthoceras sorbifolia oil, litsea cubeba oil or pistacia chinensis oil.
4. The method for preparing hydrogenated biodiesel by catalytic grease directional hydrodeoxygenation according to claim 2, wherein the hydrocarbon solvent is cyclohexane, and the grease raw material is 20% of the solvent by mass.
5. The method for preparing hydrogenated biodiesel by catalytic directional hydrodeoxygenation of grease according to claim 1 or 2, wherein the molecular sieve supported catalyst is Ni2P/SAPO-11, the mass of Ni element is 15 wt.% of the SAPO-11 carrier.
6. The method for preparing hydrogenated biodiesel by catalytic directional hydrodeoxygenation of grease according to claim 1 or 2, wherein the hydrodeoxygenation reaction temperature is 300 ℃ and the reaction time is 4 hours.
7. The method for preparing hydrogenated biodiesel by catalytic grease directional hydrodeoxygenation according to claim 1 or 2, wherein the dosage of the molecular sieve supported catalyst is 6% of the weight of the grease raw material.
8. The method for preparing hydrogenated biodiesel by catalytic grease directional hydrodeoxygenation according to claim 5, wherein the catalyst Ni is2The preparation method of the P/SAPO-11 comprises the following steps:
(1) adding SAPO-11 into an aqueous solution of a nickel source and a phosphorus source, and performing ultrasonic impregnation, drying and calcination to obtain a catalyst precursor; the phosphorus source is one or a mixture of ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the nickel source is nickel nitrate hexahydrate;
(2) adding a catalyst precursor into a tubular furnace, introducing hydrogen to carry out temperature programming reduction, and carrying out passivation treatment after the reduction is finished and the temperature is reduced to room temperature to obtain a catalyst Ni2P/SAPO-11；H2The flow rate is 100-150 mL/min; the temperature programmed processThe process is as follows: heating to 250-300 ℃ at a speed of 10-12 ℃/min, heating to 350-400 ℃ at a speed of 5-7 ℃/min, heating to 600-650 ℃ at a speed of 1-2 ℃/min, maintaining the constant temperature of 600-650 ℃, and reducing for 2-3 h, wherein the temperature is 1% O at normal temperature2/N2Passivating for 0.5-1 h.
9. The method for preparing hydrogenated biodiesel by catalytic directional hydrodeoxygenation of grease according to claim 1 or 2, characterized by comprising the following steps:
(1) adding a carrier SAPO-11 into an aqueous solution of nickel nitrate hexahydrate and diammonium hydrogen phosphate, wherein the mass of a Ni element is 15 wt.% of the carrier, ultrasonically dipping for 30min, drying for 12h at 80 ℃, transferring to a muffle furnace at 550 ℃ to calcine for 4h, and crushing and screening by using an 80-mesh screen to obtain a catalyst precursor; adding a catalyst precursor into a tubular furnace, introducing hydrogen to carry out temperature programming reduction, and carrying out passivation treatment after the reduction is finished and the temperature is reduced to room temperature to obtain a catalyst Ni2P/SAPO-11；H2The flow rate is 150 mL/min; the temperature programming process comprises the following steps: heating to 250 deg.C at 10 deg.C/min, heating to 350 deg.C at 5 deg.C/min, heating to 650 deg.C at 1 deg.C/min, and maintaining the constant temperature of 650 deg.C for reduction for 3 h; at room temperature at 1% O2/N2Passivating for 0.5 h;
(2) the catalyst Ni2Adding P/SAPO-11 and 20% pistacia chinensis bunge oil cyclohexane solution into a high-temperature high-pressure reaction kettle, displacing internal air, introducing 2.5MPa of hydrogen from the outside, stirring and heating, reacting for 4 hours at 320 ℃, and obtaining hydrogenated biodiesel after the reaction is finished; the catalyst Ni2The dosage of the P/SAPO-11 is 6 percent of the weight of the Pistacia chinensis oil.
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