CN111375431A - Solid acid catalyst, preparation method thereof and application thereof in esterification ester exchange reaction - Google Patents
Solid acid catalyst, preparation method thereof and application thereof in esterification ester exchange reaction Download PDFInfo
- Publication number
- CN111375431A CN111375431A CN202010195500.0A CN202010195500A CN111375431A CN 111375431 A CN111375431 A CN 111375431A CN 202010195500 A CN202010195500 A CN 202010195500A CN 111375431 A CN111375431 A CN 111375431A
- Authority
- CN
- China
- Prior art keywords
- acid catalyst
- solid acid
- graphene oxide
- reaction
- solid
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000011973 solid acid Substances 0.000 title claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 24
- 230000032050 esterification Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000004185 ester group Chemical group 0.000 title claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- 239000010806 kitchen waste Substances 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- -1 aluminum oxide modified graphene Chemical class 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 11
- 150000002148 esters Chemical group 0.000 abstract description 10
- 239000003225 biodiesel Substances 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 28
- 235000019198 oils Nutrition 0.000 description 28
- 239000002253 acid Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000011964 heteropoly acid Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 239000003930 superacid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910016287 MxOy Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 235000021588 free fatty acids Nutrition 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- XPQPWPZFBULGKT-UHFFFAOYSA-N methyl undecanoate Chemical compound CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a solid acid catalyst, a preparation method thereof and application thereof in esterification and transesterification. The preparation method of the solid acid catalyst comprises the steps of carrying out liquid phase deposition reaction on a graphene oxide suspension liquid dissolved with aluminum salt to obtain alumina modified graphene oxide, and mixing and reacting the alumina modified graphene oxide with concentrated sulfuric acid to obtain the solid acid catalyst. The preparation method is simple to operate and mild in condition, the prepared solid acid catalyst has a good catalytic effect on esterification and ester exchange reactions of the kitchen waste oil, the yield of the fatty acid methyl ester is higher than 90%, the solid acid catalyst is easy to separate from a product, the solid acid catalyst can be recycled through simple treatment, no pollution is caused, and the production cost of preparing the biodiesel from the kitchen waste oil is greatly reduced.
Description
Technical Field
The invention relates to a solid acid catalyst, in particular to a solid acid catalyst for catalyzing esterification or ester exchange reaction of kitchen waste oil, a preparation method and application thereof, and belongs to the technical field of solid acid catalyst preparation.
Background
At present, the catalyst used for the transesterification reaction is mainly an alkali catalyst, such as sodium hydroxide, potassium hydroxide, sodium carbonate and the like, and the catalyst has the advantages of mild reaction conditions and high reaction rate, but the alkali-catalyzed transesterification reaction is very sensitive to the contents of water and free fatty acid in raw materials, and waste cooking oil often contains a large amount of free fatty acid and moisture, so the alkali-catalyzed transesterification is not suitable for catalyzing the transesterification reaction of high-acid-value grease such as waste kitchen oil and the like. Therefore, acid catalysis is a more suitable method for catalyzing the kitchen waste oil.
Compared with alkali catalysis, acid catalysis has the advantages that the requirement on raw materials is not high, and good effect can be achieved on high-acid-value oil raw materials such as waste cooking oil and the like due to the fact that free fatty acid in the high-acid-value oil and methanol can be subjected to esterification reaction to generate fatty acid methyl ester under an acidic condition. The traditional acid catalysis adopts liquid acid such as sulfuric acid, hydrochloric acid, sulfonic acid and the like, the catalytic efficiency is higher, but the liquid acid is difficult to separate from a reaction mixture after the reaction, and a large amount of acidic wastewater is generated in the separation process to pollute the environment. Therefore, the research on high-activity solid acid catalysts which are convenient to separate is the current research hotspot.
The solid acid used in the preparation of the biodiesel at present mainly comprises heteropoly acid, solid super acid and the like.
(1) Heteropoly acid: heteropolyacids are a class of compounds formed by the linkage of a plurality of transition metals through oxygen atoms. Shu shuGentle et al (journal of Fuel chemistry, 2017,45(08):939-3PW12O40) A series of heteropoly acid catalysts are prepared for a matrix and used for preparing biodiesel by the esterification reaction of oleic acid and methanol, and heteropoly acid B-LaPW prepared by a sol-gel method12O40The best catalytic effect is obtained with/Si. After the reaction is carried out for 1 hour under the reaction conditions that the mass ratio of the oleic acid to the methanol is 1:8 and the dosage of the catalyst is 2 percent and the temperature is 65 ℃, the conversion rate of the oleic acid is up to 93 percent, and the conversion rate of the oleic acid of 86.4 percent can be obtained after the catalyst is recycled for 6 times. Although the heteropoly acid has better catalytic activity, the heteropoly acid has the defects of small specific surface area, difficult recovery and the like, and limits the application of the heteropoly acid in the production of biodiesel.
