CN105268482B - The preparation method of fatty acid methyl ester alkoxylating catalyst - Google Patents
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Abstract
The present invention relates to the preparation method of fatty acid methyl ester ethoxylation catalyst, solve the problems such as EO profile exponents in catalyst reaction product present in prior art are low.Using comprising the following steps：(1) it is 1 by mol ratio:(1~10) carboxylic acid anhydrides is mixed to get mixture i with AEO heating；(2) the one or more of one or more with rare earth metal salt of alkali salt are added in mixture i and heat to be well mixed and obtain mixture ii, wherein alkali salt, rare earth metal salt and mixture i mass ratios is (0.1~0.3):(0.01~0.10):1；(3) pH to 5~8 that mixture ii is adjusted with the concentrated sulfuric acid obtains mixture iii；(4) mixture iii is dried in vacuo below 100 DEG C and obtains the technical scheme of the catalyst, preferably solve the technical problem, in the production available for fatty acid methyl ester ethoxylation catalyst.
Description
Technical field
The present invention relates to a kind of preparation method for fatty acid methyl ester one-step method alkoxylating catalyst.
Background technology
Fatty acid methyl ester ethoxy compound (ethoxylated fatty acid methyl esters), referred to as
FMEE, it is a kind of ester-ether type nonionic surfactant of new double end-blockings.Due to fatty acid methyl ester ethoxy compound one end
With-the OCH similar to grease3, according to the principle of similar compatibility, compared with traditional fatty acid polyether, aliphatic alcohol polyether etc.,
There is stronger dirt-removing power, there is good water solubility, the advantages that fusing point is low, and emulsion dispersion ability is strong, and foam is few；The other product is easy
Degraded, it is a kind of really environment-friendly type surfactant.Fatty acid methyl ester compound is widely applied to leather, weaving, change
In cosmetic industry.FMEE, close to TX, NP and OP series containing APEO, is strict with to environmental protection abroad in various performances
Background under, replace toy, floor, textile garment that TX or NP handle etc. using FMEE, it is possible to reduce cause in exit procedure
Trade dispute.
Due to fatty acid methyl ester unlike aliphatic acid, fatty alcohol or fatty amine etc. contain active hydrogen, therefore urged with traditional soda acid
Agent is difficult ethoxylation (ethyleneoxide addition, i.e. EO addition), i.e., enabled, conversion ratio is also low, and product impurity content is high, at present
Mostly using bimetallic or poly-metal deoxide or salt as catalyst.Reaction temperature is 160~180 DEG C, and reaction pressure exists
0.3MPa or so, catalyst amount 0.1~1.0%
United States Patent (USP) US6008392 (Process for Preparing Alkoxylated Fatty Acid Alkyl
Esters a kind of fatty acid methyl ester ethoxylation catalyst) is disclosed, catalyst mainly based on Al/Mg hydrotalcites, adds simultaneously
Add a small amount of LiOH or SnO2Form.For methyl laurate ethoxylation, LiOH or SnO is not added in discovery2When, unreacted EO
Content more than 1.5%, EO profile exponents [EO adductions number account in total component in the component of the scopes of n ± 2 (not including raw alcohol and
PEG content (wherein n is the EO adductions number of major constituent))], less than 70%；Add LiOH or SnO2Preferably, but catalyst amount
All more than 1.0%, reaction speed is slow.
United States Patent (USP) US5220246 (Process for Alkoxylation of Esters and Products
Produced Therefrom) disclose a kind of active alkoxide calcium aluminium composite catalyst and be used for coconut acid methylester ethoxylation,
The average adduct numbers of EO are 8, and polyethylene glycol is higher than 2.0% in product, and unreacted fatty acid methyl ester is more than 0.5%, and catalyst is used
Measure as 1.0%.
The weak point of the catalyst of above-mentioned prior art is：EO profile exponents are low in product, accessory substance is more.
The content of the invention
One of technical problems to be solved by the invention are second present in prior art after catalyst ethoxylation
A kind of the problem of EO profile exponents are low in epoxide product, accessory substance is more, there is provided new fatty acid methyl ester ethoxylation catalyst
Preparation method, there is this method obtained catalyst to be used for during fatty acid methyl ester ethoxylation EO in ethoxylated products
The characteristics of narrowly distributing, accessory substance are few.
