CN102010332A - Method for catalytic production of trimethylolpropane oleate by using solid superacid and application of method - Google Patents
Method for catalytic production of trimethylolpropane oleate by using solid superacid and application of method Download PDFInfo
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- CN102010332A CN102010332A CN2010105110512A CN201010511051A CN102010332A CN 102010332 A CN102010332 A CN 102010332A CN 2010105110512 A CN2010105110512 A CN 2010105110512A CN 201010511051 A CN201010511051 A CN 201010511051A CN 102010332 A CN102010332 A CN 102010332A
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Abstract
The invention relates to a method for catalytic production of trimethylolpropane oleate by using solid superacid and an application of the method. The method comprises the following steps: esterification reaction: mixing trimethylolpropane with oleic acid according to the weight ratio of 1:(2.1-9.5), simultaneously adding the solid superacid, and carrying out reaction under the vacuum degree of 10-1000Pa and the temperature of 120-200 DEG C for 4-10 hours; filtration: using a 10-600 mesh filter mesh or a filter plate to filter reaction products, and removing the solid superacid; and removal of unreacted reactants: heating the reaction products after the filtration to 180-300 DEG C, keeping the vacuum degree of a system at 1-1000Pa, carrying out vacuum distillation for 40-120 minutes, and removing the unreacted reactants to obtain the trimethylolpropane oleate. The method has the advantages of solving the problems of complex product separation, poor product quality, dark color, more side reactions, environmental pollution and the like caused by the use of sulfuric acid during the traditional production processes of the trimethylolpropane and the oleic acid.
Description
Technical field
The present invention relates to the method and the application thereof of the solid superacid as catalyst production tricarboxymethyl propane oleate that contamination-free produces in a kind of production process.
Background technology
Lubricating oil in use, along with the running of machinery, the environment of 50% of lubricating oil total mass around can spilling into.And the major ingredient base oil in the conventional lubrication oil uses the separated from petroleum thing usually, and its biological degradability is poor, and general degradation rate has only about 20%, and lubricating oil pollution on the environment problem is very serious.The lubricity of vegetables oil is good, and biological degradability is good, and environmentally safe has become the first-selection of top-grade lubricating oil.The tricarboxymethyl propane oleate that with the vegetables oil is raw material is a kind of excellent lubrication agent, has good thermostability, biological degradability.The method of producing tricarboxymethyl propane oleate at present mainly contains following three kinds.
Ester-interchange method:, under the effect of alkali, react the preparation tricarboxymethyl propane oleate then earlier with oleic acid and methyl alcohol prepared in reaction Witconol 2301 with TriMethylolPropane(TMP).This method complex process, long reaction time, production cost is higher.
The sulphating method: with sulfuric acid is catalyzer, and TriMethylolPropane(TMP) and oleic acid direct reaction are obtained product.Because sulfuric acid has stronger oxidisability, can make reactant generation oxidizing reaction, the product colour that makes is darker, must just can obtain the finished product through operations such as decolourings.Also can cause to a certain degree pollution when in addition, removing remaining vitriolic in the product to environment.
The soild oxide method: with soild oxide such as zinc oxide is catalyzer, and TriMethylolPropane(TMP) and oleic acid direct reaction are obtained product, is 02111552.4 patent as the patent No..But oxide compound commonly used as zinc oxide, can generate corresponding oleate with elaidin reaction, and the product that finally obtains easily produces foam, brings difficulty for the product separation purifying.
In order to reduce the production cost of tricarboxymethyl propane oleate, eliminate the problem of environmental pollution that its production process causes, need on the basis of traditional processing technology, develop new production method.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of production method of tricarboxymethyl propane oleate, purpose is to simplify production technique, reduces the production cost of tricarboxymethyl propane oleate, eliminates in the production process harm to environment.
For reaching the method that above-mentioned purpose solid superacid as catalyst of the present invention is produced tricarboxymethyl propane oleate, constitute by following step: esterification: TriMethylolPropane(TMP) and oleic acid are pressed mass ratio 1: 2.1-9.5 mixing, add solid super-strong acid simultaneously, under 10-1000Pa vacuum tightness, 120-200 ℃ was reacted 4-10 hour; Filter: use 10-600 mesh filter screen or filter plate, reaction product is filtered, remove solid super-strong acid; Remove the unreacted reactant: the reaction product after the filtration is heated to 180-300 ℃, and system vacuum tightness remains on 1-1000Pa, removes the unreacted reactant, and obtains tricarboxymethyl propane oleate in underpressure distillation 40-120 minute.
