CN108212179B - Preparation method of immobilized catalytic particle metal felt for producing biodiesel - Google Patents
Preparation method of immobilized catalytic particle metal felt for producing biodiesel Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 133
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 133
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 100
- 239000002245 particle Substances 0.000 title claims abstract description 66
- 239000003225 biodiesel Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910001026 inconel Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000835 fiber Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229910001111 Fine metal Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000002699 waste material Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B01J35/617—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an immobilized catalytic particle metal felt for producing biodiesel, and aims to solve the problems of poor stability, short service life and low catalytic efficiency of the existing catalyst. The invention comprises the following steps: ultrasonically cleaning a metal felt by absolute ethyl alcohol and water, and drying; ZrOCl2·8H2Preparing O and nitrate into a mixed aqueous solution, adding ammonia water while stirring until the pH value of the solution is 9-10 to obtain flocculent precipitate, standing at room temperature, performing suction filtration, and washing until no Cl exists‑Drying and grinding the obtained filter cake to obtain powder; adding the powder to H2SO4In solution, forming a mixture; and adding the dried metal felt into the mixture, soaking, drying, and roasting at 400-600 ℃ for 3-7 h under an inert atmosphere to obtain the metal felt. The supported catalytic particle metal felt prepared by the invention has high catalytic efficiency and mechanical strength, good stability, long service life, simple process and easy realization of industrialized production.
Description
Technical Field
The invention relates to the technical field of biodiesel catalysis, in particular to a preparation method of an immobilized catalytic particle metal felt for producing biodiesel.
Background
Biodiesel is a fatty acid alkyl monoester prepared by transesterification of triglycerides with short-chain alcohols. The biodiesel has the advantages of no toxicity, cleaner combustion process, good biodegradability and the like, and is a clean green fuel which can replace the common diesel. At present, a polymer membrane catalysis method is a better method in the preparation method of the biodiesel. As one of heterogeneous catalysis methods, the polymer membrane catalysis method overcomes more defects and has more advantages of the heterogeneous catalyst through membrane material design and catalyst loading capacity regulation, such as: the polymer film has high catalytic activity, good selectivity, less post-treatment of the product, no pollution to the environment and reusability. However, the service temperature of the polymer film is only 200-300 ℃, the polymer film is not suitable for some reactions with higher temperature requirements, and the polymer film is easy to dissolve or swell in a solvent or a reactant, so that the service life of the polymer film is shortened.
The metal felt is also called stainless steel sintered felt, and is made up by using fine metal fibre (with diameter being accurate to micrometer) through the processes of non-woven laying, overlapping and high-temp. sintering. The metal felt has the characteristics of high filtering precision and large pollutant carrying capacity due to the pore gradient formed by different pore diameter layers; the metal felt has a three-dimensional net-shaped and porous structure, so that the metal felt has the characteristics of high porosity, large specific surface area, uniform pore size distribution and the like, at present, more metal felts are used as a filter material, and patent document CN 103949168B discloses a porous metal film prepared by adopting a stainless steel fiber sintered felt and a preparation method thereof, wherein the porous metal film is a porous metal film prepared by adhering a layer of nickel-iron composite hydroxide film on a stainless steel fiber sintered felt substrate, and the water flux of the porous metal film can reach 4650 L.m− 2·min− 1·MPa− 1The separation precision can reach about 0.3 mu m, and the porous metal film is mainly used for solid-liquid separation. Patent document CN 103801156A reports a multilayer metal fiber sintered felt, which is composed of a coarse metal fiber filter layer and a fine metal fiber filter layer, two-dimensional woven metal fiber layers are respectively sintered on the outer sides of the coarse metal fiber filter layer and the fine metal fiber filter layer, and the multilayer metal fiber sintered felt is used for high temperature gas filtration, polymer melt filtration, viscose filtration and filtration in beer fermentation process.
For a long time, researchers have been working on the use of metal felts for filtration, but less in the field of catalysis.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the preparation method of the immobilized catalytic particle metal felt for producing the biodiesel, which has the advantages of simple process, low cost and environmental friendliness.
The metal felt has the excellent characteristics of metal corrosion resistance, high hardness and the like, and also has the characteristics of flexible folding and the like of textiles, the mesh structure woven by a non-woven method can effectively make up the defects of easy blockage, easy damage and easy folding of the metal mesh, and has the characteristics of high temperature resistance and high pressure resistance. Compared with a polymer film carrier, the metal felt has higher mechanical strength, chemical stability and thermal stability. The metal felt can be used in strong solvents such as strong acid, strong alkali and the like at the use temperature of 600-800 ℃.
