CN104857977A - Supported SO42-/TiO2-Fe catalyst preparation method and application of catalyst in synthesis of tributyl citrate - Google Patents
Supported SO42-/TiO2-Fe catalyst preparation method and application of catalyst in synthesis of tributyl citrate Download PDFInfo
- Publication number
- CN104857977A CN104857977A CN201510221733.2A CN201510221733A CN104857977A CN 104857977 A CN104857977 A CN 104857977A CN 201510221733 A CN201510221733 A CN 201510221733A CN 104857977 A CN104857977 A CN 104857977A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tio
- preparation
- support type
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a supported SO42-/TiO2-Fe catalyst preparation method and application of the catalyst in synthesis of tributyl citrate. The preparation method comprises (1) preparing a mixture A; (2) preparing a mixture B; (3) dropping the mixture B into the mixture A; (4) moving the mixed solution obtained in the step (3) into a clean beaker, performing drying in an oven, and adding the mixture into vitriol to be submerged; (5) moving the mixture obtained in the step (4) into the clean beaker, performing drying in an oven, and putting the mixture in a muffle to be roasted to obtain the supported SO42-/TiO2-Fe catalyst after cooling. Esterification reaction comprises that citric acid and n-butyl alcohol are subjected to esterification reaction under the action of the supported SO42-/TiO2-Fe catalyst to obtain tributyl citrate. The catalyst is good in repeated use effect, small in pollution, low in preparation cost and corrosion-free to production equipment. The citric acid conversion rate can reach more than 99.3% during the preparation of the citric acid, and the production cost is low.
Description
Technical field
The present invention relates to a kind of preparation method and application of catalyst, be specifically related to a kind of support type SO
4 2-/ TiO
2the preparation method of-Fe catalyst and the application in ATBC synthesis thereof.
Background technology
ATBC (TBC), as a kind of nontoxic plasticizer, has the advantages such as tasteless, intermiscibility good, oil resistivity good, plasticizing efficiency is high, volatility is little, its light resistance, cold resistance and have excellent water-resistance, and also has fungus resistance.After its plasticising, plastics cold flexibility is good, nondiscolouring thermally-stabilised when molten envelope.Because the alkyl of ATBC is closed by acetyl group, therefore its volatility and water sensitivity are further improved.In plasticising performance, ATBC is the most similar with the neck different monooctyl ester of phthalic acid (DOP), complete alternative traditional Reomol plasticizer, be called as " green " Environmental-friendplastic plastic plasticizer, can be used for the plasticising of polyethylene, polyvinyl fluoride, poly-third ethene and various fibre resin, also can be used for the dose of the plastic products such as packaging material for food, medical apparatus, health care goods, toy for children and amenities; Also can be used for protein-based defoamer.China's citric acid output is comparatively large, for the production of ATBC provides advantage, makes it have broad application prospects in food and medicine field.
The production technology of conventional synthesis ATBC take the concentrated sulfuric acid as catalyst, prepared by the acetylization reaction of catalytic citric acid tributyl and acetic anhydride.Make catalyst with the concentrated sulfuric acid, though cost is low, catalytic activity is higher, but reaction time of esterification is long, selective low, there is the side reactions such as oxidation, dehydration, charing, and product color is dark, also there is serious corrosion and three-waste pollution problem simultaneously.
In recent years, the catalyst researching and developing more ATBC esterification mainly comprises: inorganic salt catalyst disclosed in Chinese invention patent 200910026014.x, resin type catalyst disclosed in Chinese invention patent 201110154724.8, Chinese invention patent 200510086546.4, 200810042466.2 and 201110163834.0 disclosed in ion liquid type catalyst, composite catalyst disclosed in Chinese invention patent 200810151998.x, these catalyst improve the conversion ratio of the concentrated sulfuric acid relative to the concentrated sulfuric acid, but there is preparation and activation process complexity all to some extent, preparation cost is high, pollute large, the shortcomings such as weak effect reused by catalyst.
