CN103172597B - The method of titanium molecular sieve catalysis synthesizing epoxy fatty acid methyl ester - Google Patents
The method of titanium molecular sieve catalysis synthesizing epoxy fatty acid methyl ester Download PDFInfo
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- CN103172597B CN103172597B CN201310113772.1A CN201310113772A CN103172597B CN 103172597 B CN103172597 B CN 103172597B CN 201310113772 A CN201310113772 A CN 201310113772A CN 103172597 B CN103172597 B CN 103172597B
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- acid methyl
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention reside in one kind is provided using HTS as oxidation catalyst, hydrogen peroxide is the clean technologies that oxidant prepares epoxy aliphatic acid methyl ester, and waste water and the alkaline residue discharge of conventional art route are eliminated from source.It is exactly specifically：Using HTS as catalyst, a certain amount of hydrogen peroxide is added dropwise to fatty acid methyl ester and carbinol mixture at a certain temperature；After reacting certain time, the titanium-silicon molecular sieve catalyst in product is filtered to isolate, catalyst recycles；The reaction product for having filtered catalyst is achieved with low acid number, iodine number, the epoxy aliphatic acid methyl ester product of high epoxy value through simple separation, oil mixture through distillation dehydration；Directly used as recirculated water after the recovered methanol of aqueous phase, methanol loop uses.
Description
Technical field
The present invention relates to a kind of epoxy aliphatic acid methyl ester process for catalytic synthesis, especially using HTS as catalyst,
With fatty acid methyl ester and methanol, the method for hydrogen peroxide synthesizing epoxy fatty acid methyl ester plasticiser.
Background technology
To improve the processing of plastic products and performance, plasticising must be added in the processing of plastic products and product
Agent.Traditional plastic plasticizer is with the dioctyl phthalate of petroleum refining Product processing（DOP）Based on, but because tradition increases
DOP be present and have to human body and environmental hazard risk in modeling agent.With the raising of countries in the world environmental consciousness, medicine and food bag
The plastic products such as dress, commodity, toy, to primary plasticizer dioctyl phthalate（DOP）Dosage propose strict limitation.
Therefore, it is developed environment-friendly epoxy plasticiser.Epoxy plasticiser is that epoxide group is carried in molecular structure
Organic compound.Compared with traditional adjacent benzene class plasticizer, have the advantages that nontoxic, heat-resisting and light resistance is good.Epoxies is plasticized
Agent mainly includes Epoxy oil and the major class of epoxy aliphatic ester two.China's waste grease resource is compared with horn of plenty, by waste grease resource
Carry out cleaning recycling production epoxy aliphatic acid methyl ester plasticizer, can both eliminate waste grease and environment and people's body are good for
The harm of health, and alternative part petroleum resources, are the technological approaches with certain social and economic benefit.
At present, the synthetic technology route of epoxy aliphatic acid methyl ester typically uses：Fatty acid methyl ester, formic acid and hydrogen peroxide are dense
Sulfuric acid isolates oil phase and aqueous phase, after removing aqueous phase, oil phase is eaten with saturation under the catalytic action of catalyst, to react a few hours
Salt water washing 2-3 times, then after washing three times, with aqueous sodium carbonate and residual acid number, finally distillation obtains epoxidised fatty
Sour methyl esters product.In conventional process techniques route, it is not used only with severe corrosive and dangerous sulfuric acid as catalyst,
Cause equipment corrosion and maintenance, investment cost height, and complex procedures, long flow path, produce the discharge of a large amount of waste water, alkaline residue.Though
Environmental friendly product so is produced, but production process causes bigger pollution to environment.
The shortcomings that to overcome conventional epoxy fatty acid methyl ester technology path, scientific worker makes numerous effort, to improve
The spatter property and economy of production process.As disclosed in CN101284821A and replaced sulfuric acid as catalyst using ionic liquid
Reported in the patents such as method, CN101885710A and CN101722003A using zirconium oxide and oxides-containing iron and be used as catalyst.
Formic acid and acetic acid is still used to cause for the carrier of oxygen in production process still aside from the effect of catalyst, but in its course of reaction
Need in washing, alkali and wait process, still to environmental emission pollutant.In addition, in CN101891713A and CN102875493A
The method that epoxy aliphatic acid methyl ester is prepared with microreactor is disclosed, due to conventional art can be reduced using minisize reaction technology
The danger and reaction rate of route, but its reaction system still uses the organic acids such as formic acid, acetic acid as the carrier of oxygen, not from essence
The pollutant emission of conventional art route is eliminated on upper and source.
