CN101402058B - Process for producing solid alkali biodiesel catalyst with shell powder as carrier - Google Patents
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- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a method for preparing a solid base biodiesel catalyst by using shell powders as a carrier. The method is to load effective alkali components on the shell powder carrier through a solid phase synthesis method or a dipping method. The dipping method is as follows: firstly, preparing an effective alkali component solution with proper concentration; secondly, loading effective alkali components; and thirdly, obtaining the catalyst through roasting at a program-controlled temperature after pretreatments of stirring and the like. The solid phase synthesis method is as follows: fully mixing and grinding one or two precursors with certain mass and more than two of the effective alkali components with certain mass of activating shell powders, and then drying and roasting the mixture to obtain the biodiesel catalyst with the solid effective alkali components immobilized by the shell powders. The solid base catalyst has the characteristics of high catalytic efficiency, good stability, easy separation, and excellent regenerability, and can be applied in the fields of biodiesel synthesis, ester exchange synthesis and the like. For the raw material source and the process, the method reduces the production cost and improves the catalytic efficiency, and is advantageous to bring environment pollution under control.
Description
Technical field:
The present invention relates to solid base catalyst and energy technology field, particularly relate to preparation method with shell powder supported solid alkali biodiesel catalyst.
Background technology:
Along with the high speed development of World Economics, cause the sharp increase of energy demand, contention also is growing more intense to the energy in countries in the world.Especially current international situation is increasingly sophisticated, and Oil Safety has become the major issue that is related to the national security and the national economic development.Meanwhile, the consumption of rapid economic development, population increase, the energy also causes the deterioration of environment: a large amount of releases of greenhouse gases, the degeneration that tills the land.Under this trend, it is extremely urgent to seek the energy new, that have environment friendly.Thereby biodiesel has caused the extensive attention of countries in the world with its superior feature of environmental protection and recyclability.The preparation biodiesel mainly adopts ester-interchange method to obtain at present, and it mainly comprises homogeneous catalysis method, heterogeneous catalysis method, biological catalysis and supercritical methanol technology.At present, industrially preparing biological diesel mainly is the homogeneous catalysis method, reaction mainly be with liquid acid, alkali or enzyme as catalyst, cause difficulty for the separation and the repeated use of catalyst.In recent years, the research that is used for ester exchange reaction of relevant solid catalyst increases gradually.
In each production technology of biodiesel, chemical liquid base catalysis method has realized industrialization, and shooting flow body technology and fatty enzyme process Catalytic processes still are in the laboratory development.Liquid base catalysis method technology has that catalyst relatively inexpensively is easy to get, the reaction time is short, the conversion ratio advantage of higher, but still there are a series of intrinsic defectives: material quality is had relatively high expectations, the acid value of raw material must be less than 1, water content must be less than 0.5%, and is promptly low to waste oil, industrial waste recovery utilization rate; Saponification easily takes place; Complex process, the energy consumption height; The alcohol consumption is big and not easy to be recycled; By-product glycerin is difficult to be recycled, and the catalyst difficulty is separated with product, thereby has increased the cost of subsequent treatment, and the spent lye discharging is importantly arranged, and forms new environomental pollution source.Liquid acid catalyst (for example CN1412278A adopts sulfuric acid to make catalyst) is not though have specific (special) requirements to the moisture and the free acid content of feedstock oil, but it has corrosivity, very high to the equipment requirement, and methyl alcohol is difficult to separate with by-product glycerin after the reaction end, makes the cost rising.In addition, adopt liquid acid, in last handling process, can discharge large amount of sewage, cause environmental pollution as catalyst.Fat enzyme process catalytically synthesizing biological diesel oil (as CN200410061280.3) does not have special requirement to material quality.The fat enzyme process not only can the catalysis refining vegetable and animals oils, simultaneously can also the catalysis acid number higher and waste cooking oil that contain certain moisture change into biodiesel, the enzyme process reaction has mild condition, the byproduct separating technology is comparatively simple, the catalyst reusable edible, waste water is few, and equipment requires advantages such as low.But there is a series of defective in lipase-catalyzed preparation biodiesel: reaction time is longer; The easy poisoning and deactivation of enzyme is if enzyme will lose catalytic activity when lower alcohol reaches a certain amount of in the reaction system; The price comparison costliness of while lipase.Supercritical methanol technology (as CN200510012660.2) need not to use catalyst, has the fast and conversion ratio advantages of higher of environmental friendliness, reaction rate, but this method needs carry out under high temperature, high pressure, and consersion unit is had very high requirement.