Summary of the invention
The object of the invention is to provide a kind of support type SO
4 2-/ TiO
2the preparation method of-Fe catalyst and the application in ATBC synthesis thereof, citric acid conversion ratio is high, catalyst reuse effective, pollute little, preparation cost is low.
For achieving the above object, the technical solution used in the present invention is: a kind of support type SO
4 2-/ TiO
2the preparation method of-Fe catalyst, comprises the steps:
(1) by absolute ethyl alcohol and water mixing, stir, add molysite, continue after mixing to add porous solid particle, obtain mixture A;
(2) absolute ethyl alcohol is fully mixed with dispersant, stir, add tetrabutyl titanate, be configured to mixed solution B;
(3) under temperature constant state, the mixed solution B of step (2) gained is added drop-wise in mixture A, then the mixed solution of gained is moved to clean beaker, after putting into oven for drying, join sulfuric acid solution, dipping;
(4) mixture after step (3) being flooded puts into baking oven, is cooled to room temperature, puts into Muffle furnace, obtain support type SO after roasting after oven dry
4 2-/ TiO
2-Fe catalyst.
Wherein, in step (1), the volume ratio of absolute ethyl alcohol and water is 1 ~ 15:1.
Wherein, in step (1), described molysite is the one in ferric sulfate, ferric nitrate and ferric carbonate, and the mass volume ratio of molysite and absolute ethyl alcohol and water mixed solution is 0.1 ~ 1g/mL.
Wherein, in step (1), described porous solid particle is the one in zeolite, active carbon and molecular sieve, and the mass volume ratio of porous solid particle and absolute ethyl alcohol and water mixed solution is 0.01 ~ 0.1g/mL.
Wherein, in step (2), described dispersant is the one in methylcellulose, hydroxypropyl cellulose and propyl cellulose, and the mass volume ratio of dispersant and absolute ethyl alcohol is 0.001 ~ 0.03g/mL.
Wherein, in step (2), the volume ratio of tetrabutyl titanate and absolute ethyl alcohol is 1:5 ~ 10.
Wherein, in step (3), the rate of addition that mixed solution B is added drop-wise in mixture A is 10 ~ 1000mL/h, and during dropping, holding temperature is 15 ~ 40 DEG C, and the bake out temperature of baking oven is 100 ~ 150 DEG C.
Wherein, in step (3), the concentration of described sulfuric acid solution is 0.5 ~ 4mol/L, and dip time is 1 ~ 5h.
Wherein, in step (4), the bake out temperature of baking oven is 100 ~ 150 DEG C, and Muffle furnace sintering temperature is 300 ~ 600 DEG C, and roasting time is 3 ~ 6h.
The embodiment of the present invention also provides a kind of above-mentioned support type SO
4 2-/ TiO
2the application of-Fe catalyst in ATBC synthesis:
Esterification condition: the mol ratio of citric acid and n-butanol is 1:4 ~ 6, support type SO
4 2-/ TiO
2the quality of-Fe catalyst is 1 ~ 5% of reactant gross mass;
Esterification reaction process:
In the three-neck flask having electromagnetic agitation, thermometer, reflux condensing tube and water knockout drum, add 0.1 ~ 0.15mol citric acid and 0.4 ~ 0.6mol n-butanol, add thermal agitation, after citric acid is entirely molten, add support type SO
4 2-/ TiO
2-Fe catalyst 0.1 ~ 0.6g, heats return stirring at 110 ~ 130 DEG C, after reaction 3 ~ 4h, obtains ATBC crude product;
Off-loading type SO is filtered after being cooled to room temperature
4 2-/ TiO
2-Fe catalyst, with in 5% ~ 10% sodium bicarbonate aqueous solution and aqueous phase be 7 ~ 8 to pH, then wash twice with saturated aqueous common salt, removed under reduced pressure n-butanol and water, collect 178 ~ 180 DEG C/400Pa cut, obtain ATBC product.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. catalyst of the present invention reuse effective, pollute little, preparation cost is low, corrosion-free to production equipment.