The two of the technical problems to be solved by the invention are the catalysis that one of above-mentioned technical problem preparation method obtains
Agent.
The three of the technical problems to be solved by the invention are two catalyst of above-mentioned technical problem in fatty acid methyl ester
Application in one-step method alkoxylate.
To solve one of above-mentioned technical problem, technical scheme is as follows：Fatty acid methyl ester one-step method alkoxylate
The preparation method of catalyst, including following preparation process：
(1) it is 1 by mol ratio:(1~10) carboxylic acid anhydrides is mixed to get mixture i with AEO heating；
(2) the one or more of one or more with rare earth metal salt of alkali salt are added in mixture i and added
Hot mixing uniformly obtains mixture ii, wherein alkali salt, rare earth metal salt and mixture i mass ratios for (0.1~
0.3):(0.01~0.10):1；
(3) pH to 5~8 that mixture ii is adjusted with the concentrated sulfuric acid obtains mixture iii；
(4) mixture iii is dried in vacuo below 100 DEG C and obtains the catalyst.
In above-mentioned technical proposal, the carboxylic acid anhydrides is preferably the carboxylic acid anhydrides that aliphatic acid is formed.
In above-mentioned technical proposal, the carboxylic acid anhydrides is preferably by C2~C10Carboxylic acid anhydrides.Such as, but not limited to ethanedioic acid acid anhydride,
At least one of succinic anhydride and maleic anhydride, but preferred succinic anhydride.
In above-mentioned technical proposal, the aliphatic acid is preferably binary acid.
In above-mentioned technical proposal, the AEO is preferably represented with below general formula：R-O-(CH2CH2O)n-
H, wherein R are preferably C2~C20Alkyl, more preferably C8~C12, n is the mean number of EO additions, and number is preferably 1~10, more
It is preferred that 6~8.
In above-mentioned technical proposal, the alkali salt and rare earth metal salt preferably independently are selected from nitrate, acetate
Or hydrochloride, more preferably acetate.
In above-mentioned technical proposal, described alkaline-earth metal preferably is selected from least one of magnesium, calcium, strontium and barium.
In above-mentioned technical proposal, the rare earth metal preferably is selected from least one of lanthanum, cerium, praseodymium, neodymium, samarium and europium.It is described
Than individually including lanthanum without good including samarium effect rare earth metal includes lanthanum and samarium simultaneously when, also than individually including samarium without including lanthanum
Effect is good.
As the most preferable technical scheme：Described alkaline-earth metal includes magnesium and barium simultaneously, and the rare earth metal is same
When include lanthanum and samarium.
In above-mentioned technical proposal, the mol ratio of carboxylic acid anhydrides and AEO is preferably 1 in step (1):(2.5
~5)；The preferred pH of pH value in step (3) is more than or equal to 5 and less than 7, and more preferably pH is 5.5~6.5.Add described in step (1)
Hot temperature is preferably 60~120 DEG C；Heat time is preferably 10~60min.Heating-up temperature described in step (2) is preferably 60~
120℃；Heat time is preferably 10~60min.Concentrated sulfuric acid mass percentage concentration described in step (3) is preferably greater than 95%, step
Suddenly the temperature of vacuum dehydration described in (4) be preferably 50 DEG C less than 100 DEG C, dewatering time is preferably 10~60min.
The catalyst of the present invention is evaluated according to following process：By 100~300g fatty acid methyl esters and catalyst (for
0.1~0.8wt% of fatty acid methyl ester) add in 1 liter of stainless steel autoclave with stirring slurry, it is warming up to 80 under stirring
DEG C, 10min is vacuumized, removes moisture and low-boiling point material；Then with nitrogen displacement at least 3 times；In 150~180 DEG C of temperature and
Under 0.3~0.6MPa of pressure, oxirane (EO) is continuously added dropwise to required amount；After aging 30min, it is cold to lead to cooling water progress
But, release, product is removed, weighs, analyze.
