CN112892590A - High-efficiency energy-saving biodiesel catalyst and preparation method thereof - Google Patents
High-efficiency energy-saving biodiesel catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112892590A CN112892590A CN202110131566.8A CN202110131566A CN112892590A CN 112892590 A CN112892590 A CN 112892590A CN 202110131566 A CN202110131566 A CN 202110131566A CN 112892590 A CN112892590 A CN 112892590A
- Authority
- CN
- China
- Prior art keywords
- parts
- alumina
- acid
- mixing
- energy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000003225 biodiesel Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 96
- 238000003756 stirring Methods 0.000 claims description 78
- 238000002156 mixing Methods 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 64
- 229910019142 PO4 Inorganic materials 0.000 claims description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 41
- 239000010452 phosphate Substances 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 32
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 32
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 32
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 32
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 32
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 32
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 229920000570 polyether Polymers 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 229960002089 ferrous chloride Drugs 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 10
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000007127 saponification reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001254 electrum Inorganic materials 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010940 green gold Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high-efficiency energy-saving biodiesel catalyst and a preparation method thereof, relating to the technical field of catalysts, wherein the high-efficiency energy-saving biodiesel catalyst is composed of the following raw materials: the modified aluminum oxide is modified by using an auxiliary agent, and the auxiliary agent can accurately and selectively react with the alkaline site of the aluminum oxide, so that the effect of reducing the alkalinity of the aluminum oxide is achieved; the catalyst does not physically or chemically react with other active sites of the alumina, so that the physicochemical properties of the alumina, such as the crystal structure, the pore structure and the like, are not changed, the alkali property can be only adjusted, other characteristics of the alumina are not basically changed, and the stability of the catalyst in application is effectively improved; no environmental pollution, no corrosion, no saponification, simple synthesis process and low production cost.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a high-efficiency energy-saving biodiesel catalyst and a preparation method thereof.
Background
With the rapid development of global economy, the demand for energy is continuously increased due to the rapid decrease of petroleum reserves, and the problem of environmental pollution caused by the combustion of petrochemical fuels is becoming serious, so that the development of novel green renewable fuel oil resources is the most widely concerned problem of people at present and is also the hot topic of the research of new energy production technology. Biodiesel is a biomass energy source, has the advantages of biodegradability, complete combustion, less emission of harmful substances and the like, is the only renewable clean fuel capable of replacing petroleum diesel in the world at present, is known as 'green gold', and is paid much attention as a clean and renewable energy source due to the advantages of simple degradation, no emission in combustion, no greenhouse effect gas and the like.
The biodiesel is an environment-friendly green fuel, but the biodiesel preparation process uses a catalyst which is not environment-friendly, and the catalyst is not in accordance with the design of green chemistry, particularly after the reaction is finished, the product needs to be neutralized and washed, saponification phenomena are easy to generate, and a large amount of waste acid and waste alkali liquor are discharged to pollute the environment, so that the post-treatment is troublesome, but in the process of preparing the biodiesel, the traditional catalyst, namely strong acid and strong base, is excessively used, so that the environment is still seriously polluted, and the occurrence of the phenomena seriously violates the design of the biodiesel at first.
Disclosure of Invention
The invention aims to provide an efficient energy-saving biodiesel catalyst and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-efficiency energy-saving biodiesel catalyst is composed of the following raw materials in parts by weight: 40-50 parts of methanesulfonic acid, 10-18 parts of chlorosulfonic acid, 4-9 parts of modified alumina, 5-8 parts of glycerol, 15-25 parts of fatty sulfonic acid, 12-18 parts of phosphoric acid monoester, 3-6 parts of stannic chloride, 12-17 parts of polyether acid phosphate and 4-7 parts of propargyl alcohol.
As a further scheme of the invention: the high-efficiency energy-saving biodiesel catalyst is prepared from the following raw materials in parts by weight: 45 parts of methanesulfonic acid, 13 parts of chlorosulfonic acid, 7 parts of modified alumina, 6 parts of glycerol, 20 parts of fatty sulfonic acid, 15 parts of phosphoric monoester, 4 parts of stannic chloride, 15 parts of polyether acid phosphate and 5 parts of propargyl alcohol.