2. when the present invention prepares ATBC, citric acid conversion ratio can reach more than 99.3%, and production cost is low.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
(1) support type SO
4 2-/ TiO
2the preparation of-Fe catalyst
By 20mL absolute ethyl alcohol and the mixing of 2mL water, stir, add 3g ferric carbonate, continue to add 1 g after mixing, particle diameter is the active carbon of 0.2nm, obtain mixture A;
20mL absolute ethyl alcohol is fully mixed with 0.02g propyl cellulose, stirs, add 4mL tetrabutyl titanate, be configured to mixed solution B;
Be added drop-wise in mixture A by above-mentioned mixed solution B with the speed of 400mL/h, this process holding temperature is 15 DEG C, the mixed solution of gained is moved to clean beaker, puts into baking oven, joins in 1mol/L sulfuric acid solution after 100 DEG C of oven dry, dipping 1h;
The mixture obtained after dipping is put into baking oven, is cooled to room temperature after 100 DEG C of oven dry, puts into Muffle furnace, at 500 DEG C, after roasting 4h, obtain support type SO
4 2-/ TiO
2-Fe catalyst.
(2) esterification
In the 100ml three-neck flask having electromagnetic agitation, thermometer, reflux condensing tube and water knockout drum, add 0.1mol citric acid and 0.45mol n-butanol, add thermal agitation, after citric acid is entirely molten, add the support type SO of above-mentioned preparation
4 2-/ TiO
2-Fe catalyst 0.1g, heats return stirring at 110 ~ 130 DEG C, after reaction 3h, obtains ATBC crude product;
Off-loading type SO is filtered after being cooled to room temperature
4 2-/ TiO
2-Fe catalyst, with in 5% sodium bicarbonate aqueous solution and aqueous phase be 7 ~ 8 to pH, to remove unreacted citric acid and the incomplete citric acid monoester of esterification, the two fat of citric acid, then wash twice with saturated aqueous common salt, removed under reduced pressure n-butanol and water, collect 178 ~ 180 DEG C/400Pa cut, obtain ATBC product, the yield of ATBC is 98.6%.
Embodiment 2:
(1) support type SO
4 2-/ TiO
2the preparation of-Fe catalyst
By 15mL absolute ethyl alcohol and the mixing of 10mL water, stir, add 3g ferric sulfate, continue after mixing to add 1.2g molecular sieve, obtain mixture A;
15mL absolute ethyl alcohol is fully mixed with 0.015g methylcellulose, stirs, add 3mL tetrabutyl titanate, be configured to mixed solution B;
Be added drop-wise in mixture A by above-mentioned mixed solution B with the speed of 600mL/h, this process holding temperature is 40 DEG C, the mixed solution of gained is moved to clean beaker, puts into baking oven, joins in 1.2mol/L sulfuric acid solution after 120 DEG C of oven dry, dipping 1.5h;
The mixture obtained after dipping is put into baking oven, is cooled to room temperature after 120 DEG C of oven dry, puts into Muffle furnace, at 550 DEG C, after roasting 4h, obtain support type SO
4 2-/ TiO
2-Fe catalyst.
(2) esterification
In the 100ml three-neck flask having electromagnetic agitation, thermometer, reflux condensing tube and water knockout drum, add 0.1mol citric acid and 0.5mol n-butanol, add thermal agitation, after citric acid is entirely molten, add the support type SO of above-mentioned preparation
4 2-/ TiO
2-Fe catalyst 0.15g, heats return stirring at 110 ~ 130 DEG C, after reaction 4h, obtains ATBC crude product;
Off-loading type SO is filtered after being cooled to room temperature
4 2-/ TiO
2-Fe catalyst, with in 5% sodium bicarbonate aqueous solution and aqueous phase be 7 ~ 8 to pH, then wash twice with saturated aqueous common salt, removed under reduced pressure n-butanol and water, collect 178 ~ 180 DEG C/400Pa cut, obtain ATBC product, the yield of ATBC is 99.3%.