Summary of the invention:
The object of the present invention is to provide with the oyster shell whiting is the preparation method of the solid alkali biodiesel catalyst of carrier, this method technology is simple, environmental protection, cheap, combine between the active component that obtains and the carrier firmly, selectivity is good, the catalytic activity height can reuse, and the life-span is long, catalysis biological diesel oil is of good quality, and post processing is simple.
The present invention's method alkali active principle is synthetic by solid phase or dipping loads on the oyster shell whiting carrier.Infusion process: at first preparation is fit to the effective alkali component solution of concentration, and this effective alkali component of load through preliminary treatment such as stirrings, obtains catalyst by the temperature programmed control roasting at last then.For improving load capacity, can repeatedly flood.Solid phase method: with a kind of of certain mass predecessor or two kinds and the two or more effective alkali component and the abundant mixed grinding of activation oyster shell whiting of certain mass, oven dry, roasting promptly obtain the immobilized solid effective alkali of oyster shell whiting component biodiesel catalyst again.
The present invention is that the preparation of the solid alkali biodiesel catalyst of carrier may further comprise the steps with the oyster shell whiting:
Infusion process: under the room temperature, with alkali metal active principle and the water-soluble by a certain percentage or organic solvent of solvable non-alkali metal active principle, make the concentration 0.1～6.0mol/L of solution, get a certain amount of activation oyster shell whiting and impregnated in this solution, 50～100 ℃ of oven dry, wash repeatedly with residue mother liquor, remove in conjunction with unstable active principle, again in 50～100 ℃ of oven dry, in Muffle furnace with 260～650 ℃ of roastings, control programming rate 1～10K/min, after being warmed up to 300 ℃, constant temperature 1～6h is warmed up to 600 ℃ then, constant temperature 1～24h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
Solid phase method: under the room temperature, with alkali metal active principle, non-alkali metal active principle and the abundant by a certain percentage mixed grinding of activation oyster shell whiting.In 50～100 ℃ of oven dry, in Muffle furnace,, control programming rate 1～10K/min again with 260～650 ℃ of roastings, after being warmed up to 300 ℃, constant temperature 1～6h is warmed up to 600 ℃ then, constant temperature 1～24h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.
Described activation oyster shell whiting is: oyster shell powder, spiral shell shell powder, Concha Meretricis Seu Cyclinae powder, oyster shell whiting or their any mixture, activation is that oyster shell whiting is cleaned with faintly acid 0.01～0.1mol/L aqueous solution at normal temperatures, 50～100 ℃ of pre-burnings of low temperature make its water evaporates, fully dehydration.
Described alkali metal active principle is oxide, hydroxide, organic and the inorganic salts or their any mixture of lithium, sodium, potassium three metals.
Described non-alkali metal active principle is oxide, hydroxide, organic and the inorganic salts or their any mixture of zinc, barium, strontium, titanium, zirconium five metals genus.
Described solid alkali biodiesel catalyst is that particle is less than 200 purpose powders.
Described alkali metal active principle, non-alkali metal active principle are 1:1～2:10～60 with the mass ratio of activation oyster shell whiting.
Described organic solvent is absolute methanol, ethanol, propyl alcohol, butanols, ether, benzene, toluene or their any mixture.
The present invention is that the preparation of the solid alkali biodiesel catalyst of carrier has following performance characteristics with the oyster shell whiting:
(1) solved the easy solution-off of active component in the catalyst, poor in conjunction with fastness, thin layer easily chaps, shortcoming pockety.The catalytic activity and the service life of catalyst have been improved.Catalyst recovery is easy, has simplified last handling process, has eliminated the sewage discharge problem, has advantages such as adaptability to raw material are good, selectivity is good, production cost is lower.
