CN113262789A - Ni/RM hydrodeoxygenation catalyst and preparation method and application thereof - Google Patents
Ni/RM hydrodeoxygenation catalyst and preparation method and application thereof Download PDFInfo
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- CN113262789A CN113262789A CN202110591670.5A CN202110591670A CN113262789A CN 113262789 A CN113262789 A CN 113262789A CN 202110591670 A CN202110591670 A CN 202110591670A CN 113262789 A CN113262789 A CN 113262789A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 101
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010926 purge Methods 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000003225 biodiesel Substances 0.000 claims abstract description 26
- 235000021314 Palmitic acid Nutrition 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000012216 screening Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 239000012263 liquid product Substances 0.000 claims description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000036632 reaction speed Effects 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- -1 fatty acid esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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Abstract
A Ni/RM hydrodeoxygenation catalyst, a preparation method and application thereof, relating to biological energy sources. Ni is used as an active metal catalytic component, RM is used as a carrier, and the mass of the active metal catalytic component accounts for 1-10% of the total mass of the catalyst. Drying, grinding and screening the original wet red mud at room temperature, collecting red mud particles with the particle size of less than 90 mu m, and roasting to obtain a red mud carrier RM; putting the mixture into a nickel nitrate solution, uniformly mixing, drying and calcining the mixture to obtain a precursor NiO/RM; and (2) placing the mixture in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, switching the purged gas into hydrogen, simultaneously starting to heat, reducing at the temperature of 350-450 ℃, and obtaining the Ni/RM hydrodeoxygenation catalyst after the reduction is finished. The Ni/RM hydrodeoxygenation catalyst can be applied to the preparation of second-generation biodiesel by the hydrodeoxygenation of palmitic acid. Before the catalyst is used, vulcanization or carbonization is not needed, the preparation process is simplified, and the operation is simple and convenient.
Description
Technical Field
The invention belongs to the field of biological energy, and particularly relates to a Ni/RM hydrodeoxygenation catalyst, and a preparation method and application thereof.
Background
With the rapid development of economy and the deepening of global integration, the human society faces the dual challenges of resource exhaustion and green development. Conventional fossil fuels have a limited reserve, and excessive use of fossil energy causes severe greenhouse effect and environmental pollution. Secondly, the global demand for energy in countries depends only on traditional fossil fuels and does not meet the goals and requirements of sustainable development. Therefore, the development of green energy, the improvement of energy structure and the improvement of the use ratio of renewable energy are imminent. The first generation of biodiesel is fatty acid esters obtained by transesterification of oils and fats. At present, the first generation biodiesel is mature in process and can be blended with petroleum diesel for use, so that the consumption of the traditional petroleum fuel and the emission of greenhouse gases are reduced. However, the first generation biodiesel also has the disadvantages of high oxygen content, low calorific value, and poor chemical stability. The second generation biodiesel directly improves the quality and deoxidizes the grease in a catalytic hydrogenation mode to obtain long-chain alkane which is consistent with the chemical structure of the traditional petrochemical fuel. Due to the complete consistency of chemical structures, the second-generation biodiesel can be mixed with the traditional petrochemical fuel in any proportion for use. And the second generation biodiesel has high cetane number and strong chemical stability, and can be directly used without modifying the traditional petrochemical fuel engine.
At present, the catalysts applied to the production of the second generation biodiesel mainly comprise two main types of noble metal and transition metal-based catalysts. Pd, Pt, Rh, and Ru are typical noble metal catalysts that exhibit excellent catalytic activity in catalytic hydrodeoxygenation reactions, but the use of noble metal catalysts leads to an increase in preparation cost; therefore, transition metal-based catalysts are attracting much attention. To increase the catalytic activity of transition metal-based catalysts, the catalysts often require sulfiding or carbonization pretreatments. This not only complicates the catalyst preparation process, but also causes environmental and product pollution. Thus, it remains a challenge to prepare a hydrodeoxygenation catalyst that does not require sulfiding and is inexpensive.
The carrier of the catalyst is also an important factor influencing the hydrodeoxygenation reaction of the grease. The prior hydrodeoxygenation catalyst carrier mainly comprises two main types of metal oxides and molecular sieves. The metal oxide has a small specific surface area and cannot effectively increase the number of catalytic active sites. The catalytic hydrodeoxygenation activity of the molecular sieve is limited due to the defects of uneven pore size distribution, unsuitable acidity, low hydrothermal stability and the like. Therefore, the key problem to be solved by the invention is to research a method for preparing the hydrodeoxygenation catalyst which is environment-friendly, simple to prepare and low in cost.
