CN101195759A - Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst katalysis - Google Patents
Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst katalysis Download PDFInfo
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Abstract
The invention relates to the production technology for preparing kernel oil and preparing biological diesel oil through solid base catalysis. The invention has the technology proposal that the ester interchange reaction is performed by utilizing solid base catalyst to prepare the biological diesel oil. The preparation method of the biological diesel oil adopts the steps that kernel crude oil is produced as raw material, under the condition that the solid base catalyst exists, the kernel crude oil happens to the ester interchange reaction with methyl alcohol, ethyl alcohol, or the mixture of the methyl alcohol and the ethyl alcohol with arbitrary proportion through being mixed, stirred, and heated, and thus the biological diesel oil is produced. The invention has the advantages that firstly, the raw material source of the catalyst is sufficient, the cost is low, the preparation and the regeneration are simple, and the catalyst can be reused after the regeneration; secondly, the catalyst is easy to be separated and regenerated after the ester exchange reaction is finished; thirdly, the catalytic condition is mild, the product is not required to be neutralized and cleaned, and the generation of a great amount of waste water in homogeneous phase production process is overcome; fourthly, on the premise of ensuring methyl ester content and biological diesel oil yield, the reaction time is shortened; fifthly, the fatty acid methyl ester content in the biological diesel oil corresponds to a homogeneous phase process taking NaOH and KOH as catalyst, and the yield rate is higher than the homogeneous phase process.
Description
Technical field: the present invention relates to prepare with Chinese tallow tree Chinese catalpa oil is the green production technology of feedstock production biofuel, particularly is used to prepare required solid base catalyst of biofuel and corresponding catalytic transesterification technology and corresponding every technic index.
Background technology: Chinese tallow tree (Sapium sebiferum (L.) Roxb.), have another name called sharpleaf privet, Aleurites montana, Euphorbiaceae (Euphorbia L.) sapium, deciduous tree, perennial plant is grown in the torrid zone and subtropics, has extremely strong drought resisting, anti-barren ability, its plantation does not only need to take to till the land, and also can improve existing ecotope.Chinese tallow tree is a kind of good biomass, is the distinctive woody oil tree species of China, and its seed oil content height, oil yield are one of China four big woody oleiferous plants plants (Chinese tallow tree, oil tea, tung oil tree and walnut) up to more than 40%.The physical and chemical index of Chinese tallow tree Chinese catalpa oil is: undecanoic acid 0.289%; 9-12 diluted acids (lauroleic acid) 3.194%; Myristic acid 0.206%; Palmitinic acid 7.518%; Stearic acid 2.657%; Oleic acid 14.554%; Isooleic acid 0.894%; Linolic acid 30.769%; 9,12-18 carbon three diluted acids 0.426%; Alpha-linolenic acid 39.298%.This plant has the cultivation history in more than 1,000 year in China, the record that cultivation is all arranged and utilize in farming in ancient times book Important Arts for the People's Welfare and " agricultural administration book ".Chinese tallow tree originates in China Qinling Mountains, on the south the Basin of Huaihe River, to the east of Taiwan, reach Hainan Island in the south, below the height above sea level 1000m of middle part, Sichuan, southwest is to Guizhou, Yunnan etc. below the ground height above sea level 2000m, main cultivation area provinces such as Zhejiang, Hubei, Sichuan, Guizhou, Anhui, Yunnan, Jiangxi, Fujian on the south the Yangtze valley.Plant the Chinese tallow tree oil crops energetically, develop into the bioenergy supply place, significant meaning is arranged solving the agriculture, rural areas and farmers problem.Its Application and Development had far-reaching economic benefit and social benefit.The development biofuel is adjusted the structure of agricultural production, developing rural economy to sustainable economic development; increase farmers' income, advance energy substitution, reduce environmental pollution; preserve the ecological environment, the control urban atmospheric pollution has the important strategic meaning, will make important contribution for China's oil safety.