(2) big with the shell powder supported alkali active principle active area of porous, the contact area of fluid and catalyst is big, it is strong to combine dynamics, and the catalytic efficiency height can be fit to industrialization production.The support material aboundresources, cheap, twice laid, environmental protection, solution impregnation is carried out under normal temperature and pressure, is easy to industrialization production.
(3) the catalyst physical stability is better.Do not have volatilization, heat resisting temperature is higher, and the alkali active principle is carried on the oyster shell whiting surface, handles by temperature programming, has improved the absorption affinity of oyster shell whiting to the alkali active principle.
(4) catalyst regeneration better performances.Catalyst is if poison or inactivation, catalyst can be toasted again or mother liquor soaks baking and just can make revivification of catalyst, and is simple.
Description of drawings:
Fig. 1 is a process chart of the present invention.
The specific embodiment:
At this is that example elaborates preparation process with the oyster shell powder.
Embodiment 1
Under the room temperature, 1g NaOH and 2g barium nitrate are dissolved in 500ml water, the oyster shell whiting of getting the 10g activation impregnated in this solution, fully stir, 60 ℃ of oven dry are washed repeatedly with residue mother liquor, to remove, again in 60 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 6K/min, after being warmed up to 300 ℃, constant temperature 2h is warmed up to 600 ℃ then, constant temperature 15h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing, in having the 100ml three-necked bottle of electromagnetic agitation, thermometer, reflux condensing tube, adding 5g corn oil, 2g methyl alcohol, the above-mentioned solid catalyst of 0.15g add hot reflux and stir 3h, and decompression distillation goes out methyl alcohol, static 10min, filter, obtain biodiesel, productive rate reaches 98.1%, the catalyst that leaches continues to recycle, under these conditions, recycle altogether 10 times, biodiesel production rate is between 96～98.1%.Every index meets existing 0
#The standard GB252-2000 of diesel oil, it the results are shown in following table.
Gained biodiesel index and 0
#Diesel oil (GB252-2000) performance is compared as follows table:
Embodiment 2
Under the room temperature, 1g lithium hydroxide and 1g zirconium nitrate are dissolved in 500ml water, the oyster shell whiting of getting the 15g activation impregnated in this solution, fully stir, 80 ℃ of oven dry are washed repeatedly with residue mother liquor, to remove, again in 80 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 4K/min, after being warmed up to 300 ℃, constant temperature 1h is warmed up to 600 ℃ then, constant temperature 20h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 99%, and this catalyst circulation is used 15 times, and biodiesel production rate is between 95.6～99%, and catalytic activity does not descend.
Embodiment 3
Under the room temperature, 1g potassium hydroxide and 1.5g zinc permanganate are dissolved in 500ml water, the oyster shell whiting of getting the 12g activation impregnated in this solution, fully stir, 70 ℃ of oven dry are washed repeatedly with residue mother liquor, to remove, again in 70 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 5K/min, after being warmed up to 300 ℃, constant temperature 5h is warmed up to 600 ℃ then, constant temperature 15h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 99.7%, and this catalyst circulation is used 10 times, and biodiesel production rate is between 97～99.7%, and catalytic activity does not descend.
Embodiment 4
Under the room temperature, 1g sodium oxide molybdena and 1.6g zinc acetate are dissolved in 500ml water, the oyster shell whiting of getting the 10g activation impregnated in this solution, fully stir, 90 ℃ of oven dry are washed repeatedly with residue mother liquor, to remove, again in 90 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 7K/min, after being warmed up to 300 ℃, constant temperature 3h is warmed up to 600 ℃ then, constant temperature 10h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 98.7%, and this catalyst circulation is used 10 times, and biodiesel production rate is between 96～98.7%, and catalytic activity does not descend.