Evaluation result shows that the fatty acid methyl ester ethoxylated products EO profile exponents of catalyst of the present invention are more than 80%,
Total byproduct (polyethylene glycol, unreacted fatty acid methyl ester) is less than 1.0wt%, and catalyst amount (accounts for total yield less than 1.0wt%
Quality).Therefore catalyst provided by the invention has the characteristics of ethoxylated products EO profile exponents are high, byproduct is few.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 2g magnesium acetates, 0.5g lanthanum acetates
With 100g mixtures i in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, mixture ii is obtained after cooling；
The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixture pH is 6.0, cooling
After obtain mixture iii；By mixture iii at 80 DEG C, vacuum dehydration 30min, required catalyst is obtained after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 2】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 2g magnesium acetates, 0.5g acetic acid samariums
With 100g mixtures i in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, mixture ii is obtained after cooling；
The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixture pH is 6.0, cooling
After obtain mixture iii；By mixture iii at 80 DEG C, vacuum dehydration 30min, required catalyst is obtained after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 3】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 2g barium acetates, 0.5g lanthanum acetates
With 100g mixtures i in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, mixture ii is obtained after cooling；
The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixture pH is 6.0, cooling
After obtain mixture iii；By mixture iii at 80 DEG C, vacuum dehydration 30min, required catalyst is obtained after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 4】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 2g barium acetates, 0.5g acetic acid samariums
With 100g mixtures i in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, mixture ii is obtained after cooling；
The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixture pH is 6.0, cooling
After obtain mixture iii；By mixture iii at 80 DEG C, vacuum dehydration 30min, required catalyst is obtained after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 5】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 1g magnesium acetates, 1g barium acetates with
And 0.5g lanthanum acetates and 100g mixtures i be in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, after cooling
Obtain mixture ii；The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixing
Thing pH is 6.0, and mixture iii is obtained after cooling；By mixture iii at 80 DEG C, vacuum dehydration 30min, institute is obtained after cooling
The catalyst needed.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 6】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 1g magnesium acetates, 1g barium acetates with
And 0.5g acetic acid samarium and 100g mixtures i be in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, after cooling
Obtain mixture ii；The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixing
Thing pH is 6.0, and mixture iii is obtained after cooling；By mixture iii at 80 DEG C, vacuum dehydration 30min, institute is obtained after cooling
The catalyst needed.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 7】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 2g magnesium acetates and 0.3g acetic acid
Lanthanum, 0.2g acetic acid Samarium and 100g mixtures i are in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, after cooling
Obtain mixture ii；The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixing
Thing pH is 6.0, and mixture iii is obtained after cooling；By mixture iii at 80 DEG C, vacuum dehydration 30min, institute is obtained after cooling
The catalyst needed.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 8】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 2g barium acetates and 0.3g acetic acid
Lanthanum, 0.2g acetic acid Samarium and 100g mixtures i are in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, after cooling
Obtain mixture ii；The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring so that last mixing
Thing pH is 6.0, and mixture iii is obtained after cooling；By mixture iii at 80 DEG C, vacuum dehydration 30min, institute is obtained after cooling
The catalyst needed.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 9】
It is C by 2mol succinic anhydrides and 5mol molecular formula8H17O(CH2CH2O)6H AEO flows back in band
In the three-necked flask of condensation, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；By 1g magnesium acetates, 1g barium acetates with
And 0.3g lanthanum acetates, 0.2g acetic acid Samarium and 100g mixtures i be in the three-necked flask with reflux condensation mode, agitating and heating at 80 DEG C
30min, mixture ii is obtained after cooling；The sulfuric acid for being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring, is made
It is 6.0 to obtain last mixture pH, and mixture iii is obtained after cooling；By mixture iii at 80 DEG C, vacuum dehydration 30min,
Required catalyst is obtained after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 10】
By 2mol succinic anhydrides in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, obtained after cooling