Disclosure of Invention
The first purpose of the invention is to provide a Ni/RM hydrodeoxygenation catalyst which does not need to be vulcanized or carbonized before use, is green in product and has strong hydrothermal stability.
The second purpose of the invention is to provide a preparation method of the Ni/RM hydrodeoxygenation catalyst, which is environment-friendly, simple to prepare and low in price.
The third purpose of the invention is to provide the application of the Ni/RM hydrodeoxygenation catalyst in the preparation of second-generation biodiesel by the hydrodeoxygenation of palmitic acid. Has positive significance for the production and preparation of the second generation biodiesel.
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal catalytic component and RM as a carrier, and the mass of the active metal catalytic component accounts for 1-10% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
1) drying, grinding and screening original wet red mud at room temperature, collecting red mud particles with the particle size of less than 90 mu m, and roasting to obtain a red mud carrier RM;
in the step 1), the roasting can be carried out in a muffle furnace at 400-600 ℃ for 3-6 h.
2) Putting the red mud carrier RM obtained in the step 1) into a nickel nitrate solution, uniformly mixing, and then drying and calcining the mixture to obtain a catalyst precursor NiO/RM;
in the step 2), the uniform mixing can be carried out for 8-14 h by using a magnetic stirrer at room temperature; the drying temperature can be 80-120 ℃, and the drying time can be 8-14 h; the calcination can be carried out for 3-6 h by using a muffle furnace at 500-600 ℃.
3) Placing the catalyst precursor NiO/RM obtained in the step 2) into a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, then switching the purged gas into hydrogen, simultaneously starting heating, reducing at the temperature of 350-450 ℃, and obtaining the Ni/RM hydrodeoxygenation catalyst after the reduction is finished.
In the step 3), the flow rate of nitrogen purging is 60-100 mL/min, and the purging time is 5-20 min; the flow rate of the hydrogen is 10-40 mL/min, the heating rate can be 5 ℃/min, and the temperature is increased to 350-450 ℃; the reduction time can be 3-6 h.
The Ni/RM hydrodeoxygenation catalyst can be applied to the preparation of second-generation biodiesel by the hydrodeoxygenation of palmitic acid.
The application comprises the following specific steps: using palmitic acid as a model compound of palm oil, using a high-temperature high-pressure reaction kettle, using dodecane as a reaction solvent in a hydrogen atmosphere, and using a Ni/RM hydrodeoxygenation catalyst to perform hydrodeoxygenation reaction, wherein an obtained liquid product is the second-generation biodiesel.
Further, the temperature of the hydrodeoxygenation reaction is 300-400 ℃, the heating rate is 5 ℃/min, the reaction time is 2-8 h, the hydrogen pressure during the reaction is 2-6 MPa, and the reaction rotating speed is 300-800 rpm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes the Red Mud (RM) rich in iron oxide as a carrier, and the prepared RM carrier has larger specific surface area and pore volume, and the specific surface area is 86.8m2Per g, pore volume of 0.274cm3The pore diameter is suitable for the fatty acid hydrodeoxygenation reaction, and the pore diameter of the carrier mesopores is mainly concentrated in the range of 3-11 nm. The active component Ni has a good dispersion state and good hydrodeoxygenation activity. Has better catalytic activity in the hydrogenation and deoxidation reaction of palmitic acid, and has positive significance for the preparation and the quality improvement of second-generation biodiesel.
2. The preparation method of the catalyst provided by the invention has the advantages that no noble metal is used, the cost is reduced, the environment is friendly, the product and the environment are not polluted, the problem of large-scale harmless utilization of the red mud is solved, the catalyst is not required to be vulcanized or carbonized before being used, the preparation process is simplified, and the operation is simple and convenient.
Drawings
FIG. 1 is an XRD spectrum of the RM carrier and the Ni/RM catalyst in example 1 of the present invention.
Fig. 2 is an SEM image of the RM support in example 1 of the present invention.
FIG. 3 is an SEM image of Ni/RM catalyst in example 1 of the present invention.
FIG. 4 shows N of the RM support and Ni/RM catalyst in example 1 of the present invention2Desorption isotherm curve.
