CN114602512B - Preparation method of esterification catalyst - Google Patents
Preparation method of esterification catalyst Download PDFInfo
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- CN114602512B CN114602512B CN202210174704.5A CN202210174704A CN114602512B CN 114602512 B CN114602512 B CN 114602512B CN 202210174704 A CN202210174704 A CN 202210174704A CN 114602512 B CN114602512 B CN 114602512B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 56
- 230000032050 esterification Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 241000209094 Oryza Species 0.000 claims description 22
- 235000007164 Oryza sativa Nutrition 0.000 claims description 22
- 235000009566 rice Nutrition 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 235000003570 Phyllostachys pubescens Nutrition 0.000 claims description 2
- 244000302661 Phyllostachys pubescens Species 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 239000011973 solid acid Substances 0.000 abstract description 9
- 229920000180 alkyd Polymers 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
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- 239000002253 acid Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
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- 239000007788 liquid Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000003930 superacid Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010442 TiO2-SnO2 Inorganic materials 0.000 description 2
- 229910010257 TiO2—SnO2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, in particular to a preparation method of an esterification catalyst. The preparation method comprises the following steps: s1, pyrolyzing and grinding a biomass material, adding the biomass material into concentrated sulfuric acid, heating for reaction, and filtering and washing to obtain sulfonated biochar; s2, mixing manganese acetate and citric acid, and heating and stirring to obtain MnO 2 sol; s3, adding the sulfonated biochar into the MnO 2 sol, stirring, drying, immersing the product in dilute sulfuric acid, stirring, and heating for reaction to obtain the esterification catalyst. The esterification catalyst prepared by the invention adopts sulfonated biochar as a carrier to load MnO 2/SO4 2‑ solid acid, has the characteristics of high stability and high catalytic activity, improves the conversion rate of alkyd esterification, and has good catalytic performance.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of an esterification catalyst.
Background
The product of the esterification reaction, namely carboxylate, is an important compound, is a raw material for a plurality of organic synthesis reactions, is widely applied to the fields of foods, medicines, daily chemicals, plastics and the like, and has higher and higher demands for carboxylate along with the increasing living standard of people. The industrial synthesis of carboxylic ester mainly uses catalysts such as concentrated sulfuric acid, phosphoric acid, p-toluenesulfonic acid and the like to catalyze the alkyd esterification, and the traditional catalysts have higher catalytic activity and low price and are easy to obtain, but the method has more defects, including: the side reaction is more, the product purity is low, the equipment corrosion is serious, the energy consumption is high, the waste acid yield is high, the environmental pollution is serious, and the like.
Therefore, the development of a novel efficient and green esterification catalyst is a hot spot of research today. At present, scholars at home and abroad have carried out more researches on esterification catalysts, and a series of novel esterification catalysts are developed to replace the traditional catalysts. The novel esterification catalyst mainly comprises a phase transfer catalyst, an ionic liquid catalyst, an inorganic salt catalyst, a resin catalyst, a molecular sieve catalyst, a heteropolyacid catalyst and a solid super acid catalyst. Wang Puli and the like prepare n-butyl acetate by taking self-made gamma-Al 2O3 loaded nano-scale SO 4 2－/TiO2 solid superacid as a catalyst and glacial acetic acid and n-butanol as raw materials, and under the optimal preparation condition, the conversion rate of the glacial acetic acid reaches 97.6%; liu Tianbao and the like prepare a Silica Gel (SG)/p-toluenesulfonic acid (p-TSA) catalyst by adopting an impregnation method, examine the synthesis of ethyl acetate, and the yield can reach 95.40%; liu, and the like take phosphotungstic acid and glycine as raw materials, amino acid functional heteropolyacid is synthesized in an aqueous solution by adopting a one-step method, and under the optimal reaction condition, the conversion rate and the selectivity can be both close to 100 percent; liu Xiuying and the like, in order to improve the yield of allyl methacrylate, cetyl trimethylammonium bromide is used as a phase transfer catalyst, and the esterification rate reaches 85%; gao Dengzheng and the like take high acid value grease and methanol as raw materials, the catalytic activity of 6 inorganic salts [ SnCl 4、CaCl2、Fe2(SO4)3、NiSO4、CuSO4 and NaHSO 4 ] in the biodiesel esterification reaction is researched, and the best catalytic esterification activity of the 6 inorganic salts is NaHSO 4, and the secondary esterification rate reaches 98% under the best test condition.
