CN107488519B - Method for preparing biodiesel by catalyzing restaurant waste oil through magnetic carbon loaded acid-base - Google Patents
Method for preparing biodiesel by catalyzing restaurant waste oil through magnetic carbon loaded acid-base Download PDFInfo
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- CN107488519B CN107488519B CN201710605289.3A CN201710605289A CN107488519B CN 107488519 B CN107488519 B CN 107488519B CN 201710605289 A CN201710605289 A CN 201710605289A CN 107488519 B CN107488519 B CN 107488519B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- 239000003225 biodiesel Substances 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000008162 cooking oil Substances 0.000 claims abstract description 32
- 239000003921 oil Substances 0.000 claims abstract description 32
- 239000002585 base Substances 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000032050 esterification Effects 0.000 claims abstract description 4
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 4
- 239000011973 solid acid Substances 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 150000002148 esters Chemical group 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims 2
- 238000005815 base catalysis Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000004519 grease Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract 3
- 239000011949 solid catalyst Substances 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 24
- 150000003839 salts Chemical class 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021191 food habits Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000010499 rapseed oil Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses a method for preparing biodiesel by catalyzing restaurant waste oil with acid and alkali loaded by magnetic carbon, belonging to the field of waste recycling. The method takes magnetic carbon as a carrier and loads acid (H)2SO4) And alkali (KOH) is used for preparing the biodiesel by two-step catalysis of the waste cooking oil. The waste cooking oil is purified and then enters an acid catalytic esterification reactor, and a proper amount of magnetic carbon/H is added2SO4The solid catalyst is reacted at the optimum temperature by introducing methanol vapor. After the reaction is finished, the solution is kept stand to separate the glycerol, the methanol and the grease. The grease enters an alkali-catalyzed transesterification reactor, and reacts at the optimal temperature by adding a proper amount of magnetic carbon/KOH solid catalyst and methanol. And standing the solution after the reaction is finished, and separating the solution to obtain the biodiesel. The magnetic carbon catalyst in the acid-base reactor can be separated, recovered and regenerated for reuse through strong magnet. Compared with the traditional process, the method has the advantages of small waste liquid generation amount, easy catalyst recovery, low cost and the like.
Description
Technical Field
The invention relates to the technical field of waste recycling, in particular to a method for preparing biodiesel by catalyzing restaurant waste oil with acid and alkali through magnetic carbon loading.
Background
With the rapid development of social economy, the energy consumption is increased rapidly, and the shortage of energy resources becomes an important factor restricting the development of the social economy in China. The economic impact of international oil price fluctuation on China is larger and larger, increasingly deficient oil resources seriously threaten the national energy safety, and the development of renewable alternative energy sources to get rid of the dependence on fossil energy sources becomes an important direction of energy research. Compared with the conventional fuel, the biodiesel serving as a green renewable biological energy source has the characteristics of no sulfur, no toxicity and easy biodegradation, and reduces the emission of toxic gases such as sulfur dioxide, particulate matters and the like in the combustion process. Qualified biodiesel is produced by using animal and vegetable oil as a raw material, but the source of the animal and vegetable oil is limited, so that the application of the biodiesel is hindered, and the key point of the industrialization of the biodiesel is to find cheap oil resources which can be collected in a large scale. The food habits in China result in the generation of a large amount of waste cooking oil, the generation amount of the waste cooking oil in China is about 1000 ten thousand tons every year, and if the waste cooking oil is not managed and recycled, the waste cooking oil can be refined into illegal cooking oil by lawbreakers and can be returned to dining tables of people. Therefore, the waste cooking oil is taken as a raw material for preparing the biodiesel, so that the high added value utilization of the waste cooking oil is realized, and the preparation cost of the biodiesel is further reduced.