Described solid super-strong acid consumption is the 0.1%-4% of TriMethylolPropane(TMP) and oleic acid total mass.
Described solid super-strong acid is meant the Hammett functional value H of expression strength of acid
0＜-11.9 solid acid.
A kind of solid super-strong acid is the application of catalyzer in the preparation tricarboxymethyl propane oleate.
Advantageous effect of the present invention: more can enhance productivity with respect to ester-interchange method; Solved in traditional TriMethylolPropane(TMP) and the oleic acid production process because product separation complexity, poor product quality, the color of using sulfuric acid to bring are dark, side reaction reaches problems such as environmental pollution more; Use contains the solid super-strong acid of zirconium, titanium or rare earth metal, does not have oleate to generate in reaction process, has solved easy foaming of product and has been difficult to the shortcoming of purifying.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Get TriMethylolPropane(TMP) 100kg, oleic acid 630kg mixes, and pulverulent solids super acids 0.73kg, solid super-strong acid are SO
4 2-/ ZrO
2-Al
2O
3Under 500Pa vacuum tightness, 180 ℃ were reacted 6 hours, products therefrom is filtered with 600 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 200 ℃, 200Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 1 hour, obtained tricarboxymethyl propane oleate, and esterification yield is 93.5% after testing.
Embodiment 2
Get TriMethylolPropane(TMP) 100kg, oleic acid 630kg mixes, and pulverulent solids super acids 0.73kg, solid super-strong acid are SO
4 2-/ ZrO
2Under 500Pa vacuum tightness, 180 ℃ were reacted 7 hours, products therefrom is filtered with 600 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 200 ℃, 200Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 1 hour, obtained tricarboxymethyl propane oleate, and esterification yield is 91.3% after testing.
Embodiment 3
Get TriMethylolPropane(TMP) 100kg, oleic acid 420kg mixes, and pulverulent solids super acids 20.8kg, solid super-strong acid are SO
4 2-/ TiO
2-Al
2O
3-SiO
2Under 400Pa vacuum tightness, 190 ℃ were reacted 5 hours, with products therefrom with 500 purpose strainer filterings, solid super-strong acid is filtered out, the underpressure distillation under 220 ℃, 600Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 1.5 hours, obtained tricarboxymethyl propane oleate, and esterification yield is 96.5% after testing.
Embodiment 4
Get TriMethylolPropane(TMP) 100kg, oleic acid 210kg mixes, and solid super-strong acid 4.2kg, solid super-strong acid are SO
4 2-/ TiO
2-WO
3, SO
4 2-/ TiO
2-WO
3Handle through granulation, particle dia 2mm, under 100Pa vacuum tightness, 120 ℃ were reacted 10 hours, products therefrom with 45 purpose strainer filterings, is filtered out solid super-strong acid, and the unreacted reactant was removed in the underpressure distillation under 180 ℃, 200Pa vacuum tightness of the reaction product after the filtration in 40 minutes, obtain tricarboxymethyl propane oleate, esterification yield is 94% after testing.
Embodiment 5
Get TriMethylolPropane(TMP) 100kg, oleic acid 950kg mixes, and pulverulent solids super acids 5.25kg, solid super-strong acid are SO
4 2-/ TiO
2-Tm, under 10Pa vacuum tightness, 200 ℃ were reacted 4 hours, products therefrom is filtered with 600 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 250 ℃, 1Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 98% after testing.
Embodiment 6
Get TriMethylolPropane(TMP) 100kg, oleic acid 320kg mixes, and pulverulent solids super acids 4.2kg, solid super-strong acid are SO
4 2-/ ZrO
2-MCM-41, under 800Pa vacuum tightness, 160 ℃ were reacted 5 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 280 ℃, 1000Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 120 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 92% after testing.
Embodiment 7
Get TriMethylolPropane(TMP) 100kg, oleic acid 460kg mixes, and pulverulent solids super acids 8.4kg, solid super-strong acid are S
2O
8 2-/ ZrO
2-Fe
2O
3Under 1000Pa vacuum tightness, 160 ℃ were reacted 10 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 230 ℃, 500Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 50 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 93% after testing.
Embodiment 8
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 14.6kg, solid super-strong acid are S
2O
8 2-/ ZrO
2-Al
2O
3Under 100Pa vacuum tightness, 185 ℃ were reacted 10 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 220 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 95% after testing.
Embodiment 9
Get TriMethylolPropane(TMP) 100kg, oleic acid 620kg mixes, and pulverulent solids super acids 14.4kg, solid super-strong acid are S
2O
8 2-/ ZrO
2-SiO
2Under 600Pa vacuum tightness, 170 ℃ were reacted 8 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 200 ℃, 500Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 50 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 97.5% after testing.
