CN115007168A - Preparation method of catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent - Google Patents
Preparation method of catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent Download PDFInfo
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- CN115007168A CN115007168A CN202210702085.2A CN202210702085A CN115007168A CN 115007168 A CN115007168 A CN 115007168A CN 202210702085 A CN202210702085 A CN 202210702085A CN 115007168 A CN115007168 A CN 115007168A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 150000004666 short chain fatty acids Chemical class 0.000 title claims abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 25
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 25
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- -1 nickel salt compound Chemical class 0.000 claims abstract description 9
- 150000002821 niobium Chemical class 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 16
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 14
- 235000021391 short chain fatty acids Nutrition 0.000 claims description 9
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
- 229940005605 valeric acid Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- YJEJFHCHLNUCBH-UHFFFAOYSA-A 2-hydroxypropane-1,2,3-tricarboxylate niobium(5+) Chemical compound [Nb+5].[Nb+5].[Nb+5].OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O YJEJFHCHLNUCBH-UHFFFAOYSA-A 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- GAGSVOVTFFOFFX-UHFFFAOYSA-D [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O Chemical compound [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O GAGSVOVTFFOFFX-UHFFFAOYSA-D 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 0.000 claims description 3
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- ZPQAKYPOZRXKFA-UHFFFAOYSA-N 6-Undecanone Chemical compound CCCCCC(=O)CCCCC ZPQAKYPOZRXKFA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- DVTHIMLUHWEZOM-UHFFFAOYSA-L nickel(2+);octanoate Chemical compound [Ni+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O DVTHIMLUHWEZOM-UHFFFAOYSA-L 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 238000005303 weighing 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/24—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/24—Hydrocarbons
- C11D7/241—Hydrocarbons linear
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of chemical industry, in particular to a preparation method of a catalyst for converting short-chain fatty acid into a hydrocarbon cleaning agent, which solves the problems of harsh catalytic reaction conditions, longer process route, overhigh investment cost and the like in the process of preparing long-chain alkane by using waste short-chain fatty acid; the method comprises the following steps: step 1) uniformly mixing a nickel salt compound and an organic reagent in a certain proportion, and stirring at a certain temperature to prepare a solution a; step 2) mixing manganese salt and water according to a certain proportion, stirring at a certain temperature to prepare a solution b, and then adding the solution b into a reaction kettle to be uniformly mixed with the solution a; step 3) mixing a certain proportion of niobium salt and water, and stirring at a certain temperature to prepare a solution c; step 4), introducing the solution c into a reaction kettle at a certain temperature and flow rate, and stirring for reaction to obtain a mixture d; step 5), continuously increasing the temperature of the reaction kettle; and 6) putting the solid e obtained by filtering in the step 6) into a high-temperature atmosphere furnace for calcining to obtain the target catalyst.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of a catalyst for converting short-chain fatty acid into a hydrocarbon cleaning agent.
Background
The cleaning of the surface of the metal part is an indispensable process of mechanical manufacturing, and the main purpose of the cleaning is to clean pollutants such as oil stains, dust and the like on the metal surface. If a small amount of oxygen and other pollutants are mixed in the cleaning liquid, corrosion points are generated on the surface of the workpiece, and the quality of the part is affected. At present, the hydrocarbon cleaning agent can effectively prevent metal corrosion and can keep the appearance of the metal part bright and clean. The main component of the latest hydrocarbon cleaning agent is saturated alkane compound with carbon number C 9 -C 12 Meanwhile, the petrochemical raw materials are converted through a series of processes at present. However, the equipment investment cost of the process is high, and the process is complex; impurities such as sulfur, aromatic hydrocarbon and the like in the product can influence the environment and the human health; the main component of the distillation tower is alkane with a plurality of isomer types and a wider distillation range.
Petrochemical raw materials are non-renewable resources, and with the increasing exhaustion of global petrochemical resources, development of biomass raw materials for conversion and upgrading into other chemical products becomes one of ideal choices. The fatty acid is a typical biomass platform compound and a renewable resource with wide sources, and the problem can be effectively solved by converting the fatty acid into the hydrocarbon compound. At present, the fat or long-chain fatty acid is used at home and abroad to obtain alkane compounds through high-temperature catalytic hydrogenation, for example, lauric acid is used for hydrogenation to directly obtain C 12 Alkanes, however, have a high raw material cost.
