CN105861163A - Preparation method of aliphatic ester by using solid catalyst - Google Patents
Preparation method of aliphatic ester by using solid catalyst Download PDFInfo
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- CN105861163A CN105861163A CN201510031495.9A CN201510031495A CN105861163A CN 105861163 A CN105861163 A CN 105861163A CN 201510031495 A CN201510031495 A CN 201510031495A CN 105861163 A CN105861163 A CN 105861163A
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- -1 aliphatic ester Chemical class 0.000 title claims abstract description 16
- 239000011949 solid catalyst Substances 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 41
- 235000014593 oils and fats Nutrition 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 239000003925 fat Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000003225 biodiesel Substances 0.000 abstract description 13
- 239000004519 grease Substances 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- 239000003921 oil Substances 0.000 description 21
- 235000019198 oils Nutrition 0.000 description 21
- 235000011187 glycerol Nutrition 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 241000283898 Ovis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 241000282894 Sus scrofa domesticus Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Abstract
The present invention provides a preparation method of aliphatic ester. The method comprises the steps of: in the presence of a composite oxide catalyst, mixing grease with C1-C6 monohydric alcohol in a reactor, reacting at a temperature of 60-220 DEG C and under the pressure of 0.3-3 Mpa, and separating aliphatic esters from the reaction products. The catalyst has a general formula of CuZnaAlbOc; a and b satisfy the relations of: a=0.04-3, and b=0.1-3; and c is the atomicity of oxygen meeting the requirements of electrically neutral compound. The method uses the solid catalyst, treats oil materials with high acid value and high oil impurities under the conditions of lower temperature and pressure, and conducts a one-step reaction to obtain high-yield biodiesel.
Description
Technical field
The method that the present invention relates to be prepared fatty acid ester (i.e. biodiesel) by oils and fats and monohydric alcohol reaction.
Background technology
Biodiesel can carry out ester exchange reaction by oils and fats and monohydric alcohol and prepare, and has fatty acid in product
Ester, also monoglyceride, two sweet esters, glycerol, and unreacted alcohol and oils and fats (i.e. triglyceride).Existing
In technology, the preparation method of biodiesel can be divided into acid catalyzed process, base catalysis method, enzyme catalysis method and supercritical methanol technology.
CN1473907A uses the leftover bits and pieces of vegetable oil refining and edible recovered oil to be raw material, catalyst by sulphuric acid,
Hydrochloric acid, p-methyl benzenesulfonic acid, DBSA, LOMAR PWA EINECS 246-676-2 etc. are inorganic and organic acid is compounding forms, acidified
Remove impurity, continuous dehydration, be esterified, be layered, the operations such as distillation that reduce pressure produce, the pressure of continuous vacuum dehydration
Being 0.08～0.09Mpa, temperature 60～95 DEG C, dehydration is to water content less than 0.2%, and esterif iotacation step catalyst adds
Enter amount 1～3%, esterification temperature 60～80 DEG C, 6 hours response time.Reaction afterproduct first neutralizes removing and urges
Agent, then, layering removes water, and the afterproduct that anhydrates obtains biodiesel through decompression distillation.
It is slow that acid catalysis there is problems of response speed compared with base catalysis, has a large amount of spent acid and produces, pollutes ring
Border.
JP9-235573 discloses a kind of discarded edible oil and methanol and prepares bavin in the presence of sodium hydroxide
Oil machine fuel, but in natural oil, usually contain free fatty, in the case of free fatty is more,
Using base metal catalysts, can produce fatty acid soaps, such base metal catalysts is wanted excess and makes fatty acid ester
Layer separates the difficulty of change with glycerin layer,
DE3444893 discloses a kind of method, with acid catalyst, and normal pressure, 50～120 DEG C, by free-fat
Acid is esterified with alcohol, oil plant carries out pre-esterification process, then carries out ester exchange under base metal catalysts anti-
Should, but the acid catalyst left over to be neutralized by alkali, and the amount of base metal catalysts can increase.Use pre-esterification, make
Work flow is elongated, equipment investment, and energy consumption is substantially increased, it addition, base catalyst need to be removed from product,
A large amount of waste water is had to produce.Recovery glycerol difficulty.
US5713965A discloses a kind of method, and in the presence of lipase, hexane makees solvent, oils and fats and alcohol
Fatty acid methyl ester is prepared in reaction, i.e. diesel fuel.
CN1472280A discloses a kind of method, using fatty acid ester as acyl acceptor, in the existence of enzyme
Under, catalysis biological carries out transesterification reaction and produces biodiesel.The deficiency using enzyme catalyst to exist is: during reaction
Between long, inefficient, enzyme is more expensive, and easy in inactivation in high purity methanol.
