CN116836757A - Method for producing biodiesel by utilizing rare earth compound and solid super acidic catalyst - Google Patents
Method for producing biodiesel by utilizing rare earth compound and solid super acidic catalyst Download PDFInfo
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- CN116836757A CN116836757A CN202311018250.3A CN202311018250A CN116836757A CN 116836757 A CN116836757 A CN 116836757A CN 202311018250 A CN202311018250 A CN 202311018250A CN 116836757 A CN116836757 A CN 116836757A
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 47
- -1 rare earth compound Chemical class 0.000 title claims abstract description 44
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000007787 solid Substances 0.000 title claims abstract description 31
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 239000003921 oil Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 43
- 238000005886 esterification reaction Methods 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 21
- 239000004519 grease Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 10
- 241001465754 Metazoa Species 0.000 claims description 8
- 239000011973 solid acid Substances 0.000 claims description 8
- 239000003930 superacid Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000010775 animal oil Substances 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 4
- 230000000813 microbial effect Effects 0.000 claims description 4
- 239000010773 plant oil Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 69
- 235000019198 oils Nutrition 0.000 description 42
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 20
- 125000001312 palmitoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 15
- 229910000420 cerium oxide Inorganic materials 0.000 description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 235000005687 corn oil Nutrition 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical group [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 2
- 229960001633 lanthanum carbonate Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 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 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/008—Refining fats or fatty oils by filtration, e.g. including ultra filtration, dialysis
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for producing biodiesel by utilizing a rare earth compound and a solid super acidic catalyst. The method can improve the catalytic effect and the biodiesel yield, and the product does not need washing operation, thereby avoiding the waste liquid discharge pollution.
Description
Technical Field
The invention relates to the technical field of biodiesel, in particular to a method for producing biodiesel by utilizing a rare earth compound and a solid super acidic catalyst.
Background
Biodiesel is a low-density and high-cetane-number fatty acid methyl ester or ethyl ester, and is a fatty acid ester product obtained by esterification reaction of vegetable oil (such as rapeseed oil, soybean oil, peanut oil, corn oil, cottonseed oil, etc.), animal oil (such as fish oil, lard, beef tallow, mutton oil, etc.), animal and vegetable acidification oil, waste grease or microbial grease and alcohols (methanol or ethanol, etc.). In the prior art, liquid acid or liquid alkali is often used as a catalyst for preparing biodiesel, but after the reaction is finished, the liquid catalyst in the product is removed by water washing, the liquid catalyst is difficult to completely separate, and a large amount of waste acid or waste alkali is inevitably generated to discharge, so that the environment is polluted. Although the solid acid catalyst is used for catalyzing the esterification reaction, the reaction yield is not ideal, the solid acid catalyst is also obtained after the reaction, and the operation is inconvenient.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for producing biodiesel by using a rare earth compound and a solid super acidic catalyst, which can improve the catalytic effect and the biodiesel yield, and the product does not need washing operation, so that the waste liquid emission pollution is avoided.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process for preparing biologic diesel oil from rare-earth compound and solid super acidic catalyst includes such steps as mixing biologic oil, alcohol and rare-earth compound, and cyclic reflux between reactor and fluidized bed with solid super acidic catalyst to obtain biologic diesel oil.
The method specifically comprises the following steps: dissolving rare earth compound in alcohol, adding biological grease, and mixing uniformly; inputting the mixture into a reaction kettle, heating to the reaction temperature, and circularly refluxing the mixture to the reaction kettle through a fluidized bed filled with a solid super acidic catalyst so as to perform a circularly flowing esterification reaction; distilling out the fraction between 150-360 ℃ in the mixture obtained by the reaction, and obtaining the distillate which is the biodiesel.
The solid super acid catalyst is GK-SHCZ-03 type solid acid catalyst manufactured by Guizhou gold bond high tech materials Co., ltd.
The biological grease accounts for 70-75% and the alcohol accounts for 25-30% based on 100% of the total mass of the biological grease and the alcohol; the rare earth compound accounts for 0.15-0.5% of the total mass of the biological grease and the alcohol substances.
The rare earth compound is at least one of rare earth oxide soluble in alcohol substances and rare earth salt soluble in alcohol substances.
The biological oil is one or more of animal and plant acidified oil, swill-cooked dirty oil, animal and plant oil and microbial oil; the alcohol is one or more of C1-C4 short chain alcohols.
The esterification reaction temperature is 65-70 ℃.
The mixture of the biological grease, the alcohol substances and the rare earth compounds is preheated and then is input into a reaction kettle, and then the circulating flow esterification reaction is carried out; the mixture is preheated to 40-50 ℃.