The preparation process at present mainly comprises the following steps: step 1, carrying out C-C coupling reaction (also called ketone decarboxylation) on two molecules of fatty acid under the action of a catalyst to generate a fatty ketone molecule; and 2, carrying out saturated hydrogenation deoxidation on the aliphatic ketone to form alkane.
The selection of the catalyst is particularly important in the process, in ketonizationEarly strong basic catalysts in the reaction such as: MgO, CaO, BaO, and the like have high catalytic activity but poor stability. Another class of amphoteric oxides is: TiO 2 2 、CeO 2 、ZrO 2 And the like, the activity, the selectivity and the stability are higher in the catalytic reaction, but the reaction condition is more severe, higher reaction temperature is required, and the energy consumption is higher. The second-step hydrodeoxygenation reaction usually uses noble metal catalysts such as Pd, Pt, Ru and the like, so that the investment cost is overlarge and the reaction process route is long.
In summary, it can be seen that a catalyst with good performance is lacked in the existing preparation process.
Disclosure of Invention
Aiming at the problems mentioned in the background technology, the invention aims to provide a preparation method of a catalyst for converting short-chain fatty acid into a hydrocarbon cleaning agent, which effectively solves the problems of harsh catalytic reaction conditions, longer process route, overhigh investment cost and the like in the process of preparing long-chain alkane by using waste short-chain fatty acid, and the catalyst prepared by the method has higher activity, stability and selectivity, is simple and practical, has lower cost, has a nano structure, and can convert short-chain fatty acid such as valeric acid, caproic acid and the like into C in one step 9 -C 12 And the like.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of a catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent comprises the following steps:
A. preparation of the catalyst:
step 1) uniformly mixing a nickel salt compound and an organic reagent in a certain proportion, stirring at a certain temperature to prepare a solution a, and adding the solution a into a reaction kettle;
step 2) mixing manganese salt and water according to a certain proportion, stirring at a certain temperature to prepare a solution b, and then adding the solution b into a reaction kettle to be uniformly mixed with the solution a;
step 3) mixing a certain proportion of niobium salt and water, stirring at a certain temperature to prepare a solution c;
step 4) introducing the solution c into a reaction kettle at a certain temperature and flow rate, and stirring for reaction to obtain a mixture d;
step 5), after the mixture d is stable, continuously raising the temperature of the reaction kettle to accelerate the formation of the catalyst structure;
after the reaction in the step 6), putting the solid e obtained by filtering into a high-temperature atmosphere furnace to calcine to obtain a target catalyst;
wherein the proportion of the solution a in the step 1) is as follows: 1-5 parts of a nickel salt compound; 95-99 parts of an organic reagent;
the mixture ratio of the solution b in the step 2) is as follows: 10-20 parts of manganese salt; 80-90 parts of a hydrosolvent;
the niobium salt in the step 3) comprises the following components in percentage by weight: 10-40 parts of niobium salt; 60-90 parts of a water solvent.
2. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents according to claim 1, wherein the nickel salt compound in step 1) is at least one of nickel acetylacetonate, nickel acetate, nickel octoate and nickel benzoate.
3. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents as claimed in claim 1, wherein the organic reagent in step 1) is at least one of valeric acid, caproic acid, enanthic acid and caprylic acid.
4. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents according to claim 1, wherein the manganese salt in step 2) is at least one of potassium permanganate, manganese nitrate, manganese acetate, manganese chloride and manganese sulfate.
5. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents as claimed in claim 1, wherein the niobium salt in step 3) is at least one of niobium pentachloride, niobium tartrate, niobium oxalate and niobium citrate.
6. The preparation method of the catalyst for converting short-chain fatty acid into the hydrocarbon cleaning agent according to claim 1, wherein the reaction temperature in the step 4) is controlled to be 0-100 ℃; the dropping speed is 0.1-10 ml/min; the stirring speed is 20-300 r/min; the reaction time is 30 min-4 h after the dripping is finished.
7. The preparation method of the catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent according to claim 1, wherein in the step 5), the temperature is 120-200 ℃ and the time is 6-36 h.
8. The preparation method of the catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent according to claim 1, wherein the temperature rise rate of the treatment in the high-temperature atmosphere furnace in the step 6) is 1-10 ℃/min, the calcination temperature is 500-800 ℃, and the time is 3-10 h.
