CN100390251C - Preparation of curcas biological diesel oil by solid phase catalytic method - Google Patents
Preparation of curcas biological diesel oil by solid phase catalytic method Download PDFInfo
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- CN100390251C CN100390251C CNB2006100509977A CN200610050997A CN100390251C CN 100390251 C CN100390251 C CN 100390251C CN B2006100509977 A CNB2006100509977 A CN B2006100509977A CN 200610050997 A CN200610050997 A CN 200610050997A CN 100390251 C CN100390251 C CN 100390251C
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The present invention relates to a method for preparing biologic diesel oil by utilizing jatropha curcas seed oil by solid-phase catalysis. The present invention has the technical scheme that the ester exchange reaction of solid phase catalysts is used for preparing biologic diesel oil with the conversion rate of triglyceride of 100% and the content of fatty acid methyl ester of no less than 96 wt%. The biologic diesel oil is prepared by the preparation method and technology of producing jatropha curcas seed oil as raw materials, mixing the jatropha curcas seed oil with methanol, stirring and heating the mixture at the existence of the solid phase catalysts for ester exchange reaction and obtaining the biologic diesel oil. The present invention has the advantages that solid phase catalysts can be reclaimed for reutilization; the power performance and the fuel oil consumption rate of the biologic diesel oil used as the substitute of diesel oil0<#> or mixed with diesel oil0<#> can reach the standard of diesel oil0<#>; the emission performance is improved obviously, so the superiority of environmental protection is obvious; the production technology has the characteristic that methanol is reclaimed before product separation with no need of water washing.
Description
Technical field
The present invention relates to barbadosnut seed oil production biofuel, particularly prepare production technique and corresponding every processing condition of needed solid-phase catalyst of biofuel and solid catalysis reaction with barbadosnut seed oil.
Background technology
Cortex jatrophae (Jatropha curcas L.) is Euphorbiaceae (Euphorbia L.) Cortex jatrophae platymiscium, the perennial woody plant is grown in the torrid zone and subtropics, has extremely strong drought resisting, anti-barren ability, its plantation not only need not take and can till the land, and also can improve existing ecotope.Leprosy seeds benevolence oil yield can be the fabulous raw material sources of production biofuel up to about 60%.Each composition is in the oil: triglyceride level 91.90%, triglyceride 1.30%, free fatty acids 3.80%, plant sterol compounds 0.27%, steroid fatty acid ester 0.22%, phospholipids compounds 1.10%.Lipid acid consists of: palmitic acid content 12.47%, and stearic acid content 6.42%, oleic acid content 32.04%, linoleic acid content 42.47%, Zoomeric acid content 2.10%, its composition is rational in infrastructure.Mainly be distributed in the southwest in Guizhou, Sichuan, Guangxi, Yunnan etc. China Cortex jatrophae, Guizhou Province is the major production areas of Cortex jatrophae natural resources.Mainly be distributed in areas such as the southeast of Guizhou Province, the south of Guizhou Province, the southwest of Guizhou Province.With Cortex jatrophae oil is that the feedstock production biofuel has significant strategic importance aspect economy, the environment: the ecotope of Guizhou Province and southwest is improved and promoted in (1); (2) quicken development of rural economy, promote the optimization of economic structure; (3) minimizing is to the dependence of petroleum import.