FIG. 5 shows the calculated pore size distribution of the RM carrier and the Ni/RM catalyst by BJH method in example 1 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
The X-ray diffraction patterns of the support RM and the Ni/RM of the catalyst were measured on a Rigaku Ultima type IV apparatus, and the crystal phase and the object image composition of the catalyst were analyzed.
And (3) carrying out a test of scanning electron microscope images of the carrier RM and the catalyst Ni/RM on a SUPRA 55 field emission scanning electron microscope, and observing the surface morphology of the catalyst.
N obtaining support RM and catalyst Ni/RM on Micromeritics ASAP 2020 Instrument2Adsorption-desorption isotherms, determination of the catalystSpecific surface area and pore size distribution.
The product liquid samples in the examples were analyzed on an Agilent 8890/5977 instrument, and the palmitic acid conversion and the selectivity of the reaction products were statistically analyzed using an external standard method, and the formula was calculated as follows:
palmitic acid conversion (%). gtorex 100%
Product selectivity (%). gtorex 100%
Example 1
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal component and RM as a carrier, wherein the mass of the active nickel metal accounts for 10% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
step 1: the raw wet red mud is dried, ground and sieved at room temperature and the red mud particles with a particle size <90 μm are collected for further use. And roasting the collected red mud particles in a muffle furnace at 400 ℃ for 6h to obtain a carrier RM.
Step 2: 0.4955g of nickel nitrate hexahydrate is dissolved in 100mL of deionized water, 1.0g of RM carrier obtained in the step 1 is weighed and placed in a nickel nitrate solution, the mixture is stirred for 12 hours at room temperature by using a magnetic stirrer, then the mixture is dried for 12 hours at 100 ℃, and finally calcined for 4 hours at 500 ℃ by using a muffle furnace. And obtaining a catalyst precursor NiO/RM.
And step 3: and (3) placing the NiO/RM precursor obtained in the step (2) in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, wherein the nitrogen flow rate is 60mL/min, the purging time is 5min, then switching the purging gas into hydrogen with the flow rate of 20mL/min, simultaneously starting heating, wherein the heating rate is 5 ℃/min, heating to 450 ℃, keeping the reduction time at 450 ℃ for 4h, and obtaining the Ni/RM catalyst after the reduction is finished.
XRD patterns of the RM carrier and the Ni/RM catalyst are shown in figure 1. SEM images of RM supports are shown in fig. 2. The SEM image of the Ni/RM catalyst is shown in FIG. 3. N of RM carrier and catalyst Ni/RM2The desorption isotherm curve is shown in FIG. 4. RM carrierThe pore size distribution of the body and catalyst Ni/RM is shown in FIG. 5.
Example 2
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal component and RM as a carrier, wherein the mass of the active nickel metal accounts for 10% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
step 1: the raw wet red mud is dried, ground and sieved at room temperature and the red mud particles with a particle size <90 μm are collected for further use. And roasting the collected red mud particles in a muffle furnace at 500 ℃ for 6h to obtain the carrier RM.
Step 2: 0.4955g of nickel nitrate hexahydrate is dissolved in 100mL of deionized water, 1.0g of RM carrier obtained in the step 1 is weighed and placed in a nickel nitrate solution, the mixture is stirred for 12 hours at room temperature by using a magnetic stirrer, then the mixture is dried for 12 hours at 100 ℃, and finally calcined for 4 hours at 500 ℃ by using a muffle furnace. And obtaining a catalyst precursor NiO/RM.
And step 3: and (3) placing the NiO/RM precursor obtained in the step (2) in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, wherein the nitrogen flow rate is 60mL/min, the purging time is 5min, then switching the purging gas into hydrogen with the flow rate of 20mL/min, simultaneously starting heating, wherein the heating rate is 5 ℃/min, heating to 450 ℃, keeping the reduction time at 450 ℃ for 4h, and obtaining the Ni/RM catalyst after the reduction is finished.
Example 3
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal component and RM as a carrier, wherein the mass of the active nickel metal accounts for 10% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
step 1: the raw wet red mud is dried, ground and sieved at room temperature and the red mud particles with a particle size <90 μm are collected for further use. And roasting the collected red mud particles in a muffle furnace at 600 ℃ for 6h to obtain the carrier RM.