A kind of method that CN1111591C discloses oils and fats and fatty acid ester is prepared in monohydric alcohol reaction, the method bag
Include and methanol is obtained fatty acid ester with oils and fats reaction, at 270～280 DEG C, under the conditions of 11～12Mpa, fat
Acid methyl ester production rate is 55～60%, and fatty acid methyl ester production rate is relatively low.
Summary of the invention
The present invention provides a kind of method preparing fatty acid ester, and the method uses solid catalyst, can be at relatively low temperature
Under degree, pressure condition, process high acid value, high impurity oil plant, i.e. be can get the life of high yield by single step reaction
Thing diesel oil.
The present invention provide the method preparing fatty acid ester include: with composite oxides as catalyst, by oils and fats with
C1～C6Monohydric alcohol mixes, and reaction temperature 60 DEG C～220 DEG C, reacts under pressure 0.3Mpa～3Mpa,
Fractionation of fatty acid esters from reacted material.
The main component of described oils and fats is fatty acid triglycercide, including Vegetable oil lipoprotein and various animal oil
Fat, additionally includes from the oil plant in the material such as microorganism, algae；Frying oil, rotten waste oil etc..Plant
Thing oils and fats such as soybean oil, Oleum Brassicae campestris, Oleum Arachidis hypogaeae semen, sunflower seed oil, Petiolus Trachycarpi oil, Oleum Cocois and come from it
The material containing fat-based of its various crops and the fruit of wild plant, stem, leaf, branch and root (includes
The tall oil produced in paper-making process).Animal oil such as Adeps Sus domestica, Adeps Bovis seu Bubali, Adeps Caprae seu ovis, fish oil etc..
The method is also applied for containing high impurity, the oils and fats of high acid value.Such as acid number can be 0.1～
200mgKOH/g, preferably 10-150mgKOH/g.
Described monohydric alcohol refers to carbon number unitary fatty alcohol between 1～6, can be saturated alcohols or not
Saturated alcohols.As methanol, ethanol, propanol, isopropanol, 1-propenol-3, n-butyl alcohol and isomer thereof, amylalcohol and
Isomer etc..Single alcohol or their mixture can be used.Preferably methanol or ethanol.
Catalyst of the present invention has below general formula: CuZnaAlbOc, wherein a=0.04～3, preferably 0.1～
2, b=0.1～3, preferably 0.1～2, c is to meet the oxygen atomicity required by compound electric neutrality.
The preparation method of the catalyst used by the present invention includes: the soluble-salt of Cu, Al, Zn is dissolved in disengaging
In sub-water, at 10 DEG C～80 DEG C, at preferably 20 DEG C～50 DEG C, do precipitant with alkaline matter, to pH=4～
11, preferably pH=5～10, aging 0～5 hour, preferably 1～3 hour, then filter, wash, collect
Precipitation, in 70～200 DEG C, preferably 100～150 DEG C, is dried 2～30 hours, then at 300～900 DEG C,
Preferably 400～700 DEG C, roasting 0.5～30 hours, obtain the catalyst that the present invention uses.
During precipitation, alkali can be added to containing in the solution of the soluble-salt of Cu, Al, Zn, it is also possible to contrary,
Can also two kinds of solution stream be precipitated, wherein soluble-salt can be to contain Cu, Al, Zn tri-simultaneously
Plant the solution of slaine, it is also possible to be to comprise only one of which or the solution of two kinds of slaines, if the latter,
First several solution containing different metal salt can be used respectively alkali precipitation, then by old after the mixing of reacted solution
Change.
The preferred respective nitrate of soluble-salt of described Cu, Al, Zn.
Described alkaline matter is the aqueous solution material in alkalescence, preferably ammonium carbonate, ammonium hydrogen carbonate, ammonia, carbon
Acid sodium, sodium hydroxide and potassium hydroxide etc..Employing ammonium carbonate, ammonium hydrogen carbonate, ammonia, can be big as precipitant
Time prepared by big minimizing catalyst, the consumption of washings, reduces washing times, improves the production efficiency of catalyst.
The concentration of alkaline solution is 5～40wt%, preferably 10～35wt%.
Specifically, the present invention can use autoclave or fixed bed i.e. tubular reactor, if using autoclave,
Oils and fats, alcohol and catalyst are added thereto, react under conditions of stirring, if using tubular reactor,
Preferably oils and fats and monohydric alcohol being entered from tubular reactor bottom, product flows out from tubular reactor upper end,
Obtain reacting coarse product, from reacting coarse product, steam monohydric alcohol, by mixed ester phase (containing fatty acid ester, list
Sweet ester, two sweet esters, unreacted triglyceride) separate with glycerol, pass through respectively to steam by mixed ester phase and glycerol
Evaporate and obtain high purity fatty acid ester and glycerol.