The invention takes the metal felt as a carrier, and catalytic particles are immobilized on the surface and the inner part of the holes of the metal felt through high-temperature sintering to prepare the metal felt immobilized with the catalytic particles. The method has simple process, can use various catalytic particles for immobilization, and prepares the catalytic metal felt suitable for different reactions; the invention can use the metal felts with different apertures (millimeter, submillimeter, micron, submicron and nanometer) or the sintering process conditions of different solid-supported catalytic particles to regulate and control the specific surface area of the catalytic metal felt, thereby improving the conversion rate of the reaction and being suitable for other catalytic reactions such as esterification reaction or ester exchange reaction. The immobilized catalytic particle metal felt prepared by the invention is used for the production of biodiesel and related esterification reactions, and has good catalytic effect.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of an immobilized catalytic particle metal felt for producing biodiesel is designed, and is characterized by comprising the following steps:
(1) ultrasonically cleaning a metal felt by using absolute ethyl alcohol and then water, and then drying;
(2) according to ZrOCl2·8H2Nitrate =1:1 to 3:1, and the ZrOCl is added2·8H2Preparing a mixed aqueous solution from O and nitrate, and adding ammonia water while stirring until the pH value of the solution is 9-10 to obtain a mixture with flocculent precipitates;
(3) standing the mixture obtained in the step (2) at room temperature, then carrying out suction filtration and washing until no Cl exists-Finally, carrying out suction filtration to obtain a filter cake;
(4) drying and grinding the filter cake obtained in the step (3) to obtain powder;
(5) adding the powder obtained in the step (4) into H2SO4In solution, forming a mixture;
(6) and (3) adding the metal felt dried in the step (1) into the mixture obtained in the step (5), soaking for 12-36 h, drying, heating to 400-600 ℃ in an inert atmosphere, and roasting for 3-7 h to obtain the metal felt.
Preferably, in the step (1), the metal felt is made of stainless steel, inconel, or hastelloy.
Preferably, in the step (1), the metal felt has a porosity of 40-80% and a specific surface area of 100-5000 m2/g。
Preferably, in the step (1), the ultrasonic cleaning is carried out in absolute ethyl alcohol and water for 15 min.
Preferably, in the step (2), the nitrate is Zn (NO)3)2·6H2O、Cu(NO3)3·3H2O、Al(NO3)3· 9H2O and Fe (NO)3)3·9H2And O is one of the compounds.
Preferably, in the step (3), the standing time is controlled to be 20-30 h.
Preferably, in the step (4), the drying temperature is controlled to be 100-120 ℃, and the drying time is controlled to be 10-14 h.
Preferably, in the step (5), the H2SO4Concentration of the solutionIs 0.5mol/L, the H2SO4Volume of solution (mL): the mass (g) = 2-10 of the powder.
Preferably, in the step (6), the inert atmosphere is at least one selected from the group consisting of ammonia, nitrogen, hydrogen, and argon.
Preferably, in the step (6), the temperature rise rate is controlled to be 2-10 ℃/min.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the supported catalytic particle metal felt prepared by the invention has high catalytic activity, large specific surface area and high catalytic efficiency, and still has good catalytic performance when being repeatedly used.
2. The supported catalytic particle metal felt prepared by the invention has high mechanical strength, good stability and long service life, and solves the problems of poor stability, low service life, low mechanical strength and low catalytic efficiency of the existing catalyst.
3. The immobilized catalytic particle metal felt prepared by the invention can be used in high-temperature and high-corrosion environments, and solves the problems of low use temperature, easy corrosion and the like of the existing polymer film.
4. The process is simple and easy to control, and can realize continuous production; the manufacturing cost is low; the process is easy to be enlarged, and the industrialized production is realized.
5. The method has the advantages of less waste liquid generated in the process, environmental friendliness and little corrosion to equipment; the prepared supported catalytic particle metal felt is easy to recover and regenerate.
6. The invention can effectively control the structural size of the prepared metal felt hole; the specific surface area of the catalytic metal felt is regulated and controlled by using the metal felt (millimeter, submillimeter, micron, submicron or nanometer) with different pore diameters or sintering process conditions of different immobilized catalytic particles, so that the catalytic performance of the metal felt is improved, an important technical support is provided for continuous catalytic reaction of the metal felt, and the catalytic metal felt has important academic research value and wide industrial application prospect.
