CN104877762A - Method for catalyzing esterification reaction by means of high-stable-acidity mesoporous-microporous molecular sieve - Google Patents
Method for catalyzing esterification reaction by means of high-stable-acidity mesoporous-microporous molecular sieve Download PDFInfo
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- CN104877762A CN104877762A CN201510233518.4A CN201510233518A CN104877762A CN 104877762 A CN104877762 A CN 104877762A CN 201510233518 A CN201510233518 A CN 201510233518A CN 104877762 A CN104877762 A CN 104877762A
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- molecular sieve
- mcm
- mesoporous
- oleic acid
- microporous molecular
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000005642 Oleic acid Substances 0.000 claims abstract description 18
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 18
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 17
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000009466 transformation Effects 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 5
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 4
- 238000001640 fractional crystallisation Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010457 zeolite Substances 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000002551 biofuel Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- -1 NaAlO 2 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for catalyzing esterification reaction by means of a high-stable-acidity mesoporous-microporous molecular sieve. The method is characterized by comprising the following steps: compounding the high-stable-acidity mesoporous-microporous molecular sieve in a step-by-step crystallization method by using self-produced beta zeolite as a guiding agent, loading a rare-earth La element, and catalyzing the esterification reaction of oleic acid and methyl alcohol by using the compounded acidic mesoporous-microporous molecular sieve. When the ratio of alcohol to oil is 10:1, the consumption of catalyst is 5 percent of the total quantity, and reaction is performed for 8 hours at the temperature of 120 DEG C, the conversion rate of oleic acid is not less than 70 percent, and the catalyst is good in hydrothermal stability and reusability.
Description
Technical field
The invention belongs to biomass energy transformation technology field, relate generally to high steady acid mesoporous-the Esterification reaction of micro porous molecular sieve catalyzed oil generates the method for biofuel.
Background technology
Biofuel is one of most important regeneratable liquors fuel of biomass energy, there is the excellent use propertieies such as energy density is high, lubricity good, storing and transporting security, anti-knocking property are good, sufficient combustion, also having recyclability, environment friendly and the good advantage such as substituting, is the most potential large bio-based liquid fuel.Wherein representative Witconol 2301, came into one's own as biofuel in recent years.Industrial production is all generally be catalyzer with fluid sulphuric acid, is prepared by the esterification of oleic acid and methyl alcohol.Strong oxidizing property due to sulfuric acid makes by-product of esterification more, and is all liquid phase with product, brings larger difficulty to separation and purification, simultaneously sulfuric acid to equipment corrosion and environmental pollution serious.And solid acid particularly molecular sieve is as heterogeneous reaction catalyzer, easily realize being separated of catalyzer and product, substituting liquid acid with molecular sieve is important research direction.The more molecular sieve for the Esterification reaction of catalyzed oil of current research is SBA-15 mesopore molecular sieve, but temperature of reaction 160 DEG C higher (Chemical Industry and Engineering, 2011,28,2:68-72; Journal of LiaoningUniversity of Petroleum & Chemical Technology, 2008,28,4:9-13) or oleic acid conversion lower, be only about 44% (Speciality Petrochemicals, 2007,24,2:58-61).As can be seen here, the kind of catalyzer and performance directly affect the condition of reaction and the transformation efficiency of oleic acid.
Summary of the invention
In order to reduce reaction conditions, improve the transformation efficiency of oleic acid, improve the hydrothermal stability etc. of catalyzer, the invention provides a kind of high steady acidity mesoporous-esterification of the synthetic method of micro porous molecular sieve and catalysis oleic acid generates the method for biofuel, the temperature of the method esterification is 120 DEG C, the transformation efficiency of oleic acid is higher, and catalyzer hydrothermal stability is high, can reuse simultaneously.
Technical scheme of the present invention is achieved in that n in molar ratio
methyl alcohol: n
oleic acidthe ratio of=6: 1 ~ 12: 1, takes reactant, is m in mass ratio
catalyzer: m
reactant=3 ~ 6% take acid mesoporous-microporous molecular sieve catalyst, it is joined in reactor simultaneously, reacting by heating still to 100-140 DEG C, reaction 2-10h, obtain dark yellow liquid.
The present invention's height used steady acid mesoporous-microporous molecular sieve catalyst is own product, concrete steps are as follows: (1) first synthesizes β guiding agent for zeolite, by NaOH, NaAlO
2, SiO
2the aqueous solution (massfraction 30%) and massfraction are the aqueous solution of the TEAOH of 25% is n (Al according to mol ratio
2o
3)/n (SiO
2)/n (Na
2o)/n (TEAOH)/n (H
2o)=1.0/60/2.5/22/800 proportioning mixing, and stir, then mixture is transferred in autoclave, dissolves 4 hours under the condition of 140 DEG C, the settled solution obtained, i.e. Beta guiding agent for zeolite.(2) Beta guiding agent for zeolite is joined in cetyl trimethylammonium bromide (CTAMBr) aqueous solution and (when β/Zr-MCM-41, β/Sn-MCM-41 Zeolite synthesis, corresponding metal-salt will be added), mix and blend 30min, by the sulfuric acid adjust ph of 5mol/L, add ethanol; Stir 1h under normal temperature condition, moved into by mixed solution in teflon-lined stainless steel reactor, sealing, after crystallization, suction filtration, washing, dry, roasting obtains β/Al (Zr, Sn)-MCM-41 molecular sieve.(3) a certain amount of lanthanum trioxide is dissolved in the sulfuric acid of 98%, make the lanthanum sulfat solution of 0.05 ~ 0.08mol/L, β/Al-MCM-41 after roasting, β/Zr-MCM-41, β/Sn-MCM-41 molecular sieve are dipped in wherein 40min (according to 1g solid 10ml solution meter), then suction filtration, washing is to neutral, dry rear 500 DEG C of roasting 3h, obtain La
3+~ β/Al-MCM-41, La
3+~ β/Zr-MCM-41, La
3+~ β/Sn-MCM-41 molecular sieve.
Invention effect
1. adopt acid mesoporous-micro porous molecular sieve is catalyzer, stable in catalytic performance, the transformation efficiency of oleic acid can reach more than 70%.
2. acid mesoporous-micro porous molecular sieve thermostability is strong, repeat performance is good.
Embodiment
Further illustrate below in conjunction with embodiment, but and unrestricted scope involved in the present invention.
Embodiment 1:
The preparation of β/Al-MCM-41 catalyzer: adopt fractional crystallization legal system for β/Al-MCM-41 catalyzer of n (Si): n (Al)=30, synthesis step is as follows: by NaOH, NaAlO
2, SiO
2the aqueous solution (massfraction 30%) and massfraction are the aqueous solution of the TEAOH of 25% is n (Al according to mol ratio
2o
3)/n (SiO
2)/n (Na
2o)/n (TEAOH)/n (H
2o)=1.0/60/2.5/22/800 proportioning mixing, and stir, then mixture is transferred in autoclave, dissolves 4 hours under the condition of 140 DEG C, the settled solution obtained, i.e. Beta guiding agent for zeolite; Beta guiding agent for zeolite is joined in cetyl trimethylammonium bromide (CTAMBr) aqueous solution, mix and blend 30min, by the sulfuric acid adjust ph of 5mol/L, add ethanol; Stir 1h under normal temperature condition, moved into by mixed solution in teflon-lined stainless steel reactor, sealing, after crystallization, suction filtration, washing, dry, roasting obtains β/Al-MCM-41 molecular sieve catalyst, for subsequent use.
By 10 grams of oleic acid, 11.33 grams of methyl alcohol (alcohol oil rate is 10: 1), 1.123 grams of β/Al-MCM-41 molecular sieve catalysts (catalyst levels accounts for 5%), be placed in compressive reaction still, be placed in oil bath, investigate temperature of reaction, reaction times, catalyst levels, the processing condition such as alcohol oil rate, before and after reaction, well-beatenly pipette 5ml mixed solution with transfer pipet simultaneously, be placed in Erlenmeyer flask, with the KOH solution titration of 0.200mol/L, record the KOH solution volume V used up
1and V
2, calculate the transformation efficiency of oleic acid.When alcohol oil rate is 10: 1, catalyst levels accounts for 5% of reactant quality, and during 120 DEG C of reaction 8h, the transformation efficiency of oleic acid is up to 74.77%.
Embodiment 2:
The preparation of β/Zr-MCM-41 catalyzer: adopt fractional crystallization legal system for β/Zr-MCM-41 catalyzer of n (Si): n (Al)=30, synthesis step is as follows: by NaOH, NaAlO
2, SiO
2the aqueous solution (massfraction 30%) and massfraction are the aqueous solution of the TEAOH of 25% is n (Al according to mol ratio
2o
3)/n (SiO
2)/n (Na
2o)/n (TEAOH)/n (H
2o)=1.0/60/2.5/22/800 proportioning mixing, and stir, then mixture is transferred in autoclave, dissolves 4 hours under the condition of 140 DEG C, the settled solution obtained, i.e. Beta guiding agent for zeolite; Joined by Beta guiding agent for zeolite in cetyl trimethylammonium bromide (CTAMBr) aqueous solution, mix and blend 30min, adds Zr (SO
4)
2the aqueous solution (Si/Zr=1/0.05) continues mix and blend 30min, by the sulfuric acid adjust ph of 5mol/L, adds ethanol; Stir 1h under normal temperature condition, moved into by mixed solution in teflon-lined stainless steel reactor, sealing, after crystallization, suction filtration, washing, dry, roasting obtains β/Zr-MCM-41 molecular sieve catalyst, for subsequent use.
Experiment condition and step, with embodiment 1, just change catalyzer β/Al-MCM-41 into catalyzer β/Zr-MCM-41, and when alcohol oil rate is 10: 1, catalyst levels accounts for 5% of reactant quality, and during 120 DEG C of reaction 8h, the transformation efficiency of oleic acid is up to 70.0%.
Embodiment 3:
The preparation of β/Sn-MCM-41 catalyzer: preparation condition and step, with embodiment 2, are by Zr (SO
4)
2the aqueous solution makes the SnCl4 aqueous solution into.
Experiment condition and step, with embodiment 1, just change catalyzer β/Al-MCM-41 into catalyzer β/Sn-MCM-41, and when alcohol oil rate is 10: 1, catalyst levels accounts for 5% of reactant quality, and during 120 DEG C of reaction 8h, the transformation efficiency of oleic acid is up to 70.12%.
Embodiment 4:
La
3+the preparation of ~ β/Al-MCM-41 catalyzer: the preparation condition of β/Al-MCM-41 catalyzer and step are with embodiment 1.Pickling process is adopted to load on β/Al-MCM-41 molecular sieve by Rare Earth Lanthanum element, 40min is about, then suction filtration respectively, washing with lanthanum sulfat solution impregnation β/Al-MCM-41 molecular sieve that volumetric molar concentration is 0.05 ~ 0.08mol/L, dry rear 500 DEG C of roasting 3h, obtain La
3+~ β/Al-MCM-41 molecular sieve is catalyzer, for subsequent use.
Experiment condition and step, with embodiment 1, just change catalyzer β/Al-MCM-41 into catalyzer La
3+~ β/Al-MCM-41, as the La adopting the lanthanum sulfat solution impregnation of 0.07mol/L to obtain
3+~ β/Al-MCM-41 is catalyzer, and alcohol oil rate is 10: 1, and catalyst levels accounts for 5% of reactant quality, and during 120 DEG C of reaction 8h, the transformation efficiency of oleic acid is up to 79.23%.
Embodiment 5:
Catalyzer, with embodiment 1, is just changed into the catalyzer reclaimed in embodiment 4 by experiment condition and step, carries out repeating reuse experiment for five times.The repetition reuse of catalyzer the results are shown in Table 1.
Table 1 La
3+~ β/Al-MCM-41 reuses result
Claims (1)
1. high steady acid mesoporous-method of micro porous molecular sieve catalytic esterification, add by a certain percentage in reactor by oleic acid, methyl alcohol and mesoporous-microporous molecular sieve catalyst, carry out esterification at a certain temperature, survey the transformation efficiency of oleic acid; Reaction terminates rear catalyst can direct reuse without any process.Wherein used mesoporous-microporous molecular sieve catalyst is own product, namely adopt fractional crystallization legal system obtain acid mesoporous-micro porous molecular sieve, be respectively β/Al-MCM-41, β/Zr-MCM-41, β/Sn-MCM-41, then adopt lanthanum sulfat solution impregnation obtained acid mesoporous-micropore La
3+~ β/Al-MCM-41, La
3+~ β/Zr-MCM-41, La
3+~ β/Sn-MCM-41 molecular sieve catalyst, particle diameter is 40 ~ 60 μm.
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Cited By (5)
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|---|---|---|---|---|
| CN106563495A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Glucose isomerization molecular sieve catalyst and preparation method thereof |
| CN109046445A (en) * | 2018-06-25 | 2018-12-21 | 万华化学集团股份有限公司 | A kind of preparation method of H β/MCM-22 composite molecular sieves and the method for preparing tert-butyl phenol |
| CN109126860A (en) * | 2018-08-20 | 2019-01-04 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using hydrogen peroxide |
| CN109225314A (en) * | 2018-08-20 | 2019-01-18 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using sodium peroxydisulfate |
| CN109248707A (en) * | 2018-08-20 | 2019-01-22 | 青岛科技大学 | It is a kind of acidity mesopore molecular sieve preparation method and its application in catalytic esterification |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106563495A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Glucose isomerization molecular sieve catalyst and preparation method thereof |
| CN109046445A (en) * | 2018-06-25 | 2018-12-21 | 万华化学集团股份有限公司 | A kind of preparation method of H β/MCM-22 composite molecular sieves and the method for preparing tert-butyl phenol |
| CN109046445B (en) * | 2018-06-25 | 2021-06-29 | 万华化学集团股份有限公司 | Preparation method of H beta/MCM-22 composite structure molecular sieve and method for preparing tert-butylphenol |
| CN109126860A (en) * | 2018-08-20 | 2019-01-04 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using hydrogen peroxide |
| CN109225314A (en) * | 2018-08-20 | 2019-01-18 | 青岛科技大学 | A kind of application for the method and acid mesopore molecular sieve preparing acid mesopore molecular sieve using sodium peroxydisulfate |
| CN109248707A (en) * | 2018-08-20 | 2019-01-22 | 青岛科技大学 | It is a kind of acidity mesopore molecular sieve preparation method and its application in catalytic esterification |
| CN109225314B (en) * | 2018-08-20 | 2021-07-06 | 青岛科技大学 | Method for preparing acidic mesoporous molecular sieve by using sodium persulfate and application of acidic mesoporous molecular sieve |
| CN109248707B (en) * | 2018-08-20 | 2021-07-06 | 青岛科技大学 | Preparation method of acidic mesoporous molecular sieve and application of acidic mesoporous molecular sieve in catalytic esterification reaction |
| CN109126860B (en) * | 2018-08-20 | 2021-09-10 | 青岛科技大学 | Method for preparing acidic mesoporous molecular sieve by using hydrogen peroxide and application of acidic mesoporous molecular sieve |
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