CN102807923A - Method for synthesizing biodiesel with high cetane number and catalyst thereof - Google Patents
Method for synthesizing biodiesel with high cetane number and catalyst thereof Download PDFInfo
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Abstract
The invention relates to a method for synthesizing biodiesel with high cetane number by catalyzing one step ester exchange of highly unsaturated fat and hydrogenation reaction, and catalyst thereof. Bifunctional catalyst alkaline earth metallic oxide loading copper oxide is prepared by chemisorption hydrolysis together with vacuum calcination with alkaline earth metallic oxide prepared by vacuum calcination as the carrier. The method includes the following steps: adding unsaturated fat, lower alcohol and catalyst to a high pressure reactor and mixing up based on the alcohol-fat molar ratio of 6-36:1 and fat-catalyst weight ratio of 1:0.01-1:0.1; filling nitrogen and hydrogen in turn to change the gas in the high pressure reactor, then sealing the reactor for heating and mixing; as the temperature rises to 150-220 DEG C, filing 1-10MPa hydrogen; after 2-20h of reaction, removing the solid catalyst of the reaction product by filtration, separating the glycerol layer, evaporating alcohol and finally getting biodiesel which contains single unsaturated oleic acid ester transformed from polyunsaturated low carbon ester with high cetane number over 51 and other properties that meet German Standard, such as low temperature liquidity and antioxidation stability.
Description
Technical field
The present invention relates to a kind of synthetic high hexadecane value method for synthesizing biological fuel-oil of high unsaturated animal-plant oil and catalyzer thereof of being used for, the preparation method and the high unsaturated animal-plant oil of catalysis thereof that specifically disclose the dual-function catalyst of catalytic one-stage transesterification reaction and selective hydrogenation carry out a step transesterification reaction and the synthetic high hexadecane value method for synthesizing biological fuel-oil of selective hydrogenation.
Background technology
Biofuel is to utilize renewable biomass production such as animal-plant oil to be used for substituting the New-type fuel of the clean and safe of petrifaction diesel; Staple is that the long-chain of 14～22 carbon is saturated, unsaturated fatty acids is with the formed fatty ester of low-carbon alcohol, is mainly fatty acid methyl ester.Along with the enhancing gradually of the worsening shortages and the environmental protection consciousness of petrochemical industry resource, biofuel has worldwide formed the research and development upsurge as a kind of eco-friendly renewable new forms of energy.
At present, biofuel mainly adopts the chemical method of transesterification reaction to produce.Traditional ester exchange process is to be the homogeneous phase technology of catalyzer with liquid acid or alkali, the purifying products of gained and separation difficulty, and also yield is lower, and high to equipment requirements.The waste water of discharging in this process in addition, brings severe contamination to environment.The applied research of solid alkali in chemical process more and more widely.Compare with liquid base; Solid alkali have can be recycled, environmental friendliness, reaction conditions are gentle, product is easy to separate, can make the serialization of reaction process process, improves equipment advantages such as throughput, thereby in production of biodiesel technology, adopt the solid alkali heterogeneous catalysis to have more advantage than liquid base homogeneous catalysis.Like Chinese patent CN200610103268, CN200910026830, CN200810035283; CN200810035282, CN200810035288, CN200910045652; CN201010162301, CN200710171903, CN200910008817 have reported the method for solid base catalyst catalysis animal-plant oil transesterification reaction biodiesel synthesis; Find that solid base catalyst preparation technology is simple; Carry out having very strong catalytic activity in the transesterification reaction biodiesel synthesis process at grease and short chain alcohol, the biofuel yield is high, and catalyzer is reusable.
Yet; The vegetables oil of business development at present is mainly edible rapeseed oil, VT 18, plam oil and sunflower seeds wet goods oil product; Basically use rapeseed oil and sunflower seed oil to do raw material like Europe, torrid areas country adopts plam oil to do raw material, and raw material is then done with VT 18 and animal tallow by the U.S..And as edible grease expensive, supply falls short of demand, and therefore, intense stimulus and utilized inedible oil to produce the development research of thing diesel oil next life.At present, more than 350 kind of oil plant (Dorado, M. P. have been discerned; Ballesteros, E., L ó pez; F. J., Mittelbach, M.. Optimization of Alkali-Catalyzed Transesterification of Brassica Carinata Oil for Biodiesel Production. Energy Fuels; 2004,18:77 – 83.), wherein 75 vegetable oil are converted into biofuel; Iodine number and cetane value be (Azam, M. M., Waris between 4.8-213 and 20.56-67.47 respectively; A., Nahar, N. M.. Prospects and potential of fatty acid methyl esters of some non-traditional seed oils for use as biodiesel in India. Biomass Bioenergy; 2005,29:293 – 302.), wherein the overwhelming majority is a consaturated oil; More have nearly 16 kinds to be high polyunsaturated vegetable oil, iodine number is between 125-213, and the cetane value of obtained biofuel is between 20.56 and 45.20.Yet, no matter adopting which kind of raw material, biofuel will realize the scale marketization, the quality of biofuel must reach corresponding quality standard.At present; The biofuel quality standard has European standard EN14214, USS ASTM D6751, DIN DIN51606 and Chinese Industrial Standards (CIS) GB/T20828-2007 etc. in the world; Standard-required biofuel iodine number is less than 120; Cetane value is greater than 49, and high consaturated oil like this just is difficult to the biofuel quality standard that reaches all.
