CN107488519A - A kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal - Google Patents
A kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal Download PDFInfo
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- CN107488519A CN107488519A CN201710605289.3A CN201710605289A CN107488519A CN 107488519 A CN107488519 A CN 107488519A CN 201710605289 A CN201710605289 A CN 201710605289A CN 107488519 A CN107488519 A CN 107488519A
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- magnetic
- acid
- charcoal
- solid
- base
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- 239000003610 charcoal Substances 0.000 title claims abstract description 68
- 239000003225 biodiesel Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005815 base catalysis Methods 0.000 title claims abstract description 16
- 239000000446 fuel Substances 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002699 waste material Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000008162 cooking oil Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000005886 esterification reaction Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000004519 grease Substances 0.000 claims abstract description 6
- 230000008929 regeneration Effects 0.000 claims abstract description 3
- 238000011069 regeneration method Methods 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 34
- 239000011973 solid acid Substances 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 21
- 235000019198 oils Nutrition 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000002023 wood Substances 0.000 claims description 16
- 230000032050 esterification Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000002148 esters Chemical group 0.000 claims description 13
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 241000196324 Embryophyta Species 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 238000006277 sulfonation reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 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 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 235000001674 Agaricus brunnescens Nutrition 0.000 claims description 2
- 235000019737 Animal fat Nutrition 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000000828 canola oil Substances 0.000 claims description 2
- 235000019519 canola oil Nutrition 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000010742 number 1 fuel oil Substances 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 239000010902 straw Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract 2
- 239000011949 solid catalyst Substances 0.000 abstract 2
- 238000010669 acid-base reaction Methods 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 abstract 1
- 238000003306 harvesting Methods 0.000 abstract 1
- 238000005809 transesterification reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- -1 efficiently solve Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
Classifications
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal, belong to changing waste into resources field.This method loads acid (H using magnetic charcoal as carrier2SO4) and alkali (KOH) be used for waste cooking oil two-step catalysis biodiesel afterwards.Waste cooking oil enters acid-catalyzed esterification reaction device after removal of impurities, by adding appropriate magnetic charcoal/H2SO4Solid catalyst and methanol steam is passed through, is reacted under optimum temperature.Reaction terminates rear solution left standstill, separation glycerine, methanol and grease.Grease enters base-catalyzed transesterification reactor, by adding appropriate magnetic charcoal/KOH solid catalysts and methanol, is reacted under optimum temperature.Reaction terminates rear solution left standstill, liquid separation harvest biodiesel.In acid-base reaction device magnetic Pd/carbon catalyst can be separated, be reclaimed by strong magnet, regeneration reuse.Compared with traditional handicraft, the present invention is with waste liquid yield is small, catalyst is easily recycled, low cost and other advantages.
Description
Technical field
The present invention relates to waste resource technology field, refers in particular to one kind using magnetic charcoal load acid-base catalysis waste cooking oil
The method of biodiesel processed.
Background technology
With the fast development of social economy, energy resource consumption sharp increase, energy resources shortage, which has become, restricts China
An important factor for socio-economic development.Economic impact of the fluctuation of International Petroleum Price to China is increasing, increasingly deficient
Petroleum resources serious threat develops reproducible alternative energy source, has broken away from dependence to fossil energy to the energy security of country
As the important directions of energy research.Fossil fuel caused sulfur dioxide, nitrogen oxides and a large amount of particles in combustion
Dust causes very big harm to ecological environment, and compared to conventional fuel, biodiesel is as the reproducible bioenergy of green, tool
Whether there is sulphur, the characteristics of nontoxic and easily biological-degradable, reduce the row of the toxic gas such as sulfur dioxide and particulate matter in combustion process
Put.China is that raw material has produced qualified biodiesel with animal and plant fat, but because these animal and plant fat sources have
Limit, hinders the application of biodiesel, thus the industrialization key of biodiesel be find it is cheap, can large scale collection oil
Fat resource.China's eating habit causes to produce substantial amounts of waste cooking oil, and the yield of the annual waste cooking oil in the whole nation is about 10,000,000
Ton, if do not managed and recycling, will be refined into gutter oil by criminal and return to the dining table of people.Therefore dining is considered
Waste oil is drunk as the raw material for preparing biodiesel, is not only realized the high value added utilization of waste cooking oil, is more reduced biological bavin
The preparation cost of oil.