Drawings
FIG. 1 is an SEM image of a metal mat without immobilized catalytic particles prepared in example 1;
fig. 2 is an SEM image of the metal felt of the supported catalytic particles prepared in example 1.
Detailed Description
The following examples are intended to illustrate the present invention in detail and should not be construed as limiting the scope of the present invention in any way.
The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the raw materials are all conventional raw materials which are sold in the market if not specifically mentioned; the test methods involved are conventional methods unless otherwise specified.
Example 1: preparation method of immobilized catalytic particle metal felt for producing biodiesel
1) The porosity is 60 percent, and the specific surface area is 1000m2Soaking the stainless steel felt in absolute ethyl alcohol, ultrasonically cleaning for 15 min, ultrasonically cleaning with deionized water for 15 min, and drying for later use.
2) ZrOCl2·8H2O and Zn (NO)3)2·6H2Preparing an aqueous solution from O according to a molar ratio of 1:1, adjusting the pH of the aqueous solution to 9-10 with strong ammonia water under magnetic stirring to obtain a mixture with flocculent precipitates, aging the mixture at room temperature for 24 hours, performing suction filtration, and washing until no Cl exists-Finally, carrying out suction filtration to obtain a filter cake, placing the filter cake in a drying oven, drying for 12H at 110 ℃ to obtain a powder, taking out, cooling to room temperature, grinding the powder, and adding 5g of the powder into 30 mL of 0.5mol/L H after grinding2SO4In the solution, a mixed solution is formed.
3) Soaking 10g of the metal felt dried in the step 1) into the mixed solution obtained in the step 2), and drying after soaking for 24 hours. Placing the dried metal felt in a tubular furnace filled with hydrogen, heating to 500 ℃ at the heating rate of 2 ℃/min, and roasting for 5h to obtain the immobilized SO4 2-/ZrO2A metal felt of catalytic particles.
Example 2: preparation method of immobilized catalytic particle metal felt for producing biodiesel
Example 1 was varied as follows: said ZrOCl2·8H2O and Zn (NO)3)2·6H2The molar ratio of O is: 2:1, finally obtaining the immobilized SO4 2-/ZrO2-a metal felt of ZnO catalytic particles; the rest is the same as in example 1.
Example 3: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: with Fe (NO)3)3·9H2O substitution of Zn (NO) in example 13)2·6H2O, finally obtaining the immobilized SO4 2-/ZrO2-Fe2O3A metal felt of catalytic particles; the rest is the same as in example 1.
Example 4: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: with Cu (NO)3)3·3H2O substitution of Zn (NO) in example 13)2·6H2O, finally obtaining the immobilized SO4 2-/ZrO2-a metal felt of CuO catalytic particles; the rest is the same as in example 1.
Example 5: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: with Al (NO)3)3· 9H2O substitution of Zn (NO) in example 13)2·6H2O, finally obtaining the immobilized SO4 2-/ZrO2-a metal felt of CuO catalytic particles; the rest is the same as in example 1.
Example 6: catalytic Properties of Metal felts carrying different catalytic particles prepared in examples 1-5
10g of soybean oil and 6g of methanol were mixed, and 1.2g of the metal felt immobilized with catalytic particles prepared in examples 1 to 5 was added, stirred and heated to 65 ℃ and condensed and refluxed for 5 hours. After the reaction is finished, evaporating out unreacted methanol, separating out the metal felt and glycerin water which are immobilized with the catalytic particles to obtain a crude product biodiesel, and washing and distilling to obtain a finished product biodiesel, wherein the catalytic performance of the metal felt is shown in the following table 1 under the condition that different catalytic particles are immobilized.
TABLE 1 catalytic Properties of Metal felts loaded with different catalytic particles
| Catalytic particles | SO4 2-/ZrO2 | SO4 2-/ZrO2-ZnO | SO4 2-/ZrO2-Fe2O3 | SO4 2-/ZrO2-CuO | SO4 2-/ZrO2-ZnO |
| Conversion of fatty acid methyl ester (%) | 92.36 | 93.28 | 94.75 | 93.90 | 95.13 |
Example 7: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: the stainless steel metal felt of example 1 was replaced with a inconel metal felt; the rest is the same as in example 1.