Step 2: 0.4955g of nickel nitrate hexahydrate is dissolved in 100mL of deionized water, 1.0g of RM carrier obtained in the step 1 is weighed and placed in a nickel nitrate solution, the mixture is stirred for 12 hours at room temperature by using a magnetic stirrer, then the mixture is dried for 12 hours at 100 ℃, and finally calcined for 4 hours at 500 ℃ by using a muffle furnace. And obtaining a catalyst precursor NiO/RM.
And step 3: and (3) placing the NiO/RM precursor obtained in the step (2) in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, wherein the nitrogen flow rate is 60mL/min, the purging time is 5min, then switching the purging gas into hydrogen with the flow rate of 20mL/min, simultaneously starting heating, wherein the heating rate is 5 ℃/min, heating to 450 ℃, keeping the reduction time at 450 ℃ for 4h, and obtaining the Ni/RM catalyst after the reduction is finished.
Example 4
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal component and RM as a carrier, wherein the mass of the active nickel metal accounts for 10% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
step 1: the raw wet red mud is dried, ground and sieved at room temperature and the red mud particles with a particle size <90 μm are collected for further use. And roasting the collected red mud particles in a muffle furnace at 600 ℃ for 6h to obtain the carrier RM.
Step 2: 0.4955g of nickel nitrate hexahydrate is dissolved in 100mL of deionized water, 1.0g of RM carrier obtained in the step 1 is weighed and placed in a nickel nitrate solution, the mixture is stirred for 12 hours at room temperature by using a magnetic stirrer, then the mixture is dried for 12 hours at 100 ℃, and finally calcined for 4 hours at 600 ℃ by using a muffle furnace. And obtaining a catalyst precursor NiO/RM.
And step 3: and (3) placing the NiO/RM precursor obtained in the step (2) in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, wherein the nitrogen flow rate is 60mL/min, the purging time is 5min, then switching the purging gas into hydrogen with the flow rate of 20mL/min, simultaneously starting heating, wherein the heating rate is 5 ℃/min, heating to 450 ℃, keeping the reduction time at 450 ℃ for 4h, and obtaining the Ni/RM catalyst after the reduction is finished.
Example 5
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal component and RM as a carrier, wherein the mass of the active nickel metal accounts for 10% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
step 1: the raw wet red mud is dried, ground and sieved at room temperature and the red mud particles with a particle size <90 μm are collected for further use. And roasting the collected red mud particles in a muffle furnace at 600 ℃ for 6h to obtain the carrier RM.
Step 2: 0.4955g of nickel nitrate hexahydrate is dissolved in 100mL of deionized water, 1.0g of RM carrier obtained in the step 1 is weighed and placed in a nickel nitrate solution, the mixture is stirred for 12 hours at room temperature by using a magnetic stirrer, then the mixture is dried for 12 hours at 100 ℃, and finally calcined for 4 hours at 500 ℃ by using a muffle furnace. And obtaining a catalyst precursor NiO/RM.
And step 3: and (3) placing the NiO/RM precursor obtained in the step (2) in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, wherein the nitrogen flow rate is 60mL/min, the purging time is 5min, then switching the purging gas into hydrogen with the flow rate of 20mL/min, simultaneously starting heating, wherein the heating rate is 5 ℃/min, heating to 450 ℃, keeping the reduction time at 450 ℃ for 4h, and obtaining the Ni/RM catalyst after the reduction is finished.
Example 6
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal component and RM as a carrier, wherein the mass of the active nickel metal accounts for 5% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
step 1: the raw wet red mud is dried, ground and sieved at room temperature and the red mud particles with a particle size <90 μm are collected for further use. And roasting the collected red mud particles in a muffle furnace at 400 ℃ for 6h to obtain a carrier RM.
Step 2: 0.2477g of nickel nitrate hexahydrate is dissolved in 100mL of deionized water, 1.0g of RM carrier obtained in the step 1 is weighed and placed in a nickel nitrate solution, the mixture is stirred for 12 hours at room temperature by using a magnetic stirrer, then the mixture is dried for 12 hours at 100 ℃, and finally calcined for 4 hours at 500 ℃ by using a muffle furnace. And obtaining a catalyst precursor NiO/RM.
And step 3: and (3) placing the NiO/RM precursor obtained in the step (2) in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, wherein the nitrogen flow rate is 60mL/min, the purging time is 5min, then switching the purging gas into hydrogen with the flow rate of 20mL/min, simultaneously starting heating, wherein the heating rate is 5 ℃/min, heating to 450 ℃, keeping the reduction time at 450 ℃ for 4h, and obtaining the Ni/RM catalyst after the reduction is finished.