The liquid soda acid two-step catalysis method that China's production of biodiesel generally uses is to use sulphuric acid catalysis grease first
Middle free fatty generation fatty acid methyl ester (biodiesel), recycle base catalysis triglycerides generation fatty acid methyl ester, catalysis
Agent is dissolved in reaction system, needs to neutralize, wash and dry after reaction, causes excessive discharge of wastewater and energy expenditure.And use
Magnetic retention acid base catalysator, catalyst do not dissolve in reaction system in, after reaction by externally-applied magnetic field can separating catalyst, with
Magnetic retention acid base catalysator substitutes homogeneous acid base catalysator, the discharge of wastewater in the preparation of biodiesel of a large amount of reductions
And energy resource consumption, production cost also accordingly reduce.
The invention discloses a kind of method that acid-base catalysis preparing biodiesel by food and beverage waste oil is loaded using magnetic charcoal, the party
Method is carbon source using abandoned biomass such as wood chips, and realization is turned waste into wealth, and resource recycles.In addition magnetic retention soda acid is used
Two-step catalysis waste cooking oil production biodiesel overcomes that waste water yield in conventional two-step is big, the difficult recovery of catalyst asks
Topic.The high value added utilization of waste cooking oil is realized simultaneously, effectively reduces the preparation cost of biodiesel.
The content of the invention
The present invention solves in conventional homogeneous catalysis for preparing biodiesel oil technique that catalyst recovery is difficult, waste liquid yield is big etc. and asked
Topic, the high value added utilization of waste cooking oil is realized, effectively reduce the preparation cost of biodiesel.
The technical solution of the present invention is to provide one kind using magnetic charcoal load acid-base catalysis waste cooking oil biology bavin
The method of oil, it is characterized in that：
This method includes the preparation of magnetic charcoal, the preparation of magnetic solid acid, the preparation of magnetic solid base, magnetic solid acid
The ester exchange reaction of pre-esterification reactor, magnetic solid base；
(1) preparation of magnetic charcoal：A certain amount of trivalent iron salt is taken to be dissolved in deionized water, configuration trivalent iron salt concentration 10%~
25% solution；Wood chip is placed in ferric salt solution after crushed；The mass ratio of trivalent iron salt and wood chip is 4:1~10:
1；Wood chip is filtered by vacuum after soaking 30~120min in ferric salt solution, and filter cake is dried into perseverance at 60 DEG C
Weight；The filter cake of drying is put into alumina crucible and is placed in high temperature process furnances, in N2With 2~20 DEG C/min speed liter under protection
Temperature is incubated 30~120min to 550~900 DEG C, and rough magnetic charcoal is made；Washing is carried out to rough magnetic charcoal with deionized water
The removal of impurity, solid-to-liquid ratio 1:10~1:200；Washing gained magnetic charcoal is dried at 105 DEG C is made magnetic charcoal finished product；
(2) preparation of magnetic solid acid：By magnetic charcoal and dense H2SO4Solution presses solid-liquid 1:10~1:50 are configured to suspension,
1~24h of sulfonation at 100~120 DEG C, it is cooled to after room temperature and adds distilled water immersion, washing, filtering in batches until filtrate is in
It is neutral；Gained filter cake is dried at 80~120 DEG C is made magnetic carbon-based solid acid catalyst finished product；
(3) preparation of magnetic solid base：Magnetic charcoal and KOH solution solution are pressed into solid-liquid 1:3~1:10 are configured to suspension,
Wherein KOH solution concentration is 1.5~2mol/L, and magnetic charcoal and KOH mass ratio are 1:3~1:10；Gained suspension is in magnetic force
It is filtered by vacuum after impregnating 1~10h under stirring condition；Gained filter cake dried at 50~120 DEG C be made magnetic charcoal based solid alkali urge
Agent finished product；
(4) pre-esterification reactor of magnetic solid acid：The waste cooking oil after a certain amount of removal of impurities is taken, by the 1%~10% of oily weight
Magnetic solid acid catalyst is added into waste cooking oil；Reactor is heated to 90~150 DEG C, and is passed through methanol vapor；Methanol
Intake is the 15%~25% of waste cooking oil weight to steam per hour；After 1~10h of pre-esterification reactor or treat waste cooking oil acid number
When dropping to below 2mgKOH/g, magnetic solid acid is taken out by externally-applied magnetic field, obtains fatty acid methyl ester；
(5) ester exchange reaction of magnetic solid base：Fatty acid methyl ester obtained in step (4) is rubbed with methanol by alcohol oil
You are than being 5:1~15:1 is added in reactor, according to 1%~10% addition magnetic solid base of oily weight into reactor；Will
Reactor is heated to 50~100 DEG C, after reacting 1~5h, after taking out magnetic solid base catalyst by externally-applied magnetic field, stands and divides
Layer, intermediate layer is coarse biodiesel.