Chinese tallow tree Chinese catalpa oil biodiesel preparation method mainly adopts the transesterification reaction crude oil that viscosity is high to change into the low-viscosity fatty acid ester through transesterification.People such as Ruan Rongsheng disclose a kind of production technology of preparing biodiesel by solid magnetic catalyst in patent CN1891787A, solid magnetic catalyst contains Ni
2O
3, Co
2O
3, Fe
2O
3Etc. the magnetic material, sintering solid magnetic catalyst together can better separate with the biofuel of liquid state under the effect in magnetic field, can reduce pollution, and the recyclable utilization again of catalyzer.But the Preparation of catalysts cost is higher, is difficult for realizing industrialization.People such as Zheng Baicun disclose in patent CN101041130A and have utilized load type solid body base catalyst to prepare method of bio-diesel oil.Catalyst system therefor is that transition metal or rare earth element are loaded on porous material (Al
2O
3, wilkinite, zeolite, kaolin, sepiolite) on, through super-dry, roasting, grind and sieve and obtain.People such as Zhu Shenlin disclose in patent CN101012389A and have utilized solid base catalyst to prepare method of bio-diesel oil.Specially refer to and utilize alkaline-earth alkoxides compound catalyst transesterification reaction to prepare method of bio-diesel oil.With metal alkoxide Mg (OCH
3)
2/ Ca (OCH
3)
2, Sr (OCH
3)
2Deng one or more, join in the reactor with the solid base catalyst that obtains as carrier with aluminum oxide, silicon oxide, ceramic honey comb, add oil plant heat up carry out transesterification reaction, through underpressure distillation, filtration, the filtrate filtered layering obtains biofuel and glycerine.It is 1: 30 that reports such as Liu use poultry grease and methyl alcohol mol ratio, and the consumption of catalyzer Mg-Al hydrotalcite is 10% of an oil quantity, reacts 8h under 120 ℃ of temperature, and transformation efficiency reaches more than 90%.[Liu Y J，Lotero E，James G，etal.Transesterification of poultry fat with methanol using Mg-Al hydrotalcitederived catalysts[J].Chemical Engineering Journal，In Press.]。MacLeod etc. load on the metal oxide serial basic metal as catalyzer, are used for catalysis rapeseed oil and methyl alcohol and carry out transesterification reaction.Discover LiNO
3/ CaO, NaNO
3/ CaO, KNO
3/ CaO and LiNO
3Four catalyzer show catalytic effect preferably behind reaction 3h.[MacLeod C S，Harvey A P，Lee A F，et al.Evaluation of the activity and stability of alkali-doped metaloxide catalysts for application to an intensified method of biodiesel production[J].Applied Catalysis A：General，2007，331：138-148.]。In sum, prior biological diesel oil technology of preparing respectively has its excellent, shortcoming: (1) homogeneous phase base catalysis method production unit and technology are simple, technology maturation, be the main method of present industrial use, but be easy to generate " three wastes " problem, disagree with the characteristic of environmental protection of biofuel.(2) overcritical transesterify process has short, transformation efficiency advantages of higher of environmentally friendly, reaction times.But usually temperature of reaction is at 300～400 ℃, pressure 30～65MPa, and reaction conditions, processing requirement are higher, are difficult to realize industrialization.(3) enzyme catalysis prepares biofuel and has mild condition, and product is easy to collect advantages such as non-pollution discharge.But enzyme price height, easy poisoning and deactivation, long reaction time.(4) Chang Yong solid base catalyst has oxidized form, loading type etc.Because the existence of heterogeneous catalyst, make advantages such as product is easily separated, catalyzer easily reclaims, aftertreatment is simple, the three wastes are few, can reduce the production cost of biofuel significantly.But solid base catalyst has long reaction time mostly, the life-span is short, cost is high, complicated process of preparation, shortcomings such as poor reproducibility.
Summary of the invention: the objective of the invention is at the deficiencies in the prior art, exploitation is used to prepare the solid base catalyst and the corresponding transesterify Catalytic processes thereof of biofuel, related solid base catalyst cost is low, preparation, separate, regeneration is simple, and provides easy, easy-operating related process.
Concrete scheme of the present invention is as follows:
Adding Chinese tallow tree Chinese catalpa oil, methyl alcohol, ethanol or methyl alcohol and alcoholic acid arbitrary proportion mixture (amount of substance than scope is: 1: 5～1: 20) in reactor mixes; Be heated to about 40 ℃, add the solid base catalyst of Chinese tallow tree Chinese catalpa weight of oil 1～8%, at 0～100 ℃ of following stirring reaction 1.5～10 h; After the reaction mixed system is cooled under methyl alcohol or the ethanol boiling point centrifugation solid base catalyst; Liquid phase reclaims methyl alcohol through underpressure distillation; Leave standstill, layering, the upper strata is a biofuel, lower floor is a glycerine.