The preparation method of curcas biological diesel oil mainly adopts the transesterification reaction crude oil that viscosity is high to change into the fatty acid ester of low-viscosity through transesterification.The method of transesterification reaction comprises: homogeneous acid catalysis method, homogeneous phase base catalysis method, enzyme catalysis method, overcritical ester-interchange method, solid phase acid catalyzed process, solid phase base catalysis method etc.Every kind of method has its relative merits: (1) homogeneous phase base catalysis method production unit and technology are simple, technology maturation, are the main method that present industrialization is used, but are easy to generate " three wastes " problem, disagree with the characteristic of environmental protection of biofuel.People such as Luo Yulin adopt homogeneous phase base catalysis preparation method in the CN200410034487.1 patent, can produce serious emulsification phenomenon comparatively with the discovery that is raw material in the process of preparation biofuel of Cortex jatrophae oil and cause the increasing that cost drops into and influence productive rate; (2) homogeneous phase, the solid phase acid catalyzed process is because the reaction process required time is long, can cause energy consumption excessive, therefore be mainly used in the higher glyceride stock of specific acid number, Xie Guojian has used sulfuric acid as catalyzer in the feedstock production biofuel, before the reaction raw material has at first been carried out the precipitation removal of impurities, acidifying is come unstuck, the water vapour deodorization, the pre-treatment of vacuum hydro-extraction, be that catalyzer reacts with sulfuric acid or phenylformic acid then, reaction times needs 10h[to thank to state's sword. and hogwash fat is produced the research [J] of biodiesel fuel. chemical science and technology, 2005,13 (4): 20～22.].(3) advantage of enzyme catalysis method is the reaction conditions gentleness, and catalyzer has environment friendly, degradable.Cost an arm and a leg but exist, enzymic activity is subject to methyl alcohol in reaction influences deactivated unfavorable factor, so methanol usage is restricted the final productive rate that influences; (4) the supercritical methanol technology reaction is fast, and the time is short, but conversion unit, and processing condition all require high being difficult for to realize; (5) people such as Zhang Suojiang uses ionic liquid as biodiesel in the CN200510082972.0 patent in addition, has features such as technology is simple, environmental friendliness, but has unfavorable factors such as Preparation of Catalyst complexity, poor stability.(6) and the problem that exists in the present solid catalysis method is mainly: the one,, the Preparation of Catalyst complexity, Processes and apparatus requires high, as hydrotalcite Mg
6Al
2(OH)
16CO
34H
2O and Mg
4Al
2(OH)
12(NO
3)
24H
2Preparation [the Lv Liang of O, my country is strong. the preparation of hydrotalcite, sign and the application in transesterification reaction [J] thereof. and Speciality Petrochemicals, 2001 (1): 9-12.], the loading type alkali metal that people such as Li Weimin use in the patent of CN200510037862.2 and oxyhydroxide γ-Al
2O
3-NaOH-Na, γ-Al
2O
3-KOH-K, Takahiro Ebiura uses the compound solid-phase catalyst K of aluminum oxide of basic metal inorganic salt
2CO
3/ Al
2O
3, LiNO
3/ Al
2O
3, RbNO
3/ Al
2O
3, KF/Al
2O
3The preparation biofuel, but Preparation of catalysts is 10
-3Prepare under the reduced pressure of Pa, product methyl esters content is at 89%～94%[Takahiro Ebiura, Tsuneo Echizen, Akio Ishikawa, et al.Selective transesterification of triolein with methanol to methyloleate and glycerol using alumina loaded with alkali metal salt as asolid-base catalyst[J] .Applied Catalysis A:General, 2005 (283): 111-116; The 2nd,, catalytic effect not good or the reaction other conditional request height, Wenlei Xie etc. uses KNO under normal pressure
3/ Al
2O
3(35wt%) with the soybean oil be the feedstock production fatty acid methyl ester, high-content is 87.4%[Wenlei Xie, Hong Peng, Ligong Chen.Transesterification of soybean oil catalyzed by potassium loaded onalumina as a solid-base catalyst[J] .Applied Catalysis A:General, 2006 (300): 67-74.], Ginosar uses many microporous crystallines solid, negatively charged ion in US6877283, Zeo-karb and use hydrochloric acid, hydrofluoric acid, sulfuric acid or other acid or alkaline purification or untreated inorganic oxide (alumina, tripoli, the silicon alumina, phosphorous oxides, titanium dioxide, zirconium dioxide, trivalent chromium oxide, zinc oxide, magnesium oxide, silicate, calcium oxide) need under overcritical, carry out transesterification reaction for catalyzer.
Summary of the invention
The objective of the invention is to be primarily aimed at above-mentioned shortcoming, provide that a kind of technology is simple, environmental protection, fatty acid methyl ester height, productive rate height, related solid-phase catalyst price is low and the technological method of reusable production biofuel.
The concrete scheme that technical solution problem of the present invention adopts is: adopt the Cortex jatrophae of squeeze and filter slightly oily, utilize solid-phase catalyst to carry out the biofuel that transesterification reaction prepares high yield.