The raw material for preparing magnetic charcoal also can use the biomass such as mushroom bran, palm shell, stalk in addition to wood chip；Prepare magnetic charcoal
Raw material broken and by 50~300 mesh sieves using preceding needing.
The trivalent ferrous solution for being used to soak the biomass such as wood chip can be the common soluble trivalents such as iron chloride, ferric nitrate
Iron salt solutions.
During the pre-esterification reactor of the magnetic solid acid, when esterification yield is less than 75%, magnetic charcoal base solid is changed
Acid catalyst；The magnetic carbon-based solid acid catalyst that fails passes through heating, attached magnetic, attached acid regeneration again after solvent soaking.
In the ester-exchange reaction of the magnetic solid base, when ester exchange rate is less than 75%, changes magnetic charcoal base and consolidate
Body base catalyst；Magnetic carbon-based solid acid catalyst fail by the way that attached magnetic, attached alkali regenerate again after heating, solvent soaking.
After the ester exchange reaction of the magnetic solid base terminates, solution is molten through upper strata methanol obtained by stratification in reactor
Liquid can be used to produce methanol vapor, with the ester-exchange reaction to magnetic solid base.
The raw material for being used to prepare biodiesel also can use soybean oil, Canola oil, palm oil, open country in addition to waste cooking oil
The water plant such as oil generation tannin plant and engineering microalgae grease and animal fat etc..
Methods described produces coarse biodiesel and can be used for refining exquisite biodiesel or directly with ordinary diesel oil by specific mixed
Cooperate as diesel oil cooking oven oil.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
(1) using magnetic charcoal load soda acid two-step catalysis preparing biodiesel by food and beverage waste oil, solves conventional homogeneous catalysis
The problem of agent recovery is difficult；
(2) present invention reduces prepare the yield of waste liquid and biodiesel recycling door in biodiesel process
Sill.
Embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
A kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal, it is characterised in that：This method
The preparation of preparation, magnetic solid acid, the preparation of magnetic solid base, pre-esterification reactor, the magnetic of magnetic solid acid including magnetic charcoal
The ester exchange reaction of property solid base；
(1) preparation of magnetic charcoal：A certain amount of trivalent iron salt is taken to be dissolved in deionized water, configuration trivalent iron salt concentration 10%~
25% solution；Wood chip is placed in ferric salt solution after crushed；The mass ratio of trivalent iron salt and wood chip is 4:1~10:
1；Wood chip is filtered by vacuum after soaking 30~120min in ferric salt solution, and filter cake is dried into perseverance at 60 DEG C
Weight；The filter cake of drying is put into alumina crucible and is placed in high temperature process furnances, in N2With 2~20 DEG C/min speed liter under protection
Temperature is incubated 30~120min to 550~900 DEG C, and rough magnetic charcoal is made；Washing is carried out to rough magnetic charcoal with deionized water
The removal of impurity, solid-to-liquid ratio 1:10~1:200；Washing gained magnetic charcoal is dried at 105 DEG C is made magnetic charcoal finished product；
(2) preparation of magnetic solid acid：By magnetic charcoal and dense H2SO4Solution presses solid-liquid 1:10~1:50 are configured to suspension,
1~24h of sulfonation at 100~120 DEG C, it is cooled to after room temperature and adds distilled water immersion, washing, filtering in batches until filtrate is in
It is neutral；Gained filter cake is dried at 80~120 DEG C is made magnetic carbon-based solid acid catalyst finished product；