Distilling the mixture obtained by the esterification reaction to remove alcohol substances, and then distilling the biodiesel fraction at 150-360 ℃ under reduced pressure.
After removing alcohol substances in the mixture obtained by the reaction, the rest mixture is firstly input into a tube furnace to be heated to 260-280 ℃, and then is input into a vacuum fractionating tower to be distilled under reduced pressure.
The beneficial effects of the invention are as follows: the solid superacid is used as a catalyst, the high activity characteristic of the rare earth compound (the surface bond state and the electronic state of the rare earth compound are different from the inside of the particles, and the surface atomic coordination is incomplete, so that the surface activity is increased) is utilized, and the biodiesel is prepared through the circulating flow esterification reaction between a reaction kettle and a fluidized bed with the solid superacid catalyst, so that the product with the quality conforming to the technical standard of the national VI-B diesel for vehicles can be obtained, the esterification catalytic effect is improved, the yield of the biodiesel is improved, and the production cost is reduced; the invention makes the product not need to be washed by water through the innovative design of the preparation process, avoids the discharge and pollution of waste liquid, is a simple process, energy-saving and environment-friendly efficient preparation method, and is suitable for the mass production of biodiesel.
Detailed Description
The invention is further described in connection with the following detailed description:
the invention mixes biological grease, alcohols and rare earth compound, completes esterification reaction by the circulation reflux of the mixture between a reaction kettle and a fluidized bed filled with solid super acidic catalyst, and obtains biodiesel, wherein the esterification reaction temperature is 65-70 ℃.
The biological grease accounts for 70-75% and the alcohol accounts for 25-30% based on 100% of the total mass of the biological grease and the alcohol; the rare earth compound accounts for 0.15-0.5% of the total mass of the biological grease and the alcohol substances. The solid super acidic catalyst is preferably GK-SHCZ-03 type solid acid catalyst manufactured by Guizhou gold bond high-tech materials, inc., with a temperature resistance of 80-90 ℃ and a particle size of 0.5-1.5 mm.
The alcohol is one or more of C1-C4 short chain alcohols (such as methanol, ethanol, etc.). The biological oil is one or more of swill-cooked dirty oil, animal and plant acidified oil, animal and plant oil, and microbial oil, such as soybean oil, cotton oil, rapeseed oil, castor oil, palm oil, corn oil, etc., and animal and plant acidified oil such as bean acidified oil, cotton acidified oil, rapeseed acidified oil, castor acidified oil, palm acidified oil, corn acidified oil, etc. The rare earth compound is at least one of rare earth oxide soluble in alcohol substances and rare earth salt soluble in alcohol substances; the rare earth oxide is preferably a nano rare earth oxide (such as nano lanthanum oxide, nano cerium oxide, etc.) which is soluble in alcohol substances; the rare earth salt is not limited to rare earth nitrate, rare earth sulfate, etc. soluble in alcohol substances, and is preferably rare earth nitrate (such as lanthanum nitrate, cerium nitrate, etc.). The biological oil and alcohol used in the present invention are sufficient to allow esterification reaction, and the rare earth compound used is sufficient to be soluble in alcohol and to promote the progress of esterification reaction, and is not limited to the above specific ones. When the rare earth compound which contains two or more rare earth elements and is soluble in alcohol substances and the GK-SHCZ-03 type solid acid catalyst are adopted, the biodiesel yield can be improved to more than 98 percent.
The specific preparation steps of the biodiesel comprise:
(a) Dissolving rare earth compound in alcohol, adding biological grease, and mixing uniformly to obtain the mixture.
(b) The mixture is input into a reaction kettle and heated to 65-70 ℃, then the mixture is circulated and reflowed to the reaction kettle through a fluidized bed filled with a solid super acidic catalyst to carry out circulated flow esterification reaction (namely, the reaction kettle and the fluidized bed form a circulation loop, the mixture in the reaction kettle is filtered through a filter and then pumped into the fluidized bed by a gear pump, and then the mixture reflows to the reaction kettle to form a circulation, and esterification is realized through the circulated reflow of the mixture between the reaction kettle and the fluidized bed); the esterification reaction temperature is 65-70 ℃ and the reaction time is 2-4h. The mixture of biological oil, alcohol and rare earth compound can be preheated to 40-50 ℃ and then input into a reaction kettle, so as to carry out circulating flow esterification reaction.