A liquid acid-alkali two-step catalysis method commonly adopted in biodiesel production in China firstly uses concentrated sulfuric acid to catalyze free fatty acid in grease to generate fatty acid methyl ester (biodiesel), then uses alkali to catalyze triglyceride to generate fatty acid methyl ester, and a catalyst is dissolved in a reaction system and needs neutralization, water washing and drying after reaction, thereby causing excessive wastewater discharge and energy consumption. The magnetic solid acid-base catalyst is adopted, the catalyst is not dissolved in a reaction system, the catalyst can be separated by an external magnetic field after reaction, the magnetic solid acid-base catalyst is used for replacing a homogeneous acid-base catalyst, the wastewater discharge and the energy consumption in the preparation process of the biodiesel are greatly reduced, and the production cost is correspondingly reduced.
The invention discloses a method for preparing biodiesel by catalyzing waste cooking oil with acid and alkali loaded with magnetic carbon. In addition, the biodiesel is produced by catalyzing waste cooking oil with magnetic solid acid and alkali in two steps, so that the problems of large waste water generation amount and difficult catalyst recovery in the traditional two-step method are solved. Meanwhile, high added value utilization of waste cooking oil is realized, and the preparation cost of the biodiesel is effectively reduced.
Disclosure of Invention
The invention solves the problems of difficult catalyst recovery, large waste liquid yield and the like in the traditional homogeneous catalysis biodiesel preparation process, realizes high value-added utilization of waste cooking oil, and effectively reduces the preparation cost of biodiesel.
The technical scheme of the invention is to provide a method for preparing biodiesel by catalyzing restaurant waste oil with acid and alkali loaded with magnetic carbon, which is characterized in that:
the method comprises the steps of preparing magnetic carbon, preparing magnetic solid acid, preparing magnetic solid alkali, pre-esterifying the magnetic solid acid and performing ester exchange reaction on the magnetic solid alkali;
(1) preparing magnetic carbon: dissolving a certain amount of ferric salt in deionized water, and preparing a solution with the concentration of the ferric salt being 10-25%; crushing sawdust and putting the crushed sawdust into a trivalent ferric salt solution; the mass ratio of the trivalent ferric salt to the wood dust is 4: 1-10: 1; soaking the wood chips in a ferric salt solution for 30-120 min, then carrying out vacuum filtration, and drying a filter cake at 60 ℃ to constant weight; placing the dried filter cake into an alumina crucible and placing the alumina crucible into a high-temperature tube furnace in a nitrogen atmosphere2Raising the temperature to 550-900 ℃ at the speed of 2-20 ℃/min under protection, and preserving the temperature for 30-120 min to prepare rough magnetic carbon; washing the rough magnetic carbon by using deionized water to remove impurities, wherein the solid-liquid ratio is 1: 10-1: 200; washing the obtained magnetic carbon, and drying at 105 ℃ to obtain a finished magnetic carbon product;
(2) preparation of magnetic solid acid: mixing magnetic carbon with concentrated H2SO4Preparing the solution into a suspension according to the solid-liquid ratio of 1: 10-1: 50, sulfonating at 100-120 ℃ for 1-24 h, cooling to room temperature, adding distilled water in batches, soaking, washing and filteringUntil the filtrate is neutral; drying the obtained filter cake at 80-120 ℃ to obtain a finished product of the magnetic carbon-based solid acid catalyst;
(3) preparation of magnetic solid base: preparing magnetic carbon and a KOH solution into a suspension according to the solid-liquid ratio of 1: 3-1: 10, wherein the concentration of the KOH solution is 1.5-2 mol/L, and the mass ratio of the magnetic carbon to the KOH is 1: 3-1: 10; dipping the obtained suspension for 1-10 h under the condition of magnetic stirring, and then carrying out vacuum filtration; drying the obtained filter cake at 50-120 ℃ to obtain a finished product of the magnetic carbon-based solid base catalyst;
(4) pre-esterification reaction of magnetic solid acid: taking a certain amount of the waste cooking oil after impurity removal, and adding a magnetic solid acid catalyst into the waste cooking oil according to 1-10% of the weight of the oil; heating the reactor to 90-150 ℃, and introducing methanol vapor; the introduction amount of the methanol vapor per hour is 15 to 25 percent of the weight of the waste cooking oil; after the pre-esterification reaction is carried out for 1-10 hours or when the acid value of the waste cooking oil is reduced to below 2 mg.KOH/g, the magnetic solid acid is taken out through an external magnetic field to obtain fatty acid methyl ester;
(5) transesterification of magnetic solid base: adding the fatty acid methyl ester obtained in the step (4) and methanol into a reactor according to the molar ratio of alcohol to oil of 5: 1-15: 1, and adding magnetic solid alkali into the reactor according to 1% -10% of the weight of the oil; heating the reactor to 50-100 ℃, reacting for 1-5 h, taking out the magnetic solid base catalyst through an external magnetic field, standing and layering, wherein the middle layer is the crude biodiesel.