(2) Solid super acid: solid superacid is the Hammett function H0The acidity of the solid superacid can reach over ten thousand times of that of 100 percent sulfuric acid with acid < -11.93. The solid superacid consists essentially of sulfated metal oxide (SO)4 2-/MxOy) Tungstic acid metal oxide (WO)3/MxOy) Phosphorylated metal oxide (P)2O3/MxOy) And the like. Louis Ohio et al (applied catalysis A: General,2005,295: 97-105) studied TiO2/SO4 2-And ZrO2/SO4 2-As the activity of the solid strong acid catalyst in the cottonseed oil transesterification reaction, both catalysts show higher activity. The sulfated titanium oxide had a specific surface area of 99.5m2Higher than 91.5m of sulfated zirconia2The yield of fatty acid methyl ester is higher. Finally, after reacting for 8 hours under the conditions of 2 wt% of catalyst addition and 12:1 alcohol/oil mass ratio, TiO2/SO4 2-And ZrO2/SO4 2-The yields of methyl ester present were 90% and 85%, respectively. Solid superacids, especially sulfated metal oxide solid acids, are currently the most used solid acid catalysts in biodiesel production. However, the sulfated metal oxide only has Lewis acid centers, and the acid centers are easy to lose and are not easy to regenerate. In view of the above, a catalyst recovery was soughtThe solid acid catalyst has the advantages of simple regeneration, high activity and small pollution, and is suitable for high-acid-value oil raw materials such as waste kitchen oil and the like, thereby having important significance.
Disclosure of Invention
Aiming at the defects of difficult recovery and regeneration, insufficient activity, environmental pollution and the like in the process of applying the conventional solid acid catalyst to the esterification and transesterification of the kitchen waste oil, the invention aims to provide the solid acid catalyst which has the advantages of large specific surface area, more active sites, Lewis and Bronsted acid active centers, difficult loss of the acid active centers and more stable catalytic performance.
The second purpose of the invention is to provide a method for preparing the solid acid catalyst, which has low raw material cost, simple preparation process and mild conditions.
The third purpose of the invention is to provide an application of a solid acid catalyst in catalytic esterification or transesterification, the solid acid catalyst has the advantages of better catalytic activity, more stable performance, easy recovery, regeneration and reuse, and the like, and is particularly suitable for the transesterification process of waste oil containing fatty acid, such as kitchen waste oil and the like.
In order to achieve the technical purpose, the invention provides a preparation method of a solid acid catalyst, which comprises the steps of carrying out liquid phase deposition on a graphene oxide suspension dissolved with an aluminum salt to obtain alumina modified graphene oxide; and mixing the alumina modified graphene oxide with concentrated sulfuric acid for reaction to obtain the graphene oxide.
According to the technical scheme, graphene oxide is used as a carrier of solid acid, the surface of the graphene oxide is provided with abundant hydrophilic groups such as hydroxyl, carboxyl and the like, the graphene oxide has good dispersibility in water due to the hydrophilic groups, and subsequent aluminum ions are favorably adsorbed on the surface of the graphene oxide through coordination, so that the aluminum ions can obtain uniformly dispersed and loaded nano aluminum oxide particles in situ on the surface of the graphene oxide in the liquid phase deposition process, and more catalytic active sites can be favorably exposed. And the solid acid adopting the graphene oxide as the carrier is beneficial to the subsequent recovery of the solid acid catalyst, and the recovery can be realized through simple filtration and separation. Particularly, after the graphene oxide loaded alumina is acidified by concentrated sulfuric acid, two acid active centers of Lewis and Bronsted are generated simultaneously, the number of the acid active centers is more, the acid active centers are not easy to lose, and the problems that the acid active centers of a common sulfated metal oxide catalyst are single and the acid active centers are easy to lose are solved.
