CN109046417A - A kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis - Google Patents
A kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis Download PDFInfo
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- 229910017922 MgLa Inorganic materials 0.000 title claims abstract description 48
- 239000003225 biodiesel Substances 0.000 title claims abstract description 40
- 239000007787 solid Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims description 11
- 238000003786 synthesis reaction Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000001298 alcohols Chemical class 0.000 claims abstract description 12
- 239000004519 grease Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 55
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 40
- 239000002585 base Substances 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 11
- 235000012424 soybean oil Nutrition 0.000 claims description 11
- 239000003549 soybean oil Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011017 operating method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
本发明公开一种K2CO3/MgLa固体碱催化油脂与醇类物质合成生物柴油的方法，所述固体碱制备方法简单、低温催化活性高、易与反应体系分离，在反应时间2h、反应温度55℃、催化剂用量5%、醇油比27:1下，生物柴油产物收率达96.8％。
The invention discloses a K 2 CO 3 /MgLa solid base catalyzed method for synthesizing biodiesel from grease and alcohols. The solid base has a simple preparation method, high catalytic activity at low temperature, and is easy to separate from the reaction system. At a temperature of 55°C, a catalyst dosage of 5%, and an alcohol-to-oil ratio of 27:1, the biodiesel yield reached 96.8%.
Description
Technical field
The invention belongs to biomass energy catalytic fields, are related to a kind of K2CO3/ MgLa catalyzed by solid base biodiesel synthesis
Method.
Background technique
Biodiesel is also known as fatty acid methyl ester, is the mixing as vegetable fat and animal tallow through ester made of transesterification
Object, most typically fatty acid methyl ester.Biodiesel can reduce the discharge of carbon monoxide in combustion gas, particulate matter and sulfur dioxide.
There is homogeneous and heterogeneous catalysis commonly used in the catalyst of preparing biodiesel by ester exchange.Homogeneous acid-base catalysis uniform intensity,
High catalytic efficiency, but there is the problems such as complicated separation, the processing of equipment burn into soda acid, discharge of wastewater.It is produced after heterogeneous catalytic reaction
Object is easily separated, and catalyst can recycle again.Liu Liuchen is by template in 40%Ar-O2It protects to roast under gas and CaO/ is made
ZrO2Composite oxide catalysts are applied to catalysis methanol and rapeseed oil biodiesel synthesis, catalyst amount 8% (wt),
Under conditions of the molar ratio 72 of methanol and rapeseed oil, 100 DEG C of reaction temperature, reaction time 6h, the yield of biodiesel up to 91%,
But its preparation process is complicated, and reaction temperature is higher, the reaction time is longer.For this problem, the present invention is by being simply co-precipitated
Method prepares the uniform and stable mixed-metal oxide support of Metal Distribution, impregnates in lower alcohols solvent methanol, ethyl alcohol negative
Carry K2CO3, then the K that thermal stability is good, catalytic activity is high is made in 650 DEG C of roastings in air2CO3/ MgLa solid base, for urging
Carburetion rouge and methanol or ethyl alcohol biodiesel synthesis have low in raw material price, and preparation is simple, and thermal stability is good, reaction condition
Mildly, catalytic activity is high, the features such as easily separating with reaction system, is 55 DEG C, catalyst amount in reaction time 2h, reaction temperature
5%, under alcohol oil rate 27:1, biodiesel oil product mass yield is up to 96.8%.
Summary of the invention
The purpose of the present invention
The present invention is intended to provide a kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis.
Technical solution of the present invention
1. a kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis is as follows:
(1) K described in2CO3In/MgLa solid base, K2CO3With MgLa carrier quality than 0.15~0.3:1, MgLa carrier
Middle Mg, La molar ratio 1:0.25~0.5, the K2CO311~40m of/MgLa solid base specific surface2/ g, basicity pKa are
12.3~18.0.