These new esterification catalysts all have certain advantages and have very high esterification activity, but at present, some problems still exist. The phase transfer catalyst can effectively control side reaction and improve the selectivity of the product, but has high price, and is difficult to realize large-scale industrialized production; the activity and stability of the ionic liquid catalyst are superior to those of other catalysts, but the ionic liquid has complex synthesis, difficult purification and high raw material price; the molecular sieve catalyst has higher activity, but has low stability and fewer types; the interaction force between the carrier and the heteropoly acid in the heteropoly acid supported catalyst is weak, and the heteropoly acid as an active component is easy to run off in the reaction, so that the catalyst is deactivated; the metal oxide solid super acidic catalyst has the advantages of high catalytic activity, simple preparation, strong acidity, small equipment corrosiveness and small environmental pollution, but the catalyst is easy to lose active components such as SO 4 2-, S 2O8 2- and the like to inactivate, has lower stability and shorter service life, and cannot meet the industrial production requirements.
Therefore, in order to solve the deficiencies of the prior art, there is a need to develop a novel esterification catalyst to meet the urgent needs of industrial production.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention discloses a preparation method of an esterification catalyst which is low in cost, efficient, green and capable of being produced in a large scale, which adopts sulfonated biochar as a carrier to load MnO 2/SO4 2- solid acid, has the characteristics of high stability and high catalytic activity, improves the conversion rate of alkyd esterification, and has good catalytic performance.
The invention aims to provide a preparation method of an esterification catalyst, which comprises the following steps:
s1, pyrolyzing and grinding a biomass material, adding the biomass material into concentrated sulfuric acid, heating for reaction, and filtering and washing to obtain sulfonated biochar;
s2, mixing manganese acetate and citric acid, and heating and stirring to obtain MnO 2 sol;
S3, adding the sulfonated biochar into the MnO 2 sol, stirring, drying, immersing the product in dilute sulfuric acid, stirring, and heating for reaction to obtain the esterification catalyst.
Further, in step S1, the biomass material is selected from one or more of rice hulls, moso bamboos, and rice bran.
Further, in the step S1, the pyrolysis temperature is 600-700 ℃ and the pyrolysis time is 2-4h.
Further, in step S1, the concentration of the concentrated sulfuric acid is 95% -98%.
Further, in the step S2, the molar ratio of the manganese acetate to the citric acid is (2-2.5): 1.
Further, in step S2, the heating temperature is 60-80 ℃.
Further, in the step S3, the concentration of the dilute sulfuric acid is 0.9% -5%.
Further, in the step S3, the time of soaking and stirring is 24-36h.
Further, in the step S3, the temperature of the heating reaction is 500-600 ℃ and the time is 3-4h.
Another object of the present invention is to provide an esterification catalyst prepared by the above preparation method of an esterification catalyst for use in an esterification reaction.
The beneficial effects of the invention are as follows:
1. The surface and the inside of the sulfonated biochar have a large number of sulfonic groups (-SO 3 H), SO that the sulfonated biochar has good catalytic activity and can effectively improve the esterification rate;
2. The sulfonated biochar has a large number of mesopores, which is beneficial to the passage of macromolecular reactants and products through the catalyst pore canal, ensures that the active site inside the catalyst is fully contacted with the reactants, and improves the catalytic efficiency;
3. The MnO 2/SO4 2- solid acid is prepared by a sol-gel method, has good dispersibility, has the property of solid super acid, contains a porous structure, is favorable for the diffusion of reactants, and has excellent catalytic activity; meanwhile, a large number of pore structures have strong structure guiding effect and super-strong capillary effect, so that the phenomenon of agglomeration and falling of active components in the reaction is avoided, the stability of the catalyst is enhanced, and the service life of the catalyst is ensured;
4. according to the invention, a synergistic effect can be generated between MnO 2/SO4 2- solid acid and sulfonated biochar, the MnO 2/SO4 2- solid acid is uniformly loaded on the sulfonated biochar, the specific surface area is obviously increased, and therefore, the acid position is increased, the surface acidity is further improved, the acid catalytic activity is further improved, and the esterification rate is obviously improved.