In order to utilize consaturated oil especially is the biofuel that production iodine number such as non-edible high consaturated oil such as hempseed oil, rubber seed oil, tung oil, oleum lini, canola oil and cetane value satisfy standard, prepared fatty acid methyl ester is carried out selective hydrogenation reduce that its degree of unsaturation improves cetane value simultaneously and antioxidative stabilizer is a feasible route.Like international monopoly WO 2006111997 A1 high consaturated oil is disclosed through the synthetic two-step process that satisfies the biofuel of standard with the improvement of fatty acid methyl ester partial hydrogenation synthesising property of fatty acid methyl ester; Two-step approach adopts two covering devices; Two reactions that separate; Two kinds of catalyzer need very long reaction times and technological operation simultaneously, have increased the cost of biofuel undoubtedly.So be necessary to develop the preparation method that the high unsaturated animal-plant oil transesterification reaction of a kind of step catalysis and selective hydrogenation synthesize the high hexadecane value method of bio-diesel oil and be used for the dual-function catalyst of this method.
Summary of the invention
The purpose of this invention is to provide a kind ofly, specifically disclose the preparation method that high unsaturated one step of the vegetable and animals oils transesterification reaction of a kind of catalysis and hydrogenation reaction are synthesized the high hexadecane value method for synthesizing biological fuel-oil and be used for the dual-function catalyst of this technology by synthetic high hexadecane value method for synthesizing biological fuel-oil of high consaturated oil and catalyzer thereof.
Technical scheme of the present invention:
A kind of dual-function catalyst that is used for high one step of consaturated oil transesterification reaction and the synthetic high hexadecane value biofuel of selective hydrogenation disclosed herein; It comprises basic oxide carrier and cupric oxide; Wherein the mass ratio of basic oxide and cupric oxide is 1.0:0.01 – 1.0:0.6; Preferred 1.0:0.05 – 1.0:0.3, more preferably 1.0:0.07 – 1.0:0.2, most preferably 1.0:0.09 – 1.0:0.1.Wherein the cupric oxide high dispersing forms the copper based compound with strong interaction in carrier surface or with carrier.
Embodiment of the present invention are summarized as follows:
⑴ the dual-function catalyst of catalytic one-stage transesterify and hydrogenation reaction and by the method for consaturated oil biodiesel synthesis; It is characterized in that dual-function catalyst is made up of the alkaline earth metal oxide loaded copper oxide, consaturated oil is through one step of dual-function catalyst catalyzed transesterification and selective hydrogenation biodiesel synthesis.
⑵ the alkaline earth metal oxide that above 1 comprises Natural manganese dioxide, quicklime, strontium oxide and barium oxide.
⑶ the alkaline earth metal oxide that above 1 or 2 is produced the alkaline earth metal oxide precursor by alkine earth metal nitrate and precipitation agent volatile salt, yellow soda ash, oxalic acid, urea reaction; Make through vacuum calcining then, perhaps make by alkaline earth metal hydroxides and the thermolysis of alkaline earth metal carbonate vacuum.
⑷ the dual-function catalyst that above 1 adopts the chemisorption hydrolysis method to make; Concrete steps are that alkaline earth metal oxide and PH are that 9 copper ammon solution mixes; Dilute afterwards, leave standstill, the cupric oxide precursor is loaded on the alkaline earth metal oxide, make through vacuum calcining then.
⑸ the mass ratio of cupric oxide and alkaline earth metal oxide is 1 %-40 % in the dual-function catalyst that above 1 and 4.
⑹ the vacuum calcining temperature that above 3 and 4 is 500-1200 ℃, and calcination time is 2-6 h.
⑺ the consaturated oil that above 1 comprises a kind of, two or more mixing oil in hempseed oil, tung oil, rapeseed oil, tea-seed oil, rubber seed oil, VT 18, canola oil, the oleum lini.