(3) preparation of magnetic solid base：Magnetic charcoal and KOH solution solution are pressed into solid-liquid 1:3~1:10 are configured to suspension,
Wherein KOH solution concentration is 1.5~2mol/L, and magnetic charcoal and KOH mass ratio are 1:3~1:10；Gained suspension is in magnetic force
It is filtered by vacuum after impregnating 1~10h under stirring condition；Gained filter cake dried at 50~120 DEG C be made magnetic charcoal based solid alkali urge
Agent finished product；
(4) pre-esterification reactor of magnetic solid acid：The waste cooking oil after a certain amount of removal of impurities is taken, by the 1%~10% of oily weight
Magnetic solid acid catalyst is added into waste cooking oil；Reactor is heated to 90~150 DEG C, and is passed through methanol vapor；Methanol
Intake is the 15%~25% of waste cooking oil weight to steam per hour；After 1~10h of pre-esterification reactor or treat waste cooking oil acid number
When dropping to below 2mgKOH/g, magnetic solid acid is taken out by externally-applied magnetic field, obtains fatty acid methyl ester；
(5) ester exchange reaction of magnetic solid base：Fatty acid methyl ester obtained in step (4) is rubbed with methanol by alcohol oil
You are than being 5:1~15:1 is added in reactor, according to 1%~10% addition magnetic solid base of oily weight into reactor；Will
Reactor is heated to 50~100 DEG C, after reacting 1~5h, after taking out magnetic solid base catalyst by externally-applied magnetic field, stands and divides
Layer, intermediate layer is coarse biodiesel.
Embodiment 1
Crude biodiesel is prepared using the above method.Specially：
(1) preparation of magnetic charcoal：By wood chip powder crushed after 200 mesh sieves with Fe (NO that mass fraction is 20%3)3Press
Mass ratio is 1:4 impregnate 60min with its solution under magnetic agitation effect.Dipping terminates, and solid-liquid is carried out by being filtered by vacuum machine
Separation, filter cake, which is placed in evaporating dish, puts baking oven into, and constant weight is dried at 60 DEG C.Filter cake is put into crucible and is placed in microwave thermal
Solve in stove, in N2700 DEG C are warming up to 5 DEG C/min speed under protection, 60min is incubated, obtains magnetic charcoal；With deionized water to production
Thing is washed, and goes the removal of impurity；
(2) preparation of magnetic solid acid：It is 1 that magnetic charcoal and the concentrated sulfuric acid are pressed into solid-to-liquid ratio:25 mixing, the sulfonation at 120 DEG C
12h, after being cooled to room temperature, dilute filtration in distilled water is added mixture to, it is in neutrality to wash repeatedly to filtrate, is filtered,
Dried at 90 DEG C；
(3) preparation of magnetic solid base：Magnetic charcoal is added in 2mol/L KOH solution, makes magnetic charcoal in system
Quality and KOH mass ratio are 1:4, it is filtered by vacuum after impregnating 3h in the presence of magnetic agitation, and filter cake is dried at 60 DEG C
Do to constant weight；
(4) preparation of biodiesel：The waste cooking oil after a certain amount of removal of impurities is taken, magnetic solid acid is added by the 1% of oily weight
Catalyst is in reactor, when being heated to 115 DEG C, is passed through methanol vapor, and methanol vapor intake is the 15% of oily weight per hour,
After catalytic reaction 4h, magnetic solid acid is taken out by externally-applied magnetic field, obtains fatty acid methyl ester；Obtained fatty acid methyl ester is taken out
With methanol according to molar ratio of methanol to oil be 9:1 is added in reactor, while adds 4% magnetic solid base of oily weight in reactor
In, 63 DEG C are heated to, after reacting 1.5h, after taking out magnetic solid base catalyst by externally-applied magnetic field, stratification, intermediate layer is
For coarse biodiesel.Sampling, it is 95.4% with the ester exchange rate of gas chromatographic detection preparing biodiesel by food and beverage waste oil.