As a still further scheme of the invention: the high-efficiency energy-saving biodiesel catalyst is prepared from the following raw materials in parts by weight: 47 parts of methanesulfonic acid, 15 parts of chlorosulfonic acid, 8 parts of modified alumina, 7 parts of glycerol, 21 parts of fatty sulfonic acid, 16 parts of phosphoric monoester, 5 parts of stannic chloride, 16 parts of polyether acid phosphate and 6 parts of propargyl alcohol.
As a still further scheme of the invention: the high-efficiency energy-saving biodiesel catalyst is prepared from the following raw materials in parts by weight: 42 parts of methanesulfonic acid, 12 parts of chlorosulfonic acid, 6 parts of modified alumina, 8 parts of glycerol, 17 parts of fatty sulfonic acid, 14 parts of phosphoric monoester, 3 parts of stannic chloride, 13 parts of polyether acid phosphate and 7 parts of propargyl alcohol.
As a still further scheme of the invention: the preparation method of the modified alumina comprises the following steps: mixing and uniformly stirring aluminum oxide and deionized water, and then drying at the temperature of 120-160 ℃ for 12-15 hours; mixing the obtained alumina and ethanol, uniformly stirring, drying at the temperature of 120-160 ℃ for 12-15 hours, treating at the temperature of 250-280 ℃ for 2-4 hours, mixing the obtained alumina, the auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; and roasting the obtained substance at the temperature of 450-500 ℃ for 3-7 hours in an argon atmosphere to obtain the modified alumina.
As a still further scheme of the invention: the mass ratio of the alumina to the deionized water is 1-4: 6-9.
As a still further scheme of the invention: in the preparation method of the modified alumina, ethanol is absolute ethanol, and the mass ratio of the alumina to the ethanol is 1-3: 2-5.
As a still further scheme of the invention: according to the preparation method of the modified alumina, the auxiliary agent is ferrous chloride, and the mass ratio of the alumina to the auxiliary agent to the deionized water is 1:2: 3.
A preparation method of a high-efficiency energy-saving biodiesel catalyst comprises the following steps:
1) weighing 40-50 parts of methanesulfonic acid, 10-18 parts of chlorosulfonic acid, 4-9 parts of modified alumina, 5-8 parts of glycerol, 15-25 parts of fatty sulfonic acid, 12-18 parts of monoester phosphate, 3-6 parts of stannic chloride, 12-17 parts of polyether acid phosphate and 4-7 parts of propargyl alcohol in sequence according to the proportion;
2) mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 85-95 ℃ for 40-60min at a stirring speed of 300-400r/min to obtain a first mixture;
3) adding the phosphoric acid monoester, the stannic chloride, the polyether acid phosphate and the propargyl alcohol into the first mixture, mixing and stirring again, wherein the mixing temperature is 90-100 ℃, the mixing time is 30-50min, the stirring speed is 200-300r/min, and then cooling to 50-60 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention carries out modification treatment on the alumina, and the alumina is modified by using the auxiliary agent which can accurately and selectively react with the alkaline site of the alumina, thereby playing a role in reducing the alkalinity of the alumina; the catalyst does not physically or chemically react with other active sites of the alumina, so that the physicochemical properties of the alumina, such as the crystal structure, the pore structure and the like, are not changed, the alkali property can be only adjusted, other characteristics of the alumina are not basically changed, and the stability of the catalyst in application is effectively improved;
2) after the reaction is finished, the components are easy to separate, the reaction mixed liquid is neutral, neutralization and washing are not needed, no waste water is generated, the environment is not polluted, no corrosion is caused, the saponification phenomenon is avoided, the treatment is convenient, the synthesis process is simple, and the production cost is low.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
The invention carries out modification treatment on the alumina, and the alumina is modified by using the auxiliary agent which can accurately and selectively react with the alkaline site of the alumina, thereby playing a role in reducing the alkalinity of the alumina; the catalyst does not physically or chemically react with other active sites of the alumina, so that the physicochemical properties of the alumina, such as the crystal structure, the pore structure and the like, are not changed, the alkali property can be only adjusted, other characteristics of the alumina are not basically changed, and the stability of the catalyst in application is effectively improved; after the reaction is finished, the components are easy to separate, the reaction mixed liquid is neutral, neutralization and washing are not needed, no waste water is generated, the environment is not polluted, no corrosion is caused, the saponification phenomenon is avoided, the treatment is convenient, the synthesis process is simple, and the production cost is low.