⑻ the method by the consaturated oil biodiesel synthesis that above 1 is one step of dual-function catalyst catalysis consaturated oil transesterification reaction and hydrogenation reaction biodiesel synthesis.
⑼ the step transesterify that above 1 and 8 and the temperature of reaction of hydrogenation reaction are 150-300 ℃, and hydrogen pressure is 1-10 MPa, and the reaction times is 1-20 h.
Alkaline earth metal oxide loaded copper oxide dual-function catalyst of the present invention comprises the steps:
1, the preparation method of alkaline earth metal oxide carrier
The preparation of said alkaline earth metal oxide can be adopted following method:
A: make alkaline earth metal oxide by the alkaline earth metal carbonate vacuum calcining; Said alkaline earth metal carbonate comprises magnesiumcarbonate, lime carbonate, Strontium carbonate powder and barium carbonate, and the vacuum calcining temperature is 500-1200 ℃, preferred 900-1000 ℃; The vacuum calcining time is 2-6 h, preferred 3-4 h.
B: make alkaline earth metal oxide by the alkaline earth metal hydroxides vacuum calcining; Said alkaline earth metal hydroxides comprises Marinco H, calcium hydroxide, strontium hydroxide and hydrated barta; The vacuum calcining temperature is 500-1200 ℃; Preferred 800-900 ℃, the vacuum calcining time is 2-6 h, preferred 3-4 h.
C: make precursor by alkine earth metal nitrate solution through precipitation agent, washing then, oven dry, vacuum calcining makes alkaline earth metal oxide.Said alkine earth metal nitrate comprises magnesium nitrate, nitrocalcite, strontium nitrate, nitrate of baryta; Precipitation agent comprises yellow soda ash, sodium hydrogencarbonate, volatile salt, bicarbonate of ammonia, ammoniacal liquor, oxalic acid; Drying course is that the vacuum calcining temperature was 500-1200 ℃ 120 ℃ of following constant temperature 12 hours, preferred 900-1000 ℃; Calcination time is 2-6 h, preferred 3-4 h.
2, alkaline earth metal oxide loaded copper oxide catalyst preparation method
The present invention adopts the precursor of chemisorption hydrolysis method loaded copper oxide on alkaline earth metal oxide, makes the alkaline earth metal oxide loaded copper oxide catalyst through calcining then.At first preparing copper ammon solution, ammoniacal liquor is joined in the copper nitrate solution, is 9 up to the solution pH value; Then alkaline earth metal oxide is added in the copper ammon solution, stirred 20-60 minute, slowly dilute then, leave standstill the copper component is homogeneously precipitated on the alkaline earth metal oxide carrier; Refilter; Washing, oven dry, vacuum calcining makes the alkaline earth metal oxide loaded copper oxide catalyst.
The mass ratio of cupric oxide and alkaline earth metal oxide is 1.0:99.0-30.0:70.0 among the preparation method of the present invention, preferred 10.0:90.0-30.0:70.0, preferred again 10.0:90.0.
The calcining temperature of alkaline earth metal oxide loaded copper oxide catalyst is 500-1100 ℃ among the preparation method of the present invention, and preferred 800-1000 ℃, calcination time is 2-5 hour, preferred 3 hours.
The method that high consaturated oil disclosed by the invention carries out a step transesterification reaction and hydrogenation reaction biodiesel synthesis is following:
Mol ratio and catalyzer by low-carbon alcohol: vegetable and animals oils=6.0:1.0-36.0:1.0: the weight ratio of vegetable and animals oils=1.0 %-10.0 %, take by weighing refining vegetable and animals oils, packing into has in the autoclave of heating, whipping appts; With the alkaline earth metal oxide loaded copper oxide catalyst with move in the autoclave in the lump after low-carbon alcohol is mixed; Air in first inflated with nitrogen in turn and the hydrogen exchange autoclave three times seals the still heated and stirred then, is warming up to temperature of reaction; Charge into predetermined pressure and begin reaction; After reaction arrives setting-up time, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is glycerine, low-carbon alcohol and catalyst mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, residual solution recycles.Lower floor's mixture obtains catalyzer through suction filtration, and filtrating obtains low-carbon alcohol through fractionation by distillation and recycles, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.The pufas linolenic and linoleic significantly reduces in the gained biofuel product; Single unsaturated fatty acids methyl linoleate significantly raises; Saturated fatty acid methyl ester such as hard fatty acids methyl esters and Uniphat A60 content are constant; Thereby greatly reduce the biofuel degree of unsaturation, make its iodine number drop to 120 gI
2Below/the 100g, cetane value is increased to more than 49, even to more than 51, the reduction of degree of unsaturation has also improved the antioxidative stabilizer of biofuel.