The preparation method of biofuel of the present invention is as raw material with Cortex jatrophae oil, under the condition that solid-phase catalyst exists, with methanol mixed stirring heating generation transesterification reaction, obtain reacting the mixture of thick ester of principal product and by-product glycerin, after reaction finishes reaction product is carried out aftertreatment, finally obtain biofuel.
The production of Cortex jatrophae oil adopts spiral oil press to squeeze, and obtains the raw materials for production of the thick oil of barbadosnut seed as biofuel through once filtering.
The preparation of solid-phase catalyst is by organic salt or the above any mixture and the carrier A l of alkali-metal organic salt, alkaline-earth metal
2O
3, NaY type zeolite, NaX type zeolite or Al
2O
3/ NaY, Al
2O
3/ NaX, NaY/NaX mix and are incorporated in pressure 0.9～1.1MPa, 400～1000 ℃ of compounding solid catalysts of calcining preparation down and getting of maturing temperature.
The alkaline metal organic salt of above indication comprises lithium formate, sodium formiate, potassium formiate, the formic acid rubidium, cesium formate, Lithium Acetate, sodium-acetate, Potassium ethanoate, the acetic acid rubidium, cesium acetate, the propionic acid lithium, Sodium Propionate, potassium propionate, the propionic acid rubidium, cesium acetate, the butyric acid lithium, Sodium propanecarboxylate, potassium butyrate, the butyric acid rubidium, the butyric acid caesium, the 2 Methylpropionic acid lithium, 2 Methylpropionic acid sodium, 2 Methylpropionic acid potassium, the 2 Methylpropionic acid rubidium, the 2 Methylpropionic acid caesium, lithium valerate, natrium valericum, valeric acid potassium, the valeric acid rubidium, the valeric acid caesium, the 2-Methyl Butyric Acid lithium, 2-Methyl Butyric Acid sodium, 2-Methyl Butyric Acid potassium, the 2-Methyl Butyric Acid rubidium, the 2-Methyl Butyric Acid caesium, the 3 Methylbutanoic acid lithium, 3 Methylbutanoic acid sodium, 3 Methylbutanoic acid potassium, the 3 Methylbutanoic acid rubidium, the 3 Methylbutanoic acid caesium, 2,2-neopentanoic acid lithium, 2,2-neopentanoic acid sodium, 2,2-neopentanoic acid potassium, 2,2-neopentanoic acid rubidium, 2,2-neopentanoic acid caesium, oxalic acid hydrogen lithium, sodium bioxalate, potassium binoxalate, oxalic acid hydrogen rubidium, oxalic acid hydrogen caesium, lithium oxalate, sodium oxalate, potassium oxalate, the oxalic acid rubidium, cesium oxalate, propanedioic acid hydrogen lithium, propanedioic acid hydrogen sodium, propanedioic acid hydrogen potassium, propanedioic acid hydrogen rubidium, propanedioic acid hydrogen caesium, the propanedioic acid lithium, sodium malonate, propanedioic acid potassium, the propanedioic acid rubidium, the propanedioic acid caesium, Succinic Acid oxygen lithium, sodium bisuccinate, Succinic Acid hydrogen potassium, Succinic Acid hydrogen rubidium, Succinic Acid hydrogen caesium, the Succinic Acid lithium, Soduxin, potassium succinate, the Succinic Acid rubidium, the Succinic Acid caesium, tartarlithine, sodium hydrotartrate, tartarus, the hydrogen tartrate rubidium, cesium bitartrate, lithium tartrate, sodium tartrate, soluble tartrate, rubidium tartrate, the tartrate caesium, the hydrogen malate lithium, sodium hydrogen malate, hydrogen malate potassium, the hydrogen malate rubidium, the hydrogen malate caesium, the oxysuccinic acid lithium, sodium malate, potassium malate, the oxysuccinic acid rubidium, the oxysuccinic acid caesium, the dihydrogen citrate lithium, Sodium citrate, potassium citrate dihydrogen, the dihydrogen citrate rubidium, the dihydrogen citrate caesium, hydrogen citrate two lithiums, Monobasic sodium citrate, the hydrogen citrate dipotassium, hydrogen citrate two rubidiums, hydrogen citrate two caesiums, Lithium Citrate de, Trisodium Citrate, Tripotassium Citrate, the citric acid rubidium, the citric acid caesium.