(c) Distilling out the fraction between 150-360 ℃ in the mixture obtained by the reaction, and obtaining the distillate which is the biodiesel. The method comprises the following steps: distilling the mixture obtained by the esterification reaction to remove alcohol substances, and distilling the biodiesel fraction at 150-360 ℃ under reduced pressure. After alcohol substances in the mixture obtained by the reaction are distilled and removed, the rest mixture is firstly fed into a tube furnace to be heated to 260-280 ℃, and then fed into a vacuum fractionating tower to be distilled under reduced pressure.
Specific examples are as follows:
example 1
Adding methanol, nano lanthanum oxide and nano cerium oxide into a mixing preheating tank, stirring to dissolve the nano lanthanum oxide and nano cerium oxide in the methanol, then adding palmitoyl oil, continuously and uniformly mixing, and preheating to 40 ℃ to obtain a mixture; 70% of palmitoyl oil and 30% of methanol based on 100% of total mass of palmitoyl oil and methanol; the addition amount of the nanometer lanthanum oxide is 0.2 percent of the total mass of the palmitoyl oil and the methanol, and the nanometer cerium oxide is 0.2 percent of the total mass of the palmitoyl oil and the methanol. The preheated mixture is metered by a gear pump and a flowmeter and then is input into a reaction kettle, the mixture is heated to 65 ℃ by the reaction kettle, then the mixture is circulated and reflowed to the reaction kettle by a fluidized bed filled with a solid super acidic catalyst to carry out circulated flowing esterification reaction, the temperature of the reaction kettle is kept between 65 ℃ and 70 ℃ in the circulation process (namely, the esterification reaction temperature is controlled between 65 ℃ and 70 ℃), and the reaction time is 3 hours; after the reaction is finished, methanol in the reaction kettle material is distilled out at 90-95 ℃ (the methanol is recovered into a methanol tank after being cooled by a heat exchanger), the residual reaction material is pumped into a middle tank (the middle tank is used for temporarily storing the material and can stir the material) through a gear pump after being filtered by a filter, then the material in the middle tank is pumped into a tubular furnace and heated to 260 ℃, then the material is input into a vacuum fractionating tower and subjected to vacuum distillation at 125-360 ℃, the obtained distillate is the biodiesel, the biodiesel is stored in a finished product tank, and the residual material in the vacuum fractionating tower is recovered into an asphalt tank.
Example 2
Adding methanol, nano lanthanum oxide and nano cerium oxide into a mixing preheating tank, stirring to dissolve the nano lanthanum oxide and nano cerium oxide in the methanol, then adding palmitoyl oil, continuously and uniformly mixing, and preheating to 50 ℃ to obtain a mixture; 75% of palmitoyl oil and 25% of methanol based on 100% of the total mass of palmitoyl oil and methanol; the addition amount of the nanometer lanthanum oxide is 0.15 percent of the total mass of the palmitoyl oil and the methanol, and the nanometer cerium oxide is 0.15 percent of the total mass of the palmitoyl oil and the methanol. The preheated mixture is metered by a gear pump and a flowmeter and then is input into a reaction kettle, the mixture is heated to 70 ℃ by the reaction kettle, then the mixture is circulated and reflowed to the reaction kettle by a fluidized bed filled with a solid super acidic catalyst to carry out circulated flowing esterification reaction, the temperature of the reaction kettle is kept between 65 ℃ and 70 ℃ in the circulation process (namely, the esterification reaction temperature is controlled between 65 ℃ and 70 ℃), and the reaction time is 4 hours; after the reaction is finished, methanol in the reaction kettle material is distilled out at 90-95 ℃ (the methanol is recovered into a methanol tank after being cooled by a heat exchanger), the residual reaction material is pumped into a middle tank (the middle tank is used for temporarily storing the material and can stir the material) through a gear pump after being filtered by a filter, then the material in the middle tank is pumped into a tubular furnace and heated to 280 ℃, then the tubular furnace is input into a vacuum fractionating tower and subjected to vacuum distillation at 125-360 ℃, the obtained distillate is the biodiesel, and the residual material in the vacuum fractionating tower is recovered into an asphalt tank.