(2) according to K described in (1)2CO3/ MgLa solid base is prepared via a method which to obtain:
1) by Mg (NO3)2.6H2O、La(NO3)3.6H2O is separately added into deionization according to Mg, La molar ratio 1:0.25~0.5
Water is configured to the Mg (NO of 0.3~1.2mol/L3)2、La(NO3)3Salting liquid, separately according to KOH and K2CO3Molar ratio is 1:0.25
~0.33 addition deionized water is configured to the KOH/K of 0.3~0.6mol/L2CO3Mixed ammonium/alkali solutions, will be aforementioned at 25~40 DEG C
Mg (NO3)2、La(NO3)3Salting liquid and KOH/K2CO3Alkali mixed ammonium/alkali solutions are slowly added to reactor simultaneously, and control maintains solution
PH is 10, and is vigorously stirred 20~40min, then mixed liquor stands to 20 at 60~80 DEG C~for 24 hours, white precipitate is formed,
Filtering, is washed to neutrality, filter cake is placed in 90~110 DEG C of insulating boxs dry 2~4h, then be placed in box Muffle furnace, with 3~
5 DEG C/min heating rate is warming up to 500~650 DEG C of 3~5h of roasting and obtains a kind of MgLa carrier after cooling.
2) by K2CO3It is added respectively with above-mentioned MgLa carrier and impregnating agent according to 0.15~0.3:1:10 of mass ratio~25 anti-
Device is answered, in 40~60 DEG C of dipping stirrings to solvent evaporating completely, by residual income white powdery solids in 60~80 DEG C of constant temperature
Dry 2~4h in case, is placed in box Muffle furnace in 500~650 DEG C of 2~4h of roasting temperature, after cooling, obtains described
K2CO3/ MgLa body alkali, the impregnating agent are deionized water, methanol, any one in ethyl alcohol.
(3) by (1), (2) described K being prepared2CO3/ MgLa solid base synthesizes life with alcohols material for being catalyzed grease
The mass ratio 0.05 of 15~30:1 of molar ratio of object diesel oil, reaction raw materials alcohols material and grease, solid base catalyst and grease
~0.1:1,55~95 DEG C of reaction temperature, 1~4h of reaction time, is cooled to room temperature after reaction, and solid base is recovered by filtration and urges
Agent, then after methanol washing 3 times, 40~60 DEG C of dryings cooling in 8~12 hours, in 500~650 DEG C of 1~3h of roasting as solid
Body base catalyst is reused standby next time, and filtrate is sufficiently washed 3 times with saturated brine, stratification, and lower layer is glycerol, unreacted
In addition methanol is handled with saturated brine mixture, upper layer is yellow solution, and wherein excessive alcohols material, centrifugation divide for evaporation recycling
From, to get target product biodiesel, product quality yield is described greater than 92% after residual catalyst powder a small amount of in concentrate
Grease includes soybean oil, palm oil, castor oil, rapeseed oil, gutter oil, and the alcohols material includes methanol, ethyl alcohol.
Preferably, it under 55 DEG C of reaction temperature, catalyst amount 5%, alcohol oil rate 27:1, reacts 1 hour biodiesel and produces
Quality yield 92.2% reacts 2 hours biodiesel oil product mass yields 96.8%.
Technical characterstic and effect of the invention
1 use preparation process is simple, preparation condition is easily controllable, synthesis cycle is short, metal component distribution is equal in catalyst
The Co deposited synthesis metal composite oxide carrier MgLa of the advantages that even, through 500~650 DEG C roasting after, then with K2CO3It is soaking
It impregnates in stain agent, is finally roasted at 500~650 DEG C, obtain a kind of novel K2CO3/ MgLa solid base.
2K2CO3The advantageous effect that/MgLa solid base has low temperature high catalytic activity short with the reaction time, for being catalyzed grease
1 hour biology is reacted as 55 DEG C of reaction temperature, catalyst amount 5%, alcohol oil rate 27:1 with alcohols material biodiesel synthesis
Diesel product mass yield reacts 2 hours biodiesel oil product mass yields up to 96.8% up to 92.2%.
Detailed description of the invention
Fig. 1 is Mg-La carrier and different loads amount K2CO3The XRD spectra of/MgLa, (a) be Mg-La, (b), (c), (d),
(e) K is respectively corresponded2CO3The K of load capacity 20%, 5%, 15%, 30%2CO3/ MgLa is consulted known to PDF card in 2 θ=15.4
°, 27.6 ° be La (OH)3Characteristic peak, in 2 θ=25.9 °, 29.8 °, 39.2 °, 45.8 °, 52.2 °, 55.6 °, 75.3 °, 79.0 °
For La2O3Characteristic peak is MgO characteristic peak in 2 θ=42.9 °, 62.1 °.La2O3Interaction prevents crystallite from reuniting between MgO, sees
Examine K2CO3/ MgLa diffraction curve is La in 2 θ=10.8 °, 22.2 °, 25.7 °, 33.8 °, 44.5 °, 47.6 °, 50.3 °2O2
(CO3)3Characteristic diffraction peak loads K2CO3New crystal phase is formd afterwards, illustrates K2CO3Instead of simple physical does not carry between carrier,
New chemical bonding being formed, and as load capacity increases, blue shift occurs for peak position, illustrate that crystal particle diameter increases, this is because
K2CO3Load capacity increases, the reason that spacing of lattice increases.