Example 8: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: replacing the stainless steel metal felt of example 1 with a nickel-base halodurite metal felt; the rest is the same as in example 1.
Example 9: catalytic performance of the catalytic particle-supported metal mats prepared in examples 1, 7 and 8
After mixing 5g of hogwash oil and 15g of methanol, 1.2g of the catalyst particle-immobilized metal mats prepared in examples 1, 7 and 8 were added, stirred and heated to 70 ℃ and then condensed and refluxed for 5 hours. After the reaction is finished, evaporating out unreacted methanol, separating out the metal felt of the immobilized catalytic particles and glycerin water to obtain a crude product biodiesel, and washing and distilling to obtain a finished product biodiesel, wherein the catalytic performance of the metal felt of the immobilized catalytic particles prepared by different metal felt types is shown in Table 2 below.
TABLE 2 Effect of different metal felt types on catalytic esterification Performance
| Kind of metal felt | Stainless steel | Chromium nickel iron alloy | Hydrochloric acid resistant nickel base alloy |
| Conversion of fatty acid methyl ester (%) | 92.36 | 95.86 | 96.14 |
Example 10: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: the specific surface area of the stainless steel metal felt is 100 m2(ii)/g; the rest is the same as in example 1.
Example 11: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: the specific surface area of the stainless steel metal felt is 500 m2(ii)/g; the rest is the same as in example 1.
Example 12: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: the specific surface area of the stainless steel metal felt is 2000 m2(ii)/g; the rest is the same as in example 1.
Example 13: catalytic performance of the catalytic particle-loaded metal mats prepared in examples 10, 1, 11, 12
5g of the acidified oil and 10g of methanol were mixed, and then 1.2g of the catalyst particle-supported metal felt prepared in examples 1, 10, 11 and 12 was added thereto, and the mixture was stirred and heated to 60 ℃ and then condensed and refluxed for 5 hours. After the reaction is finished, evaporating out unreacted methanol, separating out the metal felt carrying the catalytic particles and glycerin water to obtain a crude product biodiesel, and washing and distilling to obtain a finished product biodiesel, wherein the influence of different specific surface areas of the stainless steel metal felt on the catalytic performance of the biodiesel is shown in Table 3 below.
6g of acetic acid and 9.6g of ethanol are used for replacing 5g of acidified oil and 10g of methanol in the step, the mass of the added metal felt is 1.44g, the rest steps are the same as the steps for preparing the biodiesel, an ethyl acetate product is obtained, and the influence of different specific surface areas of the stainless steel metal felt on the catalytic performance of the ethyl acetate is shown in the following table 3.
TABLE 3 influence of different specific surface areas of stainless steel metal felts on catalytic performance
| Specific surface area (m) of metal felt2/g） | Ethyl acetate conversion (%) | Conversion of fatty acid methyl ester (%) |
| 100 | 25.69 | 40.35 |
| 500 | 30.30 | 52.68 |
| 1000 | 71.45 | 92.36 |
| 2000 | 73.94 | 95.45 |
Example 14: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: with Cu (NO)3)2·6H2O substitution of Zn (NO) in example 13)2·6H2O, obtaining the immobilized SO4 2-/ZrO2-a metal felt of catalytic particles of CuO; the rest is the same as in example 1.
Example 15: example 14 preparation of catalytic performance of Supported catalytic particle Metal felt with different number of uses
5g of lard and 20g of methanol were mixed, and 1.2g of the catalytic particle-immobilized metal felt prepared in example 14 was added, stirred and heated to 60 ℃ and then condensed and refluxed for 6 hours. After the reaction is finished, evaporating out unreacted methanol, separating out the metal felt and the glycerin water which are used for immobilizing the catalytic particles to obtain a crude product of the biodiesel, and washing and distilling to obtain a finished product of the biodiesel. The catalytic performance of each of the supported catalytic particle metal mats prepared in example 14 was used 5 times according to the above procedure, and the catalytic performance of each of the supported catalytic particle metal mats was shown in table 4 below.
6g of acetic acid and 14.8g of butanol are used for replacing lard and methanol in the steps, the mass of the added metal felt is 1.44g, the rest steps are the same as the steps for preparing the biodiesel, a butyl acetate product is obtained, the immobilized catalytic particle metal felt is used for 5 times, and the catalytic performance of each immobilized catalytic particle metal felt is shown in the following table 4.