Require through the vacuum calcining activation for the alkaline earth metal oxide loaded copper oxide catalyst that uses in the present invention.
The present invention adopts the unsaturated vegetable and animals oils of purified, comprises a kind of, two or more mixing oil in purified hempseed oil, tung oil, rapeseed oil, tea-seed oil, rubber seed oil, VT 18, canola oil, oleum lini, butter, Viscotrol C, wilson dogwood oil, numb maple oil, tea oil, Oleum Cocois, til, Thistle oil, Rice pollard oil, sweet oil, Semen Maydis oil, peanut oil, the Oleum Gossypii semen." the making with extra care " of here using refers to that purity is more than 95 % through sweet three esters of purifying, and the acid number of raw oil is at 0-2 mg KOHg
-1, moisture is at 0-2 % (w/w), and phosphatide is at 0-0.22 % (w/w).
The raw oil staple is the mixture of triglyceride, and its molecular-weight average is calculated by the size of saponification value, and formula is: greasy molecular-weight average=168300/ saponification value, wherein saponification value is measured by standard GB 5534-85.For example the soap value test of hempseed oil is 190.0, and its molecular-weight average=168300/ saponification value=885.79, the molecular-weight average of other raw oils also calculate in this way.
The low-carbon alcohol that the present invention adopts is a C1-C4 alcohol, comprises methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol and isopropylcarbinol etc., particular methanol and ethanol, particular methanol again.
Among the present invention, the mol ratio of low-carbon alcohol and vegetable and animals oils depends on the kind of low-carbon alcohol and vegetable and animals oils.The mol ratio of low-carbon alcohol and vegetable and animals oils is 6.0:1.0-36.0:1.0, preferred 12.0:1.0-18.0:1.0.
The consumption of biodiesel synthesis alkaline earth metal oxide loaded copper oxide catalyst of the present invention is 1.0 %-10.0 % of refining animal-plant material weight, preferred 3.0 %-6.0 %.
Temperature of reaction in the inventive method is 150-3000 ℃, and preferred 180-200 ℃, hydrogen pressure is 1.0 MPa-10.0 MPa, preferred 2.0-4.0 MPa, preferred again 3.0 MPa.
Reaction times in the inventive method is depended on kind and the consumption of vegetable and animals oils and low-carbon alcohol, Hong thunder and the consumption and the reflection condition of alkaline earth metal oxide loaded copper oxide catalyst.Reaction times is 1.0-20.0 h, preferred 3-5 h.
Adopt fatty acid methyl ester composition in the gas chromatograph for determination biofuel in the inventive method, used gas chromatograph model is SP3420, and chromatographic column is BFSP-0677-02, and employing acetone is solvent, and wintergreen oil is an internal standard substance.
The product quality indicator of the open fatty acid methyl ester biofuel of the present invention
| Project name | Product index | GB/T20828-2007 | EN14214 | DIN51606 | Measuring method |
| Cetane value | ≥51 | ≥49 | ≥51 | ≥49 | GB/T 386-91 |
| Kinematic viscosity (20 ℃)/mm 2·s -1 | 3.0-5.0 | 3.0-8.0 | 3.5-5.0 | 3.5-5.0 | ASTM D445 |
| Flash-point (remaining silent)/℃ | >;110 | 130 | ≥120 | >;110 | ASTM D93 |
| Moisture/mgkg -1 | <300 | Vestige | ≤500 | < 300 | SH/T 0246-92 |
| Cold filter clogging temperature/℃ | <-5 | -- | ≤-2 | 0/-10/-20 | IP 309 |
| Carbon residue/% | ≤0.02 | ≤0.3 | ≤0.3 | <0.05 | ASTM D4530 |
| Iodine number/gI 2/100 g | < 115 | -- | < 120 | < 115 | AOCS 1089 |
| Calorific value/MJkg -1 | >;38 | -- | -- | -- | ASTM D4809 |
| Density (20 ℃)/gmL -1 | 0.84-0.88 | 0.86-0.90 | 0.86-0.90 | 0.875-0.90 | GB/T1884-2000 |
| Acid value/mgKOHg -1 | <0.04 | ≤0.5 | ≤0.5 | ≤0.5 | GB 5530-85 |
Product index, biofuel quality standard and measuring method are listed in table.Biofuel product each item index of the present invention reaches Chinese GB/T20828-2007, European EN14214 and German DIN51606 biofuel quality standard.