The raw materials for preparing the magnetic carbon can also use biomass such as mushroom bran, palm shells, straws and the like besides wood chips; the raw materials for preparing the magnetic carbon are crushed and pass through a 50-300-mesh sieve before use.
The ferric iron solution used for soaking the wood chips and other biomasses can be common soluble ferric iron salt solutions such as ferric chloride and ferric nitrate.
In the pre-esterification reaction process of the magnetic solid acid, when the esterification rate is lower than 75%, replacing the magnetic carbon-based solid acid catalyst; the magnetic carbon-based solid acid catalyst is heated, soaked in a solvent and then regenerated by being magnetized and acid-attached again.
In the ester exchange reaction process of the magnetic solid base, when the ester exchange rate is lower than 75%, replacing the magnetic carbon-based solid base catalyst; the magnetic carbon-based solid acid catalyst is heated, soaked in a solvent and then regenerated by being magnetized and alkali attached again.
After the ester exchange reaction of the magnetic solid alkali is finished, the upper layer methanol solution obtained by standing and layering the solution in the reactor can be used for producing methanol vapor and is used in the ester exchange reaction process of the magnetic solid alkali.
The raw materials for preparing the biodiesel can be used for aquatic plant oil such as soybean oil, rape oil, palm oil, wild oil plants, engineering microalgae and the like, animal oil and the like besides waste cooking oil.
The crude biodiesel produced by the method can be used for refining refined biodiesel or directly mixed with common diesel oil according to specific conditions to be used as oil for diesel oil stoves.
The technical scheme of the invention has the following beneficial effects:
(1) the method adopts magnetic carbon loaded acid-base two-step catalysis waste cooking oil to prepare biodiesel, and solves the problem that the traditional homogeneous catalyst is difficult to recover;
(2) the invention reduces the production of waste liquid in the process of preparing the biodiesel and the resource utilization threshold of the biodiesel.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
A method for preparing biodiesel by catalyzing restaurant waste oil with acid and alkali loaded by magnetic carbon is characterized by comprising the following steps: the method comprises the steps of preparing magnetic carbon, preparing magnetic solid acid, preparing magnetic solid alkali, pre-esterifying the magnetic solid acid and performing ester exchange reaction on the magnetic solid alkali;
(1) preparing magnetic carbon: dissolving a certain amount of ferric salt in deionized water, and preparing a solution with the concentration of the ferric salt being 10-25%; crushing sawdust and putting the crushed sawdust into a trivalent ferric salt solution; the mass ratio of the trivalent ferric salt to the wood dust is 4: 1-10: 1; soaking the wood chips in a ferric salt solution for 30-120 min, then carrying out vacuum filtration, and drying a filter cake at 60 ℃ to constant weight; putting the dried filter cake intoPlacing the alumina crucible in a high-temperature tube furnace in a reaction vessel containing N2Raising the temperature to 550-900 ℃ at the speed of 2-20 ℃/min under protection, and preserving the temperature for 30-120 min to prepare rough magnetic carbon; washing the rough magnetic carbon by using deionized water to remove impurities, wherein the solid-liquid ratio is 1: 10-1: 200; washing the obtained magnetic carbon, and drying at 105 ℃ to obtain a finished magnetic carbon product;
(2) preparation of magnetic solid acid: mixing magnetic carbon with concentrated H2SO4Preparing a suspension from the solution according to a solid-liquid ratio of 1: 10-1: 50, sulfonating at 100-120 ℃ for 1-24 h, cooling to room temperature, adding distilled water in batches, soaking, washing and filtering until the filtrate is neutral; drying the obtained filter cake at 80-120 ℃ to obtain a finished product of the magnetic carbon-based solid acid catalyst;