Mixture i；By 2g magnesium acetates, 0.5g lanthanum acetates and 100g mixtures i in the three-necked flask with reflux condensation mode, stirred at 80 DEG C
30min is heated, mixture ii is obtained after cooling；The sulfuric acid for being 98wt% with concentration is added drop-wise to mixture ii under vigorous stirring
In so that last mixture pH is 6.0, and mixture iii is obtained after cooling；By mixture iii at 80 DEG C, vacuum dehydration
30min, required catalyst is obtained after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 11】
It is C by 5mol molecular formula8H17O(CH2CH2O)6H AEO is in the three-necked flask with reflux condensation mode
In, agitating and heating 30min at 80 DEG C, mixture i is obtained after cooling；2g magnesium acetates, 0.5g lanthanum acetates and 100g mixtures i are existed
In three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, mixture ii is obtained after cooling；It is 98wt% with concentration
Sulfuric acid be added drop-wise under vigorous stirring in mixture ii so that last mixture pH be 6.0, obtain mixture after cooling
iii；By mixture iii at 80 DEG C, vacuum dehydration 30min, required catalyst is obtained after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurates, put into while stirring in 1L autoclave；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min to EO additions in 0.4MPa, reaction 30min, is cooled to room temperature and releases material,
244g is weighed as, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various materials contain in ethoxylated products
Amount is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
The composition of 1 catalyst of the present invention of table (various salt are all anhydrous salt in table)
The ethoxylated products analyze data of table 2
Claims (10)
1. the preparation method of fatty acid methyl ester one-step method alkoxylating catalyst, including following preparation process：
(1) it is 1 by mol ratio:(1~10) carboxylic acid anhydrides is mixed to get mixture i with AEO heating；
(2) the one or more of one or more with rare earth metal salt of alkali salt are added in mixture i and heated mixed
Conjunction uniformly obtains mixture ii, and wherein alkali salt, rare earth metal salt and mixture i mass ratios is (0.1~0.3):
(0.01~0.10):1；
(3) pH to 5~8 that mixture ii is adjusted with the concentrated sulfuric acid obtains mixture iii；
(4) mixture iii is dried in vacuo below 100 DEG C and obtains the catalyst；
The alkoxylate is ethoxylation.
2. preparation method as claimed in claim 1, it is characterized in that the carboxylic acid anhydrides that the carboxylic acid anhydrides is formed by aliphatic acid.
3. preparation method as claimed in claim 2, it is characterized in that the carboxylic acid anhydrides is by C2~C10Carboxylic acid anhydrides.
4. preparation method as claimed in claim 2, it is characterized in that the aliphatic acid is binary acid.
5. preparation method as claimed in claim 1, it is characterized in that the AEO is represented with below general formula：R-
O-(CH2CH2O) n-H, wherein R are C2~C20Alkyl, n be EO additions mean number, number be 1~10.
6. preparation method as claimed in claim 1, it is characterized in that the alkali salt and rare earth metal salt independently select
From nitrate, acetate or hydrochloride.
7. preparation method as claimed in claim 1, it is characterized in that described alkaline-earth metal in magnesium, calcium, strontium and barium extremely
Few one kind.
8. preparation method as claimed in claim 1, it is characterized in that the rare earth metal is in lanthanum, cerium, praseodymium, neodymium, samarium and europium
At least one.
9. the fatty acid methyl ester one-step method alkoxylate catalysis that the preparation method in claim 1 to 8 described in any one obtains
Agent.
10. application of the catalyst in fatty acid methyl ester one-step method alkoxylate in claim 9.
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| CN107282135B (en) * | 2016-04-12 | 2020-01-03 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN107442173B (en) * | 2016-05-30 | 2020-10-16 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN107774334B (en) * | 2016-08-29 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for synthesizing fatty acid methyl ester ethoxylate |
| CN111068773B (en) * | 2018-10-18 | 2022-10-11 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5220046A (en) * | 1991-08-22 | 1993-06-15 | Vista Chemical Company | Process for alkoxylation of esters and products produced therefrom |
| CN1451476A (en) * | 2003-03-28 | 2003-10-29 | 中国日用化学工业研究院 | Catalyst for ethoxylation and use thereof |
-
2014
- 2014-07-24 CN CN201410353830.2A patent/CN105268482B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5220046A (en) * | 1991-08-22 | 1993-06-15 | Vista Chemical Company | Process for alkoxylation of esters and products produced therefrom |
| CN1451476A (en) * | 2003-03-28 | 2003-10-29 | 中国日用化学工业研究院 | Catalyst for ethoxylation and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| Comparison of the Kinetics and Composition of Ethoxylated Methyl Dodecanoate and Ethoxylated Dodecanol with Narrow and Broad Distribution of Homologs;Wieslaw Hreczuch;《Journal of Surfactants and Detergents》;19990731;第2卷(第3期);第287-292页 * |
| 脂肪酸甲酯乙氧基化物的生产与应用;徐铭勋;《化工生产与技术》;20120825;第19卷(第4期);第34-37页 * |
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| CN105268482A (en) | 2016-01-27 |
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