Embodiment 10
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 8.4kg, solid super-strong acid are SO
4 2-/ TiO
2-La
3+Under 100Pa vacuum tightness, 180 ℃ were reacted 8 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 200 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 98.5% after testing.
Embodiment 11
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 8.4kg, solid super-strong acid are S
2O
8 2-/ ZrO
2-La
2O
3Under 100Pa vacuum tightness, 180 ℃ were reacted 8 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 200 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 97.4% after testing.
Embodiment 12
Get TriMethylolPropane(TMP) 100kg, oleic acid 630kg mixes, and pulverulent solids super acids 5.3kg, solid super-strong acid are SO
4 2-/ TiO
2-MoO
3Under 900Pa vacuum tightness, 170 ℃ were reacted 10 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 220 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 50 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 98.7% after testing.
Embodiment 13
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 8.4kg, solid super-strong acid are SO
4 2-/ ZrO
2-Sm
2O
3Under 200Pa vacuum tightness, 187 ℃ were reacted 9 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 230 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 98.4% after testing.
Embodiment 13
Get TriMethylolPropane(TMP) 100kg, oleic acid 620kg mixes, and solid super-strong acid 10.8kg, solid super-strong acid are SO
4 2-/ TiO
2-Al
2O
3-SiO
2, SO
4 2-/ TiO
2-Al
2O
3-SiO
2Handle through granulation, particle is diameter 1.8mm, length is the columnar product of 10mm, under 200Pa vacuum tightness, 190 ℃ of reactions 5 hours, with products therefrom with 10 purpose strainer filterings, solid super-strong acid is filtered out, the underpressure distillation under 220 ℃, 200Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 50 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 95.5% after testing.
Embodiment 14
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 13.6kg, solid super-strong acid are SO
4 2-/ TiO
2-Fe
3O
4Under 100Pa vacuum tightness, 180 ℃ were reacted 8 hours, products therefrom is filtered with 600 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 230 ℃, 500Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 60 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 94.7% after testing.
Embodiment 15
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 11.6kg, solid super-strong acid are SO
4 2-/ ZrO
2-Pt, under 100Pa vacuum tightness, 190 ℃ were reacted 8 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 220 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 98.8% after testing.
Embodiment 16
Get TriMethylolPropane(TMP) 100kg, oleic acid 950kg mixes, and pulverulent solids super acids 21.4kg, solid super-strong acid are SO
4 2-/ ZrO
2-CeO
2Under 200Pa vacuum tightness, 185 ℃ were reacted 10 hours, products therefrom is filtered with 600 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 260 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 50 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 96.7% after testing.
Embodiment 17
Get TriMethylolPropane(TMP) 100kg, oleic acid 580kg mixes, and pulverulent solids super acids 8.5kg, solid super-strong acid are WO
3/ ZrO
2-SiO
2Under 100Pa vacuum tightness, 180 ℃ were reacted 10 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 220 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 60 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 95.8% after testing.
Embodiment 18
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 15.5kg, solid super-strong acid are SO
4 2-/ ZrO
2-SnO
2-Nd
2O
3Under 200Pa vacuum tightness, 190 ℃ were reacted 8 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 250 ℃, 300Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 94.1% after testing.
Embodiment 19
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 14.5kg, solid super-strong acid are WO
3/ TiO
2Under 100Pa vacuum tightness, 180 ℃ were reacted 9 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 270 ℃, 200Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 50 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 95.5% after testing.
Embodiment 20
Get TriMethylolPropane(TMP) 100kg, oleic acid 620kg mixes, and pulverulent solids super acids 2.5kg, solid super-strong acid are B
2O
3/ ZrO
2Under 100Pa vacuum tightness, 185 ℃ were reacted 8 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 220 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 94.5% after testing.
Embodiment 21
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 14.5kg, solid super-strong acid are WO
3/ SnO
2Under 100Pa vacuum tightness, 180 ℃ were reacted 8 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 240 ℃, 200Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 50 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 94.8% after testing.
Embodiment 22
Get TriMethylolPropane(TMP) 100kg, oleic acid 930kg mixes, and pulverulent solids super acids 14.5kg, solid super-strong acid are S
2O
8 2-/ TiO
2-MoO
3Under 100Pa vacuum tightness, 185 ℃ were reacted 7 hours, products therefrom is filtered with 500 purpose filter clothes, solid super-strong acid is filtered out, the underpressure distillation under 290 ℃, 100Pa vacuum tightness of reaction product after the filtration was removed the unreacted reactant in 40 minutes, obtained tricarboxymethyl propane oleate, and esterification yield is 95.6% after testing.