Related solid base catalyst characteristics: (1) by at least a or any mixture in marble, rhombspar, calcite, Wingdale, barite, peridotites, the gypsum, under 0.9～1.1MPa or vacuum, the solid base catalyst of 300～1200 ℃ of following roasting 0.5～10 h of maturing temperature, cooling, grinding gained.(2) at least a or any mixture at least a or any mixture in the alkali metal compound and marble, rhombspar, calcite, Wingdale, barite, peridotites, the gypsum is mixed, at least a or any mixture and the mass ratio between carrier in the alkali metal compound are 0.01～5: 1, under 0.9～1.1MPa or vacuum, the solid base catalyst of 300～1200 ℃ of following roasting 0.5～10h of maturing temperature, cooling, grinding gained.
Above-described alkali metal compound is: lithium borohydride, sodium borohydride, POTASSIUM BOROHYDRIDE, the hydroboration rubidium, lithium tetraborate, sodium tetraborate, potassium tetraborate, the peroxyboric acid lithium, Sodium peroxoborate, potassium per(oxy)borate, the peroxyboric acid rubidium, the Sodium tetrafluoroborate potassium fluoborate, sodium metaborate, potassium metaborate, sodium borohydride, POTASSIUM BOROHYDRIDE, Lithium Sulphate, sodium sulfate, vitriolate of tartar, rubidiurn sulfate, Lithium Sulphate, sodium pyrosulfate, sal enixum, dihydrogen sulfate sodium, potassium dihydrogen sulfate, the hydrogen sulfate disodium, potassium dihydrogen sulfate, lithium nitrate, SODIUMNITRATE, saltpetre, rubidium nitrate, lithium nitrite, Sodium Nitrite, potassium nitrite, the nitrous acid rubidium, Trilithium phosphate, sodium phosphate, potassiumphosphate, the phosphoric acid rubidium, disodium-hydrogen, potassium phosphate,monobasic, monometallic, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, Sodium phosphate dibasic, lithium fluoride, Sodium Fluoride, Potassium monofluoride, rubidium fluoride, lithium chloride, sodium-chlor, Repone K, rubidium chloride, lithium chlorate, sodium chlorate, Potcrate, rubidium chlorate, lithiumbromide, Sodium Bromide, Potassium Bromide, rubidium bromide, lithium iodide, sodium iodide, potassiumiodide, rubidium iodide, sodium periodate, potassium periodate, Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus, rubidium bicarbonate, disodium bicarbonate, the hydrogen-carbonate dipotassium, lithium oxalate, sodium oxalate, potassium oxalate, the oxalic acid rubidium, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, lithium formate, sodium formiate, potassium formiate, the formic acid rubidium, Lithium Acetate, sodium-acetate, Potassium ethanoate, the acetic acid rubidium, the propionic acid lithium, Sodium Propionate, potassium propionate, the propionic acid rubidium, the butyric acid lithium, Sodium propanecarboxylate, potassium butyrate, the butyric acid rubidium, the 2 Methylpropionic acid lithium, 2 Methylpropionic acid sodium, 2 Methylpropionic acid potassium, the 2 Methylpropionic acid rubidium, lithium valerate, natrium valericum, valeric acid potassium, the valeric acid rubidium, the 2-Methyl Butyric Acid lithium, 2-Methyl Butyric Acid sodium, 2-Methyl Butyric Acid potassium, the 2-Methyl Butyric Acid rubidium, the 3 Methylbutanoic acid lithium, 3 Methylbutanoic acid sodium, 3 Methylbutanoic acid potassium, the 3 Methylbutanoic acid rubidium, 2,2-neopentanoic acid lithium, 2,2-neopentanoic acid sodium, 2,2-neopentanoic acid potassium, 2,2-neopentanoic acid rubidium, oxalic acid hydrogen lithium, sodium bioxalate, potassium binoxalate, oxalic acid hydrogen rubidium, lithium oxalate, sodium oxalate, potassium oxalate, the oxalic acid rubidium, propanedioic acid hydrogen lithium, propanedioic acid hydrogen sodium, propanedioic acid hydrogen potassium, propanedioic acid hydrogen rubidium, the propanedioic acid lithium, sodium malonate, propanedioic acid potassium, the propanedioic acid rubidium, Succinic Acid hydrogen lithium, sodium bisuccinate, Succinic Acid hydrogen potassium, Succinic Acid hydrogen rubidium, the Succinic Acid lithium, Soduxin, potassium succinate, the Succinic Acid rubidium, tartarlithine, sodium hydrotartrate, tartarus, the hydrogen tartrate rubidium, lithium tartrate, sodium tartrate, soluble tartrate, rubidium tartrate, the hydrogen malate lithium, sodium hydrogen malate, hydrogen malate potassium, the hydrogen malate rubidium, the oxysuccinic acid lithium, sodium malate, potassium malate, the oxysuccinic acid rubidium, the dihydrogen citrate lithium, Sodium citrate, potassium citrate dihydrogen, the dihydrogen citrate rubidium, hydrogen citrate two lithiums, Monobasic sodium citrate, the hydrogen citrate dipotassium, hydrogen citrate two rubidiums, Lithium Citrate de, Trisodium Citrate, Tripotassium Citrate, the citric acid rubidium, sodium sorbate, at least a or any mixture in the potassium sorbate.