Preferably, the amount of the graphene oxide and the aluminum salt is controlled to control the mass ratio of the graphene oxide to the aluminum oxide in the alumina-modified graphene oxide to be 2: 1-5: 1. The ratio of the graphene oxide to the aluminum oxide mainly represents the ratio of Lewis and Bronsted acid active centers, the synergistic effect of the two acid active centers can be most reflected in the preferable ratio range, the catalyst has the best activity, the yield of the fatty acid methyl ester is high and can be kept at about 90%, and outside the ratio range, when the ratio of the graphene oxide is too high or too low, the catalytic activity of the catalyst is obviously poor, and the yield of the fatty acid methyl ester is obviously low. According to the most preferable scheme, the use amounts of the graphene oxide and the aluminum salt are controlled to control the mass ratio of the graphene oxide to the aluminum oxide in the aluminum oxide modified graphene oxide to be 2.5-3.5: 1, and the most preferable ratio is 3:1, for example, when the ratio is 2:1 and 4:1, the catalytic effect is obviously reduced.
Preferably, the liquid phase deposition is carried out at a temperature of 60-100 ℃ for 1-3 hours. The most preferred liquid deposition conditions are: the temperature was 80 ℃ and the time 2 hours. Under the preferable reaction conditions, the nano alumina particles can be generated in situ and dispersedly loaded on the surface of the graphene oxide.
As a preferable scheme, the reaction temperature of the alumina modified graphene oxide and concentrated sulfuric acid is 80-120 ℃, the reaction time is 8-15 hours, and the solid-to-solid ratio of the reaction liquid is 80-120 mg/mL. The most preferable reaction conditions are that the temperature of the reaction between the alumina modified graphene oxide and the concentrated sulfuric acid is 100 ℃, the time is 12 hours, and the solid-to-solid ratio of the reaction solution is 100 mg/mL.
As a preferred embodiment, the aluminum salt is a readily water-soluble aluminum salt commonly used in the art, such as aluminum nitrate.
As a preferable scheme, the concentration of the graphene oxide in the graphene oxide suspension is 1 mg/mL. If the concentration is too high, the stability of the graphene oxide suspension is poor.
The graphene oxide suspension of the present invention may be prepared from conventional graphene oxide in the prior art, or synthesized by reference to the following method: mixing 3g of graphite powder with 9:1 concentrated sulfuric acid and phosphoric acid, stirring for 1 hour in an ice bath, then adding 18g of potassium permanganate, heating the reaction system to 50 ℃, stirring for 12 hours at constant temperature, pouring the mixture into a beaker filled with crushed ice, dropwise adding 30% hydrogen peroxide solution until the color of the solution is changed from dark brown to bright yellow, and centrifugally washing with 30% dilute hydrochloric acid and clear water for multiple times until the pH of the supernatant reaches more than 5 after the mixture is centrifuged. And adding water into the centrifuged precipitate to dilute the precipitate to 1 liter, and performing ultrasonic treatment for 2 hours to obtain a graphene oxide suspension.
The preparation steps of the solid acid catalyst are as follows:
(1) weighing a certain amount of aluminum nitrate nonahydrate, adding the aluminum nitrate nonahydrate into the graphene oxide suspension, uniformly stirring, adjusting the pH of the mixture to be neutral by using a sodium hydroxide solution, and stirring at a constant temperature of 80 ℃ for 2 hours. Taking out the mixture, cooling, standing and aging for 10 hours, filtering, drying, washing, and drying at 100 ℃ to obtain an intermediate product, namely the alumina modified graphene oxide, wherein the reaction is shown as the following formula:
(2) placing the intermediate product in a beaker, adding concentrated sulfuric acid, performing ultrasonic dispersion for 30 minutes, placing the mixture in a drying oven at 100 ℃ for reaction for 12 hours, and filtering, washing and drying the mixed system to obtain the solid acid catalyst, wherein the reaction formula is as follows:
the invention also provides a solid acid catalyst which is obtained by the preparation method.
The invention also provides an application of the solid acid catalyst, which is applied to catalyzing esterification and/or ester exchange reaction.
As a preferable scheme, the solid acid catalyst is applied to catalyzing esterification and/or ester exchange reaction of the kitchen waste oil and formic acid.