Unreacted reactant described in the foregoing description 1-22 is responseless TriMethylolPropane(TMP) or oleic acid.
Claims (4)
1. solid superacid as catalyst is produced the method for tricarboxymethyl propane oleate, its feature is made of following step: esterification: TriMethylolPropane(TMP) and oleic acid are pressed mass ratio 1: 2.1-9.5 mixing, add solid super-strong acid simultaneously, under 10-1000Pa vacuum tightness, 120-200 ℃ was reacted 4-10 hour; Filter: use 10-600 order filter cloth or filter screen, reaction product is filtered, remove solid super-strong acid; Remove the unreacted reactant: the reaction product after the filtration is heated to 180-300 ℃, and system vacuum tightness remains on 1-1000Pa, removes the unreacted reactant, and obtains tricarboxymethyl propane oleate in underpressure distillation 40-120 minute.
2. solid superacid as catalyst according to claim 1 is produced the method for tricarboxymethyl propane oleate, it is characterized in that described solid super-strong acid consumption is the 0.1%-4% of TriMethylolPropane(TMP) and oleic acid total mass.
3. solid superacid as catalyst according to claim 2 is produced the method for tricarboxymethyl propane oleate, it is characterized in that described solid super-strong acid is meant the Hammett functional value H of expression strength of acid
0＜-11.9 solid acid.
4. a solid super-strong acid according to claim 1 is the application of catalyzer in the preparation tricarboxymethyl propane oleate.
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| CN102826999A (en) * | 2011-06-15 | 2012-12-19 | 何节玉 | Method for synthesizing neopentyl glycol oleate |
| CN102875374A (en) * | 2012-02-28 | 2013-01-16 | 四川西普化工股份有限公司 | Method for producing pentaerythritol oleate under catalysis of granular solid superacid |
| CN102887825A (en) * | 2012-09-04 | 2013-01-23 | 陕西省石油化工研究设计院 | Method for preparing polyol ester lubricating oil by using composite solid acid catalyst |
| CN107537502A (en) * | 2017-09-07 | 2018-01-05 | 南京大学昆山创新研究院 | A kind of both sexes solid catalyst, Its Preparation Method And Use |
| CN108570342A (en) * | 2018-05-24 | 2018-09-25 | 江苏昊科汽车空调有限公司 | Degradable compressor oil composition and preparation method thereof |
| CN110090667A (en) * | 2018-01-30 | 2019-08-06 | 南京大学昆山创新研究院 | The preparation method and applications of zirconium metal organic framework UiO-66 catalyst |
| WO2024050894A1 (en) * | 2022-09-08 | 2024-03-14 | 江苏正丹化学工业股份有限公司 | Synthesis method for tetraoctyl pyromellitate |
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| CN102826999A (en) * | 2011-06-15 | 2012-12-19 | 何节玉 | Method for synthesizing neopentyl glycol oleate |
| CN102826999B (en) * | 2011-06-15 | 2015-03-11 | 何节玉 | Method for synthesizing neopentyl glycol oleate |
| CN102875374A (en) * | 2012-02-28 | 2013-01-16 | 四川西普化工股份有限公司 | Method for producing pentaerythritol oleate under catalysis of granular solid superacid |
| CN102887825A (en) * | 2012-09-04 | 2013-01-23 | 陕西省石油化工研究设计院 | Method for preparing polyol ester lubricating oil by using composite solid acid catalyst |
| CN107537502A (en) * | 2017-09-07 | 2018-01-05 | 南京大学昆山创新研究院 | A kind of both sexes solid catalyst, Its Preparation Method And Use |
| CN107537502B (en) * | 2017-09-07 | 2020-02-18 | 南京大学昆山创新研究院 | Amphoteric solid catalyst, preparation method and application thereof |
| CN110090667A (en) * | 2018-01-30 | 2019-08-06 | 南京大学昆山创新研究院 | The preparation method and applications of zirconium metal organic framework UiO-66 catalyst |
| CN108570342A (en) * | 2018-05-24 | 2018-09-25 | 江苏昊科汽车空调有限公司 | Degradable compressor oil composition and preparation method thereof |
| WO2024050894A1 (en) * | 2022-09-08 | 2024-03-14 | 江苏正丹化学工业股份有限公司 | Synthesis method for tetraoctyl pyromellitate |
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Application publication date: 20110413 |