The alkaline-earth metal organic salt of above indication comprises magnesium formiate, calcium formiate, strontium formate, barium formate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, propionic acid magnesium, calcium propionate, the propionic acid strontium, barium propionate, magnesium butyrate, Calcium Butyrate, the butyric acid strontium, butyric acid barium, 2 Methylpropionic acid magnesium, 2 Methylpropionic acid calcium, the 2 Methylpropionic acid strontium, 2 Methylpropionic acid barium, valeric acid magnesium, valeric acid calcium, the valeric acid strontium, valeric acid barium, 2-Methyl Butyric Acid magnesium, 2-Methyl Butyric Acid calcium, the 2-Methyl Butyric Acid strontium, 2-Methyl Butyric Acid barium, 3 Methylbutanoic acid magnesium, 3 Methylbutanoic acid calcium, the 3 Methylbutanoic acid strontium, 3 Methylbutanoic acid barium, 2,2-neopentanoic acid magnesium, 2,2-neopentanoic acid calcium, 2,2-neopentanoic acid strontium, 2,2-neopentanoic acid barium, magnesium oxalate, caoxalate, strontium oxalate, barium oxalate, propanedioic acid magnesium, propanedioic acid calcium, the propanedioic acid strontium, propanedioic acid barium, Succinic Acid magnesium, calcium succinate, the Succinic Acid strontium, barium succinate, magnesium tartrate, calcium tartrate, strontium tartrate, barium tartrate, magnesium malate, calcium malate, strontium malate, barium malate, magnesium citrate, citrate of lime, strontium citrate, barium citrate.
The carrier A l of above indication
2O
3Comprise α-Al
2O
3, β-Al
2O
3, γ-Al
2O
3
It is raw material that transesterification reaction adopts thick oil of barbadosnut seed and methyl alcohol, catalysts consumption 0.5～20% (accounting for the weight of the thick oil of barbadosnut seed), the thick oil of barbadosnut seed is 1: 5～1: 20 with the ratio of methyl alcohol, 50～80 ℃ of temperature of reaction, pressure is 0.9～1.5MPa, and the reaction times is 1～10h.
The thick oil of the barbadosnut seed of above indication is meant the oil of barbadosnut seed through obtaining after squeezing, once filtering.
Above transesterification reaction, wherein the triglyceride level transformation efficiency is 100% after testing, fatty acid methyl ester＞96%, yield＞90%.
The preparation technology of biofuel comprises that transesterification reaction, centrifugation solid-phase catalyst, precipitation reclaim methyl alcohol, static layering is separated.Preparation technology's characteristics are: solid-phase catalyst separates treated recycling the in back; It is simple, abundant to adopt the isolating again method of first precipitation to reclaim methyl alcohol.
Embodiment
Embodiment one
1. the production technique of the thick oil of barbadosnut seed
1.1. raw materials pretreatment: remove pericarp, to remove foreign material standby.
1.2. oil expression:
(1) parch: both can go into to press to adopt the spiral oil press oil expression at 110～130 ℃ of parch 15～25min.
(2) go into to press: initial temperature is controlled at 150～170 ℃; Blob of slag gauge control is at～2mm; The oil cake residual oil content is 3～6%.
1.3. filter
It is standby both can to have obtained thick oil with 80 mesh filter screen disposable filterings.
2. the preparation of solid-phase catalyst
Sodium oxalate and β-Al
2O
3Ratio be 60: 100 (wt: wt), with sodium oxalate and β-Al
2O
3Directly at 500 ℃ of calcining 4h, taking-up is placed in the loft drier standby after fully milling.
Transesterification reaction
Be that 1: 10 ratio feeds intake according to thick oil of barbadosnut seed and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 1% of the thick oil of Cortex jatrophae, and temperature of reaction is 60 ℃, and reaction pressure is 0.9MPa, reaction times 5h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
3. post-reaction treatment
(1) centrifuging can re-use (4000 rpms of rotating speeds, centrifugation time 20min) with the solid-phase catalyst separation;
(2) precipitation steams unreacted methanol recycling;
(3) static layering is isolated raw glycerine acquisition supernatant liquor and is curcas biological diesel oil.
4. detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.7%, and yield is 96.0%.
Embodiment two
1. the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2. the preparation of solid-phase catalyst
Potassium ethanoate and γ-Al
2O
3/ NaY ratio be 30: 60: 100 (wt: wt: wt), with γ-Al
2O
3, NaY and Potassium ethanoate fully mill after directly at 550 ℃ of calcining 8h, take out be placed in the loft drier standby.
3. transesterification reaction
Be that 1: 10 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 1% of the thick oil of Cortex jatrophae, and temperature of reaction is 65 ℃, and reaction pressure is 0.9MPa, reaction times 3h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4. post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5. detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.0%, and yield is 96.3%.
Embodiment three
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Sodium formiate and γ-Al
2O
3Ratio be 50: 100 (wt: wt), with γ-Al
2O
3Placing aqueous sodium formate solution to stir dries then.At 600 ℃ of calcining 6h, taking-up is placed in the loft drier standby.
3, transesterification reaction
Be that 1: 8 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 1% of the thick oil of Cortex jatrophae, and temperature of reaction is 55 ℃, reaction times 5h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.3%, and yield is 96.5%.
Embodiment four
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Sodium tartrate and γ-Al
2O
3Ratio be 50: 100 (wt: wt), with sodium tartrate and γ-Al
2O
3Directly at 450 ℃ of calcining 3h, taking-up is placed in the loft drier standby after fully milling.
3, transesterification reaction
Be that 1: 8 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 2% of the thick oil of Cortex jatrophae, and temperature of reaction is 80 ℃, and reaction pressure is 1.0MPa, reaction times 10h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, content detection
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.4%, and yield is 97.5%.
Embodiment five
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Sodium Propionate and α-Al
2O
3Ratio be 30: 100 (wt: wt), with α-Al
2O
3Be dissolved in the Sodium Propionate methanol solution and place 2h, at 120 ℃ of baking 12h, directly at 450 ℃ of calcining 3h, taking-up is placed in the loft drier standby after fully milling.
3, transesterification reaction
Be that 1: 8 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 2% of the thick oil of Cortex jatrophae, and temperature of reaction is 65 ℃, and reaction pressure is 1.0MPa, reaction times 8h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 97.7%, and yield is 96.1%.
Embodiment six
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Sodium oxalate, magnesium oxalate and γ-Al
2O
3Ratio be 20: 30: 1 00 (wt: wt: wt), with γ-Al
2O
3After fully milling with sodium oxalate, magnesium oxalate directly at 750 ℃ of calcining 6h, take out be placed in the loft drier standby.
3, transesterification reaction
Be that 1: 7 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 1% of the thick oil of Cortex jatrophae, and temperature of reaction is 65 ℃, and reaction pressure is 1.2MPa, reaction times 4h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.9%, and yield is 97.1%.
Embodiment seven
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Magnesium acetate and NaY type zeolite ratio be 50: 100 (wt: wt), after magnesium acetate and NaY type zeolite fully milled directly at 650 ℃ of calcining 7h, take out be placed in the loft drier standby.
3, transesterification reaction
Be that 1: 9 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 1% of the thick oil of Cortex jatrophae, and temperature of reaction is 80 ℃, and reaction pressure is 1.1MPa, reaction times 7h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 97.1%, and yield is 95.9%.
Embodiment eight
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Barium acetate and NaX ratio be 50: 100 (wt: wt), after barium acetate and NaX type zeolite fully milled directly at 650 ℃ of calcining 7h, take out be placed in the loft drier standby.
3, transesterification reaction
Be that 1: 9 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 2% of the thick oil of Cortex jatrophae, and temperature of reaction is 80 ℃, and reaction pressure is 1.0MPa, reaction times 4h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.9%, and yield is 97.2%.
Embodiment nine
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Trisodium Citrate and NaY zeolite ratio be 60: 100 (wt: wt), after Trisodium Citrate and NaY fully milled directly at 650 ℃ of calcining 8h, take out be placed in the loft drier standby.
3, transesterification reaction
Be that 1: 8 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 2% of the thick oil of Cortex jatrophae, and temperature of reaction is 50 ℃, and reaction pressure is 0.9MPa, reaction times 3h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.2%, and yield is 96.4%.