Above-described Chinese tallow tree Chinese catalpa oil for the Chinese tallow tree seed through removal of impurities, soften, take off the thick oil of white, parch, squeezing, filtration gained.
Above-described catalyst regeneration process is: at least a or any mixture washing in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, normal hexane, hexanaphthene, benzene, dimethylbenzene, dry, in 300～1200 ℃ of roasting 0.5～10h, can reuse after cooling off, be ground to 40～200 orders.
The preparation technology of biofuel comprises that transesterification reaction, centrifugation solid base catalyst, precipitation reclaim methyl alcohol, standing demix and step such as separate.Preparation technology's characteristics are: overcome existing homogeneous acid, alkaline catalysts separation difficulty, aftertreatment complexity, the low many shortcomings of trade effluent that reach of product yield.Solid base catalyst separates after regenerate reusablely, has prolonged catalyzer work-ing life, has further reduced production cost.
Above transesterification reaction, fatty acid methyl, ethyl ester content 95% after testing, yield 96%.
Embodiment: embodiment one
1. the production technique of Chinese tallow tree Chinese catalpa oil
1.1 raw materials pretreatment: utilize the impurity in the rotary flat sieve separate raw materials.Contain in the Chinese tallow tree seed of selected back assorted should be less than 0.1%.
1.2 steaming seed: in softening kettle, carry out.It is wetting softening to use small amount of steam that the Chinese tallow tree seed is carried out, and the time is 30～40 min.
1.3 take off white: utilization is taken off white machine Chinese tallow tree seed surface Chinese tallow tree butter is gone.
1.4 oil expression:
(1) parch: use the rotation dry-roast machine at 130～150 ℃ of parch 20～30 min.
(2) go into to press: the Chinese tallow tree Zi Ren squeezing after using spiral oil press to parch, initial temperature is controlled at 150～170 ℃, and blob of slag gauge control is about 1.5～3.0mm, and the oil cake residual oil content is about 4%.
1.5 filter:
Can obtain thick oil with 80 mesh filter screen disposable filterings, standby.
2. the preparation of solid base catalyst
Get rhombspar at 500 ℃ of vacuum baking 6h, take out in the rearmounted moisture eliminator cooling after, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 12.35Kg (the amount of substance ratio is 1: 15), solid base catalyst 1.76Kg (8wt.%) stirs, and temperature of reaction is 55 ℃, 0.9～1.1MPa, the reaction times is 4h.Reaction finishes back centrifuging solid catalyst, methyl alcohol, standing demix are reclaimed in underpressure distillation.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 95.5% after testing, and yield is 97.0%.
Embodiment two
1. the production technique of Chinese tallow tree Chinese catalpa oil
Chinese tallow tree Chinese catalpa oil production technique is with embodiment one.
2. the preparation of solid base catalyst
Get barite at 1200 ℃ of roasting 6h, take out in the rearmounted moisture eliminator cooling after, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, ethanol 14.56Kg (the amount of substance ratio is 1: 12), roasting marble 1.43Kg (6.5wt.%) stirs, and temperature of reaction is 55 ℃, 0.9～1.1MPa, the reaction times is 3.5h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty-acid ethyl ester content is 95.7% after testing, and yield is 96.6%.
Embodiment three
1. the production technique of Chinese tallow tree Chinese catalpa oil
Chinese tallow tree Chinese catalpa oil production technique is with embodiment one.
2. the preparation of solid base catalyst
Get Wingdale at 850 ℃ of vacuum baking 3h, take out in the rearmounted moisture eliminator cooling after, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 8.45Kg (the amount of substance ratio is 1: 10), solid base catalyst 1.21Kg (5.5wt.%) stirs, and temperature of reaction is 60 ℃, 0.9～1.1MPa, the reaction times is 7.0h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 96.4% after testing, and yield is 97.1%.
Embodiment four
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with embodiment one.