(3) preparation of magnetic solid base: preparing magnetic carbon and a KOH solution into a suspension according to the solid-liquid ratio of 1: 3-1: 10, wherein the concentration of the KOH solution is 1.5-2 mol/L, and the mass ratio of the magnetic carbon to the KOH is 1: 3-1: 10; dipping the obtained suspension for 1-10 h under the condition of magnetic stirring, and then carrying out vacuum filtration; drying the obtained filter cake at 50-120 ℃ to obtain a finished product of the magnetic carbon-based solid base catalyst;
(4) pre-esterification reaction of magnetic solid acid: taking a certain amount of the waste cooking oil after impurity removal, and adding a magnetic solid acid catalyst into the waste cooking oil according to 1-10% of the weight of the oil; heating the reactor to 90-150 ℃, and introducing methanol vapor; the introduction amount of the methanol vapor per hour is 15 to 25 percent of the weight of the waste cooking oil; after the pre-esterification reaction is carried out for 1-10 hours or when the acid value of the waste cooking oil is reduced to below 2 mg.KOH/g, the magnetic solid acid is taken out through an external magnetic field to obtain fatty acid methyl ester;
(5) transesterification of magnetic solid base: adding the fatty acid methyl ester obtained in the step (4) and methanol into a reactor according to the molar ratio of alcohol to oil of 5: 1-15: 1, and adding magnetic solid alkali into the reactor according to 1% -10% of the weight of the oil; heating the reactor to 50-100 ℃, reacting for 1-5 h, taking out the magnetic solid base catalyst through an external magnetic field, standing and layering, wherein the middle layer is the crude biodiesel.
Example 1
The crude biodiesel is prepared by the method. The method specifically comprises the following steps:
(1) preparing magnetic carbon: pulverizing sawdust powder, sieving with 200 mesh sieve, and mixing with 20% Fe (NO)3)3Soaking the mixture and the solution thereof in a mass ratio of 1:4 for 60min under the action of magnetic stirring. After the impregnation is finished, carrying out solid-liquid separation by a vacuum suction filter, putting the filter cake into an evaporating dish, putting the evaporating dish into an oven, and drying the evaporating dish at the temperature of 60 ℃ until the weight is constant. Placing the filter cake in a crucible and placing in a microwave pyrolysis oven under N2Heating to 700 deg.C at a rate of 5 deg.C/min under protection, and maintaining for 60min to obtain magnetic carbon; washing the product with deionized water to remove impurities;
(2) preparation of magnetic solid acid: mixing magnetic carbon and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:25, sulfonating at 120 ℃ for 12h, cooling to room temperature, adding the mixture into distilled water for dilution and filtration, repeatedly washing until the filtrate is neutral, filtering, and drying at 90 ℃;
(3) preparation of magnetic solid base: adding magnetic carbon into 2mol/L KOH solution, enabling the mass ratio of the magnetic carbon in the system to the KOH to be 1:4, soaking for 3 hours under the action of magnetic stirring, then carrying out vacuum filtration, and drying a filter cake at 60 ℃ to constant weight;
(4) preparation of biodiesel: taking a certain amount of the impurity-removed waste cooking oil, adding a magnetic solid acid catalyst in an amount which is 1 percent of the weight of the oil into a reactor, heating the waste cooking oil to 115 ℃, introducing methanol steam, wherein the introduction amount of the methanol steam is 15 percent of the weight of the oil per hour, and after the catalytic reaction for 4 hours, taking out the magnetic solid acid through an external magnetic field to obtain fatty acid methyl ester; taking out the obtained fatty acid methyl ester, adding the obtained fatty acid methyl ester and methanol into a reactor according to the molar ratio of alcohol to oil of 9:1, simultaneously adding 4% of magnetic solid base of the oil weight into the reactor, heating to 63 ℃, reacting for 1.5h, taking out the magnetic solid base catalyst through an external magnetic field, standing for layering, and obtaining the middle layer which is the crude biodiesel. Sampling, and detecting the ester exchange rate of the biodiesel prepared from the waste cooking oil by using gas chromatography to be 95.4%.