Embodiment 2
(1) preparation of magnetic charcoal：By wood chip powder crushed after 100 mesh sieves with Fe (NO that mass fraction is 15%3)3Press
Mass ratio is 1:8 impregnate 30min with its solution under magnetic agitation effect.Dipping terminates, and solid-liquid is carried out by being filtered by vacuum machine
Separation, filter cake, which is placed in evaporating dish, puts baking oven into, and constant weight is dried at 60 DEG C.Filter cake is put into crucible and is placed in microwave thermal
Solve in stove, in N2550 DEG C are warming up to 5 DEG C/min speed under protection, 30min is incubated, obtains magnetic charcoal；With deionized water to production
Thing is washed, and goes the removal of impurity；
(2) preparation of magnetic solid acid：It is 1 that magnetic charcoal and the concentrated sulfuric acid are pressed into solid-to-liquid ratio:15 mixing, the sulfonation at 120 DEG C
10h, after being cooled to room temperature, dilute filtration in distilled water is added mixture to, it is in neutrality to wash repeatedly to filtrate, is filtered,
Dried at 90 DEG C；
(3) preparation of magnetic solid base：Magnetic charcoal is added in 1.5mol/L KOH solution, makes magnetic charcoal in system
Quality and KOH mass ratio be 1:3, it is filtered by vacuum after impregnating 2h in the presence of magnetic agitation, and by filter cake at 60 DEG C
It is dried to constant weight；
(4) preparation of biodiesel：The waste cooking oil after a certain amount of removal of impurities is taken, magnetic solid acid is added by the 2% of oily weight
Catalyst is in reactor, when being heated to 125 DEG C, is passed through methanol vapor, and methanol vapor intake is the 20% of oily weight per hour,
After catalytic reaction 2h, magnetic solid acid is taken out by externally-applied magnetic field, obtains fatty acid methyl ester.Obtained fatty acid methyl ester is taken out
With methanol according to molar ratio of methanol to oil be 7:1 is added to reaction, while adds 4% magnetic solid base of oily weight in reaction system
In, 58 DEG C are heated to, after reacting 2h, after taking out magnetic solid base catalyst by externally-applied magnetic field, stratification, intermediate layer is
Coarse biodiesel.Sampling, it is 65.3% with the ester exchange rate of gas chromatographic detection preparing biodiesel by food and beverage waste oil.
This works loads soda acid using magnetic charcoal and prepares biological bavin as esterification and catalyst for ester exchange reaction, two-step catalysis
Oil, efficiently solve, catalyst high to equipment anticorrosion performance requirement possessed by traditional biological diesel production technique and be not easy back
Receive, the shortcomings of waste liquid yield is big, have biodiesel production rate is high, operating cost is low, reaction unit is simple, environmental pollution is small,
The advantages that product purpose is extensive, available for restaurant, residential block and other places, realize the money for the waste cooking oil that grease yield is low, oil product is poor
Sourceization utilizes.This method mentality of designing agrees with the theory of national energy-saving emission reduction and sustainable development, has broad application prospects.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (8)
- A kind of 1. method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal, it is characterised in that：This method bag Include the preparation of magnetic charcoal, the preparation of magnetic solid acid, the preparation of magnetic solid base, the pre-esterification reactor of magnetic solid acid, magnetic The ester exchange reaction of solid base；(1) preparation of magnetic charcoal：A certain amount of trivalent iron salt is taken to be dissolved in deionized water, configuration trivalent iron salt concentration 10%~25% Solution；Wood chip is placed in ferric salt solution after crushed；It is 4 to make the mass ratio of trivalent iron salt and wood chip in solution:1~ 10:1；Wood chip is filtered by vacuum after soaking 30~120min in ferric salt solution, and filter cake is dried at 60 DEG C Constant weight；The filter cake of drying is put into alumina crucible and is placed in high temperature process furnances, in N2With 2~20 DEG C/min speed under protection 550~900 DEG C are warming up to, is incubated 30~120min, rough magnetic charcoal is made；Rough magnetic charcoal is washed with deionized water Go the removal of impurity, solid-to-liquid ratio 1:10~1:200；Washing gained magnetic charcoal is dried at 105 DEG C is made magnetic charcoal finished product；(2) preparation of magnetic solid acid：By magnetic charcoal and dense H2SO4Solution presses solid-liquid 