9. The method for preparing catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent according to claim 1, wherein the gas used in the atmosphere furnace in the step 6) is H 2 /Ar，H 2 /N 2 ，H 2 Mixed gas of/He, H 2 The mass fraction of (A) is 1% -10%.
In summary, the invention mainly has the following beneficial effects:
(1) the catalyst used in the invention has both ketonization activity and hydrodeoxygenation activity, can convert short-chain fatty acid into long-chain paraffin in one step, and can shorten the whole process route. The catalyst mechanism is as follows: according to the core-shell structure of the catalyst, the Mn-Nb carrier on the outer layer has more hole oxygen structures, and can efficiently catalyze fatty acid to generate ketone, and the fatty ketone enters the interior of the catalyst to contact with Ni active phase and further carry out hydrodeoxygenation reaction to generate alkane; the catalyst can reduce the discharge of three wastes, is favorable for reducing energy consumption and reduces the harm to the environment.
(2) The catalyst prepared by the invention has better performance in ketonization reaction of fatty acid compared with other patents, for example, the catalyst used in ketonization reaction is CaO, HAP and CeO as described in patent CN202010118816.X 2 、ZnO 2 、Al 2 O 3 And ZrO 2 In which the base species are susceptible to corrosion by carboxylic acids, reducing catalytic performance.
The ketonization reaction efficiency of the Nb-Mn phase is far higher than that of CeO 2 、ZrO 2 And the like, and the reaction time is shorter. In addition, the hydrogenation reaction of aliphatic ketone is suitable for noble metal Pd, Re and other catalysts, the use of Ni catalyst in the invention can save the cost of raw materials; and the activity of the prepared catalyst is not reduced below after the catalyst is repeatedly used for many times in the fatty acid ketonization reaction, which indicates that the stability of the catalyst is higher.
(3) The catalyst prepared by the invention is also suitable for the reaction of other long-chain fatty acids such as: the conversion rate can reach 100 percent, and the alkane yield can reach more than 50 percent.
Drawings
FIG. 1 is a schematic XRD representation of the Ni/MnNbOx catalyst in example 1;
FIG. 2 is a TEM representation of the Ni/MnNbOx catalyst of example 2;
FIG. 3 is a gas chromatography analysis of n-hexanoic acid converted to 6-undecanone and n-undecane (results after 1h of reaction in example 1);
FIG. 4 is a mass spectrum of nonanone of the present invention;
FIG. 5 is a mass spectrum of nonane according to the invention;
FIG. 6 is a mass spectrum of undecanone of the present invention;
FIG. 7 is a mass spectrum of undecane of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The fermentation industry produces a large amount of waste organic acids, the main components of which are valeric acid, caproic acid and the like. In order to save cost and realize sustainable development, the invention utilizes the short-chain fatty acid to prepare long-chain alkane C 9 -C 12 The cost can be effectively reduced, and a green and economic development road is realized.
[ example 1 ]
5g of acetylDissolving nickel acetonate in 95ml of valeric acid, uniformly stirring to prepare a solution a, dissolving 20g of potassium permanganate in 80ml of water, uniformly stirring, and pouring into the solution a to prepare a solution b; dissolving 40g of niobium pentachloride in 60ml of water to prepare a mixture c, dropwise adding the solution c into the solution b at 0.1ml/min, keeping the temperature of the solution b at 0 ℃, stirring at 20 r/min, and reacting for 30min after dropwise addition to form a solution d; after the solution d is stable, raising the temperature to 120 ℃, reacting for 6 hours, cooling after the reaction is finished, filtering to obtain brown solid e, putting the brown solid e into a high-temperature atmosphere furnace, and introducing 1% of H 2 The temperature of the mixed gas/Ar is raised to 500 ℃ at the rate of 1 ℃/min, and the mixed gas/Ar is calcined for 3 hours at constant temperature; cooling and taking out the solid to obtain the Ni/MnNbOx catalyst (shown in figure 1).
