CN107541234B - A kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite - Google Patents
A kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite Download PDFInfo
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- CN107541234B CN107541234B CN201710799547.6A CN201710799547A CN107541234B CN 107541234 B CN107541234 B CN 107541234B CN 201710799547 A CN201710799547 A CN 201710799547A CN 107541234 B CN107541234 B CN 107541234B
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- houghite
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- 239000011698 potassium fluoride Substances 0.000 title claims abstract description 92
- 239000007787 solid Substances 0.000 title claims abstract description 55
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 title claims abstract description 52
- 239000003225 biodiesel Substances 0.000 title claims abstract description 42
- 235000003270 potassium fluoride Nutrition 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 229910020068 MgAl Inorganic materials 0.000 claims abstract description 15
- 229910017922 MgLa Inorganic materials 0.000 claims abstract description 15
- 150000001298 alcohols Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002283 diesel fuel Substances 0.000 claims abstract description 11
- 239000004519 grease Substances 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000000047 product Substances 0.000 claims description 34
- 235000019441 ethanol Nutrition 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000003549 soybean oil Substances 0.000 claims description 8
- 235000012424 soybean oil Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 235000019198 oils Nutrition 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed 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
- 238000007598 dipping method 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
- -1 is filtered Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims 1
- 210000002700 urine Anatomy 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 32
- 238000011017 operating method Methods 0.000 description 28
- 239000010410 layer Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000011068 loading method Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses a kind of methods of houghite immobilized potassium fluoride solid base KF/MgAlLa, KF/MgAl, KF/MgLa catalysis grease and alcohols material biodiesel synthesis, the solid base has mesoporous houghite layer structure, and aperture is 12~21nm, 0.04~0.10cm of Kong Rong3/ g, 14~30m of specific surface2/ g, basicity pKa are 9.3~15.0, and catalytic activity is high, easily separates with reaction system, and reusability is good, catalytically synthesizing biological diesel oil mass yield 99.1%, and catalyst reuses 5 catalytically synthesizing biological diesel oil mass yields 80.9%.
Description
Technical field
The invention belongs to biomass energy catalytic fields, are related to a kind of immobilized potassium fluoride catalyzed by solid base synthesis life of houghite
The method of object diesel oil.
Background technique
Biodiesel is by animal and plant fat (fatty acid triglycercide) and alcohols material (methanol or ethyl alcohol) through transesterification
Obtained fatty acid monoalkyl ester is reacted, most typically fatty acid methyl ester.Compared with traditional fossil energy, sulphur and aromatic hydrocarbons
Content is low, flash-point is high, Cetane number is high, has good lubricity, can partially be added in fossil diesel fuel, as renewable energy
Source has attracted extensive attention.Conventionally used catalyst has homogeneous catalyst and heterogeneous catalysis.Homogeneous acid-base catalysis intensity
It is uniform, high catalytic efficiency, but there is the problems such as complicated separation, the processing of equipment burn into soda acid, discharge of wastewater.Heterogeneous catalysis is anti-
Product is easily separated after answering, and catalyst can recycle again.Patent 200610136799.2 discloses a kind of for producing biological bavin
The preparation method of the supported solid catalyst of oil, by hydrotalcite or houghite metal composite oxide dip loading fluoride
Such as KF, CaF2、ZnF2, NaF or K2CO3, to get solid base catalyst after being crushed after 500 DEG C of high-temperature roastings.But by fluoride
With hydrotalcite or houghite metal composite oxide dip loading again in 500 DEG C of dip loading high-temperature roasting hydrotalcites easy to damage
The layer structure of class compound, catalyst reusability are bad.For this problem, the present invention prepares porous houghite layer
Shape carrier material MgAlLa, MgAl, MgLa pass through the dip loading KF in lower alcohols solvent methanol, ethyl alcohol, then low temperature 150
DEG C roasting be made with the mesoporous immobilized potassium fluoride of houghite layer structure solid base, for being catalyzed grease and methanol or second
Alcohol biodiesel synthesis, high catalytic efficiency, convenient catalyst recycling, reusability are good.
Summary of the invention
The purpose of the present invention
The present invention is intended to provide a kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite.
Technical solution of the present invention
1. a kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite is as follows:
(1) the immobilized potassium fluoride solid base of a kind of houghite described in has mesoporous houghite layer structure, hole
Diameter is 12~21nm, 0.04~0.10cm of Kong Rong3/ g, 14~30m of specific surface2/ g, basicity pKa are 9.3~15.0.