Detailed Description
In order to more clearly illustrate the technical aspects of the present invention, the following examples are set forth, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The SO 4 2-/TiO2-SnO2 solid acid catalyst used in the comparative example of the present invention was purchased from Jiangyin, south Kogyo chemical Co., ltd.
Example 1
A preparation method of an esterification catalyst comprises the following steps:
S1, washing rice hulls with deionized water, drying, placing the rice hulls in a crucible, placing the crucible in a tubular furnace, pyrolyzing the rice hulls for 2 hours at 700 ℃ under an argon atmosphere, cooling the rice hulls to room temperature, grinding the rice hulls and sieving the rice hulls with a 100-mesh sieve to obtain biochar; adding 1g of the biochar into 10mL of 95% concentrated sulfuric acid, reacting for 10min at 80 ℃, cooling to room temperature, adding the obtained solid-liquid mixture into 100mL of distilled water, filtering, washing the solid precipitate until no sulfate ion exists in the washing liquid, and drying for 24h at 80 ℃ to obtain sulfonated biochar;
S2, dissolving manganese acetate and citric acid in a molar ratio of 2:1 into distilled water, regulating the pH value to 6 by using ammonia water, and stirring in a 60 ℃ water bath for 3 hours to obtain MnO 2 sol;
S3, adding 1g of the sulfonated biochar into 10mL of MnO 2 sol, stirring, drying, and then placing the product into 50mL of 1% dilute sulfuric acid, soaking and stirring for 24h, and reacting for 4h at 520 ℃ to obtain the esterification catalyst.
Example 2
A preparation method of an esterification catalyst comprises the following steps:
S1, washing rice hulls with deionized water, drying, placing the rice hulls in a crucible, placing the crucible in a tubular furnace, pyrolyzing the rice hulls for 3 hours at 650 ℃ under an argon atmosphere, cooling the rice hulls to room temperature, grinding the rice hulls and sieving the rice hulls with a 100-mesh sieve to obtain biochar; adding 1g of the biochar into 10mL of 96% concentrated sulfuric acid, reacting for 20min at 90 ℃, cooling to room temperature, adding the obtained solid-liquid mixture into 100mL of distilled water, filtering, washing the solid precipitate until no sulfate ion exists in the washing liquid, and drying for 24h at 80 ℃ to obtain sulfonated biochar;
S2, dissolving manganese acetate and citric acid in a molar ratio of 2:1 into distilled water, regulating the pH value to 6 by using ammonia water, and stirring in a water bath at 70 ℃ for 2.5h to obtain MnO 2 sol;
S3, adding 1g of the sulfonated biochar into 10mL of MnO 2 sol, stirring, drying, and then placing the product into 50mL of 1% dilute sulfuric acid, soaking and stirring for 26h, and reacting at 500 ℃ for 3h to obtain the esterification catalyst.
Example 3
A preparation method of an esterification catalyst comprises the following steps:
S1, washing rice hulls with deionized water, drying, placing the rice hulls in a crucible, placing the crucible in a tubular furnace, pyrolyzing the rice hulls at 600 ℃ for 3 hours under an argon atmosphere, cooling the rice hulls to room temperature, grinding the rice hulls and sieving the rice hulls with a 100-mesh sieve to obtain biochar; adding 1g of the biochar into 10mL of 98% concentrated sulfuric acid, reacting for 30min at 85 ℃, cooling to room temperature, adding the obtained solid-liquid mixture into 100mL of distilled water, filtering, washing the solid precipitate until no sulfate ion exists in the washing liquid, and drying for 24h at 80 ℃ to obtain sulfonated biochar;
S2, dissolving manganese acetate and citric acid in a molar ratio of 2:1 into distilled water, regulating the pH value to 6 by using ammonia water, and stirring in a 60 ℃ water bath for 3 hours to obtain MnO 2 sol;
S3, adding 1g of the sulfonated biochar into 10mL of MnO 2 sol, stirring, drying, and then placing the product into 50mL of 1% dilute sulfuric acid, soaking and stirring for 30h, and reacting at 550 ℃ for 3h to obtain the esterification catalyst.
Comparative example 1
The difference between this comparative example and example 1 is that: the comparative example used a commercially available SO 4 2-/TiO2-SnO2 solid acid catalyst.
Comparative example 2
A method for preparing an esterification catalyst, the comparative example differs from example 1 in that: step S2 was not performed, and in step S3, mnO 2 powder was used instead of MnO 2 sol, and the other steps were the same as in example 1.
Test example 1
Catalytic performance test
The testing method comprises the following steps:
placing 0.4mol of acetic acid, 0.44mol of n-butanol, 0.2g of the esterification catalyst prepared in the examples 1-3 or the comparative examples 1-2 of the invention and a small amount of cyclohexane with water agent into a three-neck flask provided with a water separator, a thermometer and a reflux condenser, carrying out oil bath reaction at 110 ℃ for 2 hours to obtain an n-butyl acetate sample, measuring the acid value before and after the reaction by using GB 1668-1981 (determination of acid value of plasticizer), and calculating the esterification rate according to the following formula
Wherein A 0 and A are the acid values of the system before and after the reaction respectively.
Test results:
The results of the catalytic performance test are shown in table 1.
TABLE 1 results of catalyst performance test
As shown in Table 1, the esterification catalyst prepared by the invention has sulfonated biochar and MnO 2/SO4 2- solid acid components, so that a synergistic effect can be generated on the basis of respective catalysis of the sulfonated biochar and the MnO 2/SO4 2- solid acid components, the catalytic performance is further improved, the esterification rate of the reaction is up to more than 93%, and the catalytic performance is very excellent.
Test example 2
Stability test
The testing method comprises the following steps:
the esterification reaction catalysts prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to 5 repeated experiments on the basis of test example 1, and the esterification rate was measured.
Test results:
The stability test results are shown in table 2.
TABLE 2 catalyst stability test results
As can be seen from Table 2, the catalysts prepared in comparative examples 1-2 were significantly reduced in catalytic performance after 5 reactions, and significantly reduced in esterification rate; however, the catalyst prepared by the invention can still keep good catalytic performance after being used for 5 times, the change of the esterification rate is extremely small and is kept at a high level, so that the catalyst prepared by the invention has strong stability and the service life of the catalyst is ensured.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. The preparation method of the esterification catalyst is characterized by comprising the following steps of:
S1, pyrolyzing and grinding a biomass material, adding the biomass material into concentrated sulfuric acid, heating for reaction, and filtering and washing to obtain sulfonated biochar;
s2, mixing manganese acetate and citric acid, and heating and stirring to obtain MnO 2 sol;
S3, adding the sulfonated biochar into the MnO 2 sol, stirring, drying, immersing the product in dilute sulfuric acid, stirring, and heating for reaction to obtain the esterification catalyst;
the biomass material is selected from one or more of rice hulls, moso bamboos and rice bran.
2. The method for preparing an esterification catalyst according to claim 1, wherein in the step S1, the pyrolysis is performed at a temperature of 600 to 700 ℃ for a time of 2 to 4 hours.
3. The method for preparing an esterification catalyst according to claim 1, wherein in the step S1, the concentration of the concentrated sulfuric acid is 95% -98%.
4. The method for producing an esterification catalyst according to claim 1, wherein in step S2, the molar ratio of manganese acetate to citric acid is (2-2.5): 1.
5. The method for preparing an esterification catalyst according to claim 1, wherein the heating temperature is 60 to 80 ℃ in step S2.
6. The method for preparing an esterification catalyst according to claim 1, wherein in the step S3, the concentration of the dilute sulfuric acid is 0.9% -5%.
7. The method for preparing an esterification catalyst according to claim 1, wherein in the step S3, the time of immersing and stirring is 24 to 36 hours.
8. The method for preparing an esterification catalyst according to claim 1, wherein in the step S3, the heating reaction is performed at a temperature of 500 to 600 ℃ for 3 to 4 hours.
9. Use of an esterification catalyst prepared by the method for preparing an esterification catalyst according to any one of claims 1 to 8 in an esterification reaction.
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