Embodiment ten
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Caoxalate, potassium oxalate and γ-Al
2O
3/ NaY ratio is 30: 30: 50: 100 (wt: wt: wt: wt), with caoxalate, potassium oxalate and γ-Al
2O
3, NaY fully mill after directly at 600 ℃ of calcining 6h, take out be placed in the loft drier standby.
3, transesterification reaction
Be that 1: 8 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 1% of the thick oil of Cortex jatrophae, and temperature of reaction is 55 ℃, and reaction pressure is 1.0MPa, reaction times 7h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.0%, and yield is 95.7%.
Embodiment 11
1, the production technique of the thick oil of barbadosnut seed
The production technique of the thick oil of barbadosnut seed is with embodiment one.
2, the preparation of solid-phase catalyst
Magnesium acetate and α-Al
2O
3/ NaY ratio be 30: 50: 100 (wt: wt: wt), with α-Al
2O
3, NaY and magnesium acetate fully mill after directly at 650 ℃ of calcining 6h, take out be placed in the loft drier standby.
3, transesterification reaction
Be that 1: 7 ratio feeds intake according to thick oil of Cortex jatrophae and methyl alcohol mol ratio in reactor, the solid-phase catalyst consumption is 10% of the thick oil of Cortex jatrophae, and temperature of reaction is 80 ℃, and reaction pressure is 0.9MPa, reaction times 5h.Reaction product is a fatty acid methyl ester, and by product is a raw glycerine.
4, post-reaction treatment
Transesterification reaction finishes its aftertreatment with embodiment one.
5, detect
Wherein the triglyceride level transformation efficiency is 100% after testing, and fatty acid methyl ester is 96.0%, and yield is 95.8%.
The invention has the beneficial effects as follows: simple, the cost of material of (1) preparation solid-phase catalyst technology Low and reusable; (2) simplified the biodiesel step of preparation process, solved and produced The wastewater problem that produces in the journey; (3) under the prerequisite that guarantees methyl esters content, improved biodiesel Productive rate; (4) through the test of provincial constitutional law location survey examination department, the biodiesel of this law preparation its Physicochemical property meets German EDIN51606 standard, economic stimuli performance and 0#Diesel oil is close, The consumption rate of fuel oil etc. does not have significant difference, and discharge performance has obvious improvement, particularly The carcinogen such as elimination aromatic compounds in the tail gas. And sulfide and carbide Discharging and smoke intensity value reduce significantly, and environment-friendly advantage is obvious.
Claims (7)
1. a solid catalysis method prepares method of bio-diesel oil by barbadosnut seed oil, it is characterized by: preparation Cortex jatrophae oil is as raw material, by basic metal, alkaline-earth metal organic salt and composition thereof with comprise Al
2O
3Or Zeolite support in interior calcining and the condition that exists of compound solid-phase catalyst under, with methyl alcohol generation transesterification reaction, reaction conditions: solid-phase catalyst consumption 0.5～20%, the thick oil of barbadosnut seed is 1: 5～1: 20 with the ratio of methyl alcohol, temperature of reaction 50-80 ℃, pressure is 0.9～1.5MPa, and the reaction times is 1～10h, obtain reacting the thick ester of principal product through aftertreatment, obtain the target product biofuel.
2. a kind of solid catalysis method according to claim 1 prepares method of bio-diesel oil by barbadosnut seed oil, it is characterized by: such solid catalyst is composite catalyst, be baking mixed by any mixture and the carrier of the organic salt of alkali-metal organic salt or alkaline-earth metal or above alkaline metal organic salt and alkaline-earth metal organic salt, the condition of reaction is roasting pressure 0.9～1.1MPa, 400～1000 ℃ of maturing temperatures, roasting time 1～10h, carrier is meant Al
2O
3Or NaY type zeolite, NaX type zeolite or Al2O3/NaY or Al
2O
3/ NaX or NaY/NaX.