1:10~1:50 are configured to suspension, 1~24h of sulfonation at 100~120 DEG C, it is cooled to after room temperature and adds distilled water immersion, washing, filtering in batches in filtrate is in Property；Gained filter cake is dried at 80~120 DEG C is made magnetic carbon-based solid acid catalyst finished product；(3) preparation of magnetic solid base：Magnetic charcoal and KOH solution solution are pressed into solid-liquid 1:3~1:10 are configured to suspension, wherein KOH solution concentration is 1.5~2mol/L, and magnetic charcoal and KOH mass ratio are 1:3~1:10；Gained suspension is in magnetic agitation Under the conditions of impregnate 1~10h after be filtered by vacuum；Gained filter cake is dried at 50~120 DEG C is made magnetic charcoal based solid alkali catalyst Finished product；(4) pre-esterification reactor of magnetic solid acid：The waste cooking oil after a certain amount of removal of impurities is taken, by 1%~10% addition of oily weight Magnetic solid acid catalyst is into waste cooking oil；Reactor is heated to 90~150 DEG C, and is passed through methanol vapor；Methanol vapor Intake is the 15%~25% of waste cooking oil weight per hour；After 1~10h of pre-esterification reactor or treat that waste cooking oil acid number drops to During below 2mgKOH/g, magnetic solid acid is taken out by externally-applied magnetic field, obtains fatty acid methyl ester；(5) ester exchange reaction of magnetic solid base：Fatty acid methyl ester obtained in step (4) and methanol are pressed into molar ratio of methanol to oil For 5:1~15:1 is added in reactor, according to 1%~10% addition magnetic solid base of oily weight into reactor；Will reaction Device is heated to 50~100 DEG C, after reacting 1~5h, after taking out magnetic solid base catalyst by externally-applied magnetic field, and stratification, in Interbed is coarse biodiesel.
- 2. a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal according to claim 1, It is characterized in that：The raw material for preparing magnetic charcoal can also use mushroom bran, palm shell, straw biomass in addition to wood chip；Prepare magnetic The raw material of charcoal is broken and by 50~300 mesh sieves using preceding needing.
- 3. a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal according to claim 1, It is characterized in that：The trivalent ferrous solution for being used to soak wood chip biomass is iron chloride, the common soluble ferric iron of ferric nitrate Salting liquid.
- 4. a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal according to claim 1, It is characterized in that：During the pre-esterification reactor of the magnetic solid acid, when esterification yield is less than 75%, changes magnetic charcoal base and consolidate Body acid catalyst；The magnetic carbon-based solid acid catalyst that fails passes through heating, attached magnetic, attached acid regeneration again after solvent soaking.
- 5. a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal according to claim 1, It is characterized in that：In the ester-exchange reaction of the magnetic solid base, when ester exchange rate is less than 75%, magnetic charcoal base is changed Solid base catalyst；Magnetic carbon-based solid acid catalyst fail by the way that attached magnetic, attached alkali regenerate again after heating, solvent soaking.
- 6. a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal according to claim 1, It is characterized in that：After the ester exchange reaction of the magnetic solid base terminates, solution is through upper strata first obtained by stratification in reactor Alcoholic solution is used for producing methanol vapor, during the pre-esterification reactor to magnetic solid acid.
- 7. a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal according to claim 1, It is characterized in that：It is described to be used to prepare the raw material of biodiesel in addition to waste cooking oil, moreover it is possible to soybean oil, Canola oil, palm oil, Wild oil plant and engineering microalgae water plant grease and animal fat.
- 8. a kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal according to claim 1, It is characterized in that：Produced coarse biodiesel be used for refine exquisite biodiesel or directly with ordinary diesel oil by specific blend as bavin Oil oven stove oil.
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| CN115261147A (en) * | 2022-06-23 | 2022-11-01 | 北京科技大学 | Method for catalytically synthesizing biodiesel by using carbon-based solid acid |
| CN115254143A (en) * | 2022-06-23 | 2022-11-01 | 北京科技大学 | Preparation method and application of carbon-based solid acid catalyst |
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