Advantage of the present invention
(1) a step transesterification reaction disclosed by the invention and hydrogenation reaction and catalyzer thereof not only are suitable for the not too high Oleum Gossypii semen of degree of unsaturation, peanut oil, sunflower seed oil, plam oil; And be suitable for high undersaturated hempseed oil, tung oil, rapeseed oil, tea-seed oil, rubber seed oil; Realized having widened the biodiesel raw material source by the purpose of the good biofuel of high polyunsaturated vegetable oil synthesising property.
(2) the present invention is directed to the requirement of biofuel character, combine with modification biofuel is synthetic, compare, reduced catalyst levels, simplified Production Flow Chart, reduced cost of equipment, improved the performance of biofuel with the disclosed two-step approach of international monopoly.
(3) the direct high unsaturated animal-plant oil that does not reach standard-required through transesterification reaction synthetic biofuel character; After a step transesterification reaction and hydrogenation reaction technology; Character such as iodine number and cetane value improves greatly, has reached European EN14214, German DIN51606 China GB/T20828-2007 biofuel quality standard.
(4) adopt one step of alkaline earth metal oxide loaded copper oxide catalyst catalysis vegetable and animals oils transesterification reaction and hydrogenation reaction biodiesel synthesis technological process simple; Catalyst levels is little, cost is low, and catalyst separating simply and continuously recycles, and the aftertreatment of biofuel product is easy; Its productive rate can reach more than 96 %; Sub product glycerine separates purifies simply, reacts remaining low-carbon alcohol reusable edible, has reduced the cost of production biofuel.
Embodiment
Embodiment 1
21.163 g strontium nitrates are dissolved in the 200 mL deionized waters obtain strontium nitrate solution, 19.13 g volatile salts are dissolved in the 500 mL deionized waters obtain sal volatile then.Sal volatile is dropwise splashed in the above-mentioned strontium nitrate solution, drip off the back restir and react 3 h, then filter and obtain the precursor deposition, washing then in 120 ℃ of following constant temperature dryings 12 hours, makes strontium oxide at 1000 ℃ of following vacuum calcining 5 h.3.147 g cupric nitrates being dissolved in the deionized water, adding ammoniacal liquor then, is 9 up to the solution pH value; Then strontium oxide is added in the copper ammon solution, stirred 20 minutes, slowly diluting soln makes the copper precipitation from homogeneous solution and is dispersed on the strontium oxide carrier then; Filter then; Washing in 120 ℃ of following constant temperature dryings 12 hours, makes the strontium oxide loaded copper oxide catalyst at 1000 ℃ of following vacuum calcining 5 h.
Selective finishing hempseed oil and methyl alcohol are raw material, press mol ratio and the catalyzer of methyl alcohol: hempseed oil=12.0:1.0 respectively: the mass ratio of hempseed oil=3.0:100.0 takes by weighing the refining hempseed oil of 90.54 g; Add and have in the high-pressure reactor of whisking appliance, thermopair and prolong; With the catalyzer that makes in the present embodiment 2.72 g with move in the lump in the autoclave after 39.83 g anhydrous methanols mix, in turn with the air in nitrogen and the hydrogen exchange reaction under high pressure three times, be warming up to 180 ℃ then; Charge into the hydrogen of 3.0 MPa; Constant temperature stirring reaction 3.0 h, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is catalyzer, glycerine and residue methanol mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, the distillatory methanol loop is used.Lower floor's mixture obtains catalyzer and filtrating through suction filtration, and filtrating goes out methanol loop through fractionation by distillation uses, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.Through the gas chromatographic analysis product is fatty acid methyl ester, and the productive rate of calculating is 96%.Linolenic acid methylester content is 0.49 % in the gained biofuel product, and methyl linoleate content is 41.73%, and Witconol 2301 content is 46.65%, and hard fatty acids methyl esters content is 2.76%, and Uniphat A60 content is 6.64 %, and iodine number is 113 gI
2/ 100g, cetane value is 55.
Embodiment 2
21.163 g strontium nitrates are dissolved in the 200 mL deionized waters obtain strontium nitrate solution, 9.04 g oxalic acid are dissolved in the 500 mL deionized waters obtain oxalic acid solution then.Oxalic acid solution is dropwise splashed in the above-mentioned strontium nitrate solution, drip off the back restir and react 3 h, then filter and obtain the precursor deposition, washing then in 120 ℃ of following constant temperature dryings 12 hours, makes strontium oxide at 1000 ℃ of following vacuum calcining 5 h.3.147 g cupric nitrates being dissolved in the deionized water, adding ammoniacal liquor then, is 9 up to the solution pH value; Then strontium oxide is added in the copper ammon solution, stirred 20 minutes, slowly diluting soln makes the copper precipitation from homogeneous solution and is dispersed on the strontium oxide carrier then; Filter then; Washing in 120 ℃ of following constant temperature dryings 12 hours, makes the strontium oxide loaded copper oxide catalyst at 1000 ℃ of following vacuum calcining 5 h.