Example 7
The Ni/RM hydrodeoxygenation catalyst takes Ni as an active metal component and RM as a carrier, wherein the mass of the active nickel metal accounts for 5% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
The preparation method of the Ni/RM hydrodeoxygenation catalyst comprises the following steps:
step 1: the raw wet red mud is dried, ground and sieved at room temperature and the red mud particles with a particle size <90 μm are collected for further use. And roasting the collected red mud particles in a muffle furnace at 400 ℃ for 6h to obtain a carrier RM.
Step 2: 0.0495g of nickel nitrate hexahydrate is dissolved in 100mL of deionized water, 1.0g of the RM carrier obtained in the step 1 is weighed and placed in a nickel nitrate solution, the mixture is stirred for 12 hours at room temperature by using a magnetic stirrer, then the mixture is dried for 12 hours at 100 ℃, and finally calcined for 4 hours at 500 ℃ by using a muffle furnace. And obtaining a catalyst precursor NiO/RM.
And step 3: and (3) placing the NiO/RM precursor obtained in the step (2) in a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, wherein the nitrogen flow rate is 60mL/min, the purging time is 5min, then switching the purging gas into hydrogen with the flow rate of 20mL/min, simultaneously starting heating, wherein the heating rate is 5 ℃/min, heating to 450 ℃, keeping the reduction time at 450 ℃ for 4h, and obtaining the Ni/RM catalyst after the reduction is finished.
Example 8
The Ni/RM hydrodeoxygenation catalyst prepared in the example 1 is adopted, palmitic acid is used as a raw material, and the second-generation biodiesel is prepared by catalytic hydrogenation, and the method comprises the following steps:
in a high-temperature high-pressure reaction kettle, palmitic acid is used as a reaction raw material, dodecane is used as a reaction solvent, the hydrodeoxygenation reaction of the palmitic acid is carried out under the catalytic action of a Ni/RM catalyst, the reaction temperature is 300 ℃, the reaction hydrogen pressure is 4MPa, the stirring rotation speed is 400rpm, the reaction time is 4h, and the finally obtained liquid product is second-generation biodiesel.
Example 9
The Ni/RM hydrodeoxygenation catalyst prepared in the example 5 is adopted, palmitic acid is used as a raw material, and the second-generation biodiesel is prepared by catalytic hydrogenation, and the method comprises the following steps:
in a high-temperature high-pressure reaction kettle, palmitic acid is used as a reaction raw material, dodecane is used as a reaction solvent, the hydrodeoxygenation reaction of the palmitic acid is carried out under the catalytic action of a Ni/RM catalyst, the reaction temperature is 320 ℃, the reaction hydrogen pressure is 5MPa, the stirring speed is 500rpm, the reaction time is 6 hours, and the finally obtained liquid product is second-generation biodiesel.
Example 10
The Ni/RM hydrodeoxygenation catalyst prepared in the embodiment 6 is adopted, palmitic acid is used as a raw material, and the second-generation biodiesel is prepared by catalytic hydrogenation, and the method comprises the following steps:
in a high-temperature high-pressure reaction kettle, palmitic acid is used as a reaction raw material, dodecane is used as a reaction solvent, the hydrodeoxygenation reaction of the palmitic acid is carried out under the catalytic action of a Ni/RM catalyst, the reaction temperature is 460 ℃, the reaction hydrogen pressure is 3MPa, the stirring speed is 450rpm, the reaction time is 8 hours, and the finally obtained liquid product is second-generation biodiesel.
Example 11
The Ni/RM hydrodeoxygenation catalyst prepared in example 7 is adopted, palmitic acid is used as a raw material, and the second-generation biodiesel is prepared by catalytic hydrogenation, and the method comprises the following steps:
in a high-temperature high-pressure reaction kettle, palmitic acid is used as a reaction raw material, dodecane is used as a reaction solvent, the hydrodeoxygenation reaction of the palmitic acid is carried out under the catalytic action of a Ni/RM catalyst, the reaction temperature is 480 ℃, the reaction hydrogen pressure is 4.5MPa, the stirring rotation speed is 400rpm, the reaction time is 10 hours, and the finally obtained liquid product is second-generation biodiesel.