Example 1
Weighing 40 parts of methanesulfonic acid, 10 parts of chlorosulfonic acid, 4 parts of modified alumina, 5 parts of glycerol, 15 parts of fatty sulfonic acid, 12 parts of phosphoric acid monoester, 3 parts of stannic chloride, 12 parts of polyether acid phosphate and 4 parts of propargyl alcohol in sequence according to the proportion, wherein the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying at 120 ℃ for 12 hours; mixing the obtained alumina and ethanol, uniformly stirring, drying at 120 ℃ for 12 hours, treating at 250 ℃ for 2 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; roasting the obtained substance at 450 ℃ for 3 hours in an argon atmosphere, and then obtaining modified alumina, wherein the mass ratio of the alumina to deionized water is 1:6, ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 1:2, an auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina, the auxiliary agent and the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 85 ℃ for 40min at a stirring speed of 300r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 90 ℃ for 30min at the stirring speed of 200r/min, and cooling to 50 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Example 2
Weighing 42 parts of methanesulfonic acid, 12 parts of chlorosulfonic acid, 5 parts of modified alumina, 6 parts of glycerol, 17 parts of fatty sulfonic acid, 13 parts of phosphoric acid monoester, 4 parts of stannic chloride, 13 parts of polyether acid phosphate and 5 parts of propargyl alcohol in sequence according to the proportion, wherein the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying at 130 ℃ for 13 hours; mixing the obtained alumina and ethanol, uniformly stirring, drying at 130 ℃ for 13 hours, treating at 260 ℃ for 3 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; roasting the obtained substance at 460 ℃ for 4 hours in an argon atmosphere, and then obtaining modified alumina, wherein the mass ratio of the alumina to deionized water is 2:7, the ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 2:3, the auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina, the auxiliary agent and the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 85 ℃ for 45min at a stirring speed of 350r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 95 ℃ for 35min at the stirring speed of 250r/min, and cooling to 55 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Comparative example 3
Weighing 44 parts of methanesulfonic acid, 14 parts of chlorosulfonic acid, 6 parts of modified alumina, 7 parts of glycerol, 19 parts of fatty sulfonic acid, 14 parts of phosphoric acid monoester, 5 parts of stannic chloride, 13 parts of polyether acid phosphate and 5 parts of propargyl alcohol in sequence according to the proportion, wherein the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying for 14 hours at 140 ℃; mixing the obtained alumina and ethanol, uniformly stirring, drying at 140 ℃ for 14 hours, then treating at 270 ℃ for 4 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and then directly filtering, separating and drying; roasting the obtained substance at 470 ℃ for 5 hours in an argon atmosphere to obtain modified alumina, wherein the mass ratio of the alumina to deionized water is 3:7, the ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 3:7, the auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina to the auxiliary agent to the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 90 ℃ for 50min at a stirring speed of 380r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 98 ℃ for 40min at the stirring speed of 280r/min, and cooling to 60 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Comparative example 4
47 parts of methanesulfonic acid, 15 parts of chlorosulfonic acid, 8 parts of modified alumina, 7 parts of glycerol, 21 parts of fatty sulfonic acid, 16 parts of phosphoric acid monoester, 5 parts of stannic chloride, 16 parts of polyether acid phosphate and 6 parts of propargyl alcohol are weighed in sequence according to the proportion, and the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying at 150 ℃ for 12 hours; mixing the obtained alumina and ethanol, uniformly stirring, drying at 150 ℃ for 12 hours, then treating at 260 ℃ for 3 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and then directly filtering, separating and drying; roasting the obtained substance at 480 ℃ for 6 hours in an argon atmosphere, and then obtaining modified alumina, wherein the mass ratio of the alumina to deionized water is 1:9, ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 1:5, an auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina, the auxiliary agent and the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at the mixing temperature of 95 ℃ for 40min at the stirring speed of 390r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 95 ℃ for 45min at the stirring speed of 280r/min, and cooling to 60 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Example 5