Embodiment 5
Under the room temperature, 1g sodium fluoride and 2g strontium nitrate are dissolved in 500ml water, the oyster shell whiting of getting the 15g activation impregnated in this solution, fully stir, 100 ℃ of oven dry are washed repeatedly with residue mother liquor, to remove, again in 100 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 3K/min, after being warmed up to 300 ℃, constant temperature 2h is warmed up to 600 ℃ then, constant temperature 16h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 98.8%, and this catalyst circulation is used 11 times, and biodiesel production rate is between 96.5～98.8%, and catalytic activity does not descend.
Embodiment 6
Under the room temperature, 1g sodium nitrate and 1.8g barium formate are dissolved in 500ml water, the oyster shell whiting of getting the 16g activation impregnated in this solution, fully stir, 100 ℃ of oven dry are washed repeatedly with residue mother liquor, to remove, again in 100 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 4K/min, after being warmed up to 300 ℃, constant temperature 6h is warmed up to 600 ℃ then, constant temperature 10h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 99%, and this catalyst circulation is used 8 times, and biodiesel production rate is between 95.7～99%, and catalytic activity does not descend.
Embodiment 7
Under the room temperature, 0.5g NaOH, 0.5g sodium fluoride and 1.9g zinc nitrate are dissolved in the 500ml methyl alcohol, the oyster shell whiting of getting the 20g activation impregnated in this solution, fully stir, 95 ℃ of oven dry are washed repeatedly with residue mother liquor, to remove, again in 95 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 6K/min, after being warmed up to 300 ℃, constant temperature 8h is warmed up to 600 ℃ then, constant temperature 15h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 99.5%, and this catalyst circulation is used 10 times, and biodiesel production rate is between 97.2～99.5%, and catalytic activity does not descend.
Embodiment 8
Under the room temperature, 0.5g NaOH, 0.5g lithium hydroxide, 1g zinc nitrate, 1g oxygen greening zirconium are dissolved in the 300ml methyl alcohol 200ml ethanol mixed solvent, the oyster shell whiting of getting the 17g activation impregnated in this solution, fully stir, 85 ℃ of oven dry, wash repeatedly with residue mother liquor, to remove, again in 85 ℃ of oven dry, roasting in Muffle furnace in conjunction with unstable active principle, control programming rate 2K/min, after being warmed up to 300 ℃, constant temperature 5h is warmed up to 600 ℃ then, constant temperature 24h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.For improving load capacity, can carry out repeatedly load.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 99.8%, and this catalyst circulation is used 15 times, and biodiesel production rate is between 97.6～99.8%, and catalytic activity does not descend.
Embodiment 9
Under the room temperature, with 1g sodium oxide molybdena, 1.5g titanium dioxide and the abundant mixed grinding of 10g activation oyster shell whiting.Again in 50 ℃ of oven dry, roasting in Muffle furnace, control programming rate 3K/min, be warmed up to 300 ℃ after, constant temperature 4h is warmed up to 650 ℃ then, constant temperature 19h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 98.8%, and this catalyst circulation is used 12 times, and biodiesel production rate is between 96.3～98.8%, and catalytic activity does not descend.
Embodiment 10
Under the room temperature, with 0.5g NaOH, 0.5g sodium carbonate, 1.8g hexafluorosilicic acid barium and the abundant mixed grinding of 20g activation oyster shell whiting.Again in 100 ℃ of oven dry, roasting in Muffle furnace, control programming rate 10K/min, be warmed up to 300 ℃ after, constant temperature 6h is warmed up to 650 ℃ then, constant temperature 22h promptly obtains the immobilized solid alkali biodiesel catalyst of oyster shell whiting again.
The catalyst activity property testing is with embodiment 1, and its biodiesel production rate reaches 99.5%, and this catalyst circulation is used 10 times, and biodiesel production rate is between 96.6～99.5%, and catalytic activity does not descend.