According to the inventive method, if use autoclave, the addition of catalyst be oils and fats weight 0.05%～
10%, preferably 0.1%～3%, more preferably 0.5%～2%.If employing tubular reactor, liquid hourly space velocity (LHSV)
0.1～5h-1, preferably 0.1～2h-1, more preferably 0.1～1h-1。
Temperature of reactor is 60 DEG C～220 DEG C, preferably 100 DEG C～200 DEG C, more preferably 120 DEG C～170 DEG C,
Pressure 0.3Mpa～3Mpa, preferably 0.4Mpa～2Mpa, more preferably 0.5Mpa～1.2Mpa, monohydric alcohol
It is 0.05～2:1 with the mass ratio of oils and fats, preferably 0.1～1.5:1.
Temperature raises, and reaction conversion ratio is the highest, because for aerodynamic point, temperature raises and is conducive to reaction
Carry out, but when temperature is higher than 300 DEG C, product is black, has burnt matter to produce, also results in meanwhile
Glycerol decomposes, and therefore, temperature of reactor answers ＜ 300 DEG C, best 100～200 DEG C.
Pressure is the highest the most favourable to reaction, but pressure is the highest, makes plant investment and operating cost improve more, institute
With, pressure 0.3Mpa～3Mpa, preferably 0.4Mpa～2Mpa, more preferably 0.5Mpa～1.2Mpa,
In the inventive method, monohydric alcohol can in very large range change with the mass ratio of oils and fats, methanol and oily quality
Making Methanol Recovery amount be significantly increased than too high meeting, plant energy consumption and operating cost increase, and make under the utilization rate of equipment
Fall.So, monohydric alcohol is 0.05～2:1 with the mass ratio of oils and fats, preferably 0.1～1.5:1.
Widely, acid number can change the raw oil that the inventive method is suitable within a large range, it is adaptable to high
Acid number, high impurity oil plant.
The reactive mode of compound metal oxide solid catalyst with low pressure, low temperature is combined by the present invention, passes through
Single step reaction i.e. can get the biodiesel of high yield.During single step reaction, oil plant had both carried out esterification,
Carry out again ester exchange reaction.
Detailed description of the invention
Further illustrate the present invention below by example, but the present invention is not limited to this.
Embodiment 1
By 52.2g Cu (NO3)2.3H2O、146.7g Zn(NO3)2.6H2O、12.2g Al(NO3)3.9H2O,
It is dissolved in 400ml deionized water, is stirred at room temperature, drip 20wt% ammonia, until the pH of solution is 6
± 0.5, aging 1 hour, then to filter, washing once, is collected and is precipitated, 120 DEG C of dry 2hr, 300 ± 10 DEG C
Roasting 2 hours, obtains catalyst A:CuZn1.9Al0.15O3.1。
Embodiment 2
By 52.2g Cu (NO3)2.3H2O、74.9gZn(NO3)2.3H2O、122g Al(NO3)3.9H2O, molten
In 500ml deionized water, make solution A.By 20wt%Na2CO3As solution B.At 2000ml
Beaker loads 200ml deionized water, stirs under room temperature, two kinds of solution of A.B are simultaneously introduced in beaker, control
A.B processed drips speed, makes pH remain at 5.5 ± 1, after titration aging 1 hour, then filters, and washing is many
Secondary, collect precipitation, be dried 3 hours at 120 DEG C, 550 ± 20 DEG C of roastings 2 hours, obtain catalyst
B:CuZn0.9Al1.5O4.2。
Embodiment 3
By 52.2g Cu (NO3)2.3H2O、12.9g Zn(NO3)2.6H2O、56.9g Al(NO3)3.9H2O
It is dissolved in 1000ml deionized water, as solution A, by 23wt% sodium carbonate liquor as solution B, at 60 DEG C
Under stirring, A is instilled in B, until the pH of solution be 7 ± 0.5 titration after aging 1 hour, then filter,
Washing repeatedly, collects precipitation, is dried 3 hours at 120 DEG C, and 350 ± 10 DEG C of roastings 2 hours obtain catalyst
C:CuZn0.2 Al0.7O2.3。
Embodiment 4
The waste grease of acid number 40mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.16:1, adds the catalyst A of oils and fats weight 1.2%, in autoclave temp 120 DEG C, pressure 0.4Mpa, stirring
Under conditions of speed 200 revs/min, react 1 hour, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 90.6%.
Embodiment 5
The waste grease of acid number 40mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.17:1, adds the catalyst A of oils and fats weight 0.7%, in autoclave temp 130 DEG C, pressure 0.7Mpa, stirring
Under conditions of speed 250 revs/min, react 1 hour, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 91.4%.
Embodiment 6
The waste grease of acid number 40mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.16:1, adds the catalyst B of oils and fats weight 0.6%, in autoclave temp 130 DEG C, pressure 0.7Mpa, stirring
Under conditions of speed 200 revs/min, react 1 hour, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 92%.