3. a kind of solid catalysis method according to claim 1 and 2 prepares method of bio-diesel oil by barbadosnut seed oil, it is characterized by: the alkaline metal organic salt of compound solid-phase catalyst is selected lithium formate, sodium formiate, potassium formiate, the formic acid rubidium, cesium formate, Lithium Acetate, sodium-acetate, Potassium ethanoate, the acetic acid rubidium, cesium acetate, the propionic acid lithium, Sodium Propionate, potassium propionate, the propionic acid rubidium, cesium acetate, the butyric acid lithium, Sodium propanecarboxylate, potassium butyrate, the butyric acid rubidium, the butyric acid caesium, the 2 Methylpropionic acid lithium, 2 Methylpropionic acid sodium, 2 Methylpropionic acid potassium, the 2 Methylpropionic acid rubidium, the 2 Methylpropionic acid caesium, lithium valerate, natrium valericum, valeric acid potassium, the valeric acid rubidium, the valeric acid caesium, the 2-Methyl Butyric Acid lithium, 2-Methyl Butyric Acid sodium, 2-Methyl Butyric Acid potassium, the 2-Methyl Butyric Acid rubidium, the 2-Methyl Butyric Acid caesium, the 3 Methylbutanoic acid lithium, 3 Methylbutanoic acid sodium, 3 Methylbutanoic acid potassium, the 3 Methylbutanoic acid rubidium, the 3 Methylbutanoic acid caesium, 2,2-neopentanoic acid lithium, 2,2-neopentanoic acid sodium, 2,2-neopentanoic acid potassium, 2,2-neopentanoic acid rubidium, 2,2-neopentanoic acid caesium, oxalic acid hydrogen lithium, sodium bioxalate, potassium binoxalate, oxalic acid hydrogen rubidium, oxalic acid hydrogen caesium, lithium oxalate, sodium oxalate, potassium oxalate, the oxalic acid rubidium, cesium oxalate, propanedioic acid hydrogen lithium, propanedioic acid hydrogen sodium, propanedioic acid hydrogen potassium, propanedioic acid hydrogen rubidium, propanedioic acid hydrogen caesium, the propanedioic acid lithium, sodium malonate, propanedioic acid potassium, the propanedioic acid rubidium, the propanedioic acid caesium, Succinic Acid hydrogen lithium, sodium bisuccinate, Succinic Acid hydrogen potassium, Succinic Acid hydrogen rubidium, Succinic Acid hydrogen caesium, the Succinic Acid lithium, Soduxin, potassium succinate, the Succinic Acid rubidium, the Succinic Acid caesium, tartarlithine, sodium hydrotartrate, tartarus, the hydrogen tartrate rubidium, cesium bitartrate, lithium tartrate, sodium tartrate, soluble tartrate, rubidium tartrate, the tartrate caesium, the hydrogen malate lithium, sodium hydrogen malate, hydrogen malate potassium, the hydrogen malate rubidium, the hydrogen malate caesium, the oxysuccinic acid lithium, sodium malate, potassium malate, the oxysuccinic acid rubidium, the oxysuccinic acid caesium, the dihydrogen citrate lithium, Sodium citrate, potassium citrate dihydrogen, the dihydrogen citrate rubidium, the dihydrogen citrate caesium, hydrogen citrate two lithiums, Monobasic sodium citrate, the hydrogen citrate dipotassium, hydrogen citrate two rubidiums, hydrogen citrate two caesiums, Lithium Citrate de, Trisodium Citrate, Tripotassium Citrate, the citric acid rubidium, the mixture of any one or a few in the citric acid caesium.
4. a kind of solid catalysis method according to claim 1 and 2 prepares method of bio-diesel oil by barbadosnut seed oil, it is characterized by: compounding solid catalyst alkaline-earth metal organic salt is selected magnesium formiate, calcium formiate, strontium formate, barium formate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, propionic acid magnesium, calcium propionate, the propionic acid strontium, barium propionate, magnesium butyrate, Calcium Butyrate, the butyric acid strontium, butyric acid barium, 2 Methylpropionic acid magnesium, 2 Methylpropionic acid calcium, the 2 Methylpropionic acid strontium, 2 Methylpropionic acid barium, valeric acid magnesium, valeric acid calcium, the valeric acid strontium, valeric acid barium, 2-Methyl Butyric Acid magnesium, 2-Methyl Butyric Acid calcium, the 2-Methyl Butyric Acid strontium, 2-Methyl Butyric Acid barium, 3 Methylbutanoic acid magnesium, 3 Methylbutanoic acid calcium, the 3 Methylbutanoic acid strontium, 3 Methylbutanoic acid barium, 2,2-neopentanoic acid magnesium, 2,2-neopentanoic acid calcium, 2,2-neopentanoic acid strontium, 2,2-neopentanoic acid barium, magnesium oxalate, caoxalate, strontium oxalate, barium oxalate, propanedioic acid magnesium, propanedioic acid calcium, the propanedioic acid strontium, propanedioic acid barium, Succinic Acid magnesium, calcium succinate, the Succinic Acid strontium, barium succinate, magnesium tartrate, calcium tartrate, strontium tartrate, barium tartrate, magnesium malate, calcium malate, strontium malate, barium malate, magnesium citrate, citrate of lime, strontium citrate, in the barium citrate any or several mixtures.