The content of the invention
The invention reside in one kind is provided using HTS as oxidation catalyst, hydrogen peroxide is that oxidant prepares epoxidised fatty
The clean technologies of sour methyl esters, waste water and the alkaline residue discharge of conventional art route are eliminated from source, shortens technological process, reduces production
Cost.Inventor prepares epoxy aliphatic acid methyl ester technical research process being engaged in titanium molecular sieve catalysis fatty acid methyl ester epoxidation
Middle discovery：Because the epoxidised oxidant of fatty acid methyl ester uses hydrogen peroxide, water is generated after hydrogen peroxide reduction, what is used in addition is double
Oxygen water raw material typically contains 50-75% water, in epoxidation reaction system, due to the presence of a large amount of water, in reaction system again
Contain incomplete esterified fatty acid in additional organic acid or raw material, under epoxidation reaction condition, fatty acid methyl ester or epoxy
Hydrolysis can occur for fatty acid methyl ester, cause product acid number to raise.Therefore, inventor is in fatty acid methyl ester epoxidation reaction body
The low-carbon alcohols such as methanol or ethanol are introduced in system, purpose is intended to make aliphatic acid in reaction system that esterification occurs with low-carbon alcohols,
To reduce product acid number and reduce significant loss.Found in research process, in the presence of HTS, methanol can quilt on a small quantity
Formic acid is oxidized to, increases substantially epoxidation reaction speed.
The method of titanium molecular sieve catalysis synthesizing epoxy fatty acid methyl ester disclosed by the invention is characterised by：With titanium silicon point
Son sieve is catalyst, and a certain amount of hydrogen peroxide is added dropwise to fatty acid methyl ester and carbinol mixture at a certain temperature；Reaction is certain
After time, the titanium-silicon molecular sieve catalyst in product is filtered to isolate, catalyst recycles；The reaction production of catalyst is filtered
Thing is achieved with low acid number, iodine number, the epoxy aliphatic acid methyl ester of high epoxy value through simple separation, oil mixture through distillation dehydration
Product；Directly used as recirculated water after the recovered methanol of aqueous phase, methanol loop uses.
The present invention has following advantage：
1st, eliminate washing oil-polluted water as the carrier of oxygen without using organic acids such as formic acid, acetic acid from source and neutralize alkaline residue
Discharge, realize clean manufacturing；
2nd, without using acidic catalysts such as sulfuric acid, sewage discharge and the equipment corrosion of washing Removal of catalyst is eliminated, is shortened
Technological process, reduce cost；
3rd, process without washing, in alkali and is waited due to product, reduces the loss of raw fatty acid methyl esters, improve process economicses
Property.
Embodiment
The method of titanium molecular sieve catalysis synthesizing epoxy fatty acid methyl ester disclosed by the invention, it is using HTS to urge
Agent, using hydrogen peroxide as oxidant, it is catalyzed fatty acid methyl ester epoxidation reaction.Its embodiment is：Iodine number is more than
80gI/100g fatty acid methyl ester and methanol in mass ratio 100:1-20 ratio is added in the reactor with stirring；Then press
Fatty acid methyl ester and methanol quality and 0.5-3% ratio add titanium-silicon molecular sieve catalyst；Then start stirring and will react
System is warming up to 60-75 DEG C；After question response system temperature is raised to design temperature, hydrogen peroxide is added dropwise by measuring pump by certain speed
Into reaction system, epoxidation reaction is carried out；After the addition of hydrogen peroxide reaches reaction requirement amount, stop reaction, filter out
Titanium-silicon molecular sieve catalyst, catalyst recycle；The reaction product stratification of catalyst has been filtered, upper strata is oil phase, under
Layer is aqueous phase；Oil phase obtains epoxy aliphatic acid methyl ester product after low-temperature reduced-pressure distillation dehydration；It is used as and follows after aqueous phase recovery methanol
Ring cooling water, methanol loop use.After aforesaid way is handled, the acid number of product epoxy aliphatic acid methyl ester product is less than
0.5mgKOH/g, iodine number are less than 10gI/100g, and epoxide number is more than 3.5%.
Embodiment is set forth below, the method for the present invention will be further described, but not only limit these embodiments.