Example 3
Adding ethanol, lanthanum nitrate and cerium nitrate into a mixing preheating tank, stirring to dissolve nano lanthanum oxide and nano cerium oxide in ethanol, then adding palmitoyl oil, continuously and uniformly mixing, and preheating to 45 ℃ to obtain a mixture; 70% of palmitoyl oil and 30% of methanol based on 100% of the total mass of palmitoyl oil and ethanol; the addition amount of lanthanum nitrate is 0.25% of the total mass of the palmitoyl oil and the methanol, and the addition amount of cerium nitrate is 0.25% of the total mass of the palmitoyl oil and the methanol. The preheated mixture is metered by a gear pump and a flowmeter and then is input into a reaction kettle, the mixture is heated to 65 ℃ by the reaction kettle, then the mixture is circulated and reflowed to the reaction kettle by a fluidized bed filled with a solid super acid catalyst to carry out circulated flow esterification reaction (namely, the reaction kettle and the fluidized bed form a circulation loop, the mixture in the reaction kettle is pumped into the fluidized bed by the gear pump after being filtered by a filter and then reflowed to the reaction kettle to form a circulation, the esterification is realized by the circulated and reflowed mixture between the reaction kettle and the fluidized bed), the temperature of the reaction kettle is kept at 65-70 ℃ in the circulation process (namely, the esterification reaction temperature is controlled to 65-70 ℃), and the reaction time is 3h; after the reaction is finished, ethanol in the reaction kettle material is distilled out (the ethanol is recycled to an ethanol tank after being cooled by a heat exchanger), the residual reaction material is pumped into a middle tank (the middle tank is used for temporarily storing the material and can stir the material) through a gear pump after being filtered by a filter, then the material in the middle tank is pumped into a tubular furnace and heated to 280 ℃, then the tubular furnace is input into a vacuum fractionating tower and subjected to vacuum distillation at 125-360 ℃, the obtained distillate is the biodiesel, and the residual material in the vacuum fractionating tower is recycled to an asphalt tank.
Example 4
Biodiesel was produced as in example 1, except that swill-cooked dirty oil was used instead of palmitoylated oil.
Example 5
Biodiesel was produced as in example 2, except that swill-cooked dirty oil was used instead of palmitoylated oil.
Example 6
Biodiesel was produced as in example 3, except that swill-cooked dirty oil was used instead of palmitoylated oil.
In the present invention, the vegetable oil and fat in the swill-cooked dirty oil adopted in the embodiments 4 to 6 account for 90.54 percent, the animal oil and fat account for 7.48 percent, and the balance is water.
The properties of the biodiesel produced in examples 1-6 were as shown in Table 1, and examples 1-6 all used GK-SHCZ-03 solid acid catalyst manufactured by Guizhou gold bond high tech materials Co., ltd.
TABLE 1
Example 7
Biodiesel was prepared as in example 1, except that the solid superacid catalyst of example 1 was replaced with TiO 2 -SiO 2 A solid acid catalyst.
Comparative example 1
Biodiesel was produced as in example 1, except that nano lanthanum oxide and nano cerium oxide were not added.
Comparative example 2
Biodiesel was produced as in example 1, except that the lanthanum oxide nanoparticles of example 1 were replaced with lanthanum carbonate nanoparticles, and the molar amount of lanthanum carbonate nanoparticles was the same as that of lanthanum oxide nanoparticles of example 1.
The biodiesel yields of examples 1-6 were found to be 98.51%, 98.7%, 98.47%, 98.24%, 98.32%, 98.21%, respectively; whereas the biodiesel yield of example 7 was 90.38%; the biodiesel yield of comparative example 1 was 90.03%, and that of comparative example 2 was 92.4%.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A method for producing biodiesel by utilizing rare earth compounds and solid super acidic catalyst is characterized in that: the biological grease, the alcohol substances and the rare earth compound are mixed, and the esterification reaction is completed through the circulation reflux of the mixture between the reaction kettle and the fluidized bed filled with the solid super acidic catalyst, so as to obtain the biodiesel.
2. The method for producing biodiesel by using rare earth compounds and solid super acidic catalyst as claimed in claim 1, wherein: the method specifically comprises the following steps: dissolving rare earth compound in alcohol, adding biological grease, and mixing uniformly; inputting the mixture into a reaction kettle, heating to the reaction temperature, and circularly refluxing the mixture to the reaction kettle through a fluidized bed filled with a solid super acidic catalyst so as to perform a circularly flowing esterification reaction; distilling out the fraction between 150-360 ℃ in the mixture obtained by the reaction, and obtaining the distillate which is the biodiesel.
3. A method for producing biodiesel using a rare earth compound, a solid super acidic catalyst as claimed in claim 1 or 2, characterized in that: the solid super acid catalyst is GK-SHCZ-03 type solid acid catalyst manufactured by Guizhou gold bond high tech materials Co., ltd.
4. A method for producing biodiesel using a rare earth compound, a solid super acidic catalyst as claimed in claim 1 or 2, characterized in that: the biological grease accounts for 70-75% and the alcohol accounts for 25-30% based on 100% of the total mass of the biological grease and the alcohol; the rare earth compound accounts for 0.15-0.5% of the total mass of the biological grease and the alcohol substances.