5. a kind of solid catalysis method according to claim 1 and 2 prepares method of bio-diesel oil by barbadosnut seed oil, it is characterized by: solid-phase catalyst carrier A l
2O
3Select α-Al
2O
3Or β-Al
2O
3Or γ-Al
2O
3In any one or a few mixing.
6. a kind of solid catalysis method according to claim 1 prepares method of bio-diesel oil by barbadosnut seed oil, it is characterized by: the production method of barbadosnut seed oil adopts spiral oil press to squeeze, seed parch temperature is at 50～150 ℃, press the thorax initial temperature and be decided to be 130～170 ℃, oil cake thickness is 1.5～3.0cm.
7. a kind of solid catalysis method according to claim 1 prepares method of bio-diesel oil by barbadosnut seed oil, it is characterized by: the method for its aftertreatment is a direct centrifugation catalyzer after reaction finishes, then reaction mixture is directly distilled and remove methyl alcohol, last static layering, the upper strata is the product biofuel.
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| CN101161784B (en) * | 2007-11-22 | 2011-11-16 | 中国农业科学院油料作物研究所 | Method for extracting conversion biodiesel from oil pressing cake |
| CN101427730B (en) * | 2008-10-14 | 2011-09-14 | 上海三瑞高分子材料有限公司 | Method for abstracting and removing phorbol ester from barbadosnut seed oil meal |
| CA2773546A1 (en) * | 2009-09-07 | 2011-03-10 | Council Of Scientific & Industrial Research | Integrated process for the production of jatropha methyl ester and by products |
| JP5964327B2 (en) | 2011-02-14 | 2016-08-03 | カウンスィル オブ サイエンティフィック アンド インダストリアル リサーチＣｏｕｎｃｉｌ Ｏｆ Ｓｃｉｅｎｔｉｆｉｃ ＆ Ｉｎｄｕｓｔｒｉａｌ Ｒｅｓｅａｒｃｈ | Improved process for producing fatty acid alkyl esters (biodiesel) from triglyceride oils by using environmentally friendly solid base catalysts |
| CN102336644A (en) * | 2011-07-26 | 2012-02-01 | 华中科技大学 | Alkyl substituted acetate and application of alkyl substituted acetate in organic electroluminescent device |
| CN104475160A (en) * | 2014-11-29 | 2015-04-01 | 南京威安新材料科技有限公司 | Production method of high-efficiency catalyst |
| CN108271777A (en) * | 2018-02-02 | 2018-07-13 | 安徽省厚博生态农业有限公司 | A kind of combined insecticide of agricultural high-effiency |
| CN108855030B (en) * | 2018-06-01 | 2021-04-20 | 西北大学 | Composite solid base catalyst and application of composite solid base catalyst in preparation of biodiesel by catalyzing ester exchange |
| CN108865293A (en) * | 2018-06-28 | 2018-11-23 | 鹿寨知航科技信息服务有限公司 | A method of utilizing woody oleiferous plants biodiesel synthesis |
| CN113769770B (en) * | 2020-06-09 | 2024-04-02 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate by transesterification, catalyst and application |
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| CN1557914A (en) * | 2004-02-04 | 2004-12-29 | 罗羽林 | Biological diesel oil and method for preparing same |
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| CN1279663A (en) * | 1997-11-24 | 2001-01-10 | 能源环境技术股份有限公司 | Method and equipment for producing fatty acid methyl ester |
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