Embodiment 1
By the fatty acid methyl ester that 100g iodine numbers are 92（Sinopec Shijiazhuang biodiesel base provides）Mixed with 5g methanol
Close, and be added in 250ml three-necked flask, add 1.05g HTSs（Sinopec Jian Chang catalyst branch company）
Add in the mixture of fatty acid methyl ester and methanol, be then turned on stirring and be warming up to 70 DEG C；After temperature is to design temperature, open
Hydrogen peroxide feed pump is opened, the hydrogen peroxide that concentration is 50% is added drop-wise in reaction system, hydrogen peroxide adds with 0.1ml/min speed
Enter amount to calculate by the 50% of fatty acid methyl ester quality.After hydrogen peroxide addition reaches setting value, stop hydrogen peroxide feed pump, and
Stop heating and stirring, reaction product is transferred in separatory funnel, separate oil phase and aqueous phase.Oil phase product is de- through being evaporated under reduced pressure
After water, its acid number, iodine number, epoxide number are detected, and calculates its yield, the results are shown in Table 1.
Embodiment 2
By the fatty acid methyl ester that 100g iodine numbers are 92（Sinopec Shijiazhuang biodiesel base provides）Mixed with 10g methanol
Close, and be added in 250ml three-necked flask, add 3.0g HTSs（Sinopec Jian Chang catalyst branch company）Add
In the mixture for entering fatty acid methyl ester and methanol, it is then turned on stirring and is warming up to 65 DEG C；After temperature is to design temperature, open
Hydrogen peroxide feed pump, the hydrogen peroxide that concentration is 50% is added drop-wise in reaction system with 0.2ml/min speed, hydrogen peroxide adds
Amount calculates by the 40% of fatty acid methyl ester quality.After hydrogen peroxide addition reaches setting value, stop hydrogen peroxide feed pump, and stop
Only heat and stir, reaction product is transferred in separatory funnel, separate oil phase and aqueous phase.Oil phase product is dehydrated through being evaporated under reduced pressure
Afterwards, its acid number, iodine number, epoxide number are detected, and calculates its yield, the results are shown in Table 1.
Embodiment 3
By the fatty acid methyl ester that 100g iodine numbers are 92（Sinopec Shijiazhuang biodiesel base provides）Mixed with 20g methanol
Close, and be added in 250ml three-necked flask, add 0.6g HTSs（Sinopec Jian Chang catalyst branch company）Add
In the mixture for entering fatty acid methyl ester and methanol, it is then turned on stirring and is warming up to 75 DEG C；After temperature is to design temperature, open
Hydrogen peroxide feed pump, the hydrogen peroxide that concentration is 50% is added drop-wise in reaction system, hydrogen peroxide adds with 0.05ml/min speed
Enter amount to calculate by the 50% of fatty acid methyl ester quality.After hydrogen peroxide addition reaches setting value, stop hydrogen peroxide feed pump, and
Stop heating and stirring, reaction product is transferred in separatory funnel, separate oil phase and aqueous phase.Oil phase product is de- through being evaporated under reduced pressure
After water, its acid number, iodine number, epoxide number are detected, and calculates its yield, the results are shown in Table 1.
Embodiment 4
By the fatty acid methyl ester that 100g iodine numbers are 92（Sinopec Shijiazhuang biodiesel base provides）Mixed with 1g methanol
Close, and be added in 250ml three-necked flask, add 3.01g HTSs（Sinopec Jian Chang catalyst branch company）
Add in the mixture of fatty acid methyl ester and methanol, be then turned on stirring and be warming up to 75 DEG C；After temperature is to design temperature, open
Hydrogen peroxide feed pump is opened, the hydrogen peroxide that concentration is 50% is added drop-wise in reaction system, hydrogen peroxide adds with 0.1ml/min speed
Enter amount to calculate by the 60% of fatty acid methyl ester quality.After hydrogen peroxide addition reaches setting value, stop hydrogen peroxide feed pump, and
Stop heating and stirring, reaction product is transferred in separatory funnel, separate oil phase and aqueous phase.Oil phase product is de- through being evaporated under reduced pressure
After water, its acid number, iodine number, epoxide number are detected, and calculates its yield, the results are shown in Table 1.