Weighing 42 parts of methanesulfonic acid, 12 parts of chlorosulfonic acid, 6 parts of modified alumina, 8 parts of glycerol, 17 parts of fatty sulfonic acid, 14 parts of phosphoric acid monoester, 3 parts of stannic chloride, 13 parts of polyether acid phosphate and 7 parts of propargyl alcohol in sequence according to the proportion, wherein the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying for 15 hours at 130 ℃; mixing the obtained alumina and ethanol, uniformly stirring, drying at 130 ℃ for 15 hours, treating at 250 ℃ for 2 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; roasting the obtained substance at 490 ℃ for 3 hours in an argon atmosphere, and then obtaining modified alumina, wherein the mass ratio of the alumina to deionized water is 2:9, the ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 3:5, the auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina, the auxiliary agent and the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 90 ℃ for 45min at a stirring speed of 360r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 90 ℃ for 30min at the stirring speed of 300r/min, and cooling to 60 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Example 6
Weighing 44 parts of methanesulfonic acid, 13 parts of chlorosulfonic acid, 8 parts of modified alumina, 5 parts of glycerol, 16 parts of fatty sulfonic acid, 18 parts of phosphoric acid monoester, 5 parts of stannic chloride, 14 parts of polyether acid phosphate and 4 parts of propargyl alcohol in sequence according to the proportion, wherein the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying at 140 ℃ for 12 hours; mixing the obtained alumina and ethanol, uniformly stirring, drying at 120 ℃ for 15 hours, treating at 270 ℃ for 3 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; roasting the obtained substance at 460 ℃ for 5 hours in an argon atmosphere, and then obtaining modified alumina, wherein the mass ratio of the alumina to deionized water is 4:7, the ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 3:4, the auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina, the auxiliary agent and the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 85 ℃ for 50min at a stirring speed of 360r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 95 ℃ for 40min at the stirring speed of 200r/min, and cooling to 55 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Example 7
Weighing 50 parts of methanesulfonic acid, 18 parts of chlorosulfonic acid, 9 parts of modified alumina, 8 parts of glycerol, 25 parts of fatty sulfonic acid, 18 parts of phosphoric acid monoester, 6 parts of stannic chloride, 17 parts of polyether acid phosphate and 7 parts of propargyl alcohol in sequence according to the proportion, wherein the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying for 15 hours at 150 ℃; mixing the obtained alumina and ethanol, uniformly stirring, drying at 160 ℃ for 15 hours, treating at 280 ℃ for 7 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; roasting the obtained substance at 460 ℃ for 5 hours in an argon atmosphere, and then obtaining modified alumina, wherein the mass ratio of the alumina to deionized water is 4:7, the ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 1:6, the auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina, the auxiliary agent and the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at the mixing temperature of 95 ℃ for 60min at the stirring speed of 400r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 100 ℃ for 50min at the stirring speed of 300r/min, and cooling to 60 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Comparative example 1
Weighing 42 parts of methanesulfonic acid, 12 parts of chlorosulfonic acid, 8 parts of glycerol, 17 parts of fatty sulfonic acid, 14 parts of phosphoric monoester, 3 parts of stannic chloride, 13 parts of polyether acid phosphate and 7 parts of propargyl alcohol in sequence according to the proportion; mixing and stirring methanesulfonic acid, chlorosulfonic acid, glycerol and fatty sulfonic acid, and heating, wherein the mixing temperature is 90 ℃, the mixing time is 45min, and the stirring speed is 360r/min, so as to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 90 ℃ for 30min at the stirring speed of 300r/min, and cooling to 60 ℃ to obtain the biodiesel catalyst.
Comparative example 2
Weighing 42 parts of methanesulfonic acid, 12 parts of chlorosulfonic acid, 6 parts of alumina, 8 parts of glycerol, 17 parts of fatty sulfonic acid, 14 parts of phosphoric acid monoester, 3 parts of stannic chloride, 13 parts of polyether acid phosphate and 7 parts of propargyl alcohol in sequence according to the proportion; mixing and stirring methanesulfonic acid, chlorosulfonic acid, alumina, glycerol and aliphatic sulfonic acid, heating at 90 ℃ for 45min at a stirring speed of 360r/min to obtain a first mixture; and adding the monoester phosphate, tin tetrachloride, polyether acid phosphate and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 90 ℃ for 30min at the stirring speed of 300r/min, and cooling to 60 ℃ to obtain the biodiesel catalyst.