Selective finishing hempseed oil and methyl alcohol are raw material, press mol ratio and the catalyzer of methyl alcohol: hempseed oil=12.0:1.0 respectively: the mass ratio of hempseed oil=3.0:100.0 takes by weighing the refining hempseed oil of 90.54 g; Add and have in the high-pressure reactor of whisking appliance, thermopair and prolong; With the catalyzer that makes in the present embodiment 2.72 g with move in the lump in the autoclave after 39.83 g anhydrous methanols mix, in turn with the air in nitrogen and the hydrogen exchange reaction under high pressure three times, be warming up to 180 ℃ then; Charge into the hydrogen of 3.0 MPa; Constant temperature stirring reaction 3.0 h, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is catalyzer, glycerine and residue methanol mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, the distillatory methanol loop is used.Lower floor's mixture obtains catalyzer and filtrating through suction filtration, and filtrating goes out methanol loop through fractionation by distillation uses, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.Through the gas chromatographic analysis product is fatty acid methyl ester, and the productive rate of calculating is 96%.The iodine number of analyzing the fatty acid methyl ester product is 114, and cetane value is 54.
Embodiment 3
12.164 g, eight water strontium hydroxides are made strontium oxide in 1000 ℃ of following vacuum calcining 5 h.3.147 g cupric nitrates being dissolved in the deionized water, adding ammoniacal liquor then, is 9 up to the solution pH value; Then strontium oxide is added in the copper ammon solution, stirred 20 minutes, slowly diluting soln makes the copper precipitation from homogeneous solution and is dispersed on the strontium oxide carrier then; Filter then; Washing in 120 ℃ of following constant temperature dryings 12 hours, makes the strontium oxide loaded copper oxide catalyst at 1000 ℃ of following vacuum calcining 5 h.
Selective finishing hempseed oil and methyl alcohol are raw material, press mol ratio and the catalyzer of methyl alcohol: hempseed oil=12.0:1.0 respectively: the mass ratio of hempseed oil=3.0:100.0 takes by weighing the refining hempseed oil of 90.54 g; Add and have in the high-pressure reactor of whisking appliance, thermopair and prolong; With the catalyzer that makes in the present embodiment 2.72 g with move in the lump in the autoclave after 39.83 g anhydrous methanols mix, in turn with the air in nitrogen and the hydrogen exchange reaction under high pressure three times, be warming up to 180 ℃ then; Charge into the hydrogen of 3.0 MPa; Constant temperature stirring reaction 3.0 h, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is catalyzer, glycerine and residue methanol mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, the distillatory methanol loop is used.Lower floor's mixture obtains catalyzer and filtrating through suction filtration, and filtrating goes out methanol loop through fractionation by distillation uses, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.Through the gas chromatographic analysis product is fatty acid methyl ester, and the productive rate of calculating is 96%.The iodine number of analyzing the fatty acid methyl ester product is 117, and cetane value is 53.
Embodiment 4
14.763 g Strontium carbonate powders are made strontium oxide in 1000 ℃ of following vacuum calcining 5 h.3.147 g cupric nitrates being dissolved in the deionized water, adding ammoniacal liquor then, is 9 up to the solution pH value; Then strontium oxide is added in the copper ammon solution, stirred 20 minutes, slowly diluting soln makes the copper precipitation from homogeneous solution and is dispersed on the strontium oxide carrier then; Filter then; Washing in 120 ℃ of following constant temperature dryings 12 hours, makes the strontium oxide loaded copper oxide catalyst at 1000 ℃ of following vacuum calcining 5 h.
Selective finishing hempseed oil and methyl alcohol are raw material, press mol ratio and the catalyzer of methyl alcohol: hempseed oil=12.0:1.0 respectively: the mass ratio of hempseed oil=3.0:100.0 takes by weighing the refining hempseed oil of 90.54 g; Add and have in the high-pressure reactor of whisking appliance, thermopair and prolong; With the catalyzer that makes in the present embodiment 2.72 g with move in the lump in the autoclave after 39.83 g anhydrous methanols mix, in turn with the air in nitrogen and the hydrogen exchange reaction under high pressure three times, be warming up to 180 ℃ then; Charge into the hydrogen of 3.0 MPa; Constant temperature stirring reaction 3.0 h, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is catalyzer, glycerine and residue methanol mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, the distillatory methanol loop is used.Lower floor's mixture obtains catalyzer and filtrating through suction filtration, and filtrating goes out methanol loop through fractionation by distillation uses, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.Through the gas chromatographic analysis product is fatty acid methyl ester, and the productive rate of calculating is 96%.The iodine number of analyzing the fatty acid methyl ester product is 115, and cetane value is 54.