As a preferable scheme, the conditions of the esterification and/or ester exchange reaction of the kitchen waste oil and formic acid are as follows: the reaction temperature is 60-90 ℃, the reaction time is 4-6 h, the molar ratio of methanol to the kitchen waste oil is 9: 1-12: 1, and the mass of the solid acid catalyst is 3-6% of that of the kitchen waste oil. Most preferably, the conditions for esterification and/or ester exchange reaction of the kitchen waste oil and formic acid are as follows: the reaction temperature is 60 ℃, the reaction time is 5 hours, the molar ratio of methanol to the kitchen waste oil is 9:1, and the mass of the solid acid catalyst is 3% of that of the kitchen waste oil. The catalyst already shows higher catalytic activity at a temperature of 60 ℃, and the increase is not obvious when the temperature is further increased.
The solid acid catalyst provided by the invention has acidic active centers such as sulfonic acid groups, carboxyl groups and sulfated alumina, can simultaneously catalyze esterification reaction and transesterification reaction, and has a good catalytic effect on high-acid-value grease such as kitchen waste oil.
The regeneration process of the solid acid catalyst is simple, only concentrated sulfuric acid is needed to be used for acidification again, and the catalytic activity of the regenerated catalyst is kept above 93%, so that the regeneration process has great significance for recycling of the catalyst.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the solid acid catalyst provided by the invention takes graphene oxide as a carrier, has a large specific surface area, generates sulfated alumina and a sulfonate in situ, realizes uniform dispersion and full exposure of an acid active center, shows high esterification or ester exchange catalytic activity, simultaneously has Lewis and Bronsted acid active centers, has an obvious synergistic effect when the two active centers reach a proper proportion, shows an optimal catalytic effect, shows a descending trend when the proportion of sulfated alumina is too high or the proportion of sulfated graphene oxide is too high, shows no easy loss of the acid active center in a catalytic system, and has more stable catalytic performance. Compared with the traditional modified sulfated metal oxide catalyst, the modified sulfated metal oxide catalyst has better modification effect and higher catalytic activity, and is more suitable to be used as a catalyst for the esterification and transesterification reaction of the kitchen waste oil.
The preparation process of the solid acid catalyst adopts conventional cheap raw materials, has low cost, simple preparation process and mild conditions, and is beneficial to large-scale production and application.
The solid acid catalyst of the invention has the advantages of better catalytic activity, more stable performance, easy recovery, regeneration and reuse and the like in the application process of catalytic esterification or ester exchange reaction, and is particularly suitable for the ester exchange reaction process of waste oil containing fatty acid, such as kitchen waste oil and the like.
The solid acid catalyst disclosed by the invention adopts the graphene oxide with larger specific surface area as the carrier, so that the diffusion of reaction raw materials and products in the catalytic reaction process of the catalyst is facilitated, the mass transfer effect of reactants is enhanced, the catalytic reaction efficiency can be improved, and the catalytic reaction time is shortened. The solid acid catalyst is applied to the esterification transesterification reaction of the kitchen waste oil and methanol collected by a restaurant, the time is shorter than that of the traditional solid acid catalytic reaction, the catalytic activity is higher, the higher yield of fatty acid methyl ester is obtained, the catalyst can be recycled only by filtering after the reaction, the catalyst can be recycled after simple regeneration, no pollution is caused, and the cost of the esterification transesterification reaction of the kitchen waste oil is greatly reduced.
Detailed Description
The invention is further illustrated by the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the practice of the invention.