(2) the immobilized potassium fluoride solid base of a kind of houghite described in includes KF/MgAlLa, KF/MgAl, KF/MgLa；
1) molar ratio of Mg, Al, La are 1 in the immobilized potassium fluoride solid base KF/MgAlLa of a kind of houghite described in:
The mass ratio of 0.1~0.3: 0.1~0.3, KF and MgAlLa are 0.1~0.34: 1；
2) in the immobilized potassium fluoride solid base KF/MgAl of a kind of houghite described in the molar ratio of Mg, Al be 1: 0.2~
The mass ratio of 0.4, KF and MgAl is 0.1~0.2: 1；
3) in the immobilized potassium fluoride solid base KF/MgLa of a kind of houghite described in the molar ratio of Mg, La be 1: 0.2~
The mass ratio of 0.4, KF and MgLa is 0.1~0.2: 1.
(3) a kind of method of the preparation immobilized potassium fluoride solid base of houghite is:
1) by Mg (NO3)2.6H2O、Al(NO3)3.7H2O、La(NO3)3.6H2O is respectively according in above-mentioned (1) 1), 2), 3) institute
Reactor is added in the molar ratio of Mg, Al, La or Mg of restriction, Al or Mg, La, adds 1~4 times of nitrate ion molar ratio
The deionized water of urea, 3~5 times of metal ion total moles ratios, after sealing stirring is condensed back 10~12h at 90~110 DEG C,
Mixed liquor is transferred in water heating kettle crystallization 12 at 90~110 DEG C~for 24 hours again, forms white precipitate, is filtered, filter cake is set in washing
Dry 10~12h in 40~60 DEG C of insulating boxs, then be placed in box Muffle furnace, it is warming up to 1~3 DEG C/min heating rate
400~600 DEG C of 1~5h of roasting after cooling, i.e., are made described with mesoporous houghite layer structure respectively
MgAlLa, MgAl, MgLa carrier, carrier aperture are 8~13nm, 0.06~0.13cm of Kong Rong3/ g, 17~60m of specific surface area2/g。
2) by KF respectively with obtained MgAlLa, MgAl, MgLa carrier and impregnating agent according to mass ratio 0.1~0.34: 1:
15~30 are added reactor, and in 40~60 DEG C of dipping stirrings to solvent evaporating completely, residual income white powdery solids are existed
Dry 10~12h in 40~60 DEG C of insulating boxs, then be placed in box Muffle furnace and divide after cooling in 120~250 DEG C of 1~3h of roasting
A kind of immobilized potassium fluoride solid base KF/MgAlLa, KF/ with mesoporous houghite layer structure that Zhi get be described
MgAl, KF/MgLa, these solid bases are suitable as catalyst for being catalyzed long-chain oil synthesis biodiesel, the impregnating agent
For any one in methanol, ethyl alcohol.
(4) by a kind of immobilized potassium fluoride catalyzed by solid base with mesoporous houghite layer structure prepared by (3)
For being catalyzed grease and alcohols material biodiesel synthesis, the molar ratio of reaction raw materials alcohols material and grease is 15~30 for agent:
1, the mass ratio of solid base catalyst and grease is 0.04~0.06: 1,75~95 DEG C of reaction temperature, 4~10h of reaction time, instead
Be cooled to room temperature after answering, be recovered by filtration solid base catalyst, then through methanol wash 3 times, 40~60 DEG C drying 12 hours it is cold
But it after, is reused standby next time in 120~250 DEG C of 1~3h of roasting as catalyst, filtrate is sufficiently washed 3 times with saturated brine,
Stratification, lower layer are glycerol, unreacted methanol and saturated brine mixture, and upper layer is yellow solution, evaporation recycling upper layer
After excessive alcohols material in yellow solution, then it is centrifugated wherein a small amount of salt slag, remaining liq is that target product is raw
Object diesel oil, for biodiesel product yield up to 99.1%, solid base catalyst reuses 5 its catalytically synthesizing biological diesel oil quality
Yield is 80.9%, and the grease includes soybean oil, palm oil, castor oil, rapeseed oil, gutter oil, and the alcohols material includes
Methanol, ethyl alcohol.