[ example 2 ] A method for producing a polycarbonate
1g of nickel acetate is dissolved in 99ml of caproic acid and evenly stirred to prepare a solution a, and 10g of manganese nitrate is dissolved in 90ml of water and evenly stirred and then poured into the solution a to prepare a solution b. Dissolving 10g of niobium tartrate in 90ml of water to prepare a mixture c, dropwise adding the solution c into the solution b at a rate of 10ml/min, keeping the temperature of the solution b at 100 ℃, stirring at a speed of 300 r/min, and reacting for 4 hours after dropwise addition to form a solution d. After the solution d is stable, raising the temperature to 200 ℃, reacting for 36 hours, cooling after the reaction is finished, filtering to obtain brown solid e, putting the brown solid e into a high-temperature atmosphere furnace, and introducing 5% of H 2 /N 2 And (3) mixing the gas, heating up to 800 ℃ at the heating rate of 10 ℃/min, and calcining for 10 hours at constant temperature. Cooling and taking out the solid to obtain the Ni/MnNbOx catalyst (shown in figure 2).
[ example 3 ]
3g of nickel caprylate is dissolved in 97ml of heptanoic acid and evenly stirred to prepare a solution a, and 15g of manganese chloride is dissolved in 85ml of water and evenly stirred and then poured into the solution a to prepare a solution b. And (3) dissolving 20g of niobium oxalate in 80ml of water to prepare a mixture c, dropwise adding the solution c into the solution b at the speed of 5ml/min, keeping the temperature of the solution b at 50 ℃, stirring at the speed of 150 rpm, and reacting for 2 hours after dropwise addition to form a solution d. After the solution d is stable, raising the temperature to 150 ℃, reacting for 20 hours, cooling after the reaction is finished, filtering to obtain brown solid e, putting the brown solid e into a high-temperature atmosphere furnace, and introducing 10% of H 2 The mixed gas of the gas and the liquid,the heating rate is 5 ℃/min, the temperature is raised to 600 ℃, and the constant temperature calcination is carried out for 5 h. And cooling and taking out the solid to obtain the Ni/MnNbOx catalyst.
[ example 4 ]
2g of nickel benzoate is dissolved in 98ml of caprylic acid and evenly stirred to prepare a solution a, and 20g of manganese sulfate is dissolved in 80ml of water and evenly stirred and then poured into the solution a to prepare a solution b. And dissolving 20g of niobium citrate in 80ml of water to prepare a mixture c, dropwise adding the solution c into the solution b at a rate of 5ml/min, keeping the temperature of the solution b at 100 ℃, stirring at a speed of 200 rpm, and reacting for 1h after the dropwise addition is finished to form a solution d. After the solution d is stable, raising the temperature to 180 ℃, reacting for 15 hours, cooling after the reaction is finished, filtering to obtain brown solid e, putting the brown solid e into a high-temperature atmosphere furnace, and introducing 2% of H 2 Heating the mixed gas/Ar at the heating rate of 8 ℃/min to 700 ℃, and calcining at constant temperature for 8 h. And cooling and taking out the solid to obtain the Ni/MnNbOx catalyst.
[ example 5 ]
5g of nickel acetylacetonate is dissolved in 95ml of caproic acid and uniformly stirred to prepare a solution a, and 20g of manganese sulfate is dissolved in 80ml of water and uniformly stirred and then poured into the solution a to prepare a solution b. Dissolving 25g of niobium citrate in 75ml of water to prepare a mixture c, dropwise adding the solution c into the solution b at a rate of 5ml/min, keeping the temperature of the solution b at 100 ℃, stirring at a speed of 200 rpm, and reacting for 1h after the dropwise addition is completed to form a solution d. After the solution d is stable, raising the temperature to 180 ℃, reacting for 15 hours, cooling after the reaction is finished, filtering to obtain brown solid e, putting the brown solid e into a high-temperature atmosphere furnace, and introducing 2% of H 2 Heating the mixed gas/Ar at the heating rate of 8 ℃/min to 700 ℃, and calcining at constant temperature for 8 h. And cooling and taking out the solid to obtain the Ni/MnNbOx catalyst.
Ni/MnNbO x Catalysts were used for performance testing: weighing 0.2g of fatty acid, 0.1g of catalyst and 20ml of solvent cyclohexane, charging Ar gas into the reaction kettle for three times to remove redundant oxygen, then charging Ar gas to 0.1Mpa, raising the temperature to carry out reaction, wherein the reaction temperature is 200 ℃, and the reaction time is 3 hours, and the obtained results are shown in tables 1 and 2.