Example 1
Taking a certain amount of graphene oxide suspension, carrying out ultrasonic treatment, and then weighing a certain amount of Al2(SO4)3·9H2Adding O into the GO suspension, controlling the mass ratio of graphene oxide to aluminum oxide in the product to be 2:1, uniformly stirring, adjusting the pH value of the mixture to about 7, and stirring at the constant temperature of 80 ℃ for 2 hours. Taking out the mixture, cooling, standing and aging for 10 hours, filtering and drying to obtain the alumina oxide graphiteAlkene nanocomposites, denoted GA21。
The GO-Al is added2O3Adding concentrated sulfuric acid into the nano composite material in an amount of 100mg/mL for excessive impregnation, uniformly stirring, performing ultrasonic treatment for 30 minutes, reacting at 100 ℃ for 12 hours, and simultaneously finishing Al2O3Sulfation and GO, filtration, washing and drying to obtain a solid acid catalyst, noted as GAS21。
Example 2
Taking a certain amount of graphene oxide suspension, carrying out ultrasonic treatment, and then weighing a certain amount of Al2(SO4)3·9H2Adding O into the GO suspension, controlling the mass ratio of graphene oxide to aluminum oxide in the product to be 3:1, uniformly stirring, adjusting the pH value of the mixture to about 7, and stirring at the constant temperature of 80 ℃ for 2 hours. Taking out the mixture, cooling, standing and aging for 10 hours, filtering and drying to obtain the alumina graphene oxide nanocomposite, which is recorded as GA31。
The GO-Al is added2O3Adding concentrated sulfuric acid into the nano composite material in an amount of 100mg/mL for excessive impregnation, uniformly stirring, performing ultrasonic treatment for 30 minutes, reacting at 100 ℃ for 12 hours, and simultaneously finishing Al2O3Sulfation and GO, filtration, washing and drying to obtain a solid acid catalyst, noted as GAS31。
Example 3
Taking a certain amount of graphene oxide suspension, carrying out ultrasonic treatment, and then weighing a certain amount of Al2(SO4)3·9H2Adding O into the GO suspension, controlling the mass ratio of graphene oxide to aluminum oxide in the product to be 4:1, uniformly stirring, adjusting the pH value of the mixture to about 7, and stirring at the constant temperature of 80 ℃ for 2 hours. Taking out the mixture, cooling, standing and aging for 10 hours, filtering and drying to obtain the alumina graphene oxide nanocomposite, which is recorded as GA41。
The GO-Al is added2O3Adding concentrated sulfuric acid into the nano composite material in an amount of 100mg/mL for excessive impregnation, uniformly stirring, performing ultrasonic treatment for 30 minutes, reacting at 100 ℃ for 12 hours, and simultaneously finishing Al2O3Sulfation and GO sulfonation, filtering, washing and drying to obtainTo solid acid catalyst, denoted as GAS41。
Example 4
The solid acid catalysts prepared in the above embodiments 1 to 3 are respectively used for esterification transesterification of kitchen waste oil and methanol, and the reaction conditions are as follows:
the reaction temperature is 60 ℃, the molar ratio of methanol to the kitchen waste oil is 9:1, the adding amount of the catalyst is 3% of the mass of the kitchen waste oil, and the reaction time is 5 h.
Analyzing the reaction product, namely the fatty acid methyl ester by adopting gas chromatography, wherein the chromatographic conditions are a Wax capillary chromatographic column (30m × 0.25.25 mm × 0.25.25 mu m), the injection port temperature is 250 ℃, the FID detector temperature is 280 ℃, 1mg/mL methyl undecanoate solution is used as an internal standard solution, the sample injection amount of a sample is 1 mu L, the sample is kept at the initial temperature of 100 ℃ for 1min, then the temperature is increased to 200 ℃ at the rate of 20 ℃/min, the temperature is kept for 3min, then the temperature is increased to 220 ℃ at the rate of 10 ℃/min, the temperature is kept for 3min, finally the temperature is increased to 240 ℃ at the rate of 10 ℃/min, the temperature is kept for 3min, and the yield of the fatty acid methyl ester is determined by the chromatographic analysis, and the specific results are shown in.
TABLE 1 catalytic Activity of solid acid catalysts
| Catalyst and process for preparing same | Fatty acid methyl ester yield (%) |
| GAS21 | 83.57％ |
| GAS31 | 91.23％ |
| GAS41 | 89.05％ |
As can be seen from Table 1, when the catalyst of the present invention is applied to the esterification transesterification of the kitchen waste oil and methanol, the catalyst has high activity.
The solid acid catalyst in the reaction product is recovered by a filtration method, and is repeatedly used for 3 times after being soaked and regenerated by concentrated sulfuric acid, and the secondary use effect of the catalyst is shown in table 2.
| Catalyst and process for preparing same | Fatty acid methyl ester yield after three repetitions (%) |
| GAS21 | 77.88％ |
| GAS31 | 86.25％ |
| GAS41 | 82.63％ |
As can be seen from Table 2, after the catalyst is subjected to sulfuric acid impregnation regeneration and is reused for 3 times, the yield of fatty acid methyl ester is only slightly reduced, and the catalyst has a better regeneration effect.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A method for preparing a solid acid catalyst is characterized by comprising the following steps: carrying out liquid phase deposition reaction on the graphene oxide suspension liquid dissolved with the aluminum salt to obtain aluminum oxide modified graphene oxide; and mixing the alumina modified graphene oxide with concentrated sulfuric acid for reaction to obtain the graphene oxide.