Embodiment 5
25.64 g magnesium nitrate hexahydrates are dissolved in the 200 mL deionized waters obtain strontium nitrate solution, 19.13 g volatile salts are dissolved in the 500 mL deionized waters obtain sal volatile then.Sal volatile is dropwise splashed in the above-mentioned magnesium nitrate solution, drip off the back restir and react 3 h, then filter and obtain the precursor deposition, washing then in 120 ℃ of following constant temperature dryings 12 hours, makes Natural manganese dioxide at 1000 ℃ of following vacuum calcining 5 h.6.294 g nitrate trihydrate copper dissolutions in deionized water, are added ammoniacal liquor then, are 9 up to the solution pH value; Then Natural manganese dioxide is added in the copper ammon solution, stirred 20 minutes, slowly diluting soln makes the copper precipitation from homogeneous solution and is dispersed on the magnesium oxide carrier then; Filter then; Washing, in 120 ℃ of following constant temperature dryings 12 hours, 1000 ℃ down calcining 5 h make the Natural manganese dioxide loaded copper oxide catalyst.
Selective finishing hempseed oil and anhydrous methanol are raw material, press mol ratio and the catalyzer of methyl alcohol: hempseed oil=12.0:1.0 respectively: the mass ratio of hempseed oil=3.0:100.0 takes by weighing the refining hempseed oil of 90.54 g; Add and have in the high-pressure reactor of whisking appliance, thermopair and prolong; With the catalyzer that makes in the present embodiment 2.72 g with move in the lump in the autoclave after 39.83 g anhydrous methanols mix, in turn with the air in nitrogen and the hydrogen exchange reaction under high pressure three times, be warming up to 200 ℃ then; Charge into the hydrogen of 6.0 MPa; Constant temperature stirring reaction 5.0 h, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is catalyzer, glycerine and residue methanol mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, the distillatory methanol loop is used.Lower floor's mixture obtains catalyzer and filtrating through suction filtration, and filtrating goes out methanol loop through fractionation by distillation uses, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.Through the gas chromatographic analysis product is fatty acid methyl ester, and the productive rate of calculating is 93 %.The iodine number of analyzing the fatty acid methyl ester product is 116, and cetane value is 55.
Embodiment 6
5.832 g Marinco Hs are made Natural manganese dioxide in 1000 ℃ of following vacuum calcining 5 h.1.214 g cupric nitrates being dissolved in the deionized water, adding ammoniacal liquor then, is 9 up to the solution pH value; Then Natural manganese dioxide is added in the copper ammon solution, stirred 20 minutes, slowly diluting soln makes the copper precipitation from homogeneous solution and is dispersed on the magnesium oxide carrier then; Filter then; Washing in 120 ℃ of following constant temperature dryings 12 hours, makes the Natural manganese dioxide loaded copper oxide catalyst at 1000 ℃ of following vacuum calcining 5 h.
Selective finishing hempseed oil and methyl alcohol are raw material, press mol ratio and the catalyzer of methyl alcohol: hempseed oil=12.0:1.0 respectively: the mass ratio of hempseed oil=3.0:100.0 takes by weighing the refining hempseed oil of 90.54g; Add and have in the high-pressure reactor of whisking appliance, thermopair and prolong; With the catalyzer that makes in the present embodiment 2.72 g with move in the lump in the autoclave after 39.83 g anhydrous methanols mix, in turn with the air in nitrogen and the hydrogen exchange reaction under high pressure three times, be warming up to 220 ℃ then; Charge into the hydrogen of 5.0 MPa; Constant temperature stirring reaction 6.0 h, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is catalyzer, glycerine and residue methanol mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, the distillatory methanol loop is used.Lower floor's mixture obtains catalyzer and filtrating through suction filtration, and filtrating goes out methanol loop through fractionation by distillation uses, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.Through the gas chromatographic analysis product is fatty acid methyl ester, and the productive rate of calculating is 92%.The iodine number of analyzing the fatty acid methyl ester product is 117, and cetane value is 53.