Claims (4)
1. one kind is the preparation method of the solid alkali biodiesel catalyst of carrier with the oyster shell whiting, and it is characterized in that: described method comprises following dual mode:
(1) infusion process: under the room temperature, with alkali metal active principle and the water-soluble by a certain percentage or organic solvent of soluble non-alkali metal active principle, make the concentration 0.1～6.0mol/L of solution, the oyster shell whiting of getting some activation impregnated in this solution, 50～100 ℃ of oven dry, solution with remnants washes repeatedly, to remove in conjunction with unstable active principle, again in 50～100 ℃ of oven dry, in Muffle furnace with 260～600 ℃ of roastings, control programming rate 1～10K/min, after being warmed up to 300 ℃, constant temperature 1～6h is warmed up to 600 ℃ then, constant temperature 1～24h again, promptly obtaining with the oyster shell whiting is the solid alkali biodiesel catalyst of carrier;
Oxide, hydroxide, organic salt and inorganic salts that described non-alkali metal active principle is zinc, barium, strontium, titanium or zirconium or their any mixture;
Described oyster shell whiting is oyster shell powder, spiral shell shell powder, Concha Meretricis Seu Cyclinae powder or their any mixture;
Described activation is that oyster shell whiting is cleaned with faintly acid 0.01～0.1mol/L aqueous solution at normal temperatures, and 50～100 ℃ of pre-burnings make its water evaporates, dehydration;
Described alkali metal active principle, non-alkali metal active principle are 1: 1～2: 10～60 with the mass ratio of activation oyster shell whiting;
Or (2) solid phase method: under the room temperature, with alkali metal active principle, non-alkali metal active principle and the abundant by a certain percentage mixed grinding of activation oyster shell whiting, again in 50～100 ℃ of oven dry, in Muffle furnace with 260～600 ℃ of roastings, control programming rate 1～10K/min, be warmed up to 300 ℃ after, constant temperature 1～6h, be warmed up to 600 ℃ then, constant temperature 1～24h again, promptly obtaining with the oyster shell whiting is the solid alkali biodiesel catalyst of carrier;
Oxide, hydroxide, organic salt and inorganic salts that described non-alkali metal active principle is zinc, barium, strontium, titanium or zirconium or their any mixture;
Described oyster shell whiting is oyster shell powder, spiral shell shell powder, Concha Meretricis Seu Cyclinae powder or their any mixture;
Described activation is that oyster shell whiting is cleaned with faintly acid 0.01～0.1mol/L aqueous solution at normal temperatures, and 50～100 ℃ of pre-burnings make its water evaporates, dehydration;
Described alkali metal active principle, non-alkali metal active principle are 1: 1～2: 10～60 with the mass ratio of activation oyster shell whiting.
2. method according to claim 1 is characterized in that described alkali metal active principle is the oxide of lithium, sodium or potassium, hydroxide, organic salt and inorganic salts or their any mixture.
3. method according to claim 1 is characterized in that: described solid alkali biodiesel catalyst is that particle is less than 200 purpose powders.
4. method according to claim 1 is characterized in that: described organic solvent is absolute methanol, ethanol, propyl alcohol, butanols, ether, benzene, toluene or their any mixture.
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| CN101745385B (en) * | 2010-01-08 | 2012-07-25 | 绍兴文理学院 | Preparation method of load type palladium/shell powder catalyst |
| CN105344344B (en) * | 2015-09-30 | 2018-01-05 | 榆林学院 | Modified eggshell biodiesel catalyst and its preparation method and application |
| CN109382111B (en) * | 2018-11-28 | 2021-09-28 | 泉州师范学院 | Preparation method of cobaltosic oxide catalyst for catalytic oxidation of benzene |
| CN109908950B (en) * | 2019-04-12 | 2021-08-06 | 郑州师范学院 | Solid base biodiesel catalyst and preparation method thereof |
| CN112547038A (en) * | 2020-12-18 | 2021-03-26 | 广东嘉荣环保新能源科技有限公司 | Biodiesel modified solid catalyst CaO/ZnO and preparation method and application thereof |
| CN113145159B (en) * | 2021-03-31 | 2023-03-10 | 郑州师范学院 | Biodiesel catalyst and preparation method thereof |
| CN115475613A (en) * | 2022-09-29 | 2022-12-16 | 北部湾大学 | Modified oyster shell solid base catalyst for synthesizing biodiesel and preparation method thereof |
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