Technical characterstic and effect of the invention
There is the load of mesoporous houghite layer structure by urea decomposing solution internal pH uniformity, coprecipitation
Body material MgAlLa, MgAl, MgLa, are heated to reflux at 90~110 DEG C and hydrothermal crystallizing, better crystallinity degree, uniform particle sizes crystallize
High income, then after 400~600 DEG C of roastings, impregnates in low price alcohols solvent methanol, ethyl alcohol and 120~250 DEG C of low temperature with KF
Roasting, obtains the immobilized potassium fluoride solid base catalyst for the houghite layer structure for having mesoporous, for catalyzing and synthesizing biology
5 its catalytically synthesizing biological diesel oil mass yields are reused in its mass yield 99.1% of diesel oil, solid base catalyst recycling
80.9%.
Detailed description of the invention
Fig. 1 (A), (B) are respectively Mg1Al0.27La0.07Roast the SEM photograph of front and back, (C) is 10%KF/
Mg1Al0.27La0.07SEM photograph.Mg1Al0.27La0.07Middle index number is the molar ratio of Mg, Al, La, 10% be KF with
Mg1Al0.27La0Mass ratio, it is similar below.From Mg before and after Fig. 1 (A), (B) visible roasting1Al0.27La0.07It is all in houghite
Layer structure, but its hydrotalcite-like compound a little pine comb after roasting.Fig. 1 (C) illustrates Mg1Al0.27La0.07Its class water after load KF
The more loose comb of talc lamellar structure is some.
Fig. 2 is (a) Mg1Al0.27La0.07, (b) 5%KF/Mg1Al0.27La0.07, (c) 10%KF/Mg1Al0.27La0.07、(d)
15%KF/Mg1Al0.27La0.07, (e) 20%KF/Mg1Al0.27La0.07, (f) 25%KF/Mg1Al0.27La0.07Wide-angle XRD
Spectrogram.In 2 θ=10.7 °, 22.59 °, 46.2 ° of diffraction maximum category houghite layer structure features occurred known to Fig. 2 (a)
Peak.It is La in 2 θ=25.8 °, 27.5 °, 31.0 °, 50.3 °2O3Characteristic peak is LaAlO in 2 θ=41.3 °, 54.5 °3Characteristic peak,
It is La in 2 θ=12.9 °, 29.4 °, 44.4 °2CO5Characteristic peak is MgO characteristic peak in 2 θ=36.8 °, 42.8 °, 62.2 °.By Fig. 2
(b), there is new diffraction maximum in 2 θ=30 °, 39.1 °, are respectively it is found that as KF load capacity increases in (c), (d), (e), (f)
K3AlO6、KMgF3Characteristic peak.
Fig. 3 (a1), (a2) are respectively Mg1Al0.27La0.07TG, DTA curve before roasting, (b1), (b2) are respectively to roast
Mg afterwards1Al0.27La0.07TG, DTA curve.It is by curve (a1) (a2) it is found that weightless for removing absorption water between 100~206 DEG C
Caused, between 206~322 DEG C caused by the weightless interlayer crystallization water for removing, weightless between 322~412 DEG C is that carbonate is decomposed into CO2Institute
It causes, it is weightless for caused by hydroxyl in removing houghite between 412~469 DEG C.Having after 469 DEG C weightless is mainly to remain in laminate
On hydroxyl further caused by being detached from).It is after removing roasts by curve (b1), (b2) it is found that without endothermic peak but having weightlessness
Mg1Al0.27La0.07In remain in caused by the hydroxyl on laminate.
Fig. 4 (a1), (a2) are respectively 10%KF/Mg1Al0.27La0.07TG, DTA curve, (a3) before calcining are before calcining
10%KF/Mg1Al0.27La0.07DSC curve figure.By curve (a1) (a2) it is found that thermal weight loss mainly removes before 150 DEG C
Surface adsorption water and methanol.In conjunction with Fig. 3 TG curve it is found that the weightlessness after 469 DEG C is that the hydroxyl remained on laminate is detached from institute
It causes.Mg1Al0.27La0.07Maturing temperature be 500 DEG C, it is known that 500 DEG C it still have remaining hydroxyl, it can thus be appreciated that curve (a1)
(a2) weightless to remain in the hydroxyl on laminate caused by being detached from after 150 DEG C.By curve (a3) observe 40~700 DEG C it
Between a wider endothermic peak is presented, 250 DEG C nearby caloric receptivity reach maximum, as temperature increases, caloric receptivity is gradually decreased,
Illustrate 10%KF/Mg1Al0.27La0.07Removing surface adsorption water, methanol and the hydroxyl process remained on laminate terminate substantially.