Embodiment 7
23.615 g nitrocalcite are dissolved in the 200 mL deionized waters obtain ca nitrate soln, 19.13 g volatile salts are dissolved in the 500 mL deionized waters obtain sal volatile then.Sal volatile is dropwise splashed in the above-mentioned ca nitrate soln, drip off back restir reaction 3h, then filter and obtain the precursor deposition, washing then in 120 ℃ of following constant temperature dryings 12 hours, makes quicklime at 1000 ℃ of following vacuum calcining 5 h.1.700 g cupric nitrates being dissolved in the deionized water, adding ammoniacal liquor then, is 9 up to the solution pH value; Then quicklime is added in the copper ammon solution, stirred 20 minutes, slowly diluting soln makes the copper precipitation from homogeneous solution and is dispersed on the quicklime carrier then; Filter then; Washing in 120 ℃ of following constant temperature dryings 12 hours, makes the quicklime loaded copper oxide catalyst at 1000 ℃ of following vacuum calcining 5 h.
Selective finishing hempseed oil and methyl alcohol are raw material, press mol ratio and the catalyzer of methyl alcohol: hempseed oil=12.0:1.0 respectively: the mass ratio of hempseed oil=3.0:100.0 takes by weighing the refining hempseed oil of 90.54 g; Add and have in the high-pressure reactor of whisking appliance, thermopair and prolong; With the catalyzer that makes in the present embodiment 2.72 g with move in the lump in the autoclave after 39.83 g anhydrous methanols mix, in turn with the air in nitrogen and the hydrogen exchange reaction under high pressure three times, be warming up to 200 ℃ then; Charge into the hydrogen of 6.0 MPa; Constant temperature stirring reaction 5.0 h, cooling, with mixed reaction product leave standstill, layering, separation; The upper strata is the coarse biodiesel product, and lower floor is catalyzer, glycerine and residue methanol mixture.With upper strata coarse biodiesel product with deionized water washing for several times, do not have the glycerine composition until the analyzing and testing aqueous phase, with after underpressure distillation obtains refining biodiesel, the distillatory methanol loop is used.Lower floor's mixture obtains catalyzer and filtrating through suction filtration, and filtrating goes out methanol loop through fractionation by distillation uses, and obtains crude glycerol simultaneously, continues underpressure distillation and obtains the higher refining glycerine of purity.Through the gas chromatographic analysis product is fatty acid methyl ester, and the productive rate of calculating is 89 %, and iodine number is 120, and cetane value is 51.
Claims (10)
1. the dual-function catalyst of catalytic one-stage transesterify and hydrogenation reaction and by the method for consaturated oil biodiesel synthesis; It is characterized in that dual-function catalyst is made up of the alkaline earth metal oxide loaded copper oxide, consaturated oil is through one step of dual-function catalyst catalyzed transesterification and selective hydrogenation biodiesel synthesis.
2. the alkaline earth metal oxide of claim 1 comprises Natural manganese dioxide, quicklime, strontium oxide and barium oxide.
3. claim 1 or 2 alkaline earth metal oxide are produced the alkaline earth metal oxide precursor by alkine earth metal nitrate and precipitation agent volatile salt, yellow soda ash, oxalic acid, urea reaction; Make through vacuum calcining then, perhaps make by alkaline earth metal hydroxides and the thermolysis of alkaline earth metal carbonate vacuum.
4. the dual-function catalyst of claim 1 adopts the chemisorption hydrolysis method to make; Concrete steps are that alkaline earth metal oxide and PH are that 9 copper ammon solution mixes; Dilute afterwards, leave standstill, the cupric oxide precursor is loaded on the alkaline earth metal oxide, make through vacuum calcining then.
5. the mass ratio of cupric oxide and alkaline earth metal oxide is 1 %-40 % in claim 1 and 4 the dual-function catalyst.
6. claim 3 is 500-1200 ℃ with 4 vacuum calcining temperature, and calcination time is 2-6 h.
7. the consaturated oil of claim 1 comprises a kind of, two or more the mixing oil in hempseed oil, tung oil, rapeseed oil, tea-seed oil, rubber seed oil, VT 18, canola oil, the oleum lini.
8. the method by the consaturated oil biodiesel synthesis of claim 1 is one step of dual-function catalyst catalysis consaturated oil transesterification reaction and hydrogenation reaction biodiesel synthesis.
9. the temperature of reaction of claim 1 and 8 step transesterify and a hydrogenation reaction is 150-300 ℃, and hydrogen pressure is 1-10 MPa, and the reaction times is 1-20 h.
10. claim 1 and 8 biofuel cetane value are more than 51, and iodine number is below 120.
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