TABLE 1 Valeric acid in Ni/MnNbO x Reaction result under catalysis
Note: catalyst amount 0.1g, n-pentanoic acid 0.2g, solvent cyclohexane 20ml, temperature 200 ℃, time 3h, figure 4 and figure 5 are the mass spectrogram representation of product 5-nonanone and nonane.
TABLE 2 Hexanoic acid in Ni/MnNbO x Reaction result under catalysis
Note: the catalyst dosage is 0.1g, the hexanoic acid is 0.2g, the solvent is cyclohexane 20ml, the temperature is 200 ℃, and the time is 3 h. Fig. 3 is an example of gas chromatographic trace analysis of the catalytic reaction, and fig. 6 and 7 are mass spectrogram representations of 6-undecanone and undecane.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of a catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent is characterized by comprising the following steps:
A. preparation of the catalyst:
step 1) uniformly mixing a nickel salt compound and an organic reagent in a certain proportion, stirring at a certain temperature to prepare a solution a, and adding the solution a into a reaction kettle;
step 2) mixing manganese salt and water according to a certain proportion, stirring at a certain temperature to prepare a solution b, and then adding the solution b into a reaction kettle to be uniformly mixed with the solution a;
step 3) mixing a certain proportion of niobium salt and water, stirring at a certain temperature to prepare a solution c;
step 4), introducing the solution c into a reaction kettle at a certain temperature and flow rate, and stirring for reaction to obtain a mixture d;
step 5) after the mixture d is stable, continuously raising the temperature of the reaction kettle to accelerate the catalyst structure forming;
after the reaction in the step 6), putting the solid e obtained by filtering into a high-temperature atmosphere furnace to calcine to obtain a target catalyst;
wherein the proportion of the solution a in the step 1) is as follows: 1-5 parts of a nickel salt compound; 95-99 parts of an organic reagent;
the proportion of the solution b in the step 2) is as follows: 10-20 parts of manganese salt; 80-90 parts of an aqueous solvent;
the niobium salt in the step 3) comprises the following components in percentage by weight: 10-40 parts of niobium salt; 60-90 parts of a water solvent.
2. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents according to claim 1, wherein the nickel salt compound in step 1) is at least one of nickel acetylacetonate, nickel acetate, nickel octoate and nickel benzoate.
3. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents as claimed in claim 1, wherein the organic reagent in step 1) is at least one of valeric acid, caproic acid, enanthic acid and caprylic acid.
4. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents according to claim 1, wherein the manganese salt in step 2) is at least one of potassium permanganate, manganese nitrate, manganese acetate, manganese chloride and manganese sulfate.
5. The method for preparing a catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents as claimed in claim 1, wherein the niobium salt in step 3) is at least one of niobium pentachloride, niobium tartrate, niobium oxalate and niobium citrate.
6. The preparation method of the catalyst for converting short-chain fatty acid into the hydrocarbon cleaning agent according to claim 1, wherein the reaction temperature in the step 4) is controlled to be 0-100 ℃; the dropping speed is 0.1-10 ml/min; the stirring speed is 20-300 r/min; the reaction time is 30 min-4 h after the dripping is finished.
7. The preparation method of the catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent according to claim 1, wherein in the step 5), the temperature is 120-200 ℃ and the time is 6-36 h.
8. The preparation method of the catalyst for converting short-chain fatty acid into hydrocarbon cleaning agent according to claim 1, wherein the temperature rise rate of the treatment in the high-temperature atmosphere furnace in the step 6) is 1-10 ℃/min, the calcination temperature is 500-800 ℃, and the time is 3-10 h.
9. The method for preparing the catalyst for converting short-chain fatty acids into hydrocarbon cleaning agents as claimed in claim 1, wherein the gas used in the atmosphere furnace in the step 6) is H 2 /Ar，H 2 /N 2 ，H 2 Mixed gas of/He, H 2 The mass fraction of (A) is 1-10%.
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| CN102850157A (en) * | 2012-07-30 | 2013-01-02 | 华东理工大学 | Novel technique for preparing long-chain alkane efficiently through multifunctional catalyst in one-step method |
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| CN102850157A (en) * | 2012-07-30 | 2013-01-02 | 华东理工大学 | Novel technique for preparing long-chain alkane efficiently through multifunctional catalyst in one-step method |
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