Comparative example 3
Weighing 42 parts of methanesulfonic acid, 12 parts of chlorosulfonic acid, 6 parts of modified alumina, 8 parts of glycerol, 17 parts of fatty sulfonic acid, 14 parts of phosphoric monoester, 3 parts of stannic chloride and 7 parts of propargyl alcohol in sequence according to the proportion, wherein the preparation method of the modified alumina comprises the following steps: mixing and stirring aluminum oxide and deionized water uniformly, and then drying for 15 hours at 130 ℃; mixing the obtained alumina and ethanol, uniformly stirring, drying at 130 ℃ for 15 hours, treating at 250 ℃ for 2 hours, mixing the obtained alumina, an auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; roasting the obtained substance at 490 ℃ for 3 hours in an argon atmosphere, and then obtaining modified alumina, wherein the mass ratio of the alumina to deionized water is 2:9, the ethanol in the preparation method of the modified alumina is absolute ethanol, the mass ratio of the alumina to the ethanol is 3:5, the auxiliary agent in the preparation method of the modified alumina is ferrous chloride, and the mass ratio of the alumina, the auxiliary agent and the deionized water is 1:2: 3; mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 90 ℃ for 45min at a stirring speed of 360r/min to obtain a first mixture; and adding the phosphoric acid monoester, tin tetrachloride and propargyl alcohol into the first mixture, mixing and stirring again at the mixing temperature of 90 ℃ for 30min at the stirring speed of 300r/min, and cooling to 60 ℃ to obtain the biodiesel catalyst.
Effect testing
The reaction time reduction rate and the biodiesel conversion increase rate (compared to the sulfur catalyst) of each example and comparative example of the biodiesel catalyst of the present invention were compared. The test results are given in the following table:
in conclusion, the alumina is modified by the aid of the auxiliary agent, and the auxiliary agent can accurately and selectively react with the alkaline site of the alumina, so that the effect of reducing the alkalinity of the alumina is achieved; the catalyst does not physically or chemically react with other active sites of the alumina, so that the physicochemical properties of the alumina, such as the crystal structure, the pore structure and the like, are not changed, the alkali property can be only adjusted, other characteristics of the alumina are not basically changed, and the stability of the catalyst in application is effectively improved; after the reaction is finished, the components are easy to separate, the reaction mixed liquid is neutral, neutralization and washing are not needed, no waste water is generated, the environment is not polluted, no corrosion is caused, the saponification phenomenon is avoided, the treatment is convenient, the synthesis process is simple, and the production cost is low.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (9)
1. The efficient energy-saving biodiesel catalyst is characterized by comprising the following raw materials in parts by weight: 40-50 parts of methanesulfonic acid, 10-18 parts of chlorosulfonic acid, 4-9 parts of modified alumina, 5-8 parts of glycerol, 15-25 parts of fatty sulfonic acid, 12-18 parts of phosphoric acid monoester, 3-6 parts of stannic chloride, 12-17 parts of polyether acid phosphate and 4-7 parts of propargyl alcohol.
2. The energy-efficient biodiesel catalyst according to claim 1, wherein the energy-efficient biodiesel catalyst comprises the following raw materials in parts by weight: 45 parts of methanesulfonic acid, 13 parts of chlorosulfonic acid, 7 parts of modified alumina, 6 parts of glycerol, 20 parts of fatty sulfonic acid, 15 parts of phosphoric monoester, 4 parts of stannic chloride, 15 parts of polyether acid phosphate and 5 parts of propargyl alcohol.
3. The energy-efficient biodiesel catalyst according to claim 1 or 2, wherein: the high-efficiency energy-saving biodiesel catalyst is prepared from the following raw materials in parts by weight: 47 parts of methanesulfonic acid, 15 parts of chlorosulfonic acid, 8 parts of modified alumina, 7 parts of glycerol, 21 parts of fatty sulfonic acid, 16 parts of phosphoric monoester, 5 parts of stannic chloride, 16 parts of polyether acid phosphate and 6 parts of propargyl alcohol.
4. The energy-efficient biodiesel catalyst according to claim 3, wherein: the high-efficiency energy-saving biodiesel catalyst is prepared from the following raw materials in parts by weight: 42 parts of methanesulfonic acid, 12 parts of chlorosulfonic acid, 6 parts of modified alumina, 8 parts of glycerol, 17 parts of fatty sulfonic acid, 14 parts of phosphoric monoester, 3 parts of stannic chloride, 13 parts of polyether acid phosphate and 7 parts of propargyl alcohol.