Example 2
(1) Preparing magnetic carbon: pulverizing sawdust powder, sieving with 100 mesh sieve, and mixing with 15% Fe (NO)3)3According to the mass ratio of 1:8, the solution is stirred under the action of magnetic forceSoaking for 30 min. After the impregnation is finished, carrying out solid-liquid separation by a vacuum suction filter, putting the filter cake into an evaporating dish, putting the evaporating dish into an oven, and drying the evaporating dish at the temperature of 60 ℃ until the weight is constant. Placing the filter cake in a crucible and placing in a microwave pyrolysis oven under N2Heating to 550 ℃ at the speed of 5 ℃/min under protection, and preserving heat for 30min to obtain magnetic carbon; washing the product with deionized water to remove impurities;
(2) preparation of magnetic solid acid: mixing magnetic carbon and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:15, sulfonating at 120 ℃ for 10h, cooling to room temperature, adding the mixture into distilled water for dilution and filtration, repeatedly washing until the filtrate is neutral, filtering, and drying at 90 ℃;
(3) preparation of magnetic solid base: adding magnetic carbon into a 1.5mol/L KOH solution to ensure that the mass ratio of the magnetic carbon in the system to the KOH is 1:3, soaking for 2 hours under the action of magnetic stirring, carrying out vacuum filtration, and drying a filter cake at 60 ℃ to constant weight;
(4) preparation of biodiesel: taking a certain amount of the impurity-removed waste cooking oil, adding a magnetic solid acid catalyst in an amount which is 2 percent of the weight of the oil into a reactor, heating the waste cooking oil to 125 ℃, introducing methanol steam, wherein the introduction amount of the methanol steam is 20 percent of the weight of the oil per hour, and after 2 hours of catalytic reaction, taking out the magnetic solid acid through an external magnetic field to obtain fatty acid methyl ester. Taking out the obtained fatty acid methyl ester, adding the obtained fatty acid methyl ester and methanol into a reaction system according to the molar ratio of alcohol to oil of 7:1, simultaneously adding 4% of magnetic solid base of the oil weight into the reaction system, heating to 58 ℃, reacting for 2 hours, taking out the magnetic solid base catalyst through an external magnetic field, standing and layering, and obtaining the crude biodiesel as an intermediate layer. Sampling, and detecting the ester exchange rate of the biodiesel prepared from the waste cooking oil by using gas chromatography to be 65.3 percent.