2. The method for preparing a solid acid catalyst according to claim 1, wherein: the use amount of the graphene oxide and the aluminum salt is controlled so as to control the mass ratio of the graphene oxide to the aluminum oxide in the aluminum oxide modified graphene oxide to be 2: 1-5: 1.
3. The method for producing a solid acid catalyst according to claim 1 or 2, characterized in that: the temperature of the liquid phase deposition is 60-100 ℃, and the time is 1-3 hours.
4. The method for producing a solid acid catalyst according to claim 1 or 2, characterized in that: the reaction temperature of the alumina modified graphene oxide and concentrated sulfuric acid is 80-120 ℃, the reaction time is 8-15 hours, and the solid-to-solid ratio of the reaction liquid is 80-120 mg/mL.
5. A solid acid catalyst characterized by: the preparation method of any one of claims 1 to 4.
6. The use of a solid acid catalyst according to claim 5, wherein: application to catalytic esterification and/or transesterification reactions.
7. The use of a solid acid catalyst according to claim 6, wherein: the method is applied to catalyzing esterification and/or ester exchange reaction of the kitchen waste oil and formic acid.
8. The use of a solid acid catalyst according to claim 7, wherein: the conditions of esterification and/or ester exchange reaction of the kitchen waste oil and formic acid are as follows: the reaction temperature is 60-90 ℃, the reaction time is 4-6 h, the molar ratio of methanol to the kitchen waste oil is 9: 1-12: 1, and the mass of the solid acid catalyst is 3-6% of that of the kitchen waste oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010195500.0A CN111375431B (en) | 2020-03-19 | 2020-03-19 | Solid acid catalyst, preparation method thereof and application thereof in esterification transesterification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010195500.0A CN111375431B (en) | 2020-03-19 | 2020-03-19 | Solid acid catalyst, preparation method thereof and application thereof in esterification transesterification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111375431A true CN111375431A (en) | 2020-07-07 |
| CN111375431B CN111375431B (en) | 2023-07-25 |
Family
ID=71220689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010195500.0A Active CN111375431B (en) | 2020-03-19 | 2020-03-19 | Solid acid catalyst, preparation method thereof and application thereof in esterification transesterification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111375431B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114345341A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Graphene-coated solid acid catalyst and preparation method thereof |
| CN114522701A (en) * | 2022-04-22 | 2022-05-24 | 浙江晟格生物科技有限公司 | Compound sulfate radical catalyst for biological sugar preparation, preparation method and application |
| CN114588928A (en) * | 2022-05-09 | 2022-06-07 | 浙江晟格生物科技有限公司 | Regeneration method of carbon-based sulfate catalyst in galactose waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757041A (en) * | 2012-07-30 | 2012-10-31 | 哈尔滨工业大学 | Preparation method of graphene/metal oxide nanocomposite powder |
| CN103418365A (en) * | 2013-08-06 | 2013-12-04 | 江苏大学 | Graphene based solid base catalyst preparation and application thereof in biodiesel production |
| CN106111164A (en) * | 2016-06-21 | 2016-11-16 | 上海中器环保科技有限公司 | A kind of nano composite solid acid catalyst for preparing biodiesel |
| CN107858457A (en) * | 2017-11-14 | 2018-03-30 | 天津工业大学 | A kind of method of high dispersive sulfoxidation graphene catalyzing hydrolysis cellulose |
-
2020
- 2020-03-19 CN CN202010195500.0A patent/CN111375431B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757041A (en) * | 2012-07-30 | 2012-10-31 | 哈尔滨工业大学 | Preparation method of graphene/metal oxide nanocomposite powder |
| CN103418365A (en) * | 2013-08-06 | 2013-12-04 | 江苏大学 | Graphene based solid base catalyst preparation and application thereof in biodiesel production |
| CN106111164A (en) * | 2016-06-21 | 2016-11-16 | 上海中器环保科技有限公司 | A kind of nano composite solid acid catalyst for preparing biodiesel |
| CN107858457A (en) * | 2017-11-14 | 2018-03-30 | 天津工业大学 | A kind of method of high dispersive sulfoxidation graphene catalyzing hydrolysis cellulose |
Non-Patent Citations (3)
| Title |
|---|
| M ULFAH ET AL.: "Biodiesel Production Through Waste Cooking Oil (WCO) Esterification Using Sulfated Alumina as Catalyst", 《IOP CONF. SERIES: MATERIALS SCIENCE AND ENGINEERING》 * |