5. The energy-efficient biodiesel catalyst according to claim 4, wherein: the preparation method of the modified alumina comprises the following steps: mixing and uniformly stirring aluminum oxide and deionized water, and then drying at the temperature of 120-160 ℃ for 12-15 hours; mixing the obtained alumina and ethanol, uniformly stirring, drying at the temperature of 120-160 ℃ for 12-15 hours, treating at the temperature of 250-280 ℃ for 2-4 hours, mixing the obtained alumina, the auxiliary agent and deionized water, uniformly stirring, and directly filtering, separating and drying; and roasting the obtained substance at the temperature of 450-500 ℃ for 3-7 hours in an argon atmosphere to obtain the modified alumina.
6. The energy-efficient biodiesel catalyst according to claim 5, wherein: the mass ratio of the alumina to the deionized water is 1-4: 6-9.
7. The energy-efficient biodiesel catalyst according to claim 6, wherein: in the preparation method of the modified alumina, ethanol is absolute ethanol, and the mass ratio of the alumina to the ethanol is 1-3: 2-5.
8. The energy-efficient biodiesel catalyst according to claim 7, wherein: according to the preparation method of the modified alumina, the auxiliary agent is ferrous chloride, and the mass ratio of the alumina to the auxiliary agent to the deionized water is 1:2: 3.
9. A method for preparing a high efficiency energy saving biodiesel catalyst according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
1) weighing 40-50 parts of methanesulfonic acid, 10-18 parts of chlorosulfonic acid, 4-9 parts of modified alumina, 5-8 parts of glycerol, 15-25 parts of fatty sulfonic acid, 12-18 parts of monoester phosphate, 3-6 parts of stannic chloride, 12-17 parts of polyether acid phosphate and 4-7 parts of propargyl alcohol in sequence according to the proportion;
2) mixing and stirring methanesulfonic acid, chlorosulfonic acid, modified alumina, glycerol and aliphatic sulfonic acid, heating at 85-95 ℃ for 40-60min at a stirring speed of 300-400r/min to obtain a first mixture;
3) adding the phosphoric acid monoester, the stannic chloride, the polyether acid phosphate and the propargyl alcohol into the first mixture, mixing and stirring again, wherein the mixing temperature is 90-100 ℃, the mixing time is 30-50min, the stirring speed is 200-300r/min, and then cooling to 50-60 ℃ to obtain the high-efficiency energy-saving biodiesel catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110131566.8A CN112892590A (en) | 2021-01-30 | 2021-01-30 | High-efficiency energy-saving biodiesel catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110131566.8A CN112892590A (en) | 2021-01-30 | 2021-01-30 | High-efficiency energy-saving biodiesel catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112892590A true CN112892590A (en) | 2021-06-04 |
Family
ID=76121952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110131566.8A Pending CN112892590A (en) | 2021-01-30 | 2021-01-30 | High-efficiency energy-saving biodiesel catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112892590A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074391A (en) * | 2007-07-19 | 2007-11-21 | 杨庆利 | Method and catalyst for producing biological diesel oil by high-acid value grease |
| CN101073770A (en) * | 2006-05-19 | 2007-11-21 | 李艺 | Process of biological diesel-oil composite liquefied catalyst |
| CN103464201A (en) * | 2013-09-25 | 2013-12-25 | 陕西合盛生物柴油技术开发有限公司 | Composite acid catalyst for esterification of biodiesel |
| CN103706384A (en) * | 2013-12-24 | 2014-04-09 | 内蒙古农业大学 | Preparation method of bio-diesel catalyst |
| CN107488519A (en) * | 2017-07-24 | 2017-12-19 | 北京科技大学 | A kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal |
| WO2018226087A1 (en) * | 2017-06-06 | 2018-12-13 | Universiti Putra Malaysia | Method of producing fatty acid methyl ester |
-
2021
- 2021-01-30 CN CN202110131566.8A patent/CN112892590A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101073770A (en) * | 2006-05-19 | 2007-11-21 | 李艺 | Process of biological diesel-oil composite liquefied catalyst |