Embodiment 7
The waste grease of acid number 122mgKOH/g, methanol are joined in autoclave together, alcohol oil quality ratio
0.17:1, adds the catalyst C of oils and fats weight 0.7%, at autoclave temp 140 DEG C, pressure 0.9Mpa, stirs
Under conditions of mixing speed 200 revs/min, react 1 hour, obtain reacting coarse product and distill, bottom ＜ 150 DEG C
Remove excessive methanol, and methanol reclaimed, reuses, leftover materials are isolated glycerol mutually after, right
The mixed ester obtained carries out decompression distillation mutually, and the yield obtaining biodiesel is 91.1%.
Embodiment 8
Take granularity 26-40 mesh catalyst B 5 grams and load internal diameter 8 millimeters, the stainless steel of length 391 millimeters
In the tubular reactor become, with the waste grease of acid number 110mg KOH/g as raw material, at alcohol oil quality ratio 0.2,
Liquid hourly space velocity (LHSV) 0.6h-1Under conditions of, it is anti-that oil and methanol continuously enter into tubular type from tubular reactor bottom
Answering in device, reaction temperature 130 DEG C, pressure 0.4Mpa, product flows out from tubular reactor upper end, reaction
Crude product through steaming unreacted methanol, standing separation glycerol phase, rectification under vacuum ester phase, obtain biodiesel yield
90%.
Embodiment 9
Take granularity 26-40 mesh catalyst A 5.2 grams and load internal diameter 8 millimeters, the rustless steel that length is 391 millimeters
In the tubular reactor made, with the waste grease of acid number 97mg KOH/g as raw material, at alcohol oil quality ratio
0.25, liquid hourly space velocity (LHSV) 0.4h-1Under conditions of, oil and methanol continuously enter into from tubular reactor bottom
In tubular reactor, reaction temperature 140 DEG C, pressure 1Mpa, product flows out from tubular reactor upper end,
Reacting coarse product through steaming unreacted methanol, standing separation glycerol phase, rectification under vacuum ester phase, obtain biodiesel
Yield 91.7%.
Claims (10)
1. the method preparing fatty acid ester, including: in the presence of composite oxide catalysts,
Oils and fats is mixed in the reactor with C1～C6 monohydric alcohol, reaction temperature 60 DEG C～
220 DEG C, react under pressure 0.3Mpa～3Mpa, separate from reacted material
Fatty acid ester, described catalyst has below general formula: CuZnaAlbOc, wherein a=0.04～
3, b=0.1～3, c are to meet the oxygen atomicity required by compound electric neutrality.
The most in accordance with the method for claim 1, wherein, the main component of described oils and fats is fat
Fat acid glycerol three ester, acid number is 0.1～200mgKOH/g.
The most in accordance with the method for claim 1, wherein, described monohydric alcohol refers to carbon number
Unitary fatty alcohol between 1～6.
The most in accordance with the method for claim 1, wherein, in described catalyst Formula, a=0.1～
2, b=0.1～2, c are to meet the oxygen atomicity required by compound electric neutrality.
The most in accordance with the method for claim 1, wherein, described reactor is autoclave or tubular type
Reactor.
The most in accordance with the method for claim 1, wherein, if using autoclave, catalyst
Addition is the 0.05%～10% of oils and fats weight.
The most in accordance with the method for claim 1, wherein, if using tubular reactor, during liquid
Air speed 0.1～5h-1。
The most in accordance with the method for claim 1, wherein, temperature of reactor is 120 DEG C～170 DEG C.
The most in accordance with the method for claim 1, wherein, reaction pressure 0.5Mpa～1.2Mpa.
The most in accordance with the method for claim 1, wherein, monohydric alcohol with the mass ratio of oils and fats is
0.05～2:1, preferably 0.1～1.5:1.
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| CN112661608A (en) * | 2020-12-30 | 2021-04-16 | 浙江物美生物科技有限公司 | Preparation method of natural fatty alcohol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480619A (en) * | 2009-01-05 | 2009-07-15 | 北京化工大学 | Method for preparing acidified solid catalyst for synthesizing biodiesel |
| CN102807922A (en) * | 2011-05-31 | 2012-12-05 | 中国石油化工股份有限公司 | Preparation method for fatty acid ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480619A (en) * | 2009-01-05 | 2009-07-15 | 北京化工大学 | Method for preparing acidified solid catalyst for synthesizing biodiesel |
| CN102807922A (en) * | 2011-05-31 | 2012-12-05 | 中国石油化工股份有限公司 | Preparation method for fatty acid ester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661608A (en) * | 2020-12-30 | 2021-04-16 | 浙江物美生物科技有限公司 | Preparation method of natural fatty alcohol |
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