Fig. 2 a, b are Mg-La and K2CO3The N of/MgLa2Adsorption/desorption curve, it is seen that K2CO3/ MgLa solid base catalyst exists
Relative pressure P/P0When being 0.05~0.3, adsorption curve and desorption curve are almost overlapped, in relative pressure P/P00.3~0.9
In range, desorption curve is slightly below adsorption curve, this is because specific surface area of catalyst is too small and catalysis when characterizing
Error produced by agent dosage is less belongs to nominal error range.In relative pressure P/P0In 0.9~1.0 range, when adsorption curve
There are hysteresis loops between desorption curve, this is because illustrating that catalyst has a small amount of mesoporous presence produced by capillary condensation phenomenon.
Fig. 3 is Mg-La and K2CO3/ MgLa infrared spectrogram, wherein (a) is Mg-La, (b) is K2CO3/MgLa.Infrared
In spectrogram, 3410cm-1There are superabsorbent peak, the mainly stretching vibration peak of O-H in place；1623cm-1Nearby there is hydrone H-
O-H bending vibration absorption peak, this is because in a small amount of air caused by water absorption on a catalyst；In 1400cm-1Place is CO3 2-'s
C-O vibration peak, in 404cm-1、478cm-1、615cm-1、1079cm-1Place is the M-O skeletal vibration absorption peak of metal cation M, M
Represent Mg, La metal ion.
Specific embodiment
Technical solutions and their implementation methods of the present invention are explained below by embodiment, but technical side of the invention
Case and its implementation method are not limited to following embodiment.
Embodiment 1
1. solid base K2CO3The preparation of/MgLa
By Mg (NO3)2.6H2O、La(NO3)3.6H2O by Mg, La molar ratio be 1:0.33 be separately added into it is a certain amount of go from
Sub- water is stirred the Mg (NO for being configured to 1mol/L3)2, 0.33mol/L La (NO3)3Salting liquid, separately according to KOH and K2CO3It rubs
You are than being added the KOH/K that deionized water is configured to 0.4mol/L for 4:12CO3Mixed ammonium/alkali solutions are at 30 DEG C by Mg above-mentioned
(NO3)2、La(NO3)3Salting liquid and KOH/K2CO3Alkali mixed ammonium/alkali solutions are slowly added to reactor simultaneously, and control maintenance pH value of solution is
10, and it is vigorously stirred 30min, then be warming up to 75 DEG C and stir at low speed 8h, it naturally rings to be stored at room temperature 8h, forms white precipitate, mistake
Filter, is washed to neutrality, filter cake is placed in 100 DEG C of insulating boxs dry 4h, then be placed in box Muffle furnace, with 3 DEG C/min heating
Rate is warming up to 650 DEG C of roasting 4h and obtains a kind of MgLa carrier, specific surface area 37.7m after cooling2/g。
By K2CO3, MgLa and methanol stirring 8h is impregnated at 40 DEG C according to mass ratio 0.2:1:15 to methanol evaporating completely,
Gained residue white powdery solids are dried into 3h in 80 DEG C of insulating boxs, then are placed in 3 DEG C/min heating speed in box Muffle furnace
Rate, which is warming up at 630 DEG C, roasts 4h, after cooling, obtains 20%K2CO3/ MgLa solid base, specific surface area 11.9m2/g。
By 20%K obtained by 2g2CO3/ MgLa solid base catalyst, 40g methanol, 39.5g soybean oil (methanol and soybean
The molar ratio of oil is 27:1) it is added in reactor, reaction temperature is 55 DEG C, and reaction time 2h is cooled to after reaction
The solid base catalyst is recovered by filtration in room temperature, washs 3 times, 55 DEG C of cooling repetitions standby next times in drying 12 hours through methanol
It uses, filtrate is sufficiently washed 3 times with saturated brine, stratification, and lower layer is glycerol, unreacted methanol and saturated brine mixture
In addition it handles, upper layer is yellow solution, and wherein excessive methanol, a small amount of residual catalyst in rotary-classify technology liquid are recycled in evaporation
To get target product biodiesel after powder, biodiesel product quality yield is 96.8%.