| CN101074391A (en) * | 2007-07-19 | 2007-11-21 | 杨庆利 | Method and catalyst for producing biological diesel oil by high-acid value grease |
| CN103464201A (en) * | 2013-09-25 | 2013-12-25 | 陕西合盛生物柴油技术开发有限公司 | Composite acid catalyst for esterification of biodiesel |
| CN103706384A (en) * | 2013-12-24 | 2014-04-09 | 内蒙古农业大学 | Preparation method of bio-diesel catalyst |
| WO2018226087A1 (en) * | 2017-06-06 | 2018-12-13 | Universiti Putra Malaysia | Method of producing fatty acid methyl ester |
| CN107488519A (en) * | 2017-07-24 | 2017-12-19 | 北京科技大学 | A kind of method that acid-base catalysis Bio-Diesel Fuels are loaded using magnetic charcoal |
Non-Patent Citations (6)
| Title |
|---|
| JIN, BB ET AL.: "Lewis acid-catalyzed in situ transesterification/esterification of microalgae in supercritical ethanol", 《BIORESOURCE TECHNOLOGY》 * |
| MEENAKSHI, H. N.、SHYAMALA, R.: "Effect of flow and dissolved oxygen on the compatibility of Pongamia pinnata biodiesel with common construction materials used in storage and transportation.", 《INTERNATIONAL JOURNAL OF CHEMICAL ENGINEERING 》 * |
| YUWEN JI ET AL.: "Methyl Chloride Synthesis over Metal Chlorides-Modified Mesoporous Alumina Catalyst", 《CATALYSTS》 * |
| 方健: "八角籽仁油脂理化性质及微波催化制备生物柴油的研究", 《安徽农业科学》 * |
| 肖晓明、刘桂元: "SO42－／Fe2O3－Al2O3的酯化催化活性与表面活性中心结构信息", 《湖南师范大学自然科学学报》 * |
| 郝一男等: "纳米Fe3O4-PO43-/ZrO2催化制备文冠果生物柴油", 《应用化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110665488B (en) | A kind of acid-base amphoteric solid catalyst, preparation and application of producing biodiesel | |
| CN112892590A (en) | High-efficiency energy-saving biodiesel catalyst and preparation method thereof | |
| CN106185931A (en) | A kind of preparation method of active carbon with high specific surface area | |
| CN107488519B (en) | A method for producing biodiesel from waste cooking oil using magnetic carbon-loaded acid-base catalysis | |
| CN102513132B (en) | Dedicated DYD catalyst for one-step bio-diesel production and production method thereof | |
| CN102260230A (en) | Method for preparing furfural by using two-step hydrolysis of biomass | |
| CN115254143B (en) | A kind of preparation method and application of carbon-based solid acid catalyst | |
| CN101805381A (en) | Method for directly synthesizing sucrose fatty acid ester by biodiesel and sucrose | |
| CN101362958A (en) | Alkali Catalyst Enhanced Supercritical Methanol Process to Realize Low Pressure Rapid Preparation of Biodiesel | |
| CN101215474A (en) | Method for preparing biodiesel by using waste leather oil as raw material | |
| CN108841422A (en) | A kind of hybrid diesel fuel and preparation method thereof | |
| CN114602512A (en) | Preparation method of esterification reaction catalyst | |
| CN107245379A (en) | A kind of high performance strong stability bio-synthetic diesel and preparation method thereof | |
| CN110437892B (en) | Biodiesel preparation process | |
| CN104120039A (en) | Method for preparing fatty acid methyl ester through multi-stage ester exchange | |
| CN112940804A (en) | Light cycle oil for vehicles and preparation method thereof | |
| CN1283765C (en) | Method for producing biological clean fuel | |
| CN112521050A (en) | Concrete foaming agent and preparation method thereof | |
| CN109593568A (en) | A kind of alcohol-based fuel preparation method of forge furnace | |
| CN109135844B (en) | Preparation method of environment-friendly gasoline | |
| CN117327537B (en) | Environment-friendly treatment process of industrial mixed oil | |
| US12163102B2 (en) | Method for rapidly preparing biodiesel under low temperatures | |
| CN113025399B (en) | Preparation method of biodiesel with high oxidation stability | |
| CN116273203B (en) | Method for preparing cyclohexane fuel by catalytic lignin pyrolysis oil hydrodeoxygenation through hollow NiCo/NC cage-shaped polyhedral catalyst | |
| CN114479970B (en) | Preparation method of low-doping coal water slurry additive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210604 |