5. A method for producing biodiesel using a rare earth compound, a solid super acidic catalyst as claimed in claim 1 or 2, characterized in that: the rare earth compound is at least one of rare earth oxide soluble in alcohol substances and rare earth salt soluble in alcohol substances.
6. A method for producing biodiesel using a rare earth compound, a solid super acidic catalyst as claimed in claim 1 or 2, characterized in that: the biological oil is one or more of animal and plant acidified oil, swill-cooked dirty oil, animal and plant oil and microbial oil; the alcohol is one or more of C1-C4 short chain alcohols.
7. A method for producing biodiesel using a rare earth compound, a solid super acidic catalyst as claimed in claim 1 or 2, characterized in that: the esterification reaction temperature is 65-70 ℃.
8. A method for producing biodiesel using a rare earth compound, a solid super acidic catalyst as claimed in claim 1 or 2, characterized in that: the mixture of the biological grease, the alcohol substances and the rare earth compounds is preheated and then is input into a reaction kettle, and then the circulating flow esterification reaction is carried out; the mixture is preheated to 40-50 ℃.
9. A method for producing biodiesel using a rare earth compound, a solid super acidic catalyst as claimed in claim 1 or 2, characterized in that: distilling the mixture obtained by the esterification reaction to remove alcohol substances, and then distilling the biodiesel fraction at 150-360 ℃ under reduced pressure.
10. The method for producing biodiesel using a rare earth compound, solid super acid catalyst as claimed in claim 9, wherein: after removing alcohol substances in the mixture obtained by the reaction, the rest mixture is firstly input into a tube furnace to be heated to 260-280 ℃, and then is input into a vacuum fractionating tower to be distilled under reduced pressure.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858160A (en) * | 2006-06-02 | 2006-11-08 | 中国农业科学院油料作物研究所 | Method for preparing biological diesel oil using nano solid acid or alkali catalyst |
| CN101020838A (en) * | 2007-03-23 | 2007-08-22 | 江西新时代油脂工业有限公司 | Biodiesel oil preparing process and apparatus |
| CN101085929A (en) * | 2007-02-12 | 2007-12-12 | 源华卓越能源科技（福建）有限公司 | Technique for producing biological diesel oil by Louis acid catalysis one-step method |
| CN101993784A (en) * | 2010-12-01 | 2011-03-30 | 沈阳工业大学 | Method for preparing biodiesel from hogwash oil catalyzed by solid super acid |
| CN102391914A (en) * | 2011-09-30 | 2012-03-28 | 中国计量学院 | Method for preparing biodiesel by catalysis of rare-earth oxide mesoporous material |
| CN103435488A (en) * | 2013-09-04 | 2013-12-11 | 中国林业科学研究院林产化学工业研究所 | Process for producing environment-friendly plasticizer employing conical fluidized bed and device thereof |
| CN105132192A (en) * | 2014-05-29 | 2015-12-09 | 中国石油化工股份有限公司 | Biodiesel preparation method |
| CN106433999A (en) * | 2016-06-03 | 2017-02-22 | 南京林业大学 | Preparation method of renewable hydrocarbon-rich liquid fuel |
-
2023
- 2023-08-14 CN CN202311018250.3A patent/CN116836757A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858160A (en) * | 2006-06-02 | 2006-11-08 | 中国农业科学院油料作物研究所 | Method for preparing biological diesel oil using nano solid acid or alkali catalyst |
| CN101085929A (en) * | 2007-02-12 | 2007-12-12 | 源华卓越能源科技（福建）有限公司 | Technique for producing biological diesel oil by Louis acid catalysis one-step method |
| CN101020838A (en) * | 2007-03-23 | 2007-08-22 | 江西新时代油脂工业有限公司 | Biodiesel oil preparing process and apparatus |
| CN101993784A (en) * | 2010-12-01 | 2011-03-30 | 沈阳工业大学 | Method for preparing biodiesel from hogwash oil catalyzed by solid super acid |
| CN102391914A (en) * | 2011-09-30 | 2012-03-28 | 中国计量学院 | Method for preparing biodiesel by catalysis of rare-earth oxide mesoporous material |
| CN103435488A (en) * | 2013-09-04 | 2013-12-11 | 中国林业科学研究院林产化学工业研究所 | Process for producing environment-friendly plasticizer employing conical fluidized bed and device thereof |
| CN105132192A (en) * | 2014-05-29 | 2015-12-09 | 中国石油化工股份有限公司 | Biodiesel preparation method |
| CN106433999A (en) * | 2016-06-03 | 2017-02-22 | 南京林业大学 | Preparation method of renewable hydrocarbon-rich liquid fuel |
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