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. the preparation of solid base KF/MgAlLa
By Mg (NO3)2.6H2O、Al(NO3)3.7H2O、La(NO3)3.6H2O is 1: 0.27 by the molar ratio of Mg, Al, La:
It is stirred in 0.07 addition reactor, adds urea, the 5 times of total ions mole of metal of 0.2 times of nitrate ion molar ratio
The deionized water of ratio continues at 105 DEG C after being stirred solution 10h, and mixed liquor is transferred in water heating kettle 100 DEG C of crystallization for 24 hours,
White precipitate is formed, is filtered, filter cake is placed in 55 DEG C of insulating boxs dry 12h, then is placed in box Muffle furnace by washing, with 1~
3 DEG C/min heating rate is warming up to 500 DEG C, and roasts 4h at such a temperature, obtains after cooling with mesoporous houghite
Layered vector MgAlLa, aperture are 8~13nm, 0.06~0.13cm of Kong Rong3/ g, 17~60m of specific surface area2/g.By KF,
MgAlLa and methanol impregnated at 40 DEG C according to mass ratio 0.1: 1: 15 stirring 12h to methanol evaporating completely, gained residue is white
Color pulverulent solids dry 12h in 55 DEG C of insulating boxs, then be placed in 1~3 DEG C/min heating rate in box Muffle furnace and be warming up to
2h is roasted at 150 DEG C obtains the 10%KF/ of the immobilized KF with mesoporous houghite layer structure after cooling
Mg1Al0.27La0.07Solid base, aperture are 12~21nm, 0.04~0.10cm of Kong Rong3/ g, 14~30m of specific surface area2/ g is used
It is 9.3~15 that Hammett method, which measures its basicity pKa,.
2. catalytically synthesizing biological diesel oil
By 10%KF/Mg obtained by 2g1Al0.27La0.07Solid base catalyst and 29.4g methanol be (methanol and soybean oil
Molar ratio is 20: 1), 40g soybean oil be added in reactor, catalytic reaction temperature be 85 DEG C, reaction time 6h, reaction knot
It is cooled to room temperature after beam, the solid base catalyst is recovered by filtration, after methanol washing 3 times, 55 DEG C of dryings cooling in 12 hours
Standby next time is reused, and filtrate is sufficiently washed 3 times with saturated brine, stratification, and lower layer is glycerol, unreacted methanol and saturation
Saline mixture, upper layer are yellow solution, and filtrate is evaporated and recycles excessive alcohols material, the concentrate after evaporation is stirred,
Centrifuge separation, recycling supernatant liquid are target product biodiesel, and biodiesel product quality yield is 99.10%.
La (NO is not added with case study on implementation 1 in 2 operating procedure of embodiment3)3.6H2The molar ratio of O, Mg, Al are 1: 0.3, Gu
Body alkali is 10%KF/Mg1Al0.3, obtaining biodiesel product quality yield is 96.18%.
3 operating procedure of embodiment is with embodiment 1, but solid base 10%KF/Mg1Al0.2La0.13The molar ratio of middle Mg, A, La
It is 1: 0.2: 0.13, obtaining biodiesel product quality yield is 91.25%.
4 operating procedure of embodiment is with embodiment 1, but by solid base 10%KF/Mg1Al0.13La0.2Mole of middle Mg, A, La
Than being 1: 0.13: 0.2, obtaining biodiesel product quality yield is 91.40%.
Al (NO is not added with embodiment 1 in 5 operating procedure of embodiment3)3.7H2The molar ratio of O, Mg, La are 1: 0.3, solid
Alkali is 10%KF/Mg1La0.3, obtaining biodiesel product quality yield is 94.56%.
Above embodiments 1-5 comparative illustration: solid base 10%KF/Mg1AlxLayIn, Mg, Al, La molar ratio 1: x: y works as x
Catalytically synthesizing biological diesel oil mass yield is higher when+y=0.34, and wherein the contribution of Al is greater than La.
(comparative example) operating procedure of embodiment 6 is with embodiment 1, but solid base is 5%KF/Mg1Al0.27La0.07, wherein KF
With Mg1Al0.27La0.07Mass ratio be 0.05, obtain biodiesel product quality yield be 70.96%.