(comparative example) operating procedure of embodiment 2 is with embodiment 1, but solid base is 5%K2CO3/ MgLa, i.e. K2CO3With MgLa
Carrier quality ratio 0.05:1, reaction time 4h, 85 DEG C of reaction temperature, obtaining biodiesel product quality yield is 57%.
3 operating procedure of embodiment is with embodiment 1, but solid base is 15%K2CO3/ MgLa, i.e. K2CO3With MgLa carrier matter
Amount is than 0.15:1, reaction time 4h, and 85 DEG C of reaction temperature, obtaining biodiesel product quality yield is 93.3%.
4 operating procedure of embodiment is with embodiment 1, but solid base is 30%K2CO3/ MgLa, i.e. K2CO3With MgLa carrier matter
Amount is than 0.15:1, reaction time 4h, and 85 DEG C of reaction temperature, obtaining biodiesel product quality yield is 93.8%.
(comparative example) operating procedure of embodiment 5 is with embodiment 1, but reaction temperature is 35 DEG C, obtains biodiesel product quality
Yield is 13.2%.
(comparative example) operating procedure of embodiment 6 is with embodiment 1, but reaction temperature is 45 DEG C, obtains biodiesel product quality
Yield is 29.5%.
7 operating procedure of embodiment is with embodiment 1, but reaction temperature is 65 DEG C, and obtaining biodiesel product quality yield is
94.8%.
8 operating procedure of embodiment is with embodiment 1, but reaction temperature is 85 DEG C, and obtaining biodiesel product quality yield is
95.2%.
9 operating procedure of embodiment is with embodiment 1, but reaction temperature is 95 DEG C, and obtaining biodiesel product quality yield is
96%.
(comparative example) operating procedure of embodiment 10 is with embodiment 1, but the reaction time is 0.5h, obtains biodiesel product quality
Yield is 86.9%.
11 operating procedure of embodiment is with embodiment 1, but the reaction time is 1h, and obtaining biodiesel product quality yield is
92.2%.
12 operating procedure of embodiment is with embodiment 1, but the reaction time is 3h, and obtaining biodiesel product quality yield is
95.5%.
13 operating procedure of embodiment is with embodiment 1, but the reaction time is 4h, and obtaining biodiesel product quality yield is
94.6%.
(comparative example) operating procedure of embodiment 14 is with embodiment 1, but the molar ratio of methanol and soybean oil is 15:1, is obtained biological
Diesel product mass yield is 53.1%.
(comparative example) operating procedure of embodiment 15 is with embodiment 1, but the molar ratio of methanol and soybean oil is 20:1, is obtained biological
Diesel product mass yield is 61.8%.
(comparative example) operating procedure of embodiment 16 is with embodiment 1, but the molar ratio of methanol and soybean oil is 25:1, is obtained biological
Diesel product mass yield is 87.7%.
(comparative example) operating procedure of embodiment 17 is with embodiment 1, but the molar ratio of methanol and soybean oil is 35:1, is obtained biological
Diesel product mass yield is 82.2%.
(comparative example) operating procedure of embodiment 18 is with embodiment 1, but catalyst and soybean oil mass ratio are 0.01:1, obtain life
Object diesel product mass yield is 1.8%.
(comparative example) operating procedure of embodiment 19 is with embodiment 1, but catalyst and soybean oil mass ratio are 0.03:1, obtain life
Object diesel product mass yield is 39.1%.
20 operating procedure of embodiment is with embodiment 1, but catalyst and soybean oil mass ratio are 0.07:1, obtains biodiesel production
Amount of substance yield is 94.8%.
21 operating procedure of embodiment is with embodiment 1, but catalyst and soybean oil mass ratio are 0.10:1, obtains biodiesel production
Amount of substance yield is 93.6%.
2 Examples 1 to 2 of table, 1 reaction condition and result
It * is comparative example.