Embodiment 3:
(1) support type SO
4 2-/ TiO
2the preparation of-Fe catalyst
By 10mL absolute ethyl alcohol and the mixing of 10mL water, stir, add 2g ferric nitrate, continue after mixing to add 1.5 g zeolites, obtain mixture A;
10mL absolute ethyl alcohol is fully mixed with 0.01g hydroxypropyl cellulose, stirs, add 1mL tetrabutyl titanate, be configured to mixed solution B;
Be added drop-wise in mixture A by above-mentioned mixed solution B with the speed of 800mL/h, this process holding temperature is 20 DEG C, the mixed solution of gained is moved to clean beaker, puts into baking oven, joins in 1.5mol/L sulfuric acid solution after 150 DEG C of oven dry, dipping 1.2h;
The mixture obtained after dipping is put into baking oven, is cooled to room temperature after 150 DEG C of oven dry, puts into Muffle furnace, at 400 DEG C, after roasting 4h, obtain support type SO
4 2-/ TiO
2-Fe catalyst.
(2) esterification
In the 100ml three-neck flask having electromagnetic agitation, thermometer, reflux condensing tube and water knockout drum, add 0.1mol citric acid and 0.5mol n-butanol, add thermal agitation, after citric acid is entirely molten, add the support type SO of above-mentioned preparation
4 2-/ TiO
2-Fe catalyst 0.2g, heats return stirring at 110 ~ 130 DEG C, after reaction 5h, obtains ATBC crude product;
Off-loading type SO is filtered after being cooled to room temperature
4 2-/ TiO
2-Fe catalyst, with in 8% sodium bicarbonate aqueous solution and aqueous phase be 7 ~ 8 to pH, then wash twice with saturated aqueous common salt, removed under reduced pressure n-butanol and water, collect 178 ~ 180 DEG C/400Pa cut, obtain ATBC product, the yield of ATBC is 97.7%.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from principle of the present invention; can also make some improvement or replacement, these improve or replace and also should be considered as protection scope of the present invention.
Claims (10)
1. a support type SO
4 2-/ TiO
2the preparation method of-Fe catalyst, is characterized in that, comprises the steps:
(1) by absolute ethyl alcohol and water mixing, stir, add molysite, continue after mixing to add porous solid particle, obtain mixture A;
(2) absolute ethyl alcohol is fully mixed with dispersant, stir, add tetrabutyl titanate, be configured to mixed solution B;
(3) under temperature constant state, the mixed solution B of step (2) gained is added drop-wise in mixture A, then the mixed solution of gained is moved to clean beaker, after putting into oven for drying, join sulfuric acid solution, dipping;
(4) mixture after step (3) being flooded puts into baking oven, is cooled to room temperature, puts into Muffle furnace, obtain support type SO after roasting after oven dry
4 2-/ TiO
2-Fe catalyst.
2. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (1), the volume ratio of absolute ethyl alcohol and water is 1 ~ 15:1.
3. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (1), described molysite is the one in ferric sulfate, ferric nitrate and ferric carbonate, and the mass volume ratio of molysite and absolute ethyl alcohol and water mixed solution is 0.1 ~ 1g/mL.
4. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (1), described porous solid particle is the one in zeolite, active carbon and molecular sieve, and the mass volume ratio of porous solid particle and absolute ethyl alcohol and water mixed solution is 0.01 ~ 0.1g/mL.
5. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (2), described dispersant is the one in methylcellulose, hydroxypropyl cellulose and propyl cellulose, and the mass volume ratio of dispersant and absolute ethyl alcohol is 0.001 ~ 0.03g/mL.
6. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (2), the volume ratio of tetrabutyl titanate and absolute ethyl alcohol is 1:5 ~ 10.
7. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (3), the rate of addition that mixed solution B is added drop-wise in mixture A is 10 ~ 1000mL/h, and during dropping, holding temperature is 15 ~ 40 DEG C, and the bake out temperature of baking oven is 100 ~ 150 DEG C.
8. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (3), the concentration of described sulfuric acid solution is 0.5 ~ 4mol/L, and dip time is 1 ~ 5h.
9. support type SO according to claim 1
4 2-/ TiO
2the preparation method of-Fe catalyst, in step (4), the bake out temperature of baking oven is 100 ~ 150 DEG C, and Muffle furnace sintering temperature is 300 ~ 600 DEG C, and roasting time is 3 ~ 6h.
10. the support type SO according to any one of a claim 1 ~ 9
4 2-/ TiO
2the application of-Fe catalyst in ATBC synthesis, is characterized in that,
Esterification condition: the mol ratio of citric acid and n-butanol is 1:4 ~ 6, support type SO
4 2-/ TiO
2the quality of-Fe catalyst is 1 ~ 5% of reactant gross mass;
Esterification reaction process:
In the three-neck flask having electromagnetic agitation, thermometer, reflux condensing tube and water knockout drum, add 0.1 ~ 0.15mol citric acid and 0.4 ~ 0.6mol n-butanol, add thermal agitation, after citric acid is entirely molten, add support type SO
4 2-/ TiO
2-Fe catalyst 0.1 ~ 0.6g, heats return stirring at 110 ~ 130 DEG C, after reaction 3 ~ 4h, obtains ATBC crude product;
Off-loading type SO is filtered after being cooled to room temperature
4 2-/ TiO
2-Fe catalyst, with in 5% ~ 10% sodium bicarbonate aqueous solution and aqueous phase be 7 ~ 8 to pH, then wash twice with saturated aqueous common salt, removed under reduced pressure n-butanol and water, collect 178 ~ 180 DEG C/400Pa cut, obtain ATBC product.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510221733.2A CN104857977A (en) | 2015-05-05 | 2015-05-05 | Supported SO42-/TiO2-Fe catalyst preparation method and application of catalyst in synthesis of tributyl citrate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510221733.2A CN104857977A (en) | 2015-05-05 | 2015-05-05 | Supported SO42-/TiO2-Fe catalyst preparation method and application of catalyst in synthesis of tributyl citrate |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104857977A true CN104857977A (en) | 2015-08-26 |
Family
ID=53904401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510221733.2A Pending CN104857977A (en) | 2015-05-05 | 2015-05-05 | Supported SO42-/TiO2-Fe catalyst preparation method and application of catalyst in synthesis of tributyl citrate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104857977A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105214692A (en) * | 2015-10-23 | 2016-01-06 | 湖北迅达药业股份有限公司 | Supported solid catalyst and preparation method thereof and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
CN101139288A (en) * | 2006-09-07 | 2008-03-12 | 黑龙江大学 | Method for preparating ethyl linoleate by catalysis of composite solid ultra-strong acid |
CN101518741A (en) * | 2009-03-13 | 2009-09-02 | 南京师范大学 | Supported zirconium sulfate catalyst, preparation method thereof and application thereof in synthesizing ethylene glycol monoethylether acetate or tributyl citrate |
US20100035750A1 (en) * | 2008-08-05 | 2010-02-11 | National Tsing Hua University | Carbon-coated metal oxide nano-particles and method of preparing the same |
CN101791571A (en) * | 2010-03-24 | 2010-08-04 | 南京工业大学 | Method for preparing supported photocatalyst |
CN104209124A (en) * | 2013-05-29 | 2014-12-17 | 华东理工大学 | Preparation of esterification catalyst and application |
-
2015
- 2015-05-05 CN CN201510221733.2A patent/CN104857977A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