2. the preparation of solid base catalyst
Rhombspar, Wingdale ratio are 0.4: 0.6 (mass ratio), and both ground and mixed are evenly taken out in the rearmounted moisture eliminator after the cooling at 1100 ℃ of vacuum baking 3h the back, grind standby.
3. ester exchange process
In 50 L reactors, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 16.90Kg (the amount of substance ratio is 1: 20), solid base catalyst 1.10Kg (5wt.%) stirs, and temperature of reaction is 60 ℃, 0.9～1.1MPa, the reaction times is 3h.Reaction finishes after centrifuging catalyzer, underpressure distillation remove methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 95.3% after testing, and yield is 97.6%.
Embodiment five
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with embodiment one.
2. the preparation of solid base catalyst
Rhombspar, gypsum, marble ratio are 0.33: 0.33: 0.33 (mass ratio), with three dipping, stir, dry, grind evenly the back at 850 ℃, vacuum baking 6h takes out in the rearmounted moisture eliminator after the cooling, grinds standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, ethanol 12.13Kg (the amount of substance ratio is 1: 10), solid base catalyst 1.10Kg (5wt.%) stirs, and temperature of reaction is 55 ℃, 0.9～1.1MPa, the reaction times is 10h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty-acid ethyl ester content is 95.8% after testing, and yield is 96.9%.
Embodiment six
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with embodiment one.
2. the preparation of solid base catalyst
Rhombspar and sodium tetraborate ratio are 0.99: 0.01 (mass ratio), and both ground and mixed are evenly taken out in the rearmounted moisture eliminator after the cooling at 700 ℃ of roasting 4h the back, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 8.45Kg (the amount of substance ratio is 1: 10), solid base catalyst 0.55Kg (2.5wt.%) stirs, and temperature of reaction is 70 ℃, 0.9～1.1MPa, the reaction times is 3h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 97.3% after testing, and yield is 97.0%.
Embodiment seven
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Calcite and lithium nitrate ratio are 0.75: 0.25 (mass ratio), with both dippings, stir, dry, grind evenly the back at 750 ℃ of roasting 1.5h, take out in the rearmounted moisture eliminator after the cooling, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 6.67Kg (the amount of substance ratio is 1: 8), solid base catalyst 0.66Kg (3wt.%) stirs, and temperature of reaction is 70 ℃, 0.9～1.1MPa, the reaction times is 3h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 96.5% after testing, and yield is 96.1%.
Embodiment eight
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Wingdale and Potassium monofluoride ratio are 1: 3 (mass ratio), and both ground and mixed are evenly taken out in the rearmounted moisture eliminator after the cooling at 300 ℃ of roasting 1.5h the back, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 3.38Kg, ethanol 4.85Kg (the amount of substance ratio is 1: 4: 4), solid base catalyst 0.55Kg (2.5wt.%) stirs, and temperature of reaction is 85 ℃, 0.9～1.1MPa, the reaction times is 2.5 h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl, ethyl ester content summation are 98.3% after testing, and yield is 96.8%.
Embodiment nine
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Wingdale and lithium chloride, Trisodium Citrate ratio are 1: 2.5: 2.5 (mass ratio), with three dipping, stir, dry, grind evenly the back at 700 ℃ of vacuum baking 0.5h, take out in the rearmounted moisture eliminator after the cooling, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 5.92Kg (the amount of substance ratio is 1: 7), solid base catalyst 0.33 Kg (1.20wt.%) stirs, and temperature of reaction is 80 ℃, and the reaction times is 1.5h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 97.8% after testing, and yield is 97.1%.
Embodiment ten
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Wingdale, rhombspar and sodium-acetate ratio are 0.25: 0.25: 0.5 (mass ratio), and three's ground and mixed is evenly taken out in the rearmounted moisture eliminator after the cooling at 900 ℃ of roasting 2h the back, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 7.61Kg (the amount of substance ratio is 1: 9), solid base catalyst 0.33Kg (1.5wt.%) stirs, and temperature of reaction is 65 ℃, and the reaction times is 2h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 97.3% after testing, and yield is 97.7%.
Embodiment 11
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Rhombspar, marble and salt of wormwood ratio are 0.3: 0.3: 0.4 (mass ratio), with three dipping, stir, grind evenly the back at 800 ℃ of roasting 2h, take out in the rearmounted moisture eliminator after the cooling, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 8.45Kg (the amount of substance ratio is 1: 10), solid base catalyst 0.33Kg (1.5wt.%) stirs, and temperature of reaction is 70 ℃, and the reaction times is 2.2h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 97.2% after testing, and yield is 96.4%.