| REENA D. SOUZA ET AL.: "Effect of Metal Oxides on the Catalytic Activities of Sulfonated Graphene Oxide for the Esterification of Oleic Acid and Conversion of Waste Cooking Oil to Biodiesel", 《CATALYSIS LETTERS》 * |
| 陈建军等: "氧化铝-硫酸固体酸催化剂催化油酸与甲醇酯化反应及其动力学研究", 《中国油脂》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114345341A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Graphene-coated solid acid catalyst and preparation method thereof |
| CN114345341B (en) * | 2020-10-13 | 2024-01-19 | 中石化南京化工研究院有限公司 | Graphene coated solid acid catalyst and preparation method thereof |
| CN114522701A (en) * | 2022-04-22 | 2022-05-24 | 浙江晟格生物科技有限公司 | Compound sulfate radical catalyst for biological sugar preparation, preparation method and application |
| CN114522701B (en) * | 2022-04-22 | 2022-08-09 | 浙江晟格生物科技有限公司 | Compound sulfate radical catalyst for biological sugar preparation, preparation method and application |
| CN114588928A (en) * | 2022-05-09 | 2022-06-07 | 浙江晟格生物科技有限公司 | Regeneration method of carbon-based sulfate catalyst in galactose waste liquid |
| CN114588928B (en) * | 2022-05-09 | 2022-08-23 | 浙江晟格生物科技有限公司 | Regeneration method of carbon-based sulfate catalyst in galactose waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111375431B (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111375431A (en) | Solid acid catalyst, preparation method thereof and application thereof in esterification ester exchange reaction | |
| CN101492603B (en) | Method for producing biodiesel by using tallowseed oil and special solid catalyst thereof | |
| Wu et al. | Transesterification of soybean oil to biodiesel using zeolite supported CaO as strong base catalysts | |
| CN100513521C (en) | Preparation method of biological diesel oil | |
| CN108654693A (en) | A kind of hydrophobic palladium/metal-organic framework material and preparation method thereof and the application for synthesizing 2,5- dimethyl furans | |
| CN101327437B (en) | Microwave-absorption type solid acid catalyst and use thereof in preparing biodiesel | |
| Duan et al. | Water-tolerant heteropolyacid on magnetic nanoparticles as efficient catalysts for esterification of free fatty acid | |
| Levine et al. | Triflate-catalyzed (trans) esterification of lipids within carbonized algal biomass | |
| CN106669841B (en) | A kind of organic silicon composite and preparation method based on phosphotungstic acid and sulfonic acid funtionalized with meso-hole structure | |
| CN101269331B (en) | Process for producing high-stability central-hole material Cu-Zn-Al2O3, and application of the same in producing mellow wine dehydrogenating catalyst | |
| CN101294094A (en) | Method for preparing biological diesel oil by using nano-solid heteropoly acid, heteropolybase catalyst | |
| Pan et al. | Functional nanomaterials-catalyzed production of biodiesel | |
| Yu et al. | Preparation of Rosin Pentaerythritol Ester Over an Fe 3 O 4-Supported ZnO Catalyst | |
| Yu et al. | Preparation of a garlic peel waste-derived carbon solid acid catalyst with the porous structure for biodiesel production | |
| CN101293209B (en) | Nano-solid heteropoly acid, heteropolybase catalyst suitable for producing biological diesel oil and application thereof | |
| CN107537526B (en) | Fluidized bed isomerization catalyst and preparation method and application thereof | |
| CN103249483A (en) | Process for preparation of supported catalysts and use of the catalyst for the esterification of free fatty acids in vegetable oil | |
| CN111875493A (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN114602512B (en) | Preparation method of esterification catalyst | |
| CN111167484A (en) | Hydrodeoxygenation catalyst for oxygen-containing derivatives of benzene, preparation method thereof and application of hydrodeoxygenation catalyst in preparation of cycloparaffins | |
| CN110090662B (en) | Preparation method and catalytic application of sulfonic group covalent modified vacancy polyacid composite material | |
| CN110369003B (en) | Titanium-silicon phosphotungstate composite material with mesoporous structure and preparation method thereof | |
| CN110152647A (en) | A kind of catalyst and its preparation method and application | |
| CN100348314C (en) | Synthesis reaction catalyst for loading type alkali metal biodiesel oil | |
| Zainol et al. | Preparation and characterization of sulfonated carbon cryogel doped zinc as a catalyst for glucose ethanolysis to ethyl levulinate |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |