CN103816925A - Preparation method of supported solid acid catalyst for synthetizing fatty acid methyl esters - Google Patents

Preparation method of supported solid acid catalyst for synthetizing fatty acid methyl esters Download PDF

Info

Publication number
CN103816925A
CN103816925A CN201410087585.5A CN201410087585A CN103816925A CN 103816925 A CN103816925 A CN 103816925A CN 201410087585 A CN201410087585 A CN 201410087585A CN 103816925 A CN103816925 A CN 103816925A
Authority
CN
China
Prior art keywords
catalyst
zro
sio
moo
fatty acid
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
Application number
CN201410087585.5A
Other languages
Chinese (zh)
Other versions
CN103816925B (en
Inventor
童冬梅
李秀琴
李会娟
胡常伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN201410087585.5A priority Critical patent/CN103816925B/en
Publication of CN103816925A publication Critical patent/CN103816925A/en
Application granted granted Critical
Publication of CN103816925B publication Critical patent/CN103816925B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A preparation method of a supported solid acid catalyst for synthetizing fatty acid methyl esters comprises the following steps: using SO4<2->, M0O3, ZrO2 and Nd2O3 as active components, using porous and high specific surface SiO2 of 20-40 mesh as a carrier, preparing the solid acid catalyst SO4<2->-M0O3-ZrO2-Nd2O3/SiO2 according to an immersion method. The catalyst is used for synthetizing fatty acid methyl esters through the esterification reaction between fatty acid and methanol and the transesterification between the ester of fatty acid and methanol, and under the conditions of the normal pressure reaction, the reaction temperature of 55-65 DEG C and the reaction time of 2-8 h, the yield of the fatty acid methyl esters is high; the catalyst uses SiO2 as the carrier, so that the catalyst is more in ducts, larger in specific surface, and stronger in mechanical property, the use amount of the active components is reduced, and the preparation cost of the catalyst is reduced remarkably; the catalyst is easier to be separated from the product, the post-processing method is simpler, the process steps are reduced, and the production cost can be reduced remarkably.

Description

A kind of preparation method of the load-type solid acid catalyst for the synthesis of fatty acid methyl ester
Technical field
The present invention relates to a kind of preparation method of the load-type solid acid catalyst for the synthesis of fatty acid methyl ester.
Background technology
Industrial extensive employing sulfuric acid cheap and easy to get, that catalytic activity is high makees catalyst and carrys out synthesizing fatty acid methyl ester, but existence is serious to equipment corrosion, three wastes discharge amount is large, post processing is complicated, accessory substance is many, high temperature easily makes the drawbacks such as organic matter carbonizing.Solid acid catalyst, because it has environmental friendliness, advantage easy and product separation receives much concern, demonstrates good catalytic activity in the organic synthesis such as esterification, ester exchange reaction.Sulfuric acid modified ZrO 2based solid acid is a kind of conventional solid acid catalyst.K.Suwannakarn etc. have reported the ZrO of preparation in Journal of Catalysis255 (2008) 279 – 286 2based solid acid SO 4 2--ZrO 2to tricaprylin and fatty alcohol (methyl alcohol, ethanol, n-butanol), ester exchange reaction shows high catalytic activity, but poor catalyst stability, active component SO in the time recycling 4 2-a large amount of solution-off, catalytic activity significantly declines.C.M.Garcia etc. have reported that in Bioresource Technology99 (2008) 6608 – 6613 ester exchange reaction of the sulfated zirconia of preparing with solventless method to soybean oil and the esterification of aliphatic acid all have very high catalytic activity, the conversion ratio of esterification and second esterification can reach respectively 98.6% and 92%, but reaction temperature high (120 ℃), the easy inactivation of catalyst.Chen etc. are carried on Zirconium-base solid acid the mesoporous type SiO of high-ratio surface in The Journal of Physical Chemistry C111 (2007) 18731-18737 2the SO that carrier makes 4 2--ZrO 2/ SiO 2solid acid, the catalytic activity of the esterification to long-chain free fatty acids (laurate and palmitic acid) and methyl alcohol is higher than traditional SO of load not 4 2-/ ZrO 2powdery solid acid, but no stability report.A kind of solid acid catalyst SO for methyl oleateization reaction is provided in CN101670290A 4 2-/ ZrO 2-M oo 3-Nd 2o 3, the yield of methyl oleate can reach 98.5%, catalytic activity is stable, reuse 6 times after methyl oleate yield can maintain 96%.But this catalyst preparation cost is high, and catalyst is granular structure, and, bad mechanical strength little without duct, specific surface, than preformed catalyst difficulty, increased post-reaction treatment technology difficulty and production cost with separation of products.
Summary of the invention
The present invention aims to provide a kind of reaction with methyl alcohol heterogenically catalyzed esterification for aliphatic acid and the load-type solid acid catalyst of fatty acid ester and methyl alcohol heterogeneous catalysis ester exchange reaction synthesizing fatty acid methyl ester, high with reaction temperature in solution prior art, solid acid catalyst active specy is easy solution-off, poor stability in reaction, catalyst specific surface is little, mechanical strength is low, the problem that catalyst preparation cost is high, aftertreatment technology is many, production cost is high.
With SO 4 2-, MoO 3, ZrO 2, Nd 2o 3for active component, high-ratio surface cheap and easy to get and porous SiO 2for carrier, wherein SO 4 2-/ M oo 3/ ZrO 2/ Nd 2o 3/ SiO 2mass ratio be 3.30～7.35% ﹕ 1.40～2.30% ﹕ 12.38～20.33% ﹕ 0.23～0.37% ﹕ 1, catalyst S O 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2preparation process as follows:
(1) by Zr (NO 3) 45H 2o and Nd (NO 3) 36H 2o is dissolved in respectively distilled water, and above-mentioned two kinds of solution preparations are become to mixed solution, progressively adds 20～40 object SiO under stirring condition 2carrier, ultrasonic exhaust 5～20min, 10～35 ℃ of water-bath dipping 20～24h, 80～110 ℃ are dry, and 550～650 ℃ of roasting 4h obtain ZrO 2-Nd 2o 3/ SiO 2carrier;
(2) by (NH 4) 6moO 244H 2in the O vitriolization aqueous solution, be made into the sulfuric acid solution of ammonium molybdate, dipping ZrO 2-Nd 2o 3/ SiO 2carrier 2h, 110 ℃ are dry, and 550～650 ℃ of roasting 2～12h, make solid acid catalyst SO 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2.The optimum temperature of catalyst roasting is 600 ℃, and best roasting time is 2～4h, each component S O in catalyst 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2optimum quality ratio be 6.02%～7.35% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1.。
The catalyst making is for the esterification synthesizing fatty acid methyl ester of multiple aliphatic acid and methyl alcohol, and the ester exchange reaction synthesizing fatty acid methyl ester of fatty acid ester and methyl alcohol, aliphatic acid comprises acetic acid, caproic acid, laurate, palmitic acid etc., and fatty acid ester comprises ethyl acetate, ethyl hexanoate, glyceryl triacetate etc.
Aliphatic acid/fatty acid ester and methyl alcohol are added to two neck bottles with mol ratio 1 ︰ 12～1 ︰ 6, control reaction temperature and reach after 55～65 ℃, then to add quality be the SO of aliphatic acid 5～15% 4 2--M oo 3-ZrO 2-Nd 2o 3/ SiO 2solid acid catalyst, stirring and refluxing 2～8h, obtains product liquid fatty acid methyl ester after reaction finishes, and is undertaken quantitatively by gas chromatograph.
The advantage of the load-type solid acid catalyst that the present invention makes is:
(1) load-type solid acid catalyst SO 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2can catalysis aliphatic acid and the esterification of methyl alcohol, also can be under low temperature, condition of normal pressure the ester exchange reaction synthesizing fatty acid methyl ester of catalysis fatty acid ester and methyl alcohol, and all there is good catalytic activity.
(2) with porous SiO cheap and easy to get 2for the load-type solid acid catalyst that carrier makes, increase in duct, specific surface increases, mechanical performance strengthens, active component consumption reduces, and catalyst preparation cost significantly reduces.
The physical parameter of the load-type solid acid catalyst making is as shown in table 1.
Table 1SO 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2the physical parameter of solid acid catalyst
Figure BDA0000475503440000021
(3) load-type solid acid catalyst has kept good catalyst activity, stability and reusability, and easier and product separation, and post-processing approach is more simple, and processing step reduces, and can significantly reduce production costs.
The specific embodiment
Embodiment 1:
By 7.70g Zr (NO 3) 45H 2o is dissolved in 10mL distilled water, and by 0.10g Nd (NO 3) 36H 2o is dissolved in 2mL distilled water, then above-mentioned two kinds of solution preparations is become to mixed solution, adds 10g20～40 object SiO under stirring condition 2carrier, after ultrasonic exhaust 5min, 30 ℃ of water-bath dipping 24h, 80 ℃ are dry, and then 600 ℃ of roasting 4h obtain ZrO 2-Nd 2o 3/ SiO 2carrier.90mL1moL/L sulfuric acid dissolution 0.31g (NH 4) 6moO 244H 2o, by roasting ZrO 2-Nd 2o 3/ SiO 2carrier floods 2h in the sulfuric acid solution of ammonium molybdate, and 110 ℃ dry, at 600 ℃ of roasting temperature 2h, makes solid acid 1# catalyst S O 4 2--M oo 3-ZrO 2-Nd 2o 3/ SiO 2-2h, SO in its component 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 7.35% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1, MoO 3, ZrO 2, Nd 2o 3the total load amount of three components is 20%.
Laurate and methyl alcohol are added to two neck bottles with mol ratio 1 ﹕ 9, control reaction temperature and reach after 65 ℃, then to add quality be the 1# catalyst S O of laurate 12% 4 2--M oo 3-ZrO 2-Nd 2o 3/ SiO 2-2h, stirring and refluxing 2h, obtains product methyl laurate after reaction finishes, and product is analyzed to such an extent that laurate acid methyl esters yield is 98.0% by gas chromatograph.
Embodiment 2
Make 2# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2-4h, difference is: the roasting time 4h of catalyst, SO in its component 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 6.02% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1.Active testing reaction is identical with embodiment 1 with analysis condition, analyzes to such an extent that methyl laurate productive rate is 98.4%.
Embodiment 3
Make 3# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2-6h, difference is: the roasting time 6h of catalyst, SO in its component 4 2-, MoO 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 3.86% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 3h.Analyze to such an extent that methyl laurate productive rate is 94.0%.
Embodiment 4
Make 4# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2-8h, difference is: the roasting time 8h of catalyst, SO in its component 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 4.85% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 4h.Analyze to such an extent that methyl laurate productive rate is 96.6%.
Embodiment 5
Make 5# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2-12h, difference is: the roasting time 12h of catalyst, SO in its component 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 3.30% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 6h.Analyze to such an extent that methyl laurate productive rate is 94.4%.
Embodiment 6
Make 6# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(14%)-550 ℃.Difference is: by 5.01g Zr (NO 3) 45H 2o is dissolved in 10mL distilled water, and by 0.07g Nd (NO 3) 36H 2o is dissolved in 2mL distilled water; 86mL1moL/L sulfuric acid dissolution 0.20g (NH 4) 6moO 244H 2o; The roasting time 4h of catalyst, 550 ℃ of sintering temperatures, SO in its component 4 2-, MoO 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 7.35% ﹕ 1.40% ﹕ 0.22% ﹕ 12.38% ﹕ 1, MoO 3, ZrO 2, Nd 2o 3the total load amount of three components is 14%.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 3h.Analyze to such an extent that methyl laurate productive rate is 96.9%.
Embodiment 7
Make 7# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(17%)-550 ℃.Difference is: by 6.31g Zr (NO 3) 45H 2o is dissolved in 10mL distilled water, and by 0.086gNd (NO 3) 36H 2o is dissolved in 2mL distilled water; 88mL1moL/L sulfuric acid dissolution 0.25g (NH 4) 6moO 244H 2o; The roasting time 4h of catalyst, 550 ℃ of sintering temperatures, SO in its component 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 7.35% ﹕ 1.70% ﹕ 0.27% ﹕ 15.03% ﹕ 1, MoO 3, ZrO 2, Nd 2o 3the total load amount of three components is 17%.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 3h.Analyze to such an extent that methyl laurate productive rate is 97.3%.
Embodiment 8
Make 8# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(23%)-550 ℃.Difference is: by 9.20g Zr (NO 3) 45H 2o is dissolved in 10mL distilled water, and by 0.12g Nd (NO 3) 36H 2o is dissolved in 2mL distilled water; 92mL1moL/L sulfuric acid dissolution 0.37g (NH 4) 6moO 244H 2o; The roasting time 4h of catalyst, 550 ℃ of sintering temperatures, SO in its component 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 7.35% ﹕ 2.30% ﹕ 0.37% ﹕ 20.33% ﹕ 1, MoO 3, ZrO 2, Nd 2o 3, the total load amount of three components is 23%.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 6h, analyzes to such an extent that methyl laurate productive rate is 93.9%.
Embodiment 9
Make 9# solid acid catalyst SO by the step of embodiment 6 Kaolinite Preparation of Catalysts 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(14%)-600 ℃, difference is: the sintering temperature of catalyst is 600 ℃.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 3h.Analyze to such an extent that methyl laurate productive rate is 94.3%.
Embodiment 10
Make 10# solid acid catalyst SO by the step of embodiment 7 Kaolinite Preparation of Catalysts 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(17%)-600 ℃, difference is: the sintering temperature of catalyst is 600 ℃.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 8h, analyzes to such an extent that methyl laurate productive rate is 90.5%.
Embodiment 11
Make 11# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(20%)-650 ℃, difference is: the roasting time 4h of catalyst, sintering temperature is 650 ℃, SO in its component 4 2-, M oo 3, Nd 2o 3,, ZrO 2, SiO 2mass ratio be 6.02% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: the stirring and refluxing time is 6h, analyzes to such an extent that methyl laurate productive rate is 94.6%.
Embodiment 12
Make 12# solid acid catalyst SO by the step of embodiment 10 Kaolinite Preparation of Catalysts 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(17%), difference is: ultrasonic evacuation time is 10min, and 100 ℃ dry, and 550 ℃ of roasting 4h obtain ZrO 2-Nd 2o 3/ SiO 2carrier.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: catalyst amount is laurate 15%, and the stirring and refluxing time is 5h, analyzes to such an extent that methyl laurate productive rate is 96.1%.
Embodiment 13
Make 13# solid acid catalyst SO by the step of embodiment 1 Kaolinite Preparation of Catalyst 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(20%), difference is: ultrasonic evacuation time is 15min, 35 ℃ of water-bath dipping 20h, and 110 ℃ are dry, and 550 ℃ of roasting 4h obtain ZrO 2-Nd 2o 3/ SiO 2carrier, catalyst is in 600 ℃ of roasting 4h.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: catalyst amount is laurate 15%, and the stirring and refluxing time is 5h, analyzes to such an extent that methyl laurate productive rate is 88.5%.
Embodiment 14
Make 14# solid acid catalyst SO by the step of embodiment 8 Kaolinite Preparation of Catalysts 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2(23%), difference is: ultrasonic evacuation time is 20min, 10 ℃ of water-bath dipping 20h, and 110 ℃ are dry, and 650 ℃ of roasting 4h obtain ZrO 2-Nd 2o 3/ SiO 2carrier, catalyst is in 600 ℃ of roasting 4h.Active testing reaction is identical with embodiment 1 with analysis condition, and difference is: catalyst amount is laurate 15%, and the stirring and refluxing time is 5h, analyzes to such an extent that methyl laurate productive rate is 96.5%.
Embodiment 15～18
The 2# catalyst that the 1# catalyst that embodiment 1 is made and embodiment 2 make is for the esterification active testing of following aliphatic acid and methyl alcohol, and test condition and result are as shown in table 2.
Table 2 embodiment 15～18 test conditions and result
Figure BDA0000475503440000061
Embodiment 19
Glyceryl triacetate and methyl alcohol are added to two neck bottles with mol ratio 1 ﹕ 9, controlling reaction temperature reaches after 65 ℃, adding quality is the 1# catalyst of glyceryl triacetate 12% again, stirring and refluxing 4h, after finishing, reaction obtains product methyl acetate, and intermediate product diacetine, acetin and by-product glycerin, analyze to obtain glyceryl triacetate conversion ratio and calculate methyl acetate productive rate and be respectively 99.6% and 98.3% by gas chromatograph.
Embodiment 20
Active testing reaction and the analysis condition of pressing embodiment 11, difference is: catalyst is 2# solid acid catalyst, analyzes to obtain glyceryl triacetate conversion ratio and calculate methyl acetate productive rate and be respectively 99.0% and 94.7%.
Embodiment 21
Active testing reaction and the analysis condition of pressing embodiment 11, difference is: catalyst is 3# solid acid catalyst, the stirring and refluxing time is 8h.Analyze to obtain glyceryl triacetate conversion ratio and calculate methyl acetate productive rate and be respectively 99.0% and 91.5%.
Embodiment 22～23
The 2# catalyst that the 1# catalyst that embodiment 1 is made and embodiment 2 make is for the ester exchange reaction active testing of following fatty acid ester and methyl alcohol, and test condition and result are as shown in table 3.
Table 3 embodiment 22～23 test conditions and result
Figure BDA0000475503440000062
The 1# catalyst that embodiment 1 is made and the 2# catalyst that embodiment 2 is made are reused, and reaction is identical with embodiment 1 with analysis condition.Difference is: after every secondary response finishes, catalyst washs through acetone, adds next reaction system after drying 20min at 100 ℃, and the stirring and refluxing time be 10h, the results are shown in Table 4.
Table 4SO 4 2--M oo 3-ZrO 2-Nd 2o 3/ SiO 2the stability test of load-type solid acid catalyst
Figure BDA0000475503440000063

Claims (4)

1. for the synthesis of a preparation method for the load-type solid acid catalyst of fatty acid methyl ester, it is characterized in that with SO 4 2--MoO 3-ZrO 2-Nd 2o 3for active component, 20～40 object SiO 2for carrier, wherein SO 4 2-/ M oo 3/ ZrO 2/ Nd 2o 3/ SiO 2mass ratio be 3.30～7.35% ﹕ 1.40～2.30% ﹕ 12.38～20.33% ﹕ 0.23～0.37% ﹕ 1, catalyst S O 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2preparation process as follows:
(1) by Zr (NO 3) 45H 2o and Nd (NO 3) 36H 2o is dissolved in respectively distilled water, and above-mentioned two kinds of solution preparations are become to mixed solution, progressively adds 20～40 object SiO under stirring condition 2carrier, ultrasonic exhaust 5～20min, 10～35 ℃ of water-bath dipping 20～24h, 80～110 ℃ are dry, and 550～650 ℃ of roasting 4h obtain ZrO 2-Nd 2o 3/ SiO 2carrier;
(2) by (NH 4) 6moO 244H 2in the O vitriolization aqueous solution, be made into the sulfuric acid solution of ammonium molybdate, dipping ZrO 2-Nd 2o 3/ SiO 2carrier 2h, 110 ℃ are dry, and 550～650 ℃ of roasting 2～12h, make solid acid catalyst SO 4 2--MoO 3-ZrO 2-Nd 2o 3/ SiO 2.
2. method according to claim 1, is characterized in that catalyst sintering temperature is 600 ℃.
3. method according to claim 1, is characterized in that catalyst roasting time is 2～4h.
4. method according to claim 1, is characterized in that each component S O in catalyst 4 2-/ MoO 3/ ZrO 2/ Nd 2o 3/ SiO 2mass ratio is 6.02%～7.35% ﹕ 2.00% ﹕ 0.32% ﹕ 17.70% ﹕ 1.
CN201410087585.5A 2014-03-11 2014-03-11 A kind of preparation method of the load-type solid acid catalyst for synthesizing fatty acid methyl ester Expired - Fee Related CN103816925B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410087585.5A CN103816925B (en) 2014-03-11 2014-03-11 A kind of preparation method of the load-type solid acid catalyst for synthesizing fatty acid methyl ester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410087585.5A CN103816925B (en) 2014-03-11 2014-03-11 A kind of preparation method of the load-type solid acid catalyst for synthesizing fatty acid methyl ester

Publications (2)

Publication Number Publication Date
CN103816925A true CN103816925A (en) 2014-05-28
CN103816925B CN103816925B (en) 2016-08-17

Family

ID=50752383

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410087585.5A Expired - Fee Related CN103816925B (en) 2014-03-11 2014-03-11 A kind of preparation method of the load-type solid acid catalyst for synthesizing fatty acid methyl ester

Country Status (1)

Country Link
CN (1) CN103816925B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105056976A (en) * 2015-07-16 2015-11-18 哈尔滨工业大学 Preparation method of vulcanized zirconium dioxide serving as solid acid catalyst and having high specific surface area
CN105597831A (en) * 2016-01-18 2016-05-25 张玲 Fatty acid methyl ester catalyst and preparation method thereof
CN105642315A (en) * 2015-12-29 2016-06-08 龙建新 Industrial preparation method and applications of solid acid catalyst
CN114950503A (en) * 2021-12-21 2022-08-30 常州市金坛区维格生物科技有限公司 Preparation method and application of regenerated acid catalyst

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1425500A (en) * 2002-12-31 2003-06-25 曲阜师范大学 Granular solid super strong acid catalyst and its preparing method
CN101670290A (en) * 2009-09-30 2010-03-17 四川大学 Solid acid catalyst used for synthesizing fatty acid methyl ester
JP2010098994A (en) * 2008-10-22 2010-05-06 Toyota Central R&D Labs Inc Method for producing sugar, or derivative of the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1425500A (en) * 2002-12-31 2003-06-25 曲阜师范大学 Granular solid super strong acid catalyst and its preparing method
JP2010098994A (en) * 2008-10-22 2010-05-06 Toyota Central R&D Labs Inc Method for producing sugar, or derivative of the same
CN101670290A (en) * 2009-09-30 2010-03-17 四川大学 Solid acid catalyst used for synthesizing fatty acid methyl ester

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周从山 等: "二氧化硅负载氧化锆固体酸催化合成乙酸异丁酯", 《湖南理工学院学报（自然科学版）》, vol. 21, no. 1, 31 March 2008 (2008-03-31), pages 49 - 51 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105056976A (en) * 2015-07-16 2015-11-18 哈尔滨工业大学 Preparation method of vulcanized zirconium dioxide serving as solid acid catalyst and having high specific surface area
CN105642315A (en) * 2015-12-29 2016-06-08 龙建新 Industrial preparation method and applications of solid acid catalyst
CN105642315B (en) * 2015-12-29 2018-01-05 龙建新 A kind of industrial production process of solid acid catalyst and its application
CN105597831A (en) * 2016-01-18 2016-05-25 张玲 Fatty acid methyl ester catalyst and preparation method thereof
CN114950503A (en) * 2021-12-21 2022-08-30 常州市金坛区维格生物科技有限公司 Preparation method and application of regenerated acid catalyst
CN114950503B (en) * 2021-12-21 2023-08-18 常州市金坛区维格生物科技有限公司 Preparation method and application of regenerated acid catalyst

Also Published As

Publication number Publication date
CN103816925B (en) 2016-08-17

Similar Documents

Publication Publication Date Title
CN104177319B (en) A kind of method for preparing 2,5 furandicarboxylic acid esters
CN103816925A (en) Preparation method of supported solid acid catalyst for synthetizing fatty acid methyl esters
CN107011154A (en) A kind of method that adipic acid is prepared by furans -2,5- dicarboxylic acids
CN108772100B (en) Heteropolyacid salt solid catalyst, and preparation method and application thereof
CN101879457B (en) Nano-solid strong base catalyst, preparation method thereof and application thereof
CN107552074A (en) A kind of preparation method for being used to produce the solid acid catalyst of the double isobutyrates of the pentanediol of 2,2,4 trimethyl 1,3
CN103275096A (en) Method for preparing isosorbide based on cellulose
CN114950555B (en) Zirconium-based monoatomic catalyst, preparation method and application thereof in selective synthesis of 2, 5-furandimethanol
CN103664656A (en) Synthesis and application of quaternary ammonium salt ionic liquid based on heteropolyacid
CN107245065A (en) A kind of method that catalytic hydrogenation ethyl levulinate prepares valerolactone
CN101518741A (en) Supported zirconium sulfate catalyst, preparation method thereof and application thereof in synthesizing ethylene glycol monoethylether acetate or tributyl citrate
CN108940258B (en) Weak acid catalyst for synthesizing 2,2, 4-trimethylpentanediol diisobutyrate
CN106179453A (en) A kind of carried heteropoly acid catalyst of high stability and its preparation method and application
CN106944050B (en) A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol
CN108014782A (en) A kind of method of catalytic degradation lignin
CN102500301B (en) Preparation method and product of polymer microsphere with core-shell structure and hollow structure
CN105622419B (en) A kind of method that carbohydrate prepares ethyl glycolate
CN111875493B (en) Method for synthesizing borneol by using imidazole acidic ionic liquid
CN103084162B (en) Composite oxides solid catalyst of lanthanum load and preparation method thereof and application
CN102850303B (en) New application and using method of mesoporous solid acid catalyst
CN102557889A (en) Method for synthesizing polyglycerol by using load type sodium hydroxide solid alkali catalyst
CN112517033A (en) Vanadium phosphorus oxide catalyst and preparation method and application thereof
Bao et al. Transesterification of tree-born oil with novel magnetic biobased heteropolyacid prepared via in-situ reaction
CN101830787A (en) Method for synthesizing methyl isobutyl ketone and diisobutyl ketone by acetone gas-phase one-step method
CN108129320A (en) A kind of method that carbohydrate prepares ethyl glycolate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160817

Termination date: 20190311