Embodiment 12
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Rhombspar, peridotites, Wingdale and Potassium ethanoate ratio are 0.15: 0.12: 0.23: 2 (mass ratioes), four ground and mixed are evenly taken out in the rearmounted moisture eliminator after the cooling at 950 ℃ of roasting 8h the back, and grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 4.22Kg, ethanol 4.85Kg (the amount of substance ratio is 1: 5: 4), solid base catalyst 0.35Kg (1.60wt.%) stirs, and temperature of reaction is 90 ℃, and the reaction times is 2.5h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl, ethyl ester content summation are 98.6% after testing, and yield is 97.2%.
Embodiment 13
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Rhombspar, calcite, Wingdale and sodium oxalate, Potcrate ratio are 0.10: 0.05: 0.45: 0.15: 0.25 (mass ratio), with five through dipping, dry mixed evenly after at 950 ℃ of vacuum baking 2h, after taking out in the rearmounted moisture eliminator cooling, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 9.30Kg (the amount of substance ratio is 1: 11), solid base catalyst 0.22Kg (1.00wt.%) stirs, 75 ℃ of temperature of reaction, the reaction times is 3h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 98.2% after testing, and yield is 96.3%.
Embodiment 14
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Rhombspar: calcite: Wingdale: barite: peridotites: potassiumiodide: the sodium sorbate ratio is 0.2: 0.2: 0.2: 0.2: 0.2: 2: 3 (mass ratioes), with above raw material through dipping, dry mixed evenly after at 1200 ℃ of roasting 2h, after taking out in the rearmounted moisture eliminator cooling, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, methyl alcohol 9.30Kg (the amount of substance ratio is 1: 11), solid base catalyst 0.22Kg (1.00wt.%) stirs, 100 ℃ of temperature of reaction, the reaction times is 2h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty acid methyl ester is 97.7% after testing, and yield is 96.3%.
Embodiment 15
1. the production technique of Chinese tallow tree Chinese catalpa oil
The production technique of Chinese tallow tree Chinese catalpa oil is with example one.
2. the preparation of solid base catalyst
Rhombspar: calcite: Wingdale: barite: peridotites: marble: the saltpetre ratio is 0.10: 0.10: 0.10: 0.05: 0.05: 0.15: 0.45 (mass ratio), more than each raw material through dipping, dry mixed evenly after at 900 ℃ of vacuum baking 2h, after taking out in the rearmounted moisture eliminator cooling, grind standby.
3. ester exchange process
In the 50L reactor, drop into Chinese tallow tree Chinese catalpa oil 22Kg, ethanol 12.13Kg (the amount of substance ratio is 1: 10), solid base catalyst 0.22Kg (1.00wt.%) stirs, and temperature of reaction is 80 ℃, and the reaction times is 2.5h.Reaction finishes after centrifuging catalyzer, underpressure distillation reclaim methyl alcohol, standing demix.The upper strata is a biofuel, and lower floor is a by-product glycerin.
4. detect
Fatty-acid ethyl ester content is 95.9% after testing, and yield is 97.0%.
According to the explanation of above-mentioned example, these those skilled in the art can infer, the solid base catalyst among the present invention can refer to that at least a or any mixture in marble, rhombspar, calcite, Wingdale, barite, the peridotites is through the roasting products therefrom; Also with at least a or any mixture of six kinds of ores as carrier, mix with at least a or any mixture of alkali metal compound, vacuum or 0.9～1.1MPa roasting products therefrom, do not enumerate one by one at this.