CN101139288A (en) * | 2006-09-07 | 2008-03-12 | 黑龙江大学 | Method for preparating ethyl linoleate by catalysis of composite solid ultra-strong acid |
US20100035750A1 (en) * | 2008-08-05 | 2010-02-11 | National Tsing Hua University | Carbon-coated metal oxide nano-particles and method of preparing the same |
CN101518741A (en) * | 2009-03-13 | 2009-09-02 | 南京师范大学 | Supported zirconium sulfate catalyst, preparation method thereof and application thereof in synthesizing ethylene glycol monoethylether acetate or tributyl citrate |
CN101791571A (en) * | 2010-03-24 | 2010-08-04 | 南京工业大学 | Method for preparing supported photocatalyst |
CN104209124A (en) * | 2013-05-29 | 2014-12-17 | 华东理工大学 | Preparation of esterification catalyst and application |
Non-Patent Citations (3)
Title |
---|
郭泉: "柠檬酸三丁酯合成的研究进展", 《化工时刊》 * |
陶贤平: "活性炭固载氯化铁催化合成柠檬酸三乙酯", 《精细化工中间体》 * |
陶贤平: "环境友好催化剂催化合成三醋酸甘油酯", 《精细石油化工进展》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105214692A (en) * | 2015-10-23 | 2016-01-06 | 湖北迅达药业股份有限公司 | Supported solid catalyst and preparation method thereof and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104177319A (en) | Method for preparing 2,5-furyldiformate | |
CN104028307B (en) | A kind of magnetic solid super acidic catalyst and preparation method | |
CN102941113B (en) | Catalyst for synthesizing methyl acrylate by using methyl acetate and methylal and preparation method thereof | |
CN102824924B (en) | Mesoporous solid strong base catalyst, preparation method and application | |
CN103613501B (en) | Method with macropore strong acid cation exchanger resin for catalyst preparing tributyl citrate | |
CN101518741A (en) | Supported zirconium sulfate catalyst, preparation method thereof and application thereof in synthesizing ethylene glycol monoethylether acetate or tributyl citrate | |
CN101830803A (en) | Method for synthesizing citric acid ester type compound | |
CN112138708B (en) | Solid acid catalyst and preparation method and application thereof | |
CN105251496A (en) | Catalyst and method preparing dimethyl carbonate by using catalyst | |
CN105294409A (en) | Eugenol synthesis method | |
CN102304045A (en) | Integrated process for synthesizing acetyl tributyl citrate by using activated carbon immobilized sulfuric acid catalyst | |
CN104857977A (en) | Supported SO42-/TiO2-Fe catalyst preparation method and application of catalyst in synthesis of tributyl citrate | |
CN104387234B (en) | A kind of synthetic method of 3-methyl-3-butene-1-alcohol | |
CN103739484B (en) | The preparation method of 1,4-naphthalene dicarboxylic acids | |
CN104785298A (en) | Solid base catalyst taking metal organic framework material as carrier, preparation method and application thereof | |
CN103316696B (en) | Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method | |
CN102702143A (en) | Method for preparing 2-acetylfuran | |
CN103436368B (en) | Method for synchronously preparing biodiesel and glycerol carbonate by using alkali-earth oxide as catalyst | |
CN102775290B (en) | 2-chloromethyl-5,6-dimethoxy-3-methyl isophthalic acid, the preparation method of 4-para benzoquinone | |
CN108503547A (en) | A method of by transesterification path synthesizing n-butyl acetate | |
CN104327015A (en) | Green synthetic method of epoxy unsaturated fatty acid methyl ester and catalyst | |
CN105523915B (en) | A kind of method that high yield gas phase catalysis cracking prepares two fluoracyl fluorides | |
CN102531403B (en) | Method for preparing hollow glass microspheres with cordierite wrapped on surface | |
CN105175746A (en) | Wood fiber homogeneous phase transesterification modification method | |
CN108440286A (en) | A kind of method for preparing acetylsalicylic acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150826 |