TABLE 4 catalytic performance of the use times of the catalytic particle-immobilized metal felt
| Number of times of use | Conversion of butyl acetate (%) | Conversion of fatty acid methyl ester (%) |
| 1 | 76.88 | 94.86 |
| 2 | 76.63 | 94.46 |
| 3 | 76.52 | 94.28 |
| 4 | 76.43 | 94.15 |
| 5 | 76.32 | 94.20 |
Example 16: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: the roasting time is 4 hours; the rest is the same as in example 1.
Example 17: preparation method of immobilized catalytic particle metal felt for producing biodiesel
The difference from example 1 is: the roasting time is 6 hours; the rest is the same as in example 1.
Example 18: catalytic performance of supported catalytic particle metal felt prepared by different roasting time
The catalytic performance of the supported catalytic particle metal mats prepared in examples 16, 1, 17 is shown in table 5 below.
TABLE 5 catalytic Properties of Metal felts at different calcination times
| Calcination time (h) | 4 | 5 | 6 |
| Conversion of fatty acid methyl ester (%) | 92.36 | 95.48 | 96.82 |
Example 19: SEM image of supported catalytic particle metal felt prepared in example 1
SEM test was conducted on the metal mat in example 1 without supporting the catalytic particles, and the results are shown in FIG. 1. SEM test of the metal felt after the catalytic particles are immobilized in the metal felt in the example 1 is shown in the attached figure 2.
Fig. 1 and 2 show that the metal felt for supporting the catalytic particles is composed of metal fibers and catalytic particles filled on the surface, pores and gaps of the metal fibers.
While the present invention has been described in detail with reference to the drawings and the embodiments, those skilled in the art will understand that various specific parameters in the above embodiments can be changed without departing from the spirit of the present invention, and a plurality of specific embodiments are formed, which are common variation ranges of the present invention, and will not be described in detail herein.
Claims (6)
1. A preparation method of an immobilized catalytic particle metal felt for producing biodiesel is characterized by comprising the following steps:
(1) ultrasonically cleaning a metal felt by using absolute ethyl alcohol and then water, and then drying; the porosity of the metal felt is 40-80%, and the specific surface area is 100-5000 m2(ii)/g; the metal felt is made of stainless steel, inconel or nickel-base alloy;
(2) according to ZrOCl2·8H2Nitrate =1:1 to 3:1, and the ZrOCl is added2·8H2Preparing a mixed aqueous solution from O and nitrate, and adding ammonia water while stirring until the pH value of the solution is 9-10 to obtain a mixture with flocculent precipitates; the nitrate is Zn (NO)3)2·6H2O、Cu(NO3)3·3H2O、Al(NO3)3· 9H2O and Fe (NO)3)3·9H2One of O;
(3) standing the mixture obtained in the step (2) at room temperature, and then performing suction filtration,Washing to Cl free-Finally, carrying out suction filtration to obtain a filter cake;
(4) drying and grinding the filter cake obtained in the step (3) to obtain powder;
(5) adding the powder obtained in the step (4) into H2SO4In solution, forming a mixture;
(6) and (3) adding the metal felt dried in the step (1) into the mixture obtained in the step (5), soaking for 12-36 h, drying, heating to 400-600 ℃ at the speed of 2-10 ℃/min in an inert atmosphere, and roasting for 3-7 h to obtain the metal felt.
2. The method for preparing the supported catalytic particle metal felt for biodiesel production according to claim 1, wherein in the step (1), the ultrasonic cleaning is carried out for 15 min in both absolute ethanol and water.
3. The preparation method of the supported catalytic particle metal felt for biodiesel production according to claim 1, wherein in the step (3), the standing time is controlled to be 20-30 h.
4. The preparation method of the supported catalytic particle metal felt for producing biodiesel according to claim 1, wherein in the step (4), the drying temperature is controlled to be 100-120 ℃ and the drying time is controlled to be 10-14 h.
5. The process for preparing the metal felt according to claim 1, wherein in the step (5), the H is2SO4The concentration of the solution is 0.5mol/L, the H2SO4Volume mL of solution: the mass g = 2-10 of the powder.
6. The method for preparing the metal felt with the immobilized catalytic particles for the production of biodiesel according to claim 1, wherein in the step (6), the inert atmosphere is at least one selected from nitrogen and argon.
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