15 embodiment summary sheets following (Chinese tallow tree Chinese catalpa oil quality is 22Kg):
| Embodiment | Catalyzer | Catalyst levels (Chinese tallow tree Chinese catalpa oil quality wt. %) | Chinese tallow tree Chinese catalpa oil: alcohol (mol: mol) | Reaction times (h) | Temperature of reaction (℃) | Fatty acid methyl ester, ethyl ester content (%) | Yield (%) |
| One two three four five six seven eight nine ten ten one ten two ten three ten four ten five | Dolomite barite lime stone dolomite: lime stone dolomite: gypsum: lime stone dolomite: sodium tetraborate calcite: lithium nitrate marble: potassium fluoride dolomite: lithium chloride: natrium citricum dolomite: calcite: sodium oxalate dolomite: marble: potash dolomite: olivine: lime stone: potassium acetate dolomite: calcite: lime stone: sodium oxalate: potassium chlorate dolomite: calcite: lime stone: barite: olivine: KI: sodium sorbate dolomite: calcite: lime stone: barite: olivine: marble: potassium nitrate | 8 6.5 5.5 5 5 2.5 3 2.5 1.2 1.5 1.5 1.6 1.0 1.0 1.0 | 1: 15 oil: 1: 12 oil of methyl alcohol: 1: 10 oil of ethanol: 1: 20 oil of methyl alcohol: 1: 10 oil of methyl alcohol: 1: 10 oil of ethanol: 1: 8 oil of methyl alcohol: 1: 4: 4 oil of methyl alcohol: methyl alcohol: 1: 7 oil of ethanol: 1: 9 oil of methyl alcohol: 1: 10 oil of methyl alcohol: 1: 5: 4 oil of methyl alcohol: methyl alcohol: 1: 11 oil of ethanol: 1: 11 oil of methyl alcohol: 1: 10 oil of methyl alcohol: ethanol | 4 3.5 7 3 10 3 3 2.5 1.5 2 2.2 2.5 3 2 2.5 | 55 55 60 60 55 70 70 85 80 65 70 90 75 100 80 | 95.5 95.7 96.4 95.3 95.8 97.3 96.5 97.3 95.8 97.3 97.2 98.6 98.2 97.7 95.9 | 97.0 96.6 97.1 97.6 96.9 97.0 96.1 96.8 97.1 97.7 96.4 97.2 96.3 96.3 97.0 |
The invention has the advantages that: (1) related catalyst raw material source is sufficient, cost is low, preparation, regeneration are easy, and reusable after the regeneration; (2) it is easily separated, renewable that ester exchange reaction finishes rear catalyst; (3) washing that need not neutralize of catalytic condition gentleness, product has overcome the generation of a large amount of waste water in the homogeneous phase production process; (4) under the prerequisite that guarantees methyl esters content, biodiesel production rate, shortened the reaction time. (5) fatty acid methyl esters in biodiesel is suitable with the homogeneous phase technology take NaOH, KOH as catalyst, and yield is higher than homogeneous phase technology.
Claims (5)
1. the preparation method of a biofuel, it is characterized by: with Chinese tallow tree Chinese catalpa oil is raw material, under the condition that solid base catalyst exists,, after reaction is finished mixed system is reduced to methyl alcohol or the following temperature of ethanol boiling point with methyl alcohol, ethanol or methyl alcohol and alcoholic acid arbitrary proportion mixture generation transesterification reaction, the centrifugation solid base catalyst, liquid phase steam to slip reclaims methyl alcohol or ethanol through decompression, standing demix, the upper strata diesel oil of making a living, lower floor is a glycerine, and catalyst system therefor is reusable through regenerating.
2. the preparation method of a kind of biofuel according to claim 1, it is characterized by such catalyzer is solid base catalyst: (1) is by at least a or any mixture in marble, rhombspar, calcite, Wingdale, barite, peridotites, the gypsum, under 0.9～1.1MPa or vacuum condition, maturing temperature is 300～1000 ℃, the solid base catalyst of gained after 0.5～10h roasting, cooling, grinding; (2) be carrier with at least a or any mixture in marble, rhombspar, calcite, Wingdale, barite, peridotites, the gypsum, at least a or any mixture and carrier in the alkali metal compound are mixed, at least a or any mixture and the mass ratio between carrier in the alkali metal compound are 0.01～5: 1, under 0.9～1.1MPa or vacuum condition, maturing temperature is 300～1000 ℃, the solid base catalyst of gained after 0.5～10h roasting, cooling, grinding.