7 operating procedure of embodiment is with embodiment 1, but solid base is 15%KF/Mg1Al0.27La0.07, wherein KF with
Mg1Al0.27La0.07Mass ratio be 0.15, obtain biodiesel product quality yield be 94.07%.
8 operating procedure of embodiment is with case study on implementation 1, but solid base is 20%KF/Mg1Al0.27La0.07, wherein KF with
Mg1Al0.27La0.07Mass ratio be 0.2, obtain biodiesel product quality yield be 92.17%.
9 operating procedure of embodiment is with case study on implementation 1, but solid base is 25%KF/Mg1Al0.27La0.07, wherein KF with
Mg1Al0.27La0.07Mass ratio be 0.25, obtain biodiesel product quality yield be 90.37%.
(comparative example) operating procedure of embodiment 10 roasts white powdery solids 10%KF/ with embodiment 1
Mg1Al0.27La0.07Temperature is 90 DEG C, and obtaining biodiesel product quality yield is 83.78%.
11 operating procedure of embodiment roasts white powdery solids 10%KF/Mg with embodiment 11Al0.27La0.07Temperature
It is 120 DEG C, obtaining biodiesel product quality yield is 94.52%.
12 operating procedure of embodiment roasts white powdery solids 10%KF/Mg with embodiment 11Al0.27La0.07Temperature
It is 180 DEG C, obtaining biodiesel product quality yield is 95.52%.
13 operating procedure of embodiment roasts white powdery solids 10%KF/Mg with embodiment 11Al0.27La0.07Temperature
It is 250 DEG C, obtaining biodiesel product quality yield is 93.61%.
(comparative example) operating procedure of embodiment 14 is with embodiment 1, but the reaction time is 2h, obtains biodiesel product quality receipts
Rate is 89.58%.
15 operating procedure of embodiment is with embodiment 1, but the reaction time is 4h, and obtaining biodiesel product quality yield is
98.62%.
16 operating procedure of embodiment is with embodiment 1, but the reaction time is 8h, and obtaining biodiesel product quality yield is
96.29%.
17 operating procedure of embodiment is with embodiment 1, but the reaction time is 10h, and obtaining biodiesel product quality yield is
95.65%.
(comparative example) operating procedure of embodiment 18 is with embodiment 1, but reaction temperature is 55 DEG C, obtains biodiesel product quality
Yield is 36.30%.
(comparative example) operating procedure of embodiment 19 is with embodiment 1, but reaction temperature is 65 DEG C, obtains biodiesel product quality
Yield is 87.09%.
20 operating procedure of embodiment is with embodiment 1, but reaction temperature is 75 DEG C, and obtaining biodiesel product quality yield is
98.72%.
21 operating procedure of embodiment is with embodiment 1, but reaction temperature is 95 DEG C, and obtaining biodiesel product quality yield is
93.36%.
(comparative example) operating procedure of embodiment 22 is with embodiment 1, but the molar ratio of methanol and soybean oil is 10: 1, is obtained biological
Diesel product mass yield is 81.00%.
23 operating procedure of embodiment is with embodiment 1, but the molar ratio of methanol and soybean oil is 15: 1, obtains biodiesel product
Mass yield is 95.47%.
24 operating procedure of embodiment is with embodiment 1, but the molar ratio of methanol and soybean oil is 25: 1, obtains biodiesel product
Mass yield is 99.20%.
25 operating procedure of embodiment is with embodiment 1, but the molar ratio of methanol and soybean oil is 30: 1, obtains biodiesel product
Mass yield is 97.23%.
26 operating procedure of embodiment is with embodiment 1, but catalyst is the 2nd recycling of recycling, obtains reaction product yield
It is 93.58%.
27 operating procedure of embodiment is with embodiment 1, but catalyst is the 3rd recycling of recycling, obtains biodiesel product
Mass yield is 91.21%.
28 operating procedure of embodiment is with embodiment 1, but catalyst is that recycling the 4th is recycled, and obtains biodiesel product
Mass yield is 86.72%.
29 operating procedure of embodiment is with embodiment 1, but catalyst is that recycling the 5th is recycled, and obtains biodiesel product
Mass yield is 80.93%.