The product takes magnetic carbon loaded acid-base as a catalyst for esterification and ester exchange reaction, and the biodiesel is prepared by two-step catalysis, so that the defects of high requirement on the corrosion resistance of equipment, difficult recovery of the catalyst, large waste liquid production amount and the like in the traditional biodiesel production process are effectively overcome, and the biodiesel has the advantages of high biodiesel yield, low operation cost, simple reaction device, small environmental pollution, wide product application and the like, can be used in places such as restaurants, residential areas and the like, and realizes the resource utilization of waste cooking oil with low grease yield and poor oil quality. The design idea of the method is in accordance with the national concepts of energy conservation, emission reduction and sustainable development, and the method has wide application prospect.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (2)
1. A method for preparing biodiesel by catalyzing restaurant waste oil with acid and alkali loaded by magnetic carbon is characterized by comprising the following steps: the method comprises the steps of preparing magnetic carbon, preparing magnetic solid acid, preparing magnetic solid alkali, pre-esterifying the magnetic solid acid and performing ester exchange reaction on the magnetic solid alkali;
(1) preparing magnetic carbon: pulverizing sawdust powder, sieving with 200 mesh sieve, and mixing with 20% Fe (NO)3)3Soaking the mixture and the solution thereof in a mass ratio of 1:4 for 60min under the action of magnetic stirring; after the impregnation is finished, performing solid-liquid separation by a vacuum suction filter, putting a filter cake into an evaporating dish, putting the evaporating dish into an oven, and drying the evaporating dish at the temperature of 60 ℃ until the weight is constant; placing the filter cake in a crucible and placing in a microwave pyrolysis oven under N2Heating to 700 deg.C at a rate of 5 deg.C/min under protection, and maintaining for 60min to obtain magnetic carbon; washing the product with deionized water to remove impurities;
(2) preparation of magnetic solid acid: mixing magnetic carbon and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:25, sulfonating at 120 ℃ for 12h, cooling to room temperature, adding the mixture into distilled water for dilution and filtration, repeatedly washing until the filtrate is neutral, filtering, and drying at 90 ℃;
(3) preparation of magnetic solid base: adding magnetic carbon into 2mol/L KOH solution, enabling the mass ratio of the magnetic carbon in the system to the KOH to be 1:4, soaking for 3 hours under the action of magnetic stirring, then carrying out vacuum filtration, and drying a filter cake at 60 ℃ to constant weight;
(4) pre-esterification reaction of magnetic solid acid: taking a certain amount of the impurity-removed waste cooking oil, adding a magnetic solid acid catalyst in an amount which is 1 percent of the weight of the oil into a reactor, heating the waste cooking oil to 115 ℃, introducing methanol steam, wherein the introduction amount of the methanol steam is 15 percent of the weight of the oil per hour, and after the catalytic reaction for 4 hours, taking out the magnetic solid acid through an external magnetic field to obtain fatty acid methyl ester;
in the pre-esterification reaction process of the magnetic solid acid, when the esterification rate is lower than 75%, replacing the magnetic carbon-based solid acid catalyst; heating the invalid magnetic carbon-based solid acid catalyst, soaking the invalid magnetic carbon-based solid acid catalyst in a solvent, and then re-magnetizing and regenerating the invalid magnetic carbon-based solid acid catalyst by acid adsorption;
(5) transesterification of magnetic solid base: taking out the fatty acid methyl ester obtained in the step (4), adding the fatty acid methyl ester and methanol into a reactor according to the molar ratio of alcohol to oil of 9:1, simultaneously adding 4% of magnetic solid base of the oil weight into the reactor, heating to 63 ℃, reacting for 1.5h, taking out the magnetic solid base catalyst through an external magnetic field, standing and layering, wherein the middle layer is the crude biodiesel;
in the ester exchange reaction process of the magnetic solid base, when the ester exchange rate is lower than 75%, replacing the magnetic carbon-based solid base catalyst; heating the invalid magnetic carbon-based solid acid catalyst, soaking the invalid magnetic carbon-based solid acid catalyst in a solvent, and then re-magnetizing the invalid magnetic carbon-based solid acid catalyst and regenerating the invalid magnetic carbon-based solid acid catalyst by alkali;
after the ester exchange reaction of the magnetic solid alkali is finished, the upper layer methanol solution obtained by standing and layering the solution in the reactor is used for generating methanol vapor and is used in the pre-esterification reaction process of the magnetic solid acid.
2. The method for preparing biodiesel by utilizing magnetic carbon-loaded acid-base catalysis restaurant waste oil according to claim 1, which is characterized in that: the produced crude biodiesel is used for refining and refining biodiesel or is directly mixed with common diesel according to specific conditions to be used as oil for a diesel stove.
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| CN104014342A (en) * | 2014-06-23 | 2014-09-03 | 山东大学 | Dual-function magnetic nano solid-base catalyst and preparation method and application thereof |
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| CN104014342A (en) * | 2014-06-23 | 2014-09-03 | 山东大学 | Dual-function magnetic nano solid-base catalyst and preparation method and application thereof |
| CN105536700A (en) * | 2015-12-22 | 2016-05-04 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing magnetic biochar from straw |
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