3. the preparation method of a kind of biofuel according to claim 2, it is characterized by: described alkali metal compound is: lithium borohydride, sodium borohydride, POTASSIUM BOROHYDRIDE, the hydroboration rubidium, lithium tetraborate, sodium tetraborate, potassium tetraborate, the peroxyboric acid lithium, Sodium peroxoborate, potassium per(oxy)borate, the peroxyboric acid rubidium, the Sodium tetrafluoroborate potassium fluoborate, sodium metaborate, potassium metaborate, sodium borohydride, POTASSIUM BOROHYDRIDE, Lithium Sulphate, sodium sulfate, vitriolate of tartar, rubidiurn sulfate, Lithium Sulphate, sodium pyrosulfate, sal enixum, dihydrogen sulfate sodium, potassium dihydrogen sulfate, the hydrogen sulfate disodium, potassium dihydrogen sulfate, lithium nitrate, SODIUMNITRATE, saltpetre, rubidium nitrate, lithium nitrite, Sodium Nitrite, potassium nitrite, the nitrous acid rubidium, Trilithium phosphate, sodium phosphate, potassiumphosphate, the phosphoric acid rubidium, disodium-hydrogen, potassium phosphate,monobasic, monometallic, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, Sodium phosphate dibasic, lithium fluoride, Sodium Fluoride, Potassium monofluoride, rubidium fluoride, lithium chloride, sodium-chlor, Repone K, rubidium chloride, lithiumbromide, Sodium Bromide, Potassium Bromide, rubidium bromide, lithium iodide, sodium iodide, potassiumiodide, rubidium iodide, sodium periodate, potassium periodate, Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus, rubidium bicarbonate, disodium bicarbonate, the hydrogen-carbonate dipotassium, lithium oxalate, sodium oxalate, potassium oxalate, the oxalic acid rubidium, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, lithium methoxide, sodium methylate, potassium methylate, methyl alcohol rubidium lithium formate, sodium formiate, potassium formiate, the formic acid rubidium, Lithium Acetate, sodium-acetate, Potassium ethanoate, the acetic acid rubidium, the propionic acid lithium, Sodium Propionate, potassium propionate, the propionic acid rubidium, the butyric acid lithium, Sodium propanecarboxylate, potassium butyrate, the butyric acid rubidium, the 2 Methylpropionic acid lithium, 2 Methylpropionic acid sodium, 2 Methylpropionic acid potassium, the 2 Methylpropionic acid rubidium, lithium valerate, natrium valericum, valeric acid potassium, the valeric acid rubidium, the 2-Methyl Butyric Acid lithium, 2-Methyl Butyric Acid sodium, 2-Methyl Butyric Acid potassium, the 2-Methyl Butyric Acid rubidium, the 3 Methylbutanoic acid lithium, 3 Methylbutanoic acid sodium, 3 Methylbutanoic acid potassium, the 3 Methylbutanoic acid rubidium, 2,2-neopentanoic acid lithium, 2,2-neopentanoic acid sodium, 2,2-neopentanoic acid potassium, 2,2-neopentanoic acid rubidium, oxalic acid hydrogen lithium, sodium bioxalate, potassium binoxalate, oxalic acid hydrogen rubidium, lithium oxalate, sodium oxalate, potassium oxalate, the oxalic acid rubidium, propanedioic acid hydrogen lithium, propanedioic acid hydrogen sodium, propanedioic acid hydrogen potassium, propanedioic acid hydrogen rubidium, the propanedioic acid lithium, sodium malonate, propanedioic acid potassium, the propanedioic acid rubidium, Succinic Acid hydrogen lithium, sodium bisuccinate, Succinic Acid hydrogen potassium, Succinic Acid hydrogen rubidium, the Succinic Acid lithium, Soduxin, potassium succinate, the Succinic Acid rubidium, tartarlithine, sodium hydrotartrate, tartarus, the hydrogen tartrate rubidium, lithium tartrate, sodium tartrate, soluble tartrate, rubidium tartrate, the hydrogen malate lithium, sodium hydrogen malate, hydrogen malate potassium, the hydrogen malate rubidium, the oxysuccinic acid lithium, sodium malate, potassium malate, the oxysuccinic acid rubidium, the dihydrogen citrate lithium, Sodium citrate, potassium citrate dihydrogen, the dihydrogen citrate rubidium, hydrogen citrate two lithiums, Monobasic sodium citrate, the hydrogen citrate dipotassium, hydrogen citrate two rubidiums, Lithium Citrate de, Trisodium Citrate, Tripotassium Citrate, the citric acid rubidium, sodium sorbate, at least a or any mixture in the potassium sorbate.
4. the preparation method of a kind of biofuel according to claim 1, it is characterized by: the condition of transesterification reaction is that the solid base catalyst consumption is 1～8% of a Chinese tallow tree Chinese catalpa oil quality, Chinese tallow tree Chinese catalpa oil is 1: 5～1: 20 than the scope of mixture amount of substance ratio with methyl alcohol, ethanol and methyl alcohol arbitrarily with ethanol, 0～100 ℃ of temperature of reaction, 0.9～1.1MPa, reaction times is 1.5～10h, obtains target product through aftertreatment---biofuel.
5. the preparation method of a kind of biofuel according to claim 1, it is characterized by: catalyst regeneration process is at least a or any mixture washing of solid base catalyst in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, normal hexane, hexanaphthene, benzene, dimethylbenzene with centrifugation gained after the transesterification reaction, dry, in 300～1200 ℃ of roasting 0.5～10h, can reuse after cooling off, be ground to 40～200 orders.
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