And after the reaction is finished, collecting a liquid product, analyzing the content of pentadecane, hexadecane and other products in the product by an external standard quantitative method, and evaluating the hydrodeoxygenation activity of the catalyst Ni/RM. Using HP-5MS capillary chromatographic column, the temperature of the injection port is 280 ℃, helium is used as carrier gas, the split ratio is 1:80, and the temperature rising program of the column box is as follows: the temperature was raised from 50 ℃ to 280 ℃ at a rate of 5 ℃/min. The result shows that under the better reaction condition, the conversion rate of the palmitic acid reaches 100%, the selectivity of the normal pentadecane reaches 71.37%, the selectivity of the normal hexadecane reaches 28.63%, and the selectivity of the second-generation biodiesel alkane component reaches 100%. The results show that the catalyst prepared by the invention has good hydrodeoxygenation activity.
The invention mainly relates to a preparation method of hydrocarbon biodiesel and a catalyst thereof. The catalyst takes Ni metal as an active component and Red Mud (RM) rich in iron oxide as a carrier, wherein the load of the Ni active metal component is 1-10% of that of the Ni/RM hydrodeoxygenation catalyst. The preparation method of the Ni/RM hydrodeoxygenation catalyst provided by the invention can be used without a vulcanization or carbonization process, is environment-friendly, does not cause product pollution, does not use noble metals, saves cost, is simple and convenient in preparation process, and has positive significance for preparing second-generation hydrocarbon biodiesel.
The above embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The Ni/RM hydrodeoxygenation catalyst is characterized in that Ni is used as an active metal catalytic component, RM is used as a carrier, and the mass of the active metal catalytic component accounts for 1% -10% of the total mass of the Ni/RM hydrodeoxygenation catalyst.
2. The method of claim 1, comprising the steps of:
1) drying, grinding and screening original wet red mud at room temperature, collecting red mud particles with the particle size of less than 90 mu m, and roasting to obtain a red mud carrier RM;
2) putting the red mud carrier RM obtained in the step 1) into a nickel nitrate solution, uniformly mixing, and then drying and calcining the mixture to obtain a catalyst precursor NiO/RM;
3) placing the catalyst precursor NiO/RM obtained in the step 2) into a tubular reactor, firstly purging the interior of the reactor by using nitrogen at room temperature, then switching the purged gas into hydrogen, simultaneously starting heating, reducing at the temperature of 350-450 ℃, and obtaining the Ni/RM hydrodeoxygenation catalyst after the reduction is finished.
3. The method for preparing the Ni/RM hydrodeoxygenation catalyst according to claim 2, wherein in the step 1), the roasting is carried out in a muffle furnace at 400-600 ℃ for 3-6 h.
4. The method for preparing the Ni/RM hydrodeoxygenation catalyst according to claim 2, wherein in the step 2), the uniformly mixing is performed for 8-14 hours at room temperature by using a magnetic stirrer.
5. The method for preparing the Ni/RM hydrodeoxygenation catalyst according to claim 2, wherein in the step 2), the drying temperature is 80-120 ℃, and the drying time is 8-14 h; and the calcining is carried out for 3-6 h by using a muffle furnace under the condition of 500-600 ℃.
6. The method for preparing the Ni/RM hydrodeoxygenation catalyst according to claim 2, wherein in the step 3), the flow rate of the nitrogen purge is 60-100 mL/min, and the purge time is 5-20 min.
7. The method for preparing the Ni/RM hydrodeoxygenation catalyst according to the claim 2, characterized in that in the step 3), the flow rate of the hydrogen is 10-40 mL/min, the temperature rising rate can be 5 ℃/min, and the temperature rises to 350-450 ℃; the reduction time is 3-6 h.
8. Use of the Ni/RM hydrodeoxygenation catalyst of claim 1 in the production of second generation biodiesel by hydrodeoxygenation of palmitic acid.
9. The application of claim 8, which comprises the steps of: using palmitic acid as a model compound of palm oil, using a high-temperature high-pressure reaction kettle, using dodecane as a reaction solvent in a hydrogen atmosphere, and using a Ni/RM hydrodeoxygenation catalyst to perform hydrodeoxygenation reaction, wherein an obtained liquid product is the second-generation biodiesel.
10. The method according to claim 9, wherein the hydrodeoxygenation reaction temperature is 300-400 ℃, the temperature rise rate is 5 ℃/min, the reaction time is 2-8 h, the hydrogen pressure during the reaction is 2-6 MPa, and the reaction speed is 300-800 rpm.
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