Embodiment 5
By the fatty acid methyl ester that 100g iodine numbers are 92（Sinopec Shijiazhuang biodiesel base provides）Mixed with 10g methanol
Close, and be added in 250ml three-necked flask, add 2.2g HTSs（Sinopec Jian Chang catalyst branch company）Add
In the mixture for entering fatty acid methyl ester and methanol, it is then turned on stirring and is warming up to 70 DEG C；After temperature is to design temperature, open
Hydrogen peroxide feed pump, the hydrogen peroxide that concentration is 50% is added drop-wise in reaction system with 0.1ml/min speed, hydrogen peroxide adds
Amount calculates by the 40% of fatty acid methyl ester quality.After hydrogen peroxide addition reaches setting value, stop hydrogen peroxide feed pump, and stop
Only heat and stir, reaction product is transferred in separatory funnel, separate oil phase and aqueous phase.Oil phase product is dehydrated through being evaporated under reduced pressure
Afterwards, its acid number, iodine number, epoxide number are detected, and calculates its yield, the results are shown in Table 1.
The embodiment product analysis data of table 1
Claims (2)
- A kind of 1. method of titanium molecular sieve catalysis synthesizing epoxy fatty acid methyl ester, it is characterised in that：Using HTS to urge Agent, a certain amount of hydrogen peroxide is added dropwise to fatty acid methyl ester and carbinol mixture at a certain temperature；After reacting certain time, mistake The titanium-silicon molecular sieve catalyst in product is isolated in filter, and catalyst recycles；The reaction product of catalyst has been filtered through simple Separation, oil mixture obtain low acid number, iodine number, the epoxy aliphatic acid methyl ester product of high epoxy value through distillation dehydration；Aqueous phase passes through Directly used as recirculated water after recovery methanol, methanol loop uses；The usage amount of HTS is raw fatty acid methyl esters and the 0.5-3.0% of methanol gross mass；Methanol content is the 1-20% of raw fatty acid methyl esters quality in reaction system；The concentration of oxidant hydrogen peroxide is 50%, is added dropwise with certain speed to reaction system, usage amount is fatty acid methyl ester The 40-50% of quality.
- 2. according to the method for claim 1, it is characterised in that：Epoxidation reaction temperature is 60-75 DEG C.
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| CN201310113772.1A CN103172597B (en) | 2013-04-03 | 2013-04-03 | The method of titanium molecular sieve catalysis synthesizing epoxy fatty acid methyl ester |
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| CN201310113772.1A CN103172597B (en) | 2013-04-03 | 2013-04-03 | The method of titanium molecular sieve catalysis synthesizing epoxy fatty acid methyl ester |
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| CN103172597B true CN103172597B (en) | 2017-12-22 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262550A (en) * | 1992-04-30 | 1993-11-16 | Arco Chemical Technology, L.P. | Epoxidation process using titanium-rich silicalite catalysts |
| US5374747A (en) * | 1993-12-23 | 1994-12-20 | Arco Chemical Technology, L.P. | Epoxidation process and catalyst therefore |
| CN1294586A (en) * | 1998-03-24 | 2001-05-09 | 索尔维公司 | Method for making oxirane |
| CN1639143A (en) * | 2002-03-04 | 2005-07-13 | 住友化学工业株式会社 | Method for producing propylene oxide |
-
2013
- 2013-04-03 CN CN201310113772.1A patent/CN103172597B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262550A (en) * | 1992-04-30 | 1993-11-16 | Arco Chemical Technology, L.P. | Epoxidation process using titanium-rich silicalite catalysts |
| US5374747A (en) * | 1993-12-23 | 1994-12-20 | Arco Chemical Technology, L.P. | Epoxidation process and catalyst therefore |
| US5684170A (en) * | 1993-12-23 | 1997-11-04 | Arco Chemical Technology, L.P. | Epoxidation process |
| CN1294586A (en) * | 1998-03-24 | 2001-05-09 | 索尔维公司 | Method for making oxirane |
| CN1639143A (en) * | 2002-03-04 | 2005-07-13 | 住友化学工业株式会社 | Method for producing propylene oxide |
Non-Patent Citations (2)
| Title |
|---|
| Epoxidation of unsaturated fatty esters over large-pore Ti-containing molecular sieves as catalysts: important role of the hydrophobic-hydrophilic properties of the molecular sieve;M. A. Camblor等;《Chem. Commun.》;19970101;第795页右栏第5、6段，第796页左栏表2 * |
| Titanium-Silica Catalysts for the Production of Fully Epoxidised Fatty Acid Methyl Esters;Matteo Guidotti等;《Catal. Lett.》;20071121;第122卷(第1-2期);第53-56页 * |
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