The immobilized potassium fluoride solid base physicochemical characteristic of 1 houghite of table
2 Examples 1 to 2 of table, 9 reaction condition and result
It * is comparative example
Claims (1)
1. a kind of method of the immobilized potassium fluoride catalyzed by solid base biodiesel synthesis of houghite, it is characterized in that:
(1) the immobilized potassium fluoride solid base of a kind of houghite described in has mesoporous houghite layer structure, and aperture is
12~21nm, 0.04~0.10cm of Kong Rong3/ g, 14~30m of specific surface2/ g, basicity pKa are 9.3~15.0；
(2) the immobilized potassium fluoride solid base of houghite described in is any one of KF/MgAlLa, KF/MgAl, KF/MgLa；
1) in the immobilized potassium fluoride solid base KF/MgAlLa of a kind of houghite described in the molar ratio of Mg, Al, La be 1: 0.1~
The mass ratio of 0.3: 0.1~0.3, KF and MgAlLa are 0.1~0.34: 1；
2) molar ratio of Mg, Al are 1: 0.2~0.4, KF in the immobilized potassium fluoride solid base KF/MgAl of a kind of houghite described in
Mass ratio with MgAl is 0.1~0.2: 1；
3) molar ratio of Mg, La are 1: 0.2~0.4, KF in the immobilized potassium fluoride solid base KF/MgLa of a kind of houghite described in
Mass ratio with MgLa is 0.1~0.2: 1；
(3) a kind of method of the preparation immobilized potassium fluoride solid base of houghite is:
1) by Mg (NO3)2·6H2O、Al(NO3)3·7H2O、La(NO3)3·6H2O is respectively according in above-mentioned (2) 1), 2), 3) institute
Reactor is added in Mg, Al, La or Mg of restriction, Al or Mg, La molar ratio, adds the urine of 1~4 times of nitrate ion molar ratio
The deionized water of element, 3~5 times of metal ion total moles ratios, after sealing stirring is condensed back 10~12h at 90~110 DEG C, then
Mixed liquor is transferred in water heating kettle crystallization 12 at 90~110 DEG C~for 24 hours, forms white precipitate, is filtered, filter cake is placed in by washing
Dry 10~12h in 40~60 DEG C of insulating boxs, then be placed in box Muffle furnace, 400 are warming up to 1~3 DEG C/min heating rate
~600 DEG C of 1~5h of roasting, after cooling, i.e., the obtained MgAlLa with mesoporous houghite layer structure respectively,
MgAl, MgLa carrier, carrier aperture are 8~13nm, 0.06~0.13cm of Kong Rong3/ g, 17~60m of specific surface area2/g；
2) by KF respectively with obtained MgAlLa, MgAl, MgLa carrier and impregnating agent according to mass ratio 0.1~0.34: 1: 15~
30 are added reactors, stir in 40~60 DEG C of dippings to solvent evaporating completely, by residual income white powdery solids 40~
Dry 10~12h in 60 DEG C of insulating boxs is placed in box Muffle furnace and is made respectively after cooling in 120~250 DEG C of 1~3h of roasting
A kind of described immobilized potassium fluoride solid base KF/MgAlLa, KF/MgAl, the KF/ with mesoporous houghite layer structure
MgLa, these solid bases are suitable as catalyst for being catalyzed long-chain oil synthesis biodiesel；
The impregnating agent is methanol, any one in ethyl alcohol；
(4) a kind of immobilized potassium fluoride solid base catalyst with mesoporous houghite layer structure prepared by (3) is used
In catalysis grease and alcohols material biodiesel synthesis, the molar ratio of reaction raw materials alcohols material and grease is 15~30: 1, admittedly
The mass ratio of body base catalyst and grease is 0.04~0.06: 1,75~95 DEG C of reaction temperature, 4~10h of reaction time, reaction knot
It is cooled to room temperature after beam, solid base catalyst is recovered by filtration, then after methanol washing 3 times, 40~60 DEG C of dryings cooling in 12 hours,
It is reused standby next time in 120~250 DEG C of 1~3h of roasting as catalyst, filtrate is sufficiently washed 3 times with saturated brine, is stood
Layering, lower layer are glycerol, unreacted methanol and saturated brine mixture, and upper layer is yellow solution, and evaporation recycling upper layer is yellowish
After excessive alcohols material in color solution, then it is centrifugated wherein a small amount of salt slag, remaining liq is target product biology bavin
Oil, for biodiesel product yield up to 99.1%, solid base catalyst reuses 5 its catalytically synthesizing biological diesel oil mass yields
Be 80.9%, the grease includes soybean oil, palm oil, castor oil, rapeseed oil, gutter oil, the alcohols material include methanol,
Ethyl alcohol.
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