Claims (2)
1. a kind of K2CO3The method of/MgLa catalyzed by solid base biodiesel synthesis, it is characterized in that:
(1) K described in2CO3In/MgLa solid base, K2CO3With MgLa carrier quality than 0.15 ~ 0.3:1, Mg, La in MgLa carrier
Molar ratio 1:0.25 ~ 0.5；
The K2CO311 ~ 40m2/g of/MgLa solid base specific surface, basicity pKa are 12.3 ~ 18.0；
(2) according to K described in (1)2CO3/ MgLa solid base is prepared via a method which to obtain:
1) by Mg (NO3)2.6H2O、La(NO3)3.6H2O is separately added into deionized water according to Mg, La molar ratio 1:0.25 ~ 0.5 and matches
Mg (the NO of 0.3 ~ 1.2mol/L is made3)2、La(NO3)3Salting liquid, separately according to KOH and K2CO3Molar ratio adds for 1:0.25 ~ 0.33
Enter the KOH/K that deionized water is configured to 0.3 ~ 0.6mol/L2CO3Mixed ammonium/alkali solutions, by Mg (NO above-mentioned at 25 ~ 40 DEG C3)2、
La(NO3)3Salting liquid and KOH/K2CO3Alkali mixed ammonium/alkali solutions are slowly added to reactor simultaneously, and it is 10 that control, which maintains pH value of solution, and
It it is vigorously stirred 20 ~ 40min, then mixed liquor stands to 20 at 60 ~ 80 DEG C ~ for 24 hours, forms white precipitate, filtering is washed to
Property, filter cake is placed in 90 ~ 110 DEG C of insulating boxs dry 2 ~ 4h, then be placed in box Muffle furnace, with 3 ~ 5 DEG C/min heating rate
It is warming up to 500 ~ 650 DEG C of 3 ~ 5h of roasting and obtains a kind of MgLa carrier after cooling；
2) by K2CO3Reactor is added according to 0.15 ~ 0.3:1:10 of mass ratio ~ 25 with above-mentioned MgLa carrier and impregnating agent respectively,
The stirring of 40 ~ 60 DEG C of dippings to solvent evaporating completely, by residual income white powdery solids dry 2 in 60 ~ 80 DEG C of insulating boxs ~
4h is placed in box Muffle furnace in 500 ~ 650 DEG C of 2 ~ 4h of roasting temperature, after cooling, obtains the K2CO3/ MgLa solid
Alkali；The impregnating agent is deionized water, methanol, any one in ethyl alcohol；
(3) by (1), (2) described K being prepared2CO3/ MgLa solid base is for being catalyzed grease and alcohols material synthesising biological bavin
The mass ratio 0.05 ~ 0.1 of 15 ~ 30:1 of molar ratio of oil, reaction raw materials alcohols material and grease, solid base catalyst and grease:
1,55 ~ 95 DEG C of reaction temperature, 1 ~ 4h of reaction time are cooled to room temperature after reaction, solid base catalyst are recovered by filtration, then pass through
Methanol washs 3 times, after 40 ~ 60 DEG C of drying cooling in 8 ~ 12 hours, 500 ~ 650 DEG C of 1 ~ 3h of roasting as solid base catalyst under
Secondary reuse, filtrate are sufficiently washed 3 times with saturated brine, stratification, and lower layer is glycerol, unreacted methanol and saturated brine
In addition mixture is handled, upper layer is yellow solution, is evaporated and is recycled wherein excessive alcohols material, a small amount of in rotary-classify technology liquid
To get target product biodiesel after residual catalyst powder, product quality yield is greater than 92%；
The grease includes soybean oil, palm oil, castor oil, rapeseed oil, gutter oil, and the alcohols material includes methanol, ethyl alcohol.
2. a kind of K as described in claim 12CO3The method of/MgLa catalyzed by solid base biodiesel synthesis, it is characterized in that: institute
State K2CO3/ MgLa solid base has low temperature high catalytic activity, and the reaction time is short, for being catalyzed grease and alcohols material synthesising biological
Diesel oil under 55 DEG C of reaction temperature, catalyst amount 5%, alcohol oil rate 27:1, reacts 1 hour biodiesel oil product mass yield
92.2%, react 2 hours biodiesel oil product mass yields 96.8%.
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